The present disclosure relates generally to polysiloxane formulations and coatings made from those compositions, and more particularly to polysiloxane formulations and coatings for use in optoelectronic devices and applications.
Polysiloxane coatings for electronic, optoelectronic, and display devices are disclosed, for example, in U.S. Pat. No. 8,901,268, entitled, COMPOSITIONS, LAYERS AND FILMS FOR OPTOELECTRONIC DEVICES, METHODS OF PRODUCTION AND USES THEREOF, the disclosure of which are hereby incorporated by reference in their entirety.
In a typical polysiloxane coating, the coating is formed from a hydrolysis and condensation reaction of silicon-based compounds, such as siloxane monomers or oligomers, often with the use of a condensation catalyst. Such coating formulations may be associated with certain limitations, including one or more of limited shelf life, lower pH, the presence of water in the formulation, and limited film thickness.
In some typical coatings, film thickness is limited due to restrictions on the solid content of the formulation. At too high of a solid content, the polymerization reaction has a tendency to react until the formulation becomes gelled, rendering it unsuitable for forming an electronic or optoelectronic coating. In some typical devices, the polysiloxane coating is applied to a substrate or coating that is sensitive to moisture. Application of a formulation containing water to the substrate or coating may damage the moisture sensitive material, such as siloxane materials that contain Si—H entities, which are sensitive to moisture. In some typical devices, the polysiloxane coating is applied to a substrate or coating that is sensitive to pH. Application of a formulation to the substrate or coating may damage the pH sensitive material, such as metallic patterns of interconnects that may be sensitive to acidic or basic media.
In addition, touch-enabled high pixel density (pixel per inch or ppi) displays with increasing battery life and higher viewing pleasure require increasing individual pixel operation by minimizing power consumption at the thin film transistor (TFT) level. For touch-enabled advanced displays with higher resolution individual pixels are connected to multiple thin film transistors (TFTs) to achieve maximum resolution and maximum pleasure of viewing for consumers. Building thermally-stable oxide TFTs on a smooth substrate by applying a thermally stable planarization layer on the solid substrate, preferably glass, decreases leakage during TFT operation and lowers power consumption during switching on and off of the device. Oxide TFTs, such as indium gallium zinc oxide (IGZO) have low off current, providing long battery life for a display device compared to amorphous and low temperature polysilicon TFTs. Copper, aluminum, or molybdenum interconnects require a thermally stable (350° C.-400° C., preferably 380° C.) planarizing dielectric material for oxide TFT with low out gassing. Additionally, interconnects of copper, aluminum, or molybdenum require a relatively thicker barrier material, such as silicon nitride, to prevent diffusion, which generally adds to the fabrication costs. However, typical planarization materials do not meet the requirements to be an effective diffusion barrier or a supplementary diffusion barrier.
Improvements in the foregoing are desired.
The present disclosure provides polysiloxane formulations including one or more solvents and one or more silicon-based compounds. The present disclosure further provides coatings formed from such formulations.
In one exemplary embodiment, a composition is provided. The composition includes at least one silicon-based material, wherein the at least one silicon-based material comprises a percentage of carbon atoms contained in alkyl groups from greater than 20% to 100% based on the total number of carbon atoms in the silicon-based material; and at least one solvent. In a more particular embodiment of any of the above embodiments, the at least one silicon-based material comprises a first silicon-containing resin comprising alkyl groups and aryl groups and a second silicon-containing resin comprising aryl groups. In a more particular embodiment of any of the above embodiments, the first silicon-containing resin comprises methylsiloxane and phenylsiloxane and the second silicon-containing resin comprises phenylsiloxane.
In one exemplary embodiment, a composition is provided. The composition includes at least one silicon-based material, wherein the at least one silicon-based material comprises a first siloxane resin comprising at least one of alkyl groups and aryl groups and a second siloxane resin comprising aryl groups; and at least one solvent. In one more particular embodiment, the first silicon-containing resin has a weight average molecular weight from 1000 AMU to 10,000 AMU and the second silicon-containing resin has a weight average molecular weight from 900 AMU to 5000 AMU. In a more particular embodiment of any of the above embodiments, the alkyl groups of the first siloxane resin comprise methyl groups. In a more particular embodiment of any of the above embodiments, the first siloxane resin comprises dimethyl siloxane. In a more particular embodiment of any of the above embodiments, the aryl groups of the first siloxane resin comprise phenyl groups. In a more particular embodiment of any of the above embodiments, the aryl groups of the second siloxane resin comprise phenyl groups. In a more particular embodiment of any of the above embodiments, the first silicon-containing resin comprises methylsiloxane and phenylsiloxane and the second silicon-containing resin comprises phenylsiloxane.
In one exemplary embodiment, a composition is provided. The composition includes at least one silicon-based material, wherein the at least one silicon-based material comprises a difunctional siloxane; and at least one solvent. In a more particular embodiment, the difunctional siloxane in dimethylsiloxane. In a more particular embodiment of any of the above embodiments, the silicon-based material comprises at least 0.1 mol. % difunctional siloxane, as a percent of the total moles of siloxane in the silicon-based material. In a more particular embodiment of any of the above embodiments, the at least one silicon-based material comprises a first silicon-containing resin comprising alkyl groups and aryl groups and a second silicon-containing resin comprising aryl groups, and wherein the first silicon-containing resin comprises the difunctional siloxane. In a more particular embodiment of any of the above embodiments, the first silicon-containing resin comprises methylsiloxane, dimethylsiloxane and phenylsiloxane and the second silicon-containing resin comprises phenylsiloxane.
In one exemplary embodiment, a composition is provided. The composition is a crosslinkable composition comprising a first silicon-containing resin comprising alkyl groups and aryl groups and a second silicon-containing resin comprising aryl groups; at least one solvent; and at least one heat-activated catalyst. In a more particular embodiment, the composition further includes at least one surfactant. In a more particular embodiment of either of the above embodiments, the composition further includes at least one adhesion promoter in a more particular embodiment of any of the above embodiments the first silicon-containing resin comprises methyl siloxane and phenyl siloxane and the second silicon-containing resin comprises phenylsiloxane. In a more particular embodiment of any of the above embodiments the first silicon-containing resin further comprises a difunctional siloxane, such as dimethyl siloxane. In an even more particular embodiment, the difunctional siloxane comprises at least 0.1 mol. % as a percent of the total moles of siloxane in the first silicon-containing resin. In a more particular embodiment of any of the above embodiments, a percentage of carbon atoms contained in alkyl groups from greater than 10% to 100% based on the total number of carbon atoms in the first and second silicon-containing resins, or even more particularly from greater than 20% to 100%.
In one exemplary embodiment, a composition is provided. The composition is a crosslinkable composition comprising at least one silicon-based material having a weight average molecular weight from 1000 AMU to 10,000 AMU, wherein the at least one silicon-based material comprises a percentage of carbon atoms contained in alkyl groups from greater than 20% to 100% based on the total number of carbon atoms in the silicon-based material; at least one solvent; and at least one heat-activated catalyst. In a more particular embodiment, the composition further includes one or more surfactants. In a more particular embodiment, the composition further includes one or more adhesion promoters.
In a more particular embodiment of any of the above embodiments, the composition further includes at least one heat-activated catalyst, such as a quaternary ammonium salts selected from tetramethylammonium acetate (TMAA), tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), tetrabutylammonium acetate (TBAA), cetyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN). In a more particular embodiment of any of the above embodiments, the composition further includes at least one surfactant. In a more particular embodiment of any of the above embodiments, the composition further includes at least one adhesion promoter. In a more particular embodiment of any of the above embodiments, the composition further includes at least one plasticizer. In a more particular embodiment of any of the above embodiments, the composition further includes at least one organic acid. In a more particular embodiment of any of the above embodiments, the composition further includes at least one monofunctional silane.
In a more particular embodiment of any of the above embodiments, the composition is water-free.
In one exemplary embodiment, a composition is provided. The composition includes at least one silicon-based material, wherein the at least one silicon-based material comprises at least one of alkyl groups and aryl groups; at least one solvent; at least one heat-activated catalyst; and at least one surfactant, wherein the composition is water free. In a more particular embodiment, the at least one solvent consists of water-free anhydrous solvents. In another more particular embodiment, the composition has less than 0.2 wt. % water. In another more particular embodiment, the composition has 0 wt. % water. In another more particular embodiment, the composition includes no external water. In a more particular embodiment of any of the above embodiments, the composition further includes one or more additives selected from the group consisting of: adhesion promoters, endcapping agents, and organic acids.
In a more particular embodiment of any of the above embodiments, the composition is a crosslinkable composition.
In one exemplary embodiment, a crosslinked film is provided. The crosslinked film is formed from a composition according to any of the above embodiments. In a more particular embodiment, the crosslinked film has a thickness of 1.5 μm or greater. In another more particular embodiment, the crosslinked film has a thickness of 3.0 μm or greater. In a more particular embodiment of any of the above embodiments, the crosslinked film is cured at a temperature of 350° C. or greater. In a more particular embodiment of any of the above embodiments, the crosslinked film is cured at a temperature of 390° C. or greater. In a more particular embodiment of any of the above embodiments, the crosslinked film has a transmittance to light in the visible optical wavelength range from 400 to 1000 nm of 95% or greater.
In one exemplary embodiment, a device having a surface is provided. The surface includes a crosslinked film according to any of the above embodiments, or includes a crosslinked film formed from any of the above embodiments. In a more particular embodiment of any of the above embodiments, the device is selected from the group consisting of a transistor, a light-emitting diode, a color filter, a photovoltaic cell, a flat-panel display, a curved display, a touch-screen display, an x-ray detector, an active or passive matrix OLED display, an active matrix think film liquid crystal display, an electrophoretic display, a CMOS image sensor, and combinations thereof. In a more particular embodiment of any of the above embodiments, the crosslinked film forms a passivation layer, a planarization layer, a barrier layer, or a combination thereof.
In one embodiment, a method of forming a composition is provided. The method includes combining a first siloxane resin, a second siloxane resin, and at least one solvent to form a crosslinkable composition, wherein the first siloxane resin comprises at least one of alkyl groups and aryl groups and the second siloxane resin comprises aryl groups. In a more particular embodiment, the alkyl groups of the first siloxane resin comprise methyl groups. In a more particular embodiment of any of the above embodiments. In a more particular embodiment of any of the above embodiments, the first siloxane resin comprise dimethyl siloxane. In a more particular embodiment of any of the above embodiments, the aryl groups of the first siloxane resin comprise phenyl groups. In a more particular embodiment of any of the above embodiments, the aryl groups of the second siloxane resin comprise phenyl groups in a more particular embodiment of any of the above embodiments, the composition further a total percentage of carbon atoms contained in alkyl groups from greater than 20% to 100% based on the total number of carbon atoms in alkyl and aryl groups.
In one exemplary embodiment, a method of forming a composition is provided. The method includes reacting a first organoalkoxysilane in a first solvent in the presence of a catalyst to produce a first silicon-based material, wherein the first silicon-based material includes at least one of alkyl groups and aryl groups; reacting a second organoalkoxysilane in a second solvent in the present of a catalyst to produce a second silicon-based material, wherein the second silicon-based material includes aryl groups; and combining the first and second silicon-based material to form a composition, wherein the composition comprises a percentage of carbon atoms contained in alkyl groups from greater than 20% to 100% based on the total number of carbon atoms in the first and second silicon-based materials. In a more particular embodiment, the first and second organoalkoxysilanes are independently selected from the group consisting of: methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), phenyl triethoxysilane (PTEOS), dimethyldimethoxysilane, phenyltrimethoxysilane, and combinations thereof.
In one exemplary embodiment, a method of forming a composition is provided. The method includes combining a first siloxane resin comprising alkyl groups and aryl groups, a second siloxane resin comprising aryl groups, a solvent, and a heat activated catalyst to form a crosslinkable composition; depositing the composition on a substrate; and curing the crosslinkable composition at a temperature of 350° C. or greater to form a crosslinked film, wherein the crosslinked film has a thickness of 1.5 μm or greater. In a more particular embodiment, the first siloxane resin comprises methylsiloxane and phenylsiloxane and the second silicon-containing resin comprises phenylsiloxane. In another more particular embodiment, the first siloxane resin further comprises dimethyl siloxane.
In a more particular embodiment, the method according to of any of the above embodiments, the composition further comprises at least one heat-activated catalyst and at least one surfactant. In a more particular embodiment of any of the above embodiments, the crosslinkable composition includes no water in a more particular embodiment of any of the above embodiments, the at least one solvent consists of PGMEA and PGPE. In a more particular embodiment of any of the above embodiments, the composition is a crosslinkable composition.
In a more particular embodiment, the method according any of the above embodiments further includes depositing the composition on a surface; and curing the composition to form a film. In a more particular embodiment, the film has a thickness of 1.5 μm or greater. In a more particular embodiment of any of the above embodiments, the crosslinked film has a thickness of 3.0 μm or greater. In a more particular embodiment of any of the above embodiments, curing the crosslinkable composition including curing at a temperature of 350° C. or greater. In a more particular embodiment of any of the above embodiments, curing the crosslinkable composition including curing at a temperature of 390° C. or greater.
In a more particular embodiment, according any of the above embodiments the first silicon-containing resin comprises methylsiloxane and phenylsiloxane and the second silicon-containing resin comprises phenylsiloxane, and the method further comprising reacting a phenyl TEOS-based polymer having a molecular weight of at least 1000 AMU in a solvent in the presence of a catalyst to form the second silicon-containing resin. In an even more particular embodiment, the catalyst is a basic catalyst, such as a tetraorganoammonium compound.
While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein are provided to illustrate certain exemplary embodiments and such exemplifications are not to be construed as limiting the scope in any manner.
I. Polysiloxane Formulation
In one exemplary embodiment, the polysiloxane formulation includes one or more solvents and one or more silicon-based compounds. In some exemplary embodiments, the formulation further includes one or more catalysts. In some exemplary embodiments, the formulation further includes one or more surfactants. In some exemplary embodiments, the formulation further includes one or more additional additives, such as adhesion promoters, plasticizers, organic acids, and monofunctional silanes.
a. Solvent
The formulation includes one or more solvents. Exemplary solvents include suitable pure organic molecules or mixtures thereof that are volatilized at a desired temperature and/or easily solvate the components discussed herein. The solvents may also comprise suitable pure polar and non-polar compounds or mixtures thereof. As used herein, the term “pure” means a component that has a constant composition. For example, pure water is composed solely of H2O. As used herein, the term “mixture” means a component that is not pure, including salt water. As used herein, the term “polar” means that characteristic of a molecule or compound that creates an unequal charge, partial charge or spontaneous charge distribution at one point of or along the molecule or compound. As used herein, the term “non-polar” means that characteristic of a molecule or compound that creates an equal charge, partial charge or spontaneous charge distribution at one point of or along the molecule or compound.
Exemplary solvents include solvents that can, alone or in combination, modify the viscosity, intermolecular forces and surface energy of the solution in order to, in some cases, improve the gap-filling and planarization properties of the composition. It should be understood, however, that suitable solvents may also include solvents that influence the profile of the composition in other ways, such as by influencing the crosslinking efficiency, influencing the thermal stability, influencing the viscosity, and/or influencing the adhesion of the resulting layer or film to other layers, substrates or surfaces.
Exemplary solvents also include solvents that are not part of the hydrocarbon solvent family of compounds, such as ketones, including acetone, diethyl ketone, methyl ethyl ketone and the like, alcohols, esters, ethers and amines. Additional exemplary solvents include ethyl lactate, propylene glycol propylether (PGPE), propylene glycol monomethyl ether acetate (PGMEA) or a combination thereof. In one exemplary embodiment, the solvent comprises propylene glycol monomethyl ether acetate.
In one exemplary embodiment, formulation comprises as little as 50 wt. %, 55 wt. %, 60 wt. %, as great as 80 wt,%, 85 wt,%, 90 wt. % of the one or more solvents, or within any range defined between any two of the foregoing values, such as 50 wt. % to 90 wt. %, 55 wt. % to 85 wt. %, or 65 wt. % to 85 wt. %. The determination of the appropriate amount of solvent to add to composition depends on a number of factors, including: a) thicknesses of the desired layers or films, b) desired concentration and molecular weight of the solids in the composition, c) application technique of the composition and/or d) spin speeds, when spin-coating techniques are utilized. In addition, the higher the solid concentration (or the resin or polymer) is in the formulation, the higher the viscosity. Hence, the solid content may be increased (or the solvent amount reduced) to increase the viscosity as desired for a specific coating application technique. In addition, the viscous formulation or formulation with higher solid content will typically provide a thicker film thickness such as greater than 2 μm.
