WO2015148843A1 - Dispositif d'émission de rayonnement électromagnétique - Google Patents

Dispositif d'émission de rayonnement électromagnétique Download PDF

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Publication number
WO2015148843A1
WO2015148843A1 PCT/US2015/022817 US2015022817W WO2015148843A1 WO 2015148843 A1 WO2015148843 A1 WO 2015148843A1 US 2015022817 W US2015022817 W US 2015022817W WO 2015148843 A1 WO2015148843 A1 WO 2015148843A1
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Prior art keywords
electromagnetic radiation
radiation emitting
nanoparticles
emitting device
plasma
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PCT/US2015/022817
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English (en)
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James Allen Casey
Charles SERRANO
David Lawrence WITKER
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Dow Corning Corporation
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Publication of WO2015148843A1 publication Critical patent/WO2015148843A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements

Definitions

  • the present invention generally relates to an electromagnetic radiation emitting device and, more specifically, to an electromagnetic radiation emitting device comprising nanoparticles produced via a plasma process.
  • Light emitting devices have been predominately used in the backlighting industry to provide better viewing properties of a display, such as a liquid crystal display (LCD), where the light emitting devices are placed behind the display.
  • LCD liquid crystal display
  • light emitting devices have been utilized in the general lighting industry for use in light bulbs, lamps, flashlights, etc.
  • Conventional light emitting devices in both the backlighting industry and the general lighting industry, exhibit cool white light. Cool white light is characterized by having a bluish tint when compared to natural sunlight or incandescent light, which tend to have a warmer tint.
  • Various luminescent materials have been utilized in light emitting devices. Recent developments have focused on including a red luminescent material (i.e., a phosphor) in a light emitting device. Blue light emitting diodes are commonly used in conventional light emitting devices. The combination of a blue light emitting diode, a yellow luminescent material, and a red luminescent material generally produces white light having a warmer tint that is comparable to natural sunlight. Unfortunately, such red luminescent materials are very expensive. Furthermore, these red luminescent materials impart the light emitting device with a large haze value. That is, these red luminescent materials cause a great amount of scattering of light as light is emitted from the light emitting diode. This scattering of light causes reduced clear visibility and has a negative effect on the aesthetics and light output from the light emitting device.
  • a red luminescent material i.e., a phosphor
  • the present invention provides an electromagnetic radiation emitting device.
  • the electromagnetic radiation emitting device comprises an electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting device further comprises an electromagnetic radiation emitting layer adjacent the electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting layer of the electromagnetic radiation emitting device comprises a host material and nanoparticles produced via a plasma process in the host material.
  • Figure 1 illustrates one embodiment of a low pressure high frequency pulsed plasma reactor for producing nanoparticles
  • Figure 2 illustrates another embodiment of a low pressure high frequency pulsed plasma reactor for producing nanoparticles
  • Figure 3 illustrates an embodiment of a system including a low pressure pulsed plasma reactor to produce nanoparticles and a diffusion pump to collect the nanoparticles;
  • Figure 4 illustrates a schematic view of one embodiment of a diffusion pump for collecting nanoparticles produced via a reactor.
  • the present invention provides an electromagnetic radiation emitting device.
  • the electromagnetic radiation emitting device may be utilized in any application or end use in which emission of electromagnetic radiation is desirable, as described below.
  • the electromagnetic radiation emitting device is hereinafter referred to simply as the device.
  • the device may be used for various applications.
  • the device may be utilized in applications or end uses where emission of electromagnetic radiation is desirable.
  • the electromagnetic radiation is not limited to any particular wavelength, e.g. visible light.
  • the electromagnetic radiation may have a wavelength or spectrum such that the electromagnetic radiation comprises ultraviolet radiation (e.g. extreme ultraviolet radiation or near ultraviolet radiation), infrared radiation (e.g. near infrared radiation, moderate infrared radiation, far infrared radiation), visible light, etc., as described in greater detail below.
  • the device may be used for solid-state lighting (SSL) applications.
  • one or more of the devices may be used for general lighting applications, such as for lighting residential, commercial, and/or industrial spaces. Such lighting may be direct lighting, indirect lighting, or a combination thereof.
  • the device can be used separately or in an array.
  • the device may be used for other lighting applications as well, such as for automotive applications, display applications, backlighting applications, etc.
  • the device comprises an electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting element is capable of emitting electromagnetic radiation.
  • the electromagnetic radiation emitting element is generally selected based on the desired electromagnetic radiation and may be of various types. In certain embodiments in which the electromagnetic radiation is visible light, the electromagnetic radiation emitting element may be referred to as a light emitting element or a light emitting diode.
  • the light emitting diode may alternatively be referred to in the art as a semiconductor diode, chip or die.
  • the device can further comprise at least one supplemental electromagnetic radiation emitting element spaced from the electromagnetic radiation emitting element. As such, the device may include a plurality of electromagnetic radiation emitting elements.
  • the electromagnetic radiation emitting elements may be the same as or different from each other.
  • the electromagnetic radiation emitting elements may be of the same or different sizes, shapes, and/or colors.
  • the electromagnetic radiation emitting elements may utilize different wavelengths (or spectrums) of electromagnetic radiation.
  • one electromagnetic radiation emitting element may emit infrared radiation, whereas another electromagnetic radiation emitting element may emit visible light.
  • the electromagnetic radiation emitting elements may vary within the same spectrum of electromagnetic radiation as well.
  • one electromagnetic radiation emitting element may emit blue light, one electromagnetic radiation emitting element may red light, one electromagnetic radiation emitting element may emit green light, one electromagnetic radiation emitting element may emit near-ultraviolet (near-UV) light, and/or one electromagnetic radiation emitting element may emit UV light.
  • the electromagnetic radiation emitting element can be formed from various materials.
  • the electromagnetic radiation emitting element is formed from a semiconductor material.
  • semiconductor materials may be utilized to form the electromagnetic radiation emitting element.
  • the material utilized to form the electromagnetic radiation emitting element is selected based on the desired emission.
  • the semiconductor material is one capable of emitting blue light, such as zinc selenide (ZnSe) or indium gallium nitride (InGaN). Other types of materials may be used to emit other colors.
  • the light emitting element may comprise various combinations of gallium, nitride, indium, arsenic, aluminum, phosphide, zinc, selenide, silicon, and/or carbon.
  • the light emitting element comprises gallium nitride.
  • the light emitting element comprises indium gallium nitride.
  • the electromagnetic radiation emitting element comprises indium gallium nitride (IGaN).
  • the electromagnetic radiation emitting element comprises zinc selenide (ZnSe).
  • the semiconductor material is one capable of emitting blue light or green light. The light emitting element may also emit other colors by choosing from the various combinations described above.
  • the electromagnetic radiation emitting element comprises a semiconductor substrate and an epitaxial layer disposed on the semiconductor substrate.
  • the semiconductor substrate and epitaxial layer can be formed from various materials.
  • the semiconductor substrate comprises sapphire, silicon (Si), silicon carbide (SiC), or combinations thereof.
  • the epitaxial layer comprises gallium, nitride, indium, aluminum, phosphide, zinc, selenide, gallium nitride, indium gallium nitride, aluminum gallium nitride, aluminum indium gallium nitride, zinc selenide, or combinations thereof.
  • the electromagnetic radiation emitting element emits a first radiation spectrum having an average wavelength ( ⁇ ) in the infrared to ultraviolet light range.
  • average wavelength it is generally meant that the average wavelength is the intensity weighted average wavelength resulting from the overall spectrum of radiation being emitted, such that the apparent color of the emitted spectrum would correspond to the color of radiation at the average wavelength only.
  • the average wavelength may be calculated from the formula:
  • the average wavelength weighted to the luminous intensity may be calculated by the formula:
  • the average wavelength may also be referred to as a peak and/or median wavelength of the spectrum emitted.
  • the average wavelength would be located at the center or peak. This does not mean that the average wavelength cannot be offset from center, as the peak of intensity is oftentimes located in the leftmost or rightmost area of the actual emitted spectrum as many spectrums tend to be asymmetrical.
  • the electromagnetic radiation emitting element emits an ⁇ -
  • Such average wavelengths generally correspond to "blue/green,” “bluish,” “blue,” or “true blue,” light.
  • the electromagnetic radiation emitting element emits an of from about 100 to about 570, about 250 to about 570, about 350 to about 570, about 400 to about 570, about 425 to about 570, about 450 to about 570, about 500 to about 570, about 520 to about 570, about 530 to about 560, or about 550, nm.
  • Such average wavelengths generally correspond to "blue/green,” “greenish,” or “green,” light.
  • the electromagnetic radiation emitting element emits an of from about 100 to about 400, about 125 to about 375, about 150 to about 350, about 175 to about 325, about 200 to about 300, or about 225 to about 275, nm.
  • Such average wavelengths (and their surrounding spectrum) generally correspond to UV light.
  • the supplemental electromagnetic radiation emitting element generally emits a supplemental radiation spectrum having an average wavelength (A s ) in the infrared to ultraviolet light range.
  • the supplemental electromagnetic radiation emitting element emits a A s corresponding to: "red” light having an A s of from about 575 nm to about 850 nm; "green” light having an A s of from about 475 nm to about
  • (supplemental) electromagnetic radiation emitting elements may be utilized in the device.
  • the device further comprises an electromagnetic radiation emitting layer.
  • the electromagnetic radiation emitting layer is disposed adjacent the electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting layer is disposed directly on the electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting layer is in direct contact with the electromagnetic radiation emitting element, i.e., there is not an intervening layer disposed between the electromagnetic radiation emitting layer and the electromagnetic radiation emitting element.
  • Such arrangements may be referred to in the art as "on-chip" constructs.
  • the electromagnetic radiation emitting layer is spaced from the electromagnetic radiation emitting element.
  • Such arrangements may be referred to in the art as “remote” or “remote on-chip” constructs.
  • Constructs having a plurality of such arrangements may be referred to in the art as integral on-chip or on-chip "packages.”
  • Such packages may have different combinations of various electromagnetic radiation emitting layers and/or electromagnetic radiation emitting layers, which may be the same as or different from each other, as alluded to above.
  • the present invention is not limited to any specific construct, as constructs in the art can vary in design and/or complexity.
  • the electromagnetic radiation emitting layer may cover only a portion of the electromagnetic radiation emitting element, such as a top surface of the electromagnetic radiation emitting element. In other embodiments, the electromagnetic radiation emitting layer substantially covers all of the electromagnetic radiation emitting element. If present, the supplemental electromagnetic radiation emitting element may include or be free of the electromagnetic radiation emitting layer. Such embodiments can be useful to present different colors or other differences in electromagnetic radiation. [0027]
  • the electromagnetic radiation emitting layer may be of various sizes, shapes, and configurations. Thickness of the electromagnetic radiation emitting layer may be uniform or may vary. In certain embodiments, the electromagnetic radiation emitting layer has a substantially dome-shaped cross section defined by the electromagnetic radiation emitting layer and the electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting layer has a substantially rectangular-shaped cross section defined by the electromagnetic radiation emitting layer and the electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting layer may be of other shapes as well.
