The invention generally relates to coatings for integrated circuits or other electronics packages. The invention also relates generally to methods of providing such coatings.
Conventionally integrated circuits are designed for use in relatively benign environments such as desktop PC's, cell phones, and the like. When these integrated circuit technologies are used in more demanding environments such as avionics they may experience excessively high failure rates due to the higher operating temperature, corrosion, etc. In addition, due to the sensitive nature of the information that may be stored on these components, it may be necessary to protect these devices from reverse engineering in the event that a system containing them were to fall into unfriendly hands. Modifying integrated circuits to improve their thermal performance, corrosion resistance, and tamper resistance is typically very expensive and can be detrimental to reliability.
Therefore, what is needed is a low-cost, simple method for making commercial integrated circuits more suitable for use in harsh environments. Further, what is needed is a low-cost coating for an integrated circuit which provides resistance to damage in harsh environments.
The techniques herein below extend to those embodiments which fall within the scope of the appended claims, regardless of whether they accomplish one or more of the above-mentioned needs.
What is provided is an electronics package. The electronics package comprises a substrate and at least one electronic component coupled to the substrate. The electronics package also comprises an alkali silicate coating forming a hermetic seal around at least a portion of the at least one electronic component.
What is also provided is a method of forming an electronics package. The method comprises providing at least one electronic component. The method further comprises mixing an alkali silicate material with water, micro, and or nano particles and depositing the coating onto the electronic component. Further still, the method comprises curing the alkali silicate material.
What is also provided is an electronics package. The electronics package comprises a substrate and at least one electronic component coupled to the substrate. The electronics package also comprises a low curing temperature glass coating forming a hermetic seal around at least a portion of the at least one electronic component.
Further, what is provided is a method of forming an electronics package. The method comprises providing at least one electronic component and mixing a low curing temperature glass solution with water, micro and or nano particles. The method further comprises depositing the coating onto the electronic component and curing the glass material.
Alternative exemplary embodiments relate to other features and combination of features as may be generally recited in the claims.
A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments by way of example only, in which the principles of the invention are utilized, and the accompanying drawings, of which:
Before describing in detail the particular improved system and method, it should be observed that the invention includes, but is not limited to a novel structural combination of conventional data/signal processing components and communications circuits, and not in the particular detailed configurations thereof. Accordingly, the structure, methods, functions, control and arrangement of conventional components and circuits have, for the most part, been illustrated in the drawings by readily understandable block representations and schematic diagrams, in order not to obscure the disclosure with structural details which will be readily apparent to those skilled in the art, having the benefit of the description herein. Further, the invention is not limited to the particular embodiments depicted in the exemplary diagrams, but should be construed in accordance with the language in the claims.
In accordance with an exemplary embodiment, low processing temperature hermetic glass coatings for microelectronics packaging are desirable for hermetically sealing the packaging as well as providing resistance to corrosion and high temperature. These glass coatings are applied and cured at low temperatures, typically ≦100° C. and produce tightly adhering hermetic (water impermeable) coatings capable of withstanding very high temperatures, theoretically up to ˜700° C. These glass coatings may be composed of alkali silicate glass with nanoparticle modifiers, including, but not limited to, nano calcium carbonate, nano zinc oxide and nano silicon dioxide. Aqueous alkali silicate composite solutions applied on or between surfaces of materials, dry to form a tough, tightly adhering inorganic bond that exhibits many desirable characteristics. Additionally, these solutions can be mixed with high thermal conductivity particles, such as, but not limited to, diamond, aluminum nitride, beryllium oxide, or metals to produce high thermal conductivity coatings for heat spreading.
Alkali silicate glasses are produced by fusing varying portions of sand (SiO2) and alkali carbonate, (M2CO3) at high temperatures, between 1000-1500° C. The resulting product, upon cooling from its molten state, is an amorphous glass that can, under the appropriate processing conditions (temperature and pressure), be dissolved into water to produce liquid alkali silicate solutions. In accordance with an exemplary embodiment the glass is mixed with deionized water. The proportion of SiO2 to M2O is typically defined as the weight ratio. The solution viscosity can be controlled by the concentration of water.
Alkali silicates, in general, are economical, environmentally friendly chemicals which have been used to protect a variety of materials from the corrosive effects of water. These chemicals are classified as corrosion inhibitors because they can deposit protective silicate rich films, isolating materials from corrosive attack. Additionally, they raise the pH of water which can make it less corrosive to metals. Studies have shown that alkali silicates are reactive with cationic metals and metal surfaces. This is the basis by which silicates inhibit corrosion, as illustrated in
Liquid alkali silicate solutions are commercially available in a variety of SiO2/M2O ratios. Typically, ratios of 3.25 down to 1 can be obtained in aqueous or powder form. Highly siliceous liquid alkali silicate solutions tend to air dry rapidly, are the most refractory (high melting temperature), and are the most resistant to acids and corrosion. These silica rich liquid solutions tend to contain more water than the alkaline rich solutions (per similar viscosity), and thus undergo greater shrinkage while curing. Low ratio, alkaline rich, solutions tend to have greater elasticity, lower brittleness, and less shrinkage but may exhibit poor corrosion resistance. These low ratio coatings also dry more slowly because their alkali content creates a greater affinity for water. Many chemically resistant cements and mortars are produced using high ratio (N˜3.25) alkali silicate solutions. In order for the silicate coatings to become impermeable and relatively insoluble, water must be completely removed. Air drying alone is usually not adequate for coatings which will be exposed to weather or high moisture environments. For these applications heat curing is often needed. Curing temperatures between 95 and 100° C. are often sufficient for adequate dehydration.
