CN107231747A - Electric capacity, bury condenser network plate and its manufacture method - Google Patents
Electric capacity, bury condenser network plate and its manufacture method Download PDFInfo
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- CN107231747A CN107231747A CN201710575274.7A CN201710575274A CN107231747A CN 107231747 A CN107231747 A CN 107231747A CN 201710575274 A CN201710575274 A CN 201710575274A CN 107231747 A CN107231747 A CN 107231747A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
- H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
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Abstract
The present invention relates to electric capacity, bury condenser network plate and its manufacture method.The electric capacity includes：High dielectric constant polymer composite layer；Ion implanted layer, the ion implanted layer makes conductive material ion be injected into high dielectric constant polymer composite layer at a high speed and be formed by ion injection method；And metal level, it forms and is covered on the ion implanted layer.
Description
Technical field
The present invention relates to electric capacity, bury condenser network plate and its manufacture method.
Background technology
As electronic product tends to frivolous, high frequency and multifunctional direction development, circuit level more and more higher, corresponding collection
It is more and more into circuit pin and configuration, cause noise to increase therewith., can be half in order to abate the noise or do electrical compensation
Increase passive device in conductor package structure to abate the noise and stabilizing circuit.For example, electric capacity has the effect of storage electric charge, can
High frequency noise is kept in into mode with energy to be absorbed, so as to reduce system power supply fluctuation, it is ensured that the integrality of signal transmission.
It is that passive device is incorporated on substrate with SMT surface mounting technologies to increase one of capacitive way, but is easily produced
Impedance, signal cross-talk, and exhibiting high surface attachment area is occupied, do not meet electronic product increasingly strict compact requirement.
Another is that electric capacity is embedded in package substrate or PCB, this to be referred to as burying electric capacity（Buried capacitor
Device）.The substrate or circuit board fabrication of Embedded capacitance mainly include three key technologies：Electric capacity embedment technology, internal interconnection technology
Capacitance technology is buried with used.The both sides for burying electric capacity are metal levels, and centre is Jie of " high-k (Dk), low dielectric loss "
Matter layer, usual 10 μm of -25 μ m-thick greatly promotes capacitance, and electric supply system can be helped to decouple and filter, system power is reduced
The impedance of distribution and the resonance effects of high-frequency circuit.Be mainly used in high speed data transfer/communication apparatus, server, computer,
Test measurement, medical treatment, printer, display, military field and hand-held electronic product industry.
For identical voltage, frequency and capacitance, the heat generation of electric capacity is decided by dielectric loss, it is desirable to which burying electric capacity has
Relatively low dielectric loss.Whether the surface-pasted electric capacity of circuit board SMT, or in the embedment electricity that sets of inner core of circuit board
Hold, all pursue higher, more stable capacitance.Increase capacitance, three factors can be changed：1) capacitor electrode superficial area is made
Increase；2) reduce medium thickness；3) increase dielectric layer constant Dk.Increase capacitor electrode superficial area, do not meet electricity
The compact development trend of road plate；Therefore, medium thickness (≤25 μm), which is thinned, dielectric constant Dk, low-dielectric loss is improved is
The developing direction of electric capacity will be buried from now on.
For medium thickness is thinned, have been reported that insulating barrier, without using glass fiber material, is coated on copper foil using resin
Mode, had both improved reliability or can reduce dielectric thickness to 25 μm.Have been reported that use " sputtering, CVD, anodic oxidation "
Etc. method, by the high Dk media (SiO of less than 1 μm of insulation2Or ceramic particle etc.) be attached on thick copper foil, the thickness of thin insulating medium
Degree reduces following to 1 μm of the limit, can substantially increase the capacitance for burying capacity materials, but because dielectric layer is too thin, it is easy to be crisp and lose,
Machinability and reliability are poor, are restricted burying capacitance applications field.
On the other hand, under the premise of the relatively low dielectric loss of material and machinability is ensured, insulative dielectric is improved as far as possible
Constant Dk, this is the highly difficult thing of part to burying electric capacity.
The manufacturing process for burying electric capacity is generally divided into three kinds：
1) silk-screen printing：Dielectric ink or high Dk materials are printed on copper foil, again in the oil of Screen-printed conductive thereon after solidification
Another layer of copper electrode of formation such as ink, is made electric capacity.Silk-screen printing technique is simple, low cost, but the Embedded capacitance value point made
Scattered property is larger, and capacitance precision controlling is poor.
