WO2005060635A2 - Electromagnetic control of chemical catalysis - Google Patents
Electromagnetic control of chemical catalysis Download PDFInfo
- Publication number
- WO2005060635A2 WO2005060635A2 PCT/US2004/041832 US2004041832W WO2005060635A2 WO 2005060635 A2 WO2005060635 A2 WO 2005060635A2 US 2004041832 W US2004041832 W US 2004041832W WO 2005060635 A2 WO2005060635 A2 WO 2005060635A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactant
- electromagnetic radiation
- ofclaim
- chemical reaction
- reaction
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/483—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation using coherent light, UV to IR, e.g. lasers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00495—Means for heating or cooling the reaction vessels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00497—Features relating to the solid phase supports
- B01J2219/00527—Sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00718—Type of compounds synthesised
- B01J2219/00745—Inorganic compounds
- B01J2219/00747—Catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- the present disclosure is directed to localized heating of micro or nanostructures and their associated methods of use and applications. More particularly and in one aspect, the teachings disclosed herein also provides very localized heating of specific nano and micro structures for the purpose of influencing a catalyzed chemical reaction. In one aspect providing heat for a chemical reaction that takes place on and/or adjacent to a provided structure or plurality thereof which generate heat as a result of at least a Photon-Electron resonance, as taught herein.
- the heat that is generated when coupling photons to metal nanoparticles can be derived as follows:
- micro or nanostructures and their applications are also provided.
- the present invention may be used for other fields and applications such as life sciences, chemistry, material sciences, nano technology, electronics and others.
- temperature affected chemical reactions are facilitated by selected localized heat provided by at least Photon-Electron interactions, sometimes also referred to in the literature and known in the art as plasmon resonance.
- PACND Photon-Electron assisted chemical vapor deposition
- the present disclosure provides for Photon-Electron assisted chemical vapor deposition (PACND) which utilizes heat generated by Photon-Electron interactions in nanometer sized structures as the heat source to initiate or facilitate catalytic chemical reactions associated with the deposition of material.
- a reaction product can simply be a heated reactant that is heated by Photon-Electron interactions in accordance with the teachings of the present disclosure.
- a reactant heated in this manner can be utilized in additional steps/ and or processes if so desired.
- application of particular pre-determined frequencies and/or frequency ranges of electromagnetic radiation excite at least a Photon-Electron resonance at the nanometer sized structures and controls the heating and relative temperature of nanometer sized structures by which chemical reactions occur.
- a laser provides the electromagnetic radiation utilized to excite at least a Photon-Electron resonance.
- the present disclosure provides for the use of light sources such as a laser source and conventional optics to provide the desired electromagnetic radiation which selectively drives the Photon-Electron resonance to heat the nanometer sized structures utilizing substantially lower power densities than are typically utilized by the prior art to heat material thereby encouraging, facilitation and/or initiating a reaction.
- light sources such as a laser source and conventional optics to provide the desired electromagnetic radiation which selectively drives the Photon-Electron resonance to heat the nanometer sized structures utilizing substantially lower power densities than are typically utilized by the prior art to heat material thereby encouraging, facilitation and/or initiating a reaction.
- Some exemplary implementations allow for spatial control of chemical processing, such as chemical synthesis, deposition, and/or degradation upon a catalytic substrate on a scale of nanometers. This also provides for a high degree of temporal control of the temperature of the processes/reactions. Stopping incident electromagnetic radiation flux to the nanometer sized structures results in very rapid lowering of temperature at the nanometer sized structures, i.e. a previously established Photon-Electron resonance of these structures attenuates/diminishes, as does the associated generated localized heat.
- the method includes providing reactant or reactants, such as, but not limited to, a reactive species (e.g., Ti (2,2,6,6-tetramethyl-3,5- heptanedione, SiH 4 , and GeH 4 adjacent to one or more particles and irradiating the one or more particles with electromagnetic radiation (e.g., from a laser source, or other source) which has a pre-selected frequency, i.e. substantially matches or matches the Photon-Electron resonance frequency or "P-ERF" of the surface electrons of the one or more structures, here for example, a particle or plurality of particles.
- a reactive species e.g., Ti (2,2,6,6-tetramethyl-3,5- heptanedione, SiH 4 , and GeH 4 adjacent to one or more particles and irradiating the one or more particles with electromagnetic radiation (e.g., from a laser source, or other source) which has a pre-selected frequency, i.e. substantially
- a reactant can be any element or compound that can undergo or be part of a reaction that occurs as a result of exposure to heat provided by the excitation of at least Photon-Electron resonance, as disclosed herein.
- Increases in temperature of the one or more particles to at least a selected temperature results from an influence of at least the electromagnetic radiation having the pre-selected frequency.
- the method causes a chemical reaction of the reactant from at least the increase in the temperature of the one or more particles.
- the present disclosure provides an alternative method for accelerating a catalytic chemical reaction using electromagnetic radiation.
- the method includes providing one or more particles.
- the one or more particles have a thermal characteristic.
