AU2008100144A4 - Initiation and Control of Nanothermal Plasmonic Engineering - Google Patents

Description

INNOVATION PATENT APPLICATION INITIATION AND CONTROL OF NANOTHERMAL PLASMONIC ENGINEERING Inventors: Anthony Defries A citizen of the United Kingdom Residing at 1079 Carrara Place Los Angeles, CA 90049 Mark Brongersma A citizen of The Netherlands Residing at 2474 Ohio Avenue Redwood City, CA 94061 Innovation Patent Application Page 1 Initiation and Control of Nanothermal Plasmonic Engineering [NPEIC] 2/13/08 00 0 INITIATION AND CONTROL OF NANOTHERMAL PLASMONIC ENGINEERING [0001] CROSS REFERENCE TO RELATED APPLICATIONS [0002] This application claims benefit of and priority to Australia Provisional Patent Application No. 2007901419 filed March 20, 2007 entitled "Use of Electromagnetic Excitation to Generate Localized Thermal Conditions for Control of Chemical Reactions and Catalytic Chemical Reactions" and Australia Provisional Patent Application No. 2007901422 00 filed March 20, 2007 entitled "Use of Electromagnetic Excitation to Generate Controlled Localized Thermal Conditions for Initiation of Chemical Reactions".

[0003] STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT [0004] NOT APPLICABLE [0005] BACKGROUND [0006] 1. Field [0007] The present disclosure concerns a means to use at least a form of electromagnetic excitation or light-matter interaction, including solar or laser energy to generate localized conditions that enable initiation and spatial and temporal control of catalysis, chemical reactions, deposition, synthesis, photocatalysis, electrocatalysis and catalytic processes. Initiation and spatial and temporal control may be obtained by restricting and directing the electromagnetic excitation or light-matter interactions to specific objects or features embedded or located in or on a host matrix material or substrate. In some implementations this provides a means to use electromagnetic excitation to initiate and control chemical synthesis or reactions without entirely or partially heating any of or all of the reaction chamber, reactor mass, reaction precursors and products, or reactor substrate. It may further provide for the use of temperature sensitive elements or substrates. The method Innovation Patent Application Page 2 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 of use could include initiation and control of light-matter interactions addressed at optical and other frequencies to generate controlled localized thermal conditions. A further S implementation concerns a means to employ electromagnetic excitation or light-matter interactions to generate localized thermal conditions to initiate or control or cause the combination, separation, reformation or reclamation of a gas, a combination of gasses, a material or a combination of materials in the form of a gas, plasma, solid or liquid. The method of use disclosed could provide a means to initiate and control chemical reactions for the generation, use, transfer and output of controlled localized thermal heat or energy. The method of use disclosed could provide a means to realize and control local thermal conditions 00 down to or below the length scale of a single nanometer and down to or below the timescale of a single picosecond. In some implementations surface plasmon excitations may be used to realize and control local thermal conditions down to or below the length scale of a single nanometer and down to or below the timescale of a single picosecond.

[0008] 2. Related Art [0009] Nanofabrication techniques have enabled the generation of features that can be addressed to manipulate light at the nanoscale. Nanoscale objects or apertures at the nanoscale allow electromagnetic energy to be addressed, concentrated or restricted to critical dimensions that are below the diffraction limit of the wavelength of irradiation used. These concentrated fields can be used by means of absorption to efficiently heat volumes of material down to or below the scale of a single nanometer. Due to the small heat capacity that volume of material would cool rapidly when the electromagnetic excitation or lightmatter interactions is terminated. Depending on the thermal environment of the heated volume cooling could take place on a timescale down to or below a single picosecond. Such concentration could lead to massive field enhancements resulting in extreme control of lightmatter interactions and local heating. An example of strong light-matter interactions can be found in metallic nanostructures. These interactions between electromagnetic excitations and metallic nanoparticles are studied in the field of plasmonics.

