Laboratory for Thin Films

• Prof. Aleš Omerzu, PhD
• Assoc. Prof. Ivana Jelovica Badovinac, PhD
• Assoc. Prof. Ivna Kavre Piltaver, PhD
• Prof. Gabriela Ambrožić, PhD
• Assoc. Prof. Iva Šarić Janković, PhD
• Daria Jardas Babić, PhD

Depositing thin films with Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic Layer Deposition, (PEALD). 

Over the past decade, the atomic layer deposition (ALD) has emerged as one of the most promising techniques for the growth of thin oxide films, due to its simplicity, the high conformity, an excellent thickness control and the reproducible growth of defect-free films. In recent years, plasma enhanced ALD (PEALD) technique has been successfully employed to lower the deposition temperatures, as the radicals produced in plasma can significantly improve the reaction of ALD precursors. When growing films with ALD or PEALD a certain amount of impurities, such as chlorine, carbon or hydrogen, can often be found within the films. The concentration and type of impurities and defects can have an important role in the chemical and physical properties of the material, such as conductivity or crystallinity. Therefore, in our research, we try to understand the role of impurities in the formation of the crystal structure and to control the impurity level during the ALD process.

In our recent studies, we investigated the presence of residual chlorine in thin TiO₂ films grown with TiCl₄ by PEALD and ALD at low-temperatures.

We also examined the possibility of controlling the grain size of the as-deposited ALD anatase phase of TiO₂ on any type of substrate by covering the substrate with a thin Al₂O₃ intermediate layer, grown in the same ALD sequence prior to the TiO₂ deposition. At the same time, we studied the influence of the deposition temperature and the number of ALD cycles (i.e. the film thickness) on the crystallinity and the grain size of TiO₂ films deposited on both the clean substrates and substrates covered with Al₂O₃ buffer layers. 

We have studied the properties of thin protective coating layers of Al₂O₃, grown by ALD technique on surfaces of cellulose fibrous materials.Thin barrier coating of Al₂O₃ on the surface of fibrous cellulose material effectively prevents oxygen diffusion and spontaneous ignition of cellulose at elevated temperatures. 

