Growth of dense Ti3SiC2 MAX phase films elaborated at room temperature by aerosol deposition method

Available online at www.sciencedirect.com

ScienceDirect Journal of the European Ceramic Society 34 (2014) 1063–1072

Growth of dense Ti3SiC2 MAX phase films elaborated at room temperature by aerosol deposition method Malgorzata Anna Piechowiak a,∗ , Joseph Henon a,∗ , Olivier Durand-Panteix b , Grégory Etchegoyen b , Valérie Coudert a , Pascal Marchet a , Fabrice Rossignol a b

a Centre Européen de la Céramique (CEC), SPCTS UMR 7315, 12 rue Atlantis, 87068 Limoges Cedex, France Centre de Transfert de Technologies Céramiques (CTTC), 7 rue Soyouz, Parc d’Ester, BP 36823, 87068 Limoges Cedex, France

Received 7 August 2013; received in revised form 7 November 2013; accepted 10 November 2013 Available online 2 December 2013

Abstract For the very first time, dense and thick films of Ti3 SiC2 , a popular MAX-phase material, were elaborated on glass substrates by the aerosol deposition method (ADM) at RT. The influence of some processing parameters on the deposition rate and morphology of the films was studied. The films revealed an adhesive interface with the substrate and a dense internal microstructure with nanocrystallites resulting from a high fragmentation of the initial powder at the impact. The film surface showed different types of structuration, from a flat to a rough one with the presence of craters, whose deepness and diameter were linked to the film thickness. The deposition rate and film morphology were both influenced by the distance of projection and the carrier gas flow. Films with thicknesses ranging from 0.1 to 16 ␮m were thus obtained with a high deposition rate reaching 4 ␮m min−1 , with a roughness, Ra , lower than 300 nm. © 2013 Elsevier Ltd. All rights reserved. Keywords: Aerosol deposition method; Low temperature process; Coating; MAX-phase; Ti3 SiC2

1. Introduction An original method for fabricating ceramic films, called aerosol deposition method (ADM), was developed by Akedo in the 90s.1 It is known as an original and low cost processing because many kinds of dense ceramic films can be formed at room temperature on a large panel of substrates, including glass2 and low melting temperature materials like plastics/polymers,3,4 with very good adherence, no sintering step, and wide thickness ranges. Moreover, the deposition rates attained by ADM, usually reach 50 ␮m min−1 for the deposition area of 10 × 10 mm2 .5 These rates are much higher in comparison to conventional techniques of ceramic depositions,6 such as non-assisted chemical/physical deposition methods (CVD, PVD) or sol–gel. The film elaboration by the ADM is based on shock-loading solidification resulting from impinging substrate surface by ceramic particles with a high velocity. The growth of films is influenced by many parameters such as: particles size and morphology, their physical properties,7 the carrier gas flow8,9

∗

Corresponding authors. Tel.: +33 587502390; fax: +33 587502304. E-mail address: [email protected] (M.A. Piechowiak).

0955-2219/$ – see front matter © 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jeurceramsoc.2013.11.019

and its nature,10 and the mechanical characteristics and surface roughness of the substrates.11,12 Actually, a large panel of materials has been deposited by ADM, including non-oxides like Ag,13 AlN,14 BiSbTe,15 FeB or NdFeB,16 SmFeN17 ; ceramic oxides such as simple oxides,2,18–21 perovskites PZT, BTO, LNO, MgO,2,11,22,23 and many others,24–26 spinel class of materials,27 ferrites,28 apatites29 ; and more recently ceramic–ceramic,30,31 ceramic–metal32 or ceramic–organic33,34 composites. The potential applications for these films are very large. Among all these possibilities, examples of direct applications have been demonstrated for biomedical coatings,18 membranes,35 microdevices,2 thermal barriers, electrolytes or anticorrosion coatings for SOFC.36 Among this panel, the MAX-phase family of materials has not been yet deposited by ADM. The MAX-phase family of materials was discovered at the end of the 60s by Jeitschko and Nowotny37 but a real interest was developed in the middle of the 90s with the work of Barsoum and El-Raghy.38 The general behavior of a MAX-phase is original39 as it combines some characteristics of both ceramics and metals in the same time.40 In the specific case of Ti3 SiC2 , one of the most studied materials of this family, many properties of interest for potential