- the method includes applying at least one reactant adjacent and/or on one or more particles and irradiating the one or more particles with electromagnetic radiation which has a pre-selected frequency.
- the method includes increasing a temperature of the one or more particles having the thermal characteristic to at least a selected temperature from an influence of at least the electromagnetic radiation having the preselected frequency and causing a catalytic chemical reaction of the at least one reactant from at least the increase in the temperature of the one or more particles. That heat may be used for other processes such as to initiate formation of a reaction product.
- the particles heated through irradiation and Photon-Electron interactions can themselves be the catalytic agent in the enhanced chemical reaction process, h other exemplary implementations, multiple particles may be used together; some of these particles may be used to cause a localized temperature increase through the aforementioned Photon-Electron interactions, while others act as the catalytic particles, which enhance the desired chemical reaction at a suitable temperature or temperature range.
- the benefits of spatial and temporal control may apply in one or in both cases.
- the present disclosure provides a method for forming a reaction product utilizing heat generated by at least Photon-Electron resonance of provided structures, in some implementations, disposed in a particular manner upon a substrate.
- the exemplary method includes providing a substrate comprising a pattern of at least one or more structures preferably one or more nanostructures, which is made of a selected material.
- the method includes determining a P-ERF of the selected material of the nanostructure and exciting at least portion of the selected material using an electromagnetic source providing electromagnetic radiation having a predetermined frequency at or substantially overlapping with the P-ERF to cause generation of, and an increase in, thermal energy of the selected material.
- the method includes providing at least one reactant overlying/adjacent the substrate and the selected material excited at the P-ERF and causing production of a desired reaction product, depending upon at least the provided reactant or reactants.
- the present disclosure also provides one or more of the following exemplary features, which are further described throughout the present specification and more particularly below.
- Photon-Electron excitation in metallic nanostructures to locally heat a structure , such as a pre-form, in a determined space is also disclosed.
- a brief sequence of steps can be provided as follows: a. Developing and/or providing at least one metallic nanostructures upon a substrate (a pre-form), such as, but not limited to, an array of palladium or gold particles by any effective means, including but not limited to electron beam lithography, precipitation and nano-imprinting.
- a substrate such as, but not limited to, an array of palladium or gold particles by any effective means, including but not limited to electron beam lithography, precipitation and nano-imprinting.
- P-ERF e.g., or frequency range
- step (c) Carrying out step (c) inside a determined space so that at least one reactant such as, for example, vaporized chemical precursors, is provided and is in contact with heated metallic nanostructures, which catalyze a chemical reaction.
- at least one reactant such as, for example, vaporized chemical precursors
- Controlling the electromagnetic radiation source can be used to at least turn on/off heating. Heating is induced more rapidly and dissipates more rapidly since it is the interaction of incident electromagnetic radiation with the metallic nanostructures that establishes, via at least Photon-Electron resonance, localized heating of the metallic structures and not the whole of the substrate. Removing the incident electromagnetic radiation flux, having the appropriate frequency or range of frequencies, from the metallic structures results in very fast cooling of the metallic structures due to the small size/mass of the metallic structures.
- the specific localized heating of the structures results from at least the excitation of a Photon-Electron resonance
- specific localized heating of these structures occurs as a result of other effects or combination of effects resulting from impingement of electromagnetic radiation onto the structures, resulting in heat generation to a desired temperature.
- Exemplary effects that result in the localized heating of the present invention can include excitation of a Photon-Electron resonance, phonon lattice vibrations, electron hole creation/dynamics and Landau damping, or any combination thereof.
- the teachings of the present disclosure provide a method facilitating chemical reactions utilizing localized heating, comprising the steps of providing a substrate having disposed thereon at least one structure, introducing at least one reactant adjacent the at least one structure and irradiating the at least one structure with electromagnetic radiation, some implementations, a plurality of structures is provided.
- the electromagnetic radiation has a pre-determined frequency or range of frequencies that is absorbed by the at least one structure and preferentially excites at least a Photon-Electron resonance of the at least one structure.
- This provides and generates localized heat, from the at least one structure and as a result of at least the Photon-Electron resonance, and raises the temperature to facilitate at least one catalytic chemical reaction involving the at least one reactant, which provides at least one reaction product.
- At least one structure is provided upon said substrate in a desired configuration to provide a pre-form, which determines the locality where the at least one catalytic chemical reaction takes place.
- the pre-form can include a plurality of structures or one structure, where the at least one structure or plurality has, for example, a form selected from the group consisting of a particle, a dot, a sphere, a wire, a line, a film and any combination thereof.
- the particle, dot, sphere, wire, line, film and any combination thereof have nano-scale dimensions (any one or combination of height, length, width, diameter, radius, diagonal etc).
- the particle and/or sphere can have a radius from about .5 to about 500 nanometers, or from about 1 to 100 nanometers.
- the at least one structure is or contains at least one metal.
- the metal can be one of gold, copper, silver, titanium, aluminum, nickel, palladium, platinum, ruthenium, iridium, iron, cobalt, rhodium, osmium , zinc or any combination thereof.
