Project number: 1.1.1.1/18/A/073
Duration of the project: 01.03.2019. – 28.02.2022.
Project Manager: Dr.habil.phys. Juris Purans
The project is realized in collaboration between the Institute of Solid State Physics University of Latvia (ISSP UL) and the vacuum coating SME company Inc. SIDRABE.
Agreement on implementation of EU funding project “Smart Metal Oxide Nanocoatings and HIPIMS Technology” between Institute of Solid State physics UL and Central Finance and Contracting Agency was signed on the 15th March, 2019.
The aim of this industrial research project is to develop advanced Reactive High Power Impulse Magnetron Sputtering (HiPIMS) technologies for deposition of functional transition metal oxide (TMO) multilayers for electrochromic and transparent electronics applications to produce and investigate functional TMO multilayers on the basis of ReO3-WO3 and their combination with transparent conducting oxides as novel bifunctional coatings and to develop roll-to-roll reactive R-HiPIMS technologies.
Total eligable costs of the project: 648 750,00 EUR, incl, ERDF funding 374 919,00 EUR.
On the implementation of the project (period 01.01.2022.- 28.02.2022.)
17.03.2022.
The project No. 1.1.1.1/18/A/073 has been implemented in collaboration between the Institute of Solid State Physics University of Latvia (ISSP UL, in Thin Films Laboratory (TFL)) and the vacuum coating SME company Sidrabe Vacuum, Ltd. The project is related to non-economic activity and combines fundamental and industrial research. The total cost is 648750 EUR with 600000 EUR (92.5%) EU contribution. The duration of the project is 36 months (01.03.2020-28.02.2022).
The aim of this industrial research project was to develop advanced Reactive High Power Impulse Magnetron Sputtering (R-HiPIMS) technologies for deposition of functional transition metal oxide (TMO) multilayers for electrochromic and transparent electronics applications. We proposed to produce and investigate functional TMO multilayers and their combination with transparent conducting oxides as novel bifunctional coatings. This Interdisciplinary Project consists of the research activities in Physical and Chemical sciences (1.3, 1.4) and Materials engineering (2.5).
The products of the project:
- Novel R-HiPIMS technology of deposition of functional TMO thin films and multilayers on flexible substrate, and upscale the process (4 patents are submitted: (EU) - EP20020352.9, (LV) - LVP2020000040, (EU) - EP21208104.6, (LV) - LVP2021000084, and description of the roll-to-roll process technology is prepared);
- Novel thin films of ReO3, ReO3-WO3, ReO3/WO3, WO3/Cu/WO3, and Zn-Ir-O with advanced electric and optical properties. The description of local electronic and atomic structures in conjunction with their phys-chem. properties using the state-of-art XAFS. Atomic structures of the TMO using first-principles computer modelling. Original scientific articles published in magazines or conference proceedings included in the Web of Science or SCOPUS (A or B) database) – 15 (14 published and 1 submitted) scientific papers.
The project greatly contribute to advanced materials research on oxide-based optoelectronics devices, which according to the International Technology Roadmap for Semiconductors (ITRS2.0), have global impact ensuring the competitiveness of Latvian science and Industry at the international level. In addition to the impact on the market, there are scientific benefits resulting from the use of interdisciplinary approach combining advanced plasma technologies of R-HiPIMS technology (2.5. Materials engineering) with a theoretical quantum chemical approach along with samples experimental characterisation by phys-chem. methods (1.3. Phys. sciences; 1.4. Chem. sciences) with a focus on the first-principles computer modelling of TMO and heterostructures as well as the state-of-the-art synchrotron-based techniques.
On the implementation of the project (period 01.10.2021.- 31.12.2021.)
11.01.2022.
An article entitled Reactive HiPIMS deposition process of ReOx (x = 1.6–2.9) thin films is submitted in journal Materials Chemistry and Physics (IF=4.1). Repeated XRD measurements were performed to determine the stability of the coatings under ambient conditions. Prior to the publication of the article, in-depth XPS measurements and analysis were performed, revealing Re ions of different oxidation states on the film surface (activity 1).
