WO2003010103A1 - Substrat revetu d'un film composite, procede de fabrication et applications - Google Patents
Substrat revetu d'un film composite, procede de fabrication et applications Download PDFInfo
- Publication number
- WO2003010103A1 WO2003010103A1 PCT/FR2002/002673 FR0202673W WO03010103A1 WO 2003010103 A1 WO2003010103 A1 WO 2003010103A1 FR 0202673 W FR0202673 W FR 0202673W WO 03010103 A1 WO03010103 A1 WO 03010103A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- precursor
- layer
- mesoporous
- coated substrate
- pores
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 62
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- 238000000034 method Methods 0.000 title claims description 27
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- 239000002243 precursor Substances 0.000 claims abstract description 57
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 239000000377 silicon dioxide Substances 0.000 claims description 33
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/811—Of specified metal oxide composition, e.g. conducting or semiconducting compositions such as ITO, ZnOx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/24997—Of metal-containing material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/24999—Inorganic
Definitions
- It relates more particularly to a substrate coated with a composite film based on a mesoporous mineral layer containing nanoparticles.
- nanoparticles designates solid particles of nanometric dimensions, that is to say of the order of a few nanometers or a few tens of nanometers. These particles are of particular interest insofar as they may have specific properties, in particular optical and electronic, which differ significantly from those of solid material. Thus, particular physical properties are observed for particles of nanometric size, such as increased field effects for metals, quantum confinement for semiconductors and superparamagnetism for magnetic compounds. Obtaining particles of defined size capable of being distributed in space according to a desired arrangement represents a capital challenge in the fields in particular of optoelectronics, nonlinear optics, ...
- powdered mesoporous materials such as the family of M41s: these are (alumino) silicates materials very close to zeolites and, like the latter, characterized by a periodic network of pores, most often hexagonal or cubic bi-continuous, where the pores have a perfectly defined size of 2 to 10 nm.
- the structuring of the porous material into a periodic network of pores is linked to the synthesis technique, which consists in condensing the silicate mineral matter in the presence of organic structuring agents which are organized into micelles and crystalline phases. After treatment for removing the structuring agents, a porous material is obtained, the pores of which are the perfect replica of the organic species.
- the tortuosity of the porous network is low and the developed surface very accessible. This makes it possible to envisage these materials as support hosts for particles.
- the synthesized particles are generally distributed randomly in the porous matrix and their size is not well controlled.
- a layer of SiGe or Ge is deposited and grown on the surface of the mesoporous silica film over a thickness of 6 to 70 nm at a growth rate of 0.1 ⁇ / s which is supposed to allow diffusion of the atoms in the openings of the mesopores.
- Photoluminescence measurements make it possible to identify the presence of particles which would be localized in the mesoporous layer and whose dimensions correspond to those of the pores of the silica matrix. However, the thickness penetration into the layer is not characterized.
- the method used is based on the diffusion of metal atoms in the mesoporous silica layer from the surface layer of SiGe or Ge towards the silica / substrate interface, diffusion which is no longer allowed (despite suitably chosen growth rate) as soon as the pores close to the silica / Ge or SiGe interface are filled.
- the presence of the surface layer, which contains particles of different sizes, is a drawback.
- the object of the present invention is to remedy this drawback and to provide a layered material containing nanoparticles of regular structure.
- This object was achieved with a substrate coated with a composite film based on a mesoporous mineral layer containing nanoparticles formed in situ inside the layer, characterized in that the composite film has a periodic lattice structure in most of the thickness where the nanoparticles are present, structure in which the nanoparticles are arranged periodically on the scale of domains of at least 4 periods in the thickness of the film.
- This repetition can be oriented identically throughout the volume of the material, with a structure that can be compared to that of single crystals, or can be oriented identically at the domain scale of at least 4 periods. (in general at least about 20 nm) with an overall structure which can be compared to that of polycrystals.
- this periodic structure of the composite film is obtained from a mesoporous mineral layer of periodic structure on the scale of domains of at least 4 pore periods (in general at least about 20 nm) forming a matrix on the substrate, by:
- a key element consists in generating the particles inside the pores from a precursor which undergoes a chemical modification in place in order to transform into the constituent material of the particle.
