WO2008102046A1 - Estructura multicapa formada por láminas de nanopartículas con propiedades de cristal fotónico unidimensional, procedimiento para su fabricación y sus aplicaciones - Google Patents
Estructura multicapa formada por láminas de nanopartículas con propiedades de cristal fotónico unidimensional, procedimiento para su fabricación y sus aplicaciones Download PDFInfo
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- WO2008102046A1 WO2008102046A1 PCT/ES2008/070028 ES2008070028W WO2008102046A1 WO 2008102046 A1 WO2008102046 A1 WO 2008102046A1 ES 2008070028 W ES2008070028 W ES 2008070028W WO 2008102046 A1 WO2008102046 A1 WO 2008102046A1
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- nanoparticles
- sheets
- different
- multilayer
- nanoparticulate
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
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- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/285—Interference filters comprising deposited thin solid films
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
- G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/285—Interference filters comprising deposited thin solid films
- G02B5/286—Interference filters comprising deposited thin solid films having four or fewer layers, e.g. for achieving a colour effect
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
- G02B2207/107—Porous materials, e.g. for reducing the refractive index
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
Definitions
- Multilayer structure materials have important applications as optical elements, as they act as interferential filters or Bragg reflectors, capable of selectively reflecting or transmitting a range of electromagnetic frequencies, generally between the ultraviolet and infrared areas of the spectrum, determined by the thickness e Index of refraction of the layers.
- these materials are one-dimensional photonic crystals, since they have a periodic modulation of the Index of refraction in one of the three spatial directions.
- the multilayer systems that are currently marketed are mainly manufactured using techniques that are usually included under the name of physical deposition from the vapor phase (Physical Vapor Deposition). In all of them the deposition is carried out under vacuum conditions and the solid condenses directly from the vapor phase.
- the optical coatings obtained by this type of techniques have great stability against variations in ambient conditions as well as high mechanical resistance.
- these multilayer coatings have poor mechanical stability and their properties vary with environmental conditions, both phenomena related to the present mesoporosity, so they are not suitable as passive optical elements, although they can find applications in other fields, such as of sensors.
- the pores of a layer grown by sol-gel are irregularly shaped, with a very wide distribution of sizes and with an average size between 2 and 100 nm.
- Materials with relatively controlled mesoporosity have also recently been developed and have aroused considerable interest, although applications of them have not yet been submitted. These are multilayer structures of porous silicon obtained by electrochemical dissolution.
- sol-gel techniques C. J. Brinker and GW Scherer, SoI-GeI Science: The Physics and Chemistryof Sol-Gel Processing, Academic New York, 1990] have great advantages: it is a simple method that allows a wide variety of materials to be deposited (oxides, semiconductors, piezoelectric, ferroelectric, etc.) in the form of thin films on various substrates (polymers, ceramics, metals, etc.).
- the variety of materials that can be deposited allows to design sol-gel structures in the form of devices with photonic band-gap, or photonic crystals.
- Bragg reflectors in ID are the photonic crystals that have achieved greater development by sol-gel. In these materials very high reflectivities are obtained due to the Bragg reflection phenomenon. In general, they are produced by alternating layers of materials that have high and low refractive index, forming a stack of dielectric multilayers.
- BRs synthesized by sol-gel can be obtained by spin-coating [RM Almeida, S. Portal, Photonic band gap structures by sol-gel processing, Current Opinion in Solid State and Materials Science 7 (2003) 151.
- the reflectivity of the photonic band gap (in English, Photonic Band Gap, or PBG) is greater, forbidden range of wavelengths between UV and NIR which are reflected by the dielectric mirror.
- YES2, TIO2 and ZrC> 2 are used because of the important difference between their refractive indexes (1.45-1.52, 2.07-2.55, 2.1-2.2, respectively)
- Thermal densification treatments are carried out after the synthesis of each of the layers, and when using such high temperatures, the crystallization of TIO2 of the first layers cannot be avoided, which are subjected to longer temperatures at high temperatures by the treatments repeated thermal suffering.
- the growth of the crystals must be carefully controlled as it deteriorates the optical quality of the multilayer by introducing Rayleigh dispersion and by the roughness that it generates at the interface with the SIO2 layers.
- the first layers undergo a different degree of densification than the last layers, which spend less time at high temperatures; This non-homogeneous densification also implies a lower optical quality of the multilayer by modifying the optical thickness.
- the possibility of producing stacking of layers of porous silicon (pSi) of different porosity allows Obtain structures with a predetermined refractive index profile, which results in a multilayer interference filter or BR.
- the refractive index of each layer is designed based on its porosity, which is obtained by electrochemical dissolution (in English, etching) of monocrystalline silicon wafers in an ethanolic solution of hydrofluoric acid.
- the thickness and, therefore, the optical properties can also be controlled by adjusting the synthesis conditions such as acid concentration, current density and dissolution time, [a) K. Kordás, AE Pap, S. Beke, S. Leppávuori, Optical properties of porous silicon. Part I: Fabrication and investigation of single layers, Optical Materials 25 (2004) 251. b) Part II: Fabrication and investigation of multilayer structures, Optical Materials 25 (2004) 257].