The solvents used herein may comprise any suitable impurity level. In some embodiments, the solvents utilized have a relatively low level of impurities, such as less than about 1 ppm, less than about 100 ppb, less than about 10 ppb, less than about 1 ppb, less than about 100 ppt, less than about 10 ppt and in some cases, less than about 1 ppt. These solvents may be purchased having impurity levels that are appropriate for use in these contemplated applications or may need to be further purified to remove additional impurities and to reach the less than about 10 ppb, less than about 1 ppb, less than about 100 ppt or lower levels that suitable and/or desired.
In one exemplary embodiment, the formulation includes no water. In a more particular embodiment, the solvent is an anhydrous solvent, and the silicon-based compounds, and any catalysts, surfactants, adhesion promoters, cross-linkers, initiators, or other additives are provided in a water-free anhydrous solvent. In some exemplary embodiment, “water-free” refers to a composition having less than 0.2 wt. %, 0.1 wt. %, 0.05 wt. %, 0.01 wt .% water, or 0 wt. % water. In some exemplary embodiments, “water-free” refers to a composition have no water. In some exemplary embodiments, “water-free” refers to a composition in which no external water is added, although some water may be formed from the hydrolysis-condensation reaction of the silicon-based compounds.
b. Silicon-based Compounds
The formulation includes one or more silicon-based compounds that can be crosslinked to form the polysiloxane. Exemplary silicon-based compounds comprise siloxane, silsesquioxane, polysiloxane, or polysilsesquioxane, such as methylsiloxane, methylsilsesquioxane, phenylsiloxane, phenylsilsesquioxane, methylphenylsiloxane, methylphenylsilsesquioxane, dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, polyphenylsilsesquioxane, polyphenylsiloxane, polymethylphenylsiloxane, polymethylphenylsilsesquioxane, polymethylsiloxane, polymethylsilsesquioxane, and combinations thereof. In some embodiments, the at least one silicon-based compound comprises polyphenylsilsesquioxane, polyphenylsiloxane, phenylsiloxane, phenylsilsesquioxane, methylphenylsiloxane, methylphenylsilsesquioxane, polymethylphenylsiloxane, polymethylphenylsilsesquioxane, polymethylsiloxane, polymethylsilsesquioxane or a combination thereof.
In some embodiments, the silicon-based compounds comprise a total amount of carbon atoms divided between carbon atoms in alkyl groups, such as methyl and ethyl groups, and carbon atoms in aryl groups, such as phenyl groups. In some embodiments, the number of carbon atoms contained in the alkyl groups is greater than 10%, 12%, 15% 20%, 21%, 25%, or greater than 30%, 31%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, and less than 100%, or is 100%, based on the total number of carbon atoms contained in the alkyl and aryl groups, or may be between any range defined between any two of the foregoing values, such as from greater than 10% to less than 100%, from 12% to less than 100%, from greater than 20% to 100% or greater than 30% to less than 100%.
Without wishing to be held to any particular theory, it is believed that increasing the percentage of aryl carbon increases the stearic hindrance of the polysiloxane compounds resulting in a polysiloxane coating that has less crosslinking and is more flexible. In addition increasing the percentage of alkyl or aryl carbon by using difunctional silanes such as dialkyldialkoxy silane or diaryldialkoxy silane decreases number of reactive functional groups of the polysiloxane compounds resulting in a polysiloxane coating that has less crosslinking and is more flexible. However, increasing the flexibility of polysiloxane compounds also tends to produce films or coatings that are less resistant to chemicals. In some exemplary embodiments, the silicon-based compounds include a plasticizer or other suitable material to increase the flexibility of the formed polysiloxane.
Some contemplated silicon-based compounds include compositions formed from hydrolysis-condensation reactions of at least one reactant having the formula:
R1xSi(OR2)y
where R1 is an alkyl, alkenyl, aryl, or aralkyl group, and x is an integer between 0 and 2, and where R2 is a alkyl group or acyl group and y is an integer between 1 and 4. Materials also contemplated include silsesquioxane polymers of the general formula:
(C6H5SiO1.5)x
where x is an integer greater than about 4.
In some exemplary embodiments, the silicon-based material includes one or more polysiloxane resins, such as the Glass Resin polysiloxane resins available from Techneglas Technical Products, Perrysburg, Ohio. In one exemplary embodiment, polysiloxane resins are silicon-based oligomers formed from a limited hydrolysis and condensation reaction of one or more silicon-based monomers. Exemplary suitable silicon-based monomers include organoalkoxysilanes having a Si—C bond, such as methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), phenyl triethoxysilane (PTEOS), dimethyldimethoxysilane and phenyltrimethoxysilane. Other suitable silicon-based monomers lack an Si—C bond, such as tetraethylorthosilicate (TEOS). Exemplary resin materials include glass resins derived from organoalkoxysilanes such as methylsiloxane, dimethylsiloxane, phenylsiloxane, methylphenylsiloxane, tetraethoxysilane, and mixtures thereof.
In one exemplary embodiment, the polysiloxane resins have a structure selected from the group consisting of a linear structure, a cyclic structure, a cage-type structure, a ladder-type structure, and a partial-ladder/partial-cage type structure. In a more particular embodiment, the polysiloxane resins have a partial-ladder/partial-cage type structure.
In some exemplary embodiments, the polysiloxane resins include one or more alkyl groups and/or one or more aryl groups. Exemplary polysiloxane resins containing alkyl groups include methylsiloxane and dimethylsiloxane. Exemplary polysiloxane resins containing aryl groups include phenylsiloxane. Exemplary polysiloxane resins containing both alkyl and aryl groups include methylphenylsiloxane.
In one exemplary embodiment, each polysiloxane resin has a weight average molecular weight as little as 900 atomic mass unit (AMU), 950 AMU, 1000 AMU, 1100 AMU, 1150 AMU, as great as 2000 AMU, 3000 AMU, 4000 AMU, 5000 AMU, 10,000 AMU, or within any range defined between any two of the foregoing values, such as 900 AMU to 10,000 AMU, 1000 AMU to 10,000 AMU, or 900 AMU to 5000 AMU. In a more particular embodiment, the polysiloxane resin include a first polysiloxane resin containing alkyl groups such as methylsiloxane and/or dimethylsiloxane and a second polysiloxane resin containing aryl groups such as phenylsiloxane. In one embodiment, the first polysiloxane resin further contains aryl groups such as phenylsiloxane. In an even more particular embodiment, the first polysiloxane resin has a weight average molecular weight as little as 1000 atomic mass unit (AMU), 2000 AMU, 2200 AMU, 3000 AMU, 3800 AMU, 4000 AMU, as great as 4500 AMU, 4800 AMU, 5000 AMU, 7500 AMU, 10,000 AMU or within any range defined between any two of the foregoing values, such as 1000 AMU to 10,000 AMU, 2000 AMU to 5000 AMU, or 3800 AMU to 4800 AMU and the second polysiloxane resin has a weight average molecular weight as little as 900 atomic mass unit (AMU), 950 AMU, 1000 AMU, as great as 1150 AMU, 2000 AMU, 2500 AMU, 5000 AMU or within any range defined between any two of the foregoing values, such as 900 AMU to 5000 AMU, 900 AMU to 2000 AMU, or 950 AMU to 1150 AMU.
In some exemplary embodiments, the silicon-based material includes or is formed from one or more organoalkoxysilanes. Exemplary organoalkoxysilanes include methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), phenyl triethoxysilane (PTEOS), dimethyldimethoxysilane, phenyltrimethoxysilane, and combinations of the foregoing.
In some exemplary embodiments, the silicon-based material includes a blend of two or more pre-formed polysiloxane resins. In a more particular embodiment, two or more polysiloxane resins may be combined to provide a total number of carbon atoms contained in the alkyl groups from greater than 10%, 12%, greater than 20%, 21%, 25%, greater than 30%, 31%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, less than 100%, 100%, based on the total number of carbon atoms contained in the alkyl and aryl groups, or between any range defined between any two of the foregoing values, such as from greater than 10% to 100%, from 12% to 100% from greater than 20% to 100%, or greater than 30% to less than 100%.
In another more particular embodiment, the silicon-based material may include one or more polysiloxane resins each including a difunctional silane. An exemplary difunctional slime is dimethylsiloxane. In a more particular embodiment, the silicon-based material may include as little as 0%, 0.1%, 0.5%, 1%, 2%, as high as 5%, 10%, 15%, 20% difunctional siloxane, as a molar percentage of the total moles of siloxane, or between any range defined between any two of the foregoing values, such as from 0% to 20% or from 0.1% to 2%.
c. Catalysts
In some exemplary embodiments, the formulation includes one or more catalysts. In some embodiments, the catalyst is a heat-activated catalyst. A heat-activated catalyst, as used herein, refers to a catalyst that is activated at or above a particular temperature, such as an elevated temperature. For example, at one temperature (such as room temperature) the composition maintains a low molecular weight, thus enabling good planarization ability over a surface. When the temperature is elevated (such as to greater than 50° C.), the heat-activated catalyst catalyzes a condensation reaction between two Si—OH functional groups, which results in a more dense structure and, in some cases, improved performance overall. Suitable condensation catalysts comprise those catalysts that can aid in maintaining a stable silicate solution. Exemplary metal-ion-free catalysts may comprise onium compounds and nucleophiles, such as an ammonium compound (such as quaternary ammonium salts), an amine, a phosphonium compound or a phosphine compound.
In one exemplary embodiment, the catalyst is not a photoacid, a photoacid generator, or a metal-based catalyst.
In some embodiments, the catalyst is relatively molecularly “small” or is a catalyst that produces relatively small cations, such as quaternary ammonium salts. In some embodiments, the one or more catalysts is selected from tetramethylammonium acetate (TMAA), tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), tetrabutylammonium acetate (TBAA), cetyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN), other ammonium-based catalysts, amine-based and/or amine-generating catalysts, and combinations thereof. Other exemplary catalysts include (2-hydroxyethyl)trimethylammonium chloride, (2-hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium acetate, (2-hydroxyethyl)trimethylammonium formate, (2-hydroxyethyl)trimethylammonium nitrate, (2-hydroxyethyl)trimethylammonium benzoate, tetramethylammonium formate and combinations thereof. Other exemplary catalysts include (carboxymethyl)trimethylammonium chloride, (carboxymethyl)trimethylammonium hydroxide, (carboxymethyl)trimethyl-ammonium formate and (carboxymethyl)trimethylammonium acetate.
In one exemplary embodiment, the formulation comprises as little as 0.001 wt. %, 0.004 wt. %, 0.01 wt. %, 0.1 wt. %, 0.3 wt. %, as great as 0.5 wt. %, 1 wt. %, 2 wt. %, 5 wt. %, or 10 wt. % of the one or more catalysts, or within any range defined between any two of the foregoing values, such as 0.1 wt. % to 10 wt. % or 1 wt. % to 2 wt. %.
In some exemplary embodiments, the one or more catalysts comprise TMAN. TMAN may be provided by either dissolving TMAN in water or in an organic solvent such as ethanol, propylene glycol propyl ether (PGPE), or by converting TMAA or TMAH to TMAN by using nitric acid.
d. Surfactant
In some exemplary embodiments, the formulation includes one or more surfactants. Surfactants may be added to lower surface tension. As used herein, the term “surfactant” means any compound that reduces the surface tension when dissolved in H2O or other liquids, or which reduces interfacial tension between two liquids, or between a liquid and a solid. Contemplated surfactants may include at least one anionic surfactant, cationic surfactant, non-ionic surfactant, Zwitterionic surfactant or a combination thereof. The surfactant may be dissolved directly into the composition or may be added with one of the compositions components (the at least one silicon-based compound, the at least one catalyst, the at least one solvent) before forming the final composition. Contemplated surfactants may include: polyether modified polydimethylsiloxanes such as BYK 307 (polyether modified poly-dimethyl-siloxane, BYK-Chemie), sulfonates such as dodecylbenzene sulfonate, tetrapropylenebenzene sulfonate, dodecylbenzene sulfonate, a fluorinated anionic surfactant such as Fluorad FC-93, and L-18691 (3M), fluorinated nonionic surfactants such as FC-4430 (3M), FC-4432 (3M), and L-18242 (3M), quaternary amines, such as dodecyltrimethyl-ammonium bromide or cetyltrimethylammonium bromide, alkyl phenoxy polyethylene oxide alcohols, alkyl phenoxy polyglycidols, acetylinic alcohols, polyglycol ethers such as Tergitol TMN-6 (Dow) and Tergitol minifoam 2× (Dow), polyoxyethylene fatty ethers such as Brij-30 (Aldrich), Brij-35 (Aldrich), Brij-58 (Aldrich), Brij-72 (Aldrich), Brij-76 (Aldrich), Brij-78 (Aldrich), Brij-98 (Aldrich), and Brij-700 (Aldrich), betaines, sulfobetaines, such as cocoamidopropyl betaine, and synthetic phospholipids, such as dioctanoylphosphatidylcholine and lecithin and combinations thereof.
In one exemplary embodiment, the formulation comprises as little as 0.001 wt. %, 0.005 wt. %, 0.01 wt. %, 0.05 wt. %, as great as 0.1 wt. %, 0.25 wt. %, 0.5 wt. %, 1 wt. % of the one or more surfactants, or within any range defined between any two of the foregoing values, such as 0.001 wt. % to 1 wt. % or 0.001 wt. % to 0.25 wt. %. The determination of the appropriate amount of a composition-modifying constituent to add to the composition depends on a number of factors, including: a) minimizing defects in the film, and/or b) balancing the film between good adhesion and desirable film properties.
e. Other Additives
In some exemplary embodiments, the formulation may include one or more additional additives, such as adhesion promoters, endcapping agents, and organic acids.
In one exemplary embodiment, the formulation includes one or more adhesion promoters in order to influence the ability of the layer, coating or film to adhere to surrounding substrates, layers, coatings, films and/or surfaces. The adhesion promoter may be at least one of: a) thermally stable after heat treatment, such as baking, at temperatures generally used for optoelectronic component manufacture, and/or b) promotes electrostatic and coulombic interactions between layers of materials, as well as promoting understood Van derWaals interactions in some embodiments. Exemplary adhesion promoters include aminopropyl triethoxysilane (APTEOS) and salts of APTEOS, vinyltriethoxy silane (VTEOS), glycidoxypropyltrimethoxy silane (GLYMO), and methacryloxypropyltriethoxy silane (MPTEOS). Other exemplary adhesion promoters include 3-(triethoxysilyl)propylsuccininc anhydride, dimethyldihydroxy silane, methylphenyl dihydroxysilane or combinations thereof. In one exemplary embodiment, the formulation comprises as little as 0.001 wt. %, 0.01 wt. %, 0.1 wt. %, 0.26 wt. % as great as 1 wt. %, 2.6 wt. %, 5 wt. %, 10 wt. %, 20 wt. % of the one or more adhesion promoters, or within any range defined between any two of the foregoing values, such as 0.001 wt. % to 20 wt. % or 0.26 wt % to 2.6 wt. %.
In one exemplary embodiment, the formulation includes one or more endcapping agents such as monofunctional silanes that include a single reactive functionality that is capable of reacting with silanol groups on polysiloxane molecules. Exemplary endcapping agents include trialkylsilanes such as trimethylethoxy silane, triethylmethoxy silane, trimethylacetoxy silane, trimethylsilane. In one exemplary embodiment, the formulation comprises as little as 0.1%, 0.5%, 1%, 2%, as great as 5%, 10%, 15%, 20%, or 25% of the one or more endcapping agents as a percentage of total moles of polysiloxane, or within any range defined between any two of the foregoing values, such as 2% to 20% or 5% to 10%.
In one exemplary embodiment, the formulation includes one or more organic acids. In some embodiments, the organic acid additives are volatile or decompose at high temperatures and help stabilize the formulation. Exemplary organic acids include p-toluenesulfonic acid, citric acid, formic acid, acetic acid, and trifluoroacetic acid. In one exemplary embodiment, the formulation comprises as little as 0. 1 wt. %, 0.5 wt. %, 1 wt. %, 2 wt. %, as great as 5 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, or 25 wt. % of the one or more organic acids, or within any range defined between any two of the foregoing values, such as 2 wt. % to 20 wt. % or 5 wt. % to 10 wt. %.
II. Polysiloxane Coating
In some exemplary embodiments, the polysiloxane formulation forms a polysiloxane coating on a surface located in or on an electronic, optoelectronic, or display device.
