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Title:
FACE DOWN MLCC
Document Type and Number:
WIPO Patent Application WO/2018/093626
Kind Code:
A1
Abstract:
An multilayered ceramic capacitor is provided with mitigated microphonic noise propagation. The multilayered ceramic capacitor comprising a body comprising at least one face wherein the face has a body length. Parallel internal electrodes of alternating polarity are in the body wherein each internal electrode has a tab integral thereto wherein adjacent tabs are not in registration and alternate tabs are in registration. A dielectric is between adjacent internal electrodes. External terminations wherein a first external termination are in electrical contact with first tabs in registration and a second external termination is in electrical contact with second tabs in registration wherein the first external termination and second external termination are on the face and separated by a termination separation. A ratio of the termination separation to the body length is no more than 0.6 and the body comprises an extended portion beyond the external terminations.

Inventors:
VAUGHAN, Randal, J. (2835 Kemet Way, Simpsonville, SC, 29681, US)
CROSBY, Gregory, L. (2835 Kemet Way, Simpsonville, SC, 29681, US)
GURAV, Abhijit (2835 Kemet Way, Smpsonville, SC, 29681, US)
Application Number:
US2017/060526
Publication Date:
May 24, 2018
Filing Date:
November 08, 2017
Export Citation:
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Assignee:
KEMET ELECTRONICS CORPORATION (2835 Kemet Way, Simpsonville, SC, 29681, US)
International Classes:
H01G4/12; A61N1/375; B05D3/08; B05D3/12; B05D5/12; H01B19/00; H01G2/06
Foreign References:
US20070165361A12007-07-19
US6292351B12001-09-18
US20140104750A12014-04-17
US20140002952A12014-01-02
US20140266002A12014-09-18
Attorney, Agent or Firm:
GUY, Joseph, T. et al. (Perkins Law Firm, LLC200 N. Main Street, Suite 30, Greenville SC, 29681, US)
Download PDF:
Claims:
Claimed is:

1 . A multilayered ceramic capacitor comprising:

a body comprising at least one face wherein said face has a body length; parallel internal electrodes of alternating polarity in said body wherein each internal electrode of said internal electrodes has a tab integral thereto wherein adjacent tabs are not in registration and alternate tabs are in registration;

a dielectric between adjacent said internal electrodes;

external terminations wherein a first external termination of said external

terminations is in electrical contact with first tabs in registration and a second external termination of said external terminations is in electrical contact with second tabs in registration wherein said first external termination and said second external termination are on said face and separated by a termination separation; and

wherein a ratio of said termination separation to said body length is no more than 0.6 and said body comprises an extended portion beyond said external terminations.

2. The multilayered ceramic capacitor of claim 1 wherein said ratio is no more than 0.5.

3. The multilayered ceramic capacitor of claim 1 wherein said ratio is at least 0.1 .

4. The multilayered ceramic capacitor of claim 1 wherein said ceramic is barium titanate.

5. The multilayered ceramic capacitor of claim 1 comprising external

terminations on only one face of said body.

6. The multilayered ceramic capacitor of claim 5 comprising only two external terminations.

7. An electrical component comprising:

a circuit board comprising a first trace and a second trace;

a multilayered ceramic capacitor comprising:

a body comprising at least one face wherein said face has a body length; parallel internal electrodes of alternating polarity in said body wherein each internal electrode of said internal electrodes has a tab integral thereto wherein adjacent tabs are not in registration and alternate tabs are in registration;

a dielectric between adjacent said internal electrodes;

external terminations wherein a first external termination of said external

terminations is in electrical contact with first tabs in registration and a second external termination of said external terminations is in electrical contact with second tabs in registration wherein said first external termination and said second external termination are on said face and separated by a termination separation; and

wherein a ratio of said termination separation to said body length is no more than 0.6 and said body comprises an extended portion beyond said external terminations;

wherein said first external termination is in electrical contact with said first trace and said second external termination is in electrical contact with said second trace.

8. The electrical component of claim 7 wherein said ratio is no more than 0.5.

9. The electrical component of claim 7 wherein said ratio is at least 0.1 .

10. The electrical component of claim 7 wherein said ceramic is barium titanate.

1 1 . The electrical component of claim 7 wherein said extended portion is not in mechanical contact with said circuit board.

12. The electrical component of claim 7 wherein said electrical contact is by an interconnect.

13. The electrical component of claim 12 wherein said interconnect is selected from the group consisting of solder, conductive adhesive, polymer solder, a TLPS bond, a sintered metal interconnect, a diffusion solder bond and a direct copper bond.

14. The electrical component of claim 13 wherein said interconnect comprises a low melting temperature metal and a high melting temperature metal.

15. The electrical component of claim 14 wherein said low melting point metal is selected from the group consisting of indium, tin, lead, antimony, bismuth, cadmium, zinc, gallium, tellurium, mercury, thallium, selenium, and polonium.

16. The electrical component of claim 14 wherein said high temperature melting metal is selected from the group consisting of silver, copper, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron and molybdenum.

17. The electrical component of claim 7 comprising external terminations on only one face of said body.

18. The electrical component of claim 17 comprising only two external

terminations.

19. A process of forming an electrical component comprising:

forming an interleaved stack of internal electrodes with dielectric there

between wherein each internal electrode of said internal electrodes comprises a tab wherein adjacent tabs are not in registration and alternate tabs are in registration;

laminating said stack to form a body wherein said body has a body length; forming a first external termination in electrical contact with first tabs in a first registration and forming a second external termination in electrical contact with second tabs in a second registration wherein said first external termination and said second termination are separated by a termination separation wherein a ratio of said terminal separation to said body length is no more than 0.6;

providing a circuit board comprising a first circuit trace and a second circuit trace;

electrically connecting said first external termination to said first circuit trace; and

electrically connecting said second external termination to said second circuit trace.

