PLASMA DEVICE FOR DEPOSITING FUNCTIONAL COMPOSITE FILM COMPRISING CRYSTALLIZED PARTICLES EMBEDDED IN A MATRIX AND METHOD OF DEPOSITION THEREOF.

Technical field

[0001] The invention is directed to the field of surface treatment, particularly on a device and a method for depositing a composite functional film on a substrate.

Background art

[0002] Prior art published scientific paper Tricoli, A. et al. (2009). "Anti-fogging nanofibrous S1O2 and nanostructured SiO2-TiO2 films made by rapid flame deposition and in situ annealing". Langmuir, 25: 12578-12584, discloses a method for depositing antifogging and self-cleaning SiO2-TiO2 thin film on a substrate. The method of deposition is performed by flame spray pyrolysis of organometallic solution and by stabilization of the coating by in situ flame annealing. T1O2 precursors are injected in the flame. During deposition, the burner is at a distance of 20 cm of the substrate and reaches a maximum temperature of 550°C ± 20°C. The method of deposition is unsuitable for coating functional thin composite film comprising crystalline metal oxide particles on heat-sensitive substrates.

[0003] Prior art published scientific paper Boscher, N. et al. (2014). "Photocatalytic Anatase titanium dioxide thin films deposition by an atmospheric pressure blown arc discharge". Applied Surface Science, 31 1 , 721 -728, discloses a method for depositing photocatalytic anatase titanium thin films on a substrate by atmospheric pressure blown arc discharge. The deposition is performed by passing the T1O2 precursor in the plasma torch downstream. However, the device and the method are not adapted to deposit, on heat- sensitive substrates, composite functional films of good quality comprising metal oxide crystalline particles.

Summary of invention

Technical Problem [0004] The invention has for technical problem to provide a solution that overcome at least one drawback of the mentioned prior art. Particularly, the invention has for technical problem to provide a device and a method for one-step and low-temperature deposition of a thin functional composite film on heat- sensitive and non-heat-sensitive substrates, at atmospheric pressure.

Technical solution

[0005] The invention is directed to a plasma device for depositing a functional composite film on a substrate at atmospheric pressure, said device comprising a conduit extending along a longitudinal axis with a gas inlet ; a discharge area configured to electrically excite the gas in the conduit at the inlet in order to produce a plasma at atmospheric pressure; a post-discharge area downstream of the discharge area, comprising at least one first inlet through a wall of the conduit, for injecting a first precursor or precursors mixture in the plasma; a plasma outlet; remarkable in that the post- discharge area further comprises at least one second inlet through the wall of the conduit, for injecting a second precursor or precursors mixture in the plasma downstream of the at least first inlet.

[0006] According to a preferred embodiment, the at least one first inlet is located, along the longitudinal axis, at a distance b of the discharge area, said distance b being comprised between 0 mm and 15 mm, preferably inferior to 5 mm.

[0007] According to a preferred embodiment, the at least one first inlet and the at least one second inlet are separated from each other, along the longitudinal axis, with a distance a comprised between 5 mm and 150 mm, preferably between 5 mm and 50 mm.

[0008] According to a preferred embodiment, the device is configured to produce a discharge power density superior or equal to 10 W/cm ² .

[0009] According to a preferred embodiment, the device is supported by a movable support.

[0010] According to a preferred embodiment, each of the at least one first inlet and the at least one second inlet are respectively configured to inject the first and the second precursor or precursors mixtures into a mist and/or aerosol and/or vapour in the post-discharge area. [001 1] According to a preferred embodiment, said substrate is a heat-sensitive substrate

[0012] According to a preferred embodiment said substrate is a one-dimensional, a two-dimensional substrate or a three-dimensional substrate.

[0013] The invention is also directed to a plasma-enhanced chemical vapour deposition method for depositing a functional composite film on a substrate, said method comprising the steps of: producing a plasma with a plasma device; injecting a first precursor or precursors mixture in a post-discharge area of said plasma device; remarkable in that the method further comprises a step of injecting a second precursor or precursors mixture in said post- discharge area of said plasma device, simultaneously to the step of injecting a first precursor or precursors mixture and downstream to the first injection, said plasma device being in accordance with the invention.

[0014] According to a preferred embodiment, said first precursor or precursors mixture comprises a metal oxide precursor and said second precursor or precursors mixture comprises a matrix precursor.

