Solid electrolytic capacitor with interlayer crosslinking

<u>CROSS-REFERENCE TO RELATED APPLICATIONS</u>

0001The present invention claims priority to pending <patcit id="pcit0001" dnum="US61603635A"><text>U.S. Provisional Appl. No. 61/603,635 filed February 27, 2012</text></patcit> which is incorporated herein by reference.

BACKGROUND

0002The present invention is related to an improved polymerization method for preparing solid electrolytic capacitors. More specifically, the present invention is related to an improved method of forming a solid electrolyte capacitor and an improved capacitor formed thereby. Even more specifically, the present invention is related to a capacitor comprising interlayers wherein adjacent interlayers, particularly of the cathode, are cross-linked to each other thereby providing an improved cathode as indicated by improved ESR stability.

0003The construction and manufacture of solid electrolyte capacitors is well documented. In the construction of a solid electrolytic capacitor a valve metal preferably serves as the anode. The anode body can be either a porous pellet, formed by pressing and sintering a high purity powder, or a foil which is etched to provide an increased anode surface area. An oxide of the valve metal is electrolytically formed to cover up to all of the surfaces of the anode and to serve as the dielectric of the capacitor. The solid cathode electrolyte is typically chosen from a very limited class of materials, to include manganese dioxide or electrically conductive organic materials such as 7,7,8,8 tetracyanoquinonedimethane (TCNQ) complex salt, or intrinsically conductive polymers, such as polyaniline, polypyrol, polythiophene and their derivatives. The solid cathode electrolyte is applied so that it covers all dielectric surfaces and is in direct intimate contact with the dielectric. In addition to the solid electrolyte, the cathodic layer of a solid electrolyte capacitor typically consists of several layers which are external to the anode body. In the case of surface mount constructions these layers typically include: a carbon layer; a cathode conductive layer which may be a layer containing a highly conductive metal, typically silver, bound in a polymer or resin matrix; and a conductive adhesive layer such as silver filled adhesive. The layers including the solid cathode electrolyte, conductive adhesive and layers there between are referred to collectively herein as the cathode layer which typically includes multiple interlayers designed to allow adhesion on one face to the dielectric and on the other face to the cathode lead. A highly conductive metal lead frame is often used as a cathode lead for negative termination. The various layers connect the solid electrolyte to the outside circuit and also serve to protect the dielectric from thermo-mechanical damage that may occur during subsequent processing, board mounting, or customer use.

0004In the case of conductive polymer cathodes the conductive polymer is typically applied by either chemical oxidation polymerization, electrochemical oxidation polymerization or by dipping, spraying, or printing of pre-polymerized dispersions.

0005The carbon layer serves as a chemical barrier between the solid electrolyte and the silver layer. Critical properties of the layer include adhesion to the underlying layer, wetting of the underlying layer, uniform coverage, penetration into the underlying layer, bulk conductivity, interfacial resistance, compatibility with the silver layer, buildup, and mechanical properties.

0006The cathodic conductive layer, which is preferably a silver layer, serves to conduct current from the lead frame to the cathode and around the cathode to the sides not directly connected to the lead frame. The critical characteristics of this layer are high conductivity, adhesive strength to the carbon layer, wetting of the carbon layer, and acceptable mechanical properties.

0007Today, almost all electronic components are mounted to the surface of circuit boards by means of infra-red (IR) or convection heating of both the board and the components to temperatures sufficient to reflow the solder paste applied between copper pads on the circuit board and the solderable terminations of the surface mount technology (SMT) components. A consequence of surface-mount technology is that each SMT component on the circuit board is exposed to soldering temperatures that commonly dwell above 180°C for close to a minute, typically exceeding 230°C, and often peaking above 250°C. If the materials used in the construction of capacitors are vulnerable to such high temperatures, it is not unusual to see significant positive shifts in ESR which lead to negative shifts in circuit performance. SMT reflow soldering is a significant driving force behind the need for capacitors having temperature-stable ESR.

0008Equivalent Series Resistance (ESR) stability of the capacitors requires that the interface between the cathode layer, cathodic conductive layers, conductive adhesive, and leadframe have good mechanical integrity during thermo mechanical stresses. Solid electrolytic capacitors are subject to various thermomechanical stresses during assembly, molding, board mount reflow etc. During board mount the capacitors are subjected to temperatures above 250° C. These elevated temperatures create stresses in the interfaces due to coefficient of thermal expansion (CTE) mismatches between the interfaces. The resultant stress causes mechanical weakening of the interfaces. In some cases this mechanical weakening causes delamination. Any physical separation between the interfaces causes increases in electrical resistance between the interfaces and thus an increased ESR in the finished capacitor.