- the problems of occlusion of the pores near the diffusion source are avoided, which limit the penetration of the particles at the heart of the thickness of the mesoporous layer.
- a mesoporous layer of periodic structure can be the seat of an ordered growth of particles and limited by the size of the pores, and they have accessed unexpected to a periodically structured composite film.
- the periodic structure of the composite film is obtained by impregnating the matrix layer with a liquid composition containing at least one precursor and a liquid vehicle, and controlled growth of particles derived from the precursor.
- the liquid route indeed seems to be the best method for depositing the precursor (s) inside the pores, by having homogeneous access to all the desired volume and in particular the thickness of the basic mesoporous layer, which allows in the next stage a harmonious and regular growth of the particles.
- the substrate carrying the coating can be made of various materials of the mineral type such as glass, silica, ceramics or vitroceramics, metal, or of the organic type such as plastics.
- the transparency of the substrate may be desirable.
- plastics include (poly (methyl methacrylate) (PMMA), polyvinyl butyral (PVB), polycarbonate (PC) or polyurethane (PU), thermoplastic ethylene / vinyl acetate (EVA) copolymer, poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), polycarbonate / polyester copolymers, cycloolefinic copolymer of the ethylene / norbornene or ethylene / cyclopentadiene type, ionomer resins, for example an ethylene / acid copolymer ( meth) acrylic neutralized by a polyamine, thermosetting or thermoscrosslinkable such as polyurethane, unsaturated polyester (UPE), ethylene / vinyl acetate copoly
- PMMA poly (methyl methacrylate)
- PVB polyvinyl butyral
- PC polycarbonate
- PU polyurethane
- EVA thermoplastic ethylene / vinyl acetate
- the substrate generally affects an essentially planar or two-dimensional shape with a variable contour, such as for example a plate or a wafer, but can also affect a volume or three-dimensional shape consisting of the assembly of essentially planar surfaces, for example in the form of a cube or a parallelepiped, or not, for example in the form of fibers.
- the composite film according to the invention has a thickness advantageously between 10 nm and 10 ⁇ m (these limit values being included), in particular 50 nm and 5 ⁇ m. High quality film structures are produced for film thicknesses from 100 to 500 nm.
- the mesoporous mineral layer forming the base of the composite film has a periodic structure at the domain scale of at least 4 periods.
- the characteristic dimension of these domains (in general at least about 20 nm) corresponds to a dimension of coherent diffraction domains and can be deduced in a known manner by the Scherrer formula from the width of the main peak of the X-ray diffraction diagram.
- Preferred layers are organized with a periodic structure on the scale of domains of the order of 100 nm, advantageously 200 to 300 nm.
- the mesoporous mineral layer is preferably based on at least one oxide such as silicon oxide, titanium oxide, etc.
- the material constituting the layer may be chosen so that it is transparent at certain wavelengths, in particular in the visible range.
- the mesoporous mineral layer is obtained by: • bringing the substrate into contact with a liquid composition comprising at least one oxide precursor and at least one organic agent; and
- Three-dimensional structures can be useful for establishing isotropic properties of the composite film, while two-dimensional structures give access to anisotropic properties with in particular applications in the field of nonlinear optics or optical filters.
- the resulting composite film has a periodic lattice structure which retains the same symmetries.
- chalcogenides in particular sulfides or selenides, of one or more metals, for example derivatives of zinc, lead, cadmium, manganese, in particular ZnS, PbS, (CdMn) S, (CdZn) S, CdSe, ZnSe, the photoluminescence or semiconductor properties of which can be exploited;
- oxides of one or more elements for example derived from silicon, zinc, zirconium, cerium which can confer improved mechanical properties on the surface layer;
- halides in particular chlorides, of one or more metals, in particular silver chloride with photochromic properties, or copper chloride which absorbs UV rays;
- the invention also makes it possible to optimize the quantity of particles deposited on the substrate, more particularly to maximize this quantity without aggregation of the particles.
- the volume fraction occupied by the nanoparticles in the composite film can be of the order of 10 to 70% of the volume of the organized domains, in particular around 50%.
- the invention also relates to a method of manufacturing a substrate as described above, which comprises the steps consisting in:
- the ripening of the soil allows a preliminary condensation of the oxide precursor which promotes the structuring of the oxide layer condensed on the substrate into large domains.