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industrial applications can be noticed, such as its good chemical resistance to oxidation and to thermal shock up to 1400 ◦ C,41,42 to acid/base attacks,43 its particular tribological behavior with a self-lubrication ability,44 the good thermal and electrical conductivities.45 These characteristics are very interesting for high performance coatings. In literature, Ti3 SiC2 coatings were realized by different Chemical (CVD) and Physical Vapor Deposition (PVD) such as conventional CVD,46,47 Reactive-CVD48 or Plasma Enhanced-CVD,49 Pulsed Laser Deposition (PLD),50 magnetron sputtering,51,52 or by plasma spraying53 method, but never by ADM. This processing appears to be a fast and low cost way to realize Ti3 SiC2 coatings compared to other coating methods, where, no source of energy is necessary to ablate or vaporize a target, activate or enhance a chemical reaction. Another advantage of ADM is that it requires no gaseous mixture of precursors46,47 and no specific substrates48 to get the right stoichiometry at the end of coating process. ADM allows depositing at room temperature, whereas the minimum temperature used in other processes applied to Ti3 SiC2 films fabrication is typically from 300 ◦ C,50 but most commonly at temperature above 800 ◦ C,52,53 thus limiting those processes to quite refractory substrates. In this article we study the influence of various ADM parameters, such as time, nozzle to substrate distance, and carrier gas flow on the elaboration of Ti3 SiC2 films on glass at room temperature. Films characteristics are reported using analyses of the microstructure, the roughness profile and the surface morphology.

scan repetition was in the range from 10 to 50. The displacement system and the nozzle geometry allowed obtaining film size of 5 mm × 12 mm. During all the deposition time, the apparatus was kept at room temperature, so that consolidation of the film was done without any need for a thermal treatment. 2.2. Characterization techniques The measurement of the particle size distribution was performed by a laser particle size analyzer (HORIBA Partica LA-950). The powder was previously dispersed in ethanol using an ultrasonic treatment. The composition and crystal structure of the powder were studied by X-ray diffraction (Siemens D5000) using Cu K␣ radiation. XRD analysis of the film was carried out using a home-made diffractometer deriving from the Debye–Scherrer geometry.54 The powder morphology and coatings surface aspects were observed using scanning electron microscopy (Cambridge Stereoscan 36). The powder density was measured with a helium pycnometer (Micromeritics AccuPyc II 1340) and the specific surface area with a BET analyzer (Micromeritics ASAP 2020). In order to investigate the film surface morphology we used atomic force microscopy (Agilent 5500 LS, Scientec) in contact mode for observation areas of 25 ␮m2 , 400 ␮m2 and 2500 ␮m2 . Cross sections of the films were observed using a field emission scanning electron microscope (JEOL JSM-7400F) and a high resolution field emission transmission electron microscope (JEOL JEM-2100F). Profiles and roughness of coatings were measured using a profilometer (Veeco Dektak 6M) equipped with 12.5 ␮m diamond stylus.

2. Experimental procedure 3. Results and discussion 2.1. Deposition technique 3.1. Characteristics of Ti3 SiC2 powder The deposition of the Ti3 SiC2 thick films was carried out in an ADM apparatus developed in CTTC in collaboration with the SPCTS laboratory. The apparatus scheme is presented in Fig. 1. The apparatus has been made up of two chambers connected with a narrow delivery pipe. The first chamber was the aerosol generator and the second one was the deposition chamber. The deposition chamber was evacuated during a deposition process using a vacuum pump. The aerosol generator was connected to the carrier gas system. The carrier gas used in this work was nitrogen and its flow rate was controlled in the range from 3 to 7 L min−1 . The dried primary Ti3 SiC2 micronic powder was mixed and stirred in the aerosol generator with the help of a vibration system. The formed aerosol was transferred into the deposition chamber through a pipe thanks to the differential pressure and accelerated to high velocity by a specifically designed nozzle with a rectangular aperture (0.2 mm × 5 mm). The ejected particles have formed a coating by impinging the substrate, the particles fragmentation and stacking at the impact with the substrate lead to layers formation. In this work, as substrates, we have used glass slides with thickness of 1 mm and placed at a distance of 1.5–10 mm away from the nozzle aperture. The substrate was attached to a displacement system along one axis. The deposition time was studied in the range from 2 to 10 min. The scanning speed was 1 mm s−1 and the number of