Innovation Patent Application Page 3 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 [0010] Plasmon excitations in metallic nanostructures can be exploited to S dramatically improve spatial and temporal control over chemical reactions and deposition by nanothermal plasmonic engineering. The realization of controlled, nanoscale thermal environments has great fundamental and practical importance. Research in this area is driven by a desire to better control and monitor physicochemical or biochemical reactions and to develop thermally controlled nanoscale devices. In the field of plasmonics the unique optical properties of metallic nanostructures are harnessed to enable routing and manipulation of light at the nanoscale. This control over light-matter interactions is derived from the 00 properties of nanostructured metals that support light-induced surface plasmon excitations or collective electron oscillations.

[00011] The surface plasmon resonance effect resulting from a strong interaction between light and nanostructured metals allows for development of a new generation of photonic devices and processing technologies. The surface plasmon resonance effect is identified and may be addressed by the absorption of electromagnetic energy at or near the surface plasmon resonance frequency. This phenomenon may be exploited to open new kinetic pathways for chemical synthesis and reactions that are thermodynamically unfavorable under current processing conditions. Reactions in which metallic nanoparticles provide the catalytic sites are excellent candidates for exploiting surface plasmon excitations.

Synthesis routes or chemical reactions that benefit from local heating by surface plasmons are termed plasmon enhanced. Chemical reactions can also be plasmon enhanced through the ability to locally control temperatures and enable rapid heating and cooling. This allows for rapid switching between low and high temperature states of the catalyst particles. At low temperatures reactions proceed slowly, generating high molecular sticking probabilities. At high temperatures reactions proceed quickly and rapid desorption of reactants from the particles is ensured. Rapidly cycling the temperature of the particles would permit the thermodynamics of a reaction to be exploited at preferred processing temperatures.

[0012] Generating local heat through the use of plasmon excitations allows reactions to be stimulated in a low temperature environment. In some cases quantum effects associated with metal nanoparticles can be addressed to cause further unique behavior and increase Innovation Patent Application Page 4 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 reactivity of such particles. Nanothermal plasmonic engineering provides the ability to concentrate significant amounts of electromagnetic energy into nanoscale volumes and convert that electromagnetic energy into the excitation of electrons, phonons, polaritons, or lattice vibrations, i.e. heat. Local heat generation will give rise to a local temperature increase in proximity to the heated volume of material without heating the entirety of the reactor mass or surrounding environment. In some instances high temperatures may occur in a restricted area while heating a volume many times larger. The concomitant local temperature increase in the heated volume will facilitate new chemical and physical synthesis processes with improved performance by many orders of magnitude in both the degree of 00 spatial and temporal control and energy efficiency.

[0013] Various aspects of surface plasmon excitations or plasmon-assisted reactions are being explored for the creation of new technologies including: miniature optical sensors investigations of the structure of molecules using surface enhanced Raman spectroscopy monitoring of single biomolecules which have been labeled with nanoparticle "antennas" optical microscopy with 20 nm spatial resolution cancer chemotherapy through selective heating of malignant cells that have been targeted with nanoparticles plasmon-based waveguides for microelectronics plasmon-assisted heating for chemical vapor or thin film deposition, nanostructure growth and chemical catalysis [0014] In the chemical industry metal nanostructures play a vital role as catalysts and are used in bulk quantities. It is well known that solid catalysts and systems employing solid catalysts can limit or restrict the speed and efficiency of chemical reactions. These issues require more precise control of catalyst heating and more precise placement of catalysts and chemicals. The invention described herein concerns the ability to address instantaneous delivery of localized focused heating to a desirable catalyst in a structure permitting precise placement to the desired chemical, reactant or product. Plasmon enhanced chemical reactions Innovation Patent Application Page 5 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 provide the means to determine and to change the exact location where a solid or structured catalyst is heated and by such heating to determine when and where reactions take place. The ability to focus heating in a specific area and rapidly change the delivery of that focused heating to adjacent areas permits the creation of high temperature regions surrounded by regions at lower temperatures. The large temperature gradient will result in rapid heat transport from the reaction site.