- Advantageous conditions for curing include maintaining the soil at a temperature of 40 to 60 ° C for a period of 30 min to 24 hours, the curing time being shorter the higher the temperature.
- the oxide precursor is advantageously a hydrolyzable compound, such as a halide or an alkoxide
- the structuring agent is advantageously chosen from cationic surfactants, preferably of the quaternary ammonium type, or nonionic, including the copolymers , preferably based on polyalkylene oxide, in particular di-block or tri-block copolymers based for example on ethylene or propylene oxide.
- a particularly favorable embodiment of the process of the invention for the synthesis of a mesoporous layer of silica consists in that the organic structuring agents consist of micelles of cationic surfactant molecules, the precursor of the mesoporous material is a silicon alkoxide, and they are in solution and, optionally, in hydrolyzed form.
- the cationic surfactant is cetyltrimethylammonium bromide, the precursor of the mesoporous material is a silicon alkoxide in partially or fully hydrolyzed form.
- the molar ratio of the organic structuring agent to silicon can be of the order of 10 "4 to 0.5, preferably of 10 " 3 to 0.5, advantageously of 0.01 to 0.1 .
- Step (2) of the method according to the invention consists in impregnating the mesoporous base layer with a liquid composition containing at least one precursor of nanoparticles.
- the liquid composition may contain complexing agents to avoid precipitation of the metal, in particular in the form of hydroxides in the medium aqueous.
- the impregnation composition is adapted so as not to degrade the mesoporous mineral matrix.
- an important parameter may be the pH of the impregnating composition.
- the liquid impregnation composition has a pH less than or equal to 10.
- the pH of the composition can be adjusted to optimize the interaction of the precursor with the mesoporous layer, in particular it can be adjusted within a range which promotes the adsorption of the precursor species on the walls of the pores.
- the counterions or ligands are chosen to obtain species which are soluble in the preferred pH range.
- the impregnation can be carried out by immersion or dipping of the substrate in the liquid composition or by any other method of applying liquid to a solid.
- the method can comprise an intermediate step (1 ′) in which the mineral layer is treated mesoporous to increase the reactivity of the pores with respect to the precursor (s), in particular by grafting reactive groups on the surface of the pores which interact with the precursor (s) chemically or electrostatically.
- the treatment may consist in reacting the layer with an alkoxide, in particular of silicon, functionalized by a reactive group, or with an alumina precursor functionalized by a reactive group.
- the impregnation step (2) can be followed by a rinsing step (2 ') to remove excess material, in particular to avoid the accumulation of precursor at the film-air interface which would be susceptible to '' completely block the surface pores.
- the interactions between the functional groups on the walls of the pores and the precursors, in particular metal cations are strong enough to retain the precursor in the pore despite rinsing.
- Step (3) which consists in reacting the precursor in place in the pores, can use an input of thermal energy or the action of radiation such as ultraviolet rays, or a liquid or gaseous reagent.
- a gaseous reagent is preferable because it generally guarantees instant penetration into all the pores of the material, allowing a transformation of the precursor and a growth of the particles simultaneously throughout the volume of the mesoporous matrix, which avoids the problems of diffusion. species and clogging of pores.
- the gaseous reagent can be chosen from a chalcogen-based gas, for example based on sulfur, selenium, tellurium, for example H 2 S, H 2 Se, based on halide, in particular based on chlorine, for example HCl, Cl 2 , a reducing gas, for example H 2 , and an oxidizing gas, for example O 2 , in particular as a mixture of O 2 , N 2 .
- a chalcogen-based gas for example based on sulfur, selenium, tellurium, for example H 2 S, H 2 Se
- halide in particular based on chlorine, for example HCl, Cl 2
- a reducing gas for example H 2
- an oxidizing gas for example O 2 , in particular as a mixture of O 2 , N 2 .
- impregnation (2) and reaction (3) steps can be repeated to reach the desired degree of filling, if necessary until the mesoporous mineral layer is saturated.
- the invention also relates to the application of a substrate as described above to the production of solar concentrators in particular for photovoltaic cells, to quantum dots, materials for non-linear optics or magnetism.
- the material can be treated or coated with an additional protective or functional layer (s).