1. K. Ashurbekova, E. Modin, H. Hano, K. Ashurbekova, I. Šarić, R. Peter, M. Petravić, A. Chuvilin, A. Abdulagatov, M. Knez, In Situ Investigation of Thermally Induced Surface Grapheniztion of Polymer-Derived Ceramic (PDC) Coatings from Molecular Layer (MLD) Deposited Silicon-Based Preceramic Thin Films, Chemistry of materials, 35, 8092-8100 (2023).
2. O. Yurkevich, E. Modin, I. Šarić, R. Peter, M. Petravić, M. Knez, Introducing a Robust Flexible Conductive Hybrid: Indium Oxide-ParyleneC Obtained by Vapor Phase Infiltration, Chemistry of materials, 35, 7529-7541 (2023).
3. T. Sharifi, K. Salamon, M. Bohač, R. Peter, T. Čižmar, M. Petravić, K. Juraić, I. Grčić, A. Gajović, Photocatalytic properties of semi-transparent WxTi1-xO2 thin films for water treatment, Catalysus today, 413-415, 113904 (2023).
4. I. Marić, G. Dražić, E. Radin, R. Peter, M. Škarabić, T. Jurkin, A. Pustak, N. Baran, L. Mikac, M. Ivanda et al. Impact of platinum loading and dispersion on the catalytic activity of Pt/SnO2 and Pt/a-Fe2O3, Applied surface science, 607, 155073 (2023).
5. M. Petković Didović, I. Jelovica Badovinac, Ž. Fiket, J. Žigon, M. Rinčić Mlinarić, G. Čanadi Jurešić, Cytotoxicity of Metal Ions Released from NiTi and Stainless Steel Orthodontic Applicances, Part 1: Surface Morphology and Ion Release Variations, Materials, 16, 4156 (2023).
6. R. Peter, A. Omerzu, I. Kavre Piltaver, R. Speranza, K. Salamon, M. Podlogar, K. Velican, M. Percic, M. Petravic, Large enhancement of visible light photocatalytic efficiency of ZnO films doped in-situ by copper during atomic layer deposition growth, Ceramics International 49, 35229-35238 (2023).
7. B. Mifka, M. Tališman Prtenjak, I. Kavre Piltaver, D. Mekterović, J. Kruzmić, M. Marcius, I. Ciglenečki, Intense desert dust event in the northern Adriatic (March 2020); insights from the numerical model application and chemical characterization results, Earth Space Sci.,10 e2023EA002879 (2023).
8. Đurasović, G. Štefanić, G. Dražić, R. Peter, Z. Klencsár, M. Marciuš, T. Jurkin, M. Ivanda, S. Stichleutner, M. Gotić, Microwavw-Assisted Synthesis of Pt/SnO2 for the Catalytic Reduction of 4-Nitrophenol to 4-Aminophenol, Nanomaterials 13 (17), 2481 (2023).
9. D. Čakara, R. Peter, M. Finšgar, Optical Properties and Formation of Corrosion Inhibitor Films at the Cu/Cu2O/H2O Interface, Surfaces and interfaces, 32, 1021108 (2022).
10. G. Begić, M. Petković Didović, S. Lučić Blagojević, I. Jelovica Badovinac, J. Žigon, M. Perčić, O. Cvijanović Peloza, I. Gobin, Adhesion of oral bacteria to commercial d-PTFE membranes: Polymer microstructure makes a difference, International journal of molecular sciences, 23, 2983 (2022).
11. M. Sigler Zekanović, G. Begić, S. Mežnarić, I. Jelovica Badovinac, R. Krištof, D. Tomić Linšak, I. Gobin, Effect of UV Light and Sodium Hypochlorite on Formation and Destruction of Pseudomonas fluorescens Biofilm in Vitro, Publications MDPI, 10, 1901 (2022).
12. N. Novosel, D. R. Gongora, Z. Jagličić, E. Tafra, M. Basletić, A. Hamzić, T. Klaser, Ž. Skoko, K. Salamon, I. Kavre Piltaver, M. Petravić, B. Korin-Hamzić, S. Tomić, B. P. Gorshunov, T. Zhang, T. Ivek, M. Čulo, Grain-Size Induced Collapse of Variable Range Hopping and Promotion of Ferromagnetism in Manganite La0.5Ca0.5MnO3, Crystals, 12, 724 (2022).
13. M. Tkalčević, D. Boršak, I. Periša, I. Bogdanović-Radović, I. Šarić Janković, M. Petravić, S. Bernstorff, M. Mičetić, Multiple exciton generation in 3D ordered networks of Ge quantum wires in alumina matrix, Materials, 15, 5353, 11 (2022).
14. O. Yurkevich, E. Modin, I. Šarić, M. Petravić, M. Knez, Entropy-Driven Self-Healing of Metal Oxides Assisted by Polymer-Inorganic Hybrid Materials, Adv. Mater., 2202989 (2022).
15. Ž. Petrović, A. Šarić, I. Despotović, J. Katić, R. Peter, M. Petravić, M. Ivanda, M. Petković, Surface Functionalisation of Dental Implants with a Composite Coating of Alendronate and Hydrolysed Collagen: DFT and EIS Studies, Materials, 15, 5127 (2022).
16. K. Ashurbekova, K. Ashurbekova, B. Alonso-Lerma, I. Šarić, L. Barandiaran, E. Modin, M. Petravić, R. Perez-Jimenez, M. Knez, Biocompatible Silicon-Based Hybrid Nanolayers for Functionalization of Complex Surface Morphologies, ACS. Appl. Nano Mater., 5, 2, 2762-2768 (2022).