In some exemplary embodiments, the polysiloxane formulation forms a light-transmissive coating. In a more particular embodiment, the light-transmissive coating has a transmittance to light in the visible optical wavelength range from 400 to 1000 nm. In some embodiments, the optical transmittance is as high as 80%, 85%, 90%, 95%, 97%, 98%, 99%, or higher, or within any range defined between any two of the foregoing values.
In some exemplary embodiments, one or polymer resins are selected to provide a desired refractive index. In one exemplary embodiment, the relative molar percentage of a resin having a relatively low refractive index, such as 100% methyltriethoxysilane resin, is relatively high to produce a polysiloxane coating having a relatively low refractive index. In another exemplary embodiment, the relative molar percentage of a resin having a relatively high refractive index, such as 100% phenyl triethoxysilane, is relatively high to produce a polysiloxane coating having a relatively high refractive index. In another exemplary embodiment, the relative molar proportions of a first resin having a relatively high refractive index and a second resin having a relatively low refractive index are selected to produce a polysiloxane coating having a desired refractive index between the refractive index of the first and second resins.
In some exemplary embodiments, the polysiloxane formulation forms a coating having a refractive index that is as little as less than 1.4, 1.4, 1.45, as great as 1.5, 1.55, 1.56, 1.6, or within any range defined between any two of the foregoing values, such as from less than 1.4 to 1.6 or from 1.4 to 1.56.
Exemplary devicesto which coatings of the present disclosure may be provided include CMOS Image Sensors, transistors, light-emitting diodes, color filters, photovoltaic cells, flat-panel displays, curved displays, touch-screen displays, x-ray detectors, active or passive matrix OLED displays, active matrix thin film liquid crystal displays, electrophoretic displays, and combinations thereof.
In some exemplary embodiments, the polysiloxane coating forms a passivation layer, a barrier layer, a planarization layer, or a combination thereof.
In some exemplary embodiments, the polysiloxane coating has a thickness as little as 0.1 μm, 0.3 μm, 0.5 μm, 1 μm, 1.5 μm, as great as 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, or greater, or within any range defined between any two of the foregoing values.
In some exemplary embodiments, the polysiloxane coating is formed by applying the formulation to a substrate, followed by curing the formulation. Exemplary methods of applying the formulation include spin coating, spray coating, slot-die coating techniques. Curing refers to a polymerization process in which the silicon-based materials, such as silicon-based oligomers, react in the presence of a catalyst to hydrolyze and condense with other oligomers to form a higher molecular weight polymer or matrix. In one exemplary embodiments, a baking step is provided to remove at least part or all of the solvent. In some embodiments, the baking step is as short as 1 minute, 5 minutes, 10 minutes, 15 minutes, as long as 20 minutes, 30 minutes, 45 minutes, 60 minutes, or longer, at a temperature as low as 100° C., 200° C. 220° C., as high as 250° C., 275° C., 300° C., 320° C., 350° C., or higher. In one exemplary embodiment, a curing step is provided to polymerize the at least one silicon-based material such as by activating a heat-activated catalyst. In some embodiments, the curing step is as short as 10 minutes, 15 minutes, 20 minutes, as long as 30 minutes, 45 minutes, 60 minutes, or longer, at a temperature as low as 250° C., 275° C., 300° C., as high as 320° C., 350° C., 375° C., 380° C., 400° C. or higher.
In some exemplary embodiments, multiple layers of the formulation are subsequently applied and cured to form a multilayer coating. In some exemplary embodiments, the multilayer coating includes two, three, or more polysiloxane coating layers.
In some exemplary embodiments, the polysiloxane coating is resistant to multiple heating steps, such as curing or deposition of additional coatings or layers on the formed polysiloxane coating.
III. Pretreatment of Silicon-based Compound
In some exemplary embodiments, the silicon-based compound may be formed from two or more polymerization steps.
In one exemplary embodiment, a first silicon-based resin, such as an oligomeric resin, is formed from a first polymerization step of one or more organoalkoxysilanes. Exemplary organoalkoxysilanes include methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), phenyl triethoxysilane (PTEOS), dimethyldimethoxysilane, phenyltrimethoxysilane, and combinations of the foregoing. Exemplary first polymerization steps include acidic catalyzed polymerization, such as polymerization catalyzed with a mineral or organic acid, or a base catalyzed polymerization, such as polymerization catalyzed with an ammonium compound, an amine, a phosphonium compound or a phosphine compound. Exemplary mineral acids include nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid. Exemplary organic acids include sulfonic acid, trifluorosulfonic acids, and carboxylic acids, as well as thermal acid generators (TAG) capable of generating a sulfonic acid upon exposure to an elevated temperature. Exemplary basic catalysts include tetraorganoammonium compounds and tetraorganophosphonium compounds, such as tetramethylammonium acetate (TMAA), tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), tetrabutylammonium acetate (TBAA), cetyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN), triphenylamine, trioctylamine, tridodecylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, and combinations thereof. In one exemplary embodiment, the catalyst is a mineral acid, such as nitric acid.
In one exemplary embodiment, the first silicon-based resin has a weight average molecular weight as little as 900 atomic mass unit (AMU), 950 AMU, 1000 AMU, 1100 AMU, 1150 AMU, as great as 2000 AMU, 3000 AMU, 4000 AMU, 5000 AMU, 10,000 AMU, or within any range defined between any two of the foregoing values, such as 900 AMU to 10,000 AMU, 1000 AMU to 10,000 AMU, or 900 AMU to 5000 AMU.
In one exemplary embodiment, a second silicon-based resin is formed from a second polymerization of the first polymer resin. Exemplary second polymerization steps include acidic catalyzed polymerization and base catalyzed polymerization, as described with respect to the first polymerization step, such as polymerization catalyzed with an ammonium compound, an amine, a phosphonium compound or a phosphine compound. Exemplary mineral acids include nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid. Exemplary organic acids include sulfonic acid, trifluorosulfonic acids, and carboxylic acids, as well as thermal acid generators (TAG) capable of generating a sulfonic acid upon exposure to an elevated temperature. Exemplary basic catalysts include tetraorganoammonium compounds and tetraorganophosphonium compounds, such as tetramethylammonium acetate (TMAA), tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), tetrabutylammonium acetate (TBAA), cetyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN), triphenylamine, trioctylamine, tridodecylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, and combinations thereof. In one exemplary embodiment, the catalyst is a tetraorganoammonium compounds, such as TMAH or TMAN.
The second silicon-based resin has a weight average molecular weight greater than the first silicon-based resin. In one exemplary embodiment, the second silicon-based resin has a weight average molecular weight as little as 1000 AMU, 1100 AMU, 1150 AMU, as great as 2000 AMU, 3000 AMU, 4000 AMU, 5000 AMU, 10,000 AMU, or within any range defined between any two of the foregoing values, such as 1000 AMU to 5000 AMU, 2000 AMU to 5000 AMU, or 2000 AMU to 4000 AMU.
In one exemplary embodiment, the second polymerization is performed in a solvent, such ethyl lactate, propylene glycol propylether (PGPE), propylene glycol monomethyl ether acetate (PGMEA) or a combination thereof. The first silicon-based resin is added at a concentration as little as 10 wt. %, 20 wt. %, 30 wt. % 40 wt. %, as great as 45 wt. %, 50 wt. %, 60 wt. % or within any range defined between any two of the foregoing values, such as 10 wt. % to 60 wt. % or 30 wt. % to 45 wt. %. The basic catalyst is added at a concentration as little as 100 ppm, 200 ppm, 250 ppm, as great as 300 ppm, 400 ppm, 500 ppm, or greater, or within any range defined between any two of the foregoing values, such as 100 ppm to 500 ppm or 200 ppm to 300 ppm.
In one exemplary embodiment, the second polymerization is performed at a temperature as little as 60° C., 65° C., 70° C., 75° C., as high as 80° C., 90° C., 100° C., or within any range defined between any two of the forgoing values, such as 60° C. to 100° C. or 70° C. to 100° C. In a more particular embodiment, the second polymerization mixture is held at the temperature for as little as 1 hour, 2 hours, 3 hours, as great as 5 hours, 8 hours, 10 hours, or within any range defined between any two of the foregoing values, such as 1 hour to 10 hours, 2 hours to 10 hours, 2 hours to 8 hours, or 2 to 3 hours.
In one exemplary embodiment, a polysiloxane formulation as described above includes the second silicon-based resin, and one or more solvents. In some exemplary embodiments, the formulation further includes one or more additional silicon-based material as described above. In some exemplary embodiments, the formulation further includes one or more catalysts. In some exemplary embodiments, the formulation further includes one or more surfactants. In some exemplary embodiments, the formulation further includes one or more additional additives, such as adhesion promoters, plasticizers, organic acids, and monofunctional silanes.
In one exemplary embodiment, a coating formed from the polysiloxane formulation including the second silicon-based resin is formed by applying the polysiloxane formulation In one exemplary embodiment, the coating is formed by curing the polysiloxane formulation at a temperature of as little as 350° C., 360° C., 370°, as high as 375° C., 380° C., 385° C., 390° C. or higher.
In some exemplary embodiments, the polysiloxane coating is formed by applying the formulation to a substrate, such as a glass or Si3N4 coated or capped substrate and curing the formulation. In one exemplary embodiment, the coating is formed by curing the polysiloxane formulation at a temperature of as little as 350° C., 360° C., 370°, as high as 375° C., 380° C., 385° C., 390° C. or higher.
In some exemplary embodiments, the polysiloxane coating has a thickness as little as 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 1.2 μm 1.5 μm, 2 μm, as great as, 3 μm, 4 μm, 5 μm, 10 μm or greater, or within any range defined between any two of the foregoing values, such as0.1 μm to 10 μm, 1 μm to 5 μm, 1.2 μm to 5 μm, or 4 μm or greater.
In some exemplary embodiment, the as little as 0.5 wt. %, as little as 0.2 wt. %, as little as 0.1 wt. %, as little as 0.09 wt. %, as little as 0.05 wt. %, or as little as 0.02 wt. % outgassing at 350° C. for 1 hour in air, or within any range defined between any two of the foregoing values, such as 0.5 wt. % to 0.02 wt. %, or 0.1 wt. % to 0.05 wt. %. In some exemplary embodiment, the as little as 0.5 wt. %, as little as 0.2 wt. %, as little as 0.1 wt. %, as little as 0.09 wt. %, as little as 0.05 wt. %, or as little as 0.02 wt. % outgassing at 390° C. for 1 hour in air, or within any range defined between any two of the foregoing values, such as 0.5 wt. % to 0.02 wt. %, or 0.1 wt. % to 0.05 wt. %.
In some exemplary embodiments, the polysiloxane coating has a dielectric constant as little as about 2.8, 2.9, 3.0, as great as about 3.1, 3.2, or within any range defined between any two of the foregoing values, such as 2.8 to 3.2 or 3.0 to 3.2.
Polymer A: phenyl TEOS was reacted in an isopropyl alcohol solvent in the presence of an acid catalyst and water for 24 h at 100° C. After the reaction, the solvent was distilled out to obtain solid polymer. The polymer then dissolved and reprecipitated from an appropriate solvent system and vacuum dried at 50° C. overnight and ground to powder.
Polymer B: predetermined amounts of phenyl TEOS and methyl TEOS were reacted in an isopropyl alcohol solvent in the presence of an acid catalyst and water and 0.5% DMDEOS for 24 hours at 100° C. After the reaction the solvent was distilled out to obtain solid polymer. The polymer was then dissolved and reprecipitated from an appropriate solvent system and vacuum dried at 50° C. overnight and ground to powder.
Formulation 1: 90% of polymer B and 10% of polymer A by weight in PGMEA in the presence of 1-5% by weight surfactant and catalysts 1-5% by weight of final solution weight. The formulation obtained is diluted with PGMEA to obtain a desired thickness to be deposited by slit, roller, spray or spin coating process.
Formulation 2: The formulation was prepared as in Formulation 1, except that 95% polymer B and 5% polymer A were used.
Formulation 3: The formulation was prepared as in Formulation 1, except that 85% polymer B and 15% polymer A were used.
Formulation 4: The formulation was prepared as in Formulation 1, except that 50% polymer B and 50% polymer A were used. This formulation was found to have adhesion problems and was not resistant to chemicals.
Comparative Formulation C: A polysiloxane resin comprising equimolar proportions of MTEOS and PTEOS and about 0.3 mole % of DMDEOS, GR-150F available from Techneglas Technical Products, Perrysburg, Ohio, was dissolved in PGMEA solvent at desired % resin solids loading. Coating formulations were formed by adding PGMEA solvent, a small amount of dilute aqueous TMAN solution and BYK surfactant. Each coating was spun on a substrate at 1000-2500 rpm to deposit films of desired thicknesses and cured under similar conditions. Coatings were inspected for any micro cracks under optical microscope immediately after completely curing and after several days for any latent cracking.
Exemplary Formulations 5-7: A polysiloxane resin GR-950F, derived from PTEOS, was combined with a polysiloxane resin GR-150F, comprising equimolar proportions of MTEOS and PTEOS and about 0.3 mole % of DMDEOS. Both resins, available from Techneglas Technical Products, Perrysburg, Ohio, were dissolved in PGMEA solvent at desired weight ratios and desired % solids loading. For formulation 5, the ratio of GR-950:GR-150F was 1:9, for formulation 6, the ratio was 1:4, and for formulation 7, the ratio was 1:1. Coating formulations were formed by adding PGMEA solvent, a small amount of dilute aqueous TMAN solution and BYK surfactant. Each coating was spun on a substrate at 1000-2500 rpm to deposit films of desired thicknesses and cured under similar conditions. Coatings were inspected for any micro cracks under optical microscope immediately after completely curing and after several days for any latent cracking.
Exemplary Formulations 8-10: Polysiloxane resins comprising equimolar proportions of MTEOS and PTEOS and about 5 mol. % (Formulation 8), 10 mol. % (Formulation 9), or 15 mol. % (Formulation 10) of DMDEOS, obtained from Techneglas Technical Products, Perrysburg, Ohio, were dissolved in PGMEA solvent at desired % resin solids loading. Coating formulations of each resin were formed by adding PGMEA solvent, a small amount of dilute aqueous TMAN solution and BYK surfactant. Each coating was spun on a substrate at 1000-2500 rpm to deposit films of desired thicknesses and cured under similar conditions. Coatings were inspected for any micro cracks under optical microscope immediately after completely curing and after several days for any latent cracking.
Exemplary Formulations 11 and 12: Polysiloxane resins GR-150F was combined with the second polysiloxane resin GR-950F and a third polysiloxane resin comprising equimolar proportions of MTEOS and PTEOS and about 10 mol. % of DMDEOS, in 95/2.5/2.5 (Form. 11) and 90/5/5 (Form. 12) ratios and dissolved in PGMEA solvent at desired % resin solids loading. Coating formulations of each resin combination were formed by adding PGMEA solvent, a small amount of dilute aqueous TMAN solution and BYK surfactant. Each coating was spun on a substrate at 1000-2500 rpm to deposit films of desired thicknesses and cured under similar conditions. Coatings were inspected for any micro cracks under optical microscope immediately after completely curing and after several days for any latent cracking. Coatings formed from Formulation 11 remained crack-free at up to 2.4 μm whereas those formed from Formulation 12 remained crack-free at up to 2.8 μm after curing at 400 C for 30 min.
The percent aryl and alkyl carbon in the formulations are provided in Table 1 below. Formulations 13 and 14 refer to Examples 12 and 13 below.
As shown in Table 1, compositions having greater than 20% alkyl carbon were produced. Also as shown in Table 1, compositions having varying levels of difunctional siloxane content were produced.
Samples of Comparative Formulation C (“Comp. Form. C”) and Formulation 5 (“Form. 5) as produced in Example 1 were deposited on a silicon substrate at various thicknesses as shown in Table 2 below. Duplicate samples were then cured at 380° C. for 30 minutes in a nitrogen atmosphere, followed by a second cure at 380° C. for 10 minutes in air. Following each cure, the film was inspected to determine whether the film had cracked. The results are provided in Table 2 below.
As shown in Table 2, the comparative formulation C sample had a crack threshold on silicon about 2.3 μm. In contrast, the formulation 5 sample had a crack threshold of about 3.1 μm.
Samples of the comparative formulation C and formulation 5 as produced in Example 1 were next deposited on a copper/silicon nitride substrate at various thicknesses as shown in Table 3 below. Duplicate samples were then cured at 380° C. for 30 minutes in a nitrogen atmosphere followed by a second cure at 380° C. for 10 minutes in air. Following each cure, the film was inspected to determine whether the film had cracked. The results are provided in Table 3 below.