- EXAMPLE 1 This example describes the manufacture of a layer of silica charged with nanoparticles of cadmium sulfide on a Pyrex glass substrate.
- Si (OH) 4 which is the hydrolysis product of TEOS and low molecular weight oligomers (SiO) n .
- the surfactant chosen is cetyltrimethylammonium bromide (CTAB) introduced in an amount such that the CTAB: Si molar ratio is equal to 0.1.
- CTAB cetyltrimethylammonium bromide
- the solution is deposited on Pyrex slides of 2.5 cm by 2.5 cm by centrifugation or "spin coating": according to this technique, the sample is rapidly rotating during deposition; this spin coating operation is characterized by a speed of 3000 rpm and a rotation time of the order of 100 s.
- the CTAB is then extracted from the film of each sample by calcination in a tubular oven at 450 ° C in air with a rise of 10 ° C / h.
- the film thus formed is transparent, mesoporous and its thickness, determined with the profilometer, is approximately 300 nm.
- the thickness of the mesoporous silica film can be varied.
- a volume ratio of 2: 1 to 1: 4 it is possible to obtain layer thicknesses of the order of 400 to 100 nm.
- the porous network corresponds to the volume left vacant by the elimination of the CTAB micelles, taking into account the contractions likely to occur during the heating / calcination operations, among others.
- the pore volume of this layer is 55% relative to the total volume of the film.
- the characteristics of the porous network are determined by X-ray diffraction, X-ray scattering in grazing incidence and transmission electron microscopy. These analyzes reveal a three-dimensional hexagonal structure (space group P6 3 / mmc with the hexagonal axis of symmetry perpendicular to the plane of the substrate). The pores are substantially spherical with a uniform diameter of the order of 3.5 nm.
- Figures 1 and 2 are electron microscopy images in transmission respectively in transverse and flat section.
- the mesoporous layer 2 has a periodic network structure throughout its thickness from the interface with the substrate 1 to the interface with the air 3.
- the pores 4 are aligned parallel to the substrate surface.
- FIG. 2 reveals the existence of domains 5, 6, 7 of large extent, of dimension greater than 200 nm in all the directions of the plane.
- the pores are arranged according to the repeating pattern of the hexagonal network over several tens of periods, but the orientation of the repeating axis in the plane of the substrate (a) varies by domain 5 to a neighboring domain 6 or 7. From one domain to another the orientation of the hexagonal axis of symmetry (c) is unchanged, always perpendicular to the surface of the substrate.
- This structure is similar to that of a polycrystalline material where all the grains have a common orientation relative to the substrate.
- This structure can also be obtained by immersion and drawing from the silica sol (or "dipcoating").
- An impregnation solution based on cadmium nitrate is prepared.
- an aqueous solution of 0.1 M cadmium nitrate one equivalent of ammonia and one equivalent of sodium citrate are added, and the pH is adjusted to 9.5 by addition of ammonia.
- NH 3 and citrate act as ligands which complex cadmium nitrate and prevent precipitation of cadmium hydroxide.
- the pH of 9.5 is optimal, because the adsorption of cadmium ions on silica is optimal above pH 9 while the dissolution of the silica walls becomes critical above pH 10.
- the sample is then placed in a primary vacuum enclosure into which hydrogen sulfide gas H 2 S is slowly injected up to atmospheric pressure at room temperature.
- H 2 S hydrogen sulfide gas
- the precipitation of CdS sulfide particles by reaction of sulfur with the complexed Cd is instantaneous and takes place locally in the heart of the porous cavity simultaneously in all the pores.
- the precipitation of the sulfide leads to the regeneration of the SiO " sites.
- the progress of the filling of the layer is followed by absorption spectrophotometry, illustrated by the spectra of FIG. 3: the absorbance increases with the number of cycles up to a ceiling reached in the eighth cycle, (the curve a shows the spectrum obtained after the first soaking in the cadmium solution, curve b presents the spectrum obtained after the first treatment H 2 S; curves c, d, e, f, g, present the spectra obtained respectively after 2, 3, 4 , 5, 7 cycles, and the curve h shows the spectra obtained after the gem e and e em C y C ⁇ are ⁇ yj overlap).