[0015] Highly exothermic reactions, e.g. Fischer-Tropsch (FT) and FT synthesis reactions may also be controlled by the use of plasmon enhanced chemical reactions in the 00 manner described herein. Since excess heat in an FT reaction can lead to undesirable local temperature increase and catalyst overheating, a means to control removing or transferring some of the heat is desired. Major issues of exothermic reactions in general, and FT reactions in particular, include removing the heat of reaction and avoiding local overheating of the catalysts which can be resolved with the process described herein. Improved control of both exothermic and endothermic activity may be achieved through a more precise heating and cooling methodology described herein. The efficiency and yield of chemical reactions and processing may be significantly improved as the cycling time required for repeated heating and cooling of catalyst, reactant or product is reduced.

[0016] In an exemplary embodiment the invention described herein may be used for the initiation and control of catalysis, chemical reactions, photocatalysis, electrocatalysis, catalytic chemical reactions and chemical synthesis including FT and other exothermic or endothermic reactions. The method, process, features, means or structures of the invention described herein could be expressed in any combination in any or all of the following or any other architectures, form factors, materials or combination of materials including: A metallic A nonmetallic An organic An inorganic A metal organic A silicon A silica Innovation Patent Application Page 6 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 A silicate 0 SA ceramic A composite SA polymer An organic composite thin film An organic composite coating An inorganic composite thin film An inorganic composite coating SAn organic and inorganic composite thin film 00 An organic and inorganic composite coating 0 A thin film crystal lattice nanostructure An active photonic matrix A flexible multi-dimensional film, screen or membrane A microprocessor A MEMS or NEMS device A microfluidic or nanofluidic chip A single nanowire, nanotube or nanofiber A bundle of nanowires, nanotubes or nanofibers A cluster, array or lattice of nanowires, nanotubes or nanofibers A single optical fiber A bundle of optical fibers A cluster, array or lattice of optical fibers A cluster, array or lattice of nanoparticles Designed or shaped single nanoparticles at varying length scales Nanomolecular structures Nanowires, dots, rods, particles, tubes, sphere, films or like materials in any combination Nanoparticles suspended in various liquids or solutions Nanoparticles in powder form Nanoparticles in the form of pellets, liquid, gas, plasma or otherwise Nanostructures, nanoreactors, microstructures, microreactors, macrostructures or other devices Innovation Patent Application Page 7 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 Combinations of nanoparticles or nanostructures in any of the forms described 0 or any other form Nanopatteed materials Nanopattemed nanomaterials TNanopattemed nanomaterials Nanopattered micro materials Micropattemed metallic materials Microstructured metallic materials Metallic micro cavity structures SMetal dielectric materials 00 Metal dielectric metal materials 0Combination of dielectric metal materials or metal dielectric metal materials A paint, coating, powder or film in any form containing any of the materials identified herein or any other materials in any combination All or any of the materials or forms described herein may be designed, used or deployed on or in flexible, elastic, conformable structures. Said structures or surface areas may be expanded or enlarged by the use of advanced non-planar, non-linear geometric and spatial configurations.

[0017] Further the method may incorporate metallic nanoparticle catalysts or nanostructures containing metallic nanoparticle catalysts to be included in the said structure or device. The use of light-matter interactions or electromagnetic excitation including solar energy or laser light to control and direct localized thermal conditions down to or below the length scale of a single nanometer and down to or below the timescale of a single picosecond in said catalysts or devices may allow for more precise chemical reactions to be initiated and controlled in those reactors, structures or devices. Rapid changes in the delivery and location of focused heating will reduce cycling times for repeated heating and cooling to improve the efficiency and yield of chemical reactions and processing. The following are examples of types of catalytic chemical reactions that could be initiated and controlled in this manner or otherwise by means of the invention described herein, e.g. synthesis of hydrocarbons from CO and H 2 steam reforming, acetylation, addition reactions, alkylation, dealkylation, hydrodealkylation, reductive alkylation, amination, aromatization, arylation, carbonylation, decarbonylation, reductive carbonylation, carboxylation, reductive carboxylation, reductive Innovation Patent Application Page 8 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 coupling, condensation, cracking, hydrocracking, cyclization, cyclooligomerization, dehalogenation, dimerization, epoxidation, esterification, exchange, halogenation, (Nl S hydrohalogenation, homologation, hydration, dehydration, hydrogenation, dehydrogenation, hydrocarboxylation, hydroformylation, hydrogenolysis, hydrometallation, hydrosilation, S hydrolysis, hydrotreating, hydrodesulferization/hydrodenitrogenation (HDS/HDN), isomerization, methanol synthesis, methylation, demethylation, metathesis, nitration, partial oxidation, polymerization, reduction, steam and carbon dioxide reforming, sulfonation, telomerization, transesterification, trimerization, water gas shift (WGS), and reverse water 0 gas shift (RWGS).