20. The process of forming an electrical component of claim 19 wherein said ratio is no more than 0.5.

21 . The process of forming an electrical component of claim 19 wherein said ratio is at least 0.1 .

22. The process of forming an electrical component of claim 19 wherein said ceramic is barium titanate.

23. The process of forming an electrical component of claim 19 wherein said extended portion is not in mechanical contact with said circuit board.

24. The process of forming an electrical component of claim 19 wherein said electrically connecting is by an interconnect.

25. The process of forming an electrical component of claim 24 wherein said interconnect is selected from the group consisting of solder, conductive adhesive, polymer solder, a TLPS bond, a sintered metal interconnect, a diffusion solder bond and a direct copper bond.

26. The process of forming an electrical component of claim 25 wherein said

interconnect comprises a low melting temperature metal and a high melting temperature metal.

27. The process of forming an electrical component of claim 26 wherein said low melting point metal is selected from the group consisting of indium, tin, lead, antimony, bismuth, cadmium, zinc, gallium, tellurium, mercury, thallium, selenium, and polonium.

28. The process of forming an electrical component of claim 26 wherein said high temperature melting metal is selected from the group consisting of silver, copper, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron and molybdenum.

29. The process of forming an electrical component of claim 19 comprising

external terminations on only one face of said body.

30. The process of forming an electrical component of claim 29 comprising only two external terminations.

Description:
FACE DOWN MLCC

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority to pending U.S. Provisional

Application No. 62/422,223 filed November 15, 2016 which is incorporated herein by reference.

BACKGROUND

[0002] The present invention is related to electronic components and methods of making electronic components. More specifically, the present invention is related to multilayered ceramic capacitors with reduced microphonic noise achieved through structural and mounting improvements.

[0003] Multilayer ceramic capacitors, or MLCC's, manufactured with polarized dielectrics, such as barium titanate, are prone to microphonic noise. Microphonic noise is believed to be caused by the electrostriction, also referred to as the piezoelectric effect, which is the movement of ceramic that occurs in the presence of an applied electric filed. The ceramic movement can be magnified by the circuit board on which the component is mounted ultimately producing an audible noise when an electric field is applied. Leads mitigate the microphonic noise, however, leads are contradictory to the ever present desire for miniaturization, simplification, reduced manufacturing steps and reduced cost. With leadless capacitors, and particularly leadless stacks of capacitors mounted on a circuit board, microphonic noise can be enhanced which is highly undesirable, particularly, in portable devices such as cell phones and the like. It is therefore a desire to achieve the advantages of a leadless capacitor, and particularly leadless capacitor stack, while minimizing or eliminating microphonic noise. [0004] One approach to the reduction of microphonic noise has been to isolate the vibrations, or transfer of the vibrational energy, through lead frames thereby reducing the transference of mechanical energy to the substrate or circuit board. While beneficial, these techniques still result in some microphonic noise, especially, if a multiplicity of capacitors are electrically coupled and the vibrations can be coupled or harmonic.

[0005] In spite of the efforts to minimize microphonic noise propagation there is still a need for improvements, especially, improvements which are consistent with miniaturization efforts. A significant improvement is provide herein.

SUMMARY OF THE INVENTION

[0006] The present invention is related to an MLCC with reduced microphonic noise propagation.

[0007] More specifically, the present invention is related to an MLCC which is suitable for leadless mounting in a face-down configuration with minimal microphonic noise propagation.

[0008] A particular feature of the invention is the reduced space requirement of the MLCC relative to leaded MLCC's.

[0009] These and other embodiments, as will be realized, are provided in a multilayered ceramic capacitor comprising a body comprising at least one face wherein the face has a body length. Parallel internal electrodes of alternating polarity are in the body wherein each internal electrode has a tab integral thereto wherein adjacent tabs are not in registration and alternate tabs are in registration. A dielectric is between adjacent internal electrodes. External terminations wherein a first external termination are in electrical contact with first tabs in registration and a second external termination is in electrical contact with second tabs in registration wherein the first external termination and second external termination are on the face and separated by a termination separation. A ratio of the termination separation to the body length is no more than 0.6 and the body comprises an extended portion beyond the external terminations.

[0010] Yet another embodiment is provided in an electrical component comprising a circuit board comprising a first trace and a second trace with a multilayered ceramic capacitor attached to the circuit board. The multilayered ceramic capacitor comprises a body comprising at least one face wherein the face has a body length. Parallel internal electrodes of alternating polarity are in the body wherein each internal electrode has a tab integral thereto wherein adjacent tabs are not in registration and alternate tabs are in registration. A dielectric is between adjacent internal electrodes. External terminations are provided wherein a first external termination is in electrical contact with first tabs in registration and a second external termination is in electrical contact with second tabs in registration wherein the first external termination and second external termination are on the face and separated by a termination separation. A ratio is defined by the termination separation to the body length and the ratio is no more than 0.6 and the body comprises an extended portion beyond the external terminations. The first external termination is in electrical contact with the first trace and the second external termination is in electrical contact with the second trace.

[0011] Yet another embodiment is provided by a process of forming an electrical component comprising: forming an interleaved stack of internal electrodes with dielectric there between wherein each internal electrode comprises a tab wherein adjacent tabs are not in registration and alternate tabs are in registration;

laminating the stack to form a body wherein the body has a body length;

forming a first external termination in electrical contact with first tabs in a first registration and forming a second external termination in electrical contact with second tabs in a second registration wherein the first external termination and second termination are separated by a termination separation wherein a ratio of the terminal separation to the body length is no more than 0.6;

providing a circuit board comprising a first circuit trace and a second circuit trace; electrically connecting the first external termination to the first circuit trace; and electrically connecting the second external termination to the second circuit trace.