0009<patcit id="pcit0002" dnum="US6304427B"><text>U.S. Pat. No. 6,304,427</text></patcit>, which is incorporated herein by reference, teaches a method for improving ESR stability of capacitors. The combination of materials described therein offers some ESR stability, however, the method still allows an ESR rise of a few milliohms during board mount conditions.

0010<patcit id="pcit0003" dnum="US6072694A"><text>Hahn et al., in U.S. Pat. No. 6,072,694</text></patcit>, which is incorporated herein by reference, disclose an electrolytic capacitor whose adhesion of a conducting polymer film to an oxidized porous pellet anode is improved by the incorporation of a silane coupling agent in the polymer impregnating solution, in order to improve leakage and dissipation factor thereof. <patcit id="pcit0004" dnum="US20050162815A"><text>US Patent Publ. No. 2005/0162815</text></patcit>, which is incorporated herein by reference, claims to provide an improved solid electrolytic capacitor by providing a coupling layer between a conducting polymer layer and dielectric layer, capable of bonding to both the conducting polymer layer and dielectric layer by covalent bonding, improving the adhesion and preventing voids from forming there between, thereby improving the electrical performance and reliability of the solid electrolytic capacitor

0011In the capacitor described in <patcit id="pcit0005" dnum="US7489498B"><text>US Pat. No. 7,489,498</text></patcit>, which is incorporated herein by reference, the conductive adhesive layer and the cathode terminal are connected through the organic silane layer, as a chemical bond between the organic silane layer and the conductive adhesive layer is formed. Inventors claim this enhances the adhesive property of the conductive adhesive layer and the electrode thereby improving ESR.

0012In <patcit id="pcit0006" dnum="US7800887B"><text>US Patent No. 7,800,887</text></patcit>, which is incorporated herein by reference, ESR is improved by forming an intermediate layer containing organic silane on the first electrolyte layer and a step of forming a second electrolyte layer containing a conductive polymer on the intermediate layer.

0013In <patcit id="pcit0007" dnum="US20100136222A"><text>US Pat. Publ. No. 2010/0136222</text></patcit>, which is incorporated herein by reference, a silane compound is added to the conductive polymer solution. The inventors claim the silane compounds strengthen the binding of a conductive polymer chain by a cross-linking effect.

0014<patcit id="pcit0008" dnum="US20110026191A"><text>US Pat. Publ. No. 2011/0026191</text></patcit>, which is incorporated herein by reference, teaches a method of improving the ESR stability of capacitors by providing an insulative adhesion enhancing layer with the cathode layers. Although this method gives excellent ESR stability in many solid electrolytic capacitors, this method is not universally applicable for capacitors with various types of dielectric, cathode materials, and assembly process.

0015In <patcit id="pcit0009" dnum="US6987663B"><text>US Pat. No. 6,987,663</text></patcit>, which is incorporated herein by reference, a polymeric cathode outer layer is generated by applying a dispersion comprising particles of a conductive polymer, such as polyethylene dioxythiophene:polystyrene sulfonic acid (PEDT:PSSA) and a binder. However, this method has the drawback that the ESR rises markedly under a thermal load, such as is produced for example during soldering of the capacitors. In US Patent Publ. No. <patcit id="pcit0010" dnum="US20110019339A"><text>US 2011/0019339</text></patcit>, which is incorporated herein by reference, the inventors claim that ESR stability can be improved by applying a polymeric intermediate layer between the solid electrolyte and polymeric outer layer by means of dispersions comprising particles of a conductive polypyrrole and/or polyaniline and/or polythiophene, in particular of a conductive polythiophene, having an average particle diameter in the range of 1-60 nm, and a binder.

0016Solid electrolytic capacitors containing water dispersible conductive polymer dispersion coating such as PEDT:PSSA exhibits an unusually high ESR shift on exposure to SMT conditions. In <patcit id="pcit0011" dnum="US7379290B"><text>US Patent No. 7,379,290</text></patcit>, which is incorporated herein by reference, the inventors attribute the ESR instability of PSSA containing conductive polymer dispersion to undoping of PSSA. The inventors have found that undoping of PSSA can be suppressed by adding an additive naphthalene sulfonic acid.