00 S [0018] Nanowires are typically grown in random arrays using a variety of chemical vapor deposition (CVD) techniques. The successful introduction of nanowires into electronic circuitry will require synthesis of nanowires in well-defined locations with controlled composition, diameter, and growth orientation. CVD is a key process for the fabrication of semiconductors, microelectronics, photonics and nanomaterials. There are a number of CVD methods in current use, e.g. Laser Assisted CVD (LACVD), Low Pressure CVD (LPCVD), Metal-Organic CVD (MOCVD), Plasma Enhanced CVD (PECVD) and Thermal Activation CVD (TACVD). In unique contrast to all existing methods of CVD the invention described herein includes a means to generate a thermal environment that can be controlled through the interaction of electromagnetic excitations with designed objects or apertures at length scales down to or below a single nanometer and timescales down to or below a single picosecond.

[0019] In an exemplary embodiment this invention may include initiation and control of electromagnetic energy in a structure or material, which contains an addressable plasmon resonant frequency, so as to influence one or more specific properties of said structure or material. It may also include combining conventional nanoparticle catalyzed CVD nanowire growth with surface plasmon induced local heating of the catalyst particle. Local heating of selected nanoscale regions can enable growth of nanowires in well-defined locations on a chip and thereby solve a number of issues associated with conventional CVD. Existing CVD methods for growing nanowires at positions defined by the precise placement of catalyst particles require relatively high temperatures. This makes conventional CVD unsuitable for positioning on many materials including plastics, glass and certain silicon surfaces used in Innovation Patent Application Page 9 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 standard semiconductor chip synthesis. Initiation and control of nanothermal plasmonic 0 engineering for CVD could overcome this limitation and enable the creation of entirely new S classes of devices, materials, and combinations of materials.

[0020] The importance of heat and metal catalysts in large-scale, continuous chemical processing cannot be overstated. Metals such as Al, Co, Ni, Ru, Rh, Ro, Pd, Os, Ir, Pt, Cu, Zi, Si, Mo and Fe serve as common catalysts. Typical reactions take place at hundreds or thousands of degrees Celsius. Controlled localized heating would support the function of scaling in a local reaction. Stimulating controlled localized thermal conditions could use such 00 scaling to increase the efficiency of certain reactions. Minimal energy would be required to heat the reaction mass or chamber and greater temporal control over the reaction could be achieved. By cycling through different temperatures the process could take advantage of the strongly temperature dependent kinetics, thermodynamics and sticking coefficients of molecules.

[0021] An example is the widely used Fischer-Tropsch reaction: CO H 2

CH

2 n 2

CH

2 forms hydrocarbons from the catalysis of CO and H 2 The products of the reaction include methane, methanol, aldehydes, and ethanol depending on which catalyst is used. Al, Co, Ni, Ru, Rh, Ro, Pd, Os, Ir, Pt, Cu, Zi, Si, Mo and Fe are the most commonly used catalysts with iron being widely used in industrial processes such as coal gasification, gas liquefaction, fuel refining and reformation. The generation of controlled and rapidly changeable, localized thermal conditions could be used to obtain desired reaction kinetics, enhance yield and reduce total energy consumption.