BRIEF DESCRIPTION OF DRAWINGS

[0012] Fig. 1 is a perspective side view of an embodiment of the invention.

[0013] Fig. 2 is a cross-sectional schematic view of an embodiment of the invention.

[0014] Fig. 3 is a schematic view of a layer of electrode precursors for manufacturing an embodiment of the invention.

[0015] Fig. 4 is a schematic exploded layer of electrode precursors for manufacturing an embodiment of the invention.

[0016] Fig. 5 is a bottom schematic view of an embodiment of the invention.

DESCRIPTION [0017] The present invention is related to an improved multilayered ceramic capacitor (MLCC) and more particularly to an MLCC with reduced propagation of microphonic noise and an electronic component comprising the MLCC. The MLCC of the present invention comprises external terminations on a common face, and preferably only one face, wherein the external terminations are in close proximity thereby providing for a portion of the MLCC to be physically unrestrained and capable of dissipating vibrations caused by electrostriction within the body of the MLCC thereby significantly reducing propagation of the vibration into the circuit board or into other structural components of the circuit design.

[0018] MLCC's are well known to include conductive planar layers with dielectric there between wherein adjacent layers are terminated to external terminations of opposite polarity. Whereas most MLCC's are terminated at the ends the present invention utilizes an electrode pattern which allows the external terminations of opposite polarity be in close proximity but not sufficiently close to allow for electrical arcing. By utilizing external terminations on the body, as opposed to the ends, any vibration within the body of the capacitor is isolated within the capacitor and vibrations do not transfer to the circuit board.

[0019] The invention will be described with reference to the figures forming an integral, non-limiting, component of the disclosure. Throughout the various figures similar elements will be numbered accordingly.

[0020] An embodiment of the invention is illustrated in Fig. 1 . In Fig. 1 an MLCC is illustrated schematically in isolated perspective view. In Fig. 1 , the capacitor, generally represented at 10, comprises a monolithic body, 16, wherein one face of the body comprises two external terminations, 12 and 14, of opposite polarity. An extended portion, 18, of the body extends beyond the external terminations, preferably on each side, wherein the extended portion is not in direct mechanical contact with the circuit board.

[0021] An embodiment of the invention is illustrated in schematic cross-sectional view in Fig. 2 wherein a capacitor, 10, is mounted to a circuit board, 26, in a facedown configuration forming an electrical component, 27. The circuit board

comprises pads, 22 and 24, of opposite polarity wherein the external terminations, 12 and 14, of the MLCC, are mechanically secured to, and in electrical contact with, the pads by an interconnect, 20. As would be realized the pads are traces or are in electrical contact with traces. Internal electrodes, 28, comprising tabs, 30, are interleaved with ceramic between adjacent internal electrodes wherein the tabs of adjacent electrodes are of opposite polarity as will be described further herein. The extended portion, 18, of the body, 16, extends beyond the external terminations wherein the extended portion is not in direct mechanical contact, and preferably not in any mechanical contact, with the circuit board, 26, and is therefore allowed to vibrate with minimal transfer of the vibrational energy to the centrally located external terminations and therefore minimal transfer of the vibrational energy to the pad, circuit trace or circuit board.

[0022] MLCC's are prepared by sequentially layering ceramic precursors and conductor precursors in appropriate registration as known in the art. After a sufficient number of layers are built up the assembly is heated to form alternating layers of internal conductors and sintered ceramic.

[0023] An embodiment of the invention will be described with reference to Fig. 3 wherein electrode patterns suitable for preparation of the capacitor are illustrated schematically. In Fig. 3 each layer comprises an array, 32, of electrodes, 28, formed by techniques well known to those of skill in the art, wherein each electrode has a tab, 30, integral thereto. A series of arrays, preferably identical arrays for manufacturing convenience, are stacked sequentially with a dielectric precursor layer there between. Each layer is offset relative to adjacent array layers by the period, P, of the print pattern such that the tabs, 30, of adjacent layers are offset as illustrated in Fig. 4 wherein a layered assembly is illustrated in isolated exploded view for the purposes of discussion. Dielectric, 34, separates adjacent layers as known in the art. After lamination and heating adjacent tabs are not in registration and alternate tabs are in registration. Therefore, alternate tabs are in registration and of common polarity as represented by 30 1 , all of which are in registration, and 30 2 , all of which are in registration, wherein each tab, 30 1 , is adjacent at least tab, 30 2 , and not in registration. Many layers may be stacked with the tabs of alternate layers being in registration and tabs of adjacent layers being out of registration.

[0024] The layered assembly is fired, as known in the art, to sinter the ceramic followed by cutting along the cut lines, 38, thereby provided isolated capacitor precursors. External terminations are then formed in electrical contact with the tabs.

[0025] An embodiment of the invention will be described with reference to Fig. 5 wherein an capacitor, 10, is illustrated schematically in bottom view. The external terminations, 12 and 14, are separated by a termination separation, 40, measured from the center of each electrode. An arc distance, 42, is a minimal distance necessary to insure the electrodes of opposite polarity do not electrically arc at their closest approach distance and is dependent on the material of construction and voltage. The extended portion, 18, extends from the external terminations a shelf distance, 44, which is the balance of the body width, 46, beyond the external termination. As would be realized from the discussion herein, the largest shelf distance, 44, achievable with the external terminations as close as possible but no closer than the minimal arc distance, 42, is preferable. For purposes of clarity the separation of the external electrodes will be defined by a spacing ratio which is the ratio of the termination separation, 40, to the body width, 46, with the understanding that the termination separation must be greater than the arc distance and preferably larger than the arc distance by at least 10% of the arc distance. It is preferred that the spacing ratio be no more than 0.6. Above about 0.6 the microphonic noise propagation increases significantly. More preferably, the spacing ratio is no more than 0.5. Below about 0.5 the microphonic noise propagation is mitigated and the increase of arcing increases. It is preferable that the spacing ratio be at least 0.1 to mitigate electrical arcing while also prohibiting propagation of microphonic noise.