0017Thus there is a need for a process for solid electrolytic capacitors with improved ESR and ESR stability. A particular need is for capacitor parts to have stable ESR during surface mount temperatures.

<u>SUMMARY OF THE INVENTION</u>

0018It is an object of the invention to provide an improved solid electrolytic capacitor.

0019It is an object of the invention to provide an improved method of preparing a solid electrolytic capacitor cathode and an improved solid electrolytic capacitor formed thereby.

0020Another object of the invention is to improve ESR stability of a capacitor by interlayer crosslinking of various layers in the capacitor.

0021Another object of the invention is to prepare cathode layers containing a reactive binder or a crosslinker.

0022Another object of the invention is to prepare cathode layers containing a binder with reactive functionality.

0023Another object of the invention is to prepare cathode layers containing a crosslinker which can crosslink with the reactive binder in an adjacent layer.

0024Another object of the invention is to prepare cathode layers containing a binder with multiple reactive functionality which can react with adjacent layers containing a binder with reactive multiple functionality.

0025A particular advantage is provided by improving ESR stability on exposure to SMT reflow conditions.

0026These and other advantages, as will be realized, are provided in a method for preparing a solid electrolytic capacitor. The method includes: <ul id="ul0001" list-style="none"><li>providing an anode;</li><li>forming a dielectric on the anode;</li><li>forming a cathode on the dielectric wherein the cathode comprises interlayers and at least one interlayer comprises a monomer, oligomer or polymer with multifunctional or multiple reactive groups and an adjacent layer comprises a molecule with crosslinkable functionality; and</li><li>wherein the oligomer or polymer with multifunctional or multiple reactive groups on one layer react with the crosslinkable functionality in said adjacent layer.</li></ul>

0027Yet another advantage is provided in a capacitor with an anode and a dielectric on the anode. A cathode is on the dielectric wherein the cathode comprises interlayers wherein at least one interlayer comprises a monomer, oligomer or polymer with multifunctional or multiple reactive groups and an adjacent interlayer comprises a molecule cross-linked to the multifunctional or multiple reactive groups.

FIGURES

0028<figref idref="f0001">Fig. 1</figref> is a schematic cross-sectional view of an embodiment of the invention.

0029<figref idref="f0002">Fig. 2</figref> is a schematic partial cross-sectional view of an embodiment of the invention.

0030<figref idref="f0003">Fig. 3</figref> is a flow chart representation of an embodiment of the invention.

DESCRIPTION

0031The instant invention is specific to a method of making a solid electrolytic capacitor and a solid electrolytic capacitor with interlayer crosslinking between adjacent layers of the capacitor and specifically interlayer crosslinking between adjacent cathode interlayers. More specifically, the instant invention is specific to a solid electrolytic capacitor with improved ESR achieved by the use of interlayer crosslinking between various layers of the capacitor specifically interlayer crosslinking between various cathode interlayers.

0032The invention will be described with reference to the various figures which form an integral non-limiting component of the disclosure. Throughout the disclosure similar elements will be numbered accordingly.

0033An embodiment of the invention is illustrated in cross-sectional schematic side view in <figref idref="f0001">Fig. 1</figref>. In <figref idref="f0001">Fig. 1</figref>, a capacitor, generally represented at 10, comprises an anode, 12, with an anode lead wire, 14, extending therefrom or attached thereto. The anode lead wire is preferably in electrical contact with an anode lead, 16. A dielectric, 18, is formed on the anode and preferably the dielectric encases at least a portion, and preferably the entire, anode. A cathode, 20, is on the dielectric and encases a portion of the dielectric with the proviso that the cathode and anode are not in direct electrical contact. A cathode lead, 22, is in electrical contact with the cathode. In many embodiments it is preferred to encase the capacitor in a non-conductive resin, 24, with at least a portion of the anode lead and cathode lead exposed for attachment to a circuit board as would be readily understood by one of skill in the art. The cathode comprises multiple interlayers which are cross-linked to each other as will be more fully described herein.