- the absorbance no longer changes, proving that there is no more CdS in the layer than in the previous cycle.
- the mesoporous layer is therefore saturated with CdS.
- the size of the aggregates can be determined by the energy of the energy transition. It is concluded that the particle size distribution is very narrow centered on 3.5 nm.
- the characterization by X-ray diffraction confirms that the three-dimensional hexagonal structure is preserved.
- the same layer of mesoporous silica is deposited on a substrate.
- the impregnation solution this time consists of an aqueous solution of zinc nitrate of 0.1 M concentration to which 1 molar equivalent of sodium citrate is added.
- the pH is then adjusted to 7.5 by adding ammonia.
- the adsorption of zinc ions is optimal in a pH range above pH 7. It is advantageously placed in a range of the order of 7 to 10, preferably close to neutrality between 7 and 8 , so that the silica does not suffer from a dissolving effect on the walls of the pores.
- the composite film obtained after 7 impregnation / treatment cycles has the same periodic lattice structure of particles stacked in the hexagonal mode throughout the thickness of the silica layer.
- EXAMPLE 3 This example describes the growth of CdS aggregates in another mesoporous layer of silica.
- a silica sol is prepared as in Example 1 by mixing TEOS with acidified water and ethanol in a molar ratio 1: 5: 3.8. The mixture is subjected to maturing for 1 hour at 60 ° C.
- the structuring agent is a nonionic surfactant consisting of a triblock copolymer of the polyoxyethylene-polyoxypropylene-polyoxyethylene type.
- the deposition and calcination steps are the same as in Example 1.
- a layer of mesoporous silica 200 nm thick is obtained.
- this structuring agent it is possible to choose a dilution volume ratio of 1: 1 to 1: 2 in order to obtain layers of silica of the order of 400 to 200 nm in thickness.
- the porous network which corresponds to the volume left vacant by the elimination of the Pluronic micelles, also has a three-dimensional structure of monodisperse pores in size.
- FIG. 5 is a transmission electron microscopy image in cross section which illustrates the periodic distribution of the pores.
- HMDS hexamethyldisilazane
- the impregnated substrate is placed in a cell containing 200 ⁇ l of HMDS and the cell is placed under vacuum and hermetically closed, then heated to a temperature of approximately 70 ° C. for approximately 5 minutes. The cell is then purged to remove excess HMDS. Finally, the Ag + ions are reduced, which can be carried out under an atmosphere of argon and hydrogen at 100 ° C for 4 hours or under an atmosphere of pure hydrogen for one hour.
- the final product is characterized by transmission electron microscopy, where the cross-sectional image reveals a film filled with nanoparticles.
- This image shows that the particles have a narrow size distribution, and have particle alignments.
- the size distribution is narrow with an average of 3.4 nm and a standard deviation of 0.64.
- the diffraction of the image shows that the particles are distributed according to the 3D hexagonal structure of the space group P6 3 / mmc.
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- Organic Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020047001097A KR100870711B1 (ko) | 2001-07-25 | 2002-07-25 | 복합 필름으로 코팅된 기판 및 이를 제조하는 방법 |
EP02774836A EP1427678A1 (fr) | 2001-07-25 | 2002-07-25 | Substrat revetu d'un film composite, procede de fabrication et applications |
US10/484,721 US7348054B2 (en) | 2001-07-25 | 2002-07-25 | Substrate coated with a composite film, method for making same and uses thereof |
MXPA04000722A MXPA04000722A (es) | 2001-07-25 | 2002-07-25 | SUSTRATO RECUBIERTO CON UNA PELICULA COMPUESTA, MeTODO DE FABRICACION Y SUS USOS. |
JP2003515463A JP4184958B2 (ja) | 2001-07-25 | 2002-07-25 | 複合フィルムを塗布された基体、製造方法および用途 |
