Integrated circuit tampering protection and reverse engineering prevention coatings and methods

Information

  • Patent Grant
  • 8664047
  • Patent Number
    8,664,047
  • Date Filed
    Friday, December 16, 2011
    12 years ago
  • Date Issued
    Tuesday, March 4, 2014
    10 years ago
Abstract
A method of protecting an electronics package is discussed along with devices formed by the method. The method involves providing at least one electronic component that requires protecting from tampering and/or reverse engineering. Further, the method includes mixing into a liquid glass material at least one of high durability micro-particles or high-durability nano-particles, to form a coating material. Further still, the method includes depositing the coating material onto the electronic component and curing the coating material deposited.
Description
BACKGROUND

The invention generally relates to applications of coatings for integrated circuits or other electronics packages. The invention also relates generally to methods of using such coatings to prevent reverse engineering of integrated circuits and other electronics packages.


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 resistant to tampering and reverse engineering. Further, what is needed is a low-cost simple method whereby reverse engineering of proprietary or secretive circuits or electronics packages is rendered difficult, impossible or nearly impossible by a coating applied to the circuit or electronics package.


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.


SUMMARY

What is provided is a method of protecting an electronics package. The method includes providing at least one electronic component. The method also includes the use of a low temperature curing alkali silicate (liquid glass) solution. Further, the method includes mixing into the alkali silicate material at least one of high durability micro-particles or high-durability nano-particles, to form a coating material. Further still, the method includes depositing the coating material onto the electronic component. Yet further still, the method includes curing the coating material deposited.


What is also provided is a method of forming a protected electronics package. The method includes providing at least one electronic component. The method also includes the use of an alkali silicate material. Further, the method includes mixing into the alkalai silicate material at least one of high durability micro-particles or high-durability nano-particles, to form a coating material. Further still, the method includes depositing the coating material onto the electronic component. Yet further still, the method includes curing the alkali silicate material to form a coated electronics package. The coated electronics package resists tampering and reverse engineering of the electronic component.


What is also provided is an electronics device. The electronic device includes a substrate and at least one electronic component coupled to the substrate. The electronic device also includes a low curing temperature glass coating encasing at least a portion of at least one electronic component. The low curing temperature glass coating including at least one of high durability micro-particles or high-durability nano-particles.


Alternative exemplary embodiments relate to other features and combination of features as may be generally recited in the claims.





BRIEF DESCRIPTION OF THE DRAWINGS

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:



FIG. 1 is an exemplary embodiment of the reaction of silica onto metal, glass, or ceramic surfaces;



FIG. 2 is an exemplary graph of resultant performance of the thermal properties of alkali silicate glass composites.



FIGS. 3-8 depict exemplary embodiments of various coating configurations for microelectronic packages.



FIG. 9 is an exemplary process diagram in accordance with an exemplary embodiment.



FIG. 10 is an exemplary process diagram in accordance with an exemplary embodiment.





DETAILED DESCRIPTION

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 any one or any combination of tampering, reverse engineering, corrosion and high temperature. These glass coatings are applied and cured at low temperatures, typically around or below 120° 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 and or microparticle modifiers, including, but not limited to, alkaline earth carbonates or oxides, metal oxides, rare-earth metal oxides, and non-metal oxides. Aqueous alkali silicate composite solutions applied on or between surfaces of materials, dry to form tough, tightly adhering inorganic bonds that exhibit many desirable characteristics.


Other particles such as but not limited to diamond, aluminum nitride, and other inorganics may also be combined with aqueous alkali silicate based solutions and cured to form very hard and durable composites. Varying combination and concentrations of the various particles allows the production of composites with specific thermal expansion, durability, and adhesion properties. These composites have been shown to bond very well to integrated circuit materials, including but not limited to silicon, silica, silicon nitride, metals, and other inorganics. These alkali silicate glass coatings are very hard and corrosion resistant, making them extremely difficult to remove. Accordingly, it is desirable to add micro- and nano-particles to create a very hard glass composite coating that is difficult, impossible, or nearly impossible to mechanically remove without damaging the underlying integrated circuit. Therefore, many applications exist for utilizing these composites for reverse engineering protection of integrated circuits and/or electronics packages.