- the at least one metal can act as a catalyst in the at least one chemical reaction and/or act as a localized heating source to provide heat at a reaction temperature.
- the at least one reactant can be a gas, a liquid, a plasma, a solid or any combination thereof.
- the at least one structure is or contains at least one element, or combination of elements as found in the Periodic Table of the elements or any combination thereof.
- the at least one structure can act as a catalyst in the at least one chemical reaction and/or act as a localized heating source to provide heat at a chemical reaction temperature.
- the at least one reactant can be a gas, a liquid, a plasma, a solid or any combination thereof.
- the at least one chemical reaction involving the least one reactant can be, for example, a decomposition reaction where the at least one reaction product is or contains a component of the at least one reactant.
- the at least one reactant is a compound having a particular ratio of elements, where the at least one reaction product has the same ratio of elements as the compound and the at least one chemical reaction results in a change of at least one characteristic of the compound. Exemplary changes include, for example, a re-arrangement of atoms, change in bond number, change in bond type, change in bond angle.
- the reaction brings about a change of at least one characteristic resulting in isomer production of the at least one reactant. In some implementations, such isomer production can result in the production of enantiomers.
- the at least one chemical reaction involving the least one reactant can be, for example, any of a substitution reaction, an addition reaction, an elimination reaction, a condensation reaction or any combination thereof.
- the at least one reactant combines with at least a second reactant to form a reaction product.
- the electromagnetic radiation utilized in some implementations is in the form of a laser provided by a laser source.
- a laser source can be utilized in accordance with the present disclosure.
- Electromagnetic radiation for example, can be ultraviolet, visible or infrared radiation or any combination thereof.
- provided electromagnetic radiation irradiates at least a portion of the substrate.
- the present disclosure provides methods wherein the at least one reactant is a carbon containing compound.
- at least a second reactant is provided, wherein the at least one reactant is a carbon containing compound and the second reactant is a hydrogen containing compound
- the substrate is comprised of silicon, or Group II N materials or silicon on insulator or germanium or quartz or glass or any combination thereof.
- electromagnetic radiation having the predetermined frequency or range of frequencies is directed upon a plurality of structures or a subset of the plurality of structures.
- the plurality of structures can comprise at least a first subset and a second subset of structures, each subset differing in composition from another subset, hi one implementation, the first subset heats up to a first reaction temperature that is a result of the interaction of the provided electromagnetic radiation irradiation with the first subset, to drive at least one catalytic chemical reaction.
- additional electromagnetic radiation is provided, wherein the additional electromagnetic radiation has a pre-determined frequency or range of frequencies that differs from the electromagnetic radiation previously provided and excites at least a Photon-Electron resonance in the second subset of structures and thus provides heat for an additional reaction.
- the present disclosure also provides methods and apparatus wherein localized heat is provided, at least in part, by at least one of phonon lattice vibrations, electron hole creation/dynamics, Landau damping, or any combination thereof, in addition to said Photon- Electron resonance to provide disclosed heat.
- the present disclosure also provides for exemplary apparatus for Photon-Electron assisted deposition.
- such apparatus include a determined space, at least one inlet in communication with the determined space for conducting at least one reactant into the determined space, a substrate having disposed thereon at least one structure, the substrate being located within the determined space.
- a source of electromagnetic radiation is also provided, positioned to irradiate the substrate with electromagnetic radiation having a pre-determined frequency or range of frequencies, that is absorbed by the at least one structure and excites at least a Photon-Electron resonance of the at least one structure.
- the electromagnetic radiation is provided such that it irradiates at least a portion of the substrate having the at least one structure disposed thereon.
- the apparatus further comprises and at least one outlet in communication with the determined space.
- the at least one outlet can be for conducting at least one reaction product from the determined space.
- Some implementations can include a second inlet in communication with the determined space and/or a second outlet from the determined space.
- the least one structure contains at least one metal such as, but not limited to, any one of gold, copper, silver, titanium, aluminum, nickel, palladium, platinum, ruthenium, iridium, iron, zinc and any combination thereof.
- the at least one structure has a form/shape that can be any one of a particle, a dot, a sphere, a wire, a line, a film and any combination thereof.
- some implementations of the apparatus utilize at least one structure having a shape/form such as a particle, dot, sphere, wire, line, film and any combination thereof, having nano-scale dimensions. Exemplary dimensions, such as height, width, thickness, etc can be anywhere from .5 to 500 nanometers. Some implementations utilize such structures having dimensions of 1 to 100 nanometers, and still others of 10 to 50 nanometers, or thereabouts or any range therebetween.
- the at least one metal of the at least one structure can be a catalyst in the at least one deposition reaction and/or acts as a heat source for the reaction.
- Exemplary at least one reactant can be any one or any combination of gas, liquid, plasma or solid.
- Figure 1 is an illustrative structure and at least one reactant.
- Figure 1 A is an illustrative close-up of a surface of a structure, incident electromagnetic radiation, exemplary surface electrons of the structure's surface and at least one reactant.