BRPI0211413-5A BR0211413B1 (pt) | 2001-07-25 | 2002-07-25 | substrato revestido de um filme compósito, e, processo de fabricação do mesmo. |
Applications Claiming Priority (2)
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FR01/09901 | 2001-07-25 | ||
FR0109901A FR2827854B1 (fr) | 2001-07-25 | 2001-07-25 | Substrat revetu d'un film composite, procede de fabrication et applications |
Publications (1)
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WO2003010103A1 true WO2003010103A1 (fr) | 2003-02-06 |
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PCT/FR2002/002673 WO2003010103A1 (fr) | 2001-07-25 | 2002-07-25 | Substrat revetu d'un film composite, procede de fabrication et applications |
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US (1) | US7348054B2 (fr) |
EP (1) | EP1427678A1 (fr) |
JP (1) | JP4184958B2 (fr) |
KR (1) | KR100870711B1 (fr) |
CN (1) | CN1297505C (fr) |
BR (1) | BR0211413B1 (fr) |
FR (1) | FR2827854B1 (fr) |
MX (1) | MXPA04000722A (fr) |
PL (1) | PL368602A1 (fr) |
RU (1) | RU2288167C2 (fr) |
WO (1) | WO2003010103A1 (fr) |
ZA (1) | ZA200400522B (fr) |
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US8024531B2 (en) | 2005-04-18 | 2011-09-20 | Turbo Data Laboratories, Inc. | Information processing system and information processing method |
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2001
- 2001-07-25 FR FR0109901A patent/FR2827854B1/fr not_active Expired - Fee Related
-
2002
- 2002-07-25 WO PCT/FR2002/002673 patent/WO2003010103A1/fr active Application Filing
- 2002-07-25 PL PL02368602A patent/PL368602A1/xx not_active Application Discontinuation
- 2002-07-25 KR KR1020047001097A patent/KR100870711B1/ko not_active IP Right Cessation
- 2002-07-25 BR BRPI0211413-5A patent/BR0211413B1/pt not_active IP Right Cessation
- 2002-07-25 US US10/484,721 patent/US7348054B2/en not_active Expired - Fee Related
- 2002-07-25 RU RU2004105271/28A patent/RU2288167C2/ru not_active IP Right Cessation
- 2002-07-25 MX MXPA04000722A patent/MXPA04000722A/es active IP Right Grant
- 2002-07-25 JP JP2003515463A patent/JP4184958B2/ja not_active Expired - Fee Related
- 2002-07-25 CN CNB028188063A patent/CN1297505C/zh not_active Expired - Fee Related
- 2002-07-25 EP EP02774836A patent/EP1427678A1/fr not_active Withdrawn
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1690838A1 (fr) * | 2003-11-17 | 2006-08-16 | National Institute of Advanced Industrial Science and Technology | Poudre ou film mince mesoporeux de composite oxyde/verre nanocristallin, processus de production et d'utilisation de cette poudre ou de ce film, divers dispositifs et accumulateur auxiliaire et dispositifs de stockage de lithium |
EP1690838A4 (fr) * | 2003-11-17 | 2008-08-13 | Nat Inst Of Advanced Ind Scien | Poudre ou film mince mesoporeux de composite oxyde/verre nanocristallin, processus de production et d'utilisation de cette poudre ou de ce film, divers dispositifs et accumulateur auxiliaire et dispositifs de stockage de lithium |
US8024531B2 (en) | 2005-04-18 | 2011-09-20 | Turbo Data Laboratories, Inc. | Information processing system and information processing method |
CN100374215C (zh) * | 2005-04-25 | 2008-03-12 | 北京化工大学 | 一种介孔二氧化硅膜的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
RU2288167C2 (ru) | 2006-11-27 |
ZA200400522B (en) | 2004-05-20 |
KR100870711B1 (ko) | 2008-11-27 |
US7348054B2 (en) | 2008-03-25 |
CN1558877A (zh) | 2004-12-29 |
FR2827854B1 (fr) | 2003-09-19 |
KR20040024590A (ko) | 2004-03-20 |
BR0211413B1 (pt) | 2011-02-22 |
EP1427678A1 (fr) | 2004-06-16 |
FR2827854A1 (fr) | 2003-01-31 |
JP4184958B2 (ja) | 2008-11-19 |
MXPA04000722A (es) | 2004-04-20 |
BR0211413A (pt) | 2004-11-09 |
JP2004535925A (ja) | 2004-12-02 |
CN1297505C (zh) | 2007-01-31 |
RU2004105271A (ru) | 2005-03-27 |
US20040219348A1 (en) | 2004-11-04 |
PL368602A1 (en) | 2005-04-04 |
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