In accordance with exemplary embodiments, the micro- or nano-particles may include but are not limited to those mentioned above as well as boron nitride, silicon carbide, high durability ceramics, non-metallics, different types of glass particles. When these or other durable, high hardness particles are added to the glass, the coating becomes exceptionally durable. Without the particles in the coating the coating may be potentially etched away. The addition of the particles can provide near the durability of the particles in the coating.


Generally, alkali silicate glasses are produced by fusing varying portions of sand (SiO2) and alkali metal carbonate (M2CO3) or oxide (M2O), 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. The solution can be further modified by the addition of metal hydroxides and or silica. In accordance with an exemplary embodiment the glass solutions may be 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 FIG. 1. Although alkali silicates have been used to protect materials from corrosion, alkali silicates have not been applied to protecting microelectronics, because in standard, off the shelf configuration, they may not cure appropriately and may not exhibit resultant properties which are desirable for protecting microelectronics in harsh environments.


Liquid alkali silicate solutions are commercially available in a variety of SiO2/M2O ratios. Typically, ratios of 3.25 down to 1 are readily available 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 120° C. are often sufficient for adequate dehydration.


It may be 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 can 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 nano- and or micro-particles, such as 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 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 200+ micron silica rich (R=3.22) coatings, whereas little or no 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 (several microns or less), 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 coatings applied to copper clad PCB boards and silicon die have been demonstrated. Also, these coatings can be adapted for strength and durability to prevent tampering and reverse engineering.


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 barrier. Also, when properly adapted and applied, these coatings may exhibit high strength and durability to prevent tampering and reverse engineering.


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 curing at 150° C. Multiple layers may be applied to 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 FIG. 2.


Referring to FIG. 2, alkali silicate glass composites have been applied over power dissipating devices mounted on both laminate and copper metal substrates. The resulting package temperatures were reduced by more than 50%, while standard encapsulants caused device temperatures to increase up to 130%.


In a further exemplary embodiment, the addition of nanoparticles to the alkali silicate glass thermal composites provides additional corrosion resistance.


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, FIG. 3 depicts a coating applied to a flip chip and to a wire bonded dies for corrosion and tamper resistance.


It may be particularly desirable to add particles to the coating discussed above 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 FIG. 4 which depicts the coating with opaque filler for the tamper resistance of wire bonded and flip chip dies. Alternatively, the solution could also be applied under a flip chip.


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 and may be applied in conjunction with, or in addition to the high strength and durability of the coating for anti-tampering and reverse engineering prevention or resistance. 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 and the high durability and strength of the coatings will lead to ant-tampering and anti-reverse engineering properties.


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 (≦120° C.). Alternatively, to decrease the cure time, it may be desirable cure these coatings at high temperatures that are greater than 120° 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 and may be applied in conjunction with, or in addition to the high strength and durability of the coating for anti-tampering and reverse engineering prevention or resistance. See FIG. 5 for an exemplary illustration.


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 FIG. 6.


It may also be desirable to 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 FIG. 7, for example. Therefore, because of the high re-melting temperature of the glass coating, disassembly and reverse engineering of the electronic component(s) is rendered more difficult.


These coatings may also be used for applying 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. Further, by the addition of certain particles, increased durability and hence anti-tampering and anti-reverse engineering properties may be achieved. See FIG. 8 for an example.


As discussed briefly above, in accordance with an exemplary embodiment, micro- and nano-particles can be added to an alkalai silicate solution to make it opaque. The solution can then be coated onto a wirebonded die using a low curing temperature (for example ˜110° C.). Once the material has been cured, the material will be nearly impossible to remove without etching or mechanically damaging the underlying integrated circuit. Thus, the wirebonded die will be nearly impossible to remove, due to its exceptional adhering properties or to see through the coating to the die because of the opacity of the coating. The cured alkali silica glass may sufficiently be well bonded to the die such that attempting to remove it from the die will irreversibly damage it. For example, an attempt to dice or cleave the coating would lead to damage of the integrated circuit due to the hardness of the particle fillers contained within the composite. One particular advantage of the glass composites discussed is that they provide reverse engineering and tamper resistance without exposing the device to high curing temperatures.