- Figure IB depicts an exemplary first material layer disposed upon the structure and a second incident electromagnetic radiation, a second reactant and exemplary surface electrons of the deposited exemplary first material layer.
- Figure 1C depicts a second material deposition layer upon the first material layer.
- Figure 2A is a depiction of an exemplary substrate, plurality of structures.
- Figure 2B is a schematic, enlarged view of a structure shown in FIG. 2 A and a reactant undergoing an exemplary chemical reaction.
- Figure 3 A is a depiction of an exemplary substrate, plurality of structures and two reactants.
- Figure 3B is a schematic, enlarged view of a structure shown in FIG. 3 A and another exemplary reaction.
- Figure 4A is a depiction of an exemplary substrate, plurality of structures and a reactant.
- Figure 4B is a schematic, enlarged view of a structure shown in FIG. 4A and another exemplary reaction.
- Figure 5 is a schematic, enlarged view of another exemplary structure, heat and yet another exemplary reaction.
- Figure 6 is a schematic configuration of an exemplary apparatus in accordance with teachings disclosed herein.
- the generation of heat via at least Photon-Electron resonance excitation of dissociated surface electrons by incident electromagnetic radiation of particular structures can be utilized in and for various manufacturing techniques, particularly nano-scale manufacturing, chemical processing and other uses where very localized heat generation is desired.
- the size of such structures which will provide/generate heat upon exposure to electromagnetic radiation as described herein and in accordance with the teachings disclosed, can have dimensions of about .5 to about 500 nanometers, preferably from about 1 to 100 nanometers, or any specific range therebetween where at least a Photon-Electron resonance can be provided that provides heat at a desired temperature, such as a reaction temperature.
- a method for fabricating a film of material using a Photon-Electron assisted process may be outlined as follows:
- a substrate having a surface region is provided, onto which is disposed a metallic structure, preferable a metallic nanostructure.
- this metallic structure can be one or more particles having a particular thermal characteristic, e.g. the ability to provide appropriate Photon-Electron resonance upon exposure to appropriate electromagnetic radiation having the appropriate P-ERF or range of P-ERFs.
- the P-ERF is the frequency at which electromagnetic energy from an electromagnetic wave is efficiently converted into a collective electron motion in a solid structure.
- the Photon-Electron resonance frequency may be derived by solving Maxwell's equations with the appropriate boundary conditions or it can be measured empirically from a reflection or absorption spectrum.
- the one of more particles are disposed on at least a portion of the surface region of the substrate.
- At least one reactant is provided within a vicinity of the one or more particles.
- the at least one reactant is composed of at least one component, although the reactant can include two or more components.
- the one or more particles are irradiated with electromagnetic radiation having a pre-selected frequency, in a selected spatial region.
- the spatial region can be substantially defined by the position of the one or more particles upon the substrate.
- the impacted spatial region can also include areas of the substrate upon which the one or more particles are not disposed.
- the spatial region can also include areas less than the areas of the substrate upon which the one or more particles is disposed, e.g. irradiation falls upon some particles but not others at a given time.
- the pre-selected frequency of the irradiating electromagnetic radiation is of a frequency concordant/substantially concordant with a P-ERF of the disposed metallic structure, here the one or more particles.
- the surrounding substrate does not appreciably heat up relative to the one or more particles disposed thereon. This very specific and localized heating, due to the Photon-Electron resonance occurring as a result of the interaction of the electromagnetic radiation, of preselected frequency, with the delocalized surface electrons of the one or more particles, provides the required energy (i.e.
- Metallic structure 8 in Figures 1 and 1 A-1C are depicted as squares simply for illustrative purposes and can be any desired shape, as previously disclosed.
- Incident electromagnetic radiation 4 excites a Photon-Electron resonance of metallic structure 8, for example in an array on a substrate 2 in a CVD environment, which includes at least one reactant such as, but not limited to, a vaporized chemical precursor 6.
- FIGs 1A-1C are up-close illustrative schematics of the surface of a structure from which heat is generated by photon-electron interactions in nanometer sized structures, in accordance with the teachings disclosed herein.
- the dissociated surface electrons are depicted as "e " ".
- Incident electromagnetic radiation 4 having a frequency that is consonant with the Photon-Electron resonance of these surface electrons excites and establishes a Photon-Electron resonance, which in turn generates heat to a reaction temperature at which a reaction between metallic structure 8 and at least one reactant such as a chemical precursors 6 for example and/or between chemical precursors 6 themselves, result in formation of material and deposition 10.
- the at least one structure plays the dual role of a catalyst as well as heat generator. As taught herein, when heat is localized, so may be the chemical reaction and any deposition which may be associated therewith .
- material that makes up deposition 10 itself has dissociated surface electrons which are here depicted as e " .
- a second incident electromagnetic radiation 20 and second reactant, such as a second chemical precursor 21, are introduced.
- the second incident electromagnetic radiation 20 has a frequency that is consonant with the Photon- Electron resonance of these surface electrons (e " ) and excites and establishes at least a second Photon-Electron resonance and associated generated heat.
