Inkjet printing of oxide thin films and nanoparticles with potential use for anti-counterfeiting films and patterns

Transcription

1 1 Inkjet printing of oxide thin films and nanoparticles with potential use for anti-counterfeiting films and patterns M. Vilardell, V.R. Vlad, X. Sintas, A. Calleja Oxolutia S.L., Edifici Eureka, PRUAB, Campus de la UAB, Bellaterra, Spain S. Ricart, X. Granados, T. Puig, X. Obradors Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus de la UAB, Bellaterra, Spain

2 Motivation Functional ceramic oxides The unique and high value-added properties of functional ceramic oxides have enabled a significant number of scientific questions and applications Motivation To fully exploit these developments, both the search for and the implementation of low cost and scalable technologies are crucial if they are to have an impact in fields such as electronics, medicine and science, industrial processes, transport and power engineering 2 2

3 Functional ceramic oxides Functionalities: magnetoresistance, UV-upconversion, semiconductivity, piezoelectricity, thermocromicity, etc. Applications Functional devices Films Patterns Chemical approach (CSD, CVD, MOCVD ) Physical approach (PLD, PVD, sputtering ) 3

4 Functional ceramic oxides Functionalities: superconductivity, magnetoresistance, semiconductivity, ferroelectricity, piezoelectricity, etc. Applications Functional devices Full coatings Patterned coatings Chemical approach (CSD, CVD, MOCVD ) Physical approach (PLD, PVD, sputtering ) Chemical Solution Deposition (CSD) 4

5 Chemical Solution Deposition (CSD) and functional ceramic oxides YBa 2 Cu 3 O 7-x on LaAlO 3 SrTiO 3 on silicon BaTiO 3 on silicon Obradors et al, (2006), Supercond. Sci. Technol., 19, S13 (2006) La 0.7 Sr 0.3 MnO 3 on quartz Schwartz et al, C.R. Chimie 7, 433 (2004) CeO 2 on LaAlO 3 Schwartz et al, C.R. Chimie 7, 433 (2004) Pb(Zr x Ti 1-x )O 3 /SrTiO 3 Carretero-Genevrier et al, Adv, Mater., 20, 3672 (2008) CSD versatile, low-cost processing and scalable to large areas Deposition in standard room conditions 0.5 µm Gibert et al., Adv, Mater., 19, 3937(2007) 400 nm Szafraniak et al., APL, 83, 2211 (2003) High degree of control over the composition of the functional oxide 5

6 6 Chemical Solution Deposition (CSD) 1) Precursor solution synthesis Metalorganic precursors in appropriate solvents 2) Precursor solution deposition Spin coating, dip coating, inkjet printing 3) Thermal treatment to obtain the ceramic oxide Two-step process: removal of the organic precursors at low temperatures ( ºC under special circumstances) (pyrolysis process), and crystallization into the desired ceramic phase in a second step at higher temperatures ( 700ºC) (growth process).

7 Precursor solution deposition Full coatings Full coatings Full and patterned coatings Y X Spin coating Homogeneous thin films Lab scale Not available for long length samples Dip coating Industrial scalability Deposition in two sides of the substrate Solution stored in an opened container: o Solvent loss due to the evaporation that may destabilizes the solution o Changes in concentration and rheological properties: variation in film thickness Inkjet printing 7

8 Precursor solution deposition Why inkjet printing in functional oxide manufacturing? 8 Industrial scalability in a continuous reel to reel system Ink supply Cavity PZT Solution stored in a closed vial ink composition and rheological parameters control during deposition Y Nozzle X Possibility to control film thickness high repeatability of drop ejection mechanism Inkjet printing Possibility to deposit according to patterns: versatility to switch on the flight the deposited material and the pattern design for device manufacturing

9 9 Inkjet printing technology Numerous printing processes Continuous mode Drop on demand Thermal inkjet printing Electromagnetic valve Piezoelectric inkjet printing Broad gallery of printed materials Functional ceramic oxides from inks Dispersion of nanoparticles Printed configuration Continuous films Patterns

10 RFID Inkjet printing: applications Printed boards Biomedical applications Biochemical array LED displays Microlenses Sensors Films LSMO film PLC Antennas Photovoltaics 1 µm 10