Referring now to FIG. 10, a process 1000 of protecting an electronics package includes providing at least one electronic component that requires protection against tampering and/or reverse engineering as well as other outside factors (process 1010). Process 1000 also includes mixing a low temperature curing glass material with a solvent, to form a liquid glass material (process 1020). In order to change the properties of the coating the process includes mixing into the liquid glass material at least one of high durability micro-particles or high-durability nano-particles, to form a coating material (process 1030). The coating material is deposited onto the electronic component (process 1040). The coating material is then cured to form a hardened coating (process 1050).


Referring now to FIG. 9, a process for forming a protected electronics package includes providing at least one electronic component that requires protection against tampering and/or reverse engineering as well as other outside factors (process 910). Process 900 also includes mixing an alkali silicate material with a solvent (process 920). Further, process 900 includes mixing into the alkalai silicate material at least one of high durability micro-particles or high-durability nano-particles, to form a coating material (process 930). The coating material is then deposited onto the electronic component (process 940). The alkali silicate material is then deposited to form a coated electronics package (process 950). The coated electronics package resists tampering and reverse engineering of the electronic component (process 960).


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 may be 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.

Claims
  • 1. A method of forming a coated electronic component, comprising: providing at least one electronic component;mixing into a liquid silicate glass material at least one of (i) high durability micro-particles and (ii) high-durability nano-particles to form a coating material;depositing the coating material onto at least a portion of the electronic component; andcuring the coating material deposited.
  • 2. The method of claim 1, wherein the liquid silicate glass material comprises alkali silicate glass.
  • 3. The method of claim 1, further comprising mixing a solvent with the silicate liquid glass material.
  • 4. The method of claim 1, further comprising mixing a solvent with the liquid silicate glass material at a ratio of solvent to glass material of at least 3 to 1.
  • 5. The method of claim 1, further comprising mixing SiO2 and (i) alkali metal carbonate (M2CO3) or (ii) M2O, wherein M is an alkali metal, to form the silicate glass material.
  • 6. The method of claim 1, wherein the electronic component is a part of an integrated circuit.
  • 7. The method of claim 1, further comprising mixing a solvent comprising water with the liquid silicate glass material.
  • 8. The method of claim 1, wherein the micro-particles or nano-particles are selected from the group consisting of diamond, aluminum nitride, boron nitride, and silicon carbides.
  • 9. The method of claim 1, wherein a portion of the electronic component is a wire bond die or a flip chip die, and the method further comprising depositing the coating material onto the portion.
  • 10. A method of forming a coated electronics package, comprising: providing at least one electronic component;mixing an alkali silicate material with a solvent;mixing into the alkali silicate material at least one of (i) high durability micro-particles and (ii) high-durability nano-particles, to form a coating material;depositing the coating material onto at least a portion of the electronic component; andcuring the alkali silicate material to form a coated electronics package,wherein the coated electronics package resists tampering and reverse engineering of the electronic component.
  • 11. The method of claim 10, wherein the alkali silicate material comprises alkali silicate glass.
  • 12. The method of claim 10, wherein the solvent comprises deionized water.
  • 13. The method of claim 10, wherein the curing is carried out at room temperature.
  • 14. The method of claim 10, wherein the curing is carried out at a temperature that is approximately 90° C. to approximately 150° C.
  • 15. The method of claim 10, wherein the micro-particles or nano-particles are selected from the group consisting of high durability ceramics and non-metallics.
  • 16. The method of claim 10, wherein the coating material forms an opaque coating.
  • 17. A method of forming a coated electronic component, comprising: providing at least one electronic component;depositing a coating material onto at least a portion of the electronic component; andcuring the coating material;wherein the coating material comprises a liquid alkali silicate glass material and at least one of (i) high durability micro-particles and (ii) high-durability nano-particles.
  • 18. The method of claim 17, further comprising fusing SiO2 and (i) alkali metal carbonate (M2CO3) or (ii) M2O, wherein M is an alkali metal, to form the alkali silicate glass material.
  • 19. The method of claim 17, further comprising mixing SiO2 and (i) alkali metal carbonate (M2CO3) or (ii) M2O at a ratio of SiO2 to (i) or (ii) at greater than or equal to 3.25, wherein M is an alkali metal, to form the alkali silicate glass material.
  • 20. The method of claim 17, further comprising mixing the alkali silicate glass with a water solvent to form the liquid alkali silicate glass material.
CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser. No. 11/784,932 by Lower et al. filed on Apr. 10, 2007, entitled INTEGRATED CIRCUIT TAMPERING PROTECTION AND REVERSED ENGINEERING PREVENTION COATINGS AND METHODS, which is a continuation-in-part of U.S. application Ser. No. 11/508,782, entitled INTEGRATED CIRCUIT PROTECTION AND RUGGEDIZATION COATINGS AND METHODS by Lower et al.; filed on Aug. 23, 2006, each of which is incorporated by reference in its entirety.