- the heating effects from photon-electron interactions in nanoparticles is related to the average kinetic energy of the conduction electrons, and incident electromagnetic radiation will cause oscillations of electrons in the surface region of a metal, thereby increasing the average kinetic energy.
- the kinetic energy of the surface electrons is eventually transferred in a somewhat random fashion to electrons interior to the surface, namely bulk electrons. This is the basis of radiative heating. If however, the electromagnetic radiation is at or near the P-ERF , there will be collective oscillations or a resonance of the surface electrons, and the heating will be maximized. As the size of a structures decreases, there is an increase in the surface-to- volume, ratio which is proportional to 1/R, where R is the radius of the particle. Nanoparticles, in particular, have high surface-to-volume ratios so that there are a larger number of surface electrons relative to bulk electrons. It is generally believed that this accounts for the efficient heating of nanoparticles by electromagnetic radiation at the plasmon resonance frequency.
- the optimal absorption frequency can depend both on the shape of individual nanoparticles as well as the geometric arrangement of a collection of nanoparticles (e.g on a surface).
- the calculation of the absorption spectrum dates back to the work of Mie in the early part of the last century. Recent experimental evidence suggests that this heating process can occur on very fast time scales.
- the heat generated can raise the temperature sufficiently to initiate a chemical reaction.
- the heat may be applied between deposition 10 and second chemical precursor 21 and/or between second chemical precursors 21 themselves, resulting in a second material formation and deposition 18 upon previously provided deposition 10.
- Exemplary metals which may be used to form metallic structures
- metallic structures such as, Cu, Ag, Au, Ni, Pd, Pt, Rh, and hr
- plasmons disassociated surface electrons known as plasmons.
- nanometer sized structures i.e. nanostructures, such as but not limited to spheres, lines, arrays and rods to temperatures suitable for facilitating deposition reactions including but not limited to material growth.
- the underlying substrate can be comprised of one or any combination of silicon, or Group III/V materials (of the periodic table), silicon on insulator, germanium, or quartz or glass.
- provided electromagnetic radiation can be provided at a constant rate and/or pulsed upon the structures to generate heat as a result of at least a Photon-Electron interaction with some components of the structure or plurality of structures, i some embodiments, those components are metal containing nanostructures.
- Facilitated reactions that provide any number of types of reaction products some of which may be deposited upon substrate 2.
- substrate can be comprised of one or any combination of silicon, or Group III/V materials (of the periodic table), silicon on insulator, germanium, or quartz or glass.
- provided electromagnetic radiation can be provided at a constant rate and/or pulsed upon the structures to generate heat as a result of at least a Photon-Electron resonance of the structure or plurality of structures, in some implementations metal containing nanostructures.
- Various chemical reactions can take place on and or adjacent the at least one structure, or plurality of structures (such as an array, for example). Furthermore, the at least one structure which acts as a localized heat source can simultaneously act as a catalyst in at least one chemical reaction .
- the at least one structure preferably contains a metal, such as, but not limited to, gold, copper, silver, titanium, aluminum, nickel, palladium, platinum, ruthenium, iridium, iron, cobalt, osmium, zinc, rhodium or any combination thereof, hi some implementations, a plurality of nanostructe particles are provided, at least some acting as only heat sources and some acting as only catalytic units, hi some implementations where a plurality of structures are provided, at least a first and second subset of structures can be provided.
- the subsets can be comprised of the same materials and have differing shapes/forms from one another, disposed upon substrate 2 (e.g. an array and a set of wires).
- contemplated implementations include subsets of structures upon a substrate which are comprised of differing materials, providing each subset of structures particular thermal characteristics, e.g. at least Photon-Electron resonances, that provide heat as a result if exposure to particular electromagnetic radiation frequencies or range of frequencies that do not excite at least Photon-Electron resonances in the other subset. This provides specific heat, by a specific subset, for a specific chemical reaction, all happening adjacent the other second subset upon the substrate.
- thermal characteristics e.g. at least Photon-Electron resonances
- the at least one structure can be provided, as mentioned previously, as a particle, dot, sphere, wire, line, film or any combination thereof, having nano-scale dimensions, that is, having one or any appropriate combination of height, length, width, radius, diagonal, diameter of anywhere from .5 to 500 nanometers, preferably between 1 to 100 nanometers or any range therebetween and thereabouts.
- Reactants of exemplary chemical reactions can be any one or combination of a gas, liquid, plasma or solid.
- Various types of reactions can be provided in accordance with the present teachings.
- An exemplary reaction can be a decomposition reaction wherein at least one reaction product is or contains a component of the at least one reactant. This is exemplified in Figure 2 A, where a plurality of metallic structures 8 are depicted on substrate 2, being irradiated by electromagnetic radiation 4 having the pre-determined frequencies or range of frequencies that excite at least a Photon-Electron resonance in each metallic structure 8. Exemplary decomposition reactant 62 is also provided.
