Tuneable emissivity ceramics and coating in the infrared range

Transition metal oxide materials are finding many applications in electronic and optical devices due to their wide range of electrical, magnetic, and optical properties. Among these interesting properties, the optimization of thermochromic switching in the infrared range is challenging. One of the potential applications of thermochromic IR coating is their use in the field of the IR discretion or furtivity. The concept of thermal furtivity is the ideal situation when an object or a material is undetectable whatever its temperature, comparatively to the observed background, which is supposed to be at constant temperature. In other words, the object and the background have ideally the same emittance whatever the temperature of the object, at least in the detection band of the camera. This situation can be approached if one considers an adaptative material with partial emissivity in band II or III decreasing with temperature. Thus, materials with a low temperature, semiconductor like behavior, and a high temperature metallic state, with a transition temperature adjustable around room temperature, are good candidates for such applications.

The manganite system
In recent work [Appl. Phys. Lett. 89, 081909 (2006), Appl. Phys. Lett. 93, 151910 (2008)], we showed that electron doped (Sm1−x,Cax)MnO3 perovskite manganite are potential infrared thermochromic materials and we have measured the thermal emittance changes at the charge ordering transition of (Sm0.35Ca0.65)MnO3. This property was evidenced in bulk ceramics [Appl. Phys. Lett. 89, 081909 (2006), Appl. Phys. Lett. 93, 151910 (2008)] and more recently in Sm0.5Ca0.5MnO3 films [J. Appl. Phys. 111, 113517 (2012)].


Absorptance spectrum at different temperature for Sm0.35Ca0.65MnO3 ceramic. [Appl. Phys. Lett. 89, 081909 (2006), Appl. Phys. Lett. 93, 151910 (2008)]


Relative integrated intensity in the range 8–14 μm showing the evolution with temperature of the sample opacity of Sm-Ca-Mn bulk ceramics. [Appl. Phys. Lett. 89, 081909 (2006), Appl. Phys. Lett. 93, 151910 (2008)]


Evolution of the infrared transmittance at different temperatures 77 K to 420 K for the Sm0.5Ca0.5MnO3 coating annealed at 1070 K. [J. Appl. Phys. 111, 113517 (2012)].


Average intensity versus temperature of the Sm0.5Ca0.5MnO3 films annealed at 1070 K for each transparency band of the atmosphere: BI (1-2.8 µm), BII (3-5 µm) and B III (8-14 µm) ref [J. Appl. Phys. 111, 113517 (2012)].


The nickelate system
The rare earth nickelate perovskite ReNiO3 has been strongly investigated in the past due to its metal insulator transition easily controllable by changing the rare earth nature. Such compound are however difficult to synthesize, an often need high oxygen pressure for the stabilisation of Ni3+.
In recent work, [Journal of solid state chemistry, 183 (2010) 1663-1669] by using polymeric precursor associated with moderate pressure annealing, we showed that it is possible to obtain rare earth nickelates with metal insulator transition. The perovskite structure was confirmed by electron diffraction and high resolution electon microscopy. The thermal infrared characterization confirmed the metal insulator transition.

Electron diffraction patterns of the Nd0.3Sm0.7NiO3 samples synthesised at 20bar (after [Journal of solid state chemistry, 183 (2010) 1663-1669])

Slight contrast differences can be observed in the [0 1 0] oriented images for the Nd0.3Sm0.7NiO3 prepared at 20 bar.
Thermochromic behavior of Nd0.3Sm0.7NiO3 samples annealed under 20 and 175bar at 278 and 373K.

Recent publication on the topic

Regular papers

F. CAPON, P. RUELLO, J.F. BARDEAU, P.SIMON, P.LAFFEZ, B. DKHIL, L.REVERSAT, K.GALICKA, A.RATUSZNA, « Metal-Insulator transition in thin films of RxR’1-xNiO3 compounds : DC electrical conductivity and IR spectroscopy measurement » Journal of Physics : Condensed Matter 17 (2005) 1137-1150.

P. RUELLO, B. PERRIN, T.PÉZERIL, V.E. GUSEV, P. LAFFEZ, S. GOUGEON, N. CHIGAREV, P. PICART, D. MOUNIER, J.M. BRETEAU, Opto-acoustical spectrum of the Metal-Insulator transition compound NdNiO3 : sub-picosecond pump-probe study, Physica B : Condensed Matter (2005).