[0015] According to a preferred embodiment, the first precursors mixture further comprises at least one metal oxide doping precursor.

[0016] According to a preferred embodiment, in steps of injecting a first precursor or precursors mixture and a second precursor or precursors mixture, the first precursor or precursors mixture and the second precursor or precursors mixture are injected at a flow speed comprised between 1 and 1000 μΙ_/ηηίη.

[0017] According to a preferred embodiment, in each of the steps of injecting a first precursor or precursors mixture and a second precursor or precursors mixture, said precursors or precursors mixtures are injected with a gas carrier, preferably N2.

[0018] According to a preferred embodiment, the gas carrier is injected at a flow speed comprised between 0.5 and 20 L/min for the first and the second precursor or precursor mixtures.

[0019] According to a preferred embodiment, during deposition, the at least one second inlet is placed, along the longitudinal axis, at a distance c of the substrate to be coat which is comprised between 1 mm and 150 mm. [0020] According to a preferred embodiment, during deposition, the device moves in relation to the substrate.

[0021] According to a preferred embodiment, in step of producing a plasma, a gas is introduced in the gas inlet at a flow speed comprised between 10 and 100

L/min.

[0022] According to a preferred embodiment, the gas introduced in the gas inlet is selected from the group consisting of: Argon, Nitrogen, a mixture of Argon with maximum 20% of Oxygen, a mixture of Nitrogen with maximum 20% of Oxygen or compressed air.

[0023] According to a preferred embodiment, the deposition is carried out at an atmospheric pressure and/or at a substrate temperature comprised between 50 °C and 500°C.

[0024] According to a preferred embodiment, the first precursor or precursors mixture comprises a ΤΊΟ2 precursor or a V2O5 precursor and/or the second precursor or precursors mixture comprises a S1O2 precursor.

[0025] According to a preferred embodiment, the ΤΊΟ2 precursor is selected from the group consisting : titanium isopropoxide, titanium tetrachloride, titanium butoxide, titanium diisopropoxide bis (acetylacetonate) and titanium ethoxide and the S1O2 precursor is selected from the group consisting of hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexaethyldisiloxane, tetraethylorthosilicate, aminopropyl-trimethoxysilane, tetramethyldisiloxane, pentamethylcyclopentasiloxane, octamethylcyclooctasiloxane, vinyltrimethoxysilane, trimethoxypropylsilane, preferably hexamethyldisiloxane.

[0026] The invention is also directed to an antifog composite film comprising a S1O2 matrix, said composite film being produced with the method in accordance with the invention, wherein the first precursor or precursors mixture comprises a T1O2 precursor and the second precursor or precursors mixture comprise a S1O2 precursor.

Advantages of the invention [0027] The invention is particularly interesting in that the device and the method of the invention allows a one-step deposition, at low-temperature, of a functional composite film comprising metal oxide crystalline particles embedded in a matrix. The invention is particularly interesting for depositing functional composite film on heat-sensitive substrates, such as polymers, plastics and/or glass without deteriorating said substrates, while providing a coating of good quality. The invention allows the simultaneous synthesis of metal oxide crystalline particles and their embedding into a matrix deposited with a low substrate temperature thanks to spatially separated, but simultaneously, operated injections of two precursors or precursors mixtures into the stream of the post-discharge area of the plasma device.

Brief description of the drawings

[0028] Figure 1 is a schematic representation of a plasma device in accordance with the invention.

[0029] Figure 2: Raman spectrum of TiO2 SiO2 thin film on a PEN substrate.

[0030] Figure 3a-3d: SEM images of the TiO2/SiO2thin film elaborated from various

HMDSO delivery rates.

[0031] Figure 4a: Graphic of the growth rate ratio of the deposited film as a function of the content of silicon in the film.

[0032] Figure 4b: Graphic of Si/(Si/Ti) ratio of the deposited film as a function of various HMDSO delivery rates.

[0033] Figure 5a: XPS analysis of titanium environment.

[0034] Figure 5b: XPS analysis of silicon environment.

[0035] Figure 6a: Photocatalytic activity of anatase TiO2 SiO2 coatings as function of the Si/(Si/Ti) ratio before and after immersion in an ultrasonic bath.

[0036] Figure 6b: Graphic of the water contact angle of the deposited film as a function of the Si/(Si/Ti) ratio.