0034An embodiment of the invention is illustrated in partial cross-sectional schematic view in <figref idref="f0002">Fig. 2</figref>. In <figref idref="f0002">Fig. 2</figref>, the cathode, 20, comprises multiple interlayers, 201-204, which are illustrated schematically, wherein the cathode is formed on the dielectric, 18. Cross-linkable functionality in adjacent interlayers are caused to react to form a covalent linkage, 26, between adjacent interlayers which is referred to in the art as cross-linking or cross-linked layers. While not limited thereto the cathode interlayers are preferably selected from layers of conductive polymer, carbon containing layers and metal containing layers most preferably in sequential order. In a particularly preferred embodiment a first interlayer, 201, is at least one conductive polymer layer formed either by in-situ polymerization or by repeated dipping in a slurry of conductive polymer with at least partial drying between dips. It is well understood that soldering a lead frame, or external termination, to a polymeric cathode is difficult. It has therefore become standard in the art to provide conductive interlayers which allow solder adhesion. A second interlayer, 202, which is preferably at least one carbon interlayer, is typically applied to the conductive polymer interlayer, 201. The carbon interlayer, or series of carbon interlayers, provides adhesion to the conductive polymer interlayer and provides a layer upon which a third interlayer, which is preferably at least one metal containing interlayer, 203, will adequately adhere. Particularly preferred metal layers comprise silver, copper or nickel. The metal interlayer is a solderable layer thereby allowing external terminations, such as a cathode lead, 22, to be attached to the cathodic side of the capacitor such as by solder or an adhesive interlayer, 204. In a particularly preferred embodiment crosslinking occurs between a carbon interlayer and a conductive polymer interlayer.

0035An embodiment of the invention is illustrated in flow chart form in <figref idref="f0003">Fig. 3</figref>. In <figref idref="f0003">Fig. 3</figref>, the method of forming a solid electrolytic capacitor of the instant invention is illustrated. In <figref idref="f0003">Fig. 3</figref>, an anode is provided at 32. A dielectric is formed on the surface of the anode at 34 with a particularly preferred dielectric being the oxide of the anode. A cathode layer is formed at 36 wherein the cathode comprises multiple interlayers. Interlayers may include at least one intrinsically conducting polymer layer; at least one carbon containing layer and at least one metal containing layer. At least one interlayer comprises crosslinkable functionality and an adjacent interlayer comprises multifunctional or multiple reactive groups. In a particularly preferred embodiment a first interlayer comprising an intrinsically conductive polymer layer is cross-linked with a second interlayer comprising carbon. In another particularly preferred embodiment a first interlayer comprising carbon is cross-linked with a second interlayer comprising metal. Anode and cathode leads are attached to the anode and cathode respectively at 38 and the capacitor is optionally, but preferably, encased at 40 and tested.

0036Cross-linking adjacent interlayers are formulated to comprise cross-linkable functionality wherein the cross-linkable functionality of one interlayer can be cross-linked with cross-linkable functionality of the adjacent interlayer thereby forming a covalent bond which spans across the boundary of the two adjacent interlayers.

0037The invention thus provides a process for improved ESR stability by providing a molecule, oligomer, or polymer with crosslinkable functionality in one interlayer and another molecule, oligomer, or polymer with crosslinkable functionality and preferably multifunctional or multiple reactive groups in an adjacent interlayer. Once exposed to curing conditions, which is typically thermal curing, the crosslinkable molecules in adjacent interlayers react with each other thus forming a strongly covalently bound interpenetrating network integral to both adjacent interlayers. Due to this significantly enhanced adhesion, the cathode interlayers resist delamination when exposed to surface mount temperatures.

0038The interlayer crosslinkable materials preferably comprise two components with one component preferably being a compound, oligomer or polymer with multifunctional or multiple reactive groups. The second component is preferably a molecule with crosslinkable functionality preferably selected from the group consisting of carboxylic, hydroxyl, amine, epoxy, anhydride, isocyanate, imide and amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylates, vinyls, maleates, maleimides, itaconates, allyl alcohol esters, dicyclo-pentadiene-based unsaturations, unsaturated C₁₂-C₂₂ fatty esters or amides, carboxylic acid salts or quaternary ammonium salts.

0039In one embodiment the invention includes a solid electrolytic capacitor comprising an interlayer crosslinkable material system where oligomer or polymer comprising multifunctional reactive groups selected from the group consisting of polyester, polyurethane, polyamide, polyamine, polyimide, silicone polyester, hydroxyl functional silicone, hydroxyethyl cellulose, polyvinyl alcohol, phenolic, epoxy, butyral, copolymers of these or mixture of these multifunctional polymers such as epoxy/amine, epoxy/anhydride, isocyanate/amine, isocyanate/alcohol, unsaturated polyesters, vinyl esters, unsaturated polyester and vinyl ester blends, unsaturated polyester/urethane hybrid resins, polyurethane-ureas, reactive dicyclopentadiene resins or reactive polyamides. The oligomer or polymer with multifunctional or multiple reactive groups preferably includes at least one carboxylic acid group and at least one hydroxyl function group. A particularly preferred oligomer or polymer with multifunctional reactive groups is a polyester containing carboxylic and hydroxyl functionality. In addition to oligomers or polymers, particles with surface functional groups can also take a part in the interlayer crosslinking. Particles with functional groups slected from carboxylic, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylates, vinyls, maleates, maleimides, itaconates, allyl alcohol esters, dicyclo-pentadiene-based unsaturations, unsaturated C₁₂-C₂₂ fatty esters or amides, carboxylic acid salts or quaternary ammonium salts. Particles can be nanoparticles or microparticles. One example of functionalized nanoparticles is organomodified nanoclay.