  • the electromagnetic radiation emitting layer can have a substantially frustoconical-shaped cross section defined by the electromagnetic radiation emitting layer and the electromagnetic radiation emitting element.
  • the electromagnetic radiation emitting layer is configured such that it includes a textured surface, a gradient, a concave surface, a convex surface, etc. In this way, the electromagnetic radiation emitting layer can be tailored to provide various optical properties. Some of these features can be imparted by controlling thickness aspects of the electromagnetic radiation emitting layer as it is formed. For example, the electromagnetic radiation emitting layer can be molded into various shapes and configurations.
  • the electromagnetic radiation emitting layer is "non- scattering" such that the electromagnetic radiation emitting layer is further defined as a non-scattering electromagnetic radiation emitting layer.
  • the electromagnetic radiation emitting layer may have a degree of scattering.
  • reference to the non-scattering electromagnetic radiation emitting layer may be used interchangeably with the electromagnetic radiation emitting layer and vice versa.
  • the electromagnetic radiation emitting layer comprises a host material.
  • the host material can be of various chemistries.
  • the host material may also be referred to in the art as a binder, a carrier, and/or a matrix.
  • the host material may comprise a silicone and/or an organic polymer.
  • the organic polymer generally has a carbon-based backbone or chain, whereas silicones generally comprise siloxane bonds (Si-O-Si). However, carbon-carbon bonds may also be present in silicones formed via hydrosilylation, although such silicones still predominately comprise siloxane bonds.
  • the host material comprises a silicone.
  • silicones can be utilized to form the electromagnetic radiation emitting layer.
  • the silicone is optically transparent so as to not interfere with light emitted by the electromagnetic radiation emitting element or the electromagnetic radiation emitting layer. Such properties provide excellent aesthetics and light output of the device.
  • the host material may be non-scattering which provides similar benefits and excellent efficiency of the device.
  • the silicone is selected from the group of a silicone resin, a silicone elastomer, a silicone liquid, a silicone gel, or combinations thereof.
  • the silicone may be continuous or discontinuous in terms of its composition.
  • the silicone resin may comprise a DT resin, an MT resin, an MDT resin, a DTQ resin, an MTQ resin, an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin, or an MDQ resin.
  • the silicone comprises a silicone fluid, e.g. a non-curable silicone fluid.
  • the silicone fluid is typically PDMS, although the silicone fluid can be linear, branched, cyclic, or a mixture thereof. Mixtures of the aforementioned fluids may also be used. Many of the linear, branched, and cyclic silicone fluids have melting points below about 25° C. Such materials are also commonly described as silicone liquids, silicone fluids, or silicone oils.
  • the host material is formed from a curable silicone, e.g. by curing the curable silicone to form the host material.
  • the curable silicone is not particularly limited and may be further defined as a curable silicone fluid, gel, resin, etc.
  • curable silicones include, but are not limited to, hydrosilylation-curable silicones, condensation-curable silicones, radiation-curable silicones, peroxide-curable silicones, epoxy-curable silicones, and acid or amine cured silicones.
  • the curable silicone once cured to form the host material, may comprise a thermoset silicone or a thermoplastic silicone.
  • thermoplastic describes a silicone that has the physical property of converting to a fluid (flowable) state when heated and of becoming rigid (non-flowable) when cooled.
  • thermoplastics do not “cure” as that term is typically understood in the art, for purposes of this disclosure, the terminology “curable” or “cure” can describe the hardening of thermoplastics.
  • the term “thermoset” may describe a cured (i.e., cross-linked) silicone that does not convert to a fluid state on heating.
  • thermaloset typically describes a silicone having the property of becoming permanently rigid (non-flowable) when cured (i.e., cross-linked).
  • a hydrosilylation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule; an organosilicon compound in an amount sufficient to cure the silicone organopolysiloxane, wherein the organosilicon compound has an average of at least two silicon-bonded hydrogen atoms or silicon-bonded alkenyl groups per molecule capable of reacting with the silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the organopolysiloxane; and a catalytic amount of a hydrosilylation catalyst.
  • a condensation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups per molecule and, optionally, a cross-linking agent having silicon-bonded hydrolysable groups and/or a condensation catalyst.
  • a radiation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded radiation-sensitive groups per molecule and, optionally, a cationic or free-radical photoinitiator depending on the nature of the radiation- sensitive groups in the silicone organopolysiloxane.
  • a peroxide-curable silicone typically includes an organopolysiloxane having silicon- bonded unsaturated aliphatic hydrocarbon groups and an organic peroxide.
  • An epoxy-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded epoxy-functional organic groups.
  • the uncured silicone typically includes a proton source, such as an amine, SiH, acid generator, or a cationic photo-acid generator.
  • the curable silicone can be cured to form the host material by exposing the silicone to ambient temperature, elevated temperature, moisture, or radiation, depending on the type of curable silicone.
  • ambient temperature elevated temperature, moisture, or radiation
  • curing conditions associated with the curing of such silicones.
  • the curable silicone may be utilized as a single component or as a series of components, e.g. as a one part, two part, or multi-part component system.
  • various compounds in the curable silicone may be segregated into "A” and "B" portions such that when the "A" and "B" portions are combined, the curable silicone may cure to form the host material.
  • the curable silicone comprises the condensation-curable silicone.
  • the condensation-curable silicone comprises (A) an organosiloxane block copolymer, which may also be described as a "resin-linear" organosiloxane block copolymer.
  • the organosiloxane block copolymer typically has a weight average molecular weight (M w ) of at least 20,000 g/mole.
  • the organosiloxane block copolymer has a weight average molecular weight of at least 40,000, 50,000, 60,000, 70,000, or 80,000, g/mole.
  • the organosiloxane block copolymer may have a weight average molecular weight of from 40,000 to 100,000, from 50,000 to 90,000, from 60,000 to 80,000, from 60,000 to 70,000, from 100,000 to 500,000, from 150,000 to 450,000, from 200,000 to 400,000, from 250,000 to 350,000, from 250,000 to 300,000, g/mol.
  • the organosiloxane block copolymer has a weight average molecular weight of from 40,000 to 60,000, from 45,000 to 55,000, or about 50,000, g/mol.
  • the weight average molecular weight may be determined via Gel Permeation Chromatography (GPC) techniques using polystyrene (PS) standards.
  • Linear organopolysiloxanes typically include mostly D or ( 2S1O2/2) siloxy units, which results in polydiorganosiloxanes that are fluids of varying viscosity, depending on the "degree of polymerization” or DP as indicated by the number of D units in the polydiorganosiloxane.
  • "Linear" organopolysiloxanes typically have glass transition temperatures (Tg) that are lower than 25 °C.
  • Resin organopolysiloxanes include a weight or molar majority of T or Q siloxy units. When T siloxy units are predominately used to prepare an organopolysiloxane, the resulting organosiloxane is often described as a "silsesquioxane resin". Increasing the amounts of T or Q siloxy units in an organopolysiloxane typically results in organopolysiloxane copolymers having increasing hardness and/or glass like properties. "Resin" organopolysiloxanes typically have higher Tg values than linear organopolysiloxanes. For example, organopolysiloxane resins often have Tg values greater than 50 °C.
  • the organosiloxane block copolymer may also be described as a "resin-linear" organosiloxane block copolymer.
  • the terminology "resin-linear” typically describes organosiloxane block copolymer including "linear” D siloxy units in combination with "resin” T siloxy units.
  • the present organosiloxane copolymers are "block” copolymers, as opposed to "random" copolymers.
  • the present organosiloxane block copolymer describes an organopolysiloxane including D and T siloxy units, where the D units are primarily bonded together to form polymeric chains having 10 to 400 D units, which are described herein as "linear blocks".
  • the T units are primarily bonded to each other to form branched polymeric chains, which are described as “non-linear blocks”.
  • One or more nonlinear blocks may further aggregate to form "nano-domains" in the organosiloxane block copolymer.
  • the organosiloxane block copolymer of this disclosure includes:
  • the organosiloxane block copolymer further comprises:
  • At least 30% of the non-linear blocks are crosslinked with another non-linear block and aggregated in nano-domains.
  • at least at 40% of the non-linear blocks are crosslinked with another non-linear block, and alternatively at least at 50% of the non-linear blocks are crosslinked with another non-linear block.
  • each linear block is linked to at least one non-linear block.
  • a may vary from 0.4 to 0.9, from 0.5 to 0.9, or from 0.6 to 0.9.
  • b can vary from 0.1 to 0.6, from 0.1 to 0.5 or from 0.1 to 0.4.
  • R ⁇ may be independently a C-
  • the hydrocarbyl may independently be an alkyl, aryl, or alkylaryl group. As used herein, hydrocarbyl also includes halogen substituted hydrocarbyls.
  • R ⁇ may be a C-
  • R ⁇ may be methyl.
  • R ⁇ may be an aryl group, such as phenyl, naphthyl, or an anthryl group.
  • R ⁇ may be any combination of the aforementioned alkyl or aryl groups.
  • R ⁇ is phenyl, methyl, or a combination of both.
  • each R ⁇ may independently be a C-
  • hydrocarbyl also includes halogen substituted hydrocarbyls.
  • R2 may alternatively be an aryl group, such as a phenyl, naphthyl, or anthryl group.
  • R ⁇ may be an alkyl group, such as methyl, ethyl, propyl, or butyl.
  • R ⁇ may be any combination of the aforementioned alkyl or aryl groups.
  • R2 is phenyl or methyl.
  • the organosiloxane block copolymer may include additional siloxy units, such as M siloxy units, Q siloxy units, other unique D or T siloxy units (e.g. having a organic groups other than R1 or R2), SO long as the organosiloxane block copolymer includes the mole fractions of the disiloxy and trisiloxy units as described above.
  • the sum of the mole fractions as designated by subscripts a and b do not necessarily have to sum to one.
  • the sum of a + b may be less than one to account for amounts of other siloxy units that may be present in the organosiloxane block copolymer.
  • the sum of a + b may be greater than 0.6, greater than 0.7, greater than 0.8, greater than 0.9, greater than 0.95, or greater than 0.98 or 0.99.
  • the organosiloxane block copolymer consists essentially of the disiloxy units of the formula [RI 2S1O2/2] and trisiloxy units of the formula [R2S1O3/2], in the aforementioned weight percentages, while also including 0.5 to 25 mole percent silanol groups [ ⁇ SiOH], wherein R ⁇ and R2 are as described above.
  • the sum of a+b when using mole fractions to represent the amount of disiloxy and trisiloxy units in the copolymer) is greater than 0.95, alternatively greater than 0.98.
  • the terminology "consisting essentially of” describes that the organosiloxane block copolymer is free of other siloxane units not described immediately above.
  • the organosiloxane block copolymer includes at least 30, at least 50, at least 60, or at least 70, weight percent of disiloxy units.
  • the amount of disiloxy and trisiloxy units in the organosiloxane block copolymer may be described according to the weight percent of each in the organosiloxane block copolymer.