[0022] The technology described herein may support low power, low cost, solar or other forms of photosynthesis or photocatalysis for controlled localized production of methane and hydrogen. In the near term existing hydrocarbon materials could be used.

Ultimately decomposition or conversion of organic materials could serve as a clean renewable energy resource. This offers the potential for a prolonged and broadly based development of alternatives to hydrocarbon and fossil fuels.

[0023] The following are some examples of industries or applications in which the Innovation Patent Application Page 10 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 invention described herein might enable significant scaling improvements, energy savings, 0 cost efficiencies or disruptive technologies: Energy and Transportation T Semiconductors Photonics Electronics Fuel Cells Waste Treatment SDesalinization 00 Catalysis 0Pharmaceuticals Diamond Material Production Composite Materials Photolithography Photovoltaics (solar cells) Photocatalysis Fertilizer Food Production Chemicals Coal Gasification and Liquefaction Methane and Hydrogen Production Biotech Carbon Reclamation Cosmetics Medical Memory Storage Coating Finishing Plastics Polymers Gas to Liquid Conversion Direct Methane Conversion Microfluidics Gas Synthesis Water Treatment Innovation Patent Application Page 11 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 Food Production 0 Light Emitting Diodes SThermal Energy Conversion SPower Generation [0024] DESCRIPTION OF THE INVENTION [0025] Metals can be thought of as a gas of conduction electrons. Similar to sound waves in a real gas, metals exhibit plasmon phenomena, i.e. electron density waves. Electron 00 density waves can be excited at the interface between a metal and a dielectric. There is also a strong interaction of light with a metallic nanoparticle. At the surface plasmon resonance frequency, the electric field of a light wave induces a collective electron oscillation in the particle. Due to inelastic scattering processes, the kinetic energy of the electrons is rapidly converted to heat and the temperature of the nanoparticle is raised.

[0026] The time-varying electric field associated with light waves can exert a force on the gas of negatively charged electrons and drive them into a collective oscillation. There are interesting analogies of this phenomenon to driving a gas of molecules into a resonant collective oscillation by blowing on a flute. The motion of the oscillating electrons in the particles is strongly damped in collisions with other electrons and lattice vibrations (phonons) and the kinetic energy of the electrons is rapidly converted into heat on a 1-10 femtosecond timescale (one femtosecond one quadrillionth of a second).

[0027] This process can be used for the rapid, controlled heating and cooling of particles to enable new methods for micro, nano manufacturing and molecular synthesis. It is important to note that very low energy input is required to obtain a significant temperature rise in nanoscale particles. This energy could be delivered in a spatially and temporally controlled fashion by solar energy, a lamp, a laser or a broadband solid-state light source.

When the light source is interrupted the particle cools and the thermal energy gained rapidly dissipates into a larger, cooler thermal mass on which the particle is positioned (10ps- ins).

This process can be used for very fast switching between low and high temperature states of the particle.

Innovation Patent Application Page 12 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC] 00 O [0028] This invention concerns the use of electromagnetic energy alone or combined with surface plasmon resonance frequency effects to generate controlled localized thermal conditions. As a function of this invention said thermal conditions could be used for the control of chemical reactions, deposition, synthesis, and catalytic chemical reactions without entirely or partially heating all or any of the reaction chamber, reactor mass, reactant, product, or reactor substrate. This invention concerns the use of said frequency effects to enable controlled, localized plasmon assisted reactions to obtain improved results in a low temperature environment. This invention provides the ability to concentrate significant 00 amounts of electromagnetic energy into nanoscale volumes and convert that electromagnetic energy into the excitation of electrons, phonons, polaritons, or lattice vibrations, i.e. heat.