0040Polyester comprising carboxylic acid with an acid number of from about 3 to 200 (mg KOH/g resin solids) is a particularly preferred oligomer or polymer with multifunctional reactive groups. More preferable is polyester comprising carboxylic acid with an acid number of from about 3 to 100 (mg KOH/g resin solids) and even more preferably about 20 to 50 or about 50 to 100 (mg KOH/g resin solids)

0041Polyester comprising carboxylic acid with a hydroxy number of from about 3 to 200 (mg KOH/g resin solids) is a particularly preferred oligomer or polymer with multifunctional reactive groups and even more preferred is a polyester comprising carboxylic acid with a hydroxy number of from about 50 to 100 (mg KOH/g resin solids).

0042In one embodiment the invention includes a solid electrolytic capacitor comprising polyester where the hydroxy number number of the polyester is from about 3 to 100 (mg KOH/g resin solids).

0043Particularly preferred molecules with crosslinkable functionality includes compounds and polymers comprising melamines, isocyanates, epoxies, hexamethoxymelamines, glyoxals, furfural aldehydes and melamine formaldehyde condensates. The compounds and polymers may further comprise additional crosslinkable functionality. A particularly preferred crosslinker is hexakis (methoyxymethyl) melamine.

0044In a preferred embodiment at least one interlayer further comprises organic or inorganic particles or fibers with reactive functional groups or carbon particle filled polymer, a metal particle filled polymer and a conductive particle filled polymer or particles of fibers with reactive functional groups or crosslinkable groups.

0045The anode is a conductor preferably selected from a metal or a conductive metal oxide. More preferably the anode comprises a mixture, alloy or conductive oxide of a valve metal preferably selected from Al, W, Ta, Nb, Ti, Zr and Hf. Most preferably the anode comprises at least one material selected from the group consisting of Al, Ta, Nb and NbO. An anode consisting essentially of Ta is most preferred. Conductive polymeric materials may be employed as an anode material. Particularly preferred conductive polymers include polypyrrole, polyaniline and polythiophene.

0046The cathode is a conductor preferably comprising at least one of manganese dioxide and a conductive polymeric material. Particularly preferred conductive polymers include intrinsically conductive polymers most preferably selected from polypyrrole, polyaniline and polythiophene. Metals can be employed as a cathode material with valve metals being less preferred. The cathode may include multiple interlayers wherein adhesion layers are employed to improved adhesion between the conductor and the termination. Particularly preferred adhesion interlayers include carbon, silver, copper, or another conductive material in a binder.

0047The dielectric is a non-conductive layer which is not particularly limited herein. The dielectric may be a metal oxide or a ceramic material. A particularly preferred dielectric is the oxide of a metal anode due to the simplicity of formation and ease of use.

0048The anode lead wire is chosen to have low resistivity and to be compatible with the anode material. The anode lead wire may be the same as the anode material or a conductive oxide thereof. Particularly preferred anode lead wires include Ta, Nb and NbO. The sacrificial lead wire may comprise the same material as the anode lead wire. When electrolyte formation of a dielectric is desired the sacrificial lead wire is preferably highly conductive with low electrical resistivity. The shape of the anode lead wire and sacrificial lead wire is not particularly limiting. Preferred shapes include round, oval, rectangular and combinations thereof. The shape of the anode lead wire is chosen for optimum electrical properties of the ultimate capacitor whereas the shape of the sacrificial lead wire is selected for strength when moving the anode.

0049The dielectric is preferably formed by dipping the anode into an anodizing solution with electrochemical conversion. Alternatively, a dielectric precursor can be applied by spraying or printing followed by sintering to form the layer. When the dielectric is an oxide of the anode material dipping is a preferred method whereas when the dielectric is a different material, such as a ceramic, a spraying or coating technique is preferred.