  • the disiloxy units have the formula [(Ch ⁇ SiC ⁇ ]- In a further embodiment, the disiloxy units have the formula [(CH3)(C6H 5 )SiC>2/2]-
  • the amount of silanol groups present in the organosiloxane block copolymer typically varies from 0.5 to 35 mole percent silanol groups [ ⁇ SiOH], alternatively from 2 to 32 mole percent silanol groups [ ⁇ SiOH], and alternatively from 8 to 22 mole percent silanol groups [ ⁇ SiOH].
  • the silanol groups may be present in any siloxy units within the organosiloxane block copolymer.
  • the amounts described above represent the total amount of silanol groups in the organosiloxane block copolymer.
  • a molar majority of the silanol groups are bonded to trisiloxy units, i.e., the resin component of the block copolymer.
  • the silanol groups present on the resin component of the organosiloxane block copolymer may allow the organosiloxane block copolymer to further react or cure at elevated temperatures or to cross-link.
  • the crosslinking of the non-linear blocks may be accomplished via a variety of chemical mechanisms and/or moieties.
  • crosslinking of non-linear blocks within the organosiloxane block copolymer may result from the condensation of residual silanol groups present in the non-linear blocks of the organosiloxane block copolymer.
  • Crosslinking of the non-linear blocks within the organosiloxane block copolymer may also occur between "free resin” components and the non-linear blocks.
  • "Free resin” components may be present in the organosiloxane block copolymer as a result of using an excess amount of an organosiloxane resin during the preparation of the organosiloxane block copolymer.
  • the free resin components may crosslink with the non-linear blocks by condensation of the residual silanol groups present in the non-blocks and in the free resin components.
  • the free resin components may alternatively provide crosslinking by reacting with lower molecular weight compounds such as those utilized as crosslinkers, as described in greater detail below.
  • certain compounds can be added during preparation of the organosiloxane block copolymer to crosslink non-resin blocks.
  • These crosslinking compounds may include an organosilane
  • organosiloxane block copolymer utilized during the formation of the organosiloxane block copolymer (see, for example, step II of the method as described below).
  • X is typically a hydrolysable group
  • q is typically 0, 1 , or 2.
  • R5 may alternatively be a C-
  • X may be any hydrolyzable group, such as an oximo, acetoxy, halogen atom, hydroxyl (OH), or an alkoxy group.
  • the organosilane is an alkyltriacetoxysilane, such as methyltriacetoxysilane, ethyltriacetoxysilane, or a combination of both.
  • alkyltriacetoxysilanes include ETS-900 (Dow Corning Corp., Midland, Ml).
  • organosilanes useful as crosslinkers include methyl-tris(methylethylketoxime)silane (MTO), methyl triacetoxysilane, ethyl triacetoxysilane, tetraacetoxysilane, tetraoximesilane, dimethyl diacetoxysilane, dimethyl dioximesilane, methyl tris(methylmethylketoxime)silane.
  • MTO methyl-tris(methylethylketoxime)silane
  • methyl triacetoxysilane ethyl triacetoxysilane
  • tetraacetoxysilane tetraoximesilane
  • dimethyl diacetoxysilane dimethyl dioximesilane
  • methyl tris(methylmethylketoxime)silane methyl-tris(methylethylketoxime)silane
  • crosslinks within the organosiloxane block copolymer are siloxane bonds ⁇ S
  • the amount of crosslinking in the organosiloxane block copolymer may be estimated by determining an average molecular weight of the organosiloxane block copolymer, such as with GPC techniques. Typically, crosslinking the organosiloxane block copolymer increases average molecular weight.
  • an estimation of the extent of crosslinking may be made, given the average molecular weight of the organosiloxane block copolymer, the selection of the linear siloxy component (i.e., chain length as indicated by degree of polymerization), and the molecular weight of the non-linear block (which may be primarily controlled by the selection of the organosiloxane resin used to prepare the organosiloxane block copolymer).
  • the organosiloxane block copolymer may be isolated in a solid form, for example by casting films of a solution of the organosiloxane block copolymer in an organic solvent and allowing the solvent to evaporate. Upon drying or forming a solid, the non-linear blocks of the organosiloxane block copolymer typically aggregate together to form "nano- domains". As used herein, "predominately aggregated" describes that a majority of nonlinear blocks of the organosiloxane block copolymer are typically found in certain regions of the organosiloxane block copolymer, described herein as the "nano-domains".
  • nano-domains describes phase regions within the organosiloxane block copolymer that are phase separated and possess at least one dimension, e.g. length, width, depth, or height, sized from 1 to 100 nanometers.
  • the nano-domains may vary in shape, providing at least one dimension of the nano-domain is sized from 1 to 100 nanometers.
  • the nano-domains may be regular or irregularly shaped.
  • the nano- domains may be spherically shaped, tubular shaped, and in some instances lamellar shaped.
  • the organosiloxane block copolymer may include a first phase and an incompatible second phase, the first phase including predominately the disiloxy units [RI 2S1O2/2] and the second phase including predominately the trisiloxy units [R2S1O3/2], wherein the nonlinear blocks are aggregated into nano-domains which are incompatible with the first phase.
  • the structural ordering of the disiloxy and trisiloxy units, and characterization of the nano-domains, may be determined using analytical techniques such as Transmission Electron Microscopic (TEM) techniques, Atomic Force Microscopy (AFM), Small Angle Neutron Scattering, Small Angle X-Ray Scattering, and Scanning Electron Microscopy.
  • TEM Transmission Electron Microscopic
  • AFM Atomic Force Microscopy
  • Small Angle Neutron Scattering Small Angle X-Ray Scattering
  • Scanning Electron Microscopy Scanning Electron Microscopy.
  • the structural ordering of the disiloxy and trisiloxy units in the block copolymer, and formation of nano-domains may be inferred by determining certain physical properties of the organosiloxane block copolymer, e.g. when the organosiloxane block copolymer is used as a coating.
  • a coating formed from the organosiloxane block copolymer and/or organosiloxane block copolymer has an optical transmittance of visible light greater than 95%. Such optical clarity is typically only possible when visible light is able to pass through a medium and not be diffracted by particles (or domains as used herein) having a size greater than 150 nanometers. As the particle size (domains) decreases, optical clarity may increase.
  • the organosiloxane block copolymer of this disclosure may include phase separated "soft" and “hard” segments resulting from blocks of linear D units and aggregates of blocks of non-linear T units, respectively. These respective soft and hard segments may be determined or inferred by differing glass transition temperatures (Tg).
  • a linear segment may be described as a "soft" segment typically having a low Tg for example less than 25 °C, alternatively less than 0 °C, or alternatively even less than -20 °C.
  • the linear segments typically maintain "fluid” like behavior in a variety of conditions.
  • non-linear blocks may be described as "hard segments" having higher Tg , values, for example greater than 30 °C, alternatively greater than 40 °C, or alternatively even greater than 50 °C.
  • the organosiloxane block copolymer can be processed several times if a processing temperature (Tp r0 cessing) ' s ' ess tnan a temperature required to cure (T cure ), i.e., if Tp rocess j n g ⁇ T cure .
  • T cure a temperature required to cure
  • the organosiloxane block copolymer will cure and achieve high temperature stability when " ⁇ processing > ⁇ cure-
  • the organopolysiloxane block copolymer may offer the advantage of being "re-processable" in conjunction with the benefits typically associated with silicones, such as hydrophobicity, high temperature stability, and moisture/UV resistance.
  • the solid composition may be described as "melt processable.”
  • the solid composition may exhibit fluid behavior at elevated temperatures, e.g. upon “melting".
  • the melt flow temperature may be determined by measuring the storage modulus (G'), loss modulus (G") and tan delta as a function of temperature storage using commercially available instruments.
  • a commercial rheometer such as TA Instruments' ARES-RDA -with 2KSTD standard flexular pivot spring transducer, with forced convection oven
  • G' storage modulus
  • G loss modulus
  • tan delta as a function of temperature storage
  • Test specimens may be loaded in between parallel plates and measured using small strain oscillatory rheology while ramping the temperature in a range from 25°C to 300°C at 2°C/min (frequency 1 Hz).
  • the flow onset may be calculated as the inflection temperature in the G' drop (e.g. flow), the viscosity at 120°C is reported as a measure for melt processability and the cure onset is calculated as the onset temperature in the G' rise (e.g. cure).
  • the flow of the solid composition will also correlate to the glass transition temperature of the non-linear segments (i.e. the resin component) in the organosiloxane block copolymer.
  • the "melt processability" and/or cure of the solid composition may be determined by rheological measurements at various temperatures.
  • the solid composition may have a melt flow temperature of from 25 to 200, from 25 to 160, or from 50 to 160, °C.
  • the solid composition is "curable".
  • the solid composition may undergo further physical property changes through curing the organosiloxane block copolymer.
  • the organosiloxane block copolymer includes a certain amount of silanol groups. The presence of these silanol groups may allow for further reactivity, i.e. a cure mechanism. Upon curing, the physical properties of solid composition may be further altered.
  • the host material comprises the organic polymer.
  • the organic polymer is selected from the group of polycarbonates, polyamides, polyimides, polysulfones, polyesters, polycarbonates, polyolefins, polynorbornenes, (meth)acrylic polymers, epoxy polymers, episulfide polymers, polystyrenes, celluloses, polyvinyl chlorides), polyvinyl alcohols), poly(ethylene vinyl alcohols), polyacetylenes, polyarylenes, polyarylene vinylenes, polyarylene ethynylenes, or an interpolymer thereof.
  • the nanoparticles may be combined with an uncured organic compound, which is subsequently cured or polymerized to form the host material. Alternatively, the nanoparticles may be combined, e.g. compounded, with a pre-formed host material.
  • the electromagnetic radiation emitting layer further comprises nanoparticles in the host material.
  • the nanoparticles are typically dispersed in the host material.
  • the nanoparticles may be homogenously dispersed in the host material or have heterogeneous concentrations.
  • the nanoparticles do not substantially contribute to a haze value of the electromagnetic radiation emitting layer while in the electromagnetic radiation emitting layer.
  • the haze value of the electromagnetic radiation emitting layer can be used as a measure of the degree of scattering imparted by the nanoparticles. Haze values can be determined by utilizing the test method as described in ASTM D1003 or a modification thereof.
  • the electromagnetic radiation emitting layer is non- scattering as alluded to above.
  • "non-scattering" is generally indicated by a haze value of no greater than about 30%, no greater than about 20%, no greater than about 15%, no greater than about 10%, no greater than about 8%, no greater than about 6%, no greater than about 5%, no greater than about 4%, no greater than about 3%, or no greater than about 2%, according to ASTM D1003-07, modified.
  • the test method is modified such that a test specimen (i.e., a sample of the electromagnetic radiation emitting layer formed from the host material and nanoparticles) has an average thickness of about 3.2 mm rather than the thickness required by the standard test method. Little to no haze in the electromagnetic radiation emitting layer provides for excellent aesthetics, light output, and efficiency of the device.
  • the nanoparticles dispersed in the host material are produced via a plasma process.