In order to obtain good coatings using the ADM, literature showed that a great attention must be paid to the powder.55,56 In fact, on one hand, the size of particles has to be small enough to form easily an aerosol. On the other hand, the inertia needed to impact these particles is linked to elevated size and density. For this reason, a good compromise is observed for particle sizes in the range of 0.5–7 ␮m.57,58 Furthermore, this range concerns dispersed particles, in order to avoid projection of agglomerates that leads to absorption of energy for agglomerates crushing instead of particles fragmentation.55–59 In this study, the commercial Ti3 SiC2 powder Maxthal 312 synthesized by KANTHAL without any size adaptation treatment was used. The powder grain size d50 in volume percentage was measured at 7 ␮m and in number percentage at 1 ␮m (Fig. 2). SEM images presented in Fig. 3 confirmed the range of the particle size and clearly disclosed the layered structure of the powder grains. The density and specific surface area of the powder were measured at 4.54 ± 0.01 g cm−3 and 2.55 ± 0.03 m2 g−1 , respectively. The X-ray diffraction analysis (Fig. 4) confirmed information given by the powder supplier indicating the presence of Ti3 SiC2 in majority and beside impurity phase of TiC (JCPDS files – Ti3 SiC2 : 04-012-0631, TiC: 04-002-5248).

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Fig. 1. Schematic of the prototype of aerosol deposition method apparatus.

3.2. Formation of Ti3 SiC2 films by ADM 3.2.1. Grains fragmentation and film microstructure The actual mechanism of a film formation using aerosol deposition method has not been fully understood and clarified yet. Nevertheless, it is proposed that, for formation of ceramic coating by ADM, particle–substrate and particle–particle bonding is promoted due to conversion of a part of the particles’ kinetic energy into thermal energy at the point of impact and particle fragmentation.6 From particles speed measurement and motion energy assessment, it is also considered that, during ADM carried out at room temperature, a dense structure is obtained as a result of the reduction of elementary grains as crystallites or polycrystalline particles by fracture and/or plastic deformation of aerosol particles.2–60 The ADM does not demand preparation of the substrate surface such as intermediate layers,52 cleaning or poling. It is assumed that substrates undergo cleaning during the very early stage of the process, because of particles impacting the substrate and acting in a similar way as sandblasting does.6 After the cleaning phase, the first deposition stage starts. Hereafter, we propose an assumption for the film growth on relatively hard substrates from a powder exhibiting a wide particles size distribution from hundred nanometers up to several microns

Fig. 2. Particles size distribution of Ti3 SiC2 powder in (a) number and (b) volume percentage.

and a rather large average particles size above 1 ␮m. We suggest that, in the first stage, the aerosol particles crash onto the substrate (Fig. 5(a)), forming at first thin and not very rough layer. With time, in the second stage of the process (Fig. 5(b)), following particles experience fragmentation; while particles from the first layer get impinged and so that they are compressed and/or slid aside. This may cause a laminar wavelike internal

Fig. 3. SEM images of the Ti3 SiC2 powder (a) presenting the powder size distribution and (b) the typical laminar structure of powder grains.

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Fig. 4. X-ray diffraction pattern of Ti3 SiC2 powder. Fig. 7. SEM image of representative fractured cross-section of Ti3 SiC2 film.

Fig. 5. Model of mechanism of film formation by aerosol deposition method.

organization of the coating layers and an increase of roughness of the surface. The observation of a representative film surface using FEG-SEM (Fig. 6(a)) and AFM (Fig. 6(b)) revealed particular surface microstructure that is not porous but rough due to the presence of many craters. These results confirm the simple formation mechanism proposed above. The observations of the surface carried out with higher magnifications (Fig. 6(c) and (d)) show clearly that the coating is made up from grains in the range of 50–200 nm, what is the obvious result of particles fragmentation at the impact. Fig. 7 shows the fractured cross-sectional SEM images of the representative Ti3 SiC2 film elaborated by ADM. As expected the transversal section shows a high density, free of microcracks

Fig. 6. Surface images of a representative Ti3 SiC2 film analyzed using (a, c) FEG-SEM and (b, d) AFM.

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10 (c)

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0 0

2000

4000

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Displacement (µm) Fig. 10. Sectional profile of Ti3 SiC2 films elaborated for d = 1.5 mm and D = 5 L min−1 for different deposition times (a) 2 (b) 4 (c) 8 and (d) 10 min.