Description of an embodiment

[0037] Figure 1 illustrates a plasma device 2 for depositing a functional film on a substrate in accordance with the invention. Particularly, the plasma device 2 is configured to deposit a functional and thin composite film comprising metal oxide crystallized particles on a substrate 4, especially on a heat- sensitive substrate. [0038] The plasma device 2 comprises a conduit 6 extending along a longitudinal axis. The conduit has preferably a tubular shape. The conduit comprises a gas inlet 8 and a plasma outlet 10. The conduit 6 of the device also comprises a discharge area or portion 12 configured to electrically excite the gas so as to produce a plasma at atmospheric pressure. The discharge area 12 can comprise electric means configured to excite the gas. More precisely, the discharge area 12 can comprise two electrodes (not represented) configured to produce an electrical arc when supplying said electrodes with an electrical power source, the discharge area extending approximatively along said electrodes. The gas used to produce the plasma is a plasmagenic gas or non-condensable gas, preferably N2. Preferably, the gas is injected in the gas inlet 8 at a flow speed comprised between 10 and 100 L/min.

[0039] The conduit 6 of the plasma device 2 also comprises a post-discharge area or portion 14 downstream of the discharge area 12 and adjacent to the discharge area 12. The plasma is configured to flow axially from the discharge area 12 through the post-discharge area 14 in a working direction 16, toward the plasma outlet 10 in a coating area 18. The post-discharge area of the plasma device 2 comprises at least one first inlet 20 through a wall of the conduit, for injecting a first precursor or precursors mixture in the plasma. The first inlet 20 or each first inlet 20 is configured to inject a first precursor or precursors mixture in the post-discharge area 14, in the working direction 16. The post-discharge area 14 of the device of the invention further comprises at least one second inlet 22 on the wall of the conduit, for injecting a second precursor or precursors mixture in the plasma downstream of the at least one first inlet 20. The second precursor or precursors mixture is injected in the post-discharge area 14 in the working direction 16. The at least one second inlet 22 is located, along the longitudinal axis, between the at least one first inlet 20 of a first precursor or precursors mixture and the plasma outlet 10.

[0040] The first precursor or precursors mixture comprises a metal oxide precursor.

The first precursors mixture can further comprise at least one metal oxide doping precursor. [0041] The second precursor or precursors mixture comprises a matrix precursor. The term matrix precursor refers herein to any chemical precursor suitable for forming a matrix.

[0042] Metal oxide doping precursor refers herein to any chemical precursor suitable for the doping of the metal oxide material. The choice of the doping precursor will be made according the expected properties of the composite film.

[0043] Each of the at least one first inlet 20 and the at least one second inlet 22 is transversally to the longitudinal axis of the plasma device. The plasma device 2 can comprise several first inlets 20 and several second inlets 22, localised around the conduit 6 of the plasma device, in the post-discharge area 14. As represented in figure 1 , the plasma device 2 can comprise, for example, two opposed first inlets 20 and two opposed second inlets 22, represented by an arrow.

[0044] Each of the at least one first inlet 20 and the at least one second inlet 22 is respectively configured to inject the first and the second precursors or precursors mixtures, respectively, into a mist and/or aerosol and/or vapour in the post-discharge area 14.

[0045] The at least one first inlet and the at least one second inlet are preferably ultrasonic nozzles. Ultrasonic nebulization nozzles Sono-Tek Corporation ™ can be used at a frequency of 120 kHz and a power of 2 W.

[0046] In case of one first inlet and one second inlet, each inlet extends preferably circumferentially around the conduit, in the post-discharge area in order to inject each precursor or precursors mixture homogeneously in the post- discharge area 14.

[0047] As illustrated in figure 1 , the plasma device 2 comprises two opposed first inlets 20 and two opposed second inlets 22, the number of inlets does not limit the invention. The first inlets 20 and the second inlets 22 are separated from each other, along the longitudinal axis, with a distance a comprised between 5 mm and 150 mm, preferably between 5 mm and 50 mm.

[0048] Each first inlet 20 is located at a distance b of the discharge area 12, said distance b being comprised between 0 mm and 15 mm, preferably inferior to 5 mm, more preferably between 1 and 3 mm, along the longitudinal axis. More precisely, each first inlet is located at a distance b of the end of the discharge area, said end being opposed to the gas inlet 8.

[0049] The first and the second precursor or precursors nnixtures are injected in the post-discharge area with a gas carrier, preferably N2.

