Source: https://patents.google.com/patent/US7968010
Timestamp: 2018-03-18 19:54:43
Document Index: 551298869

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 07', 'Application No. 06', 'Application No. 07', 'Application No. 07813508', 'Application No. 07813509', 'Application No. 200780028607', 'Application No. 200780028607', 'Application No. 200780028617', 'Application No. 200680043467']

US7968010B2 - Method for electroplating a substrate - Google Patents
US7968010B2
US7968010B2 US12703723 US70372310A US7968010B2 US 7968010 B2 US7968010 B2 US 7968010B2 US 12703723 US12703723 US 12703723 US 70372310 A US70372310 A US 70372310A US 7968010 B2 US7968010 B2 US 7968010B2
US12703723
US20100147697A1 (en )
Lex Kosowsky
Shocking Technologies Inc
H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
H01C17/0652—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component containing carbon or carbides
H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
H05K2201/0242—Shape of an individual particle
H05K2201/0248—Needles or elongated particles; Elongated cluster of chemically bonded particles
H05K2201/0257—Nanoparticles
H05K2201/026—Nanotubes or nanowires
H05K2201/0263—Details about a collection of particles
H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
H05K2201/0738—Use of voltage responsive materials, e.g. voltage switchable dielectric or varistor materials
H05K2203/0723—Electroplating, e.g. finish plating
H05K2203/105—Using an electrical field; Special methods of applying an electric potential
Y10S977/779—Possessing nanosized particles, powders, flakes, or clusters other than simple atomic impurity doping
This application is a Divisional of U.S. patent application Ser. No. 11/881,896, filed Jul. 29, 2007 now U.S. Pat. No. 7,695,644, which claims priority to the following applications:
(a) Provisional U.S. Patent Application No. 60/820,786, filed Jul. 29, 2006;
(b) Provisional U.S. Patent Application No. 60/826,746, filed Sep. 24, 2006;
(c) Is a Continuation-In-Part of U.S. patent application Ser. No. 11/562,289, filed Nov. 21, 2006; and
(d) Is a Continuation-In-Part of U.S. patent application Ser. No. 11/562,222, filed Nov. 21, 2006.
All of the aforementioned priority applications are hereby incorporated by reference in their entirety.
Various kinds of conventional VSDM exist. Examples of voltage switchable dielectric materials are provided in references such as U.S. Pat. Nos. 4,977,357, 5,068,634, 5,099,380, 5,142,263, 5,189,387, 5,248,517, 5,807,509, WO 96/02924, and WO 97/26665. VSD material can be “SURGX” material manufactured by the SURGX CORPORATION (which is owned by Littlefuse Inc.).
FIG. 7 illustrates a process for electroplating, using organic VSD material in accordance with any of the embodiments described with FIG. 1-5C.
FIG. 8 is a simplified diagram of an electronic device on which VSD material in accordance with embodiments described herein may be provided.
In general, “voltage switchable material” or “VSD material” is any composition, or combination of compositions, that has a characteristic of being dielectric or non-conductive, unless a voltage is applied to the material that exceeds a characteristic voltage level of the material, in which case the material becomes conductive. Thus, VSD material is a dielectric unless voltage exceeding the characteristic level (e.g. such as provided by ESD events) is applied to the material, in which case the VSD material is conductive. VSD material can further be characterized as any material that can be characterized as a nonlinear resistance material.
Accordingly, one or more embodiments further include a binder for a VSD composition that includes “nanoscale” dimensioned conductive or semi-conductive particles. These may include HAR particles, and in some cases super HAR particles (having aspect ratios of the order of 1000 or more). In this application, nanoscale particles are particles for which a smallest dimension (e.g. diameter or cross-section) is less than 500 nanometers. One or more embodiments contemplate nanoscale particles having a smallest dimension that is less than 100 nm, and still further, other embodiments contemplate a dimension that is less than 50 nm. Examples of such particles include carbon nanotubes, although numerous other kinds of particles are contemplated. Carbon nanotubes are examples of super HAR particles, with aspect ratios of an order of 1000:1and more. Materials with lesser aspect ratios are also contemplated as an alternative or addition to carbon nanotubes, including one or more of carbon black (L/D of order of 10:1) particles and carbon fiber (L/D of an order of 100:1) particles.