17. M. Vrankić, A. Šarić, T. Nakagawa, Y. Ding, I. Despotović, L. Kanižaj, H. Ishii, N. Hiraoka, G. Dražić, D. Lützenkirchen-Hecht, R. Peter, M. Petravić, Pressure-induced and flaring photocatalytic diversity of ZnO particles hallmarked by finely tuned pathways, J. Alloy Compd., 894, 162444 (2022).
18. G. Ondrašek, I. Jelovica Badovinac, R. Peter, M. Petravić, J. Macan, Z. Rengel, Humates and Chlorides Synergistically Increase Cd Phytoaccumulation in Strawberry Fruits, Heightening Health Risk from Cd in Human Diet, Exposure and Health, 14, 393–410 (2022).
19. S. Mežnarić, I. Jelovica Badovinac, I. Šarić, R. Peter, M. Kolympadi Markovic, G. Ambrožić, Ivana Gobin, Superior UVA-photocatalytic antibacterial activity of a double-layer ZnO/Al2O3 thin film grown on cellulose by atomic layer deposition (ALD), J. Environ. Chem. Eng., 10, 108095 (2022).
20. I. Šarić, M. Kolympadi Markovic, R. Peter, P. Linić, K. Wittine, I. Kavre Piltaver, I. Jelovica Badovinac, D. Marković, M. Knez, G. Ambrožić, In-situ multi-step pulsed vapor phase surface functionalization of zirconia nanoparticles via copper-free click chemistry, Appl. Surf. Sci, 539, 148254, 10 (2021).
21. K. Ashurbekova, K. Ashurbekova, I. Saric, E. Modin, M. Petravic, I. Abdulagatov, A. Abdulagatov, M. Knez, Radical-triggered cross-linking for molecular layer deposition of SiAlCOH hybrid thin films, ChemComm, 57, 2160-2163(2021).
22. K. Ashurbekova, K. Ashurbekova, I. Saric, M. Gobbi, E. Modin, A. Chuvilin, M. Petravic, I. Abdulagatov, M. Knez, Ultrathin Hybrid SiAlCOH Dielectric Films through Ring-Opening Molecular Layer Deposition of Cyclic Tetrasiloxane, Chem. Mater., 33, 1022-1030 (2021).
23. A. Omerzu, R. Peter, D. Jardas, I. Turel, K. Salamon, M. Podlogar, D. Vengust, I. Jelovica Badovinac, I. Kavre Piltaver, M. Petravic, Large enhancement of photocatalytic activity in ZnO thin films grown by plasma-enhanced atomic layer deposition, Surfaces and Interfaces, 23, 100984 (2021).
24. R. Peter, M. Petravić, Initial stages of oxide formation on copper surfaces during oxygen bombardment at room temperature, J. Phys. Chem. C, 125, 25290–25297 (2021).
25. H. Otmančić, M. Ivanko, D. Pop Acev, E. Kamenar, I. Jelovica Badovinac, S. Šapalj, Corrosion of dental alloys used for mini implants in simulated oral environment, International journal of electrochemical science, 16, 21085 (2021).
26. M. Malenica, M. Vukomanović, M. Kurtjak, V. Masciotti, S. dal Zilio, S. Greco, M. Lazzarino, V. Krušić, M. Perčić, I. Jelovica Badovinac et al. Perspectives of Microscopy Methods for Morphology Characterization of Extracellular Vesicles from Human Biofluids, Biomedicine, 9, 603 (2021).
27. G. Ondrašek, F. Kranjčec, L. Filipović, V. Filipović, M. Bubalo Kovačić, I. Jelovica Badovinac, R. Peter, M. Petravić, J. Macan, Z. Rengel, Biomass bottom ash & dolomite similarly ameliorate an acidic low-nutrient soil, improve phytonutrition and growth, but increase Cd accumulation in radish, Sci. Total Environ. 753, 141902 (2021).
28. G. Ambrožić, M. Kolympadi Markovic, R. Peter, I. Kavre Piltaver, I. Jelovica Badovinac, Duško Čakara, D. Marković, M. Knez, Building organosilica hybrid nanohemispheres via thiol-ene click reaction on alumina thin films deposited by atomic layer deposition (ALD), J. Colloid Interface Sci. 560 (2020).
29. M. K. Markovic, R. Peter, I. Jelovica Badovinac, I. Sarić, M. Perčić, R. Radičić, D. Marković, M. Knez, G. Ambrožić, ‘Sandwich’-like hybrid ZnO thin filmsproduced by a combination of atomic layer deposition and wet-chemistry using a mercapto silane as single organic precursor, Nanotechnology 31,185603 (2020).
30. R. Peter, K. Salamon, A. Omerzu, J. Grenzer, I. Jelovica Badovinac, I. Šarić, M. Petravić, Role of Hydrogen-Related Defects in Photocatalytic Activity of ZnO Films Grown by Atomic Layer Deposition, J. Phys. Chem. C 124, 8861–8868 (2020).
31. I. Jelovica Badovinac, R. Peter, A. Omerzu, K. Salamon, I. Šarić, A. Samaržija, M. Perčić, I. Kavre Piltaver, G. Ambrožić, M. Petravić, Grain size effect on photocatalytic activity of TiO2 thin films grown by atomic layer deposition, Thin Solid Films 709, 138215 (2020).
32. Ž. Petrović, A. Šarić, I. Despotović, J. Katić, R. Peter, M. Petravić, M. Petković, A New Insight into Coating’s Formation Mechanism Between TiO2 and Alendronate on Titanium Dental Implant, Materials 13, 3220 (2020).