  • the process by which nanoparticles are produced generally impacts the physical properties and characteristics of the resulting nanoparticles.
  • the nanoparticles are MH-functional nanoparticles, where M being an independently selected Group IV element.
  • the group designations of the periodic table are generally from the CAS or old lUPAC nomenclature, although Group IV elements are referred to as Group 14 elements under the modern lUPAC system, as readily understood in the art.
  • the nanoparticles are produced via an RF plasma-based process.
  • a constricted RF plasma may be utilized to produce the nanoparticles. More specifically, these processes utilize an RF plasma operated in a constricted mode to produce nanoparticles from a precursor gas.
  • the process of producing the nanoparticles may be carried out by introducing a precursor gas and, optionally, a buffer gas into a plasma chamber and generating an RF capacitive plasma in the chamber.
  • the RF plasma may be created under pressure and RF power conditions that promote the formation of a plasma instability (i.e., a spatially and temporally strongly non-uniform plasma) which causes a constricted plasma to form in the chamber.
  • the constricted plasma sometimes also referred to as contracted plasma, leads to the formation of a high-plasma density filament, sometimes also referred to as a plasma channel.
  • the plasma channel is characterized by a strongly enhanced plasma density, ionization rate, and gas temperature as compared to the surrounding plasma.
  • the filament can be either stationary or non-stationary. Periodic rotations of the filament in the discharge tube may be observed, e.g. the filament may randomly change its direction of rotation, trajectory and frequency of rotation.
  • the filament may appear longitudinally nonuniform, or striated. In other cases, the filament may be longitudinally uniform.
  • An inert buffer or carrier gas such as neon, argon, krypton or xenon, may desirably be included with the precursor gas.
  • the inclusion of such gases in the constricted plasma- based methods is particularly desirable because these gases promote the formation of the thermal instability to achieve the thermal constriction.
  • dissociated precursor gas species i.e., the dissociation products resulting from the dissociation of the precursor molecules nucleate and grow into nanoparticles.
  • constricted RF plasma promotes crystalline nanoparticle formation because the constricted plasma results in the formation of a high current density current channel (i.e., filament) in which the local degree of ionization, plasma density and gas temperature are much higher than those of ordinary diffuse plasmas which tend to produce amorphous nanoparticles.
  • a high current density current channel i.e., filament
  • gas temperatures of at least about 1000 K with plasma densities of up to about 10 ⁇ 3 cm ⁇ 3 may be achieved in the constricted plasma. Additional effects could lead to further heating of the nanoparticles to temperatures even higher than the gas temperature.
  • nanoparticles may be heated to temperatures several hundred degrees Kelvin above the gas temperature.
  • the plasma may be continuous, rather than a pulsed plasma.
  • some embodiments of the present processes use an RF plasma constriction to provide high gas temperatures using relatively low plasma frequencies.
  • Conditions that promote the formation of a constricted plasma may be achieved by using sufficiently high RF powers and gas pressures when generating the RF plasma. Any RF power and gas pressures that result in the formation of a constricted RF plasma capable of promoting nanoparticle formation from dissociated precursor gas species may be employed. Appropriate RF power and gas pressure levels may vary somewhat depending upon the plasma reactor geometry. However, in one illustrative embodiment of the processes provided herein, the RF power used to ignite the RF plasma is at least about 100 Watts and the total pressure in the plasma chamber in the presence of the plasma (i.e., the total plasma pressure) is at least about 1 Torr.
  • the RF power is at least about 1 10 Watts and further includes embodiments where the RF power is at least about 120 Watts.
  • Conditions that promote the formation of a non-constricted RF plasmas may be similar to those described above for the production of constricted plasmas.
  • nanoparticles are generally formed in the non-constricted plasmas at lower pressures, higher precursor gas flow rates, and lower buffer gas flow rates.
  • the nanoparticles are produced in an RF plasma at a total pressure less than about 5 Torr and, desirably, less than about 3 Torr. This includes embodiments where the total pressure in the plasma reactor in the presence of the plasma is about 1 to 3 Torr.
  • Typical flow rates for the precursor gas in these embodiments may be at least 5 seem, including embodiments where the flow rate for the precursor gas is at least about 10 seem.
  • Typical flow rates for buffer gases in these embodiments may be about 1 to 50 seem.
  • the frequency of the RF voltage used to ignite the radiofrequency plasmas may vary within the RF range. In certain embodiments, a frequency of 13.56 MHz is employed, which is the major frequency used in the RF plasma processing industry. However, the frequency may desirably be lower than the microwave frequency range, i.e., lower than about 1 GHz. This includes embodiments where the frequency will desirably be lower than the very high frequency (VHF) range (e.g. lower than about 30 MHz). For example, the present methods may generate radiofrequency plasmas using radiofrequencies of 25 MHz or less.
  • VHF very high frequency
  • the nanoparticles are prepared in a low pressure plasma reactor, such as a low pressure high frequency pulsed plasma reactor.
  • pulsing the plasma enables an operator to directly set the resident time for particle nucleation and thereby control the particle size distribution and agglomeration kinetics in the plasma.
  • the operating parameters of the pulsed reactor may be adjusted to form crystalline nanoparticles or amorphous nanoparticles.
  • Semiconductor containing precursors enter into the dielectric discharge tube where the capacitively coupled plasma, or inductively coupled plasma, is operated. Nanoparticles start to nucleate as the precursor molecules are dissociated in the plasma.
  • the charged nanoparticles can be evacuated to the reactor chamber where they may be deposited on a substrate or subjected to further processing.
  • the power may be supplied via a variable frequency radio frequency power amplifier that is triggered by an arbitrary function generator to establish the high frequency pulsed plasma.
  • the radiofrequency power is capacitively coupled into the plasma using a ring electrode, parallel plates, or an anode/cathode setup in the gas.
  • the radiofrequency power may be inductively coupled mode into the plasma using an RF coil setup around the discharge tube.
  • the precursor gases can be controlled via mass flow controllers or calibrated rotometers.
  • the pressure differential from the discharge tube to the reactor chamber can be controlled through a changeable grounded or biased orifice. Depending on the orifice size and pressures, the nanoparticle distributions into the reactor chamber may change, thus providing another process parameter that can be used to adjust the properties of the resulting nanoparticles.
  • the plasma reactor may be operated in the frequency from 10 MHz to 500 MHz at pressures from 100 mTorr to 10 Torr in the discharge tube and powers from 5 watts to 1000 watts.
  • precursor gas may be introduced to a vacuum evacuated dielectric discharge tube 1 1 .
  • the discharge tube 1 1 includes an electrode configuration 13 that is attached to a variable frequency RF amplifier 10.
  • the other portion of the electrode 14 is either grounded, DC biased, or operated in a push-pull manner relative to electrode 13.
  • the electrodes 13, 14 are used to couple the very high frequency (VHF) power into the precursor gas (or gases) to ignite and sustain a glow discharge or plasma 12.
  • VHF very high frequency
  • the precursor gas (or gases) may then be disassociated in the plasma and nucleate to form nanoparticles.
  • the electrodes 13, 14 for a plasma source inside the dielectric tube 1 1 that is a flow-through showerhead design in which a VHF radio frequency biased upstream porous electrode plate 13 is separated from a down stream porous electrode plate 14, with the pores of the plates aligned with one another.
  • the pores could be circular, rectangular, or any other desirable shape.
  • the dielectric tube 1 1 may enclose an electrode 13 that is coupled to the VHF radio frequency power source 10 and has a pointed tip that has a variable distance between the tip and a grounded ring 14 inside the dielectric tube 1 1.
  • the VHF radio frequency power source 10 operates in a frequency range of about 10 to 500 MHz.
  • the pointed tip 13 can be positioned at a variable distance between the tip and a VHF radio frequency powered ring 14 operated in a push-pull mode (180° out of phase).
  • the electrodes 13, 14 include an inductive coil coupled to the VHF radio frequency power source so that radio frequency power is delivered to the precursor gas (or gases) by an electric field formed by the inductive coil. Portions of the dielectric tube 1 1 can be evacuated to a vacuum level between 1x10 "7 to 500 Torr.
  • the nucleated nanoparticles may pass into a larger vacuum evacuated reactor 15, where collection on a solid substrate 16 (including a chuck) or into an appropriate liquid substrate/solution can occur.
  • the nanoparticles may be collected in a capture fluid and subsequently incorporated into the host material.
  • the solid substrate 16 can be electrically grounded, biased, temperature controlled, rotating, positioned relative the electrodes producing the nanoparticles, or on a roll-to-roll system. If deposition onto substrates is not the choice, then the particles are evacuated into a suitable pump for transition to atmospheric pressure.
  • the nanoparticles can then be sent to an atmospheric classification system, such as a differential mobility analyzer, and collected for further functionalization or other processing.
  • the plasma is initiated with a high frequency plasma via an RF power amplifier such as an AR Worldwide Model KAA2040 or an Electronics and Innovation 3200L.
  • the amplifier can be driven (or pulsed) by an arbitrary function generator (e.g., a Tektronix AFG3252 function generator) that is capable of producing up to 200 watts of power from 0.15 to 150 MHz.
  • the arbitrary function may be able to drive the power amplifier with pulse trains, amplitude modulation, frequency modulation, or different waveforms.
  • the power coupling between the amplifier and the precursor gas typically increases as the frequency of the RF power increases. The ability to drive the power at a higher frequency may therefore allow more efficient coupling between the power supply and discharge.
  • nanoparticles having varying agglomeration lengths can be produced by nucleating the nanoparticles from at least one precursor gas in a VHF radio frequency low pressure plasma discharge and collecting the nucleated nanoparticles by controlling the mean free path of the nanoparticles as an aerosol, thus allowing particle - particle interactions prior to collection.
  • the nucleated nanoparticles may be collected on a solid substrate within a vacuum environment where the collection distance is greater than the mean free path of the particles controlled via the pressure. The agglomeration lengths of the nanoparticles can thereby be controlled.
  • the nucleated nanoparticles may be collected in a liquid substrate within a vacuum environment where the collection distance is greater than the mean free path of the particles controlled via the pressure thus controlling the agglomeration lengths of the nanoparticles.
  • the synthesized nanoparticles may be evacuated out of the low pressure environment into an atmospheric environment as an aerosol so that the agglomeration length is at least partially controlled by the concentration of the aerosol.
  • nanoparticles can be produced by synthesizing crystalline or amorphous core nanoparticles using VHF radio frequency low pressure plasma that is discharged in a low pressure environment by pulsing the discharge to control the plasma residence time.
  • the amorphous core nanoparticles can be synthesized at increased plasma residence time relative to the precursor gas molecular residence time through a VHF radio frequency low pressure plasma discharge.
  • crystalline core nanoparticles can be synthesized at lower plasma residence times at the same operating conditions of discharge drive frequency, drive amplitude, discharge tube pressure, chamber pressure, plasma power density, gas molecule residence time through the plasma, and collection distance from plasma source electrodes.