It is desirable to use highly corrosion resistant coatings in microelectronics packaging. While off-the-shelf alkali silicate solutions applied and processed in an appropriate manner could potentially provide a temporary hermetic barrier for microelectronic devices, they may not hold up in harsh testing environments, such as those produced during Highly Accelerated Stress Testing (HAST). In order to produce highly corrosion resistant coatings, modifiers must be added to the base alkali silicate solutions. Studies have shown that adding colloidal silicon dioxide to liquid alkali silicates can produce coatings that are comparable to that of current chromium based passivation, as characterized by salt spray testing. The purpose of these coatings is to protect steel and other metals from environmental corrosion. While a broad range of alkali silicate compositions may be used, highly silica rich coatings (R≧3.25) are the most corrosion resistant. These high ratio solutions can be made by adding additional SiO2 to the base alkali silicate. However, these silica rich coatings often crack during the curing process. This cracking may be avoided by applying the appropriate solution mixture, thickness, and using an appropriate curing process, all of which may be application specific. Successful silicate rich coatings (R≧4) have been applied to the surfaces of silicon die and other inorganic substrates, which can be cured quickly, are crack free, and possess excellent adhesion strength and durability. These silica enhanced alkali silicate solutions provide improved corrosion resistance, but they can be made more corrosion resistant with the addition of calcium carbonate and or zinc oxide. Silicate solutions can react with calcium to form insoluble calcium-silicate compounds. Similarly, zinc oxide has been used to produce silicate coatings that are actually capable of shedding water. In order to achieve good mixing and dispersion, nano-sized particles of these constituents may be used in the coatings described herein. The large surface area per weight of the nanoparticles helps to maximize silicate glass modification for improved corrosion resistance of the composite.
It has been shown that increasing the silicate ratio, for alkali silicate glass coatings, may lead to cracking in thick coatings.
In an exemplary lab test, a particular amount of cracking was observed in thick silica rich (R=3.22) coatings, whereas no or little cracking was seen in the alkali rich coatings. In the silica rich coating, delamination was observed around the periphery and significant cracking throughout. When this same solution is applied in the appropriate thickness, a much stronger, crack free, fast curable coating can be formed. Such coatings have been applied to copper clad PCB substrates, aluminum and copper metals, and silicon die. These coatings are thin (<2 microns), but can be applied in multiple layers to build up the thickness. It has been observed that even these very thin coatings can provide a rugged moisture barrier at high temperatures (≧450° C.). The corrosion protection of silicate coating applied to a copper clad PCB board has been demonstrated.
When compared with conventional silicon Room Temperature Vulcanizing (RTV) (polymer) coatings, very little oxidation protection is seen while the alkali silicate glass coating provided a hermetic seal.
In another exemplary embodiment, silica rich coatings may be applied to wire bonded dies. The purpose of the coatings is to prevent galvanic corrosion at the wire bond/pad interface, a primary failure mechanism in these devices. Preventing this galvanic corrosion leads to significantly greater reliability and can potentially eliminate the need for hermetic packaging.
In an exemplary and non-limiting embodiment, the alkali silicate glass coated wire bond pads may be formed by applying alkali silicate solutions onto chip surfaces then quickly curing at 150° C. for 5 minutes. Multiple layers may be applied to each of the coated wire bonds. The result of the coating process has been exemplary shown that the shear strength of coated joints were up to a 25% stronger than uncoated joints. Additionally, pull testing has shown no ball lifts (i.e. there were no separations between ball and pad) in the testing environment.
In addition to thin coatings, composites may be made by mixing the silicate solutions with high thermal conductivity particles such as aluminum nitride, beryllium oxide, diamond, and or metals. These coatings have been found to significantly improve heat transfer when coated over power dissipating devices. For example, thermal improvements in these coated devices are shown in
Referring to
In a further exemplary embodiment, the addition of nanoparticles to the alkali silicate glass thermal composites provides additional corrosion resistance.
In an alternative exemplary embodiment, a low temperature bonding (LTB) solution, a proprietary composition, available from SCHOTT North America, Inc. may also be used.
In accordance with exemplary embodiments, numerous ways may be applied in which to provide heat and corrosion resistance to microelectronics packages. These are detailed below and include but are not limited to the following:
Coating bare dies that have been wire bonded or flip chip attached with a coating to form a hermetic glass barrier over the electronics. The coated device could then presumably be encapsulated using standard processing methods. The coating would be a thin layer of glass (≧100 nm) that will provide a hermetic seal to the die and therefore protect it from corrosive elements. For example,
Adding particles to the coating to make it opaque and then coating the solution onto a wire bonded or flip chip die. Thus, the coating would provide tamper resistance to the device without exposing it to high processing temperatures. An illustration of this is shown in
Adding high thermal conductivity particles, such as diamond, beryllium oxide, and or aluminum nitride to the coating prior to applying it to a wire bonded or flip chip die. The resulting coating (or paste) over the die may possess a very high thermal conductivity without creating an electrically conductive path. Thus, hot spots on the die could be easily spread over the entire die surface and conceivably to the boar to which the component is attached.