Local heat generation will give rise to a local temperature increase in proximity to the heated volume of material without heating the entirety of the reactor mass or surrounding environment. In some instances high temperatures may occur in a restricted area while heating a volume many times larger. The concomitant local temperature increase in the heated volume will facilitate new chemical and physical synthesis processes with improved performance by many orders of magnitude in both the degree of spatial and temporal control and energy efficiency [0029] An exemplary embodiment of the invention described herein may include the ability to extend the effects of local heating to adjacent particles, materials or structures.

Electromagnetic excitation of specific objects or features may be used to drive reactions, e.g.

growth of particles, materials or structures in proximity to the heated object or feature. An electromagnetic excitation induced in a metallic particle could generate a thermal environment in particles, materials or structures in proximity to the excited particle and cause subsequent catalysis or growth, e.g. on a silicon wafer. This embodiment may include cycling of temperatures in particles, materials or structures in proximity to the heated objects or features in the manner described by this invention.

[0030] In an alternative embodiment, this invention could provide for initiating and controlling localized heating effects to be induced in non-metallic, organic or inorganic materials as the continuation of a plasmon assisted deposition, reaction or similar process.

Innovation Patent Application Page 13 2/13/08 Initiation and Control of Nanothermal Plasmonic Engineering [NPEIC] 00 The method may employ the use of plasmon resonant frequency effects on a metallic catalyst 0 to initiate and control a reaction in an adjacent non-catalyzed, non-metallic material.

Continued plasmon resonant frequency oscillation of the catalyst may cause prolonged heating of the selected adjacent material. This would provide for the use of selected electromagnetic excitation or light-matter interactions to generate controlled localized thermal conditions in organic or inorganic materials for a variety of purposes.

[0031] This invention further concerns the use of resonant light-matter interaction effects to attain controlled localized thermal conditions. In one implementation this invention 00 could provide a means to deliver at least one form of electromagnetic energy to cause at least the combination, separation, reformation or reclamation of at least a gas, a combination of gasses, a material or a combination of materials in the form of a gas, plasma, solid or liquid.

In an alternative implementation this invention could provide a means to initiate and control the generation, use, transfer and output of controlled localized thermal energy.

[0032] The method of use disclosed could provide a means to realize local thermal conditions at the nanoscale below the diffraction limit for the electromagnetic waves used. In some implementations surface plasmon excitations may be used to achieve desired thermal conditions at the nanoscale. Nanoscale objects or apertures at the nanoscale allow electromagnetic energy to be addressed, concentrated or restricted to critical dimensions that are below the diffraction limit of the wavelength of irradiation used. These concentrated fields can be used by means of absorption to efficiently heat volumes of material down to or below the scale of a single nanometer. Due to the small heat capacity that volume of material would cool rapidly when the electromagnetic excitation or light-matter interactions is terminated. Depending on the thermal environment of the heated volume cooling could take place on a timescale down to or below a single picosecond. The concentration could lead to massive field enhancements resulting in extreme control of light-matter interactions and local heating.

[0033] The method of use could further provide for surface plasmon resonance effects or light-matter interactions to take place in a thermally controlled environment, particle, material or structure. In some circumstances the method may include changing, reducing or Innovation Patent Application Page 14 2/13/08 Initiation and Control of Nanothermal Plasmonic Engineering [NPEIC] 00 controlling the temperature of said environment, particle, material or structure in order to 0 achieve greater efficiency in realizing any of the effects obtained by the invention described herein.

[0034] In an exemplary embodiment of the invention described herein the selective excitation of electrons, molecules, particles, materials and structures may be controlled by means of a surface plasmon resonant frequency excited by the use of electromagnetic radiation or energy transfer.

00 [0035] In any exemplary embodiment or description contained herein the method of enabling the various functions, tasks or features contained in this invention includes performing the operation of some or all of the steps outlined in conjunction with the preferred processes or devices. This description of the operation and steps performed is not intended to be exhaustive or complete or to exclude the performance or operation of any additional steps or the performance or operation of any such steps or any of the steps in any different sequence or order.

[0036] The foregoing means and methods are described as exemplary embodiments of the invention. Those examples are intended to demonstrate that any of the aforementioned steps, processes or devices may be used alone or in conjunction with any other in the sequence described or in any other sequence.