[0026] The capacitor is mounted in a face-down orientation with the external terminations between the body of the MLCC and the circuit board in accordance with standard practice. The area beyond the external terminations, or extended portion, is preferably not otherwise attached to the board, electrically or mechanically, thereby providing a region extending beyond the connection to the board wherein the extended region is physically unrestrained and therefore any vibration is effectively dampened or maintained within the capacitor body and not effectively transferred to the circuit board.

[0027] While not limited to theory, it is hypothesized that the shorter length of circuit board between the mounting points is effectively stiffer and more resistant to bending and vibration. Also, the ends of the MLCC which are beyond the

terminations are not coupled to the circuit board and are thus free to move, in a vibrational manner without significant transfer of that movement to the circuit board.

[0028] The dielectric layers are not particularly limited herein and any dielectric suitable for use in an MLCC can be utilized, however, the advantages are specific to dielectrics which are susceptible to electrostriction and therefore the invention is best demonstrated with polar dielectrics such as barium titanate.

[0029] Each dielectric layer has a preferred thickness of up to about 50 pm, more preferably up to about 20 pm. The lower limit of thickness is about 0.5 pm, preferably about 2 pm. The number of dielectric layers stacked is generally from 2 to about 1000, preferably from 2 to about 450.

[0030] The conductor which forms the internal electrode layers is not limited herein, although a base metal is preferably used since the dielectric material of the commonly employed dielectric layers typically has anti-reducing properties. Typical base metals are nickel and nickel alloys. Preferred nickel alloys are alloys of nickel with at least one member selected from Mn, Cr, Co, and Al, with such nickel alloys containing at least 95 wt % of nickel being more preferred. It is to be noted that nickel and nickel alloys may contain up to about 0.1 wt % of phosphorous and other trace components. Other conductors which may be employed as internal electrodes include copper, precious metals or alloys thereof with particularly preferred precious metals selected from palladium and silver. It would be understood that with copper or precious metal containing internal electrodes lower temperature firing is preferred.

[0031] The thickness of the internal electrode layers may be suitably determined in accordance with a particular purpose and application although the upper limit is typically about 5 pm, more preferably about 2.5 pm, and the lower limit is typically about 0.5 pm. Most preferable is a thickness of about 1 pm.

[0032] The conductor which forms the external electrodes is not particularly limited, although inexpensive metals such as nickel, copper, and alloys thereof are preferred. The thickness of the external electrodes may be suitably determined in accordance with a particular purpose and application although it generally ranges from about 10 m to about 50 m. In one embodiment a conductive metal, preferably silver, filled epoxy termination is utilized as a termination.

[0033] The multilayer ceramic chip capacitor of the present invention is generally fabricated by forming a green chip by conventional printing and sheeting methods using pastes. After firing of the chip the external terminations, also referred to as external electrodes, are formed by printing or transferring precursors of the external termination followed by baking.

[0034] Paste for forming the dielectric layers can be obtained by mixing a raw dielectric material with an organic vehicle. The raw dielectric material may be a mixture of oxides and composite oxides. Also useful are various compounds which convert to such oxides and composite oxides upon firing. These include, for example, carbonates, oxalates, nitrates, hydroxides, and organometallic compounds. The dielectric material is obtained by selecting appropriate species from these oxides and compounds and mixing them. The proportion of such compounds in the raw dielectric material is determined such that after firing, the specific dielectric layer composition may be met. The raw dielectric material is generally used in powder form having a mean particle size of about 0.1 to about 3 pm, preferably about 0.5 pm.

[0035] Paste for forming internal electrode layers is obtained by mixing an electro-conductive material with an organic vehicle. The conductive material used herein includes conductors such as conductive metals and alloys as mentioned above and various compounds which convert into such conductors upon firing, for example, oxides, organometallic compounds and resinates. The binder used herein is not critical and may be suitably selected from conventional binders such as ethyl cellulose. Also, the organic solvent used herein is not critical and may be suitably selected from conventional organic solvents such as terpineol, butylcarbinol, acetone, and toluene in accordance with a particular application method such as a printing or sheeting method.

[0036] Paste for forming external electrodes is prepared by the same method as the internal electrodes layer-forming paste.

[0037] No particular limit is imposed on the organic vehicle content of the respective pastes. Often the paste contains about 1 to 5 wt % of the binder and about 10 to 50 wt % of the organic solvent. If desired, pastes may contain any other additives such as dispersants, plasticizers, dielectric compounds, and insulating compounds. The total content of these additives is preferably up to about 10 wt %.

[0038] A green chip may be prepared from the dielectric layer-forming paste and the internal electrode layer-forming paste. In the case of a printing method, a green chip is prepared by alternately printing the pastes onto a substrate of polyethylene terephthalate (PET), for example, to form a laminar stack, cutting the laminar stack to a predetermined shape and separating it from the substrate.

[0039] Also useful is a sheeting method wherein a green chip is prepared by forming green sheets from the dielectric layer-forming paste, printing the internal electrode layer-forming paste on the respective green sheets, and stacking the printed green sheets. A capacitor with a large number of layers can be prepared in this manner as well known in the art.

[0040] The method of forming the capacitor is not particularly limiting herein.

[0041] The binder is removed from the green chip and fired. Binder removal may be carried out under conventional conditions, preferably under the conditions where the internal electrode layers are formed of a base metal conductor such as nickel and nickel alloys.