Using high thermal conductivity “filled” coating solution for creating low cost thermal bridges between high temperature components or power dissipating die and thermal sinks. The solution may be applied and cured at low temperature (≦100° C.). High thermal conductivity particles such as aluminum nitride, beryllium oxide, and or diamond (thermal conductivity near 2000 W/mK) can be used in this application to provide a highly thermally conducting path. See
Adding a coefficient of thermal expansion (CTE) matching filler, such as glass or ceramics, to the coating liquid to increase the bond layer thickness so that the solution can be used as an underfill for flip chip devices. This may provide both tamper resistance protection to the die while improving its thermal cycle and shock loading reliability as do many other underfills. Another advantage to this configuration is that these coatings may provide a high-temperature underfill solution (>700° C.). Current underfills are limited to relatively low operating temperatures (≦200° C.). An illustration of this is shown in
Use these coatings to create 3D wire bondable or flip chip stacked IC's. These coatings provide a unique high-temperature (>200° C.) solution for chip stacking. The coating bond layer thickness can be made as thin as 100 nm, allowing for the thinnest possible interface formed at low temperature. The coating bonds are very strong and rigid allowing the possibility of wire bonding at higher stack levels without stack compliance (smashing) causing problems. The thinner bonding layers would decrease thermal resistance, thus improving heat transfer. High thermal conductivity particles may also be added to improve heat transfer. The majority of chip or wafer stacking adhesives are not hermetic, which can lead to corrosion and degradation of the bonding interface over time. See
Applying coating over high frequency electronic components to create a low dielectric coating (Er=3 to 10) to improve RF performance. These devices may then be encapsulated using standard methods and encapsulants to improve their reliability and handling characteristics without degrading their electrical performance. See
While the detailed drawings, specific examples, and particular formulations given described exemplary embodiments, they serve the purpose of illustration only. It should be understood that various alternatives to the embodiments of the invention described maybe employed in practicing the invention. It is intended that the following claims define the scope of the invention and that structures within the scope of these claims and their equivalents be covered thereby. The hardware and software configurations shown and described may differ depending on the chosen performance characteristics and physical characteristics of the computing and analysis devices. For example, the type of computing device, communications bus, or processor used may differ. The systems shown and described are not limited to the precise details and conditions disclosed. Method steps provided may not be limited to the order in which they are listed but may be ordered any way as to carry out the inventive process without departing from the scope of the invention. Furthermore, other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangements of the exemplary embodiments without departing from the scope of the invention as expressed in the appended claims.
This application is a divisional of U.S. application Ser. No. 11/508,782 filed Aug. 23, 2006, which is herein incorporated by reference in its entirety.
Number | Name | Date | Kind |
---|---|---|---|
3170813 | Duncan et al. | Feb 1965 | A |
3508974 | Bressler | Apr 1970 | A |
3654528 | Barkan | Apr 1972 | A |
3723790 | Dumbaugh et al. | Mar 1973 | A |
3812404 | Barkan et al. | May 1974 | A |
3830892 | Wada | Aug 1974 | A |
4177015 | Davidson | Dec 1979 | A |
4294658 | Humphreys et al. | Oct 1981 | A |
4410874 | Scapple et al. | Oct 1983 | A |
4505644 | Meisner et al. | Mar 1985 | A |
4512808 | Pesch et al. | Apr 1985 | A |
4513029 | Sakai | Apr 1985 | A |
4560084 | Wolfson | Dec 1985 | A |
4572924 | Wakely et al. | Feb 1986 | A |