11 Actors involved in inkjet printing 11 ink Ink properties influencing ink performances viscosity (0.5-15mPa. s ) Density Surface tension (20-30mN/m) Evaporation of solvent Stability substrate Interaction ink-substrate: wettability contact angle surface energy Drop volume Drop speed Drop aim ink properties nozzle diameter printhead Drop formation process Driving waveform

12 OXOLUTIA facilities related to inkjet printing Laboratory tests: Single nozzle piezoelectric printheads Manufacturing R+D: Multinozzle batch printer Manufacturing: Reel to reel continuous system Multinozzle piezoelectric printhead Single nozzle piezoelectric printhead (Ø nozzle : 60µm) 512 Konika-Minolta multinozzle piezohead 12

13 13 Inkjet printing technology Reel-to-Reel IJP setup: continuous deposition Batch deposition printer Reel to reel inkjet equipment R2R deposition system Screening of different tape speed and drop frequencies Optimization of the drying process Take-up reel Drying module XY batch printer Printing module Feeding reel R2R system

14 14 Potential applications: anti-counterfeiting INKJET PRINTING Low cost Scalability Broad range of printed materials Versatility in printed materials and configurations Anti-counterfeit printing applications with oxides?

15 15 Patterning by inkjet printing: magnetoresistive patterns Contactless analog encoder based on Wheatstone bridge LSMO 10mm 10mm Resistance of each branch is in the range of 10KΩ with <20% dispersion between branches Fe 3 O 4 magnetic nanorods La 0.7 Sr 0.3 MnO 3 20 µm 10 µm 1 µm

16 Patterning by inkjet printing: multifilamentary patterns Optical microscopy after pyrolysis Triple perovskite SEM after YBa 2 Cu 3 O 7-x (YBCO) growth 100 µm LAO YBCO LAO LAO K β 200 µm LAO LAO YBCO 50 µm 0,7 30 µm Thickness (µm) 0,6 0,5 0,4 0,3 0,2 0,1 300nm 150µm 0, Width (µm) 5 µm Thin Solid Films 548 (2013) Homogeneous epitaxial tracks are obtained 16

17 Nanoparticle deposition by inkjet printing Fluorescent nanoparticles: Eu, Yb based nanoparticles for anticounterfeiting applications 300 µm 300 µm 300 µm 300 µm 300 µm 300 µm 300 µm 300 µm 300 µm 300 µm 300 µm 300 µm 2 mm 2 mm 2 mm 2 mm Nanoscale 7 (2015)

18 Patterning by inkjet printing: images LAO ICMAB logo paper ICMAB logo by inkjet 10mm 2 mm 10mm After YBCO growth Journal of Imaging Science and Technology 55 (2011) Nanoscale 7 (2015)

19 Nanorelief patterns by CSD Cerium oxide nanoislands: tuning by growth conditions 0.25 M 0.01 M M Solutions concentration 30 min-8 h 1000 o C Ar-H 2 CGO/LAO, a model system Temperature 600 O C 800 O C 900 O C 0.5 µm 0.5 µm 0.5 µm M 1 h Ar-H 2 30 min 1 h 2 h Time M 900 o C Ar-H µm 0.5 μm 0.5 µm

20 Nanorelief patterns by CSD Manganite (La 0.7 Sr 0.3 MnO 3 ) nanowires La 0.7 Sr 0.3 MnO 3 nanowires La 0.7 Sr 0.3 MnO 3 nanowires LaAlO 3 single crystal substrate Chem Mater. 26 (2014) Adv. Funct. Mater. 20 (2010)

21 Microrelief patterns by CSD 21 Stress relaxation: film inhomogeneities as identity signs 100 µm Buckling effect: stress relaxation way during thermal decomposition

22 Layering by inkjet printing: functional oxide films R2R inkjet deposition 20 nm in a continuous mode OM after Ce 0.9 Zr 0.1 O 2 growth 500µm 500µm Sample length: 30cm Reflectometric pattern Reflectance CZO films give a particular reflectometric pattern which may be used as an anti-counterfeiting system Wavelength (nm) 22

23 23 Conclusions Combination of the inkjet printing technology with the Chemical Solution Deposition (CSD) methodology has been demonstrated. Long length functional oxides films and patterns can be manufactured with a tape speed of about 36 m/h and 30 mm wide. This technology opens a broad gallery for anti-counterfeiting applications. 0.5 µm 2 mm

24 Inkjet printing of oxide thin films and nanoparticles with potential use for anti-counterfeiting films and patterns Thank you for your attention!!!!