- PSi films are interesting for their high specific surface area (200 m 2 / cm 3 ), which can be used to collect and concentrate molecular species, and for the considerable changes that their optical and electrical properties undergo when they interact with gases and fluids.
- An additional advantage of porous silicon systems is that their surface can be chemically modified with specific or non-specific recognition elements [M. Arroyo-Hernández, RJ Mart ⁇ n-Palma, J. Pérez-Rigueiro, JP Garc ⁇ a-Ruiz, JL Garc ⁇ a-Fierro, JM Mart ⁇ nez-Duart, Biofunctionalization of surfaces of nanostructured porous silicon, Materials Science and Engineering C 23 (2003) 697. VS -Y. Lin, K. Motesharei, K.
- BRs In the form of BRs, a large number of layers can be obtained without the structural integrity problems of the multilayer films obtained by sol-gel, and the thickness and porosity of each layer can be controlled very precisely.
- the main problem of these materials is their long-term altered stability.
- the application of pSi BRs in air or aqueous media generates oxide on the surface within a few hours, so they must be chemically modified to increase their resistance to oxidation.
- This type of multilayer is manufactured by alternating deposition, using spin-coating techniques (SY Choi, M. Mamak, G. von Freymann, N. Chopra, GA Ozin, Mesoporous Bragg Stack Color Tunable Sensors, Nano Letters 6 (2006 ) 2456) or dip-coating (MC Fuertes, G. Soler-Illia, H. Miguez, Spanish patent with application number: 200602405), of sheets having mesopores ordered and obtained using an organic tempered mold or mold mixed with the compounds that give rise to the inorganic phase in the precursor solution that is deposited to form each layer.
- the porosity of these layers allows to modify their optical response by infiltration of liquids.
- the possibility of functionalizing the walls of Mesopores make this response selective to a particular type or group of compounds.
- An object of the present invention is a mesoporous multilayer structure with properties of Bragg reflector or one-dimensional photonic crystal, hereinafter nanoparticulate multilayer structure of the invention, comprising periodically alternating sheets of different index of refraction, each of thickness between 1 nm and 200 nm and composed of nanoparticles.
- the nanoparticulate mesoporous multilayer structure of the invention is deposited on a substrate during the process of obtaining, being able to Nanoparticles of several different materials are used, which gives each sheet a different index of refraction and, therefore, different characteristics to each multilayer structure.
- Another object of the present invention is a manufacturing process of the nanoparticulate multilayer structure with one-dimensional photonic crystal properties, hereinafter the method of the invention, comprising the following steps: a) preparation of nano-sized particle suspensions comprised in the range 1-100 nm, whose composition is that of any material that can be obtained in the form of a nanoparticle, where the medium of the suspension is any liquid in which these particles can be dispersed, and where the concentration of them is between 1% and 99%, and b) formation of the structure of the invention by alternating deposition, on any substrate, of controlled thickness sheets of nanoparticles from the suspensions described in a) such that an alternation in value is created of the refractive index and in which the thickness of each of the sheets of nanoparticles that fo rman the multilayer is between. nm and 1 miera and where the number of nanoparticulate sheets present in the multilayer can range between 1 and 100 layers.
- Another object of the invention is the use of the mesoporous nanoparticulate multilayer structure of the invention in the manufacture preferably of optical elements for use in, by way of illustration and without limiting the scope of the invention, preferably, sensor devices, photoelectrochemical, colored coatings and reflective coatings.
- the present invention is based on the fact that the inventors have observed that it is possible to obtain, from a novel procedure where optically uniform sheets of nanoparticles are periodically alternated, a new multilayer mesoporous structure (with pores between 1 nm and 100 nm) with alternation of refractive index and presenting high reflectances at different wavelengths.
- These properties of Bragg reflector or one-dimensional photonic crystal are observed in the ultraviolet, visible and near-infrared range of the electromagnetic spectrum.
- This one-dimensional photonic crystal formed by sheets of different refractive index of controlled thickness composed of nanoparticles can be deposited on different types of substrates by a simple and reliable procedure.
- This periodic interlayer of high interconnected porosity, accessible from the outside, and with properties of one-dimensional photonic crystal is formed by the alternating deposition of sheets of controlled thickness of nanoparticles of oxides or semiconductors such that a periodic alternation in the value of the refractive index. From this alternation comes the photonic crystal behavior of the multilayer.
- the periodic alternation of sheets of different index of refraction results in a strong reflectance easily observable to the naked eye or measurable with a spectrophotometer.
- the mesoporous structure of this reflector is such that it allows the diffusion of liquids through it. This gives rise to the possibility of controlling the color of the multilayer structure in a controlled manner depending on the infiltrated liquid and is therefore a material that can be used in the manufacture of a sensor.