  • the plasma reactor system 20 comprises a plasma generating chamber 22 having a reactant gas inlet 29 and an outlet 30 having an aperture or orifice 31 therein.
  • a particle collection chamber 26 is in communication with the plasma generating chamber 22.
  • the particle collection chamber 26 contains a capture fluid 27 in a container 32.
  • the container 32 may be adapted to be agitated (by means not shown).
  • the container 32 may be positioned on a rotatable support (not shown) or may include a stirring mechanism.
  • the capture fluid is a liquid at the temperatures of operation of the system.
  • the plasma reactor system 5 also includes a vacuum source 28 in communication with the particle collection chamber 26 and plasma generating chamber 22.
  • the plasma generating chamber 22 comprises an electrode configuration 24 that is attached to a variable frequency RF amplifier 21.
  • the plasma generating chamber 22 also comprises a second electrode configuration 25.
  • the second electrode configuration 25 is either ground, DC biased, or operated in a push-pull manner relative to the electrode configuration 24.
  • the electrodes 24, 25 are used to couple the very high frequency (VHF) power to the reactant gas mixture to ignite and sustain a glow discharge of plasma within the area identified as 23.
  • the first reactive precursor gas (or gases) is then dissociated in the plasma to provide charged atoms which nucleate to form nanoparticles.
  • VHF very high frequency
  • other discharge tube configurations are contemplated, and may be used in carrying out the method disclosed herein.
  • the nanoparticles are collected in the particle collection chamber 26 in the capture fluid.
  • the distance between the aperture 31 in the outlet 22 of plasma generating chamber 22 and the surface of the capture fluid ranges between about 5 to about 50 aperture diameters. It has been found that positioning the surface of the capture fluid too close to the outlet of the plasma generating chamber may result in undesirable interactions of plasma with the capture fluid. Conversely, positioning the surface of the capture fluid too far from the aperture reduces particle collection efficiency.
  • an acceptable collection distance is from about 1 to about 20, alternatively from about 5 to about 10, cm. Said differently, an acceptable collection distance is from about 5 to about 50 aperture diameters.
  • the plasma generating chamber 22 also comprises a power supply.
  • the power is supplied via a variable frequency radio frequency power amplifier 21 that is triggered by an arbitrary function generator to establish high frequency pulsed plasma in area 23.
  • the radiofrequency power is capacitively coupled into the plasma using a ring electrode, parallel plates, or an anode/cathode setup in the gas.
  • the radiofrequency power may be inductively coupled mode into the plasma using an RF coil setup around the discharge tube.
  • the plasma generating chamber 1 1 may also comprise a dielectric discharge tube.
  • a reactant gas mixture enters the dielectric discharge tube where the plasma is generated. Nanoparticles which form from the reactant gas mixture start to nucleate as the first reactive precursor gas molecules are dissociated in the plasma.
  • the vacuum source 28 may comprise a vacuum pump.
  • the vacuum source 28 may comprise a mechanical, turbo molecular, or cryogenic pump.
  • the electrodes 24, 25 for a plasma source inside the plasma generating chamber 22 comprise a flow-through showerhead design in which a VHF radio frequency biased upstream porous electrode plate 24 is separated from a down stream porous electrode plate 25, with the pores of the plates aligned with one another.
  • the pores may be circular, rectangular, or any other desirable shape.
  • the plasma generating chamber 22 may enclose an electrode 24 that is coupled to the VHF radio frequency power source and has a pointed tip that has a variable distance between the tip and a grounded ring inside the chamber 22.
  • the VHF radio frequency power source may be operated in a manner substantially similar to that described above with respect to the embodiment of Figure 1.
  • the plasma in area 23 may be initiated with a high frequency plasma via an RF power amplifier such as an AR Worldwide Model KAA2040, or an Electronics and Innovation Model 3200L, or an EM Power RF Systems, Inc. Model BBS2E3KUT.
  • the amplifier can be driven (or pulsed) by an arbitrary function generator, as described above relative to the embodiment of Figure 1.
  • the power and frequency of the plasma system is preselected to create an optimal operating space for the formation of the nanoparticles.
  • tuning both the power and frequency creates an appropriate ion and electron energy distribution in the discharge to help dissociate the molecules of the reactive precursor gas and nucleate the nanoparticles.
  • the plasma reactor system 20 illustrated in Figure 2 may be pulsed to enable an operator to directly manage the resident time for particle nucleation, and thereby control the particle size distribution and agglomeration kinetics in the plasma.
  • the pulsing function of the system 20 allows for controlled tuning of the particle resident time in the plasma, which affects the size of the nanoparticles.
  • the nucleating particles By decreasing the "on" time of the plasma, the nucleating particles have less time to agglomerate, and therefore the size of the nanoparticles may be reduced on average (i.e., the nanoparticle distribution may be shifted to smaller diameter particle sizes).
  • the operation of the plasma reactor system 20 at higher frequency ranges and pulsing the plasma provides the same conditions as in conventional constricted/filament discharge techniques that use a plasma instability to produce the high ion energies/densities, but with the additional advantage that users can control operating conditions to select and produce nanoparticles having various sizes, which impacts their characteristic physical properties, e.g. photoluminescence..
  • the synthesis of the nanoparticles can be done with a pulsed energy source, such as a pulsed very high frequency RF plasma, a high frequency RF plasma, or a pulsed laser for pyrolysis.
  • a pulsed energy source such as a pulsed very high frequency RF plasma, a high frequency RF plasma, or a pulsed laser for pyrolysis.
  • the VHF radiofrequency is pulsed at a frequency ranging from about 1 to about 50 kHz.
  • Another method to transfer the nanoparticles to the capture fluid is to pulse the input of the reactant gas mixture while the plasma is ignited. For example, one could ignite the plasma in which a first reactive precursor gas is present to synthesize the nanoparticles, with at least one other gas present to sustain the discharge, such as an inert gas.
  • the nanoparticle synthesis is stopped when the flow of first reactive precursor gas is stopped with a mass flow controller.
  • the synthesis of the nanoparticles continues when the flow of the first reactive precursor gas is started again. This produces a pulsed stream of nanoparticles.
  • This technique can be used to increase the concentration of nanoparticles in the capture fluid if the flux of nanoparticles impinging on the capture fluid is greater than the absorption rate of the nanoparticles into the capture fluid.
  • the nucleated nanoparticles are transferred from the plasma generating chamber 22 to particle collection chamber 26 containing capture fluid via the aperture or orifice 31 which creates a pressure differential.
  • the pressure differential between the plasma generating chamber 22 and the particle collection chamber 26 can be controlled through a variety of ways.
  • the discharge tube inside diameter of the plasma generating chamber 22 is much less than the inside diameter of the particle collection chamber 26, thus creating a pressure drop.
  • a grounded physical aperture or orifice may be placed between the discharge tube and the collection chamber 26 that forces the plasma to reside partially inside the orifice, based on the Debye length of the plasma and the size of the chamber 22.
  • Another configuration comprises using a varying electrostatic orifice in which a positive concentric charge is developed that forces the negatively charged plasma through the aperture 31.
  • the capture fluid may be used as a material handling and storage medium.
  • the capture fluid is selected to allow nanoparticles to be absorbed and disperse into the fluid as they are collected, thus forming a dispersion or suspension of nanoparticles in the capture fluid. Nanoparticles will be adsorbed into the fluid if they are miscible with the fluid.
  • the capture fluid is selected to have the desired properties for nanoparticle capture and storage.
  • the vapor pressure of the capture fluid is lower than the operating pressure in the plasma reactor.
  • the operating pressure in the reactor and collection chamber 26 range from about 1 to about 5 mTorr.
  • Other operating pressures are also contemplated.
  • the capture fluid may comprise a silicone fluid such as polydimethylsiloxane, phenylmethyl-dimethyl cyclosiloxane, tetramethyltetraphenyltrisiloxane, and/or pentaphenyltrimethyltrisiloxane.
  • the capture fluid may be agitated during the direct capture of the nanoparticles, e.g. by stirring, rotation, inversion, and other suitable methods of providing agitation. If higher absorption rates of the nanoparticles into the capture liquid are desired, more intense forms of agitation are contemplated, e.g. ultrasonication.
  • nanoparticles form and are entrained in the gas phase.
  • the distance between the nanoparticle synthesis location and the surface of capture fluid must be short enough so that no unwanted functionalization occurs while the nanoparticles are entrained. If the nanoparticles interact within the gas phase, agglomerations of numerous individual small nanoparticles will form and be captured in the capture fluid. If too much interaction takes place within the gas phase, the nanoparticles may sinter together and form nanoparticles having larger average diameters.
  • the collection distance is defined as the distance from the outlet of the plasma generating chamber to the surface of the capture fluid.
  • the nanoparticles are prepared in a system having a reactor for producing a nanoparticle aerosol (e.g., nanoparticles in a gas) and a diffusion pump in fluid communication with the reactor for collecting the nanoparticles of the aerosol.
  • a nanoparticle aerosol e.g., nanoparticles in a gas
  • a diffusion pump in fluid communication with the reactor for collecting the nanoparticles of the aerosol.
  • nanoparticles of various size distributions and properties can be prepared by introducing a nanoparticle aerosol produced in a reactor (e.g. a low-pressure plasma reactor) into a diffusion pump in fluid communication with the reactor, capturing the nanoparticles of the aerosol in a condensate from a diffusion pump oil, liquid, or fluid (e.g. silicone fluid), and collecting the captured nanoparticles in a reservoir.
  • a nanoparticle aerosol e.g., nanoparticles in a gas
  • a diffusion pump in fluid communication with the reactor
  • Example reactors are described in WO 2010/027959 and WO 201 1/109229, each of which is described above and incorporated by reference in its entirety herein.
  • Such reactors can be, but are not limited to, low pressure high frequency pulsed plasma reactors.
  • Figure 3 illustrates the plasma reactor of the embodiment of Figure 2, but includes the diffusion pump in fluid communication with the reactor. To this end, description relative to this particular plasma reactor is not repeated herein with respect to the embodiment of Figure 3.
  • the plasma reactor system 50 includes a diffusion pump 120.
  • the nanoparticles can be collected by the diffusion pump 120.
  • a particle collection chamber 26 may be in fluid communication with the plasma generating chamber 22.
  • the diffusion pump 120 may be in fluid communication with the particle collection chamber 26 and the plasma generating chamber 22.
  • the system 50 may not include the particle collection chamber 26.
  • the outlet 30 may be coupled to an inlet 103 of the diffusion pump 120, or the diffusion pump 120 may be in substantially direct fluid communication with the plasma generating chamber 22.
  • Figure 4 is a cross-sectional schematic of an example diffusion pump 120 suitable for the system 50 of the embodiment of Figure 3.
  • the diffusion pump 120 can include a chamber 101 having an inlet 103 and an outlet 105.
  • the inlet 103 may have a diameter of about 2 to about 55 inches, and the outlet may have a diameter of about 0.5 to about 8 inches.
  • the inlet 103 of the chamber 101 is in fluid communication with the outlet 30 of the reactor 20.