Innovation Patent Application Page 15 2/13/08 Initiation and Control ofNanothermal Plasmonic Engineering [NPEIC]

Claims (3)

1. A method to initiate or control at least one form of electromagnetic excitation or light matter interaction in the process of thermal energy generation including: a means to initiate and control localized heating at or below the length scale of a single nanometer caused by electromagnetic excitation; a means to initiate and control thermal energy caused by electromagnetic O excitation; Oa means to spatially and temporally initiate and control the increase or O decrease in temperature of a material structure caused by electromagnetic excitation; a means to initiate and control the local temperature of one or more of the materials or structures subjected to electromagnetic excitation; a means to control thermal energy caused by electromagnetic excitation; a means to control the increase or decrease in temperature caused by electromagnetic excitation; a means to control the local temperature of one or more of the materials subjected to electromagnetic excitation; a means to initiate and control local heating by changing any one or any number of the focus, wavelength, power density, polarization, or pulsing of the excitation beam causing the heating; a means to initiate and control local heating by employing a resonant excitation beam in combination with conventional resistive heating technology; a means to initiate and control local heating and cooling by control of the thermal properties of the surrounding host or the substrate; a means to initiate and control the thermal environment of the host material or structure for resonant light-matter interactions; a means to change the temperature of the host material or structure for resonant light-matter interactions; a means to increase, reduce, maintain or control the temperature of the host material, structure or environment provided for the performance of resonant light-matter interactions; Innovation Patent Application Initiation and Control of Nanothermal Plasmonic Engineering CLAIMS Page 1 2/13/08 a means to control the thermal environment adjacent or in proximity to an O electromagnetically excited structure or material; a means to change the temperature of the environment adjacent or in proximity to an electromagnetically excited structure or material; a means to increase, reduce, maintain or control the temperature of the host material, structure or environment by exploiting electromagnetic excitations; J- a means to use plasmon enhanced light-matter interactions in metallic particles to extend the effects of local heating to adjacent particles, materials or structures, whether O metallic or non-metallic; a means to use plasmon enhanced light-matter interactions in metallic particles O to initiate and control local heating in adjacent particles, materials or structures, whether metallic or non-metallic; a means to use plasmon enhanced light-matter interactions in metallic particles to extend the effects of local heating to adjacent particles, materials or structures, whether organic or inorganic; a means to use plasmon enhanced light-matter interactions in metallic particles to initiate and control local heating in adjacent particles, materials or structures, whether organic or inorganic; a means to control localized heating caused by electromagnetic excitation.

2. A method to initiate or control at least one form of electromagnetic excitation or light matter interaction for catalysis or photocatalysis including: a means to initiate and control catalytic chemical reactions caused by light- matter interactions in metallic nanoparticles; a means to initiate and control the use of light-matter interactions to cause a catalytic chemical reaction without heating the entire reaction chamber; a means to initiate and control the use of light-matter interactions to cause a catalytic chemical reaction without heating the entire reactor mass; a means to initiate and control the use of light-matter interactions to cause a catalytic chemical reaction without heating the entire reactant; a means to initiate and control the use of light-matter interactions to cause a catalytic chemical reaction without heating the entire product; Innovation Patent Application Initiation and Control of Nanothermal Plasmonic Engineering CLAIMS Page 2 2/13/08 a means to initiate and control the use of light-matter interactions to cause a O catalytic chemical reaction without heating the entire reactor substrate; a means to initiate and control the use of electromagnetic excitation to cause a catalytic chemical reaction without heating the entire reaction chamber; a means to initiate and control the use of electromagnetic excitation to cause a catalytic chemical reaction without heating the entire reactor mass; J- a means to initiate and control the use of electromagnetic excitation to cause a catalytic chemical reaction without heating the entire reactant; O a means to initiate and control the use of electromagnetic excitation to cause a catalytic chemical reaction without heating the entire reaction product; O a means to initiate and control the use of electromagnetic excitation to cause a catalytic chemical reaction without heating the entire reactor substrate; a means to use plasmon enhanced light-matter interactions in metallic particles to extend the effects of catalytic chemical reactions to adjacent particles, materials or structures, whether metallic or non-metallic; a means to use plasmon enhanced light-matter interactions in metallic particles to initiate and control catalytic chemical reactions in adjacent particles, materials or structures, whether metallic or non-metallic; a means to use plasmon enhanced light-matter interactions in metallic particles to extend the effects of catalytic chemical reactions to adjacent particles, materials or structures, whether organic or inorganic; a means to use plasmon enhanced light-matter interactions in metallic particles to initiate and control catalytic chemical reactions in adjacent particles, materials or structures, whether organic or inorganic; a means to perform gas analysis on the reactants and the products in-situ during growth or catalysis.