0050The cathode is preferably formed by dipping, coating or spraying either a conductor or a conductive precursor. Conductive precursors are materials which form a conductor after heating or activation.

0051The reaction of the crosslinkable functionality and the crosslinker occurs at elevated temperature which occurs during the normal processing steps of capacitor manufacture.

<u>Examples</u>

Comparative Example 1

0052A series of tantalum anodes using two different sets of anodes was prepared. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was dipped into a solution of iron (III) toluenesulfonate oxidant for 1 minute and sequentially dipped into ethyldioxythiophene monomer for 1 minute. The anodes were washed to remove excess monomer and by-products of the reactions after the completion of 60 minutes polymerization, which formed a thin interlayer of conductive polymer (PEDOT) on the dielectric of the anodes. This process was repeated 6 times. A commercial conductive polymer dispersion (Clevios KV2) was applied 2- 4 times to form a thick external polymer interlayer. A prior art graphite coating was applied followed by a silver interlayer. Parts were assembled and ESR before and after surface mount was measured.

Comparative Example 2

0053Parts were prepared in the same manner as in comparative Example 1 except the conductive polymer dispersion was prepared with a polyester binder. A prior art graphite coating was applied followed by a silver interlayer. Parts were assembled and ESR before and after surface mount was measured.

Example 1:

0054A series of tantalum anodes using two different sets of anodes was prepared. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was dipped into a solution of iron (III) toluenesulfonate oxidant for 1 minute and sequentially dipped into ethyldioxythiophene monomer for 1 minute. The anodes were washed to remove excess monomer and by-products of the reactions after the completion of 60 minutes polymerization, which formed a thin interlayer of conductive polymer (PEDOT) on the dielectric of the anodes. This process was repeated 6 times. An inventive conductive polymer dispersion containing binder with carboxylic and hydroxy functionality was applied 2- 4 times to form a thick external layer. A carbon containing hexamethoxymelamine, as a multifunctional crosslinker, was applied to the polymer layer. A silver layer was applied on both groups. Parts were assembled and ESR before after surface mount was measured.

Example 2:

0055A series of tantalum anodes using two different sets of anodes was prepared. The tantalum was anodized to form a dielectric on the tantalum anode. The anode thus formed was dipped into a solution of iron (III) toluenesulfonate oxidant for 1 minute and sequentially dipped into ethyldioxythiophene monomer for 1 minute. The anodes were washed to remove excess monomer and by-products of the reactions after the completion of 60 minutes polymerization, which formed a thin layer of conductive polymer (PEDOT) on the dielectric of the anodes. This process was repeated 6 times. An inventive conductive polymer dispersion containing binder with carboxylic and hydroxy functionality was applied 2-4 times to form a thick external layer. A carbon layer containing a binder with carboxylic and hydroxyl functionality was applied to the polymer layer. A silver layer was applied on both groups. Parts were assembled and ESR before (QC Final) and after surface mount (SMT) was measured. <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="39mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="22mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="top">QC Final ESR</entry><entry align="center" valign="top">SMT 5 Pass</entry><entry align="center" valign="top">ESR Shift</entry></row></thead><tbody><row><entry align="center">Comparative example 1</entry><entry align="center">45.3</entry><entry align="center">68.5</entry><entry align="center">23.2</entry></row><row><entry align="center">Inventive example 1</entry><entry align="center">46.27</entry><entry align="center">49.89</entry><entry align="center">3.62</entry></row><row><entry align="center">Inventive example 2</entry><entry align="center">49.7</entry><entry align="center">56.85</entry><entry align="center">7.15</entry></row><row><entry namest="col1" nameend="col4" align="center" /></row></tbody></tgroup><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="39mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="22mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="top">QC Final ESR</entry><entry align="center" valign="top">SMT 5 Pass</entry><entry align="center" valign="top">ESR Shift</entry></row></thead><tbody><row><entry align="center">Comparative example 2</entry><entry align="char" char="." charoff="15">39.8</entry><entry align="center">61.4</entry><entry align="center">21.6</entry></row><row><entry align="center">Inventive example 2</entry><entry align="char" char="." charoff="15">38.9</entry><entry align="center">42.25</entry><entry align="center">3.35</entry></row></tbody></tgroup></table></tables>

0056The invention has been described with reference to the preferred embodiments without limit thereto. One of skill in the art would realize additional embodiments and improvements which are not specifically set forth herein but which are within the scope of the invention as more specifically set forth in the claims appended hereto.