Fig. 8. TEM images of Ti3 SiC2 film cross section presenting (a) the dense structure composed of fragmented grains and (b) the small crystallites.

microstructure. Moreover, the obtained cross-section discloses wavelike laminar structures as discussed above. The TEM analysis (Fig. 8(a)) of the cross-section of a representative film confirms that the film is composed of grains significantly smaller than the average size of the impacting primary Ti3 SiC2 powder. Selected area diffraction pattern gives an evidence of the polycrystalline structure of the film and implies on small size of crystallites. Image in Fig. 8(b) confirms the presence of small crystallites with a size of 5–20 nm, indicating on fragmentation of primary powder particles into pieces during deposition process, thus forming the typical nanostructure of coatings obtained by the ADM.2 The X-ray analysis of the representative film deposited on glass slide (see Fig. 9) shows the amorphous phase for 2θ from 15 to 35 degrees that might come

Fig. 9. X-ray diffraction pattern of (a) primary powder and (b) the film deposited on glass.

from the substrate or partial amorphization of the film. Nevertheless the diffractogram confirms the presence of the crystalline phases whose diffraction peaks correspond well to those ones of phase Ti3 SiC2 previously found for the primary powder, as well as to the minor phase TiC. This indicates that the primary powder formulation is preserved into the film deposited by ADM and no new crystalline phase is created. This is a great advantage compared to previously synthesized Ti3 SiC2 films that contains impurities in significant proportions.51,53 Observed peaks are much larger than those of the powder what indicates on discussed before the microstructure composed of small crystallites with no preferential organization of the film. However, one must admit that the microstructure and the surface morphology of our ADM films are very particular in comparison to those obtained following other processing routes. The mechanisms involved necessary induce a disordered structure with defects. In our case, due to the pseudo-ductile nature of the Ti3 SiC2 phase, a polycrystalline structure is obtained, with well fragmented nanocrystalline grains, but possibly a bit of amorphization as well. This is for sure far from well organized epitaxial and crystalline structures obtained by PVD for instance.52 One must also be aware that some authors managed to recover a partial order in ADM films of anisotropic grains by post-annealing treatments allowing a posteriori grain growth.61 This is a possibility that is offered to further improve the functional properties of ADM coatings. 3.2.2. Influence of deposition parameters on film growth and surface morphology 3.2.2.1. Deposition time. One series of Ti3 SiC2 films was elaborated for a carrier gas flow D = 5 L min−1 and with a projection distance d = 1.5 mm with different deposition times ranging from 2 to 10 min. The section profiles of these films are reported in Fig. 10 for different deposition times. Their corresponding thicknesses and roughness values Ra were measured for the flat part of the profile (e.g. for displacement from 2000 to 4000 ␮m in Fig. 10) and they are reported in Fig. 11 as a function of the deposition time. The roughness of the glass substrate is presented for t = 0 min and its value is equal to 12 nm. The thickness of films increases quite linearly with time from 1.2 to 10 ␮m, so that the maximum deposition rate is equal to

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300 (b)

250 200

6

150 4

100

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e (µm)

8

50 0

0 0

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4

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8

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Time (min) Fig. 11. (a) Thicknesses e and (b) roughness Ra of Ti3 SiC2 films elaborated for d = 1.5 mm and D = 5 L min−1 as a function of the deposition time.

1 ␮m min−1 . For a short deposition time, the films exhibit a flat profile (Fig. 10(a)). When increasing of the deposition time and hence the films thickness, large edges appear and their size is amplified (Fig. 10(b)–(d)). This is probably due to the geometry of the nozzle used and to the aerosol velocity profile at the outlet of the nozzle.62 The obtained values of films roughness range from 50 to 300 nm for films thicknesses from 1.2 to 10 ␮m, respectively (see Fig. 11). The relatively low substrate roughness used in this study (12 nm) does not influence significantly the final film roughness. The effect of the substrate roughness was shown in Refs. 7–12. The correlation between the roughness and the film thickness is confirmed by SEM images and by AFM topographies (areas 50 × 50 ␮m2 ) presented in Fig. 12(a), (b) and (c), respectively.