Still further, alternative embodiments contemplate use of nanoscale particles that have moderate aspect ratios. For example, one or more embodiments include combining nanorods with the binder of the VSD material. Some variations of nanorods, formed from metals or semiconductors, have aspect ratios that range between 3-10 nm. Thus, one or more embodiments contemplate use of nanoscale conductors or semiconductors that have moderate aspect ratios.
Generally, the characteristic voltage of VSD material is measured at volts/length (e.g. per 5 mil). One or more embodiments provide that the VSD material has a characteristic voltage level that exceeds that of an operating circuit. Such voltage levels may be associated with transient conditions, like electrostatic discharge, although embodiments contemplate planned electrical events. Furthermore, one or more embodiments provide that in the absence of the voltage exceeding the characteristic voltage, the material behaves similar to the binder.
In one embodiment, the binder 130 is a matrix that retains the HAR particles 110 and the conductor/semi-conductor particles 120. In one embodiment, the HAR particles 110 are dispersed as nanoscale particles. In one embodiment, the amount of HAR particles that are dispersed in the binder place the binder at just below the percolation threshold. As dispersed nanoscale particles, the HAR particles 110 include particles that are both nanoscaled in one or more dimensions (e.g. cross-section, diameter, width) and individually separated from one another. Thus, the formulation process 150 may uniformly distribute the particles within the binder 130.
According to one or more embodiments, other ingredients or components for use in the formation process 150 include solvents and catalysts. Solvents may be added to the binder 130 to separate particles that would otherwise be lumped or agglomerated at nanoscale. A mixing process may also be used to uniformly space separated particles. In one embodiment, the result of the mixing process is that the composition is uniformly mixed to disperse particles at the nanoscale. Thus, particles such as carbon nanotubes or other HAR particles may be separated out individually and distributed relatively evenly in the material. In order to achieve nanoscale dispersion, one or more embodiments provide for use of sonic agitators and sophisticated mixing equipment (e.g. such as rotor-stator mixers, ball mills, mini-mills, and other high shear mixing technologies), over a duration that lasts several hours or longer. Once mixed, the resulting mixture may be cured or dried.
In step 230, a mixing process may be performed over a designated duration. In one embodiment, the mixing process is performed with mixing equipment, including sonic agitators, for a duration that that extends for minutes or hours. The mixing process serves to disperse the HAR particles at a nanoscale level. One result of mixing to such degree is that at least some of the HAR particles substantially are suspended apart from one another within the binder, so as to not agglomerated or lumped together. Given that the HAR particles individually may include one or more dimensions at the nanoscale, such mixing further enables nanoscale dispersion within the binder.
CheapTubes 5.4
Epon 828 100
Gelest Aminopropyltriethoxysilane 4
Total Epoxy 104
Nanophase Bismuth Oxide 98
HC Starck TiN— 164
Degussa Dyhard T03 4.575
NMP 25.925
Curative Soln. 30.5
1-methylimidazole 0.6
HC Stark TiB2— 149
Millenium Chemical Doped TiO2— 190
NMP 250
Total Solution 986.1
Total Solids 715.575
Epoxy:Amin Equiv Ratio % Solids 72.6%
Device 302 may be used with any one of many kinds of electrical devices. In an embodiment, device 302 may be implemented as part of a printed circuit board. For example, the VSD material 300 may be provided as a thickness that is on the surface of the board, or within the board's thickness. Device 302 may further be provided as part of a semi-conductor package, or discrete device.
Material Example 1
Ishihara Corp FS-10P ATO nanorods 14.4
HC Starck TiB2 150.0
Gelest SIA610.1 4.0
Millenium Chemical TiO2 190.0
Lubrizole D510 9.8
Nanophase Bi2O3 98.0
HC Starck TiN 164.0
Epon 828 (Hexion) 87.15
Degussa Dyhard T03 4.49
1-methylimidazole 0.62
N-methylpyrrolidinone 275.4
Gap 5 mil
Trigger Voltage 447
Clamp Voltage 320
Table 2 lists several additional examples in which the VSD material is composed of carbon nanotubes as the HAR particles. in accordance with one or more embodiments described herein. Table 2 lists generically measured electrical properties (meaning no differentiation is provided between forms of input signal and/or manner in which data for electrical properties is determined), as quantified by clamp and trigger voltages, that result from use of the VSD material in accordance with the stated composition.