- the proven nanoparticulate character of each layer that forms the multilayer implies an important qualitative structural difference with respect to previously manufactured mesoporous multilayers.
- an object of the present invention is a mesoporous multilayer structure with properties of Bragg reflector or one-dimensional photonic crystal, hereinafter nanoparticulate multilayer structure of the invention, comprising periodically alternated sheets of different Index of refraction, each of thickness comprised between 1 nm and 200 nm and composed of nanoparticles.
- the nanoparticulate mesoporous multilayer structure of the invention is deposited on a substrate during the process of obtaining, nanoparticles of several different materials can be used, which gives each sheet a different index of refraction and, therefore, different characteristics to each multilayer structure. .
- a particular object of the present invention is the nanoparticulate multilayer structure of the invention comprising sheets with nanoparticles of different materials (Example 2, Figure 3).
- nanoparticulate multilayer structure of the invention comprising sheets with nanoparticles of the same material (Example 3, Figure 4).
- the nanoparticles present in the nanoparticulate multilayer structure of the invention can be of any material that can be obtained in the form of nanoparticles of size between 1 nm and 100 nm, and that allow obtaining the desired contrast of the Index of refraction between the sheets.
- the material of the nanoparticles belongs to the following group: metal oxides, metal halides, nitrides, carbides, chalcogenides, metals, semiconductors, polymers or a mixture thereof.
- the oxides are selected from the group of inorganic oxides both in their amorphous or crystalline phase; and more preferably, these materials are selected from the group: YES2, TIO2, SnO 2 , ZnO, Nb 2 O 5 , CeO 2 , Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , Cr 2 O 3 , HfO 2 , MnO 2 , Mn 2 O 3 , Co 3 O 4 , NiO, Al 2 O 3 , In 2 O 3 , SnO 2 .
- a particular embodiment of the present invention is the multilayer nanoparticulate structure in which the chosen nanoparticles are of material belonging to the following groups: SiO 2 / TiO 2 and SiO 2 / SnO 2 . Examples of structures composed of these nanoparticles are shown in Examples 1, 2, 4, 5 and 6.
- nanoparticulate multilayer structure of the invention comprising sheets with nanoparticles, of the same or different material, but with different distribution of nanoparticle sizes.
- the difference or equal size of the nanoparticles determines a different porosity and gives each layer a different index of refraction.
- a particular embodiment is a nanoparticulate multilayer structure of the invention comprising sheets with nanoparticles, of the same material as for example TiO 2 , but with different nanoparticle size distribution (Example 3, Figure 4).
- Another object of the present invention is the nanoparticulate multilayer structure of the invention comprising one or more ruptures of the periodicity of the sheets.
- This nanoparticulate multilayer structure has a spatial periodicity interrupted by the presence of a thicker or thicker sheet than those that form the periodicity, so that optical states of defect are generated in the one-dimensional photonic crystal.
- This nanoparticulate multilayer structure of the invention with rupture or interruption of periodicity can also be extended by including sheets of different thicknesses, for example between 1 nm and 200 nm, formed by nanoparticles of different material and size and, therefore, of the porosity.
- the final properties of the different mesoporous multilayer structures of the invention that can be manufactured are controlled through different parameters involved in the manufacturing process: ) the concentration of oxide particles in the starting suspensions, which allows the thicknesses of each of the deposited sheets to be modified in a controlled manner, showing a clear example of the effect of this modification of the concentration on the precursor colloidal suspensions on the optical properties in the Figure 1 ; b) through the preparation of said multilayer structures with the use of the same particulate material but with different porosity, as described in Example 3 and can be seen in Figure 4; c) through the intentional breaking of the periodicity of the multilayer structure, which results in the creation of optical defect states with which special optical properties are associated, d) through the number of sheets that are inserted in the structure, so that increasing the number of sheets allows to increase the intensity of the maximum reflection characteristic of multilayer structures with photonic crystal properties ( Figure 2), and e) the deposition of the sheets at different speed of
- Another object of the present invention is a manufacturing process of the nanoparticulate multilayer structure with one-dimensional photonic crystal properties, hereinafter the method of the invention, comprising the following steps: a) preparation of nano-sized particle suspensions comprised in the range 1-100 nm, whose composition is that of any material that can be obtained in the form of a nanoparticle, where the medium of the suspension is any liquid in which these particles can be dispersed, and where the concentration of them is between 1% and 99%, and b) formation of the structure of the invention by alternating deposition, on any substrate, of controlled thickness sheets of nanoparticles from the suspensions described in a) such that an alternation in value is created of the refractive index and in which the thickness of each of the sheets of nanoparticles that fo The multilayer rman is between 2 nm and 1 m and where the number of nanoparticulate sheets present in the multilayer can range between 1 and 100 layers.
- the nanoparticles of the process of the invention can be of any material that can be obtained in the form of nanoparticles of size between 1 nm and 100 nm.
- the materials used in the form of nanoparticles (or a mixture thereof) for the deposition of the multilayer structure with photonic crystal properties will be those that allow obtaining the desired contrast of the Index of refraction between the layers.