4622433 | Frampton | Nov 1986 | A |
4678868 | Kraska et al. | Jul 1987 | A |
4761518 | Butt et al. | Aug 1988 | A |
4765948 | Deluca et al. | Aug 1988 | A |
4773826 | Mole | Sep 1988 | A |
4802531 | Nathenson et al. | Feb 1989 | A |
4882212 | Singhdeo et al. | Nov 1989 | A |
4940858 | Taylor et al. | Jul 1990 | A |
4963503 | Aoki et al. | Oct 1990 | A |
5041342 | Umeda et al. | Aug 1991 | A |
5136365 | Pennisi et al. | Aug 1992 | A |
5140109 | Matsumoto et al. | Aug 1992 | A |
5184211 | Fox | Feb 1993 | A |
5195231 | Fanning et al. | Mar 1993 | A |
5232970 | Solc et al. | Aug 1993 | A |
5244726 | Laney et al. | Sep 1993 | A |
5265136 | Yamazaki et al. | Nov 1993 | A |
5288769 | Papageorge et al. | Feb 1994 | A |
5315155 | O'Donnelly et al. | May 1994 | A |
5405808 | Rostoker et al. | Apr 1995 | A |
5502889 | Casson et al. | Apr 1996 | A |
5581286 | Hayes et al. | Dec 1996 | A |
5650759 | Hittman et al. | Jul 1997 | A |
5686703 | Yamaguchi | Nov 1997 | A |
5690837 | Nakaso et al. | Nov 1997 | A |
5702963 | Vu et al. | Dec 1997 | A |
5863605 | Bak-Boychuk et al. | Jan 1999 | A |
5916944 | Camilletti et al. | Jun 1999 | A |
5958794 | Bruxvoort et al. | Sep 1999 | A |
5965947 | Nam et al. | Oct 1999 | A |
5991351 | Woolley | Nov 1999 | A |
6010956 | Takiguchi et al. | Jan 2000 | A |
6019165 | Batchelder | Feb 2000 | A |
6021844 | Batchelder | Feb 2000 | A |
6027791 | Higashi et al. | Feb 2000 | A |
6028619 | Saita et al. | Feb 2000 | A |
6039896 | Miyamoto et al. | Mar 2000 | A |
6048656 | Akram et al. | Apr 2000 | A |
6087018 | Uchiyama | Jul 2000 | A |
6110656 | Eichorst et al. | Aug 2000 | A |
6121175 | Drescher et al. | Sep 2000 | A |
6124224 | Sridharan et al. | Sep 2000 | A |
6159910 | Shimizu et al. | Dec 2000 | A |
6356334 | Mathew et al. | Mar 2002 | B1 |
6370015 | Noda et al. | Apr 2002 | B2 |
6423415 | Greene et al. | Jul 2002 | B1 |
6451283 | Kuznicki et al. | Sep 2002 | B1 |
6452090 | Takato et al. | Sep 2002 | B2 |
6486087 | Saling et al. | Nov 2002 | B1 |
6496359 | Clark et al. | Dec 2002 | B2 |
6541083 | Landa et al. | Apr 2003 | B1 |
6541832 | Coyle | Apr 2003 | B2 |
6586087 | Young | Jul 2003 | B2 |
6586675 | Bealka et al. | Jul 2003 | B1 |
6599643 | Heimann et al. | Jul 2003 | B2 |
6617041 | Hahn et al. | Sep 2003 | B2 |
6624276 | Lamers et al. | Sep 2003 | B2 |
6658861 | Ghoshal et al. | Dec 2003 | B1 |
6663793 | Parkhill et al. | Dec 2003 | B2 |
6664567 | Kyoda et al. | Dec 2003 | B2 |
6665186 | Calmidi et al. | Dec 2003 | B1 |
6708501 | Ghoshal et al. | Mar 2004 | B1 |
6768629 | Allen et al. | Jul 2004 | B1 |
6798072 | Kajiwara et al. | Sep 2004 | B2 |
6800326 | Uchiyama | Oct 2004 | B1 |
6800330 | Hayashi et al. | Oct 2004 | B2 |
6844023 | Schulman et al. | Jan 2005 | B2 |
6918984 | Murray et al. | Jul 2005 | B2 |
6960878 | Sakano et al. | Nov 2005 | B2 |
6986859 | Mazany et al. | Jan 2006 | B2 |
7045905 | Nakashima | May 2006 | B2 |
7078263 | Dean | Jul 2006 | B2 |
7114251 | Mashino | Oct 2006 | B2 |
7131286 | Ghoshal et al. | Nov 2006 | B2 |
7175937 | Cho et al. | Feb 2007 | B2 |
7176564 | Kim | Feb 2007 | B2 |
7202598 | Juestel et al. | Apr 2007 | B2 |
7265977 | Martin et al. | Sep 2007 | B2 |
7293416 | Ghoshal | Nov 2007 | B2 |
7296417 | Ghoshal | Nov 2007 | B2 |
7297206 | Naruse et al. | Nov 2007 | B2 |
7307286 | Ito et al. | Dec 2007 | B2 |
7327039 | Charles et al. | Feb 2008 | B2 |
7340904 | Sauciuc et al. | Mar 2008 | B2 |
7342787 | Bhatia | Mar 2008 | B1 |
7348665 | Sauciuc et al. | Mar 2008 | B2 |
7365984 | Jeong | Apr 2008 | B2 |
7391060 | Oshio | Jun 2008 | B2 |
7441087 | Hakura et al. | Oct 2008 | B2 |
7473460 | Meguro et al. | Jan 2009 | B2 |
7491431 | Chiruvolu et al. | Feb 2009 | B2 |
7497961 | Keenan et al. | Mar 2009 | B2 |
7651556 | Komiyama et al. | Jan 2010 | B2 |
7671468 | Kanazawa et al. | Mar 2010 | B2 |
7692259 | Suehiro | Apr 2010 | B2 |
7709093 | Makowski et al. | May 2010 | B2 |
7737356 | Goldstein | Jun 2010 | B2 |
7910403 | Hirano et al. | Mar 2011 | B2 |
7915527 | Lower et al. | Mar 2011 | B1 |
7985392 | Hayashi et al. | Jul 2011 | B2 |
8017872 | Cripe et al. | Sep 2011 | B2 |
8075185 | Hecht et al. | Dec 2011 | B2 |
8076185 | Lower et al. | Dec 2011 | B1 |