Bulk and (001) surface F-center ab initio computations in ABO3 perovskites in their high-symmetry cubic phase were performed for SrZrO3, PbTiO3, BaTiO3 and SrTiO3 perovskites, as well as SrF2, BaF2 and CaF2 fluorites, by means of the CRYSTAL computer program package. Results allow to report comprehensive ab initio computation results dealing with F-centers in SrZrO3, PbTiO3, BaTiO3 and SrTiO3 matrixes, as well as SrF2, BaF2 and CaF2 fluorites. As result the publication "Tendencies in ABO3 perovskite as well as SrF2, BaF2 and CaF2 bulk and surface F-center ab initio computations at high symmetry cubic structure", Roberts I. Eglitis, Juris Purans, Anatoli I. Popov, Ran Jia has been prepared and submitted to a scientific journal Symmetry (activity 3).
Article “Unraveling the Structure and Properties of Layered and Mixed ReO3-WO3 Thin Films Deposited by Reactive DC Magnetron Sputtering” written by Boris Polyakov, Edgars Butanovs, Andrejs Ogurcovs, Anatolijs Sarakovskis, Martins Zubkins, Liga Bikse, Jevgenijs Gabrusenoks, Sergei Vlassov, Alexei Kuzmin, and Juris Purans was accepted for publication in ACS Omega journal (IF= 3.5, Q1, 70th Percentile in Chemical Engineering) (activity 4).
In this study, we developed a novel method to produce layered ReO3/WO3 and mixed ReO3-WO3 thin films by reactive DC magnetron sputtering and subsequent film annealing in air. The crystalline structure of obtained films, their optical and electrical properties were studied by several methods, and the formation of ReO3-WO3 solid solutions was proposed. Additionally, first-principles density functional theory (DFT) calculations were performed for selected compositions of solid solutions to model their structural and electronic properties. Our work significantly complements the previous research performed on ReO3-WO3 solid solution thin films and will stimulate future studies on practical applications of the films, such as electro- and photo-catalysis (activity 4).
On the implementation of the project (period 01.07.2021.- 30.09.2021.)
06.10.2021.
During the appropriate time period, the results on the deposition of ReOx thin films by reactive HiPIMS were presented at the international conference “11th International Conference on HIPIMS” and a publication entitled “Reactive HiPIMS deposition process of ReOx thin films” has been prepared for submission to a scientific journal (Activity 1).
Taking into account the analysis of systematic trends of different surfaces, the scientific article “Comparative hybrid Hartree-Fock-DFT calculations 2 of WO2-terminated cubic WO3 as well as SrTiO3, 3 BaTiO3, PbTiO3 and CaTiO3 (001) surfaces” was published (activity 3) in a journal Crystals whose citation index reaches at least 50 per cent of the industry average citation index.
The calculations with Hybrid Density Functional Theory (DFT) and experiments with X-ray absorption spectroscopy (XAS) were performed to conduct the studies of of the local atomic structure around Ir ions in ZnO thin films. The results were used in the analysis of the first principles of thermoelectric properties of materials. A scientific article “The local atomic structure and thermoelectric properties of Ir-doped ZnO: hybrid DFT calculations and XAS experiments” was published (activity 3) in a journal žurnālā Journal of Materials Chemistry C and access to the article in the form of Open Access is being prepared.
A study was conducted, and a novel method was developed to produce layered ReO3/WO3 and mixed ReO3-WO3 thin films by reactive DC magnetron sputtering and subsequent film annealing in air. The crystalline structure of obtained films, their optical and electrical properties were studied by several methods, and the formation of ReO3-WO3 solid solutions was proposed. Additionally, first-principles density functional theory (DFT) calculations were performed for selected compositions of solid solutions to model their structural and electronic properties. Our theoretical predictions qualitatively agree with the experimental results. The publication entitled "Unraveling the Structure and Properties of Layered and Mixed ReO3-WO3 Thin Films Deposited by Reactive DC Magnetron Sputtering" has been prepared for submission to a scientific journal ACS Omega (Activity 4).
The preparation and characterization of ReO3-WO3 thin film samples on quartz was continued.