- the composition may be that of any of the metal oxides, metal halides, nitrides, carbides, chalcogenides, metals, semiconductors, polymers or a mixture thereof.
- these materials are selected from the group of inorganic oxides both in their amorphous or crystalline phase.
- these materials are selected from the group YES2, TIO2, SnO 2 , ZnO, Nb2 ⁇ 5 , CeO 2 , Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , Cr 2 O 3 , HfO 2 , MnO 2 , Mn 2 O 3 , Co 3 O 4 , NiO, Al 2 O 3 , In 2 O 3 , SnO 2 .
- the nanoparticles chosen are of the materials SiO 2 , TiO 2 and SnO 2 . Examples of structures composed of these nanoparticles are shown in examples 1, 2, 4, 5 and 6.
- the precursor dispersions or suspensions to obtain the thin sheets of nanoparticles that form the multilayer structure use any dispersant thereof as a liquid medium.
- the liquid medium will also be volatile.
- this liquid medium is selected from the group of water, alcohols, aliphatic, alicyclic or aromatic hydrocarbons. More preferably, pure or mixed water, ethanol, ethylene glycol and methanol are used in any proportions, and with a weight concentration of the compound in the medium between 1% and 99%.
- the precursor suspensions of nanoparticles of the different sheets that are used in the process of the invention can be of the same or different material, and at the same time each sheet of which they are part of the multilayer can have a different porosity by the use of the same or different size of nanoparticle so that it results in a different index of refraction in each one.
- An example of preparation of this alternative is described in Example 3.
- the deposition of the layers of b) can be carried out by different methods for each of these sheets, and can be any that allows to obtain a sheet of uniform thickness between 2 nm and 1 miera, belonging, by way of illustration and without limiting the scope of the invention, to the following group: spin-coating, dip-coating and Langmuir-Blodgett. More preferably, the technique employed is spin-coating, since it is commonly used in the preparation of thin sheets of different materials and in the preparation of planarized devices.
- a defect or rupture of the periodicity of the multilayer structure may be intentionally included. , for example, by the presence of a thicker sheet.
- crystals were used as substrates that were cleaned and treated by known procedures, which, like the techniques used, can, with the information of the present invention, be easily carried out by an expert. qualified in this sector of the technique.
- the multilayer structure is manufactured following the general procedure set forth in the previous sections, a multilayer with properties of Bragg reflector or one-dimensional photonic crystal is obtained in a wide range of wavelengths (examples 1, 2, 3 and 4).
- the reflectance obtained in each case will depend, to a large extent, on the thicknesses of the sheets formed with the nanoparticles of the materials with different refractive indices. Said thicknesses can be controlled with some parameters of the deposition process, such as speed of rotation of the substrate if the technique used is spin-coating, or through the dispersions of nanoparticles prepared.
- the interruptions of the periodicity of the multilayer structure are achieved starting from the nanoparticle suspensions prepared as described in a).
- the material that allows us to obtain the desired refractive index in the defect or optical dopant introduced into the multilayer structure will be chosen.
- An example of obtaining a nanoparticulate multilayer structure in which a defect or optical dopant has been introduced in a controlled manner is shown in Example 5.
- the nanoparticulate multilayer structure of the invention can be used as a starting material for which, by modifications or additions, improve the properties of this structure; Such modifications can be carried out by a person skilled in the art and with the information existing in the state of the art.
- the reflectance spectrum of the multilayer structure of the invention can be modified after solvent infiltration with different index of refraction within the structure, so that this structure can function as an optical sensor of certain liquids.
- Another object of the invention is the use of the mesoporous nanoparticulate multilayer structure of the invention in the manufacture preferably of optical elements for use in, by way of illustration and without limiting the scope of the invention, preferably, sensor devices, photoelectrochemicals, coatings colored and reflective coatings.
- Another particular object of the invention is the use of the mesoporous nanoparticulate multilayer structure of the invention in which the optical element is a sensor device of liquid, gaseous, or dispersed compounds in the form of nanoparticles, making use of the high interconnected porosity of the nanoparticulate multilayer structure and its color dependence with the refractive index of the infiltrated compound.
- the optical element is a sensor device of liquid, gaseous, or dispersed compounds in the form of nanoparticles
- Another particular object of the invention is the use of the mesoporous nanoparticulate multilayer structure of the invention in which the optical element is a colored coating of ornamental or technological application, such as reflective coatings of a range of wavelengths of interest.
- Another particular object of the invention is the use of the mesoporous nanoparticulate multilayer structure of the invention in which the optical element is a reflective coating of a wavelength range of interest in photovoltaic and photocatalytic devices, where the implementation of mirrors of High reflectance and at the same time porous can serve to increase its efficiency.
- These described coatings may be useful in the colored coating of materials, for example, ceramic.
- Figure 1 Spectrum reflectance spectra for different one-dimensional photonic crystals composed of sheets of controlled thickness of SIO2 and TIO2 nanoparticles.