  • the diffusion pump 120 may have, for example, a pumping speed of about 65 to about 65,000 liters/second or greater than about 65,000 liters/second.
  • the diffusion pump 120 includes a reservoir 107 in fluid communication with the chamber 101.
  • the reservoir 107 supports or contains a diffusion pump fluid.
  • the reservoir may have a volume of about 30 cc to about 15 liters.
  • the volume of diffusion pump fluid in the diffusion pump may be about 30 cc to about 15 liters.
  • the diffusion pump 120 can further include a heater 109 for vaporizing the diffusion pump fluid in the reservoir 107 to a vapor.
  • the heater 109 heats up the diffusion pump fluid and vaporizes the diffusion pump fluid to form a vapor (e.g., liquid to gas phase transformation).
  • the diffusion pump fluid may be heated to about 100 to about 400 °C or about 180 to about 250 °C.
  • a jet assembly 1 1 1 can be in fluid communication with the reservoir 107 comprising a nozzle 1 13 for discharging the vaporized diffusion pump fluid into the chamber 101.
  • the vaporized diffusion pump fluid flows and rises up though the jet assembly 1 1 1 and emitted out the nozzles 1 13.
  • the flow of the vaporized diffusion pump fluid is illustrated in Figure 4 with arrows.
  • the vaporized diffusion pump fluid condenses and flows back to the reservoir 107.
  • the nozzle 1 13 can discharge the vaporized diffusion pump fluid against a wall of the chamber 101.
  • the walls of the chamber 101 may be cooled with a cooling system 1 13 such as a water cooled system.
  • the cooled walls of the chamber 101 can cause the vaporized diffusion pump fluid to condense.
  • the condensed diffusion pump fluid can then flow along and down the walls of the chamber 101 and back to the reservoir 107.
  • the diffusion pump fluid can be continuously cycled through diffusion pump 120.
  • the flow of the diffusion pump fluid causes gas that enters the inlet 103 to diffuse from the inlet 103 to the outlet 105 of the chamber 101.
  • a vacuum source 33 may be in fluid communication with the outlet 105 of the chamber 101 to assist removal of the gas from the outlet 105.
  • nanoparticles in the gas can be absorbed by the diffusion pump fluid, thereby collecting the nanoparticles from the gas.
  • a surface of the nanoparticles may be wetted by the vaporized and/or condensed diffusion pump fluid.
  • the agitating of cycled diffusion pump fluid may further improve absorption rate of the nanoparticles compared to a static fluid.
  • the pressure within the chamber 101 may be less than about 1 mTorr.
  • the diffusion pump fluid with the nanoparticles can then be removed from the diffusion pump 120.
  • the diffusion pump fluid with the nanoparticles may be continuously removed and replaced with diffusion pump fluid that substantially does not have nanoparticles.
  • the diffusion pump 120 can be used not only for collecting nanoparticles but also evacuating the reactor 20 (and collection chamber 26).
  • the operating pressure in the reactor 20 can be a low pressure, e.g. less than atmospheric pressure, less than 760 Torr, or between about 1 and about 760 Torr.
  • the collection chamber 26 can, for example, range from about 1 to about 5 mTorr. Other operating pressures are also contemplated.
  • the diffusion pump fluid can be selected to have the desired properties for nanoparticle capture and storage.
  • the diffusion pump fluid may be the same as the capture fluid described above relative to the embodiment of Figure 2.
  • the nanoparticles may be separated or isolated from the diffusion pump fluid prior to incorporation into the host material.
  • the diffusion pump fluid may be centrifuged and/or decanted to concentrate or isolate the nanoparticles therein.
  • Other diffusion pump fluids and oils may include hydrocarbons, phenyl ethers, fluorinated polyphenyl ethers, and ionic fluids.
  • the fluid may have a viscosity of from 0.001 to 1.0, from 0.005 to 0.50, or from 0.01 to 0.10, Pa s at 23 ⁇ 3 °C.
  • the fluid may have a vapor pressure of less than about 1 x 10 "4 Torr.
  • the system 50 may also include a vacuum pump or vacuum source 33 in fluid communication with the outlet 105 of the diffusion pump 120.
  • the vacuum source 33 can be selected in order for the diffusion pump 120 to operate properly.
  • the vacuum source 33 comprises a vacuum pump (e.g., auxiliary pump).
  • the vacuum source 33 may comprise a mechanical, turbo molecular, or cryogenic pump.
  • other vacuum sources are also contemplated.
  • One method of producing nanoparticles with the system 50 of Figure 3 can include forming a nanoparticle aerosol in the reactor 20.
  • the nanoparticle aerosol can comprise nanoparticles in a gas, and the method further includes introducing the nanoparticle aerosol into the diffusion pump 120 from the reactor 5.
  • the method also may include heating the diffusion pump fluid in a reservoir 107 to form a vapor, sending the vapor through a jet assembly 1 1 1 , emitting the vapor through a nozzle 1 13 into a chamber 101 of the diffusion pump 120, condensing the vapor to form a condensate, and flowing the condensate back to the reservoir 107.
  • the method can further include capturing the nanoparticles of the aerosol in the condensate and collecting the captured nanoparticles in the reservoir 107.
  • the method can further include removing the gas from the diffusion pump with a vacuum pump.
  • the plasma system generally relies on a precursor gas, as introduced above in the various embodiments.
  • the precursor gas may alternatively be referred to as a reactant gas mixture or a gas mixture.
  • the precursor gas is generally selected based on a desired composition of the nanoparticles, as described in greater detail below with reference to the nanoparticles. For example, when the nanoparticles comprise silicon nanoparticles, the precursor gas may contain silicon, and when the nanoparticles comprise germanium, the precursor gas may contain germanium.
  • the precursor gas may be selected from silanes, disilanes, halogen-substituted silanes, halogen-substituted disilanes, C-1-C4 alkyl silanes, C-1 -C4 alkyldisilanes, and mixtures thereof.
  • precursor gas may comprise silane which comprises from about 0.1 to about 2% of the total gas mixture.
  • the gas mixture may also comprise other percentages of silane and/or additional or alternative precursor gasses, as described below with reference to the nanoparticles formed therefrom.
  • the precursor gas may be mixed with other gases such as inert gases to form a gas mixture.
  • inert gases that may be included in the gas mixture include argon, xenon, neon, or a mixture of inert gases.
  • the inert gas may comprise from about 1 % to about 99% of the total volume of the gas mixture.
  • the precursor gas may have from about 0.1 % to about 50% of the total volume of the gas mixture.
  • the precursor gas may comprise other volume percentages such as from about 1 % to about 50% of the total volume of the gas mixture.
  • the reactant gas mixture also comprises a second precursor gas which itself can comprise from about 0.1 to about 49.9 volume % of the reactant gas mixture.
  • the second precursor gas may comprise BCI3, B2H5, PH3,
  • the second precursor gas may also comprise other gases that contain carbon, germanium, boron, phosphorous, or nitrogen.
  • the combination of the first precursor gas and the second precursor gas together may make up from about 0.1 to about 50% of the total volume of the reactant gas mixture.
  • the reactant gas mixture further comprises hydrogen gas.
  • Hydrogen gas can be present in an amount of from about 1 % to about 10% of the total volume of the reactant gas mixture. However, it is also contemplated that the reactant gas mixture may comprise other percentages of hydrogen gas.
  • the nanoparticles can be prepared by any of the methods described above. Contingent on the precursor gas and molecules utilized in the plasma process, nanoparticles of various composition may be produced.
  • the nanoparticles may be semiconducting nanoparticles comprising at least one element selected from Group IV, Group IV-IV, Group ll-IV, and Group lll-V.
  • the nanoparticles may be metal nanoparticles comprising at least one element selected from Group 11 A, Group IMA, Group IVA, Group VA, Group IB, Group MB, Group IVB, Group VB, Group VIB, Group VI IB, and Group VIIIB metals.
  • the nanoparticles may be metal alloy nanoparticles, metal oxide nanoparticles, metal nitride nanoparticles, ceramic nanoparticles, etc.
  • the processes provided herein are particularly well-suited for use in the production of nanoparticles that are single-crystal and comprise Group IV semiconductors, including silicon, germanium and tin, from precursor molecules containing these elements.
  • Silane and germane are examples of precursor molecules that may be used in the production of nanoparticles comprising silicon and germanium, respectively.
  • Organometallic precursor molecules may also be used. These molecules include a Group IV metal and organic groups.
  • Organometallic Group IV precursors include, but are not limited to organosilicon, organogermanium and organotin compounds.
  • Group IV precursors include, but are not limited to, alkylgermaniums, alkylsilanes, alkylstannanes, chlorosilanes, chlorogermaniums, chlorostannanes, aromatic silanes, aromatic germaniums and aromatic stannanes.
  • silicon precursors include, but are not limited to, disilane (Si2Hg), silicon tetrachloride (S1CI4), trichlorosilane
  • HS1CI3 and dichlorosilane (H2SiCl2).
  • suitable precursor molecules for use in forming crystalline silicon nanoparticles include alkyl and aromatic silanes, such as dimethylsilane (H3C-SiH2-CH3), tetraethyl silane ((CH3CH2)4Si) and diphenylsilane (Ph-
  • germanium precursor molecules that may be used to form crystalline Ge nanoparticles include, but are not limited to, germanium tetrachloride (GeCl4), tetraethyl germane ((CH3CH2)4Ge) and diphenylgermane (Ph-GeH2-Ph).
  • the nanoparticles comprise at least one of silicon and germanium. Further, the nanoparticles may comprise silicon alloys and/or germanium alloys. Silicon alloys that may be formed include, but are not limited to, silicon carbide, silicon germanium, silicon boron, silicon phosphorous, and silicon nitride. The silicon alloys may be formed by mixing at least one first precursor gas with the second precursor gas or using a precursor gas that contains the different elements. However, other methods of forming alloyed nanoparticles are also contemplated.
  • the nanoparticles may undergo an additional doping step.
  • the nanoparticles may undergo gas phase doping in the plasma, where a second precursor gas is dissociated and is incorporated in the nanoparticles as they are nucleated.
  • the nanoparticles may also undergo doping in the gas phase downstream of the production of the nanoparticles, but before the nanoparticles are captured in the liquid.
  • doped nanoparticles may also be produced in the diffusion pump fluid where the dopant is preloaded into the diffusion pump fluid and interacts with the nanoparticles after they are captured.
  • Doped nanoparticles can be formed by contact with organosilicon gases or liquids, including, but not limited to trimethylsilane, disilane, and trisilane.
  • Gas phase dopants may include, but are not limited to, BCI3, B2H6, PH3, GeH4, or GeCl4.
  • the nanoparticles may exhibit a number of unique electronic, magnetic, catalytic, physical, optoelectronic and optical properties due to quantum confinement effects.
  • many semiconductor nanoparticles exhibit photoluminescence effects that are significantly greater than the photoluminescence effects of macroscopic materials having the same composition.
  • the nanoparticles may have a largest dimension or average largest dimension less than 50, less than 20, less than 10, or less than 5, nm. Furthermore, the largest dimension or average largest dimension of the nanoparticles may be between 1 and 50, between 2 and 50, between 2 and 20, between 2 and 10, or between about 2.2 and about 4.7, nm.