As shown in Table 3, the comparative formulation C sample had a crack threshold on Cu/SiN about 2.3 μm. In contrast, the formulation 5 sample had a crack threshold less than 3.1 μm.
Next, a lower cure temperature of 350° C. was investigated. Samples of the comparative formulation C and formulation 5 as produced in Example 1 were next deposited on a silica or glass substrate at various thicknesses as shown in Table 4 below. Samples were cured at 350° C. for 1 hour in nitrogen at the thickness shown in Table 4 to form a film. Following curing, the film was visually inspected to determine whether the film had cracked. The results are provided in Table 4 below.
As shown in Table 4, reducing the cure temperature to 350° C. for formulation 5 resulted in no cracking as high as 3.1 μm on silicon and 3 μm on glass. In contrast, the comparative formulation C sample cracked at only 1.3 μm.
Formulation 5 films of 3.1 μm and 3.4 μm thickness were cured on silicon or glass as above and visually inspected for any latent cracking at 2, 7, 11, and 21 days after cure. The results are provided in Table 5.
As shown in Table 5, formulation 5 did not crack over 21 days after cure at a thickness as high as 3.4 μm on either silicon or glass.
Similar examples of formulation 5 at about 3.6 μm were then cured at various temperatures in air. The results are provided in Table 6.
As shown in Table 6, reducing the temperature lead to no crack forming at temperatures below 300° C. even at a thickness as great as about 3.6 μm.
Samples of the comparative formulation C and formulation 5 as produced in Example 1 were deposited on a silicon or glass substrate at various thicknesses as shown in Table 7 below. Samples were then cured at 380° C. for 30 minutes in a nitrogen atmosphere, followed by a second identical cure. Following each cure, the film was inspected to determine whether the film had cracked. The results are provided in Table 7 below.
Samples of the comparative formulation C and formulations 5, 6, and 7 as produced in Example 1 were deposited on a silicon or glass substrate at various thicknesses as shown in Table 8 below. Samples were then cured at 350° C. for 60 minutes. Following curing, the film was visually inspected to determine whether the film had cracked. The results are provided in Table 8 below.
As shown in Tables 7 and 8, the formulations 5, 6, and 7 had a higher crack threshold than the comparative formulation C film.
As shown in Example 2, the formulations 5, 6, and 7 were able to form films of substantially greater thickness than the comparative formulation C without cracking on various substrates and cured under different conditions. The formulation 5 films were stable at thickness up to 3 μm or greater at cure temperatures of 380° C., and up to 3.6 μm or greater at lower cure temperatures.
Samples of the control comparative formulation C and formulations 8, 9, and 10 as produced in Example 1 were deposited on a substrate at various thicknesses and cured in air as shown in Table 9 below. The crack threshold limit for each sample is provided in Table 9.
As seen in Table 9, the crack threshold limit for each of formulations 8, 9, and 10 exceeded the 1.3 μm thickness for the comparative formulation C film.
As shown in Example 3, formulations 8, 9, and 10 were able to form films of substantially greater thickness than the comparative formulation C without cracking when cured under different conditions.
A 6000 Å sample of the comparative formulation C and formulation 5 as produced in Example 1 were each deposited on a glass substrate and cured for 1 hour at 350° C. The results are provided in
As shown in Table 10, both the comparative formulation C and formulation 5 had a higher transmittance than uncoated glass. In addition, the substantially thicker 3.1-3.4 μm samples of formulation 5 had similar transmittance to the relatively thin 1.1 μm samples of the comparative formulation C. The control comparative formulation C and formulation 5 films had similar transmittance results.
A sample of the comparative formulation C and formulation 5 were deposited on a substrate, based at 230° C. for 30 minutes in air, followed by cure for 390° C. for 30 minutes in nitrogen. The reflectance from 400 nm to 1050 nm was determined. The results are provided for the comparative formulation C in
As shown in Example 4, the comparative formulation C and formulation 5 films had similar optical properties, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact optical design considerations.
The viscosity of the comparative formulation C and formulation 5 formulations as produced in Example 1 was determined at 25° C. The results are provided in Table 1 below.
As shown in Table 11, each of the three formulations had similar viscosities, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact processability of coating formulations by spin coating, spray coating, slot-die coating techniques.
A sample of the comparative formulation C and formulation 5 formulations as produced in Example 1 were deposited on a substrate at 1.9 μm and cured at 390° C. for 30 minutes in nitrogen. The coatings were subjected to a heating and cooling cycle between room temperature and 400° C. The residual stress as a function of temperature for the comparative formulation C coating is provided in
The coefficient of thermal expansion (CTE) for the comparative formulation C and formulation 5 coatings at various temperatures is provided in Table 12 and
As shown in Table 12 and
A sample of the comparative formulation C and formulation 5 formulations as produced in Example 1 were deposited on a substrate and cured for 30 minutes at 380° C. A thermal gravimetric analysis (TGA) was performed, heating the coating from room temperature to about 380° C. The results are presented in
A sample of the comparative formulation C and formulation 5 formulations as produced in Example 1 were deposited on a substrate, baked for 30 minutes in air at 230° C., followed by curing for 1 hour in air at 380° C. The thickness of each coating was measured after the baking step and the curing step, and a percent shrinkage during the cure was determined. The results are provided in Table 13 below.
As shown in Table 13, both coating exhibited similar shrinkage during the cure, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact planarization performance.
As shown in Example 6-8, the comparative formulation C and formulation 5 formulations had similar properties, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact outgassing performance during downstream thermal exposure.
A sample of the comparative formulation C and formulation 5 formulations as produced in Example 1 were deposited on a substrate at 1.9 μm and cured at 390° C. for 30 minutes in nitrogen. Coating thickness was measured by ellipsometery using an N&K tool or a Nanometrics tool.
The hardness of the coatings is shown in
The profile of the depth in nm against load in μN for the comparative formulation C coating is provided in
Formulation 5 was deposited on a silicon substrate and cured for 1 hour at 350° C. in either nitrogen or air. A tape test was performed according to ASTM D3359-09E2, Standard Test methods for Measuring Adhesion by Tape Test to evaluate the adhesion of the coating to the base. The substrate was then heated to 85° C. and cooled in 15 minutes to −20° C. three times. After each cycle, the coating was checked for cracks. After the final cycle, the tape test was again performed. The results are provided in Table 14 below.
As shown in Table 14, the formulation 5 coating had no cracking due to thermal cycling, and showed excellent adhesion both before and after the thermal cycling, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact adhesion.
As shown in Example 9, the comparative formulation C and formulation 5 formulations had similar mechanical resilience, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact mechanical resilience.
A sample of the comparative formulation C, formulation 5, and formulation 8 formulations as produced in Example 1 were deposited on a substrate and cured at 230° C. Each sample was exposed to either TOK-106 for 10 minutes at 70° C. or 2.38% TMAH for 10 minutes at room temperature. The results are provided in Table 15 below. Negative etch rates are the result of film swelling.
As shown in Table 15, the three formulations have similar etch rates in TOK-106 and TMAH.
A sample of the formulation 5 formulation as produced in Example 1 was deposited on silicon and cured as indicated for 1 hour. The initial thickness was measured, followed by exposing the coating to NMP solution at 70° C. for 10 minutes. The coating was again measured, and an etch rate (Å/min) was determined. The coating was next exposed to Piranha solution, a 3:1 mixture of concentrated sulfuric acid and hydrogen peroxide, at 70° C. for 10 minutes. The coating was again measured, and an etch rate (Å/min) was determined. The coating was then exposed to 2.38% TMAH solution at room temperature for 10 minutes. The coating was again measured, and an etch rate (Å/min) was determined. The results of the wet etch testing are provided in Table 16 below. Negative etch values are due to film swelling.
Next, a sample of the formulation 5 formulation as produced in Example 1 was deposited was deposited a substrate and cured in air. The coating was visually inspected with an optical microscope, an initial thickness was measured, along with an initial % transmittance, and the tape test to measure adhesion. The coating was then exposed to TOK-106 photoresist stripper at 70° C. for 10 minutes. The TOK-106 solution is an amine-based photoresist stripper comprising monoethanolamine and DMSO solvent available from Tokyo Ohka Kogyo America, Inc., Hillsboro, Oreg. The coating was again visually inspected under an optical microscope, the thickness was again measured, and an etch rate (Å/min) was determined. An after transmittance, tape adhesion, and OM inspection were performed. The results are provided in Table 17 below.
As shown in Tables 16 and 17,the formulation 5 coating was resistant for 10 minutes to NMP, Piranha, and TOK-106 at 70° C. and TMAH at room temperature, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact chemical resilience
As shown in Example 10, the comparative formulation C, formulation 5, and formulation 8 formulations have similar chemical resilience.
Next, samples of the comparative formulation C and formulation 5 formulations as produced in Example 1 were deposited on a substrate, spun at the RPM listed in Table 18, baked at 230° C., followed by curing as shown in Table 13 below. The coating was then plasma etched at a power of 200 watts, 200 mTorr pressure, and 15 sccm SF6, 20 sccm O2 and 20 sccm Ar. The results are provided in Table 18 below.
As shown in Table 18, formulation 5 had similar plasma etch rate to the comparative formulation C, which suggests that modifications by using resin blends and/or using higher content of dialkylsiloxane will not impact plasma etch rate.
Formulation 13, a polysiloxane resin GR-650F, derived from MTEOS, available from Techneglas Technical Products, Perrysburg, Ohio, was dissolved in PGMEA solvent at desired % solids loading and divided into two samples. To the first sample, a small amount of dilute aqueous TMAN solution was added. To the second sample, an equal amount of TMAN dissolved in PGPE solvent was added. Coating formulations were formed from each sample by adding PGMEA solvent and BYK surfactant. Each coating was spun on a substrate at 1000-1500 rpm to deposit films of desired thicknesses and cured under similar conditions. The refractive index (1.4) and adhesion performance by tape test (100% pass) were identical for the two coatings, which suggests that coating formulations can be formulated without using any external water without impacting optical or physical properties of coatings.
Formulation 14, a polysiloxane resin GR-650F, derived from MTEOS, available from Techneglas Technical Products, Perrysburg, Ohio, was dissolved in PGMEA solvent at desired % solids loading. A small amount of dilute aqueous TMAN solution, PGMEA solvent, BYK surfactant, and VTEOS were added. Coating was spun on a substrate at 1000-1500 rpm to deposit films of desired thicknesses and cured under similar conditions.
Formulation 15—a 45 wt. % solution of a phenyl TEOS based polymer with a molecular weight of 1100 AMU in PGMEA was reacted in the presence of 250 ppm of the basic catalyst TBAH for 2 hours at 100° C. Following the reaction, the resulting resin had a molecular weight of 5000 AMU. Formulation 15 was spun on a silicon substrate and cured for 1 hour at 380° C. The resulting coating had a crack threshold greater than 4 μm.
Formulation 16—a mixture of Formulation 15 and a second polymer having a molecular weight of 4200 AMU and formed of about 50% phenyl TEOS and about 50% methyl TEOS was applied by slot die coating and cured on patterned thin film transistor (FTF) and interconnect dielectric substrate. The resulting coating was tested for planarization and chemical resistance. The coating was perfectly planarized, and had complete resistance to NMP (70° C. for 10 minutes), 2.38 wt. % TMAH (room temperature for 10 minutes), TOK-106 (70° C. for 10 minutes), DHF (room temperature for 5 minutes), and Piranha (70° C. for 10 minutes) solvents. Thermal gravimetric analysis at 350° C. for 4 hours (isothermal) determined that the coating had outgassing at or below 0.09 wt. %.
Formulation 17—a 45 wt. % solution of a phenyl TEOS based polymer with a molecular weight of 1100 AMU in PGMEA was reacted in the presence of 250 ppm of the basic catalyst TBAH for 2-3 hours at 70° C. Following the reaction, the resulting resin had a molecular weight of 2500 AMU. Formulation 15 was spun on a silicon substrate and cured for 1 hour at 380° C. The resulting coating had a crack threshold greater than 4 μm.
Formulation 18—a mixture of Formulation 17 and a second polymer having a molecular weight of 4200 AMU and formed of about 50% phenyl TEOS and about 50% methyl TEOS was applied by slot die coating and cured on patterned thin film transistor (FTF) and interconnect dielectric substrate. The resulting coating was tested for planarization and chemical resistance. The coating was perfectly planarized, and had complete resistance to NMP (70° C. for 10 minutes), 2.38 wt. % TMAH (room temperature for 10 minutes), TOK-106 (70° C. for 10 minutes), DHF (room temperature for 5 minutes), and Piranha (70° C. for 10 minutes) solvents.
Formulation 19—a 30 wt. % solution of a phenyl TEOS based polymer with a molecular weight of 1100 AMU in PGMEA was reacted in the presence of 200 ppm of the basic catalyst TBAH for 8 hours at 100° C. Following the reaction, the resulting resin had a molecular weight of 6000 AMU.
Formulation 20—a 30 wt. % solution of a phenyl TEOS based polymer with a molecular weight of 1100 AMU in PGMEA was reacted in the presence of 300 ppm of the basic catalyst TBAH for 8 hours at 100° C. Following the reaction, the resulting resin had a molecular weight of 8000 AMU.
Formulation 21—a 30 wt. % solution of a phenyl TEOS based polymer with a molecular weight of 1100 AMU in PGMEA was reacted in the presence of 400 ppm of the basic catalyst TBAH for 8 hours at 100° C. Following the reaction, the resulting resin gelled and precipitated out of solution.
Formulation 22—a 30 wt. % solution of a phenyl TEOS based polymer with a molecular weight of 1100 AMU and a second polymer having a molecular weight of 4200 AMU and formed of about 50% phenyl TEOS and about 50% methyl TEOS in PGMEA was reacted in the presence of 200 ppm of the basic catalyst TBAH for 8 hours at 100° C. Following the reaction, the resulting resin gelled and precipitated out of solution at room temperature.
Various modifications and additions can be made to the exemplary embodiments discussed without departing from the scope of the present invention. For example, while the embodiments described above refer to particular features, the scope of this invention also includes embodiments having different combinations of features and embodiments that do not include all of the above described features.