P. LAFFEZ , X. Y. CHEN, , G. BANERJEE, T. PEZERIL, M. D. ROSSELL, G. VAN TENDELOO, P. LACORRE, « Growth of La2Mo2O9 films on porous Al2O3 substrates by Radio Frequency Magnetron Sputtering, Thin Solid Films 500 (2006), 27-33.

P. LAFFEZ, M. ZAGHRIOUI, L. REVERSAT, P. RUELLO Electron doped (Sm1-x, Cax)MnO3 Perovskite Manganite as potential infra red switch, Applied Physics Letter, 89 8 (2006) 081909

P RUELLO, S. ZHANG, P LAFFEZ, B PERRIN, V GUSEV, Ultrafast electronic dynamics in the Insulator-Metal transition NdNiO3 compound, Phys Rev B 76, 165107 (2007)

P LAFFEZ, C. NAPIERALA, M. ZAGHRIOUI, V.TA PHUOC, A. HASSINI, MR. AMMAR "Thermal emittance changes at the charge ordering transition of (Sm0.35Ca0.65)MnO3" accepté, Applied Physics Letters 93-15 (2008) 15198

P. RUELLO, P. BABILLOTTE, S.ZHANG, D. MOUNIER, J-M BRETAU, M. EDELY, P. LAFFEZ, V. GOUSSEV. On the optical generation and detection of high frequency ultrasounds: thermal and non-thermal processes J. Acoust. Soc. Am. 123, 3154 (2008)

K. GALICKA, J. SZADE, P. RUELLO, P. LAFFEZ, A. RATUSZNA, « The photoemission study of NdNiO3/NdGaO3 thin films through the metal-insulator transition Applied Surface Science, 225 8 (2009) 4355-4361.

P. LAFFEZ, C. NAPIERALA, R. AMMAR, V TA PHUOC , M ZAGHRIOUI,
(Sm1-x,Cax)MnO3 ceramics with Tunable Emissivity, Advances in Science and Technology 55 (2009) 13-17

C. NAPIERALA, M. EDELY, P. LAFFEZ, L. SAUQUES, Thermo-optical properties of Nd0.3Sm0.7NiO3 ceramic, Advances in Science and Technology 55 (2009) pp 7-12

MR. AMMAR, C. NAPIERALA, P. LAFFEZ, Infrared thermochromic behaviour of Sm0,65Ca0,35MnO3, polymeric composites film, Smart Materials and Structures, 18-5 (2009), 055002

C.NAPIERALA, M. EDELY, P. LAFFEZ, L SAUQUES, Thermo-optical effect of Nd0.3Sm0.7NiO3 ceramic in infrared range, optical materials 31-10 (2009) 1498–1501

P. RUELLO, S. ZHANG, P. LAFFEZ, B. PERRIN, V. GUSEV, Laser induced coherent acoustical phonons mechanisms in metal-insulator transition compound NdNiO3 : thermal and non-thermal processes., Phys Rev B, 79 (2009) 094303.

F CAPON, D HORWAT, J F PIERSON, M ZAGHRIOUI AND P LAFFEZ, Thermochromic effect in NdNiO3−δ thinfilms annealed in ambient air, J. Phys. D: Appl. Phys. 42-18 (2009) 182006.

C. NAPIERALA, C. LEPOITTEVIN M. EDELYL. SAUQUES F. GIOVANELLI P. LAFFEZ, G. VANTEDELOO, Moderate pressure synthesis of rare earth nickelate with metal–insulator transition using polymeric precursors, Journal of Solid State Chemistry, Volume 183, Issue 7, July 2010, Pages 1663–1669

A. BOILEAU, F. CAPON, S. BARRAT, P. LAFFEZ AND J.F. PIERSON “Thermochromic effect at room temperature of Sm0.5Ca0.5MnO3thin films”, Journal of Applied Physics. 111, 113517 (2012)