[0042] For binder removal the heating rate is preferably about 5 to 300°C/hour, more preferably 10 to 100°C/hour. The holding temperature is preferably about 200 to 400°C, more preferably 250 to 300°C and the holding time is preferably about 1/2 to 24 hours, more preferably 5 to 20 hours in air. An inert or reducing atmosphere may be provided at temperatures exceeding 225°C to limit oxidation of the inner electrodes. The green chip is fired in an atmosphere which may be determined in accordance with the type of conductor in the internal electrode layer-forming paste. Where the internal electrode layers are formed of a base metal conductor such as nickel and nickel alloys, the firing atmosphere may have an oxygen partial pressure of 10 "8 to 10 "12 atm. Extremely low oxygen partial pressure should be avoided, since at such low pressures the conductor can be abnormally sintered and may become disconnected from the dielectric layers. At oxygen partial pressures above the range, the internal electrode layers are likely to be oxidized.

[0043] For firing, the chip preferably is held at a temperature of 1 , 100 °C to 1 ,400°C, more preferably 1 ,250 to 1 ,400°C. Lower holding temperatures below the range would provide insufficient densification whereas higher holding temperatures above the range can lead to poor DC bias performance. The heating rate is preferably 50 to 500°C /hour, more preferably 200 to 300°C/hour with a holding time of 1/2 to 8 hours, more preferably 1 to 3 hours. The cooling rate is preferably 50 to 500 °C/hour, more preferably 200 to 300 °C/hour. The firing atmosphere preferably is a reducing atmosphere. An exemplary atmospheric gas is a humidified mixture of N 2 and H 2 gases. [0044] Firing of the capacitor chip in a reducing atmosphere is preferably followed by annealing. Annealing is effective for re-oxidizing the dielectric layers, thereby optimizing the resistance of the ceramic to dielectric breakdown. The annealing atmosphere may have an oxygen partial pressure of at least 10 "6 atm., preferably 10 " 5 to 10 "4 atm. The dielectric layers are not sufficiently re-oxidized at low oxygen partial pressures below the range whereas the internal electrode layers are likely to be oxidized at oxygen partial pressures above this range.

[0045] For annealing, the chip is preferably held at a temperature of lower than 1 , 100 °C, more preferably 500 °C to 1 ,000 °C. Lower holding temperatures below this range would oxidize the dielectric layers to a lesser extent, thereby leading to a shorter life. Higher holding temperatures above the range can cause the internal electrode layers to be oxidized, which leads to a reduced capacitance, and to react with the dielectric material, which leads to a shorter life. Annealing can be

accomplished simply by heating and cooling. In this case, the holding temperature is equal to the highest temperature on heating and the holding time is zero.

[0046] The binder removal, firing, and annealing may be carried out either continuously or separately. If done continuously, the process includes the steps of binder removal, changing only the atmosphere without cooling, raising the

temperature to the firing temperature, holding the chip at that temperature for firing, lowering the temperature to the annealing temperature, changing the atmosphere at that temperature, and annealing.

[0047] If done separately, after binder removal and cooling down, the temperature of the chip is raised to the binder-removing temperature in dry or humid nitrogen gas. The atmosphere then is changed to a reducing one, and the temperature is further raised for firing. Thereafter, the temperature is lowered to the annealing temperature and the atmosphere is again changed to dry or humid nitrogen gas, and cooling is continued. Alternatively, once cooled down, the temperature may be raised to the annealing temperature in a nitrogen gas atmosphere. The entire annealing step may be done in a humid nitrogen gas atmosphere.

[0048] The resulting chip may be polished at end faces by barrel tumbling and sand blasting, for example, before the external electrode-forming paste is printed or transferred and baked to form external electrodes. Firing of the external electrode- forming paste may be carried out in an inert nitrogen atmosphere gases at about 600 to 800°C, and about 10 minutes to about 1 hour.

[0049] Pads are preferably formed on the external electrodes by plating or other methods known in the art.

[0050] The external terminations are preferably formed by dipping with other methods, such as ink-jet spraying being suitable. Once deposited these external terminations are sintered or cured to adhere them to the ceramic and connect to the internal electrodes.

[0051] The multilayer ceramic chip capacitors of the invention can be mounted on printed circuit boards, for example, by soldering.

[0052] The external terminations of the electronic components are not particularly limited herein with the proviso that they can be attached to a pad, either active or mechanical, by an interconnect such as solder, conductive adhesive, polymer solder, TLPS bond, sintered metal interconnects, diffusion solders or direct copper bonds. TLPS is the preferred interconnect between the external termination of the electronic component and pad. The external termination may be one component of TLPS, as will be more fully described herein, wherein additional components of the TLPS are either inserted between the external termination to be bound or is integral to the surface to which the external termination is to be bound. The TLPS materials are compatible with surface finishes containing silver, tin, gold, copper, platinum, palladium, nickel, or combinations thereof, either as lead frame finishes, component connections or inner electrodes to form an electronically conductive metallurgical bond between two surfaces.

[0053] Transient liquid phase sintering (TLPS) adhesives form a termination to an electronic element or attach external terminations to a surface such as a solder pad thereby functioning as an interconnect. TLPS terminations have the advantage of being able to accommodate different surface finishes as well as electronic elements of differing lengths. Furthermore, since no solder balls are formed electronic elements can be stacked on top of each other with only TLPS there between and without the gaps normally required for cleaning as with solder attachment

technology. TLPS can be directly bonded with the inner electrodes of the electronic component, when the electronic element is an MLCC, and the termination can be formed at low temperature. In an embodiment higher density terminations can be prepared by using a thermo-compression process thereby forming improved external lead attachment bonds.

[0054] Solders are alloys which do not undergo a change in composition after the first reflow. Solders have only one melting point and can be remelted an indefinite number of times. The most common solder is 60%Sn40%Pb. Solders have been the materials of choice in electronics to provide the mechanical and electrical

interconnects between electronic elements and circuit boards or substrates. Solders are very well suited for mass volume production assembly processes. The physical properties of solder can be altered simply by changing the ratios or the metals used to create a solder alloy. When solder is referenced herein it will imply an alloy of at least two metals that can be remelted multiple times at nearly the same temperature.