- the multilayer structure in all cases, is constituted by the stacking of 6 alternating sheets of said materials obtained with silica dispersions, with concentrations ranging from 1-6% by weight, and titanium oxide, to 5% by weight in all cases.
- the liquid medium of the suspension is a mixture of solvents with a volume ratio of 79% in methanol and 21% in water.
- Figure 2. Evolution of the optical response of a multilayer structure with photonic crystal properties. This evolution has been obtained by stacking 8 sheets alternated in S ⁇ O2 and T ⁇ O2, the number of layers (N). As can be seen, as the number of layers in the system increases, the reflection peak narrows and increases in intensity.
- Figure 3. Specular reflectance (a) and will show scanning electron microscopy (SEM) genes (b) for a photonic crystal of the invention.
- SEM scanning electron microscopy
- the photonic crystal is a 6-layer unidimensional crystal formed by sheets of controlled thickness of silica nanoparticles and titanium oxide.
- concentrations of the suspensions used were 2% in silica and 5% in titanium oxide, with a content of 79% by volume of methanol and 21% in water.
- the rotation speed of the substrate is 100 rps. In the MEB images, the different thicknesses of the silica sheets deposited can be compared with respect to the previous figure.
- FIG 4. - Reflectance spectrum (a) and MEB images (b) of the cross section of a photonic crystal of the invention.
- the photonic crystal is a one-dimensional crystal obtained by stacking sheets of the same material with different porosity. This multilayer structure was obtained with 9 alternating sheets of 8.5% by weight titanium oxide (water) with different size distribution. The rotation speed of the substrate during the deposition process was 125 rps. The reflection peak is narrower due to the lower contrast indexes of refraction between the layers, and can also achieve high reflectances over a wide range of wavelengths.
- Figure 5. Reflectance spectrum (a) and MEB images (b) of the cross section of a one-dimensional photonic crystal. The crystal has been obtained by stacking sheets of titanium oxide and tin oxide nanoparticles.
- This multilayer structure is achieved with 7 alternating sheets of both materials.
- TiO 2 5% by weight suspensions were used, with a mixture of 79% by volume of methanol and 21% by volume of water, and in the case of SnO 2 suspensions by 4.5% in water.
- the rotation speed applied was 100 rps.
- the reflectance spectra show the optical response of a multilayer of 6 sheets in SiO 2 -TiO 2 , obtained with suspensions of 3% silica and 5% titanium by weight with a content of 79% by volume of methanol and 21% in volume of water, as well as that obtained for different thicknesses in the silica defect. Increasing the thickness of the defect also increases the defect states within the photonic gap.
- the MEB images show cross sections of the multilayer structure, as well as the defect in volume within the photonic crystal.
- Example 1 Procedure for preparing a multilayer structure with photonic crystal properties using colloidal silica and titanium oxide nanoparticles with a maximum reflectance of 685 ⁇ 5 nm
- multilayer structures with high reflectances are going to grow, alternating materials in the form of a nanoparticle that allow obtaining a high contrast index of refraction between the layers.
- amorphous silica Lidox colloidal suspension 34% by weight, Aldrich
- crystalline titanium oxide in anatase phase
- the latter was obtained in the form of nanoparticles in colloidal suspension synthesized after a process of hydrolysis, condensation, and peptization in basic medium and under hydrothermal conditions (120 0 C for 3 hours).
- the reagents used are titanium tetraisopropoxide IV (20 ml), MiIIiQ water (36 ml) and tetramethylammonium hydroxide 0.6 M (3.9 ml).
- the resulting suspension was centrifuged as many times as necessary at 14,000 rpm for 10 minutes to remove a possible fraction of aggregates present in the sample.
- the suspension of titanium oxide nanocrystals thus obtained, with a concentration of 24% by weight, has a particle size in the range of 5-15 nm.
- the final methanol content in both cases was 79% by volume.
- the suspensions thus prepared were well homogenized, and reserved for use in the spin-coating deposition process.
- the glass substrates Prior to the deposition process, the glass substrates, of dimensions 2.5 cm X 2.5 cm, were prepared and treated as follows: they were first washed with distilled water, acetone, and ultrasonicated for 30 minutes in carbon tetrachloride; then, they were washed in isopropanol, distilled water and ultrasonicated again in a mixture of sulfuric acid and hydrogen peroxide in volumetric ratio of 4: 1 for 1 hour; and finally they were washed with distilled water several times. After all this treatment, the substrates to be used were thoroughly cleaned with ethanol and dried with a stream of nitrogen gas.
- the substrate was placed in the spin-coater sample holder, a rotation speed of 100 rps was applied and a volume of 250 ⁇ l of silica suspension was added maintaining rotation for 1 minute from the addition.
- An equal volume of titanium oxide nanoparticles was dispensed on the deposited silica sheet, the entire surface of the substrate was well covered and a rotation speed of 100 rps was applied for 1 minute. By repetition of this process, until a total number of 8 layers alternated in S ⁇ O2 and T ⁇ O2 was achieved, the desired multilayer photonic crystal was obtained.