8084855 | Lower et al. | Dec 2011 | B2 |
8119040 | Lower et al. | Feb 2012 | B2 |
8174830 | Lower et al. | May 2012 | B2 |
8581108 | Boone et al. | Nov 2013 | B1 |
8617913 | Lower et al. | Dec 2013 | B2 |
20010015443 | Komoto | Aug 2001 | A1 |
20010030493 | Noda et al. | Oct 2001 | A1 |
20010033012 | Kommerling et al. | Oct 2001 | A1 |
20020054976 | Nakamura et al. | May 2002 | A1 |
20020076192 | Bartholomew et al. | Jun 2002 | A1 |
20020189894 | Davis et al. | Dec 2002 | A1 |
20030218258 | Charles et al. | Nov 2003 | A1 |
20040194667 | Reuscher | Oct 2004 | A1 |
20050099775 | Pokharna et al. | May 2005 | A1 |
20050116237 | Voutsas | Jun 2005 | A1 |
20050133863 | Werner et al. | Jun 2005 | A1 |
20060017069 | Bergmann et al. | Jan 2006 | A1 |
20060045755 | McDonald et al. | Mar 2006 | A1 |
20060068218 | Hooghan et al. | Mar 2006 | A1 |
20060113066 | Mongia et al. | Jun 2006 | A1 |
20060135342 | Anderson et al. | Jun 2006 | A1 |
20060210790 | Horio et al. | Sep 2006 | A1 |
20060250731 | Parkhurst et al. | Nov 2006 | A1 |
20060283546 | Tremel et al. | Dec 2006 | A1 |
20070102833 | Hack et al. | May 2007 | A1 |
20070108586 | Uematsu et al. | May 2007 | A1 |
20080006204 | Rusinko et al. | Jan 2008 | A1 |
20080063875 | Robinson et al. | Mar 2008 | A1 |
20080299300 | Wilcoxon et al. | Dec 2008 | A1 |
20090110904 | Mack et al. | Apr 2009 | A1 |
20090183774 | Atanackovic | Jul 2009 | A1 |
20090279257 | Lower et al. | Nov 2009 | A1 |
20100064518 | Lower et al. | Mar 2010 | A1 |
20100064695 | Wilcoxon et al. | Mar 2010 | A1 |
20100065256 | Wilcoxon et al. | Mar 2010 | A1 |
20100066178 | Lower et al. | Mar 2010 | A1 |
20120118623 | Lower et al. | May 2012 | A1 |
Number | Date | Country |
---|---|---|
55-120083 | Sep 1980 | JP |
57-027942 | Feb 1982 | JP |
60-013875 | Jan 1985 | JP |
02-064071 | Mar 1990 | JP |
11-095246 | Apr 1994 | JP |
2003-332505 | Nov 2003 | JP |
2006-045420 | Feb 2006 | JP |
WO2006095677 | Sep 2006 | WO |
Entry |
---|
Notice of Allowance for U.S. Appl. No. 12/493,022, mail date Sep. 20, 2012, 5 pages. |
Notice of Allowance for U.S. Appl. No. 11/732,982, mail date Nov. 8, 2012, 8 pages. |
Office Action for U.S. Appl. No. 13/359,105, mail date May 8, 2012, 12 pages. |
Office Action for U.S. Appl. No. 12/240,775, mail date Sep. 6, 2012, 9 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date Sep. 25, 2012, 16 pages. |
Office Action for U.S. Appl. No. 13/359,105, mail date Oct. 19, 2012, 7 pages. |
Advisory Action for U.S. Appl. No. 11/959,225, mail date Jul. 31, 2012, 3 pages. |
Advisory Action for U.S. Appl. No. 12/240,775, mail date Nov. 14, 2012, 2 pages. |
Amendment and Reply for U.S. Appl. No. 11/732,982, mail date Oct. 25, 2010, 6 pages. |
Amendment and Reply for U.S. Appl. No. 11/732,982, mail date Sep. 28, 2012, 7 pages. |
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Jul. 5, 2011, 6 pages. |
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Jun. 25, 2012, 14 pages. |
Amendment and Reply for U.S. Appl. No. 12/240,775, mail date Jul. 2, 2012, 12 pages. |
Amendment and Reply for U.S. Appl. No. 12/240,775, mail date Nov. 6, 2012, 8 pages. |
Amendment and Reply for U.S. Appl. No. 12/493,022, mail date Aug. 28, 2012, 7 pages. |
Amendment and Reply for U.S. Appl. No. 12/493,022, mail date Mar. 23, 2012, 3 pages. |
Notice of Allowance for U.S. Appl. No. 11/732,982, mail date Dec. 19, 2012, 2 pages. |
Office Action for U.S. Appl. No. 13/359,105, mail date Jan. 17, 2013, 7 pages. |
Request for Continued Examination for U.S. Appl. No. 11/959,225, mail date Aug. 27, 2012, 19 pages. |
Restriction Requirement for U.S. Appl. No. 11/732,982, mail date Sep. 24, 2010, 5 pages. |
Restriction Requirement for U.S. Appl. No. 12/493,022, mail date Feb. 22, 2012, 6 pages. |
Restriction Requirement for U.S. Appl. No. 13/329,068, mail date Jan. 15, 2013, 5 pages. |
U.S. Appl. No. 11/732,982, filed Apr. 5, 2007, Boone et al. |
U.S. Appl. No. 11/959,225, filed Dec. 18, 2007, Lower et al. |
Click et al., Schott Low Temperature Bonding for Precision Optics, http://optics.nasa.gov/tech—days/tech—days—2004/docs/18%20Aug%202004/23%20Schott%20Low%20Temperature%20Bonding.pdf, 20 pages. |