Publications:
1. Comparative Hybrid Hartree-Fock-DFT Calculations of WO2-Terminated Cubic WO3 as Well as SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) Surfaces
R.I.Eglitis, Juris Purans and Ran Jia
Crystals 2021, 11(4), 455;
DOI: https://doi.org/10.3390/cryst11040455
2. The local atomic structure and thermoelectric properties of Ir-doped ZnO: hybrid DFT calculations and XAS experiments
Andrei Chesnokov, Denis Gryaznov, Natalia V. Skorodumova, Eugene A. Kotomin, Andrea Zitolo, Martins Zubkins, Alexei Kuzmin, Andris Anspoks and Juris Purans
Journal of Materials Chemistry C, 2021,9, 4948-4960
DOI: https://doi.org/10.1039/D1TC00223F
On the implementation of the project (period 01.04.2021. - 30.06.2021.)
23.07.2021.
As part of Project production of new TMO/Me/TMO samples and optimization of parameters were carried out (activity 1).
A scientific publication entitled "Reactive HiPIMS deposition process of ReOx thin films" is in preparation process (activity 1), which includes all the results obtained from the study of the reactive HiPIMS process using the Re target and the characterization of ReOx thin films. The publication describes in detail the changes in pulse current profiles and plasma optical emission spectra (OES) depending on the process parameters. In addition, a comprehensive description of the structure, composition and physical properties of the films is provided.
The first first‐principles calculations were performed for the WO2‐terminated cubic WO3 (001) surface and analyzed the systematic trends for different surfaces. As result the article “Comparative hybrid Hartree-Fock-DFT calculations 2 of WO2-terminated cubic WO3 as well as SrTiO3, 3 BaTiO3, PbTiO3 and CaTiO3 (001) surfaces” were published (activity 3).
The study of the local atomic structure around Ir ions in ZnO thin films with different iridium content was conducted and combined with the hybrid density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS) experiments. Results was then used in the first principles analysis of the thermoelectric properties of material. The research allowed to look at the sensitivity of calculated Seebeck coefficient dependences to the atomic and electronic structure. As result scientific publication "The local atomic structure and thermoelectric properties of Ir-doped ZnO: hybrid DFT calculations and XAS experiments" was prepared and published (activity 3).
The ReO3 and WO3 thin films deposition technology using magnetron sputtering and thermal anneling methods was developed and improved.
The preparation and characterization of ReO3-WO3 thin film samples on quartz was continued.
An article related to experiments with Zinc-Iridium Oxide (Zn-Ir-O) thin films as a p-type conducting material in different conditions is in the process of preparation (Activity 4).
On the implementation of the project (period 01.01.2021. - 31.03.2021.)
April 10 2021
A scientific publication entitled "Reactive HiPIMS deposition process of ReOx thin films" is currently being prepared (activity 1), which includes all the results obtained from the study of the reactive HiPIMS process using the Re target and the characterization of ReOx thin films. The publication describes in detail the changes in pulse current profiles and plasma optical emission spectra (OES) depending on the process parameters. In addition, a comprehensive description of the structure, composition and physical properties of the films is provided.
The formation of CdTe and CdO nanocrystals in a-SiO2/n-Si ion track templates were synthesized by electrochemical and chemical deposition as well as the results of a study of the electrical properties of such new systems were studied. As result the scientific study “Ion track template technology for fabrication of CdTe and CdO nanocrystals” were published.
A study was conducted in which the hybrid density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS) experiments with different parameters were combined and used in the first principles analysis of thermoelectric properties of ZnO material. As result scientific publication "The local atomic structure and thermoelectric properties of Ir-doped ZnO: hybrid DFT calculations and XAS experiments" was submitted and positively reviewed (activity 3). The final version is being prepared (activity 3).
The article “Comparative hybrid Hartree-Fock-DFT calculations 2 of WO2-terminated cubic WO3 as well as SrTiO3, 3 BaTiO3, PbTiO3 and CaTiO3 (001) surfaces” (DOI: 10.1016/j.nimb.2020.08.009), which is based on the first principle calculations for different surfaces has been submitted and accepted for publication.
EXAFS experiments were also held on amorphous ReO3 and preparation of publication is in progress (activity 4). Two more articles are prepared. One related to experiments with Zinc-Iridium Oxide (Zn-Ir-O) thin films as a p-type conducting material in different conditions with focusing on the structure and the electrical properties of Zn-Ir-O films in the large Ir concentration range (activity 4). Additionally, two different substrate temperatures were used – without intentional heating and at 300 OC. Second article is related to research held with nanocrystalline zinc peroxide (nano-ZnO2), its structure, optical and vibrational properties (activity 4). Nanocrystalline zinc peroxide was synthesized through a hydrothermal process and comprehensively studied using several experimental techniques.