This application is the U.S. national stage of PCT/US2016/020373, published as WO 2016/167892, filed Mar. 2, 2016, which claims the benefit under Title 35, U.S.C. § 119(e) of U.S. Provisional Patent Application Serial No. 62/146,593, filed Apr. 13, 2015, each of which is hereby incorporated by reference herein in its entirety.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/US2016/020373 | 3/2/2016 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2016/167892 | 10/20/2016 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
31987 | Light | Apr 1861 | A |
35239 | Jacobs | May 1862 | A |
35368 | Ehrman | May 1862 | A |
35447 | Howard | Jun 1862 | A |
58929 | Wood | Oct 1866 | A |
106376 | Lerch | Aug 1870 | A |
172896 | Stebins | Feb 1876 | A |
677386 | Teeguarden et al. | Jul 1901 | A |
2783263 | Merker | Feb 1957 | A |
2986548 | McLoughlin | May 1961 | A |
3294737 | Krantz | Dec 1966 | A |
3615272 | Collins et al. | Oct 1971 | A |
3635529 | Nass | Jan 1972 | A |
3647508 | Gorrell | Mar 1972 | A |
3784378 | Gramas | Jan 1974 | A |
3873361 | Franco et al. | Mar 1975 | A |
3884702 | Koshimo et al. | May 1975 | A |
3925077 | Lewis et al. | Dec 1975 | A |
3929489 | Arcesi et al. | Dec 1975 | A |
4018606 | Contois et al. | Apr 1977 | A |
4018607 | Contois | Apr 1977 | A |
4043812 | Stolka et al. | Aug 1977 | A |
4048146 | Wilson | Sep 1977 | A |
4052367 | Wilson | Oct 1977 | A |
4053313 | Fan | Oct 1977 | A |
4102683 | DiPiazza | Jul 1978 | A |
4191571 | Nonogaki et al. | Mar 1980 | A |
4257826 | Matalone, Jr. | Mar 1981 | A |
4290896 | Gordon et al. | Sep 1981 | A |
4299938 | Green et al. | Nov 1981 | A |
4308371 | Tanaka et al. | Dec 1981 | A |
4312970 | Gaul, Jr. | Jan 1982 | A |
4328262 | Kurahashi et al. | May 1982 | A |
4348471 | Shelnut et al. | Sep 1982 | A |
4349609 | Takeda et al. | Sep 1982 | A |
4351935 | Reesink et al. | Sep 1982 | A |
4362809 | Chen et al. | Dec 1982 | A |
4363859 | Sasaki et al. | Dec 1982 | A |
4369284 | Chen | Jan 1983 | A |
4388449 | Bonnet et al. | Jun 1983 | A |
4399255 | Smith et al. | Aug 1983 | A |
4399266 | Matsumura et al. | Aug 1983 | A |
4413052 | Green et al. | Nov 1983 | A |
4413088 | Frye | Nov 1983 | A |
4419437 | Noonan et al. | Dec 1983 | A |
4423135 | Chen et al. | Dec 1983 | A |
4430153 | Gleason et al. | Feb 1984 | A |
4434127 | Baile | Feb 1984 | A |
4442197 | Crivello et al. | Apr 1984 | A |
4456679 | Leyrer et al. | Jun 1984 | A |
4483107 | Tomoyori et al. | Nov 1984 | A |
4510283 | Takeda et al. | Apr 1985 | A |
4513132 | Shoji et al. | Apr 1985 | A |
4515828 | Economy et al. | May 1985 | A |
4546017 | Flackett et al. | Oct 1985 | A |
4557996 | Aoyama et al. | Dec 1985 | A |
4563241 | Tanaka et al. | Jan 1986 | A |
4587138 | Yau et al. | May 1986 | A |
4594309 | Guillet | Jun 1986 | A |
4595599 | Brown et al. | Jun 1986 | A |
4600685 | Kitakohji et al. | Jul 1986 | A |
4603168 | Sasaki et al. | Jul 1986 | A |
4609614 | Pampalone et al. | Sep 1986 | A |
4617252 | Cordes, III et al. | Oct 1986 | A |
4618213 | Chen | Oct 1986 | A |
4620986 | Yau et al. | Nov 1986 | A |
4624912 | Zweifel et al. | Nov 1986 | A |
4626556 | Nozue et al. | Dec 1986 | A |
4657843 | Fukuyama et al. | Apr 1987 | A |
4657965 | Watanabe et al. | Apr 1987 | A |
4663414 | Estes et al. | May 1987 | A |
4670299 | Fukuyama et al. | Jun 1987 | A |
4674176 | Tuckerman | Jun 1987 | A |
4676867 | Elkins et al. | Jun 1987 | A |
4678835 | Chang et al. | Jul 1987 | A |
4681795 | Tuckerman | Jul 1987 | A |
4687216 | Kawamoto et al. | Aug 1987 | A |
4693959 | Ashcraft | Sep 1987 | A |
4702990 | Tanaka et al. | Oct 1987 | A |
4705729 | Sheats | Nov 1987 | A |
4705739 | Fisch | Nov 1987 | A |
4708925 | Newman | Nov 1987 | A |
4723978 | Clodgo et al. | Feb 1988 | A |
4731264 | Lin et al. | Mar 1988 | A |
4732858 | Brewer et al. | Mar 1988 | A |
4745169 | Sugiyama et al. | May 1988 | A |
4746693 | Meder | May 1988 | A |
4752649 | Neckers | Jun 1988 | A |
4753855 | Haluska et al. | Jun 1988 | A |
4756977 | Haluska et al. | Jul 1988 | A |
4762767 | Haas et al. | Aug 1988 | A |
4763966 | Suzuki et al. | Aug 1988 | A |
4767571 | Suzuki et al. | Aug 1988 | A |
4774141 | Matsui et al. | Sep 1988 | A |
4778624 | Ohashi et al. | Oct 1988 | A |
4782009 | Bolon et al. | Nov 1988 | A |
4783347 | Doin et al. | Nov 1988 | A |
4806504 | Cleeves | Feb 1989 | A |
4808553 | Yamazaki | Feb 1989 | A |
4814578 | Tuckerman | Mar 1989 | A |
4816049 | Hata et al. | Mar 1989 | A |
4822697 | Haluska et al. | Apr 1989 | A |
4822718 | Latham et al. | Apr 1989 | A |
4826943 | Ito et al. | May 1989 | A |
4831188 | Neckers | May 1989 | A |
4839274 | Logan | Jun 1989 | A |
4839427 | Mormile | Jun 1989 | A |
4847152 | Jabs et al. | Jul 1989 | A |
4847162 | Haluska et al. | Jul 1989 | A |
4849296 | Haluska et al. | Jul 1989 | A |
4855199 | Bolon et al. | Aug 1989 | A |
4863827 | Jain et al. | Sep 1989 | A |
4863829 | Furuta et al. | Sep 1989 | A |
4863833 | Fukuyama et al. | Sep 1989 | A |
4876165 | Brewer et al. | Oct 1989 | A |
4885262 | Ting et al. | Dec 1989 | A |
4895914 | Saitoh et al. | Jan 1990 | A |
4898907 | Haluska et al. | Feb 1990 | A |
4904721 | Hanaoka et al. | Feb 1990 | A |
4910122 | Arnold et al. | Mar 1990 | A |
4911992 | Haluska et al. | Mar 1990 | A |
4913846 | Suzuki et al. | Apr 1990 | A |
4921317 | Suzuki et al. | May 1990 | A |
4921778 | Thackeray et al. | May 1990 | A |
4923638 | Ohno et al. | May 1990 | A |
4925772 | Quella et al. | May 1990 | A |
4926383 | Kertis et al. | May 1990 | A |
4927732 | Merrem et al. | May 1990 | A |
4935320 | Rohde et al. | Jun 1990 | A |
4935583 | Kyle | Jun 1990 | A |
4940651 | Brown et al. | Jul 1990 | A |
4942083 | Smith, Jr. | Jul 1990 | A |
4943511 | Lazarus et al. | Jul 1990 | A |
4950577 | Grieve et al. | Aug 1990 | A |
4950583 | Brewer et al. | Aug 1990 | A |
4954414 | Adair et al. | Sep 1990 | A |
4962996 | Cuellar et al. | Oct 1990 | A |
4970134 | Bronstert et al. | Nov 1990 | A |
4973510 | Tanaka | Nov 1990 | A |
4973526 | Haluska | Nov 1990 | A |
4981530 | Clodgo et al. | Jan 1991 | A |
4981778 | Brault | Jan 1991 | A |
4988514 | Fukuyama et al. | Jan 1991 | A |
4999397 | Weiss et al. | Mar 1991 | A |
5004660 | Van Andel et al. | Apr 1991 | A |
5008320 | Haluska et al. | Apr 1991 | A |
5009669 | Jollenbeck et al. | Apr 1991 | A |
5009809 | Kosin et al. | Apr 1991 | A |
5009810 | Wason et al. | Apr 1991 | A |
5013608 | Guest et al. | May 1991 | A |
5024923 | Suzuki et al. | Jun 1991 | A |
5026624 | Day et al. | Jun 1991 | A |
5034189 | Cox et al. | Jul 1991 | A |
5037580 | Garcia et al. | Aug 1991 | A |
5043789 | Linde et al. | Aug 1991 | A |
5045570 | Mooney et al. | Sep 1991 | A |
5045592 | Weiss et al. | Sep 1991 | A |
5049414 | Kato | Sep 1991 | A |
5055372 | Shanklin et al. | Oct 1991 | A |
5055376 | Saeva | Oct 1991 | A |
5059448 | Chandra et al. | Oct 1991 | A |
5059500 | Needham et al. | Oct 1991 | A |
5063134 | Horiguchi et al. | Nov 1991 | A |
5063267 | Hanneman et al. | Nov 1991 | A |
5077085 | Schnur et al. | Dec 1991 | A |
5079600 | Schnur et al. | Jan 1992 | A |
5100503 | Allman et al. | Mar 1992 | A |
5102695 | Guest et al. | Apr 1992 | A |
5104692 | Belmares | Apr 1992 | A |
5106534 | Wason et al. | Apr 1992 | A |
5112728 | Tanji et al. | May 1992 | A |
5116637 | Baney et al. | May 1992 | A |
5116715 | Roland et al. | May 1992 | A |
5126289 | Ziger | Jun 1992 | A |
5137655 | Kosin et al. | Aug 1992 | A |
5140396 | Needham et al. | Aug 1992 | A |
5152834 | Allman | Oct 1992 | A |
5153254 | Chen | Oct 1992 | A |
5166093 | Grief | Nov 1992 | A |
5173368 | Belmares | Dec 1992 | A |
5179185 | Yamamoto et al. | Jan 1993 | A |
5194364 | Abe et al. | Mar 1993 | A |
5199979 | Lin et al. | Apr 1993 | A |
5212046 | Lamola et al. | May 1993 | A |
5212218 | Rinehart | May 1993 | A |
5219788 | Abernathey et al. | Jun 1993 | A |
5227334 | Sandhu | Jul 1993 | A |
5236984 | Yamamoto et al. | Aug 1993 | A |
5239723 | Chen | Aug 1993 | A |
5250224 | Wason et al. | Oct 1993 | A |
5252340 | Honeycutt | Oct 1993 | A |
5252618 | Garcia et al. | Oct 1993 | A |
5256510 | Bugner et al. | Oct 1993 | A |
5262201 | Chandra et al. | Nov 1993 | A |
5262468 | Chen | Nov 1993 | A |
5271768 | Morishima et al. | Dec 1993 | A |
5272026 | Roland et al. | Dec 1993 | A |
5272042 | Allen et al. | Dec 1993 | A |
5278010 | Day et al. | Jan 1994 | A |
5300402 | Card, Jr. et al. | Apr 1994 | A |
5302198 | Allman | Apr 1994 | A |
5302455 | Wason et al. | Apr 1994 | A |
5302849 | Cavasin | Apr 1994 | A |
5317044 | Mooney et al. | May 1994 | A |
5320868 | Ballance et al. | Jun 1994 | A |
5324222 | Chen | Jun 1994 | A |
5324591 | Georger, Jr. et al. | Jun 1994 | A |
5328975 | Hanson et al. | Jul 1994 | A |
5334646 | Chen | Aug 1994 | A |
5336708 | Chen | Aug 1994 | A |
5340644 | Babcock et al. | Aug 1994 | A |
5359022 | Mautner et al. | Oct 1994 | A |
5360692 | Kawabe et al. | Nov 1994 | A |
5380621 | Dichiara et al. | Jan 1995 | A |
5382615 | Godfrey | Jan 1995 | A |
5384357 | Levinson et al. | Jan 1995 | A |
5387480 | Haluska et al. | Feb 1995 | A |
5389496 | Calvert et al. | Feb 1995 | A |
5391463 | Ligler et al. | Feb 1995 | A |
5395734 | Vogel et al. | Mar 1995 | A |
5396311 | Fukushima et al. | Mar 1995 | A |
5401614 | Dichiara et al. | Mar 1995 | A |
5403680 | Otagawa et al. | Apr 1995 | A |
5414069 | Cumming et al. | May 1995 | A |
5417977 | Honeycutt | May 1995 | A |
5418136 | Miller et al. | May 1995 | A |
5432007 | Naito | Jul 1995 | A |
5439766 | Day et al. | Aug 1995 | A |
5439872 | Ito et al. | Aug 1995 | A |
5441765 | Ballance et al. | Aug 1995 | A |
5449639 | Wei et al. | Sep 1995 | A |
5449712 | Gierke et al. | Sep 1995 | A |
5455145 | Tarumoto | Oct 1995 | A |
5455208 | Leung et al. | Oct 1995 | A |
5457081 | Takiguchi et al. | Oct 1995 | A |
5458982 | Godfrey | Oct 1995 | A |
5467626 | Sanders | Nov 1995 | A |
5468591 | Pearce et al. | Nov 1995 | A |
5472488 | Allman | Dec 1995 | A |
5475890 | Chen | Dec 1995 | A |
5482817 | Dichiara et al. | Jan 1996 | A |
5498345 | Jollenbeck et al. | Mar 1996 | A |
5498468 | Blaney | Mar 1996 | A |
5498748 | Urano et al. | Mar 1996 | A |
5500315 | Calvert et al. | Mar 1996 | A |
5508334 | Chen | Apr 1996 | A |
5510628 | Georger, Jr. et al. | Apr 1996 | A |
5512418 | Ma | Apr 1996 | A |
5518818 | Kidai et al. | May 1996 | A |
5520855 | Ito et al. | May 1996 | A |
5523163 | Ballance et al. | Jun 1996 | A |
5527562 | Balaba et al. | Jun 1996 | A |
5527872 | Allman | Jun 1996 | A |
5552260 | Vogel et al. | Sep 1996 | A |
5554485 | Dichiara et al. | Sep 1996 | A |
5576144 | Pearce et al. | Nov 1996 | A |
5576247 | Yano et al. | Nov 1996 | A |
5576359 | Urano et al. | Nov 1996 | A |
5578318 | Honeycutt | Nov 1996 | A |
5580606 | Kai | Dec 1996 | A |
5580819 | Li et al. | Dec 1996 | A |
5583195 | Eckberg | Dec 1996 | A |
5597408 | Choi | Jan 1997 | A |
5624294 | Chen | Apr 1997 | A |
5629437 | Linder et al. | May 1997 | A |
5635240 | Haluska et al. | Jun 1997 | A |
5638724 | Sanders | Jun 1997 | A |
5648201 | Dulcey et al. | Jul 1997 | A |
5655947 | Chen | Aug 1997 | A |
5661196 | Mayer et al. | Aug 1997 | A |
5661992 | Sanders | Sep 1997 | A |
5662109 | Hutson | Sep 1997 | A |
5663286 | Ahmed et al. | Sep 1997 | A |
5665845 | Allman | Sep 1997 | A |
5670295 | Namba et al. | Sep 1997 | A |
5672243 | Hsia et al. | Sep 1997 | A |
5674624 | Miyazaki et al. | Oct 1997 | A |
5674648 | Brewer et al. | Oct 1997 | A |
5677112 | Urano et al. | Oct 1997 | A |
5679128 | Latting et al. | Oct 1997 | A |
5683095 | Astier et al. | Nov 1997 | A |
5693691 | Flaim et al. | Dec 1997 | A |
5693701 | Camilletti et al. | Dec 1997 | A |
5695551 | Buckingham et al. | Dec 1997 | A |
5695910 | Urano et al. | Dec 1997 | A |
5707883 | Tabara | Jan 1998 | A |
5719249 | Fujita et al. | Feb 1998 | A |