Golubev et al., Modeling of Acid Base Properties of Binary Alkali-Silicate Melts, 2004, http://www.ipme.ru/e-journals/RAMS/no—1604/golubev/golubev.pdf, 8 pages. |
Kennedy, Strength and Fracture Toughness of Binary Alkali Silicate Glasses (Abstract only), http://www.oai.dtic.mil/oai/oai?verb=getRecord&metadataPrefix=html&identifier=ADA016820, Feb. 14, 1974, 1 page. |
Lewis et al., Direct Writing in Three Dimension, Materials Today, Jul./Aug. 2004, 8 pages. |
Mysen et al., Properties and Structure (Developments in Geochemistry), Silicate Glasses and Melts, http://www.amazon.com/Silicate-Glasses-Melts-Developments-Geochemistry/dp/0444520112, 4 pages. |
Nascimento et al., Universal Curve of Ionic Conductivities in Binary Alkali Silicate Glasses, http://www.springerlink.com/content/p7535075×1872016/, Journal of Materials Science, 2005, 3 pages. |
Optomec® Systems M3D® Breakthrough Technology for Printable Electronics, 2 pages. |
Pedone et al., Insight into Elastic Properties of Binary Alkali Silicate Glasses; Prediction and Interpretation through Atomistic Simulation Techniques, http://pubs.acs.org/doi/abs/10.1021/cm062619r, Chemistry of Materials, 2007, 2 pages. |
PQ Corporation, Bonding and Coating Applications of PQ® Soluble Silicates, Bulletin Dec. 31, 2003, 1 page. |
PQ Corporation, PQ® Soluble Silicates in Refractory and Chemical-Resistant Cements, Bulletin Jan. 24, 2003, 1 page. |
Shermer, Thermal Expansion of Binary Alkali Silicate Glasses, http://nvl.nist.gov/pub/nistpubs/jres/057/2/V57.N02.A05, Journal of Research of the National Bureau of Standards, Aug. 1956, 5 pages. |
Technical Standard Order, TSO-C115b, Airborne Area Navigation Equipment Using Multi-Sensor Inputs, Sep. 30, 1994, 11 pages. |
Techpowerup, NanoCoolers Puts Liquid Metal in Your PC, http://www.techpowerup.com/?3105, May 4, 2005, 19 pages. |
The Mixed-Alkali Effect for the Viscosity of Glasses, http://glassproperties.com/viscosity/mixed-alkali-effect-viscosity/, 7 pages. |
The Structure of Glasses, Alkali Silicate Glasses, http://www.ptc.tugraz.at/specmag/struct/ss.htm, 1 page. |
Thresh, The Action of Natural Waters on Lead, The Analyst, Proceedings of the Society of Public Analysts and Other Analytical Chemists, Nov. 1922, 10 pages. |
Amendment and Reply for U.S. Appl. No. 11/508,782, mail date Sep. 2, 2008, 7 pages. |
Office Action for U.S. Appl. No. 11/508,782, mail date Dec. 24, 2008, 9 pages. |
Amendment and Reply for U.S. Appl. No. 11/508,782, mail date Mar. 24, 2009, 10 pages. |
Office Action for U.S. Appl. No. 11/508,782, mail date Jun. 16, 2009, 13 pages. |
Amendment and Reply for U.S. Appl. No. 11/508,782, mail date Aug. 14, 2009, 12 pages. |
Advisory Action for U.S. Appl. No. 11/508,782, mail date Aug. 31, 2009, 3 pages. |
Response for U.S. Appl. No. 11/508,782, mail date Nov. 13, 2009, 14 pages. |
Office Action for U.S. Appl. No. 11/508,782, mail date Feb. 24, 2010, 12 pages. |
Amendment and Reply for U.S. Appl. No. 11/508,782, mail date Jun. 24, 2010, 10 pages. |
Office Action for U.S. Appl. No. 11/508,782, mail date Sep. 2, 2010, 13 pages. |
Amendment and Reply for U.S. Appl. No. 11/508,782, mail date Nov. 2, 2010, 12 pages. |
Supplemental Amendment and Reply for U.S. Appl. No. 11/508,782, mail date Nov. 3, 2010, 4 pages. |
Advisory Action and Examiner Interview Summary for U.S. Appl. No. 11/508,782, mail date Nov. 23, 2010, 5 pages. |
Request for Continued Examination for U.S. Appl. No. 11,508,782, mail date Dec. 2, 2010, 10 pages. |
Examiner Interview Summary for U.S. Appl. No. 11/508,782, mail date Jan. 5, 2011, 2 pages. |
Office Action for U.S. Appl. No. 11/508,782, mail date Jan. 19, 2011, 9 pages. |
Amendment and Reply for U.S. Appl. No. 11/508,782, mail date Apr. 5, 2011, 9 pages. |
Notice of Allowance for U.S. Appl. No. 11/508,782, mail date May 31, 2011, 9 pages. |
Notice of Allowance for U.S. Appl. No. 11/508,782, mail date Jul. 26, 2011, 4 pages. |
Request for Continued Examination for U.S. Appl. No. 11/508,782, mail date Aug. 30, 2011, 6 pages. |
Notice of Allowance for U.S. Appl. No. 11/508,782, mail date Sep. 20, 2011, 7 pages. |
Restriction Requirement for U.S. Appl. No. 11/959,225, mail date Jul. 22, 2009, 10 pages. |