PUBLICATIONS:
1. A. Chesnokov, D. Gryaznov, N. V. Skorodumova, E. A. Kotomin, A. Zitolo, M. Zubkins, A. Kuzmin, A. Anspoks, J. Purans.
The local atomic structure and thermoelectric properties of Ir-doped ZnO: hybrid DFT calculations and XAS experiments.
2. ERAF-HIPIMS A.Popov Aktiv 3 : Nopublicēta WoS, Scopus (100%). Kvalificējas 52% >virs 50%.
A. Akilbekov, R. Balakhayeva, M. Zdorovets, Z. Baymukhanov, F.F. Komarov, K. Karim, A.I. Popov, A. Dauletbekova.
Ion track template technology for fabrication of CdTe and CdO nanocrystals.
Nucl. Instrum. Methods Phys. Res. B, 2020, 481, pp. 30–34.
DOI: 10.1016/j.nimb.2020.08.009
On the implementation of the project (period 01.10.2020. - 31.12.2020.)
January 10 2021
As part of Project No 1.1.1.1/18/A/073 “Smart Metal Oxide Nanocoatings and HIPIMS Technology” Thin films of rhenium oxide on quartz substrates were deposited by reactive high power impulse magnetron sputtering (R-HiPIMS) (activity 1). They were made by varying the synthesis parameters - substrate temperature and gas composition during deposition. The surface morphology of the films was studied by high-resolution electron microscopy and demonstrated at different substrate temperatures and post-treatment (annealing). Depending on the manufacturing conditions, both crystalline and amorphous structures were detected. In addition, film composition (XPS), visible and near infrared absorption, and electrical conductivity were measured (activity 4).
Comparative first principles calculations (activity 3) for the ReO2-terminated ReO3 as well as TiO2-terminated SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) surfaces were carried out. The first principles calculations showed systematic trend for the ReO2-terminated ReO3 as well as for TiO2-terminated SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) surfaces is inward relaxation of all upper layer and outward relaxation of all second layer atoms. The only two exceptions from this systematic trend is outward relaxation of the first layer O atom on the TiO2-terminated PbTiO3 (001) surface as well as inward relaxation of the ReO2-terminated ReO3 (001) surface second layer O atom.
Our calculated band gaps at the G-G point for the ReO2-terminated ReO3 as well as TiO2-terminated SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) surfaces in all cases are decreased regarding to the respective bulk values. Just opposite to the TiO2-terminated SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) surfaces, where the Ti-O chemical bond population are larger than in the bulk, near the ReO2-terminated ReO3 (001) surface, the Re-O chemical bond population is reduced in comparison to the bulk value.
The publication “Comparative hybrid Hartree-Fock-DFT calculations of ReO3, SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) surfaces” were prepared (activity 3) within the project.
On the implementation of the project (period 01.05.2020. – 31.07.2020.)
July 31 2020
Research activities (activity 1) on the production of ReO3 and WO3 thin films and their heterostructures were continued within the project activities “Development of the reactive R-HiPIMS sputtering TMO thin film deposition technology” and “Characterization of the obtained TMO and EC samples”. Successfully developed ReO3 and WO3 thin film deposition technology using reactive high power impulse magnetron sputtering (R-HiPIMS) mode and thermal annealing. The R-HiPIMS mode at different pulse configurations and oxygen flows has been studied using I-V-t curves and plasma optical emission spectroscopy. In total, 10 ReO3-WO3 thin film samples on quartz and 18 ReOx samples on capton, glass and quartz were prepared and characterized. International patent (EU) - EP20020352.9 submitted 04.09.2020.
Development (activity 2) of the roll-to-roll reactive R-HiPIMS sputtering TMO thin film deposition technology (activity 2). One patent (LV) - LVP2020000040 already submitted and roll-to-roll R-HIPIMS process technology is described (2 reports). 10 samples synthesized (planned 10), deposition reports are delivered by Ltd.Sidrabe Vacuum. Samples are used for activity N.4. Connecting R-HIPIMS power supply to the chamber with two magnetrons installed Ltd.Sidrabe Vacuum. Choosing optimal hardware for in situ plasma spectroscopy and installing it in the chamber using optical fiber in the way that it gives trustworthy results with stationary installments. Choosing necessary targets and substrates for the experiment.