[0050] The first and the second precursor or precursors nnixtures are preferably injected in the post-discharge area in the form of droplets with a droplet's diameter comprises preferably between 10 and 20 μηη. According to a preferred embodiment, the first precursor or precursors mixture is heated to 90°C during injection in the post-discharge area.

[0051] The device is configured to produce a discharge power density superior or equal to 10 W/cm ² . The discharge power density allows the formation of crystalline metal oxide particles and a solid matrix.

[0052] The first precursor or precursors mixture is thus injected at the nearest position of the discharge area 12. The injection of the first precursor or precursors mixture in this part of the post-discharge area 14 promotes the formation of crystalline metal oxide particles thanks to the high density of reactive species and the relatively high gas temperature in said part. In order to optimize the production of crystalline nanoparticles, the first precursor or precursors mixture is injected in the post-discharge area of the plasma device with a flow speed which is comprised between 1 and 1000 μΙ_-ηηίη- ¹

[0053] On the other hand, the second precursor or precursors mixture is simultaneously injected in a lower part of the plasma stream in the post- discharge area and preferably close to the substrate to coat, in order to promote heterogeneous chemical reactions at the substrate surface and consequently, the growth of a matrix layer embedding the crystalline nanoparticles formed above. The second precursor or precursors mixture is preferably injected in the post-discharge area at a flow speed comprised between 1 and 1000 μΙ_/ηηίη. According to a preferred embodiment, during deposition or the coating, the at least one second inlet 22 is placed at a distance c of the substrate 4 to be coated, said distance c being comprised between 1 mm and 150 mm, along the longitudinal axis. The short distance between the at least one second inlet 22 and the substrate allows a dense coating on said substrate. [0054] Advantageously, the device is supported by a moveable support (not represented). During deposition or the coating, the device moves in relation to the substrate in order to facilitate the coating of the substrate.

[0055] According to a preferred embodiment of the invention, the gas carrier is injected at a flow speed comprised between 0.5 and 20 L/min for the first and the second precursors or precursors mixtures.

[0056] The deposition is carried out at atmospheric pressure and/or at a substrate temperature comprised between 50 °C and 550°C.

[0057] As an example, the metal oxide precursor is a titanium dioxide (T1O2) precursor in order to synthetize anatase T1O2, known as having photocatalytic properties.

[0058] The T1O2 precursor can be selected from a group consisting, but not limited to, titanium isopropoxide (TTIP), titanium tetrachloride, titanium butoxide, titanium diisopropoxide bis (acetylacetonate) and titanium ethoxide, preferably titanium isopropoxide. The synthetized particles of T1O2 contain a large part of crystalline anatase T1O2 phase.

[0059] As another example, the metal oxide precursor can be a vanadium pentoxide (V2O5) precursor or a vanadium dioxide (VO2) precursor, which will provide photochromic properties to the composite film.

[0060] The V2O5 and/or VO2 precursor can be selected from a group consisting, but not limited to, vanadium oxychloride (VOC ), vanadyl acetylacetonate (CioHi ₄ O5V), vanadium tetrakisdimethylamide (V(NMe2)4) and vanadium tetrachloride (VCI ₄ ). The synthetized particles of V2O5 contain a large part of crystalline V2O5 and/or VO2 phase.

[0061] As other example, the metal oxide precursor can be a tungsten trioxide (WO3) precursor, which will provide electrochromic properties to the composite film. WO3 is also known for photocatalytic water splitting applications.

[0062] The WO3 precursor can be selected from a group consisting, but not limited to, tungsten ethoxide (W(OEt)6) and tungsten hexachloride (WCI6). The synthetized particles of WO3 contain a large part of crystalline WO3 phase. [0063] As other examples, the metal oxide can be a zinc oxide (ZnO) precursor or a eerie oxide (CeO2) precursor or an indium oxide (Ιη2θ3) precursor or a zirconium dioxide (ZrO2) precursor.

[0064] Moreover, the first precursors mixture can also comprise metal and/or non- metal dopant precursors.

[0065] In case of ΤΊΟ2, the anatase titanium dioxide particles can be doped in order to enhance their photocatalytic properties and/or to expand the photocatalytic activity of anatase ΤΊΟ2 to the visible-light region of the solar spectrum.