US Referenced Citations (158)
Number Name Date Kind
3508974 Bressler Apr 1970 A
3654528 Barkan Apr 1972 A
3723790 Dumbaugh et al. Mar 1973 A
3812404 Barkan et al. May 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
4513029 Sakai Apr 1985 A
4560084 Wolfson Dec 1985 A
4572924 Wakely et al. Feb 1986 A
4622433 Frampton Nov 1986 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
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
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
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
6798072 Kajiwara et al. Sep 2004 B2
6800326 Uchiyama Oct 2004 B1
6800330 Hayashi et al. Oct 2004 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
7476981 Bergmann 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
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
20010015443 Komoto Aug 2001 A1
20010030493 Noda et al. Oct 2001 A1
20010046933 Parkhill et al. Nov 2001 A1
20020000630 Coyle Jan 2002 A1
20020054976 Nakamura et al. May 2002 A1
20020076192 Bartholomew et al. Jun 2002 A1
20020078856 Hahn et al. Jun 2002 A1
20020086115 Lamers et al. Jul 2002 A1
20020170173 Mashino Nov 2002 A1
20020189495 Hayashi et al. Dec 2002 A1
20020189894 Davis et al. Dec 2002 A1
20030047735 Kyoda et al. Mar 2003 A1
20030080341 Sakano et al. May 2003 A1
20030218258 Charles et al. Nov 2003 A1
20030228424 Dove et al. Dec 2003 A1
20040106037 Cho et al. Jun 2004 A1
20040116577 Naruse et al. Jun 2004 A1
20040156995 Komiyama et al. Aug 2004 A1
20040194667 Reuscher Oct 2004 A1
20050003947 Mazany et al. Jan 2005 A1
20050082691 Ito et al. Apr 2005 A1
20050099775 Pokharna et al. May 2005 A1
20050116237 Voutsas Jun 2005 A1
20050123684 Makowski et al. Jun 2005 A1
20050179742 Keenan et al. Aug 2005 A1
20060045755 McDonald et al. Mar 2006 A1
20060068218 Hooghan et al. Mar 2006 A1
20060095677 Hakura et al. May 2006 A1
20060135342 Anderson et al. Jun 2006 A1
20060154004 Hayashi et al. Jul 2006 A1
20060158849 Martin et al. Jul 2006 A1
20060250731 Parkhurst et al. Nov 2006 A1
20060268525 Jeong Nov 2006 A1
20060283546 Tremel et al. Dec 2006 A1
20070075323 Kanazawa et al. Apr 2007 A1
20070102833 Hack et al. May 2007 A1
20070108586 Uematsu et al. May 2007 A1
20070224400 Meguro et al. Sep 2007 A1
20080006204 Rusinko et al. Jan 2008 A1
20080050512 Lower et al. Feb 2008 A1
20080063875 Robinson et al. Mar 2008 A1
20080142966 Hirano et al. Jun 2008 A1
20080299300 Wilcoxon et al. Dec 2008 A1
20090110904 Mack et al. Apr 2009 A1
20090183774 Atanackovic Jul 2009 A1
20090246355 Lower et al. Oct 2009 A9
20090279257 Lower et al. Nov 2009 A1
20120118623 Lower et al. May 2012 A1
Foreign Referenced Citations (8)
Number Date Country
55-120083 Sep 1980 JP
57027942 Feb 1982 JP
60013875 Jan 1985 JP
02064071 Mar 1990 JP
11-095246 Apr 1994 JP
2003332505 Nov 2003 JP
2006045420 Feb 2006 JP
WO2006095677 Sep 2006 WO
Non-Patent Literature Citations (116)
Entry
Office Action for U.S. Appl. No. 13/287,734, mail date Apr. 11, 2013, 18 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. 12/240,775, mail date Apr. 2, 2012, 8 pages.
Office Action for U.S. Appl. No. 11/732,982, mail date Apr. 16, 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. 12/493,022, mail date May 30, 2012, 13 pages.