5729563 | Wang et al. | Mar 1998 | A |
5731091 | Schmidt et al. | Mar 1998 | A |
5741623 | Namba et al. | Apr 1998 | A |
5744243 | Li et al. | Apr 1998 | A |
5744244 | Camilletti et al. | Apr 1998 | A |
5747223 | Allen et al. | May 1998 | A |
5747553 | Guzauskas | May 1998 | A |
5750292 | Sato et al. | May 1998 | A |
5755867 | Chikuni et al. | May 1998 | A |
5756257 | Landgrebe et al. | May 1998 | A |
5759625 | Laubacher et al. | Jun 1998 | A |
5760117 | Chen | Jun 1998 | A |
5767014 | Hawker et al. | Jun 1998 | A |
5773170 | Patel et al. | Jun 1998 | A |
5776559 | Woolford | Jul 1998 | A |
5780206 | Urano et al. | Jul 1998 | A |
5786125 | Tsuchiya et al. | Jul 1998 | A |
5800926 | Nogami et al. | Sep 1998 | A |
5837568 | Yoneda et al. | Nov 1998 | A |
5837801 | Yahata et al. | Nov 1998 | A |
5840821 | Nakano et al. | Nov 1998 | A |
5843617 | Patel et al. | Dec 1998 | A |
5851730 | Thackeray et al. | Dec 1998 | A |
5851738 | Thackeray et al. | Dec 1998 | A |
5853808 | Arkles et al. | Dec 1998 | A |
5855960 | Ohnishi et al. | Jan 1999 | A |
5858547 | Drage | Jan 1999 | A |
5868597 | Chen | Feb 1999 | A |
5873931 | Scholz et al. | Feb 1999 | A |
5877228 | Mine et al. | Mar 1999 | A |
5883011 | Lin et al. | Mar 1999 | A |
5884639 | Chen | Mar 1999 | A |
5905109 | Shimizu et al. | May 1999 | A |
5910021 | Tabara | Jun 1999 | A |
5922299 | Bruinsma et al. | Jul 1999 | A |
5929159 | Schutt et al. | Jul 1999 | A |
5935758 | Patel et al. | Aug 1999 | A |
5938499 | Chen | Aug 1999 | A |
5939236 | Pavelchek et al. | Aug 1999 | A |
5939510 | Sato et al. | Aug 1999 | A |
5944431 | Becker et al. | Aug 1999 | A |
5945172 | Yamaya et al. | Aug 1999 | A |
5945249 | Patel et al. | Aug 1999 | A |
5948600 | Roschger et al. | Sep 1999 | A |
5949518 | Belmares et al. | Sep 1999 | A |
5953627 | Carter et al. | Sep 1999 | A |
5962067 | Bautista et al. | Oct 1999 | A |
5962572 | Chen | Oct 1999 | A |
5964917 | Latting | Oct 1999 | A |
5965305 | Ligler et al. | Oct 1999 | A |
5972616 | O'Brien et al. | Oct 1999 | A |
5976666 | Narang et al. | Nov 1999 | A |
5981675 | Valint, Jr. et al. | Nov 1999 | A |
5985444 | Olson et al. | Nov 1999 | A |
5986344 | Subramanion et al. | Nov 1999 | A |
5994431 | Olson et al. | Nov 1999 | A |
5997621 | Scholz et al. | Dec 1999 | A |
5998300 | Tabara | Dec 1999 | A |
5998522 | Nakano et al. | Dec 1999 | A |
6008350 | Roschger et al. | Dec 1999 | A |
6020410 | Hacker et al. | Feb 2000 | A |
6022812 | Smith et al. | Feb 2000 | A |
6025077 | Yamaki et al. | Feb 2000 | A |
6033283 | Chen | Mar 2000 | A |
6037275 | Wu et al. | Mar 2000 | A |
6040053 | Scholz et al. | Mar 2000 | A |
6040251 | Caldwell | Mar 2000 | A |
6042994 | Yang et al. | Mar 2000 | A |
6043330 | Hacker et al. | Mar 2000 | A |
6043547 | Hsia et al. | Mar 2000 | A |
6048804 | Smith et al. | Apr 2000 | A |
6050871 | Chen | Apr 2000 | A |
6051310 | Cano et al. | Apr 2000 | A |
6057239 | Wang et al. | May 2000 | A |
6072018 | Wilkes et al. | Jun 2000 | A |
6074695 | Kobayashi et al. | Jun 2000 | A |
6087068 | Sato et al. | Jul 2000 | A |
6090448 | Wallace et al. | Jul 2000 | A |
6096460 | French et al. | Aug 2000 | A |
6103456 | Tobben et al. | Aug 2000 | A |
6103770 | Trouve | Aug 2000 | A |
6103779 | Guzauskas | Aug 2000 | A |
6107167 | Bhakta | Aug 2000 | A |
6117176 | Chen | Sep 2000 | A |
6117360 | Miyazawa et al. | Sep 2000 | A |
6124369 | Kudo et al. | Sep 2000 | A |
6126733 | Wallace et al. | Oct 2000 | A |
6137175 | Tabara | Oct 2000 | A |
6137634 | Li | Oct 2000 | A |
6140254 | Endisch et al. | Oct 2000 | A |
6143855 | Hacker et al. | Nov 2000 | A |
6144083 | Yin | Nov 2000 | A |
6147407 | Jin et al. | Nov 2000 | A |
6148830 | Chen | Nov 2000 | A |
6149778 | Jin et al. | Nov 2000 | A |
6149934 | Krzysik et al. | Nov 2000 | A |
6149966 | Kobayashi et al. | Nov 2000 | A |
6150250 | Tabara et al. | Nov 2000 | A |
6150440 | Olson et al. | Nov 2000 | A |
6152906 | Faulks et al. | Nov 2000 | A |
6161555 | Chen | Dec 2000 | A |
6165697 | Thackeray et al. | Dec 2000 | A |
6166163 | Kudo et al. | Dec 2000 | A |
6171766 | Patel et al. | Jan 2001 | B1 |
6174631 | French et al. | Jan 2001 | B1 |
6174977 | Ariyoshi et al. | Jan 2001 | B1 |
6177199 | Hacker et al. | Jan 2001 | B1 |
6177360 | Carter et al. | Jan 2001 | B1 |
6180025 | Schoenfeld et al. | Jan 2001 | B1 |
6180317 | Allen et al. | Jan 2001 | B1 |
6187505 | Lin et al. | Feb 2001 | B1 |
6187689 | Tabara | Feb 2001 | B1 |
6190830 | Leon et al. | Feb 2001 | B1 |
6190839 | Pavelchek et al. | Feb 2001 | B1 |
6190955 | Ilg et al. | Feb 2001 | B1 |
6191030 | Subramanian et al. | Feb 2001 | B1 |
6194121 | Namba et al. | Feb 2001 | B1 |
6194534 | Baumann et al. | Feb 2001 | B1 |
6204202 | Leung et al. | Mar 2001 | B1 |
6208041 | Majumdar et al. | Mar 2001 | B1 |
6210862 | Day et al. | Apr 2001 | B1 |
6214104 | Iida et al. | Apr 2001 | B1 |
6217890 | Paul et al. | Apr 2001 | B1 |
6218020 | Hacker et al. | Apr 2001 | B1 |
6218497 | Hacker et al. | Apr 2001 | B1 |
6225033 | Onishi et al. | May 2001 | B1 |
6225671 | Yin | May 2001 | B1 |
6231989 | Chung et al. | May 2001 | B1 |
6232424 | Zhong et al. | May 2001 | B1 |
6235456 | Ibok | May 2001 | B1 |
6238379 | Keuhn, Jr. et al. | May 2001 | B1 |
6238838 | Gaschler et al. | May 2001 | B1 |
6251486 | Chandross et al. | Jun 2001 | B1 |
6255671 | Bojarczuk, Jr. et al. | Jul 2001 | B1 |
6261676 | Olson et al. | Jul 2001 | B1 |
6261743 | Pavelchek et al. | Jul 2001 | B1 |
6268108 | Iguchi et al. | Jul 2001 | B1 |
6268294 | Jang et al. | Jul 2001 | B1 |
6268457 | Kennedy et al. | Jul 2001 | B1 |
6271273 | You et al. | Aug 2001 | B1 |
6277750 | Pawlowski et al. | Aug 2001 | B1 |
6280911 | Trefonas, III | Aug 2001 | B1 |
6284428 | Hirosaki et al. | Sep 2001 | B1 |
6287286 | Akin et al. | Sep 2001 | B1 |
6291143 | Patel et al. | Sep 2001 | B1 |
6291586 | Lasch et al. | Sep 2001 | B2 |
6296862 | Paul et al. | Oct 2001 | B1 |
6306736 | Alivisatos et al. | Oct 2001 | B1 |
6313045 | Zhong et al. | Nov 2001 | B1 |
6313257 | Abbey | Nov 2001 | B1 |
6315946 | Focht | Nov 2001 | B1 |
6316013 | Paul et al. | Nov 2001 | B1 |
6316160 | Shao et al. | Nov 2001 | B1 |
6316165 | Pavelchek et al. | Nov 2001 | B1 |
6318124 | Pavelchek et al. | Nov 2001 | B1 |
6319855 | Hendricks et al. | Nov 2001 | B1 |
6323268 | Fisher et al. | Nov 2001 | B1 |
6324703 | Chen | Dec 2001 | B1 |
6326231 | Subramanian et al. | Dec 2001 | B1 |
6329117 | Padmanaban et al. | Dec 2001 | B1 |
6329118 | Hussein et al. | Dec 2001 | B1 |
6333374 | Chen | Dec 2001 | B1 |
6335234 | Wu et al. | Jan 2002 | B2 |
6335235 | Bhakta et al. | Jan 2002 | B1 |
6337089 | Yoshioka et al. | Jan 2002 | B1 |
6340735 | Yagihashi | Jan 2002 | B1 |
6342249 | Wong et al. | Jan 2002 | B1 |
6344284 | Chou | Feb 2002 | B1 |
6344305 | Lin et al. | Feb 2002 | B1 |
6348240 | Calvert et al. | Feb 2002 | B1 |
6350818 | Hong et al. | Feb 2002 | B1 |
6352931 | Seta et al. | Mar 2002 | B1 |
6358294 | Latting | Mar 2002 | B1 |
6358559 | Hacker et al. | Mar 2002 | B1 |
6359096 | Zhong et al. | Mar 2002 | B1 |
6359099 | Hacker et al. | Mar 2002 | B1 |
6361820 | Hacker et al. | Mar 2002 | B1 |
6365266 | MacDougall et al. | Apr 2002 | B1 |
6365529 | Hussein et al. | Apr 2002 | B1 |
6365765 | Baldwin et al. | Apr 2002 | B1 |
6368400 | Baldwin et al. | Apr 2002 | B1 |
6368681 | Ogawa | Apr 2002 | B1 |
6374738 | Lewis et al. | Apr 2002 | B1 |
6380621 | Ando et al. | Apr 2002 | B1 |
6383466 | Domansky et al. | May 2002 | B1 |
6387519 | Anderson et al. | May 2002 | B1 |
6391524 | Yates et al. | May 2002 | B2 |
6399269 | Mizutani et al. | Jun 2002 | B2 |
6403464 | Chang | Jun 2002 | B1 |
6409883 | Makolin et al. | Jun 2002 | B1 |
6410150 | Kurosawa et al. | Jun 2002 | B1 |
6410209 | Adams et al. | Jun 2002 | B1 |
6413647 | Hayashi et al. | Jul 2002 | B1 |
6420088 | Angelopoulos et al. | Jul 2002 | B1 |
6420441 | Allen et al. | Jul 2002 | B1 |
6420475 | Chen | Jul 2002 | B1 |
6426125 | Yang et al. | Jul 2002 | B1 |
6432191 | Schutt | Aug 2002 | B2 |
6433037 | Guzauskas | Aug 2002 | B1 |
6441452 | Yin | Aug 2002 | B2 |
6444584 | Hsiao | Sep 2002 | B1 |
6448185 | Andideh et al. | Sep 2002 | B1 |
6448331 | Ioka et al. | Sep 2002 | B1 |
6448464 | Akin et al. | Sep 2002 | B1 |
6451503 | Thackeray et al. | Sep 2002 | B1 |
6455207 | Katoh et al. | Sep 2002 | B1 |
6455416 | Subramanian et al. | Sep 2002 | B1 |
6456358 | Lu | Sep 2002 | B1 |
6461717 | Rutter et al. | Oct 2002 | B1 |
6461970 | Yin | Oct 2002 | B1 |
6465358 | Nashner et al. | Oct 2002 | B1 |
6465889 | Subramanian et al. | Oct 2002 | B1 |
6472012 | Nakada et al. | Oct 2002 | B2 |
6472128 | Thackeray et al. | Oct 2002 | B2 |
6475892 | Bhakta | Nov 2002 | B1 |
6485368 | Jones et al. | Nov 2002 | B2 |
6488394 | Mabe et al. | Dec 2002 | B1 |
6491840 | Frankenbach et al. | Dec 2002 | B1 |
6492441 | Hong et al. | Dec 2002 | B2 |
6495264 | Hayashi et al. | Dec 2002 | B2 |
6497893 | Everhart et al. | Dec 2002 | B1 |
6503233 | Chen et al. | Jan 2003 | B1 |
6503413 | Uchiyama et al. | Jan 2003 | B2 |
6503525 | Paul et al. | Jan 2003 | B1 |
6503526 | Krzysik et al. | Jan 2003 | B1 |
6503586 | Wu et al. | Jan 2003 | B1 |
6503692 | Angelopoulos et al. | Jan 2003 | B2 |
6504525 | Knights | Jan 2003 | B1 |
6505362 | Scipio | Jan 2003 | B1 |
6506497 | Kennedy et al. | Jan 2003 | B1 |
6509259 | Wang et al. | Jan 2003 | B1 |
6509279 | Fujii et al. | Jan 2003 | B2 |
6512071 | Hacker et al. | Jan 2003 | B1 |
6514677 | Ramsden et al. | Feb 2003 | B1 |
6515073 | Sakamoto et al. | Feb 2003 | B2 |
6517951 | Hacker et al. | Feb 2003 | B2 |
6528235 | Thackeray et al. | Mar 2003 | B2 |
6541107 | Zhong et al. | Apr 2003 | B1 |
6544717 | Hirosaki et al. | Apr 2003 | B2 |
6548113 | Birnbaum et al. | Apr 2003 | B1 |
6552109 | Chen | Apr 2003 | B1 |
6558363 | Keuhn, Jr. et al. | May 2003 | B2 |
6558880 | Goswami et al. | May 2003 | B1 |
6559070 | Mandal | May 2003 | B1 |
6562192 | Hamilton et al. | May 2003 | B1 |
6565813 | Garyantes | May 2003 | B1 |
6566479 | Bublewitz et al. | May 2003 | B1 |
6573175 | Yin et al. | Jun 2003 | B1 |
6573328 | Kropp et al. | Jun 2003 | B2 |
6576382 | Day et al. | Jun 2003 | B2 |
6576408 | Meador et al. | Jun 2003 | B2 |
6576651 | Bandyopadhyay et al. | Jun 2003 | B2 |
6582861 | Buxbaum et al. | Jun 2003 | B2 |
6587147 | Li | Jul 2003 | B1 |
6589862 | Wang et al. | Jul 2003 | B2 |
6592980 | MacDougall et al. | Jul 2003 | B1 |
6592999 | Anderson et al. | Jul 2003 | B1 |
6593388 | Crivello | Jul 2003 | B2 |
6596314 | Wong et al. | Jul 2003 | B2 |
6596404 | Albaugh et al. | Jul 2003 | B1 |
6596467 | Gallagher et al. | Jul 2003 | B2 |
6599995 | Hwang et al. | Jul 2003 | B2 |
6602552 | Daraskevich et al. | Aug 2003 | B1 |
6602652 | Adams et al. | Aug 2003 | B2 |
6605359 | Robinson et al. | Aug 2003 | B2 |
6605360 | Kizaki et al. | Aug 2003 | B2 |
6605362 | Baldwin et al. | Aug 2003 | B2 |
6605542 | Seta et al. | Aug 2003 | B2 |
6607991 | Livesay et al. | Aug 2003 | B1 |
6610457 | Kim et al. | Aug 2003 | B2 |
6612828 | Powers et al. | Sep 2003 | B2 |
6613834 | Nakata et al. | Sep 2003 | B2 |
6617257 | Ni et al. | Sep 2003 | B2 |
6617609 | Kelley et al. | Sep 2003 | B2 |
6623791 | Sadvary et al. | Sep 2003 | B2 |
6627275 | Chen | Sep 2003 | B1 |
6632535 | Buazza et al. | Oct 2003 | B1 |
6635281 | Wong et al. | Oct 2003 | B2 |
6635341 | Barancyk et al. | Oct 2003 | B1 |
6645685 | Takata et al. | Nov 2003 | B2 |
6645881 | Yamada et al. | Nov 2003 | B2 |
6649212 | Payne et al. | Nov 2003 | B2 |
6649534 | Fujii et al. | Nov 2003 | B2 |
6649741 | O'Brien et al. | Nov 2003 | B1 |
6652766 | Frankenbach et al. | Nov 2003 | B1 |
6653049 | Pavelchek et al. | Nov 2003 | B2 |
6655946 | Foreman et al. | Dec 2003 | B2 |
6664199 | Fujii et al. | Dec 2003 | B2 |
6667424 | Hamilton et al. | Dec 2003 | B1 |
6670284 | Yin | Dec 2003 | B2 |