- Figure 2 shows the result in terms of optical response, morphology of the layers and their thickness in the photonic crystals with multilayer structure obtained by this procedure.
- Figure 2a) shows the specular reflectance spectra measured in the same area of the photonic crystal at Increase the number of layers.
- Figure 2b) shows cross-sectional images of the multilayer structure obtained by scanning electron microscopy (SEM).
- Example 2 Procedure for preparing a multilayer structure with photonic crystal properties using colloidal silica and titanium oxide nanoparticles with a maximum reflectance at 445 ⁇ 5 nm.
- This example starts with the same colloidal suspensions used in the previous case.
- the use of different concentrations in the dispersions and / or the deposition of the sheets at different speed of rotation allowed to obtain reflectance spectra in a wide range of wavelengths.
- the possibility of controlling the position of the Bragg peak was modified by modifying the concentrations of the suspensions used for deposition (more specifically of the silica dispersion), keeping the rest of the parameters constant.
- Example 3 Procedure for preparing a multilayer structure with photonic crystal properties using the same particulate material with different size distribution.
- colloidal suspensions were obtained after the hydrothermal synthesis at 120 0 C in this detailed example; while the other, with different size distribution, was obtained using the same amounts of reagents except that after the hydrothermal synthesis at 120 0 C is performed further heating at higher temperatures, specifically at 190 0 C for 4.5 hours After this treatment at a higher temperature, the resulting suspension was centrifuged at 3,000 rpm for 10 minutes. In both cases, titanium oxide is in the anatase crystalline phase.
- the suspensions obtained with a weight concentration of 24% (120 0 C) and 16% (190 0 C) were diluted with distilled water to a concentration of 8.5% by weight in both cases.
- the multilayer structure was achieved by alternating the suspensions prepared from TiO 2 nanoparticles obtained after synthesis at 190 and 120 0 C respectively.
- the nanoparticles synthesized at 190 0 C are larger, and it was observed that each suspension had a different size distribution, not just a different average value, which is key to achieving the properties of the structure of the invention.
- a suspension volume of 250 ⁇ l was dispensed on the treated substrates, as specified in detail above, and a rotation speed of 125 rps was maintained for a time of 1 minute. After stacking 9 layers, the results presented in Figure 4 were achieved.
- Figure 4a) shows in detail the response regarding specular reflectance of the multilayer structure consisting of the same material, as well as microscopy images scanning electronics
- Example 4 Procedure for preparing a multilayer structure with photonic crystal properties using colloidal titanium oxide nanoparticles.
- colloidal particles of TiO 2 -SnO 2 were used as precursor materials of the structure.
- the suspension of titanium oxide nanoparticles was prepared from that obtained at 120 0 C, diluted with methanol up to 5% by weight.
- colloidal tin oxide particles were prepared by a method of forced hydrolysis at elevated temperatures, where it favors the hydrolysis and condensation of the complexes formed in solution. The synthesis was carried out by preparing 0.5 L of tin (IV) chloride solution pentahydrate 0.003 M (537 mg) in 0.3 M HCl.
- the multilayer structure was achieved by alternating colloidal suspensions of titanium and tin oxide, dispensing a volume of 250 ⁇ l on the glass substrate and applying a rotation speed of 100 rps for 1 minute.
- Figure 5a) shows the reflectance spectrum obtained for a multilayer structure of 7 alternating sheets in TiO 2 -SnO 2 , with its corresponding scanning electron microscopy image ( Figure 5b).
- Figure 5b shows the reflectance spectrum obtained for a multilayer structure of 7 alternating sheets in TiO 2 -SnO 2 , with its corresponding scanning electron microscopy image.
- the morphology and the similar size of the different nanoparticles do not allow to distinguish the different thicknesses of each of the sheets. This can be seen in the images of backscattered electrons in the electron microscope, more sensitive to the presence of materials of different electronic density, such as TiO 2 and SiO 2 .
- Example 5 Procedure for preparing a multilayer structure with photonic crystal properties using colloidal silica and titanium oxide nanoparticles with a defect in silica volume.
- an interruption in the periodicity of the multilayered photonic crystal of the invention can be obtained by introducing a thicker sheet, which results in defect states within the photonic gap. That is, wavelengths appear within the prohibited band of the gap that can be transmitted.
- the procedure for obtaining a defect in the volume of silica within a multilayer structure with the materials used in Examples 1 and 2 is described in detail. In this case, suspensions of silica and titania at 3 and 3 were used. 5% by weight, respectively, with a content of 79% by volume of methanol.
- Figure 6a shows the measured reflectance spectrum for the multilayer structure formed by stacking of 6 SiO sheets 2 -TiO 2 , as well as the optical response for different thicknesses in the silica defect within the multilayer achieved by repetition of the deposition process of the same suspension 3 and 5 times.
- Figure 6b shows scanning electron microscopy images of the cross-section of the multilayer and the defect in volume of silica within the photonic crystal, obtained by repeating the deposition process with the silica suspension at 3 times. % in weigh.