- Figure 2B is a schematic close-up of a single metallic structure 8, that is generating heat, here depicted as a plurality of wavy line 29, at a chemical reaction temperature as a result of at least the excited Photon-Electron resonance provided as a result of the interaction of metallic structure's 8 Photon-Electron electrons with electromagnetic radiation 4 at the appropriate Photon-Electron resonance frequency or range of frequencies.
- This increase in temperature occurs adjacent to, upon, and /or in the local vicinity of the catalyst (which may be the metallic structures).
- Exemplary decomposition reactant 62 undergoes the decomposition and breaks apart into at least two portions 62A and 62B, providing at least one desired reaction product.
- the exemplary reaction depicted in Figures 2A and 2B is sometimes referred to as an elimination reaction, wherein a reactant is eliminated by breakdown into component parts.
- Another exemplary chemical reaction can be a substitution reaction, where the least one reactant reacts with at least a second reactant and substitutes itself or a portion of itself in place of a portion of the second reactant an/or adds to the second reactant to produce a reaction product.
- a substitution reaction where the least one reactant reacts with at least a second reactant and substitutes itself or a portion of itself in place of a portion of the second reactant an/or adds to the second reactant to produce a reaction product.
- heat 29 provides the desired reaction temperature adjacent to, upon, and /or in the local vicinity of the catalyst (which may be the metallic structures) and at least one chemical reaction takes place.
- the catalyst which may be the metallic structures
- one of the triangles which can be a portion of the exemplary first reactant, switches places with one of portion of the second reactant to provide at least one reaction product having a portion of the first reactant and a portion of the second reactant.
- this is symbolized as the connected circle and triangle 64.
- wholesale combination of a first reactant with at least a second reactant can result in an addition reaction product.
- the at least one reactant of a provided at least one chemical reaction is a starting compound 73 having a particular ratio of elements, as exemplified in Figure 4A by a circle, square and triangle, symbolizing an exemplary starting compound.
- appropriate electromagnetic radiation 4 is provided, appropriate heat is generated via at least a Photon-Electron resonance of metallic structure 8 to a chemical reaction temperature and at least one chemical reaction takes place, exemplified in the schematic of Figure 4B.
- the at least one reaction and at least one reaction product, indicated as altered compound 79 have the same ratio of elements as starting compound 73 and the at least one chemical reaction results in a change of at least one characteristic of starting compound 73.
- Exemplary changes include any one of a re-arrangement of atoms, change in bond number, change in bond type, change in bond angle, or any combination thereof.
- the at least one reaction brings about a change of at least one characteristic of starting compound 73, for example resulting in isomer production of the at least one reactant.
- such isomer production can result in the production of enantiomers.
- the apparatus includes a determined space 1200, at least one inlet 1217 in communication with determined space 1200 for conducting at least one reactant from at least one reactant supply 1204 into determined space 1200, a substrate 2 having disposed thereon at least one structure, here an array 7 comprising a plurality of a metallic structure 8, for example.
- a substrate 2 having disposed thereon at least one structure, here an array 7 comprising a plurality of a metallic structure 8, for example.
- Substrate 2 is located within the determined space and a source of electromagnetic radiation 1202 is also provided.
- the electromagnetic radiation 1202 source 1202 is positioned to irradiate the substrate having the at least one structure disposed thereon and/or a portion thereof, with electromagnetic radiation having a pre-determined frequency or range of frequencies that is absorbed by the at least one structure, exemplarily shown here as an array 7 having a plurality of a metallic structures 8, and exciting at least a Photon-Electron resonance of the plurality of a metallic structures 8.
- the electromagnetic radiation 4 is provided such that it irradiates at least a portion of the substrate having the at least one structure disposed thereon.
- This provides localized heat, from the at least one structure and as a result of at least a Photon-Electron resonance, at a chemical reaction temperature to facilitate at least one chemical reaction involving at least one reactant provided by reactant supply 1204.
- the at least one outlet 1219 can be for conducting at least one reaction product from determined space 1200.
- Some implementations can include a second inlet 1218 in communication with determined space 1200 and a second reactant supply 1206 containing a second reactant.
- an additional outlet 1220 can also be provided, in fluid communication with determined space 1200 and a analyzing apparatus 1210, such a gas chromato graph, for example.
- a vacuum 1208 can also be provided and can function to collect at least one reaction product and/or to pull reaction products to analyzing apparatus 1210.
- appropriate valves 1205 are exemplarily provided as shown in Figure 6.
- the overall operation of the apparatus and monitoring and control of reactions in accordance with the teachings provided herein can be provided by at least one computer system 1021, which is in operable communication with various components of the apparatus set up, as exemplarily shown in Figure 6.
- Reactants of reactant supplies 1204 and 1206 can be provided to determined space 1200 in a desired state, such as a gas, liquid, solid or plasma, or any combination thereof.
- the least one structure here the plurality of metallic structures 8, contains at least one metal such as, but not limited to, any one of gold, copper, silver, titanium, aluminum, nickel, palladium, platinum, ruthenium, rhodium, iridium, iron , zinc and any combination thereof.