33. M. Tkalčević, L. Basioli, K. Salamon, I. Šarić, J.S. Parramon, M. Bubaš, I. Bogdanović-Radović, S. Bernstorff, Z. Fogarassy, K. Balázsi, M. Petravić, M. Mičetić, Ge quantum dot lattices in alumina prepared by nitrogen assisted deposition: Structure and photoelectric conversion efficiency, Solar Energy Materials and Solar Cells 218,110722 (2020).
34. K. Ashurbekova, K. Ashurbekova, I. Šarić, E. Modin, M. Petravić, I. Abdulagatov, A. Abdulagatov, M. Knez, Molecular layer deposition of hybrid siloxane thin films by ring opening of cyclic trisiloxane (V3D3) andazasilane, Chem. Commun. 56, 8778-8781 (2020).
35. M. Fenero, M. Knez, I. Saric, M. Petravic, H. Grande, J. Palenzuela, Omniphobic Etched Aluminum Surfaces with Anti-Icing Ability, Langmuir, 36, 37, 10916-10922 (2020).
36. I. Jelovica Badovinac, I. Kavre Piltaver, R. Peter, I. Šarić, M. Petravić, Formation of oxides on CoCrMo surfaces at room temperature: An XPS study, Appl.Surf.Sci. 471, 475 (2019).
37. I. Šarić, R. Peter, M.K. Markovic, I.Jelovica Badovinac, C. Rogero, M. Ilyn, M. Knez, G. Ambrožić, Introducing the concept of pulsed vapor phase copper-free surface click-chemistry using the ALD technique, Chem. Commun. 55, 3109-3112 (2019).
38. K. Salamon, M. Mičetić, J. Sancho-Parramon, I. Bogdanović Radović, Z. Siketić, I. Šarić, M. Petravić, B. Bernstorff, -TaON thin films: production by reactive magnetron sputtering and the question of non-stoichiometry, J. Phys. D. 52, 30 (2019).
39. N. Nekić, I. Šarić, K. Salamon, L. Basioli, J. Sancho-Parramon, J. Grenzer, R. Hübner, S. Bernstorff, M. Petravić, M. Mičetić, Preparation of non-oxidized Ge quantum dot lattices in amorphous Al2O3, Si3N4 and SiC matrices, Nanotechnology 30, 33 (2019).
40. M. Vrankić, A. Šarić, S. Bosnar, D. Pajić, J. Dragović, A. Altomare, A. Falcicchio, J. Popović, M. Jurić, M. Petravić, I. Jelovica Badovinac, G. Dražić, Magnetic oxygen stored in quasi-1D form within BaAl2O4 lattice, SciRep, 9, 15158 (2019).
41. A. Omerzu, I. Šarić, I. Kavre Piltaver, M.Petravić, T. Kapun, J. Zuleb, S. Stifter, K. Salamon, Prevention of spontaneous combustion of cellulose with a thin protective Al2O3 coating formed by atomic layer deposition, Surf.Coat.Techn. 333, 81 (2018).
42. I. Šarić, J. Jurec, E. Reijerse, N. Maltar-Strmečki, B. Rakvin, M. Kveder, Impact of disorder on formation of free radicals by gamma-irradiation: Multi-frequency EPR studies of trehalose polymorphs, Journal of physics and chemistry of solids, 123, 124-132(2018).
43. I. Šarić, J. Jurec, E. Reijerse, B. Rakvin, M. Kveder, Impact of disorder on formation of free radicals by gamma-irradiation: Multi-frequency EPR studies of trehalose polymorphs, J. Phys. Chem. Solids 123, 124-132 (2018).
44. I. Šarić, R. Peter, I. Kavre Piltaver, I. Jelovica Badovinac, K. Salamon, M.Petravić, Residual chlorine in TiO2 films grown at low temperatures by plasma enhanced atomic layer deposition, Thin Solid Films 628, 142 (2017).
45. I. Kavre Piltaver, R. Peter, I. Šarić, K. Salamon, I. Jelovica Badovinac, K. Koshmak, S. Nannarone, I. Delač Marion, M.Petravić, Controlling the grain size of polycrystalline TiO2 films grown by atomic layer deposition, Appl. Surf. Sci. 419, 564 (2017).
46. S. Kraljević Pavelić, V. Micek, A. Filošević, D. Gumbarević, P. Žurga, A. Bulog, T. Orct, Y. Yamamoto, T. Preočanin, J. Plavec, R. Peter, M. Petravić, D. Vikić-Topić, K.Pavelić, Novel, oxygenated clinoptilolite material efficiently removes aluminium from aluminium chloride-intoxicated rats in vivo, Micropor.Mesoporous Materials 249, 146 (2017).
47. J. Katić, M. Metikoš-Hukovića, I. Šarić, M. Petravić, Electronic structure and redox behavior of tin sulfide films potentiostatically formed on tin, J. Electrochem. Soc. 164, C383 (2017).
48. R. Peter, I. Šarić, I. Kavre Piltaver, I. Jelovica Badovinac, M. Petravić, Oxide formation on chromium metal surfaces by low-energy oxygen implantation at room temperature, Thin Solid Films 636, 225 (2017).
49. R. Peter, I. Šarić, M.Petravić, Enhanced Oxidation of Nickel at Room Temperature by Low-energy Oxygen Implantation, Croat. Chem. Acta 90, 2 (2017).
50. I. Kavre Piltaver, I. Jelovica Badovinac, R. Peter, I. Šarić, M.Petravić, Modification of molybdenum surface by low-energy oxygen implantation at room temperature, Appl. Surf. Sc. 425, 416 (2017).
51. K. Salamon, M. Buljan, I. Šarić, M. Petravić, S. Bernstorff, Ta2N3 nanocrystals grown in Al2O3 thin layers, Beilstein J. Nanotechnol. 8, 2162 (2017).