  • the nanoparticles can be measured by a variety of methods, such as with a transmission electron microscope (TEM). For example, as understood in the art, particle size distributions are often calculated via TEM image analysis of hundreds of different nanoparticles.
  • the nanoparticles may comprise quantum dots, typically silicon quantum dots. Quantum dots have excitons confined in all three spatial dimensions and may comprise individual crystals, i.e., each quantum dot is a single crystal.
  • the nanoparticles may be photoluminescent when excited by exposure to UV light. Depending on the average diameter of the nanoparticles, they may photoluminescence in any of the wavelengths in the visible spectrum and may visually appear to be red, orange, green, blue, violet, or any other color in the visible spectrum. For example, nanoparticles with an average diameter less than about 5 nm may produce visible photoluminescence, and nanoparticles with an average diameter less than about 10 nm may produce near infrared (IR) luminescence.
  • the photoluminescent silicon nanoparticles have a photoluminescent intensity of at least 1 x 10 6 at an excitation wavelength of about 365 nm.
  • the photoluminescent intensity may be measured with a Fluorolog3 spectrofluorometer (commercially available from Horiba of Edison, NJ) with a 450 W Xe excitation source, excitation monochromator, sample holder, edge band filter (400 nm), emission monochromator, and a silicon detector photomultiplier tube.
  • a Fluorolog3 spectrofluorometer commercially available from Horiba of Edison, NJ
  • the excitation and emission slit width are set to 2 nm and the integration time is set to 0.1 s.
  • the photoluminescent silicon nanoparticles may have a quantum efficiency of at least 4% at an excitation wavelength of about 395 nm as measured on an HR400 spectrophotometer (commercially available from Ocean Optics of Dunedin, Florida) via a 1000 micron optical fiber coupled to an integrating sphere and the spectrophotometer with an absorption of >10% of the incident photons. Quantum efficiency was calculated by placing a sample into the integrating sphere and exciting the sample via a 395 nm LED driven by an Ocean Optics LED driver. The system was calibrated with a known lamp source to measure absolute irradiance from the integrating sphere.
  • the quantum efficiency was then calculated by the ratio of total photons emitted by the nanoparticles to the total photons absorbed by the nanoparticles.
  • the nanoparticles may have a full width at half maximum emission of from 20 to 250 at an excitation wavelength of 270-500 nm.
  • both the photoluminescent intensity and luminescent quantum efficiency may continue to increase over time when the nanoparticles (optionally in the capture fluid or diffusion pump fluid) are exposed to air.
  • the maximum emission wavelength of the nanoparticles shifts to shorter wavelengths over time when exposed to oxygen.
  • the luminescent quantum efficiency of the directly captured silicon nanoparticle composition may be increased by about 200% to about 2500% upon exposure to oxygen.
  • other increases in the luminescent quantum efficiency are also contemplated.
  • the photoluminescent intensity may increase from 400 to 4500% depending on the time exposure to oxygen and the concentration of the nanoparticles in the fluid. However, other increases in the photoluminescent intensity are also contemplated.
  • the wavelength emitted from the direct capture composition also experiences a blue shift of the emission spectrum.
  • the maximum emission wavelength shifts about 100 nm, based on about a 1 nm decrease in nanoparticle core size, depending on the time exposed to oxygen.
  • other maximum emission wavelength shifts are also contemplated.
  • the nanoparticles can be used in the host material in various amounts to form the luminescent layer.
  • the nanoparticles is present in an amount of from about 1 to about 80, about 1 to about 50, about 1 to about 35, about 1 to about 25, about 5 to about 25, about 15 to about 25, about 20, about 1 to about 10, about 1 to about 5, or about 5, weight %, each based on 100 parts by weight of the host material.
  • the electromagnetic radiation layer may be formed via various methods.
  • the host material may be formed in situ in the presence of the nanoparticles such that the nanoparticles are dispersed in the host material as the host material is formed.
  • the nanoparticles may be mixed or blended with the host material, or a precursor thereof.
  • the electromagnetic radiation layer may be formed in accordance with the methods disclosed in U.S. Appln. Ser. No. 61/971 ,252, which is incorporated by reference herein in its entirety.
  • the electromagnetic radiation layer may be formed in accordance with the methods disclosed in U.S. Appln. Ser. No. 61/971 ,236, which is filed herewith and incorporated by reference herein in its entirety.
  • the nanoparticles emit the which is generally in the infrared to ultraviolet light range.
  • the nanoparticles emit an ⁇ 2 of from about 350 to about 1 ,000, about 550 to about 900, about 550 to about 800, about 575 to about 775, about 600 to about 750, about 600 to about 725, about 600 to about 700, about 600 to about 650, or about 625, nm.
  • the lattermost spectrums narrowing in around 625 nm generally correspond to "orange/red,” “reddish,” “red,” “true red,” or “shallow red,” light.
  • the nanoparticles emit an ⁇ 2 of from about 450 to about
  • the nanoparticles emit an ⁇ 2 of from about 450 to about 1 ,200, about 700 to about 1 ,200, about 750 to about 1 ,100, about 800 to about 1 ,050, about 850 to about 1 ,000, or about 950 to about 1 ,000, nm.
  • These spectrums, particularly those narrowing from about 700 to about 1 ,200 nm generally correspond to near infrared light.
  • the nanoparticles emit an K2 of from about 550 to about 600, about 575 to about 600, or about 575, nm, which generally correspond to "yellow" light. While red, green, and yellow spectrums are generally described above, it is to be appreciated that various other lights/mixtures of lights may also be emitted based in part on the particular nanoparticles utilized. Other additives may also be used to control color mixing and/or other optical properties of the device.
  • the device generally emits a combination of the A-j and the and if present, the
  • a s having an average wavelength (A c ) in the visible spectrum.
  • the combination of the various emission spectrums may be referred to as the total emission spectrum of the device.
  • a substantial portion of the total emission spectrum is within the visible spectrum.
  • the total emission spectrum can range from about 350 nm to about 850 nm.
  • the total emission spectrum can have two or more peak intensities, depending on the components and amounts thereof, utilized to form the device.
  • the amount of weighing in the upper, mid, and lower spectra of the total emission will generally dictate a color temperature and coloring index of the device.
  • the device may present white light of various warmth values, or a color such as red, orange, yellow, green, cyan, blue, violet, etc., as well as various colors therebetween.
  • the device emits a combination of a combination of the ⁇ -
  • Examples of a device that emits a combination of the A-j and the and if present, the A s , having an average wavelength (A c ) other than that of visible light include, but are not limited to, remote controllers for household appliances, e.g. those having a total emission spectrum of about 940 nm; medical treatment appliances, e.g. those having a total emission spectrum of about 808 nm; space optical communication devices, e.g. those having a total emission spectrum of about 808 nm; infrared illumination devices, e.g. those having a total emission spectrum of about 808 nm; automated card reader systems, e.g.
  • the device can emit various color temperatures.
  • the device emits a color temperature of from: about 1 ,000 to about 10,000, about 1 ,500 to about 4,000, or about 2,700 to about 3,500, Kelvin (K).
  • K Kelvin
  • the device may further comprise a supplemental luminescent compound different from the nanoparticles.
  • the supplemental luminescent compound is present along with the nanoparticles in the host material.
  • the supplemental luminescent compound is useful for emitting a radiation spectrum different from the nanoparticles and may impact aesthetic properties of the device.
  • the supplemental luminescent compound can be or various types of conventional luminescent compounds.
  • the supplemental luminescent compound is a lanthanide selected from the group of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and combinations thereof.
  • the supplemental luminescent compound is selected from the group of trivalent Ce, divalent Eu, trivalent Er, trivalent Tb, trivalent Dy, trivalent Sm, divalent Mn, or combinations thereof.
  • the supplemental luminescent compound comprises a quantum dot, a transition metal dye, or combinations thereof. These compounds may be used in addition or alternate to the lanthanides described immediately above.
  • the supplemental luminescent compound can be used in the host material in various amounts.
  • the supplemental luminescent compound is present in the electromagnetic radiation emitting layer in an amount of from about 1 to about 80, about 1 to about 50, about 1 to about 35, about 1 to about 25, about 5 to about 25, about 15 to about 25, about 20, about 1 to about 10, about 1 to about 5, or about 5, weight %, each based on 100 parts by weight of the host material.
  • the electromagnetic radiation emitting layer further comprises one or more additives.
  • the electromagnetic radiation emitting layer further comprises a compatibilizer, a sensitizer, or a combination thereof.
  • the electromagnetic radiation emitting layer further comprises a filler.
  • the filler may be used in addition or alternate to the other additives described above. Examples of suitable fillers include silicas, e-powder, etc.
  • Other additives, suitable for inclusion in one or more of the layers, e.g. the electromagnetic radiation emitting layer include a light scatterer, a moisture absorber, and/or a colorant. Some of these additives, as well as the supplemental luminescent compounds introduced above, can be used to control properties, such as optical properties, of the electromagnetic radiation emitting layer, such as controlling the amount of scattering and/or color mixing independent from the nanoparticles.
  • the sensitizer may be utilized in certain embodiments.
  • the sensitizer is typically a photosensitizer. If utilized, the photosensitizer generally imparts a larger peak emission intensity to the nanoparticles at a desired excitation wavelength.
  • the photosensitizer if utilized is not particularly limited.
  • the photosensitizer is chosen from (i) a ⁇ -diketone, (ii) a ⁇ -diketonate, (iii) a salicylic acid, (iv) an aromatic carboxylic acid, (v) an aromatic carboxylate, (vi) a polyaminocarboxylic acid, (vii) a polyaminocarboxylate, (viii) a N-heterocyclic aromatic compound, (ix) a Schiff base, (x) a phenol, (xi) an aryloxide, and combinations thereof.
  • the photosensitizer is (i) a ⁇ -diketone, or (ii) a ⁇ -diketonate, or (iii) a salicylic acid, or (iv) an aromatic carboxylic acid, or (v) an aromatic carboxylate, or (vi) a polyaminocarboxylic acid, or (vii) a polyaminocarboxylate, or (viii) a N-heterocyclic aromatic compound, or (ix) a Schiff base, or (x) a phenol, or (xi) an aryloxide, or a combination of one or more of the aforementioned compounds.
  • the photosensitizer is a ⁇ -diketone or a ⁇ -diketonate.
  • the photosensitizer is an aromatic carboxylic acid or aromatic carboxylate.
  • the photosensitizer may be a salicylic acid or a salicylate.
  • the photosensitizer may be any one of the aforementioned types of compounds and/or may be further defined as a mixture of two or more of any of the aforementioned types of compounds.
  • the device further comprises a supplemental electromagnetic radiation emitting layer disposed adjacent the electromagnetic radiation emitting layer.
  • the supplemental electromagnetic radiation emitting layer generally comprises a supplemental host material.
  • the supplemental host material may be formed from various materials and may be the same as or different from the host material of the electromagnetic radiation emitting layer.