- the at least one structure has a form shape that can be any one of a particle, a dot, a sphere, a wire, a line, a film and any combination thereof, as disclosed previously.
- some implementations of the apparatus utilize at least one structure having a shape/form such as a particle, dot, sphere, wire, line, film and any combination thereof, having nanoscale dimensions.
- Exemplary dimensions of such structures are of about .5 to about 500 nanometers, hi some implementations the at least one structure has dimensions of about 1 to 100 nanometers, and in still others, of about 10 to 50 nanometers.
- the overall sizes provide for establishment and utilization of at least a Photon-Electron resonance that provides heat at a desired reaction temperature.
- the at least one metal of the at least one structure is a catalyst in the at least one chemical reaction and/or acts as a heat source for the chemical reaction.
- Exemplary chemical reaction temperatures can be several hundred Celsius ( C ) 60 C to 1200 C and thus localized heating, as disclosed and provided by the present teachings can reach such temperatures.
- by pulsing a laser for example, it is possible to control chemical reaction times and temperatures.
- Exemplary apparatus provided herein can host a variety of chemical reactions in accordance with the present disclosure, as discussed above.
- exemplary apparatus includes at least one electromagnetic radiation source 1202, can be derived from a laser source, such as, but not limited to, a solid state laser, a semiconductor diode laser, a helium neon gas laser, an argon ion gas laser, a krypton ion gas laser, an xenon ion gas, tunable lasers, and or lamps.
- a laser source such as, but not limited to, a solid state laser, a semiconductor diode laser, a helium neon gas laser, an argon ion gas laser, a krypton ion gas laser, an xenon ion gas, tunable lasers, and or lamps.
- the pre-selected wavelength ranges from about 100 nm to about 10 ⁇ m.
- Exemplary electromagnetic radiation 4 provided and utilized by exemplary apparatus can include one or any combination of ultraviolet, visible or infrared radiation.
- the exemplary source of electromagnetic radiation provides pulsed electromagnetic radiation having the predetermined frequency or range of frequencies.
- Electromagnetic radiation utilized in accordance with the present disclosure can be provided by any number of sources such as a laser source or lamp, for example.
- Electromagnetic radiation 4 can be any one or a combination of ultraviolet, visible or infrared electromagnetic radiation.
- Photon-Electron resonance has been discussed in detail, it is further contemplated that various other effects, alone or in any combination, may be contributing to the very localized, specific heat generation methodologies discussed above. These may include landau damping, electron hole creation/dynamics as well as phonon lattice vibrations, in any combination and contribution.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002549475A CA2549475A1 (en) | 2003-12-15 | 2004-12-14 | Electromagnetic control of chemical catalysis |
AU2004305048A AU2004305048A1 (en) | 2003-12-15 | 2004-12-14 | Electromagnetic control of chemical catalysis |
JP2006544100A JP2007525315A (en) | 2003-12-15 | 2004-12-14 | Electromagnetic control method of chemical catalyst |
EP04818015A EP1694822A2 (en) | 2003-12-15 | 2004-12-14 | Electromagnetic control of chemical catalysis |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52986903P | 2003-12-15 | 2003-12-15 | |
US60/529,869 | 2003-12-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005060635A2 true WO2005060635A2 (en) | 2005-07-07 |
WO2005060635A3 WO2005060635A3 (en) | 2007-05-03 |
Family
ID=34710144
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/041832 WO2005060635A2 (en) | 2003-12-15 | 2004-12-14 | Electromagnetic control of chemical catalysis |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1694822A2 (en) |
JP (1) | JP2007525315A (en) |
KR (1) | KR20070026370A (en) |
CN (2) | CN101090990A (en) |
AU (1) | AU2004305048A1 (en) |
CA (1) | CA2549475A1 (en) |
WO (1) | WO2005060635A2 (en) |
ZA (1) | ZA200604251B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10046298B2 (en) | 2013-05-21 | 2018-08-14 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Chemical conversion process |
WO2023123067A1 (en) * | 2021-12-29 | 2023-07-06 | 陆一平 | Method and combined structure for forming and adjusting surface plasma pattern of material |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI401205B (en) | 2008-01-31 | 2013-07-11 | Ind Tech Res Inst | Fabricating method for an applied substrate employing photo-thermal effect |
CN101519184B (en) * | 2008-02-29 | 2012-05-23 | 财团法人工业技术研究院 | Method for manufacturing application substrate through photo-thermal effect |
CN101799420B (en) * | 2010-03-10 | 2012-02-29 | 中国科学院光电技术研究所 | Manufacture method of metal micro-nano structure for improving Raman scattering of molecule |
CN102517566B (en) * | 2011-12-16 | 2015-02-04 | 姜谦 | Method for selectively depositing atom layer to film by spray head device |
EP3581371B1 (en) * | 2018-06-14 | 2021-04-14 | Fundació Institut de Ciències Fotòniques | A method and a system for self-repairing an object |