[0066] Non-metal, such as boron, nitrogen, carbon, phosphorus or sulphur, and metal elements, such as tungsten, vanadium, chromium, iron, silver, niobium or nickel have been proved to be effective dopants for ΤΊΟ2.

[0067] Suitable precursors for the doping of anatase ΤΊΟ2 with boron (Β-ΤΊΟ2) include triethyl borate ((C2H5O)3B), trimethyl borate (B(OCH3)3 and boric

[0068] Suitable precursors for the doping of anatase ΤΊΟ2 with nitrogen (Ν-ΤΊΟ2) include NH3. An alternative is the injection of a small amount of nitrogen gas to the plasma gas or to the titanium precursor carrier gas.

[0069] Suitable precursors for the doping of anatase ΤΊΟ2 with sulfur (S-T1O2) include thiourea (CH ₄ N2S).

[0070] Suitable precursors for the doping of anatase ΤΊΟ2 with carbon (C-T1O2) include ethanol and sucrose (C12H22O11).

[0071] Suitable precursors for the doping of anatase ΤΊΟ2 with phosphorus (P-

ΤΊΟ2) include triethyl phosphate [(C ₂ H ₅ O) ₃ PO].

[0072] Suitable precursors for the doping of anatase ΤΊΟ2 with tungsten (W-T1O2) include tungsten ethoxide [W(OEt)6] .

[0073] Suitable precursors for the doping of anatase TiO2 with vanadium (V-T1O2) include vanadium tetrachloride (VCI ₄ ) and vanadyl acetylacetonate

[0074] Suitable precursors for the doping of anatase ΤΊΟ2 with chromium (Cr-TiO2) include chromium nitrate [Cr(NO3)3] .

[0075] Suitable precursors for the doping of anatase ΤΊΟ2 with iron (Fe-TiO2) include ferrous nitrate [Fe(NO3)3] . [0076] Suitable precursors for the doping of anatase T1O2 with silver (Ag-Tio2) include silver nitrate (AgNOs).

[0077] Suitable precursors for the doping of anatase ΤΊΟ2 with nickel (Ni-TiO2) include nickel nitrate [Ni(NO3)2].

[0078] Suitable precursors for the doping of anatase ΤΊΟ2 with Nb (Nb-TiO2) include nickel nitrate Nb ethoxide [Nb(OEt) ₅ ].

[0079] In case of V2O5 and/or VO2, the crystalline vanadiunn oxide particles can be doped in order to tune their photochromic properties.

[0080] Non-metal, such as fluorine or magnesium, and metal elements, such as tungsten, molybdenum, zirconium, hafnium or titanium have been proved to be effective dopants for V2O5 and VO2.

[0081] In case of WO3, the crystalline tungsten oxide particles can be doped in order to tune their electrochromic properties or enhance their photocatalytic water splitting performances.

[0082] Non-metal, such as nitrogen, and metal elements, such as iron, cobalt, nickel, copper, niobium, molybdenum or zinc have been proved to be effective dopants for WO3.

[0083] As an example, the matrix precursor is a S1O2 precursor selected from a group consisting, but not limited to, hexamethyldisiloxane (HDSMO), hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexaethyldisiloxane, tetraethylorthosilicate, aminopropyl-trimethoxysilane, tetramethyldisiloxane,pentamethylcyclopentasiloxane,octameth ylcycloocta siloxane, vinyltrimethoxysilane and trimethoxypropylsilane, preferably hexamethyldisiloxane. The S1O2 precursor will provide anti-fog properties to the functional composite film.

[0084] As an example, the matrix precursor is an organic precursor, preferably comprising at least one polymerizable bond, including unsaturated groups such as allyl, vinyl, acrylic or ethynyl groups or a cyclic structure.

[0085] Experimental tests have been done in order to deposit a thin functional composite film comprising crystalline particles, with the device and method of the invention. A ΤΊΟ2 precursor and more particularly titanium tetra- isopropoxide (TTIP, Sigma Aldrich™, 98 %) was used as the first precursor and a S1O2 precursor, more particularly hexamethyldisiloxane (HMDSO, Sigma Aldrich™, 98 %), was used as the second precursor.

[0086] The experimental results are shown on figure 2 to figure 6b.