Fig. 12. Ti3 SiC2 films elaborated for d = 1.5 mm and D = 5 L min−1 : SEM images of top surfaces of films observed at magnification (a) 1000×, (b) 4000× and (c) 50 × 50 ␮m2 AFM topographies for samples elaborated after t = 2, 4 and 10 min.

Fig. 13. Optical pictures of Ti3 SiC2 films deposited on glass for D = 5 L min−1 and t = 4 min and different d equal to (a) 1.5, (b) 5 and (c) 10 mm.

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Fig. 14. Ti3 SiC2 films elaborated for D = 5 L min−1 and t = 4 min: (a) profile, (b) SEM images at magnification 1000× and (c) 20 × 20 ␮m2 AFM results of the surface of films elaborated for d = 1.5, 5 and 10 mm.

In fact, after 2 min, the surface of samples is not very rough and made of well fragmented particles. With the increase of deposition time, a typical surface structure for materials deposited by ADM is observed. This surface is made of craters formed by particles impaction. The craters diameter (SEM images) and deepness (AFM data) increase with time. The relative deepness of the craters, expressed in percent of global sample thickness, decreases from 60% for the sample with e = 1.2 ␮m to 25% for the film with e = 10 ␮m. As a conclusion, the impacted particles seem to have a better penetration on films with higher thickness. Actually, we cannot argue if it is caused either by the evolution of the fragmentation and mechanical characteristics of the films along with the thickness, or if it should be attributed to the slide of already fixed layers. 3.2.2.2. Nozzle–substrate distance. In order to see the impact of the projection distance d on the film formation, experiments were carried out for constant carrier gas flow and time (D = 5 L min−1 and t = 4 min) but for d = 1.5, 5 and 10 mm. Simple optical pictures of the samples are presented in Fig. 13. The films look more spread and their borders seem less delimited with the distance. To go further, the film profile obtained with the profilometer, the SEM images and AFM topographies of the surface of the samples are presented in Fig. 14. For constant conditions but

different d values, the deposited films are strongly affected. First, their profiles display different morphology and thicknesses. Their thicknesses profiles (Fig. 14(a)) display a hyperbolic evolution with parameter d and an optimum thickness (13 ␮m) is obtained for d = 5 mm. This corresponds to an improved deposition rate equal to 3.25 ␮m min−1 (multiplied by 4 compared to the sample for d = 1.5 mm). This film has more roughness at its surface and larger base that is also manifested in the form of already discussed less delimited borders in Fig. 13(b). Moreover, its borders are very straight. On the contrary, the film fixed with d = 10 mm also has a significant but lower thickness, and mainly a conic aspect so that the majority of impacted particles seems to be concentrated in a restricted zone. This is probably due the velocity profile, at the outlet of the nozzle, of the tested particles. Secondly, the thickness evolution with d also implies a structuration of the surface, visible in Fig. 14(b) and (c). The thicker the film is, the more its surface will be organized with a crater-like aspect. Although this tendency was previously deduced with the projection time, there is another point that must be added here for the implication of parameter d. In fact, the samples obtained for the distance d = 5 mm and d = 10 mm have similar thicknesses but the deepness of the craters observed on their respective surfaces becomes more important for d = 10 mm. This is confirmed on 20 × 20 ␮m2 AFM observations. As a consequence, the

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Fig. 15. SEM images of the surface for films elaborated with d = 10 mm and D = 5 L min−1 respectively at magnifications (a) 1000× and (b) 5000×.

3.2.2.3. Carrier gas flow. As the particle velocity is directly linked to their density and the carrier gas nature and flow, different gas flows were tested with parameters d = 1.5 mm and t = 4 min. The results of films thickness and roughness obtained as a function of the gas flow are reported in Fig. 16. A minimum carrier gas flow of 3 L min−1 is necessary to have a deposit of

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deepness and diameter of craters not only depends on the sample thickness, but on the distance of projection. A further observation of the surface of the samples reveals some impacted but not fragmented particles inside craters only observable for the film elaborated with d = 10 mm. Fig. 15 illustrates this point, with SEM images on which it is shown some un-fragmented particles laying inside craters. These particles have a diameter around 3–5 ␮m and are close to the average size of non-agglomerated primary particles of the powder (Fig. 2). An explanation could be either an insufficient flow to accelerate enough the biggest particles for a good fragmentation at the distance of 10 mm, or a deceleration of these particles during their course and from a decelerating distance due to possible reverse forces induces by the substrate–gas interaction, as already demonstrated by Katanoda et al.63 with numerical simulations of ADM projection. In fact, these stacked particles were not present at the surface of a sample obtained with a higher flow of 7 L min−1 and at the same distance d = 10 mm.