Office Action for U.S. Appl. No. 11/732,982, mail date Jul. 3, 2012, 15 pages.
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.
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://www.optics.nasa.gov/tech—days/tech—days—2004/docs/18%20Aug%202004/23%20Schott%20Low%20Temperature%20Bonding, 20 pages.
Golubev et al., Modeling of Acid-Base Properties of Binary Alkali-Silicate Melts, Rev. Adv. Mater. Sci. 6, http://www.ipme.ru/e-journals/RAMS/no—1604/golubev/golubev. (2004), 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, Materialstoday, Jul./Aug. 2004, 8 pages.
Mysen et al., Properties and Structure (Developments in Geochemistry), Silicate Glasses and Melts, vol. 10, 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/p7535075x1872016/, 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 12-31, (2003) 1 page.
PQ Corporation, PQ® Soluble Silicates in Refractory and Chemical-Resistant Cements, Bulletin 24-1, (2003), 1 page.
Shermer, Thermal Expansion of Binary Alkali Silicate Glasses, http://nvl.nist.gov/pub/nistpubs/jres/057/2A/57.N02.A05, Journal of Research of the National Bureau of Standards, Aug. 1956, Research Paper No. 2698, 5 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, printed on Dec. 3, 2010 from website: 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, pp. 459-468, vol. XLVII, No. 560.
International Search Report and Written Opinion for International Application No. PCT/US2008/074224, mail date Jan. 30, 2009, 9 pages.
International Search Report and Written Opinion for International Application No. PCT/US2008/075591, mail date Apr. 8, 2009, 7 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/US2009/031699, mail date Aug. 18, 2009, 16 pages.
Office Action for U.S. Appl. No. 11/508,782, mail date Dec. 24, 2008, 9 pages.
Office Action for U.S. Appl. No. 11/508,782, mail date Jun. 16, 2009, 13 pages.
Advisory Action received 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.
Advisory Action and Examiner Interview Summary for U.S. Appl. No. 11/508,782, mail date Nov. 23, 2010, 5 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.
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.
Office Action for U.S. Appl. No. 11/784,158, mail date Apr. 21, 2009, 10 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.
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. 11/732,981, mail date Oct. 6, 2010, 9 pages.
Office Action for U.S. Appl. No. 11/732,981, mail date Mar. 16, 2011, 7 pages.
Notice of Allowance for U.S. Appl. No. 11/732,981, mail date Jul. 26, 2011, 7 pages.
Notice of Allowance for U.S. Appl. No. 11/784,932, mail date Aug. 23, 2011, 8 pages.
Notice of Allowance for U.S. Appl. No. 11/784,932, mail date May 12, 2011, 6 pages.
Office Action for U.S. Appl. No. 11/784,932, mail date Apr. 3, 2009, 8 pages.
Office Action for U.S. Appl. No. 11/784,932, mail date Feb. 16, 2010, 10 pages.
Office Action for U.S. Appl. No. 11/784,932, mail date Nov. 10, 2010, 9 pages.
Request for Continued Examination for U.S. Appl. No. 11/784,932, mail date Aug. 10, 2011, 6 pages.
Response for U.S. Appl. No. 11/784,932, mail date Jul. 2, 2009, 8 pages.
Office Action for U.S. Appl. No. 12/284,670, mail date Sep. 28, 2010, 10 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.