Four articles have been published (ativity3) in internationally cited journals. We performed, for first time, ab initio calculations for the ReO2-terminated ReO3 (001) surface and analyzed systematic trends in the ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surfaces using first-principles calculations. According to the ab initio calculation results, all ReO3, SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surface upper-layer atoms relax inwards towards the crystal bulk, all second-layer atoms relax upwards and all third-layer atoms, again, relax inwards.
The ReO2-terminated ReO3 and ZrO2-terminated SrZrO3, BaZrO3, PbZrO3 and CaZrO3 (001) surface band gaps at the G–G point are always reduced in comparison to their bulk band gap values. The Zr–O chemical bond populations in the SrZrO3, BaZrO3, PbZrO3 and CaZrO3 perovskite bulk are always smaller than those near the ZrO2-terminated (001) surfaces. In contrast, the Re–O chemical bond population in the ReO3 bulk (0.212e) is larger than that near the ReO2-terminated ReO3 (001) surface (0.170e). Nevertheless, the Re–O chemical bond population between the Re atom located on the ReO2-terminated ReO3 (001) surface upper layer and the O atom located on the ReO2-terminated
ReO3 (001) surface second layer (0.262e) is the largest.
Research activities (activity 4). Two articles have been published in internationally cited journals on ReOx, ReO3 and ReS2: 1) "Understanding the Conversion Process of Magnetron-Deposited Thin Films of Amorphous ReOx to Crystalline ReO3 upon Thermal Annealing", Polyakov et al, Cryst. Growth Des. 2020, 20, 6147−6156 ; 2) "Synthesis and characterization of GaN/ReS2, ZnS/ReS2 and ZnO/ReS2 core/ shell nanowire heterostructures", Butanovs et al, Applied Surface Science 536 (2021) 147841.
1. Crystals 2020, 10, 745; doi.org/10.3390/cryst10090745.
2. J Mater Sci (2020) 55:203–217; doi.org/10.1007/s10853-019-04016-3.
3. International Journal of Modern Physics B Vol. 33, No. 32 (2019) 1950390; DOI: doi.org/10.1142/S0217979219503909;
4. IP Conference Proceedings 2174, 020181 (2019); doi.org/10.1063/1.5134332
5. Surface & Coatings Technology 401 (2020) 126269; doi.org/10.1016/j.surfcoat.2020.126269;
6. Applied Surface Science 536 (2021) 147841; doi.org/10.1016/j.apsusc.2020.147841
7. Cryst. Growth Des. 2020, 20, 6147−6156; dx.doi.org/10.1021/acs.cgd.0c00848 Rights to technologies – patents (2 patents: International patent (EU) - EP20020352.9) and Latvian patent - LVP2020000040.
8. Patent EU Aktiv 1.3 EU EP20020352_9.
9. Patent LV Aktiv 2.3 LVP2020000040.
Technical reports (4 reports).
Awards:
The best achievement of Latvian Science in 2019. Roberts Eglītis, Juris Purāns, ...
Baltic Assembly Prize in Science. Dr. R. Eglitis was awarded for his work cycle “Theoretical predictions of new materials for energy storage and harvesting”, 2020.
On the implementation of the project (period 01.02.2020. - 30.04.2020.)
April 30 2020
As part of Project No 1.1.1.1/18/A/073 “Smart Metal Oxide Nanocoatings and HIPIMS Technology” metal oxide coating samples were made. In the framework of the project activity “Development of the application technology for reactive R-HiPIMS TMO thin film application” injection gas and optical emission systems were adjusted to obtain necessary process parameters and the planned studies were carried out. The planned coating samples were produced, described and the data for the parameters of the coating technological process was prepared. The deposition process parameters were optimized according to the results of the coating measurement analysis.
During the reporting period, the technical report on the design of the R-HiPIMS power supply in a chamber with two magnetic elements was supplemented. Injection gas and optical emission systems were adjusted to obtain optimum process parameters. The planned metal oxide coatings were produced. The effect of technological coating process parameters on the reactive HiPIMS coating results was analyzed. Preparation, description of the sample coatings and data of the parameters of the technological process of coating were prepared and presented. The parameters of the coating process were re-optimized according to the results of the coating measurement analysis.