- Example 6 Modification of the optical response of the nanoparticulate multilayer structure with photonic crystal properties when infiltrated with solvents of different refractive index.
- Solvent infiltration tests were performed by adding a few drops of it with a pasteur pipette on the surface of the one-dimensional glass.
- the solvents used are water, ethylene glycol and chlorobenzene. When observing this process under the optical microscope, it was found that there was infiltration of the multilayer, which is confirmed by analyzing the variation of its optical response.
- the reflectance measurement obtained for each infiltrated solvent is shown in Figure 7a).
- Figure 7b) shows the variation of the position of the maximum reflection in energy values (eV) that takes place according to the refractive index of the solvent (n ⁇ ).
- Figures 7c) and d) show results of a similar experiment performed for a one-dimensional crystal with a defect in the volume of nanoparticulate silica.
- a 6-layer multilayer structure is first formed by alternating the deposition of 3% by weight suspended silica nanoparticles and 5% by weight titanium oxide nanoparticles.
- the suspension medium is a mixture of methanol (79% by volume) and water (the remaining volume).
- the rotation speed of the substrate on which the layers are deposited was 100 rps.
- the last layer of TIO2 deposited grew a thicker silica sheet, which was achieved by repetition 3 times of the deposition process of this material.
- the substrates that have been used on this occasion are glass microscopic slides, which were cut into squares of dimensions 2.5 cm X 2.5 cm, washed with distilled water, acetone, and ultrasonic for 30 minutes in carbon tetrachloride. They were then washed in isopropanol, distilled water and ultrasonicated again in a mixture of sulfuric acid and hydrogen peroxide in a volumetric ratio of 4: 1 for 1 hour. Finally they are washed with distilled water several times. After all this treatment, the substrates to be used are cleaned well with ethanol and dried with a stream of nitrogen gas.
- colloidal titanium oxide nanoparticles are synthesized using a sol-gel technique followed by a peptization process in basic medium and under hydrothermal conditions.
- the titanium precursor used is the titanium tetraisopropoxide IV (97%, Aldrich). Given the high reactivity of these alkoxid precursors against water, their handling is carried out in an inert atmosphere. Once the required amount of precursor is obtained under These conditions and properly sealed, the rest of the experimental procedure is performed in an uncontrolled atmosphere. In this way, 20 ml of titanium tetraisopropoxide (0.0652 mol) are poured onto 36 ml of MiIIiQ water (2.02 mol) with magnetic stirring in a beaker placed on a stirring plate.
- the synthesis of nanoparticles of TIO2 with different size distribution from the previous one (and, therefore, different porosity and different index of refraction) is achieved by the same sol-gel technique followed by a peptization process in basic and low medium hydrothermal conditions, to which particle growth is also added under higher temperature hydrothermal conditions, more specifically at 190 0 C for 4.5 hours.
- the experimental procedure is identical to that described above, using the same reagents and at the same concentrations.
- the whitish suspension obtained from titanium oxide (anatase) is centrifuged at 3,000 rpm for 10 minutes to remove the added fraction.
- the oxide concentration by weight, calculated by drying in an oven between 60-100 0 C for 2-3 hours, is between 14-17% by weight.
- Colloidal tin oxide particles are obtained by a method of forced hydrolysis at elevated temperatures. Aqueocomplexes formed in solution hydrolyze and condense over time, a very slow reaction at room temperature that can be accelerated with an increase in it. The nature of the precipitated particles obtained will depend on factors such as reagent concentration, pH, aging time, temperature and nature of the ions present in solution.
- the tin precursor used is tin (IV) chloride pentahydrate ⁇ 98%, Riedel-de Haén) dissolved in acid solution, specifically in HCl (37%, Fluka). 0.5 L of tin salt solution in 0.3 M dilute HCl are prepared.
- the final concentration of tin in the solution is 0.003 M, for which 537 mg (0.0015 mol) of the compound must be dissolved.
- the prepared solution is transferred to a glass container closed with plug for subsequent aging in oven at 100 0 C for 2 hours. After this time the resulting suspension is cooled in a water bath and centrifuged at 8000 rpm for 10 minutes removing the supernatant solution. The solid obtained is redispersed in distilled water using an ultrasonic bath. This procedure is repeated three times. After the last centrifugation, the particles were redispersed in a volume of approximately 2 ml of distilled water. Be Calculate the concentration by weight of the oxide in the suspension by drying in an oven between 60-100 0 C for 2-3 hours, which is between 4-5% by weight.
- the dispersions necessary for the spin-coating deposition process were achieved.
- colloidal suspensions Preparation of colloidal suspensions.
- the materials used in nanoparticle form to obtain the multilayer structure with photonic crystal properties are those that allow obtaining a refractive index contrast between the layers.
- three types of colloidal particles have been used as described: titanium oxide, silicon oxide and tin.