[0055] Transient liquid phase sintering (TLPS) bonds are distinguishable from solders. TLPS materials are mixtures of two or more metals or metal alloys prior to exposure to elevated temperatures thereby distinguishing the thermal history of the material. TLPS materials exhibit a low melting point prior to exposure to elevated temperatures, and a higher melting point following exposure to these temperatures. The initial melting point is the result of the low temperature metal or an alloy of two low temperature metals. The second melting temperature is that of the intermetallic formed when the low temperature metal or alloy forms a new alloy with a high temperature melting point metal thereby creating an intermetallic having a higher melting point. TLPS materials form a metallurgical bond between the metal surfaces to be joined. Unlike tin/lead or lead (Pb) free solders, the TLPS adhesives do not spread as they form the intermetallic joint. Rework of the TLPS system is very difficult due to the high secondary reflow temperatures. Transient Liquid Phase Sintering is the terminology given to a process to describe the resulting metallurgical condition when two or more TLPS compatible materials are brought in contact with one another and raised to a temperature sufficient to melt the low temperature metal. To create a TLPS process or interconnect at least one of those metals is from a family of metals having a low melting point, such as tin (Sn) or indium (In), and the second metal is from a family having high melting points, such as copper (Cu) or silver (Ag). When Sn and Cu are brought together, and the temperature elevated, the Sn and Cu form CuSn intermetallics and the resulting melting point is higher than the melting point of the metal having a low melting point. In the case of In and Ag, when sufficient heat is applied to the In to cause it to melt it actually diffuses into the Ag creating a solid solution which in turn has a higher melting point than the In itself. TLPS will be used to generically reference the process and the TLPS compatible materials used to create a metallurgical bond between two or more TLPS compatible metals. TLPS provides an electrical and mechanical interconnect that can be formed at a relatively low temperature (< 300°C) and having a secondary re-melt

temperature >600°C. These temperatures are determined by the different

combination of TLPS compatible metals. TLPS will be used to generically pertain to the process and materials used to create a TLPS metallurgical bond or interconnect. The rate of diffusion or sintering is a time temperature function and is different for the different combinations of metals. The result is a solid solution having a new melt temperature approaching that of the high temperature melting metal.

[0056] The TLPS technology is particularly suited to providing both a mechanical and electrical conductive metallurgical bond between two mating surfaces preferably that are relatively flat. The metals typically used for the TLPS process are selected from two metal families. One consists of low melting temperature metals such as indium, tin, lead, antimony, bismuth, cadmium, zinc, gallium, tellurium, mercury, thallium, selenium, or polonium and a second family consist of high temperature melting metals such as silver, copper, aluminum, gold, platinum, palladium, beryllium, rhodium, nickel, cobalt, iron and molybdenum to create a diffused solid solution.

[0057] It is highly desirable to use a flux free process to eliminate any potential voids within the joint. Since TLPS is a sintering based process, the bond line is uniform and void free. Fluxes, which are necessary with solders, get entrapped in the joint and are subsequently burned out leaving a void. In the case with the semiconductor industry, and specifically with die attach processes, these voids can create hot spots within the integrated circuit (l/C) which can lead to premature failure and reliability issues. TLPS addresses this issue since TLPS is a sintering process and free of fluxes. When the two metals are mated together and heat is applied, the lower melting metal diffuses into the higher melting metal to create a solid solution across the mating surface area. To create a solid uniform bond line it is mandatory that the mating surfaces be flat and coplanar to insure intimate contact across the entire mating surface. The required flatness of the mating surfaces also limits the application of this technology because there are many surfaces that are not sufficiently planar to yield a good joint.

[0058] The use of TLPS in paste form allows uneven surfaces to be joined. More specifically, the use of TLPS in paste form allows two irregular shaped surfaces to be joined with no intimate, or continuous, line of contact. A TLPS compatible metal particle core combined with a liquid carrier material to form a paste can be applied between two non-planar non-uniform surfaces having mixed surface preparation technologies such as plating, sintered thick film, and or plated sintered thick film and then heating to the melting temperature of the metal having the lowest melting point and holding that temperature for a sufficient amount of time to form a joint. A single metal particle core eliminates the need for multiple metals in a paste thus making the ratios of metals a non-issue. It is also possible to create a single particle by using silver, a metal having a high melting point of approximately 960°C as a core particle, and then coating that particle with a metal shell having a low temperature metal such as indium having a melting point of 157°C.

[0059] A two-step reflow can also be used with the transient liquid phase sintering process wherein in the first step an electrically conductive metallurgical bond is formed at low temperature using a relatively short time cycle, in the range of 5 seconds to 5 minutes, and low temperature, in the range of 180°C to 280°C, depending on the metals being used in the TLPS alloying process. In the second step the part is subjected to an isothermal aging process using a temperature range of 200°C to 300°C for a longer duration such as, but not limited to, 5 minutes to 60 minutes. The shorter times required to form the initial bond are well suited for an automated process. In another method a single step process can be used wherein the TLPS forms a terminal, or conductive metallurgical bond, between the external leads and electronic element(s) at temperatures of, for example, 250°C to 325°C for a duration of, for example, 10 seconds to 30 seconds. Lower temperatures, such as 175°C to 210°C, can be used for a longer duration, such as 10 to 30 minutes. This is particularly useful when the electronic component itself is sensitive to temperature.