Response to Restriction Requirement for U.S. Appl. No. 11/959,225, mail date Aug. 24, 2009, 2 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date Dec. 2, 2009, 14 pages. |
Response for U.S. Appl. No. 11/959,225, mail date Mar. 2, 2010, 9 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date May 26, 2010, 16 pages. |
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Aug. 26, 2010, 11 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date Oct. 27, 2010, 11 pages. |
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Jan. 27, 2011, 9 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date Apr. 13, 2011, 16 pages. |
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Jun. 13, 2011, 12 pages. |
Advisory Action for U.S. Appl. No. 11/959,225, mail date Jul. 5, 2011, 3 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date Nov. 18, 2011, 16 pages. |
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Feb. 15, 2012, 15 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date Apr. 25, 2012, 17 pages. |
Office Action for U.S. Appl. No. 11/732,982, mail date Feb. 2, 2011, 15 pages. |
Amendment and Reply for U.S. Appl. No. 11/732,982, mail date May 2, 2011, 12 pages. |
Office Action for U.S. Appl. No. 11/732,982, mail date Jun. 21, 2011, 14 pages. |
Request for Continued Examination for U.S. Appl. No. 11/732,982, mail date Aug. 22, 2011, 11 pages. |
Office Action for U.S. Appl. No. 11/732,982, mail date Sep. 14, 2011, 13 pages. |
Amendment and Reply for U.S. Appl. No. 11/732,982, mail date Jan. 13, 2012, 11 pages. |
Office Action for U.S. Appl. No. 11/732,982, mail date Apr. 16, 2012, 15 pages. |
Reply for U.S. Appl. No. 11/732,982, mail date Jun. 13, 2012, 11 pages. |
Office Action for U.S. Appl. No. 11/732,982, mail date Jul. 3, 2012, 15 pages. |
Office Action for U.S. Appl. No. 11/784,158, mail date Apr. 21, 2009, 10 pages. |
Amendment and Reply for U.S. Appl. No. 11/784,158, mail date Jul. 21, 2009, 10 pages. |
Office Action for U.S. Appl. No. 11/784,158, mail date Oct. 8, 2009, 7 pages. |
Response for U.S. Appl. No. 11/784,158, mail date Jan. 8, 2010, 10 pages. |
Office Action for U.S. Appl. No. 11/784,158, mail date Mar. 26, 2010, 7 pages. |
Amendment and Reply for U.S. Appl. No. 11/784,158, mail date May 26, 2010, 12 pages. |
Terminal Disclaimer for U.S. Appl. No. 11/784,158, mail date May 26, 2010, 1 page. |
Terminal Disclaimer Decision for U.S. Appl. No. 11/784,158, mail date Jun. 8, 2010, 1 page. |
Office Action for U.S. Appl. No. 11/784,158, mail date Jun. 17, 2010, 6 pages. |
Notice of Allowance for U.S. Appl. No. 11/784,158, mail date Nov. 29, 2010, 4 pages. |
Office Action for U.S. Appl. No. 12/116,126, mail date Nov. 20, 2009, 7 pages. |
Response for U.S. Appl. No. 12/116,126, mail date Feb. 22, 2010, 10 pages. |
Office Action for U.S. Appl. No. 12/116,126, mail date Apr. 22, 2010, 7 pages. |
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Jun. 22, 2010, 7 pages. |
Advisory Action for U.S. Appl. No. 12/116,126, mail date Jun. 29, 2010, 4 pages. |
Request for Continued Examination for U.S. Appl. No. 12/116,126, mail date Jul. 22, 2010, 4 pages. |
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Jul. 22, 2010, 9 pages. |
Office Action for U.S. Appl. No. 12/116,126, mail date Oct. 25, 2010, 8 pages. |
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Jan. 25, 2011, 8 pages. |
Office Action for U.S. Appl. No. 12/116,126, mail date Feb. 25, 2011, 9 pages. |
Request for Continued Examination for U.S. Appl. No. 12/116,126, mail date Apr. 29, 2011, 4 pages. |
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Apr. 29, 2011, 9 pages. |
Office Action for U.S. Appl. No. 12/116,126, mail date May 10, 2011, 8 pages. |
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Aug. 10, 2011, 11 pages. |
Office Action for U.S. Appl. No. 12/116,126, mail date Sep. 12, 2011, 11 pages. |
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Dec. 12, 2011, 10 pages. |
Notice of Allowance for U.S. Appl. No. 12/116,126, mail date Jan. 5, 2012, 10 pages. |
Office Action for U.S. Appl. No. 12/240,775, mail date May 26, 2011, 9 pages. |