6673982 | Chen et al. | Jan 2004 | B1 |
6674106 | Tanaka et al. | Jan 2004 | B2 |
6676398 | Foreman et al. | Jan 2004 | B2 |
6676740 | Matsumura et al. | Jan 2004 | B2 |
6677392 | Ravichandran et al. | Jan 2004 | B2 |
6678026 | Maeda et al. | Jan 2004 | B2 |
6689932 | Kruchoski et al. | Feb 2004 | B2 |
6696538 | Ko et al. | Feb 2004 | B2 |
6699647 | Lynch et al. | Mar 2004 | B2 |
6702564 | Foreman et al. | Mar 2004 | B2 |
6703169 | Fuller et al. | Mar 2004 | B2 |
6703462 | Lee | Mar 2004 | B2 |
6709257 | Foreman et al. | Mar 2004 | B2 |
6712331 | Foreman et al. | Mar 2004 | B2 |
6716566 | Aoshima | Apr 2004 | B2 |
6717181 | Murakami et al. | Apr 2004 | B2 |
6720125 | Nakamura et al. | Apr 2004 | B2 |
6726463 | Foreman | Apr 2004 | B2 |
6730454 | Pfeiffer et al. | May 2004 | B2 |
6730461 | Hunt et al. | May 2004 | B2 |
6737121 | Yang et al. | May 2004 | B2 |
6740685 | Li et al. | May 2004 | B2 |
6743856 | Hacker et al. | Jun 2004 | B1 |
6749765 | Rutter et al. | Jun 2004 | B2 |
6749860 | Tyrrell et al. | Jun 2004 | B2 |
6750308 | Andoh et al. | Jun 2004 | B2 |
6752613 | Foreman | Jun 2004 | B2 |
6756103 | Thompson et al. | Jun 2004 | B2 |
6756124 | Kanamori et al. | Jun 2004 | B2 |
6756520 | Krzysik et al. | Jun 2004 | B1 |
6758663 | Foreman et al. | Jul 2004 | B2 |
6767689 | Pavelchek et al. | Jul 2004 | B2 |
6770726 | Arkles et al. | Aug 2004 | B1 |
6773861 | Takashima et al. | Aug 2004 | B2 |
6773864 | Thackeray et al. | Aug 2004 | B1 |
6776094 | Whitesides et al. | Aug 2004 | B1 |
6777092 | Hayashi et al. | Aug 2004 | B1 |
6780498 | Nakata et al. | Aug 2004 | B2 |
6783468 | Sullivan et al. | Aug 2004 | B2 |
6787281 | Tao et al. | Sep 2004 | B2 |
6790024 | Foreman | Sep 2004 | B2 |
6794440 | Chen | Sep 2004 | B2 |
6797343 | Lee | Sep 2004 | B2 |
6800330 | Hayashi et al. | Oct 2004 | B2 |
6803034 | DuVal et al. | Oct 2004 | B2 |
6803168 | Padmanaban et al. | Oct 2004 | B1 |
6803476 | Rantala et al. | Oct 2004 | B2 |
6808381 | Foreman et al. | Oct 2004 | B2 |
6812551 | Hawker et al. | Nov 2004 | B2 |
6818289 | MacDougall et al. | Nov 2004 | B2 |
6819049 | Bohmer et al. | Nov 2004 | B1 |
6824879 | Baldwin et al. | Nov 2004 | B2 |
6824952 | Minsek et al. | Nov 2004 | B1 |
6825303 | Lee | Nov 2004 | B2 |
6831189 | Rantala et al. | Dec 2004 | B2 |
6832064 | Simpson et al. | Dec 2004 | B2 |
6838182 | Kropp et al. | Jan 2005 | B2 |
6840752 | Foreman et al. | Jan 2005 | B2 |
6844131 | Oberlander et al. | Jan 2005 | B2 |
6846614 | Timpe et al. | Jan 2005 | B2 |
6849209 | Minami et al. | Feb 2005 | B2 |
6849373 | Pavelchek et al. | Feb 2005 | B2 |
6849923 | Seta et al. | Feb 2005 | B2 |
6852421 | Wayton et al. | Feb 2005 | B2 |
6852766 | DeVoe | Feb 2005 | B1 |
6855466 | Pavelchek et al. | Feb 2005 | B2 |
6864040 | Müller et al. | Mar 2005 | B2 |
6867253 | Chen | Mar 2005 | B1 |
6869747 | Sabnis et al. | Mar 2005 | B2 |
6875005 | Foreman | Apr 2005 | B2 |
6875262 | Shibuya et al. | Apr 2005 | B1 |
6884568 | Timpe et al. | Apr 2005 | B2 |
6887644 | Nozaki et al. | May 2005 | B1 |
6887648 | Pavelchek et al. | May 2005 | B2 |
6888174 | Höhn et al. | May 2005 | B2 |
6890448 | Pavelchek | May 2005 | B2 |
6890605 | Nishikawa et al. | May 2005 | B2 |
6890855 | Cotte et al. | May 2005 | B2 |
6890865 | Yin et al. | May 2005 | B2 |
6891237 | Bao et al. | May 2005 | B1 |
6893245 | Foreman et al. | May 2005 | B2 |
6893797 | Munnelly et al. | May 2005 | B2 |
6896821 | Louellet | May 2005 | B2 |
6896955 | Mandal et al. | May 2005 | B2 |
6899988 | Kidnie et al. | May 2005 | B2 |
6900000 | Sabnis et al. | May 2005 | B2 |
6902771 | Shiota et al. | Jun 2005 | B2 |
6902861 | Tao et al. | Jun 2005 | B2 |
6908722 | Ebata et al. | Jun 2005 | B2 |
6909220 | Chen | Jun 2005 | B2 |
6911514 | Bublewitz et al. | Jun 2005 | B2 |
6914114 | Baldwin et al. | Jul 2005 | B2 |
6921578 | Tsujino et al. | Jul 2005 | B2 |
6924384 | Rantala et al. | Aug 2005 | B2 |
6942083 | Barnes et al. | Sep 2005 | B2 |
6942918 | MacDougall et al. | Sep 2005 | B2 |
6956097 | Kennedy et al. | Oct 2005 | B2 |
6962727 | Bedwell et al. | Nov 2005 | B2 |
6969753 | Baldwin et al. | Nov 2005 | B2 |
6974970 | Rantala et al. | Dec 2005 | B2 |
6984476 | Kobayashi et al. | Jan 2006 | B2 |
7001463 | Jones | Feb 2006 | B2 |
7011889 | Bedwell et al. | Mar 2006 | B2 |
7012125 | Kennedy et al. | Mar 2006 | B2 |
7014982 | Thackeray et al. | Mar 2006 | B2 |
7015061 | Lu et al. | Mar 2006 | B2 |
7015256 | Ito et al. | Mar 2006 | B2 |
7018717 | Pavelchek | Mar 2006 | B2 |
7026053 | Shiota et al. | Apr 2006 | B2 |
7026427 | Koehler et al. | Apr 2006 | B2 |
7056989 | Hwang et al. | Jun 2006 | B2 |
7060634 | Rantala et al. | Jun 2006 | B2 |
7074874 | Kobayashi et al. | Jul 2006 | B2 |
7081272 | Sasaki et al. | Jul 2006 | B2 |
7098346 | Rantala et al. | Aug 2006 | B2 |
7109519 | Gerlach | Sep 2006 | B2 |
7119354 | Yagihashi et al. | Oct 2006 | B2 |
7122880 | Peterson et al. | Oct 2006 | B2 |
7128944 | Becker et al. | Oct 2006 | B2 |
7128976 | Hayashi et al. | Oct 2006 | B2 |
7132473 | Ogihara et al. | Nov 2006 | B2 |
7135064 | Shibuya et al. | Nov 2006 | B2 |
7135223 | Tofuku et al. | Nov 2006 | B2 |
7144827 | Rantala et al. | Dec 2006 | B2 |
7153783 | Lu et al. | Dec 2006 | B2 |
7157503 | Wakamura | Jan 2007 | B2 |
7161019 | Rantala et al. | Jan 2007 | B2 |
7163751 | Wayton et al. | Jan 2007 | B2 |
7169477 | Lyu et al. | Jan 2007 | B2 |
7172913 | Lee et al. | Feb 2007 | B2 |
7173371 | Pang et al. | Feb 2007 | B2 |
7173372 | Koo et al. | Feb 2007 | B2 |
7176493 | So et al. | Feb 2007 | B2 |
7176535 | Chae | Feb 2007 | B2 |
7176994 | Maeda et al. | Feb 2007 | B2 |
7177000 | Hu et al. | Feb 2007 | B2 |
7179673 | Song et al. | Feb 2007 | B2 |
7179757 | Ramachandrarao et al. | Feb 2007 | B2 |
7180090 | Chen et al. | Feb 2007 | B2 |
7180198 | Kim | Feb 2007 | B2 |
7180559 | Chang et al. | Feb 2007 | B2 |
7180563 | Kim | Feb 2007 | B2 |
7180565 | Hong et al. | Feb 2007 | B2 |
7189490 | Kanagasabapathy et al. | Mar 2007 | B2 |
7189663 | Bao et al. | Mar 2007 | B2 |
7192910 | Wojtczak et al. | Mar 2007 | B2 |
7198823 | Lee et al. | Apr 2007 | B2 |
7202013 | Ogihara et al. | Apr 2007 | B2 |
7211365 | Barclay et al. | May 2007 | B2 |
7244960 | Spreitzer et al. | Jul 2007 | B2 |
7251404 | Shelnut et al. | Jul 2007 | B2 |
7251405 | Shelnut et al. | Jul 2007 | B2 |
7294585 | Peterson et al. | Nov 2007 | B2 |
7297464 | Sakurai et al. | Nov 2007 | B2 |
7303855 | Hatakeyama et al. | Dec 2007 | B2 |
7306892 | Barclay et al. | Dec 2007 | B2 |
7326442 | Babich et al. | Feb 2008 | B2 |
7338689 | Shin et al. | Mar 2008 | B2 |
7358025 | Hatakeyama | Apr 2008 | B2 |
7358300 | Sakurai et al. | Apr 2008 | B2 |
7361444 | Angelopoulos et al. | Apr 2008 | B1 |
7374812 | Mizuno | May 2008 | B2 |
7381441 | Leung et al. | Jun 2008 | B2 |
7381442 | Lu et al. | Jun 2008 | B2 |
7425347 | Takei et al. | Sep 2008 | B2 |
7445953 | Lu et al. | Nov 2008 | B2 |
7470634 | Shin et al. | Dec 2008 | B2 |
7517917 | Yim et al. | Apr 2009 | B2 |
7563844 | Osawa et al. | Jul 2009 | B2 |
7575809 | Glaubitt et al. | Aug 2009 | B2 |
7582360 | Wayton et al. | Sep 2009 | B2 |
7582412 | Cameron et al. | Sep 2009 | B2 |
7582718 | Lee et al. | Sep 2009 | B2 |
7595144 | Kishioka et al. | Sep 2009 | B2 |
7598168 | Han et al. | Oct 2009 | B2 |
7645404 | Paar et al. | Jan 2010 | B2 |
7648894 | Moon et al. | Jan 2010 | B2 |
7678462 | Kennedy et al. | Mar 2010 | B2 |
7682701 | Sakurai et al. | Mar 2010 | B2 |
7687590 | Sakurai et al. | Mar 2010 | B2 |
7709177 | Angelopoulos et al. | May 2010 | B2 |
7736833 | Angelopoulos et al. | Jun 2010 | B2 |
7820769 | Seifalian et al. | Oct 2010 | B2 |
7855043 | Ogihara et al. | Dec 2010 | B2 |
7915353 | Lee et al. | Mar 2011 | B2 |
8053159 | Li et al. | Nov 2011 | B2 |
8053173 | Lee et al. | Nov 2011 | B2 |
8080614 | Morita et al. | Dec 2011 | B2 |
8101015 | Kennedy et al. | Jan 2012 | B2 |
8188576 | Lee et al. | May 2012 | B2 |
8258502 | Yoshitake et al. | Sep 2012 | B2 |
8344088 | Kennedy et al. | Jan 2013 | B2 |
8475666 | Ramos et al. | Jul 2013 | B2 |
8569792 | Mitani et al. | Oct 2013 | B2 |
8652750 | Ogihara et al. | Feb 2014 | B2 |
8697828 | Li et al. | Apr 2014 | B2 |
8728710 | Sun | May 2014 | B2 |
8846828 | Sagawa et al. | Sep 2014 | B2 |
8859673 | Rutter et al. | Oct 2014 | B2 |
8871425 | Zhang et al. | Oct 2014 | B2 |
8889334 | Kennedy et al. | Nov 2014 | B2 |
8890139 | Ahn et al. | Nov 2014 | B2 |
8894877 | Detterbeck | Nov 2014 | B2 |
8895664 | Ko et al. | Nov 2014 | B2 |
8901268 | Krishnamoorthy et al. | Dec 2014 | B2 |
8906993 | Sekito et al. | Dec 2014 | B2 |
8911932 | Sun | Dec 2014 | B2 |
8916327 | Takei et al. | Dec 2014 | B2 |
8927681 | Wayton et al. | Jan 2015 | B2 |
8932702 | Philips et al. | Jan 2015 | B2 |
8961918 | Chang et al. | Feb 2015 | B2 |
8992806 | Li et al. | Mar 2015 | B2 |
9069133 | Baldwin et al. | Jun 2015 | B2 |
9158195 | Karkkainen | Oct 2015 | B2 |
20010006759 | Shipley et al. | Jul 2001 | A1 |
20010024685 | Boulton et al. | Sep 2001 | A1 |
20020020327 | Hayashi et al. | Feb 2002 | A1 |
20020031729 | Trefonas et al. | Mar 2002 | A1 |
20020034626 | Liu et al. | Mar 2002 | A1 |
20020034630 | Cano et al. | Mar 2002 | A1 |
20020068181 | Baldwin et al. | Jun 2002 | A1 |
20020074625 | Wang et al. | Jun 2002 | A1 |
20020090519 | Kursawe et al. | Jul 2002 | A1 |
20020095018 | Baldwin et al. | Jul 2002 | A1 |
20020102396 | MacDougall et al. | Aug 2002 | A1 |
20020102417 | Schutt et al. | Aug 2002 | A1 |
20020123592 | Zhang et al. | Sep 2002 | A1 |
20020127330 | Jin et al. | Sep 2002 | A1 |
20020128388 | Kennedy et al. | Sep 2002 | A1 |
20020169269 | Hwang et al. | Nov 2002 | A1 |
20020192981 | Fujii et al. | Dec 2002 | A1 |
20030003176 | Foreman et al. | Jan 2003 | A1 |
20030091838 | Hayashi et al. | May 2003 | A1 |
20030104225 | Shiota et al. | Jun 2003 | A1 |
20030105246 | Andoh et al. | Jun 2003 | A1 |
20030111748 | Foreman | Jun 2003 | A1 |
20030120018 | Baldwin et al. | Jun 2003 | A1 |
20030125430 | Adedeji et al. | Jul 2003 | A1 |
20030148228 | Toyoda et al. | Aug 2003 | A1 |
20030157311 | MacDougall et al. | Aug 2003 | A1 |
20030157340 | Shiota et al. | Aug 2003 | A1 |
20030157391 | Coleman et al. | Aug 2003 | A1 |
20030171729 | Kaun et al. | Sep 2003 | A1 |
20030176614 | Hacker et al. | Sep 2003 | A1 |
20030191269 | Ko et al. | Oct 2003 | A1 |
20030192638 | Yang et al. | Oct 2003 | A1 |
20030193624 | Kobayashi et al. | Oct 2003 | A1 |
20030198578 | Lee et al. | Oct 2003 | A1 |
20030199633 | Leon et al. | Oct 2003 | A1 |
20030224611 | Seta et al. | Dec 2003 | A1 |
20030227021 | Yamazaki et al. | Dec 2003 | A1 |
20030230548 | Sievert et al. | Dec 2003 | A1 |
20040020689 | Kagami et al. | Feb 2004 | A1 |
20040028915 | Shibuya et al. | Feb 2004 | A1 |
20040028918 | Becker et al. | Feb 2004 | A1 |
20040067436 | Kinsho et al. | Apr 2004 | A1 |
20040067437 | Wayton et al. | Apr 2004 | A1 |
20040072420 | Enomoto et al. | Apr 2004 | A1 |
20040072436 | RamachandraRao et al. | Apr 2004 | A1 |
20040077757 | Araki et al. | Apr 2004 | A1 |
20040087184 | Mandal et al. | May 2004 | A1 |
20040089238 | Birnbaum et al. | May 2004 | A1 |
20040091811 | Munnelly et al. | May 2004 | A1 |
20040096666 | Knox et al. | May 2004 | A1 |
20040110084 | Inomata et al. | Jun 2004 | A1 |
20040122197 | Putzer | Jun 2004 | A1 |
20040131979 | Li et al. | Jul 2004 | A1 |
20040166434 | Dammel et al. | Aug 2004 | A1 |
20040180011 | Schlosser | Sep 2004 | A1 |
20040180223 | Shibuya et al. | Sep 2004 | A1 |
20040201007 | Yagihashi et al. | Oct 2004 | A1 |
20040219372 | Ogihara et al. | Nov 2004 | A1 |
20040229158 | Meador et al. | Nov 2004 | A1 |
20040247900 | Ogihara et al. | Dec 2004 | A1 |
20040253461 | Ogihara et al. | Dec 2004 | A1 |
20040253532 | Wu et al. | Dec 2004 | A1 |
20040253535 | Cameron et al. | Dec 2004 | A1 |