[0060] Indium powder mixed with a flux and solvent to form a paste can be applied to produce a TLPS metallurgical bond between two coupons having a base metal of copper overplated with Ni and then overplated with about 5 microns (200 μ inches) of silver. The samples can be prepared by dispensing the indium paste onto a coupon having the plated surfaces as mentioned and then placing two coupons in contact with one another and heating to 150°C for 5 seconds, followed by increasing the temperature to about 320°C for about 60 seconds. The joint strength of the sample thus prepared can exhibit a pull weight in the range of 85-94 pounds equating to shear stress of 4, 177 psi and a pull peel weight in the range of 5-9 pounds with an average of 7 pounds can be achieved. These results are comparable to results for SnPb solders having shear strengths of approximately 3000 psi and pull peel strengths in the 7-10 pounds range. One major difference is that the Agin joint can withstand secondary melt temperatures exceeding 600°C. These results indicate that the In paste used to bond two silver plated coupons is at least equivalent if not stronger than current solder SnPb solders but also has a much higher secondary melt temperature thus yielding a material suitable for high temperature interconnect applications and also being lead free. The TLPS paste or preform may have inert fillers therein to serve two purposes. One purpose is to minimize the cost due to expensive metals and the second purpose is to make direct electrical and

metallurgical bonds directly to the non-terminated ends of the electronic element and exposed internal electrodes. The cost can be reduced, particularly, when a gap is to be filled by replacing a portion of, particularly, the high melting metal component with an inert material or with a lower cost conductive material. Particularly preferred fillers for use in place of the high melting point metal are non-metals such as ceramics with melting points > 300°C and glasses or high temperature polymers with glass transition temperatures (T g ) > 200°C. An example would be thermosetting polymers such as polyimide. Two particular advantages of replacing the high melting point metal with one of these non-metals is that the active low melting point metal of the TLPS with not be consumed by diffusion during the TLPS bond formation. The second advantage of inert fillers when selected from a family of glasses having low melting points is that the glass within the mixture of the TLPS paste or preform will create a bond with the exposed glass frit of the non-terminated and exposed ceramic body of, for example, an MLCC. The non-metals can also be coated with the low melting point metal by methods such a spraying or plating.

[0061] Sintered metal interconnects of silver as well as nano-silver and nano- copper can also be used to form interconnects. The resulting interconnect can be formed at using a low temperature sintering process but the bond formed has the high melting point of the associated with the metal, in the case of silver 960°C.

However, these processes often require elevated pressures for prolonged times in batch operation that can limit throughput compared CuSn TLPS. Also, nano-sized metals can be prohibitively expensive.

[0062] Diffusion soldering can also be used as a joining method to form the interconnect. This combines features of conventional soldering and diffusion bonding processes. The process relies on reaction between a thin layer of molten solder and metal on the components to form one or more intermetallic phases that are solid at the joining temperature. Since a low melting point material, solder reacts with a higher melting point metal this may also be considered in the broader definition of TLPS.

[0063] Direct copper bonding can also be used but this is a high temperature diffusion process primarily used in die attach so could be detrimental to some components.

[0064] Methods to adhere an external termination to a solder pad can comprise coating two mating surfaces one with a high melting point metal and its mating surface with a low melting point metal. The coating process may consist of vapor deposition or plating. A second method is to sandwich a preform film made from a low melting point metal or an alloy of two or more low melting point metals between two planar surfaces coated with a high melting point metal. A third method is to create a paste consisting of particles of a high melting point metal such as copper and then adding particles of two alloyed low melting point metals and mixed into a dual purpose liquid that cleans the surfaces to be bonded and also serves as the liquid ingredient to the metal particles to form a paste mixture.

[0065] If full diffusion of the two metals is not complete in the stated cycle time and the maximum secondary reflow temperature is not reached, the joint can be subjected to a second heating process. In this case the joint, or assembly, can be subjected to a temperature higher than that of the low melting point material and held for a period of time of from 15 minutes up to 2 hours. The time and temperature can be varied to provide a desirable secondary reflow temperature as dictated by secondary assembly processes or final environmental application requirements. In the case of the indium/silver TLPS, secondary melt temperatures in excess of 600°C can be achieved.

[0066] In addition to applying a paste to form a TLPS alloy joint between suitable surfaces this can also be achieved with a preform. In its simplest manifestation the preform can be a thin foil of the low temperature TLPS component. Alternatively, the preform can be produced by casting and drying the paste to remove the solvent. The resulting solid preform can be placed between the surfaces to be bonded. In this case it may be necessary to add a suitable binder to the paste for additional strength after drying. In all these cases the preform should be malleable such that it can conform to the surfaces to be bonded.

[0067] An interconnect comprising a single metal, such as indium, contained within a paste can be used to form a bond to a surface coated with a high melting point metal, such as silver. The diffusion of the indium into silver allows a lower temperature transient liquid phase to form that subsequently reacts to achieve a higher temperature bond. Achieving a high rate of diffusion in the lower melting point paste is critical to this bond formation. In order to achieve the desired properties in the final joint, such as reduced voids and a homogeneous phase the addition of other metals to the paste may be desirable. However, it is critical to retain the high diffusivity of the low melting point material. For this reason if one or more metals are required in addition to the low melting point metal it is preferred that these be incorporated by coating the metal powders prior to forming the paste. Coating the lowest melting point metal onto the higher melting point metal is preferred to retain an active surface. Coatings also have the desired effect of reducing the diffusion lengths between the different metallic elements of the paste allowing preferred phases to be more readily formed as opposed to a simple mixing of one or more additional metal powders to the single metal paste.

[0068] Conductive adhesives are typically cross linking polymers filled with silver or gold particles that cure or cross link within a specified temperature range, generally 150°C, to form a mechanical bond to the materials to be joined. Their conductivity is created by the metal particles making intimate contact with one another, within the confines of the polymer matrix, to form an electrically conductive path from one particle to another. Because the binder is organic in nature, they have relatively low temperature capabilities, normally in the range of about 150°C to about 300°C. Conductive epoxies, once cured, cannot be reworked. Unlike TLPS bonds, exposure to high heat or corrosive environments may decompose the polymeric bonds and oxidize the metal particles degrading the electrical properties. Both the electrical and mechanical performance of the interconnect can be compromised resulting in increased ESR and decreased mechanical strength.