WO2023123069A1 (en) * | 2021-12-29 | 2023-07-06 | 陆一平 | Method for adjusting electromagnetic wave reaction on surface of material, and combined structure thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020127170A1 (en) * | 2000-09-22 | 2002-09-12 | Eun-Hwa Hong | Method of synthesizing carbon nanotubes and apparatus used for the same |
-
2004
- 2004-12-14 AU AU2004305048A patent/AU2004305048A1/en not_active Abandoned
- 2004-12-14 EP EP04818015A patent/EP1694822A2/en not_active Withdrawn
- 2004-12-14 CN CNA2004800373641A patent/CN101090990A/en active Pending
- 2004-12-14 CA CA002549475A patent/CA2549475A1/en not_active Abandoned
- 2004-12-14 WO PCT/US2004/041832 patent/WO2005060635A2/en active Application Filing
- 2004-12-14 CN CNA2004800373092A patent/CN1894438A/en active Pending
- 2004-12-14 KR KR1020067014444A patent/KR20070026370A/en not_active Application Discontinuation
- 2004-12-14 ZA ZA200604251A patent/ZA200604251B/en unknown
- 2004-12-14 JP JP2006544100A patent/JP2007525315A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020127170A1 (en) * | 2000-09-22 | 2002-09-12 | Eun-Hwa Hong | Method of synthesizing carbon nanotubes and apparatus used for the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10046298B2 (en) | 2013-05-21 | 2018-08-14 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Chemical conversion process |
WO2023123067A1 (en) * | 2021-12-29 | 2023-07-06 | 陆一平 | Method and combined structure for forming and adjusting surface plasma pattern of material |
Also Published As
Publication number | Publication date |
---|---|
WO2005060635A3 (en) | 2007-05-03 |
CN1894438A (en) | 2007-01-10 |
KR20070026370A (en) | 2007-03-08 |
CN101090990A (en) | 2007-12-19 |
JP2007525315A (en) | 2007-09-06 |
ZA200604251B (en) | 2008-05-28 |
AU2004305048A1 (en) | 2005-07-07 |
EP1694822A2 (en) | 2006-08-30 |
CA2549475A1 (en) | 2005-07-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7998538B2 (en) | Electromagnetic control of chemical catalysis | |
US5695617A (en) | Silicon nanoparticles | |
Cao et al. | Plasmon-assisted local temperature control to pattern individual semiconductor nanowires and carbon nanotubes | |
Ruffino et al. | Controlled dewetting as fabrication and patterning strategy for metal nanostructures | |
JP3077655B2 (en) | Apparatus and method for producing carbon nanotube | |
US10323318B2 (en) | Method for forming a silver/carbon nanocomposite coating | |
US20130011574A1 (en) | Graphene production method and graphene production apparatus | |
Chuang | Laser-induced molecular processes on surfaces | |
Kim et al. | Light-assisted surface reactions on metal nanoparticles | |
WO2005060635A2 (en) | Electromagnetic control of chemical catalysis | |
US20160053370A1 (en) | Scalable processing of nanocomposites using photon-based methods | |
Baldi et al. | Pulsed photothermal heterogeneous catalysis | |
Ouacha et al. | Laser-assisted growth of gold nanoparticles: Shaping and optical characterization | |
US7504136B2 (en) | Method and system for forming a film of material using plasmon assisted chemical reactions | |
MXPA06006817A (en) | Electromagnetic control of chemical catalysis | |
Cheng et al. | Reactive Magnetron Sputtering of Large‐Scale 3D Aluminum‐Based Plasmonic Nanostructure for Both Light‐Induced Thermal Imaging and Photo‐Thermoelectric Conversion | |
US10618810B2 (en) | Free atom nanotube growth | |
NL2036637A (en) | Pellicle membrane for a lithographic apparatus and method | |
Mouane et al. | Formation of monodispersed carbon nanospheres by pulsed laser irradiation of HOPG | |
US11247901B2 (en) | Free atom nanotube growth | |
EP4309784A1 (en) | Embedding of catalytically active nanoparticles into superstructures of plasmonic nanoparticles to enhance the photocatalytic activity | |
Wu et al. | Nanophotonic catalytic combustion enlightens mid-infrared light source | |
Iwahori et al. | Thermally and photoinduced structural and chemical changes of a silver nanocube array on Au (111) | |
Mondal et al. | On the size control of nanoparticles synthesis without chemicals | |
Nedyalkov et al. | Formation and initial evolution of nanoparticles at ultrashort laser ablation of gold: molecular dynamics simulation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200480037364.1 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2549475 Country of ref document: CA Ref document number: 2006544100 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2006/006817 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004818015 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200605519 Country of ref document: ZA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020067014444 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2004818015 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004305048 Country of ref document: AU |
|
WWP | Wipo information: published in national office |
Ref document number: 1020067014444 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref document number: 2004305048 Country of ref document: AU Date of ref document: 20041214 Kind code of ref document: A |
|
WWP | Wipo information: published in national office |
Ref document number: 2004305048 Country of ref document: AU |