[0087] N2 was used as a gas carrier. The gas carrier was injected, for the T1O2 precursor, at a flow speed comprised between 5 and 7 μΙ_/ηηίη, preferably between 2 and 4 μΙ_/ηηίη, more preferably 3 μΙ_/ηηίη. For the S1O2 precursor, the gas carrier is injected at a flow speed comprised between 2 and 10 μΙ_/ηηίη, preferably between 4 and 6 μΙ_/ηηίη, more preferably 5 μΙ_/ηηίη.

[0088] N2 was used to produce the plasma and was injected in the plasma device at a flow speed comprised between 10 and 100 L/min.

[0089] Figure 2 represents a Raman spectroscopy analysis of an anatase TiO2 SiO2 nanocomposite coating or film elaborated from a 2μΙ_/ηηίη HDSMSO delivery rate on a PEN substrate. The Raman spectra were recorded with a Renishaw inVia™ micro-Raman spectrometer at an excitation wavelength of 532 nm with a laser power of approximately 2.5 mW focused on a 5 μηη ² spot. The results highlight the presence of numerous particles. Most of these particles were composed of anatase T1O2 such as highlighted with the presence of bands at 144, 197, 399 and 640 cm ^-1 . No rutile T1O2 and nor other phase was detected.

[0090] Figures 3a to 3d show SEM observations of TiO2 SiO2 coating deposited on a substrate performed with HDMSO flow varying from 0 to 10 μΙ_/ηηίη.

[0091] The morphology of the coatings was observed by Scanning Electron Micorscope Hitachi™ U70 at a magnification of 50,000. To avoid any charging effect of the electron beam, the samples were preliminary coated with a platinum thin film of ca. 5 nm by magnetron sputtering deposition

[0092] Figure 3a shows the SEM analysis of a film deposited without HMDSO. The analysis reveals a film structure composed of grains with size ranging from 10 to 50 nm, all over the surface and the presence of few nanograins agglomeration. Up to a 2 μΙ_/ηηίη HMDSO delivery rate (figure 3 b), the morphology of the deposited coatings was not significantly different from the one grown without addition of HMDSO. Further increase of the HMDSO delivery rate slowly led to a conversion of the microstructure of the films toward cauliflower morphology (Figure 3c and 3d). SEM observations confirmed that the films deposited with the device and method of the invention are dense, homogeneous and with a complete coverage of the substrate surface.

[0093] Figure 4a represents a graphic of the deposition rate of the films as a function of the silicon content in the film.

[0094] Figure 4b represents the evolution of the ratio of the silicon content over the total amount of silicon and titanium (Si/(Si+Ti)) as a function of the HMDSO delivery rate from 0 to 10 L-mirr ¹ . The silicon concentration of the films increases while adding a more important flow of HMDSO into the post- discharge area. The ratio of the silicon content over the total amount of silicon and titanium (Si/(Si+Ti) increased linearly from 0 to 60 % when increasing the HMDSO delivery rate from 0 to 10 L-mirr ¹ , respectively.

[0095] Figure 5a and 5b respectively shows the XPS analysis of the titanium environment and the XPS analysis of the silicon environment in the deposited film. XPS analyses were performed on a Kratos™ Axis Ultra DLD instrument using a monochromatic Al Ka X-ray source (hv = 1486.6 eV) at pass energy of 20 eV for high resolution spectra. Argon sputtered cleaning at 3 keV and 2 mA was used for approximately 500 s in a scanning mode in order to clean the surface and to get the most representative information on the coating elemental composition in the film.

[0096] Irrespective of the deposition conditions, the positions of the Ti 2pi/2 and Ti

2p3/2 peaks, observed at 464.4 eV and 458.7 eV, respectively indicate the formation of T1O2 (Figure 5a). The high-resolution Si 2p core level (Si 2pi/2 and Si 2p3/2) was measured at 103.4 eV with a full width at half maximum (FWHM) of 2.2 eV, suggesting the formation of S1O2 (Figure 5b). No evidence of SiTiOx bonding is observed. This contrasts with results obtained during preliminary experiments of this work, which only allowed to form a single SiTiOx phase when injecting the TTIP and HMDSO precursors in the same area of the plasma post-discharge (not shown). Thus, a separated injection of the TTIP and HMDSO precursors, in accordance with the invention, is necessary to generate a two-phase's structure with crystalline T1O2 phase separated from the silicon oxide phase. The prepared films are anatase TiO2 SiO2 nanocomposites coatings.