20040258929 | Glaubitt et al. | Dec 2004 | A1 |
20050003215 | Hacker et al. | Jan 2005 | A1 |
20050003681 | Lyu et al. | Jan 2005 | A1 |
20050019842 | Prober et al. | Jan 2005 | A1 |
20050020837 | Doherty et al. | Jan 2005 | A1 |
20050026092 | Nagase | Feb 2005 | A1 |
20050032357 | Rantala et al. | Feb 2005 | A1 |
20050042538 | Babich et al. | Feb 2005 | A1 |
20050058929 | Kennedy et al. | Mar 2005 | A1 |
20050064726 | Reid et al. | Mar 2005 | A1 |
20050074689 | Angelopoulos et al. | Apr 2005 | A1 |
20050074981 | Meagley et al. | Apr 2005 | A1 |
20050077639 | Foreman et al. | Apr 2005 | A1 |
20050080214 | Shin et al. | Apr 2005 | A1 |
20050090570 | Lyu et al. | Apr 2005 | A1 |
20050092206 | Sakamoto et al. | May 2005 | A1 |
20050096408 | Wakamura | May 2005 | A1 |
20050106376 | Leung et al. | May 2005 | A1 |
20050119394 | Sakurai et al. | Jun 2005 | A1 |
20050136268 | Shin et al. | Jun 2005 | A1 |
20050136687 | Lu et al. | Jun 2005 | A1 |
20050171277 | Li et al. | Aug 2005 | A1 |
20050221225 | Kawana et al. | Oct 2005 | A1 |
20050234167 | Bae et al. | Oct 2005 | A1 |
20050245717 | Kennedy et al. | Nov 2005 | A1 |
20050255326 | Sakurai et al. | Nov 2005 | A1 |
20060027803 | Lu et al. | Feb 2006 | A1 |
20060035419 | Lu et al. | Feb 2006 | A1 |
20060046079 | Lee et al. | Mar 2006 | A1 |
20060047034 | Sakurai et al. | Mar 2006 | A1 |
20060052566 | Sakurai et al. | Mar 2006 | A1 |
20060057491 | Wayton et al. | Mar 2006 | A1 |
20060057801 | Rantala et al. | Mar 2006 | A1 |
20060110682 | Thackeray et al. | May 2006 | A1 |
20060115658 | Mah et al. | Jun 2006 | A1 |
20060127587 | Kang et al. | Jun 2006 | A1 |
20060131753 | Rantala et al. | Jun 2006 | A1 |
20060132459 | Huddleston et al. | Jun 2006 | A1 |
20060133756 | Shelnut et al. | Jun 2006 | A1 |
20060134441 | Mah et al. | Jun 2006 | A1 |
20060135633 | Lee et al. | Jun 2006 | A1 |
20060141163 | Choi et al. | Jun 2006 | A1 |
20060141641 | Fan et al. | Jun 2006 | A1 |
20060145306 | Lee et al. | Jul 2006 | A1 |
20060155594 | Almeida et al. | Jul 2006 | A1 |
20060159938 | Lee et al. | Jul 2006 | A1 |
20060175685 | Shin et al. | Aug 2006 | A1 |
20060205236 | Li et al. | Sep 2006 | A1 |
20060255315 | Yellowaga et al. | Nov 2006 | A1 |
20060257575 | Macor et al. | Nov 2006 | A1 |
20060258146 | Rantala et al. | Nov 2006 | A1 |
20060264595 | Lyu et al. | Nov 2006 | A1 |
20060286813 | Meredith et al. | Dec 2006 | A1 |
20060289849 | Yagihashi et al. | Dec 2006 | A1 |
20070004587 | Chebiam et al. | Jan 2007 | A1 |
20070018926 | Shin et al. | Jan 2007 | A1 |
20070020899 | Hirai et al. | Jan 2007 | A1 |
20070021025 | Kim et al. | Jan 2007 | A1 |
20070022909 | Kennedy et al. | Feb 2007 | A1 |
20070023837 | Lee et al. | Feb 2007 | A1 |
20070023864 | Khater | Feb 2007 | A1 |
20070024181 | Oh | Feb 2007 | A1 |
20070024766 | Song et al. | Feb 2007 | A1 |
20070024770 | Jang et al. | Feb 2007 | A1 |
20070024775 | Lee et al. | Feb 2007 | A1 |
20070024783 | Joo | Feb 2007 | A1 |
20070024788 | Kamiya et al. | Feb 2007 | A1 |
20070024790 | Chang et al. | Feb 2007 | A1 |
20070026104 | Nakano | Feb 2007 | A1 |
20070027225 | Lyu et al. | Feb 2007 | A1 |
20070029547 | Parker | Feb 2007 | A1 |
20070030407 | Kwak et al. | Feb 2007 | A1 |
20070030428 | Lu et al. | Feb 2007 | A1 |
20070030431 | Lee et al. | Feb 2007 | A1 |
20070030434 | Hirabayashi et al. | Feb 2007 | A1 |
20070030437 | Kim et al. | Feb 2007 | A1 |
20070034879 | Park et al. | Feb 2007 | A1 |
20070035225 | Lee et al. | Feb 2007 | A1 |
20070035673 | Sakurai et al. | Feb 2007 | A1 |
20070035675 | Um et al. | Feb 2007 | A1 |
20070051274 | Saito et al. | Mar 2007 | A1 |
20070088144 | Kang et al. | Apr 2007 | A1 |
20070111014 | Katsoulis et al. | May 2007 | A1 |
20070134435 | Ahn et al. | Jun 2007 | A1 |
20070197727 | Lewin et al. | Aug 2007 | A1 |
20080032052 | Kourtakis et al. | Feb 2008 | A1 |
20080157065 | Krishnamoorthy et al. | Jul 2008 | A1 |
20080185041 | Sharma et al. | Aug 2008 | A1 |
20080196626 | Wu | Aug 2008 | A1 |
20080206690 | Kennedy et al. | Aug 2008 | A1 |
20090004606 | Albaugh et al. | Jan 2009 | A1 |
20090029145 | Thies et al. | Jan 2009 | A1 |
20090068377 | Kuki | Mar 2009 | A1 |
20090087665 | Suzuki et al. | Apr 2009 | A1 |
20090101203 | Sharma | Apr 2009 | A1 |
20090146175 | Bahadur et al. | Jun 2009 | A1 |
20090264572 | Liao et al. | Oct 2009 | A1 |
20090275694 | Baldwin-Hendricks et al. | Nov 2009 | A1 |
20090298671 | Weigel et al. | Dec 2009 | A1 |
20100092763 | Kleiman-Shwarsctein et al. | Apr 2010 | A1 |
20100255412 | Sun | Oct 2010 | A1 |
20110117746 | Maruyama et al. | May 2011 | A1 |
20110135847 | Phillps et al. | Jun 2011 | A1 |
20110171447 | Krishnamoorthy et al. | Jul 2011 | A1 |
20110201827 | Lichtenhan et al. | Aug 2011 | A1 |
20110241175 | Koh et al. | Oct 2011 | A1 |
20120070689 | Kennedy et al. | Mar 2012 | A1 |
20120146088 | Tanikawa et al. | Jun 2012 | A1 |
20120196225 | Li | Aug 2012 | A1 |
20120237676 | Kalyankar et al. | Sep 2012 | A1 |
20130071560 | Rao | Mar 2013 | A1 |
20130131265 | Inoue | May 2013 | A1 |
20130164545 | Evans | Jun 2013 | A1 |
20130233826 | Seko et al. | Sep 2013 | A1 |
20130256264 | Tanaka et al. | Oct 2013 | A1 |
20140011932 | Ahn et al. | Jan 2014 | A1 |
20140335698 | Singh et al. | Nov 2014 | A1 |
20150041959 | Koh et al. | Feb 2015 | A1 |
20150050597 | Ahn et al. | Feb 2015 | A1 |
20150056457 | Kerstetter et al. | Feb 2015 | A1 |
20150073069 | De Gans et al. | Mar 2015 | A1 |
20150079792 | Shigaki et al. | Mar 2015 | A1 |
20150116827 | Wang et al. | Apr 2015 | A1 |
20150218410 | Matsubayashi et al. | Aug 2015 | A1 |
20150240126 | Wigglesworth et al. | Aug 2015 | A1 |
20150249167 | Zhang et al. | Sep 2015 | A1 |
20150294880 | Anderson et al. | Oct 2015 | A1 |
20160032147 | Maghsoodi et al. | Feb 2016 | A1 |
20160244581 | Brink et al. | Aug 2016 | A1 |
20170260419 | Iwamoto et al. | Sep 2017 | A1 |
Number | Date | Country |
---|---|---|
102566278 | Jul 2012 | CN |
104177619 | Dec 2014 | CN |
104262628 | Aug 2016 | CN |
106062042 | Oct 2016 | CN |
19852852 | May 2000 | DE |
0144880 | Jun 1985 | EP |
0152377 | Dec 1987 | EP |
0184248 | Aug 1989 | EP |
0229629 | Mar 1991 | EP |
0146411 | Jul 1991 | EP |
0217137 | Apr 1992 | EP |
0159428 | Nov 1992 | EP |
0204963 | Jan 1993 | EP |
0388503 | Sep 1993 | EP |
0323186 | Mar 1994 | EP |
0458651 | Mar 1994 | EP |
0225676 | Jul 1994 | EP |
0327311 | Sep 1994 | EP |
0401499 | Dec 1995 | EP |
0422570 | Dec 1995 | EP |
0427395 | Apr 1996 | EP |
0449263 | Jun 1996 | EP |
0725103 | Aug 1996 | EP |
0727711 | Aug 1996 | EP |
0494744 | Sep 1996 | EP |
0423446 | Mar 1998 | EP |
0659904 | Jul 1998 | EP |
0881678 | Dec 1998 | EP |
0911875 | Apr 1999 | EP |
0669010 | Jun 2000 | EP |
0902067 | Jul 2001 | EP |
0851300 | Oct 2001 | EP |
1149412 | Oct 2001 | EP |
0687004 | Dec 2002 | EP |
1046689 | Jun 2003 | EP |
1142832 | Dec 2004 | EP |
1376671 | Jun 2007 | EP |
1829945 | Sep 2007 | EP |
1674904 | Dec 2008 | EP |
1296365 | Sep 2010 | EP |
1659423 | Jan 2011 | EP |
1316144 | May 1973 | GB |
385241 | Feb 1975 | GB |
601288 | Oct 1981 | GB |
S63191868 | Aug 1988 | JP |
H03257027 | Nov 1991 | JP |
4021438 | Jan 1992 | JP |
H0570738 | Mar 1993 | JP |
H08208840 | Aug 1996 | JP |
2001092122 | Apr 2001 | JP |
2001152023 | Jun 2001 | JP |
4697363 | Feb 2002 | JP |
2002129103 | May 2002 | JP |
4862217 | Aug 2002 | JP |
2002235037 | Aug 2002 | JP |
2003050459 | Feb 2003 | JP |
2003064306 | Mar 2003 | JP |
2003064307 | Mar 2003 | JP |
2003183575 | Jul 2003 | JP |
2003253204 | Sep 2003 | JP |
2003257963 | Sep 2003 | JP |
2004277501 | Oct 2004 | JP |
2005042118 | Feb 2005 | JP |
2005048190 | Feb 2005 | JP |
2005072615 | Mar 2005 | JP |
2005099693 | Apr 2005 | JP |
2005105281 | Apr 2005 | JP |
2005105282 | Apr 2005 | JP |
2005105283 | Apr 2005 | JP |
2005105284 | Apr 2005 | JP |
2005136429 | May 2005 | JP |
2005139265 | Jun 2005 | JP |
2005146282 | Jun 2005 | JP |
2006045352 | Feb 2006 | JP |
2006182811 | Jul 2006 | JP |
2006183028 | Jul 2006 | JP |
2006183029 | Jul 2006 | JP |
2006213908 | Aug 2006 | JP |
2006241407 | Sep 2006 | JP |
2006249181 | Sep 2006 | JP |
2006276598 | Oct 2006 | JP |
4563894 | Mar 2007 | JP |
2007254677 | Oct 2007 | JP |
200833016 | Feb 2008 | JP |
4564735 | Oct 2010 | JP |
2010532792 | Oct 2010 | JP |
4922292B2 | Apr 2012 | JP |
2012222202 | Nov 2012 | JP |
2014208838 | Nov 2014 | JP |
2015146332 | Aug 2015 | JP |
2015155541 | Aug 2015 | JP |
100845403 | Jul 2008 | KR |
101113037 | Jan 2010 | KR |
20110074677 | Jul 2011 | KR |
1020110074677 | Jul 2011 | KR |
101390605 | Apr 2014 | KR |
101492251 | Dec 2014 | KR |
1026211 | Jul 2017 | KR |
WO1990003598 | Apr 1990 | WO |
WO2000031183 | Jun 2000 | WO |
WO2000041231 | Jul 2000 | WO |
WO2000077575 | Dec 2000 | WO |
WO0124244 | Apr 2001 | WO |
WO0129052 | Apr 2001 | WO |
WO2001029052 | Apr 2001 | WO |
WO2002006402 | Jan 2002 | WO |
WO2002016477 | Feb 2002 | WO |
WO2003044077 | May 2003 | WO |
WO2003044078 | May 2003 | WO |
WO2003044600 | May 2003 | WO |
WO2003088343 | Oct 2003 | WO |
WO2003088344 | Oct 2003 | WO |
WO2003089992 | Oct 2003 | WO |
WO2004044025 | May 2004 | WO |
WO2003070809 | Jul 2004 | WO |
2004101651 | Nov 2004 | WO |
WO2005036270 | Apr 2005 | WO |
WO2005037907 | Apr 2005 | WO |
WO2005049757 | Jun 2005 | WO |
WO2005080629 | Sep 2005 | WO |
WO2006128232 | Dec 2006 | WO |
2008124711 | Oct 2008 | WO |
WO2009038250 | Mar 2009 | WO |
WO2010079495 | Jul 2010 | WO |
2014152686 | Sep 2014 | WO |
2015026652 | Feb 2015 | WO |
Entry |
---|
International Search Report and Written Opinion issued in PCT/US2016/020373, dated Jun. 17, 2016, 9 pages. |
Katayama, M. “TFT-LCD Technology.” Elsevier, Thin Solid Films, 341:140-147, 1999. |
Matsumura, Hideki. “Silicon Nitride Produced by Catalytic Chemical Vapor Deposition Method.” Journal of Applied Physics, 66:3612-3617, 1989. |
Mok, T.S., et al. “Study of Process Dependent Reliability in SiOC Dielectric Interconnects and Film.” IEEE, Proceedings of 11th IPFA 2004, Taiwan, pp. 181-184. |
Ogawa, E. T., et al. “Stress-Induced Voiding Under Vias Connected to Wide Cu Metal Leads.” IEEE, 40th Annual International Reliability Physics Symposium, Dallas, Texas, 2012, pp. 312-321. |
Ruelke, Hartmut, et al. “Implementation of CVD low-k dielectrics for high-volume production.” Solid State Technology, Copper/Low-K, Jan. 2004, pp. 60-63. |
Hogan, Zach L., et al. “Patterned Nanoporous Poly(Methylsilsesquioxane) Thin Films: A Potential High Density Substrate.” Materials Science and Engineering, C 24:487-490, 2004. |
International Preliminary Report on Patentability issued in PCT/US2016/020373, dated Oct. 26, 2017, 8 pages. |
International Search Report and Written Opinion issued in PCT/US20171020652, dated Jul. 17, 2017, 12 pages. |
Kim, B.R., et al. “Adhesion Properties of Polymethylsilsesquioxane Based Low Dielectric Constant Materials by the Modified Edge Lift-Off Test.” Microelectronic Engineering, 85:74-80, 2008. |
Kim, Hie-Joon, et al. “Observation of Low Molecular Weight Poly(methylsilsesquioxane)s by Graphite Plate Laser Desorption/Ionization Time-of-Flight Mass Spectrometry.” Anal. Chem., 72:5673-5678, 2000. |
Lee, Jin-Kyu, et al. “Synthetic Control of Molecular Weight and Microstructure of Processible Poly(Methylsilsesquioxane)s for Low-Dielectric Thin Film Applications.” Polymer, 42:9085-9089, 2001. |
Saviour A. Umoren et al., “Polymer Characterization: Polymer Molecular Weight Determination”, Polymer Science: research advances, practical applications and educational aspects, Formatex Research Center S.L.; 1 edition (Jun. 14, 2016), pp. 412-419. |
Supplemental European Search Report issued in EP application 16780418.6, dated Apr. 17, 2018, 7 pages. |
Number | Date | Country | |
---|---|---|---|
20180022957 A1 | Jan 2018 | US |
Number | Date | Country | |
---|---|---|---|
62146593 | Apr 2015 | US |