Research on the synthesis of ReO3 thin films has been continued in the framework of the project activity “Production of the TMO samples and optimization of the reactive R-HIPIMS parameters”. A laser crystallization device for the crystallization of amorphous ReO3 thin film at room temperature has been developed and successfully tested.
The structure and conductivity study of the ReO3 films obtained within the project activity “Characterization of the obtained TMO and EC samples” will be performed using an electrically conductive atomic force microscope (C-AFM, contact mode) depending on the synthesis parameters (annealing temperature - RT, 200 °, 250 ° and 300 ° C). Different scale control maps correlated with topographic maps (scanning area size 1x1, 5x5 and 10x10 microns^2) were recorded, as well as current-voltage characteristics were measured. The topographic image coincides well with the previously obtained SEM data. The optimum annealing temperature is 250 ° -300 ° C, which is in good agreement with previously obtained macroscopic conductivity measurement data.
Recently, using the ab initio Hartree-Fock method, we performed first in the world ab initio calculations also for another, namely, O-terminated ReO3 polar (001) surface by means of the CRYSTAL computer code. According to our ab initio calculations, the upper layer O atoms on the O-terminated ReO3 polar (001) surface relax inwards by 5.32% of our ab initio calculated ReO3 lattice constant (3.758Å). The second layer Re atoms on the ReO3 crystal O-terminated (001) surface relax upwards by 2.66% of a0. Also the second layer O atoms relax upwards, but by a smaller relaxation magnitude, only 0.53% of the ReO3 lattice constant a0. Finally, the third layer O atoms, again, the same as first layer O atom relax inwards, but in this time by a smaller relaxation magnitude, only 0.98% of the lattice constant a0.
Computer modeling of the TMO and TMO/TCO properties (Activity N3). An abstract outlining the results of calculations has been submitted to the E-MRS conference under a title “ZnO-embedded IrO2: a first-principles approach to electronic defects”. It has been accepted, and the talk was scheduled in the conference program as a part of Symposium M: defect-induced effects in nanomaterials.
In the framework of the project activity “Characterization of the obtained TMO and EC samples”, structural and morphology analysis were performed (XRD and SEM measurements), as well as optical (light absorption and transmittance in UV-VIS region) and electrical properties (electrical conductivity and charge carrier mobility) were studied of the as-prepared thin films in relation to the synthesis parameters. EXAFS measurements were also performed on amorphous ReOx-WO3-x and crystalline ReO3, WO3 thin films.
On the implementation of the project (period 01.11.2019. - 31.01.2020.)
January 31 2020
Among the most important achievements in Latvian science 2019 are also researchers of the Project No 1.1.1.1/18/A/073: Dr. Roberts Eglītis, Dr.Juris Purāns.
As part of Project No 1.1.1.1/18/A/073 “Smart Metal Oxide Nanocoatings and HIPIMS Technology” metal oxide coating samples were made. In the framework of the project activity “Development of the application technology for reactive R-HiPIMS TMO thin film application” injection gas and optical emission systems were adjusted to obtain necessary process parameters and the planned studies were carried out.
Testing results for injectable gases and optical emissions systems were analysed and conclusions were reached. The planned sample coatings were manufactured, described and the data for the parameters of the coating technological process was prepared. The coverage process parameters were optimized according to the results of the coating measurement analysis.
Research on the synthesis of ReO3 thin films has been continued in the framework of the project activity “Production of the TMO samples and optimization of the reactive R-HIPIMS parameters”. Successfully developed ReO3-WO3 thin films deposition technology using magnetron sputtering and thermal anneling methods. The ten ReO3-WO3 thin films samples were selected and characterized. Preparation, description of the sample coatings and data of the parameters of the technological process of coating were prepared and presented. The parameters of the coating process were re-optimized according to the results of the coating measurement analysis.
During the reporting period, the technical report on the design of the R-HiPIMS power supply in a chamber with two magnetic elements was supplemented. Injection gas and optical emission systems were adjusted to obtain optimum process parameters. The planned metal oxide coatings were manufactured. The effect of technological coating process parameters on the reactive HiPIMS coating results was analyzed. Preparation, description of the sample coatings and data of the parameters of the technological process of coating were prepared and presented. The parameters of the coating process were re-optimized according to the results of the coating measurement analysis.