[0097] The photocatalytic activity of the anatase TiO2 SiO2 nanocomposite coatings under UV (ultraviolet) light was assessed for each of the prepared coatings, before and after immersion in an ultrasonic bath (at 7 hours). The photocatalytic activity measurements were done with coatings deposited on a double side polished undoped silicon wafer. 5 μΙ of steric acid diluted at 0.05 M in methanol was deposited on the coated wafer using a spin coater rotating at 1 ,000 rpm during 30 s. Afterward, the sample was placed into a box at a distance of 20 cm from an 8 W UV light with a wavelength of 254 nm. The kinetic degradation of the steric acid was followed by analysis using Fourier transform infrared spectroscopy (FTIR) in transmission mode thanks to the decrease of the CH2-CH3 absorption band in the range 2,800- 3,000 cm- ¹ as a function of illumination duration. The results are represented in Figure 6a.

[0098] The highest acid stearic degradation rate, i.e. 0.24 hr ¹ , was measured for the pure T1O2 coating ([HMDSO] = 0 μΙ_-ηηίη- ¹ ). Incorporation of HMDSO into the post-discharge only led to a decrease of the photocatalytic activity down to 0.12 hr ¹ . It is interesting to note that the photocatalytic activity of the anatase TiO2 SiO2 nanocomposite coatings never decreased below 50 % of the one of the pure T1O2 sample. More interestingly, after 7 hours immersion in an ultrasonic bath, the acid stearic degradation rate of sample elaborated from the highest HMDSO delivery rate remained unchanged, i.e. 0.12 IT ¹ . This contrasts with photocatalytic activity of all the others samples, which was reduced in various proportions. While the degradation rate of samples was reduced from 0.2 hr ¹ to 0.1 hr ¹ (i.e. -50 %) for the sample deposited with a 6 pL-min- ¹ , it was reduced from 0.24 hr ¹ to 0.02 hr ¹ (i.e. -83 %) for the pure T1O2 sample. This results clearly highlights the benefit of the proposed nanocomposite approach, which allows to maintain a good photocatalytic activity that remain unaltered even after sonication for 7 hours. Also, on the growth layer mechanism study, this result clearly shows that the anatase T1O2 is mostly synthesized by gas homogeneous reactions that produced crystallize clusters on the surface. The simultaneous growing of a silica layer makes possible their embedment and the synthesis of a mechanical resistant nanocomposite TiO2 SiO2 coating.

[0099] Figure 6b shows the evolution of the water contact angle (WCA) as a function of the content of silicon in the film which is related to the HDMSO precursor flow (Figure 4b). The WCA measurements and the pictures of the droplets (not shown) were obtained using a Kruss™ DSA16 EasyDrop USB contact angle meter. The volume of the de-ionized water drop used for the measurements was 3 μΙ_.

[00100] In addition to afford a better mechanical stability to the deposited films, addition of the HMDSO precursor is inducing a lowering of the water contact angle of the as-deposited films. While the WCA of the pure T1O2 coating was evaluated to 66°, WCA as low as 5° was measured for the film with the highest content of silicon. This superhydrophilic behavior is assumed to benefit to the observed photocatalytic properties thanks to a better wetting of the surface of the TiO2 SiO2 nanocomposite coating and the subsequent photocatalytic degradation ensure by the anatase T1O2 moiety.

[00101] The simultaneous but spatially separated injections of two precursors or precursors mixtures into the stream of the post-discharge area provide a solution towards the deposition of functional nanocomposite coatings comprising crystallized nanoparticles on both 2D and 3D substrates. In contrast with thermal CVD approaches, the particles are synthesized, more precisely crystallized, remotely from the substrate's surface, making the developed method suitable for the coating of heat-sensitive substrates such as, but not limited to, polymers, glass, metal etc... The consecutive immobilization of the crystallized nanoparticles into a matrix is ensuring the mechanical stability of the resulting nanocomposite coatings. In case of anatase TiO2-SiO2 film, the photocatalytic activity of the anatase TiO2 SiO2 nanocomposite coatings, albeit lower than for the pure T1O2 coating (i.e. -50 %), is still significant and more importantly is fully retained even after prolonged sonication. It is also interesting to note that the photocatalytic, superhydrophilic and adherent nanocomposite coatings are also optically transparent (not shown). The method and the device of the invention are particularly interesting in that the in-situ synthesis and deposition of nanoparticles in the same process is allowing to avoid any handling of these potentially harmful materials.