- the precursor suspensions, used to obtain sheets of controlled thickness with different index of refraction, are achieved by dilution with different solvents from the suspensions obtained after the synthesis process, as detailed in previous sections.
- the suspensions of nanoparticles of titanium oxide and tin are obtained, more specifically, by dilution with distilled water and / or methanol (Multisolvent HPLC grade) in different proportions.
- the final oxide concentration used in both cases during the spin-coating process is between 1-10% by weight.
- the colloidal amorphous silica particles used are commercial (LUDOX TMA colloidal silica, Aldrich), 34% suspension in water. These dispersions are also diluted with the solvent mixture indicated above until reaching concentrations ranging from 1-6% by weight of silica. Preparation of the multilayer structure from colloidal suspensions.
- the one-dimensional photonic crystal is achieved by repetition of the process of deposition of sheets of nanoparticles of materials of different index of refraction alternately.
- Important factors to control the thickness of the sheets and, therefore, the reflectance spectrum obtained in each case are, among others, the concentration of the suspension used and the speed of rotation in the spin-coating process. In this way, multilayer structures with Bragg reflector properties over a wide range of wavelengths can be prepared.
- the previously treated glass substrates cleaned with ethanol and dried with a stream of nitrogen gas were used. These substrates were placed in the spin-coater sample holder
- Novocontrol GMBH which operates at atmospheric pressure, and proceeded as follows: a volume of 250 ⁇ l of the precursor dispersions prepared with the solvent mixture is suspended, the entire surface of the substrate is well covered and a speed is applied of rotation between 80-130 rps for a time of one minute.
- the deposition of silica on the substrate is started, using the suspensions of concentrations between 1% and 6% by weight of SIO2 with a mixture of solvents (21% by volume of solvent). water and 79% by volume of methanol). The volume of suspension is dispensed and a rotation speed is applied for 1 minute between 80-130 rps. Subsequently, the titanium oxide suspension is similarly processed, with a weight concentration of 5% prepared by dilution with methanol from that obtained in the hydrothermal synthesis at 120 ° C.
- the desired multilayer structure is achieved, achieving greater reflectances by increasing the number of deposited layers.
- the use of different concentrations in the silica dispersions and / or the deposition of the sheets at different rotation speed allowed to obtain reflectance spectra in a wide range of wavelengths.
- the multilayers obtained by the procedure described above were structurally characterized using scanning electron microscopy (SEM) and optically using spectroscopy in reflection mode in the visible and near-infrared range of the EM spectrum, where most of the photonic crystal properties of the same.
- SEM scanning electron microscopy
- the reflectance spectra were measured using a Bruker IFS-66 FTIR equipment attached to a Jan 1 microscope that used a 4X lens with a numerical aperture of 0.1 (angle of light cone ⁇ 5.7 °).
- the MEB images were taken with a Hitachi field emission microscope of different cross sections of the samples.
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CN2008800131335A CN101663599B (zh) | 2007-02-23 | 2008-02-20 | 由具有一维光子晶体性质的纳米颗粒薄层形成的多层结构、其生产方法及其应用 |
EP08718475.0A EP2116872B1 (en) | 2007-02-23 | 2008-02-20 | Multilayer structure formed by nanoparticular lamina with unidimensional photonic crystal properties, method for the production thereof and use thereof |
US12/528,438 US9182528B2 (en) | 2007-02-23 | 2008-02-20 | Multilayer structure formed by nanoparticular lamina with unidimensional photonic crystal properties, method for the production thereof and use thereof |
NZ579404A NZ579404A (en) | 2007-02-23 | 2008-02-20 | Multilayer structure formed by nanoparticular lamina with unidimensional photonic crystal properties, method for the production thereof and use thereof |
ES08718475.0T ES2469831T3 (es) | 2007-02-23 | 2008-02-20 | Estructura multicapa formada por láminas de nanopart�culas con propiedades de cristal fotónico unidimensional, procedimiento para su fabricación y sus aplicaciones |
AU2008217670A AU2008217670B2 (en) | 2007-02-23 | 2008-02-20 | Multilayer structure formed by nanoparticular lamina with unidimensional photonic crystal properties, method for the production thereof and use thereof |
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CN101663599A (zh) | 2010-03-03 |
US20100178480A1 (en) | 2010-07-15 |
ES2469831T3 (es) | 2014-06-20 |
NZ579404A (en) | 2012-04-27 |
EP2116872A4 (en) | 2011-03-16 |
EP2116872B1 (en) | 2014-05-21 |
EP2116872A1 (en) | 2009-11-11 |
CN101663599B (zh) | 2012-07-04 |
AU2008217670B2 (en) | 2013-03-14 |
RU2454688C2 (ru) | 2012-06-27 |
AU2008217670A1 (en) | 2008-08-28 |
ES2304104B1 (es) | 2009-08-25 |
ES2304104A1 (es) | 2008-09-01 |
RU2009135393A (ru) | 2011-03-27 |
PT2116872E (pt) | 2014-07-25 |
US9182528B2 (en) | 2015-11-10 |
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