Atomic Layer Deposition (ALD)

Laboratory equipment is purchased as part of the project “Research Infrastructure for Campus-based Laboratories at the University of Rijeka” (RISK), which is co-financed by the European Union under the European Regional Development Fund.

Short description:

Atomic Layer Deposition (ALD) is a technique used for a deposition of thin anorganic films, characterized with an excellent precision of thickness of deposited films (in Å-nm range).

Main purpose:

ALD can be used to coat wafers, planar objects and porous bulk materials, as well as particles and complex 3D objects. The essence of this technique is to alternately expose surface of the substrate to two different gas compounds (precursors), and this process is repeated in a cyclic manner. The self-limiting aspect of ALD leads to excellent step coverage and conformal deposition, i.e. the deposited film is homogenious and non-porous. Most commonly synthesized materials in our ALD system are semiconductor or isolating thin films such as oxides: ZnO, Al₂O₃, TiO₂, SiO₂ and nitrides: AlN, TiN, Si₃N₄.

Technical specifications:

Atomic Layer Deposition (ALD) instrument is a Beneq TFS 200 system

• substrate temperature range: 25 – 500 °C
• Maximal substrate dimensions (regular chamber): 200 mm in diameter,
• 3 mm in height
• Maximal substrate dimensions for 3D chamber: 200 mm in diameter,
• 95 mm in height
• Capacitive coupled plasma system (operates at RF of 13,6 MHz and
• plasma power up to 300 W)
• Ozone generator (ozone can be used as an oxygen source for ALD synthesis)
• 4 liquid sources attached to the instrument.

Year of manufacture:

2015.

Source of founding:

“Research Infrastructure for Campus-based Laboratories at the University
of Rijeka” project financed by ERDF

Contacts:

Assoc. Prof. Iva Šarić Janković, PhD (+ 385 51 584 638, iva.saric@uniri.hr)

Sandblaster LN-SBC420

Specification:

• Pedal-controlled blasting gun
• The cyclone assures the continuous extraction of the dust and the sand
• Flexible hose, built into the blasting cabinet
• Inner lighting
• Large sized window
• Large doors on both sides
• Large door on the top
• Water-separating device

Technical details:

• Total size : 1210x610x1700mm
• Blasting cabinet size : 1200x600x370/600mm
• Side door size : 600×370/600mm
• Top door size : 390x1200mm
• Nozzle sizes : 6,7mm
• Air consumption : 160-700ltr/min
• Working pressure : 3,5-5,5bar
• Max. working pressure : 8bar
• Power supply : 220V, 50Hz Control unit : 12V

Industrial Compressor 270ltr, 5.5kW

Technical details:

• Power 5.5kW
• Voltage 400V
• Tank 270l
• Air displacement 827l/min
• Rotation speed 1450rpm
• Operating pressure 10bar
• Number of cylinders 1
• Number of piston 2
• Weight 159kg
• Size 600X1500X1200mm

Carbolite Wire Wound Tube Furnace CTF 12/65/550 1200°C 550mm with Controller 301