Book chapter
P. LAFFEZ, P. RUELLO, M. EDELY, Electrical and Infrared properties of RF sputtering rare earth nickelate (RNiO3) thin films with metal Insulator transition, in Leading-Edge Materials Science Research Nova science publisher, article revue, Editors: Paul W. Lamont, ISBN: 1-60021-798-2, 2008

Conferences
P. RUELLO, B. PERRIN, T. PEZERIL, V.E. GUSEV, P. LAFFEZ, N. CHIGAREV, P. PICART, D. MOUNIER, J.M. BRETEAU, Opto-acoustical spectrum of the Metal-Insulator transition compound NdNiO3 : sub-picosecond pump-probe study. Journées Ultrasons-Lasers, Leuven, Belgique 2005.

T. PEZERIL, N. CHIGAREV, P. RUELLO, S. GOUGEON, C. LAUNAY, P. LAFFEZ, D. MOUNIER, P. PICART, J.M. BRETEAU, V. GUSEV, Optical generation and detection of picosecond shear acoustic pulses, Journées Ultrasons-Lasers, Leuven, Belgique, 2005.

T. PEZERIL, N. CHIGAREV, P. RUELLO, S. GOUGEON, C. LAUNAY, P. LAFFEZ, D. MOUNIER, P. PICART, J.M. BRETEAU, V. GUSEV, Generation and detection of picosecond shear acoustic pulses by laser, World congress on ultrasonics merged with Ultrasonics International, Beijing, 2005.

K GALICKA, P. LAFFEZ, A. BULOU, J SZADE, P. RUELLO, A. RATUZNA, Contribution to the study of the electronic state of the rare earth nickelate thin films (NdNiO3/NdGaO3) by XPS and Raman spectroscopy. EMRS 2006 spring meeting 1st European Materials Conference, 29 mai-2 Juin 2006, Nice, France

P LAFFEZ , M ZAGHRIOUI , L REVERSAT, P RUELLO, Infrared Transmission properties of (Sm-Ca-Mn) oxide for thermochromic switching International Symposium on Structure-Property Relationships in Solid State Materials, June 27-30, 2006, Bordeaux France

PATRICK LAFFEZ , MUSTAPHA ZAGHRIOUI , LUC REVERSAT, PASCAL RUELLO,Thermochromic Infrared switching of (Sm-Ca-Mn) oxide 6eme International Conference on Inorganic Materials. 23-26 September 2006. Lubjana Slovénie..

C. NAPIERALA, M. EDELY, P. LAFFEZ, L. SAUQUES, « Infra-Red thermal properties of RNiO3 compounds films with tunable emissivity coating » 3rd international Conference of Smart materials structures systems, 8-13 juin, 2008 Acireale Sicile

P. LAFFEZ, C. NAPIERALA, M. EDELY, S. GOUGEON, L. SAUQUES
SmxNd1-xNiO3 films with tunable emissivity coating 3rd international Conference of Smart materials structures systems, 8-13 juin, 2008 Acireale Sicile

P. RUELLO, P. BABILOTTE, S. ZHANG, D. MOUNIER, J.-M. BRETEAU, M. EDELY, P. LAFFEZ, A. BULOU, B. PERRIN AND V. GUSEV « On the optical generation and detection of high frequency ultrasounds : thermal and non-thermal processes » ACOUSTIC’S 08 Paris 29 June 4 July 2008

BOILEAU, F. CAPON, J.F. PIERSON, S. BARRAT AND P. LAFFEZ “Study of the working pressure effect on NdNiO3 reactive sputter deposited films and annealing process improvement” E-MRS ICAM IUMRS 2011 Spring Meeting – 10-12 mai 2011 Nice France.

BOILEAU, F. CAPON, J.F. PIERSON, S. BARRAT AND P. LAFFEZ “Influence of sputtering parameters and annealing process on NdNiO3 thermochromic thin films” E-MRS Fall Meeting 2011– 19-23 septembre 2011 Varsovie Pologne.

BOILEAU, F. CAPON, J.F. PIERSON, S. BARRAT AND P. LAFFEZ “Thermochromic effect in SmR0.5RCaR0.5RMnOR3R thin films elaborated by DC magnetron co-sputtering” ITFPC & MIATEC 2011– 14-17 novembre 2011 Nancy France.