Smart Metal Oxide Nanocoatings and HIPIMS Technology (2019 - 2022)

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 01.05.2020. – 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.