50 1 0

0 0

2

4

6

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Carrier Gas Flow (L.min-1) Fig. 16. Ti3 SiC2 films elaborated for d = 1.5 mm and t = 4 min: (a) thickness e and (b) roughness Ra values as a function of the carrier gas flow.

100 nm on the glass. Then, as predicted, the velocity of particles is higher when the flow increases. Again, the roughness of the surface is linked to the thickness of the sample. The evolution of the surface morphology of the sample (not represented here) with the flow is very similar to the one with time. In fact, the same structuration is observed SEM images of films surface for different carrier gas flows (Fig. 17). Despite of similar tendency, the internal fragmentation is expected to be different for higher flows.

Fig. 17. Ti3 SiC2 films elaborated for d = 1.5 mm and t = 4 min: SEM images of the surface observed at magnification 1000× for different carrier gas flows D = 3, 4 and 5 L min−1 .

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4. Conclusion

References

For the first time, dense, polycrystalline and adhesive Ti3 SiC2 films with a controlled thickness ranging between 0.1 and 16 ␮m were successfully elaborated by ADM on glass substrates. The influence of parameters such as deposition time, substrate–nozzle distance and carrier gas flow (t, d, D) on the films growth, its 3D architecture and surface morphology, as well the films deposition rates were studied. It was shown that the surface of the films evolves with deposition time, from a smooth and flat surface to a structured rough craterlike surface. Moreover, deposition rate appears to be almost constant with time. Nevertheless, the projection distance can seriously modify both the general morphology of the film, and this tendency is amplified with the carrier gas flow. Using the same powder, and with a constant scanning rate, carrier gas, nozzle and agitation, it is therefore possible to optimize the deposition rate with the carrier gas flow and the projection distance. As an example in this work, for a carrier gas flow D = 5 L min−1 and a time of experiment t = 4 min, the deposition rate was multiplied by a factor 4 just by changing the deposition distance. A maximum deposition rate of 4 ␮m min−1 was obtained for D = 7 L min−1 and d = 5 mm, but it is possible to improve this rate with a higher flow and a fine optimization of the distance d. Then, a processing compromise must be found between a high deposition rate and a good evacuation of the non-impacted particles outside of the deposition chamber. Finally, it appears that the macroscopic surface roughness (Ra ) increases with the thickness of the sample, whatever the parameters used in this work. It is not excluded that the internal grain fragmentation is influenced by these parameters. One of the important parameters influencing the impact velocity is the carrier gas flow. Complementary TEM observations along the thickness of samples might help to study this issue. Studied ADM coatings exhibit valuable properties, as an example, preliminary electrical characterizations show very promising results in terms of the conductivity level. In a future work, complementary electrical and mechanical properties of the Ti3 SiC2 films fabricated by ADM will be explored and compared to the state of the art in the literature.