Material Weight (g) Weight (g) Weight (g) Weight (g)
Hyperion CP-1203 0 31.29 0 40.86
Nickel INP400 216.27 221.49 0 0
Momentive TiB2 0 0 55.36 55.4
Saint Gobain BN 0 0 0 0
Epon 828 (Hexion) 40.13 10.09 51.06 12.18
Degussa Dyhard T03 1.83 1.83 2.34 2.33
1-methylimidazole 0.1 0.13 0.3 0.3
imidazoledicarbonitrile 0 0 0 0
Methylaminoantracene 0 0 0 0
Millenium Chemical 0 0 85.03 85.79
N-methylpyrrolidinone 80.37 80.46 83.5 123.4
Gap 5 mil 5 mil 5 mil 5 mil
Trigger Voltage 250 170 1475 775
Clamp Voltage 100 70 1380 220
Example 3 also illustrates a VSD composition that lacks carbon nanotubes as HAR particles, while Example 4 illustrates effect of including carbon nanotubes into the mixture. As shown, a dramatic reduction in the trigger and clamp voltages is shown. With regard to Example 3 and Example 4, both compositions illustrate compositions that have desirable mechanical characteristics, as well as characteristics of off-state resitivity and current-carrying capacity (neither of which are referenced in the chart). However, the clamp and trigger voltage values of Example 3 illustrate the composition, without inclusion of carbon nanotubes, is difficult to turn on and maintain on. Abnormally high trigger and clamp voltages thus reduce the usefulness of the composition.
Material Weight (g) Weight (g) Weight (g)
Hyperion CP1203 21.0 0 1.0
Hexion Epon 828 50.25 0 5
Cabosil coated Aluminum 40.33 26.33 0
ATA5669 aluminum 0 0 13.76
Degussa Dyhard T03 3.22 0.8 0.6
Methoxyethanol 25.8 6.39 4.68
1-methylimidazole 0.06 0.04 0.04
Hexion Epon SU-8 0 19.55 14.32
Methyl ethyl ketone 0 11.73 6.6
Cabosil coated Alumina 0 15.31 0
In FIG. 5B, a conventional VSD material is shown without addition of HAR particles. Metal particles 510, 520 are relatively closely spaced in order to pass charge when voltage exceeding the characteristic voltage is applied. As a result of more closely spaced conductors, more metal loading is required to enable the device to switch to a conductor state. In comparison to an embodiment such as illustrated by FIG. 5A, under a conventional approach shown by FIG. 5B, the particles 510, 520 are spaced by glass particle spaces (e.g. Cab-O-Sil), an embodiment such as shown in FIG. 5A substitutes metal volume with conductive fillers 530 that are conductive, have desirable physical properties, and have dimensions to adequately substitute for metal.
FIG. 6A and FIG. 6B each illustrate different configurations for a substrate device that is configured with VSD material having high aspect-ration particles as filler (“HAR particled VSD”), under an embodiment of the invention. In FIG. 6A, the substrate device 600 may correspond to, for example, a printed circuit board. In such a configuration, HAR particled VSD 610 may be provided on a surface 602 to ground a connected element. As an alternative or variation, FIG. 6B illustrates a configuration in which the HAR particled VSD forms a grounding path within a thickness 610 of the substrate.
Embodiments described with reference to the drawings are considered illustrative, and Applicant's claims should not be limited to details of such illustrative embodiments. Various modifications and variations may be included with embodiments described, including the combination of features described separately with different illustrative embodiments. Accordingly, it is intended that the scope of the invention be defined by the following claims. Furthermore, it is contemplated that a particular feature described either individually or as part of an embodiment can be combined with other individually described features, or parts of other embodiments, even if the other features and embodiments make no mentioned of the particular feature.
conductor and/or semiconductor particles other than said HAR particles;
said conductor and/or semiconductor particles being distributed in the binder;
forming a pattern using the VSD material;
applying the voltage that exceeds the characteristic voltage level so that the VSD material is conductive;
while applying the voltage, exposing the target region of the device to an electrolytic medium;
and wherein said characteristic voltage level exceeds about 14 volts per mil across a gap formed by a thickness of the VSD material.
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US20100147697A1 true US20100147697A1 (en) 2010-06-17
US7968010B2 true US7968010B2 (en) 2011-06-28
ID=42239229
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