[0069] Polymer solders may comprise conventional solder systems based on Pb/Sn alloy systems or lead free systems, such as Sn/Sb, which are combined with crosslinking polymers which serve as cleaning agents. The cross-linked polymers also have the ability to form a cross-linked polymer bond, such as an epoxy bond, that forms during the melting phase of the metals thereby forming a solder alloy and a mechanical polymeric bond. An advantage of polymer solders is that the polymeric bond provides additional mechanical bond strength at temperatures above the melting point of the solder, thus giving the solder joint a higher operating temperature in the range of about 5 to 80°C above the melting point of the solder. Polymer solders combine current solder alloys with a cross linking polymer within the same paste to provide both a metallurgical bond and a mechanical bond when cured, such as by heating, to provide additional solder joint strength at elevated temperatures. However, the upper temperature limits and joint strength has been increased, just by the physical properties of the materials. A practical limit of 300°C remains whereas the bonds created by TLPS can achieve higher temperatures.

[0070] In many applications a high degree of porosity may be acceptable.

However, in harsh environments, such a high humidity or in circuit board mounting processes, high porosity is not desirable since water or other chemicals may penetrate through the bond which may cause the bond to fail. A preferred

embodiment of this invention is therefore to form a low porosity termination within the transient liquid phase sintering joint using a thermo-compression bonding process. This process has the added advantage of using a low process time of 15 to 30 seconds at a temperature in the range of 225°C to 300°C in a single step making it suitable for automation. Robust joints can be created for the application of attaching external leads to electronic elements, when leads are used, with a one-step low temperature in less than 30 seconds and in combination with thermo-compression bonding.

[0071] Thermo compression bonding is also a preferred processing method when using polymer solder because it assists in the formation of a high-density

metallurgical bond between the contacting surfaces. The advantages of thermo- compression include a more robust bond with respect to secondary attachment processes and attachments with higher strength are achieved. A compressive force of 0.5 to 4.5 Kilograms/cm2 (7.1 to 64 psi) and more preferably 0.6 to 0.8 Kilograms/cm 2 (8.5 to 1 1 psi) is sufficient for demonstration of the thermo- compression teachings herein. About 0.63 Kilograms/cm2 (9 psi) is a particularly suitable pressure for demonstration of the teachings.

[0072] It is highly desirable to create a joint with minimum porosity that exhibits the following characteristics: strong mechanical strength in excess of 5 Lbs. /inch for Pull Peel test, Tensile, and Shear high electrical conductivity, low initial process temperature in the range of 150°C to 225°C, a secondary reflow temperature in excess of 300°C or higher, between non-uniform surfaces making intimate contact or having gaps up to .015 inches.

[0073] The material of construction for the circuit board is not particularly limited herein with standard printed circuit board (PCB) materials being suitable for use. Laminates, fiber reinforced resins, ceramic filled resins, specialty materials and flexible substrates are particularly suitable. Flame Retardant (FR) laminates are particularly suitable as an circuit board material and especially FR-1 , FR-2, FR-3, FR-4, FR-5 or FR-6. FR-2 is a phenolic paper, phenolic cotton paper or paper impregnated with phenol formaldehyde resin. FR-4 is particularly preferred which is a woven fiberglass cloth impregnated with epoxy resin. Composite epoxy materials (CEM) are suitable and particularly CEM-1 , CEM-2, CEM-3, CEM-4 or CEM-5 each of which comprise reinforcement such as a cotton paper, non-woven glass or woven glass in epoxy. Glass substrates (G) are widely used such as G-5, G-7, G-9, G-10, G-1 1 and others with G-10 and G-1 1 being most preferred each of which is a woven glass in epoxy. Polytetrafluoroethylene (PTFE), which can be ceramic filled, or fiberglass reinforced such as in RF-35, is a particularly suitable substrate. Electronic grade ceramic materials such as polyether ether ketone (PEEK), alumina or yttria stabilized zirconia are available with 96% AI2O3 and 99.6% AI2O3 being readily available commercially. Bismaleimide-Triazine (BT) epoxy is a particularly suitable substrate material. Flexible substrates are typically a polyimide such as a polyimide foil available commercially as Kapion or UPILEX or a polyimide-fluorpolymer composite commercially available as Pyra ux. Ferous alloys are also used such as Alloy 42, Invar, Kovar or non-ferrous materials such as Cu, Phosphor Bronze or BeCu.

[0074] The MLCC can be over-molded by a non-conductive polymer or resin. The material used for overmolding is not particularly limited herein. Overmolding can be done to isolate MLCC from electrical interaction with other elements of a circuit or to protect the package, or components therein, from environmental variations.

Overmolding can also be beneficial for labeling and for use with pick-and-place equipment since the over-molding can be applied with specific geometry identifiable by optical or mechanical equipment.

EXAMPLES

[0075] A series of conventional capacitors was prepared using barium titanate ceramic. The body of the capacitors was 6.47 mm (0.2549 inches) long 1 .78 mm (0.071 inches) wide. The capacitors were identical except for the spacing of the external terminations which were spaced as detailed in Table 1 wherein the termination separation and spacing ratio and average decibals (dBA) are provided. Table 1

[0076] As realized from the results presented in Table 1 , a significant reduction in noise is observed as indicated by as much as 10-fold reduction in the noise propagation as indicated in decibels which is logarithmic. The results of the noise testing illustrated that a spacing/chip length ratio of below 0.6, and preferably below 0.5 is sufficient to reduce the noise level by many orders of magnitude.

[0077] The invention has been described with reference to the preferred embodiments without limit thereto. Additional embodiments and improvements may be realized 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.