3. A method to initiate or control at least one form of electromagnetic excitation or light matter interaction to cause reactions or chemical reactions including: a means to initiate and control chemical reactions caused by light-matter interactions in metallic nanoparticles; a means to initiate and control chemical vapor deposition using light-matter Innovation Patent Application Initiation and Control of Nanothermal Plasmonic Engineering CLAIMS Page 3 2/13/08 interactions in metallic nanoparticles; O a means to initiate and control chemical reactions caused by electromagnetic excitation; a means to initiate and control the processing of materials or structures using chemical reactions caused by electromagnetic excitation; a means to initiate and control the use of light-matter interactions to cause a chemical reaction without heating the entire reaction chamber; a means to initiate and control the use of light-matter interactions to cause a O chemical reaction without heating the entire reactor mass; a means to initiate and control the use of light-matter interactions to cause a O chemical reaction without heating the entire reactant; a means to initiate and control the use of light-matter interactions to cause a chemical reaction without heating the entire reaction product; a means to initiate and control the use of light-matter interactions to cause a chemical reaction without heating the entire reactor substrate; a means to initiate and control the use of electromagnetic excitation to cause a chemical reaction without heating the entire reaction chamber; a means to initiate and control the use of electromagnetic excitation to cause a chemical reaction without heating the entire reactor mass; a means to initiate and control the use of electromagnetic excitation to cause a chemical reaction without heating the entire reactant; a means to initiate and control the use of electromagnetic excitation to cause a chemical reaction without heating the entire reaction product; a means to initiate and control the use of electromagnetic excitation to cause a chemical reaction without heating the entire reactor substrate; a means to initiate and control chemical reactions caused by plasmon assisted heating; a means to initiate and control chemical reactions caused by plasmon assisted reactions; a means to initiate and control chemical reactions caused by electromagnetic excitation; a means to initiate and control the processing of materials using chemical Innovation Patent Application Initiation and Control of Nanothermal Plasmonic Engineering CLAIMS Page 4 2/13/08 reactions caused by electromagnetic excitation; O a means to use plasmon enhanced light-matter interactions in metallic particles to extend the effects of chemical reactions to adjacent particles, materials or structures, whether metallic or non-metallic; a means to use plasmon enhanced light-matter interactions in metallic particles to initiate and control chemical reactions in adjacent particles, materials or structures, whether metallic or non-metallic; a means to use plasmon enhanced light-matter interactions in metallic particles O to extend the effects of chemical reactions to adjacent particles, materials or structures, whether organic or inorganic; O a means to use plasmon enhanced light-matter interactions in metallic particles to initiate and control chemical reactions in adjacent particles, materials or structures, whether organic or inorganic; a means to control chemical vapor deposition using plasmon assisted reactions; a means to control plasmon assisted reactions spatially and temporally; a means to perform gas analysis on the reactants and the products in-situ during growth or a chemical reaction; a means to use plasmon enhanced light-matter interactions in metallic particles to control chemical reactions in adjacent particles, materials or structures, whether metallic or non-metallic. Innovation Patent Application Initiation and Control of Nanothermal Plasmonic Engineering CLAIMS Page 5 2/13/08