1. Akedo J, Lebedev M. Microstructure and electrical properties of lead zirconate titanate (Pb(Zr52 /Ti48 )O3 ) thick films deposited by aerosol deposition method. Jpn J Appl Phys 1999;38(9B):5397–401. 2. Akedo J. Room temperature impact consolidation (RTIC) of fine ceramic powder by aerosol deposition method and applications to microdevices. J Therm Spray Technol 2008;17(2):181–98. 3. Ryu J, Kim KY, Choi JJ, Hahn BD, Yoon WH, Lee BK, et al. Flexible dielectric Bi1.5 Zn1.0 Nb1.5 O7 thin films on a Cu–polyimide foil. J Am Ceram Soc 2009;92(2):524–7. 4. Taira Y, Hatono H, Tokita M, Sawase T. Thickness and surface structure of a ceramic layer created on three indirect resin composites with aerosol deposition. J Prosthodontic Res 2010;54(4):168–72. 5. Akedo J, Lebedev M, Iwata A, Nakano S, Ogiso H. Aerosol deposition for nanocomposite material synthesis – a novel method of ceramics processing without firing. Ceram Eng Sci Proc 2003;24(3):9–14. 6. Akedo J. Aerosol deposition (AD) integration techniques and their application to microdevices. In: Singh M, Ohji T, Asthana R, Mathur S, editors. Ceramic integration and joining technologies: from macro to nanoscale. 1st ed. Hoboken: John Wiley & Sons Inc; 2011. p. 489–520. 7. Lee DW, Nam SM. Factors affecting roughness of Al2 O3 films deposited on Cu substrates by aerosol deposition method. J Ceram Processing Res 2010;11(1):100–6. 8. Sugimoto S, Maeda T, Kobayashi R, Akedo J, Lebedev M, Inomata K. Magnetic properties of Sm–Fe–N thick film magnets prepared by the aerosol deposition method. IEEE Trans Magn 2003;39(5): 2986–8. 9. Uemishi Y, Takino J, Nishikawa K, Sato Y, Yoshikado S. Optical and electrical properties of Al2 O3 films grown by aerosol deposition. J Aust Ceram Soc 2012;48(1):64–8. 10. Imanaka Y, Takenouchi M, Akedo J. Ceramic dielectric film for microwave filter deposited at room temperature. J Cryst Growth 2005;275(1–2):e1313–9. 11. Oh JM, Nam SM. Role of surface hardness of substrates in growing BaTiO3 thin films by aerosol deposition method. Jpn J Appl Phys 2009;48(9 Pt 2) [article no. 09KA07:1–5]. 12. Kim CW, Choi JH, Kim HJ, Lee DW, Hyun CY, Nam SM. Effects of interlayer roughness on deposition rate and morphology of aerosol deposited Al2 O3 thick films. Ceram Int 2012;38(7):5621–7. 13. Kim YH, Lee JW, Kim HJ, Yun YH, Nam SM. Silver metallization for microwave device using aerosol deposition. Ceram Int 2012;38(S1): S201–4. 14. Heo YJ, Kim HT, Kim KJ, Nahm S, Yoon YJ, Kim J. Enhanced heat transfer by room temperature deposition of AlN films on aluminum for light emitting diode package. Appl Therm Eng 2013;50(1):799–804. 15. Baba S, Huang L, Sato H, Funahashi R, Akedo J. Room temperature fast deposition and characterization of nanocrystalline (Bi0.4 Sb1.6 Te3 ) thick films by aerosol deposition. J Phys: Conf Ser 2012;379(1) [article no. 012011:1–7]. 16. Sugimoto S, Nakamura M, Maki T, Kagotani T, Inomata K, Akedo J, et al. Nd2 Fe14 B/Fe3 B nanocomposite film fabricated by aerosol deposition method. J Alloys Compd 2006;408–412:1413–6. 17. Sugimoto S, Hirayama T, Maki T, Kogatani T, Inomata K, Akedo J. Fabrication of anisotropic SmFeN films using the aerosol deposition method. J Jpn Soc Powder Powder Metall 2006;53(3):258–62. 18. Ryu J, Park DS, Hahn BD, Choi JJ, Yoon WH, Kim KY, et al. Photocatalytic TiO2 thin films by aerosol deposition: from micron sized particles to nano-grained thin film at room temperature. Appl Catal B: Environ 2008;83(1–2):1–7. 19. Lee BK, Park DS, Yoon WH, Ryu J, Hahn BD, Choi JJ. Microstructure and properties of yttria film prepared by aerosol deposition. J Korean Ceram Soc 2009;46(5):441–6. 20. Choi JJ, Choi JH, Ryu J, Hahn BD, Kim JW, Ahn CW, et al. Microstructural evolution of YSZ electrolyte aerosol-deposited on porous NiO–YSZ. J Eur Ceram Soc 2012;32(12):3249–54. 21. Hsiao CC, Yu SY. Rapid deposition process for zinc oxide film applications in pyroelectric devices. Smart Mater Struct 2012;21(10) [article no. 105012].

Acknowledgments This work is part of the INPACT1 (Inorganic Nanostructured Parts by Aerosol Cold Technology) research project (Patent FR1160790) granted by the Limousin Regional Council. We gratefully acknowledge the help provided by Prof. Christelle Dublanche-Tixier for films profile characterization and Ing. Pierre Carles for TEM characterization. We would also like to thank Prof. Martine Lejeune for general discussions, constructive comments and advices on this work. 1

Grant numbers: 33032/33033/33034.

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