We performed B3LYP and B3PW calculations for the upper three layer atom relaxation for the BO2-terminated SrZrO3, BaZrO3, PbZrO3 and CaZrO3 as well as ReO3 (001) surfaces. It is worth to notice that the ReO3 has exactly the cubic ABO3 perovskite structure, but with the only exception, missing A atom. For the case of SrZrO3, BaZrO3, PbZrO3 and CaZrO3 perovskites as well as ReO3 BO2-terminated (001) surfaces, according to our calculations, all upper layer atoms relax in the direction towards the bulk. The ReO2-terminated ReO3 (001) surface upper layer Re atom displacement magnitude (3.19% of a0) is larger than the calculated ABO3 perovskite BO2-terminated (001) surface B atom relaxation magnitudes, which are in the range from 1.30% of a0 for the CaZrO3 till 2.37% of a0 for the PbZrO3. Just opposite, all SrZrO3, BaZrO3, PbZrO3 and CaZrO3 perovskite second layer atoms relax outwards. The only exception from this systematic trend is the second layer ReO2-terminated ReO3 (001) surface O atom inwards relaxation in the direction towards the bulk by a very small relaxation magnitude of -0.32% of a0. All third layer atoms for BO2-terminated SrZrO3, BaZrO3, PbZrO3 and CaZrO3 as well as ReO3 (001) surfaces, again, relax inwards, towards the bulk. Nevertheless, the relaxation magnitudes of all first layer atoms for SrZrO3, BaZrO3, PbZrO3 and CaZrO3 as well as ReO3 BO2-terminated (001) surfaces are much larger than the relaxation magnitudes of the third layer atoms.
In the framework of the project activity “Characterization of the obtained TMO and EC samples”, structural and morphology analysis were performed (XRD and SEM measurements), as well as optical (light absorption and transmittance in UV-VIS region) and electrical properties (electrical conductivity and charge carrier mobility) were studied of the as-prepared thin films in relation to the synthesis parameters. EXAFS measurements were also performed on amorphous ReOx-WO3-x and crystalline ReO3, WO3 thin films.
On the implementation of the project (period 01.07.2019. - 30.10.2019.)
December 16 2019
As part of Project No 1.1.1.1/18/A/073 “Smart Metal Oxide Nanocoatings and HIPIMS Technology” the adaptation of the laboratory equipment and the selection of optimal magnetres were made to obtain heterostructures for metal oxide coatings. In the framework of the project activity “Development of the application technology for reactive R-HiPIMS TMO thin film application” the planned studies were carried out.
Testing results for injectable gases and optical emissions systems were analysed and conclusions were reached. The planned sample coatings were manufactured, described and the data for the parameters of the coating technological process was prepared. The coverage process parameters were optimized according to the results of the coating measurement analysis.
Research on the synthesis of ReO3 thin films has been continued in the framework of the project activity “Production of the TMO samples and optimization of the reactive R-HIPIMS parameters”. Deposition technology of ReO3 thin films has been successfully developed using reactive DC magnetron sputtering. ReO3 samples on quartz, oxidized silicon and Kapton substrates were successfully prepared. The formation of ReO3 from amorphous ReOx was studied at different temperatures (200, 250, 300, 350° C).
Calculating properties of transparent conducting oxides. A new set of calculations has been completed, thus enriching the existing body of knowledge about the material. A summary of the results has been presented in Warsaw on 16.09.2019 during the E-MRS 2019 Fall Meeting as a talk titled “Hybrid density functional calculations of Ir-doped ZnO”. A publication with a working title “Ir+Oi complex in ZnO: hybrid PBE0 calculations and experiment” is a work in progress. This publication will enclose all so far obtained results on the iridium-oxygen complex in the zinc oxide matrix.In the framework of the project activity “Characterization of the obtained TMO and EC samples”, structural and morphology analysis were performed (XRD and SEM measurements), as well as optical (light absorption and transmittance in UV-VIS region) and electrical properties (electrical conductivity and charge carrier mobility) were studied of the as-prepared thin films in relation to the synthesis parameters. EXAFS measurements were also performed on amorphous ReOx and crystalline ReO3 thin films, and it was shown that the EXAFS spectrum of amorphous ReOx films matches ReO2 spectrum.