Notice of Allowance for U.S. Appl. No. 12/286,207, mail date Jun. 27, 2011, 12 pages.
Office Action for U.S. Appl. No. 11/732,982, mail date Feb. 2, 2011, 15 pages.
Office Action for U.S. Appl. No. 11/732,982, mail date Jun. 21, 2011, 14 pages.
Office Action for U.S. Appl. No. 11/959,225, mail date Jul. 22, 2009, 10 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 Oct. 27, 2010, 11 pages.
Office Action for U.S. Appl. No. 11/959,225, mail date Apr. 13, 2011, 16 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.
Office Action for U.S. Appl. No. 12/116,126, mail date Oct. 25, 2010, 8 pages.
Office Action for U.S. Appl. No. 12/116,126, mail date Feb. 25, 2011, 9 pages.
Office Action for U.S. Appl. No. 12/116,126, mail date May 10, 2011, 8 pages.
Office Action for U.S. Appl. No. 12/240,775, mail date May 26, 2011, 9 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. 12/116,126, mail date Jun. 29, 2010, 4 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. 12/116,126, mail date Jul. 22, 2010, 9 pages.
Amendment and Reply for U.S. Appl. No. 11/732,981, mail date Jan. 6, 2011, 9 pages.
Amendment and Reply for U.S. Appl. No. 11/732,982, mail date Jun. 14, 2012, 11 pages.
Amendment and Reply for U.S. Appl. No. 11/732,982, mail date May 2, 2011, 12 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. 11/784,158, mail date Jul. 21, 2009, 10 pages.
Amendment and Reply for U.S. Appl. No. 11/784,932, mail date Jun. 14, 2010, 9 pages.
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Aug. 24, 2009, 2 pages.
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Aug. 26, 2010, 11 pages.
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Feb. 15, 2012, 15 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. 12/116,126, mail date Apr. 29, 2011, 9 pages.
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Jan. 25, 2011, 8 pages.
Amendment and Reply for U.S. Appl. No. 12/116,126, mail date Jun. 22, 2010, 7 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. 12/284,670, mail date Apr. 18, 2011, 9 pages.
Amendment and Reply for U.S. Appl. No. 12/286,207, mail date Mar. 28, 2011, 12 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.
Amendment and Reply for U.S. Appl. No. 13/359,105, mail date Aug. 8, 2012, 10 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. 11/784,932, mail date Jun. 14, 2010, 4 pages.
Request for Continued Examination for U.S. Appl. No. 11/959,225, mail date Aug. 27, 2012, 19 pages.
Request for Continued Examination for U.S. Appl. No. 12/116,126, mail date Apr. 29, 2011, 4 pages.
Request for Continued Examination for U.S. Appl. No. 12/116,126, mail date Jul. 22, 2010, 4 pages.
Request for Continued Examination for U.S. Appl. No. 12/286,207, mail date Sep. 26, 2011, 4 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.
Amendment and Reply for U.S. Appl. No. 11/959,225, mail date Jul. 22, 2013, 7 pages.
Amendment and Reply for U.S. Appl. No. 13/287,734, mail date Jul. 9, 2013, 10 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.
Related Publications (1)
Number Date Country
20120088338 A1 Apr 2012 US
Divisions (1)
Number Date Country
Parent 11784932 Apr 2007 US
Child 13329068 US
Continuation in Parts (1)
Number Date Country
Parent 11508782 Aug 2006 US
Child 11784932 US