Amendment and Reply for U.S. Appl. No. 12/240,775, mail date Sep. 26, 2011, 11 pages. |
Restriction Requirement for U.S. Appl. No. 12/240,775, mail date Jan. 12, 2012, 5 pages. |
Office Action for U.S. Appl. No. 12/240,775, mail date Apr. 2, 2012, 8 pages. |
Office Action for U.S. Appl. No. 11/732,981, mail date Oct. 6, 2010, 9 pages. |
Amendment and Reply for U.S. Appl. No. 11/732,981, mail date Jan. 6, 2011, 9 pages. |
Office Action for U.S. Appl. No. 11/732,981, mail date Mar. 16, 2011, 7 pages. |
Request for Continued Examination for U.S. Appl. No. 11/732,981, mail date May 16, 2011, 12 pages. |
Terminal Disclaimer for U.S. Appl. No. 11/732,981, mail date May 16, 2011, 1 page. |
Terminal Disclaimer Decision for U.S. Appl. No. 11/732,981, mail date Jul. 11, 2011, 1 page. |
Notice of Allowance for U.S. Appl. No. 11/732,981, mail date Jul. 26, 2011, 7 pages. |
Request for Continued Examination for U.S. Appl. No. 11/732,981, mail date Oct. 25, 2011, 4 pages. |
Notice of Allowance for U.S. Appl. No. 11/732,981, mail date Dec. 29, 2011, 7 pages. |
Office Action for U.S. Appl. No. 11/784,932, mail date Apr. 3, 2009, 8 pages. |
Response for U.S. Appl. No. 11/784,932, mail date Jul. 2, 2009, 8 pages. |
Office Action for U.S. Appl. No. 11/784,932, mail date Feb. 16, 2010, 10 pages. |
Amendment and Reply for U.S. Appl. No. 11/784,932, mail date Jun. 14, 2010, 9 pages. |
Request for Continued Examination for U.S. Appl. No. 11/784,932, mail date Jun. 14, 2010, 4 pages. |
Office Action for U.S. Appl. No. 11/784,932, mail date Nov. 10, 2010, 9 pages. |
Notice of Allowance for U.S. Appl. No. 11/784,932, mail date May 12, 2011, 6 pages. |
Request for Continued Examination for U.S. Appl. No. 11/784,932, mail date Aug. 10, 2011, 6 pages. |
Notice of Allowance for U.S. Appl. No. 11/784,932, mail date Aug. 23, 2011, 8 pages. |
Office Action for U.S. Appl. No. 12/284,670, mail date Sep. 28, 2010, 10 pages. |
Amendment and Reply for U.S. Appl. No. 12/284,670, mail date Apr. 18, 2011, 9 pages. |
Office Action for U.S. Appl. No. 12/284,670, mail date Feb. 17, 2011, 12 pages. |
Notice of Allowance for U.S. Appl. No. 12/284,670, mail date May 11, 2011, 7 pages. |
Office Action for U.S. Appl. No. 12/286,207, mail date Dec. 27, 2010, 14 pages. |
Amendment and Reply for U.S. Appl. No. 12/286,207, mail date Mar. 28, 2011, 12 pages. |
Notice of Allowance for U.S. Appl. No. 12/286,207, mail date Jun. 27, 2011, 12 pages. |
Request for Continued Examination for U.S. Appl. No. 12/286,207, mail date Sep. 26, 2011, 4 pages. |
Notice of Allowance for U.S. Appl. No. 12/286,207, mail date Oct. 6, 2011, 8 pages. |
Office Action for U.S. Appl. No. 12/493,022, mail date May 30, 2012, 13 pages. |
Amendment and Reply for U.S. Appl. No. 13/359,105, mail date Aug. 8, 2012, 10 pages. |
International Search Report and Written Opinion for Application No. PCT/US2009/031699, mail date Aug. 18, 2009, 16 pages. |
International Search Report and Written Opinion for Application No. PCT/US2009/036355, mail date Jun. 30, 2009, 11 pages. |
International Search Report and Written Opinion for Application No. PCT/US2008/074224, mail date Jan. 30, 2009, 9 pages. |
International Search Report and Written Opinion for Application No. PCT/US2008/075591, mail date Apr. 8, 2009, 7 pages. |
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Jul. 22, 2013, 7 pages. |
Notice of Allowance for U.S. Appl. No. 11/732,982, mail date Jul. 10, 2013, 6 pages. |
Notice of Allowance for U.S. Appl. No. 13/359,105, mail date Jun. 24, 2013, 9 pages. |
Office Action for U.S. Appl. No. 13/329,068, mail date Jun. 7, 2013, 6 pages. |
Office Action for U.S. Appl. No. 11/959,225, mail date Apr. 23, 2013, 6 pages. |
Office Action for U.S. Appl. No. 13/071,316, mail date Nov. 27, 2013, 8 pages. |
Notice of Allowance on U.S. Appl. No. 14/055,746 Dated Oct. 21, 2014, 8 pages. |
Non-Final Office Action on U.S. Appl. No. 13/071,316 Dated Jan. 29, 2015, 5 pages. |
Non-Final Office Action on U.S. Appl. No. 14/140,192 Dated Jul. 20, 2015, 31 pages. |
Notice of Allowance on U.S. Appl. No. 13/071,316 Dated Jul. 20, 2015, 7 pages. |
Number | Date | Country | |
---|---|---|---|
Parent | 11508782 | Aug 2006 | US |
Child | 13287734 | US |