  • the supplemental electromagnetic radiation emitting layer further comprises a luminescent compound the same as or different from the nanoparticles of the electromagnetic radiation emitting layer.
  • the luminescent compound may be of the types, and used in the amounts, as described above.
  • the supplemental electromagnetic radiation emitting layer is useful for emitting a radiation spectrum having an average wavelength in the infrared to ultraviolet light range and can be used to alter aesthetic properties of the device.
  • the supplemental luminescent layer may include one or more additives as introduced above.
  • the device further comprises an encapsulant layer disposed over the electromagnetic radiation emitting layer opposite the electromagnetic radiation emitting element.
  • the encapsulant layer is typically in contact with the electromagnetic radiation emitting layer, e.g. disposed directly on the electromagnetic radiation emitting layer.
  • the encapsulant layer may be formed from various materials and may be formed from a material that is the same as or different from the host material of the electromagnetic radiation emitting layer. Other examples of suitable materials include organic polymers, silicon-containing polymers, glass, and sapphire.
  • the encapsulant layer is free of any luminescent compounds, such as nanoparticles, so as to not scatter/interfere with radiation emitted by electromagnetic radiation emitting element and electromagnetic radiation emitting layer.
  • the encapsulant layer is useful for protecting the electromagnetic radiation emitting layer and the electromagnetic radiation emitting element.
  • the encapsulant layer may include one or more additives as introduced above.
  • the device can further include one or more encapsulant layers disposed over the electromagnetic radiation emitting layer and/or the electromagnetic radiation emitting element.
  • the device further comprises a light transmissive cover disposed over the electromagnetic radiation emitting layer opposite the electromagnetic radiation emitting element. If utilized, the light transmissive cover is typically spaced from the electromagnetic radiation emitting layer.
  • the light transmissive cover may be formed from various materials and may be formed from a material that is the same as or different from the material of the host material of the electromagnetic radiation emitting layer.
  • the light transmissive cover is formed from a glass, an epoxy, or a polycarbonate. The light transmissive cover is useful for protecting the electromagnetic radiation emitting layer and the electromagnetic radiation emitting element.
  • the device further comprises at least one reflector disposed adjacent at least one of the electromagnetic radiation emitting layer and the electromagnetic radiation emitting element.
  • the reflector can be of various shapes, and typically has a dish, parabolic, or frustoconical shape.
  • the electromagnetic radiation emitting element is typically disposed in the middle of the reflector; however, the electromagnetic radiation emitting layer may also be offset from center.
  • the reflector can be formed from various materials, such as a metal or alloy. Various types of metals can be used to form the reflector and other materials may be used as well provided they provide a degree of reflection.
  • the reflector is useful for directing radiation emitted by the electromagnetic radiation emitting element and, optionally, the electromagnetic radiation emitting layer, outwardly away from the device.
  • the device can comprise any number of other additional components generally associated with conventional light emitting devices.
  • the device can include one or more wire bonds, and/or a lead frame generally having a cathode and anode.
  • the device can comprise a circuit board, a heat sink, a lens, and/or a submount. If utilized, the circuit board can be programmed to include lighting controls such as dimming, light sensing and pre-set timing. Such controls are especially useful for packages.
  • the device may be of various constructs.
  • the device may be configured as a light bulb, a luminaire, a light engine, or a lamp.
  • any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range such as "at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.
  • Electromagnetic radiation emitting devices are formed in accordance with the disclosure.
  • Nanoparticles are produced via a plasma process.
  • the nanoparticles are produced via the plasma process with a turbo pump.
  • the reactor has a base pressure of less than 2x10 "8 Torr.
  • a capture fluid (phenyl methyl siloxane) is disposed into the chamber of the capture fluid
  • the reactor operates at 120 W coupled plasma power at 127 MHz in the discharge tube at 3.5 Torr.
  • Nanoparticles are synthesized and injected into the capture fluid located about 5 cm downstream from the orifice.
  • the nanoparticles are produced at a rate of about 0.01 wt% Si nanoparticles per 5 minutes.
  • the nanoparticles and the capture fluid are centrifuged and the nanoparticles are separated from the capture fluid.
  • a 13 mm diameter pellet die (commercially available from Carver, Inc. of Wabash, IN) is loaded with polycarbonate infused with the nanoparticles produced via Preparation Example 1.
  • the pellet die is placed in a vacuum oven at 200 °C for 30 minutes. 16,000 lbs of pressure are applied to the die for 15 minutes, which results in a solid pellet having a mass of 0.27 g, a diameter of 13 mm, and a height of 1.7 mm.
  • a device is formed that includes the solid pellet.
  • the device also includes an electromagnetic radiation emitting element spaced from the solid pellet and capable of emitting blue light.
  • Nanoparticles are produced via a plasma process.
  • the nanoparticles are produced via the plasma process with a turbo pump.
  • a capture fluid (commercially available under the tradename Dow Corning® 704 from Dow Corning Corporation of Midland, Ml) is disposed into the chamber of the capture fluid (commercially available under the tradename Dow Corning® 704 from Dow Corning Corporation of Midland, Ml) is disposed into the chamber of the capture fluid (commercially available under the tradename Dow Corning® 704 from Dow Corning Corporation of Midland, Ml) is disposed into the chamber of the capture fluid (commercially available under the tradename Dow Corning® 704 from Dow Corning Corporation of Midland, Ml) is disposed into the chamber of the
  • the reactor operates at 120 W coupled plasma power at 127 MHz in the discharge tube at 3.5 Torr.
  • Nanoparticles are synthesized and injected into the capture fluid located about 5 cm downstream from the orifice. The nanoparticles are produced at a rate of about 0.01 wt% Si nanoparticles per 5 minutes.
  • the nanoparticles are removed from the reactor along with the capture fluid in the form of a suspension and transferred to a glass vial.
  • the suspension comprising nanoparticles is centrifuged to concentrate the nanoparticles. After centrifuging, a packed solid and a top fluid results. The top fluid is removed and discarded and the packed solid (which comprises the nanoparticles) is washed by repeated suspension in toluene and subsequent centrifugation. Concentrated and dry nanoparticles are obtained.
  • 0.05 grams of a benzoyl peroxide initiator (commercially available under the tradename Luperox® A98 from Sigma Aldrich of St. Louis, MO) are dissolved in 10 g of methyl methacrylate, i.e., an uncured organic compound, to form a solution. 3 ml. of the solution is combined with the nanoparticles of Preparation Example 2 to form an organic composition. The organic composition is placed in a sonic bath and sonicated for 15 minutes to disperse the nanoparticles in the organic composition. The organic composition is disposed in a new 15 mL centrifuge tube and placed in a 90 °C water bath under constant stirring and periodic vortexing to prevent settling of the nanoparticles.
  • a benzoyl peroxide initiator commercially available under the tradename Luperox® A98 from Sigma Aldrich of St. Louis, MO
  • the organic composition is a highly viscous mixture and is placed in a 60 °C oven overnight to polymerize the methyl methacrylate and form a composite article, which is utilized as an electromagnetic radiation emitting layer. The following day, the composite article is removed from the centrifuge tube by cutting.
  • a device is formed that includes the composite article.
  • the device also includes an electromagnetic radiation emitting element spaced from the composite article and capable of emitting UV light.
  • Nanoparticles are produced via a plasma process.
  • the nanoparticles are produced via the plasma process with a turbo pump.
  • 90 seem Ar, 17 seem S1H4 (2% vol. in Ar), and 6 seem H2 gas are delivered to the reactor via mass flow controllers.
  • the reactor has a base pressure of less than 2x10 " Torr.
  • a capture fluid (phenyl methyl siloxane) is disposed into the chamber of the
  • the reactor operates at 120 W coupled plasma power at 127 MHz in the discharge tube at 3.5 Torr.
  • Nanoparticles are synthesized and injected into the capture fluid located about 5 cm downstream from the orifice.
  • the nanoparticles are produced at a rate of about 0.01 wt% Si nanoparticles per 5 minutes.
  • the nanoparticles are removed from the reactor along with the capture fluid and transferred to a glass vial that was sealed under nitrogen. The nanoparticles are isolated from the capture fluid.
  • the nanoparticles produced in Preparation Example 3 1 gram of methyl methacrylate, i.e., an uncured organic compound, and 0.2 mL of a 30% H2O2 solution are disposed in a small glass vial to form an organic composition.
  • the vial is placed in a sonic bath and is sonicated for 10 minutes so as to disperse the nanoparticles in the organic composition.
  • the organic composition is then disposed onto several 1 x1 inch square quartz substrates and spread with a meier rod to form uncured films.
  • the uncured films are heated at 85 °C for about 1 hour to polymerize the methyl methacrylate, i.e., the uncured organic compound, thereby forming a composite article, which is utilized as an electromagnetic radiation emitting layer.
  • a device is formed that includes the composite article.
  • the device also includes an electromagnetic radiation emitting element spaced from the composite article and capable of emitting UV light.
  • Nanoparticles are produced via a plasma process.
  • the nanoparticles are produced via the plasma process exemplified above via the embodiment of Figure 3 including the diffusion pump.
  • the reactor has a base pressure of less than 2x10 "8 Torr.
  • a diffusion pump fluid poly(ethylene glycol) methyl ether methacrylate, having a molecular weight of about 475, along with 100 ppm of 2-methoxyhydroquinone as a
  • the reactor operates at 120 W coupled plasma power at 127 MHZ in the discharge tube at 3.5 Torr.
  • Nanoparticles are synthesized and injected into the diffusion pump fluid located about 5 cm downstream from the orifice. The nanoparticles are produced at a rate of about 0.01 wt% Si nanoparticles per 5 minutes.
  • An organic composition is formed in situ upon capturing the nanoparticles in the uncured organic compound, i.e., the poly(ethylene glycol) methyl ether methacrylate. After forming the organic composition, the organic composition is transferred to a glass vial and is sealed under nitrogen. The vial is placed into an iced sonic bath to disperse the nanoparticles throughout the organic composition for 1 hour via sonification. During sonification, the uncured organic compound polymerized to form a composite article, which is utilized as an electromagnetic radiation emitting layer.
  • the uncured organic compound i.e., the poly(ethylene glycol) methyl ether methacrylate.
  • a device is formed that includes the composite article.
  • the device also includes an electromagnetic radiation emitting element spaced from the composite article and capable of emitting UV light.

Abstract

Dispositif d'émission de rayonnement électromagnétique qui comprend un élément émetteur de rayonnement électromagnétique. Le dispositif d'émission de rayonnement électromagnétique comprend en outre une couche d'émission de rayonnement électromagnétique adjacente audit élément d'émission de rayonnement électromagnétique. La couche d'émission de rayonnement électromagnétique du dispositif émetteur de rayonnement électromagnétique comprend un matériau hôte et des nanoparticules produites par l'intermédiaire d'un procédé utilisant du plasma dans le matériau hôte.
PCT/US2015/022817 2014-03-27 2015-03-26 Dispositif d'émission de rayonnement électromagnétique WO2015148843A1 (fr)

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