2) less than 1 μm thin film dielectrics method：Have been reported that using methods such as sputtering, CVD, anodic oxidations, by the insulation below 1 μm
High Dk media (generally inorganic ceramic material) are attached on thick copper foil or semi-conductor silicon chip, are formed close to 800oC high-temperature calcinations,
The thickness of thin insulating medium reduces to ultimate attainment, then makes another metal electrode；The technique can substantially increase electric capacity because of thin dielectric substance
Amount, but because dielectric layer is too thin, poor (dielectric layer high-temperature calcination easily produces trickle cracking or gas for machinability and reliability
Bubble, the easy leakage current of capacitor, insulation proof voltage hydraulic performance decline), it is restricted burying the application of electric capacity field.
3) lamination+etching：The industry overwhelming majority is all made with laminating buries electric capacity in copper-clad plate form.Common practice is
High Dk material resins are coated on thick copper foil (RZ2-3 μm), dried, semi-solid preparation, then another layer of copper foil pressed and
Into；Its two sides copper foil is 18,35 and 70 μm, be easy to be not easy embrittlement, clamp when etching, process operation using thicker copper foil
Deng；Intermediate dielectric layer is generally 8,12,16,25 μm.Copper foil is covered to the copper-clad plate two sides to be etched, and forms the electricity of capacitance body
Pole, then the contact laminating formation multilayer circuit board in the way of core material, will bury electric capacity and are placed in multilayer circuit board.Should " lamination
It is similar with custom circuit plate manufacturing process that capacitive way is buried in etching " technique formation, and simply, PCB producers are easily mastered technique.The work
Utilize epoxy resin and the strong feature of copper foil bonding force more skill, high Dk inorganic particles (BaTiO3 etc.) are added wherein composite wood is made
Material, but addition exceedes certain limit, have impact on the adhesion of resin and copper foil, easily peels off or bubbles during lamination copper foil, or
The fragility of person's material becomes big, causes subsequent conditioning circuit plate processability to be deteriorated.In addition, wrinkled in order to avoid copper face is laminated, the lamination work
Skill must use more than 18 μm copper foils, cause the area allowance control of capacitance electrode and become difficult, have impact on actual capacitance value
Control accuracy (general capacitance control accuracy is in 5-10%)；On the other hand, in the electrode embedment package substrate of thick copper foil, envelope is made
Substrate or the increase of semiconductor packages integral thickness are filled, is unfavorable for the development trend of thin panel design from now on.There is a kind of reduction to bury electric capacity
The method of copper thickness is to use carrier copper foil, and mainly 18 μm copper foils or other materials do carrier, it is ensured that rigidity, 2-5 μm thin
Copper foil is attached on carrier, peel-away removal carrier after lamination, is left thin copper and is made copper electrode；This carrier thin copper foil price is very
It is expensive, and be still difficult to overcome laminating copper foil roughness larger, the problem of insulating reliability is poor under thin insulating ambient condition.
4) sputtering method：Copper electrode is etched on circuit board core material, " the lower floor's copper electrode " for burying electric capacity is used as；At it
On " lower floor's copper electrode ", spray to form dielectric material (such as high Dk inks) using 3D spraying methods, then sputter on the dielectric material
The metals such as target Ni, and dry film pattern transfer, etching etc. are pasted, form copper thick relatively thin " upper strata copper electrode "；This method only side
Copper electrode thickness is reduced, and the function influence for reducing the circuit board gross thickness for burying electric capacity is limited；And cumbersome, too long in flow is made, it is difficult
The shortcoming that copper electrode surface pinholes is excessive, capacitive property is unstable is sputtered to overcome, and peel strength is less than normal, easily peelable and curved
The problems such as folding, therefore, the process, are difficult to commercially extensive use.
In summary, a kind of high-k Dk is developed（Dk>15）, high-capacitance, low-loss (Df ＜ 0.02), 25 μ m-thicks
Polymer composites below degree are as dielectric layer, dielectric thickness be uniform, heat-resisting and moisture-proof is high, levels copper electrode is thin
Copper design, copper electrode pin hole is less, cover copper high-peeling strength, it is resistant to bending, easy processing bury electric capacity and cover copper product, be to bury electricity from now on
Hold the inevitable requirement of development trend.
The content of the invention
To solve problem above, the present invention relates to a kind of electric capacity, condenser network plate and its manufacture method are buried, using " ion
Technology is right for injection "≤25 μ m thick the metallization of " polymer+high Dk particles " composite, solve that high Dk granule contents are high to answer
Condensation material or thin-film material cover thin copper, cover the problem of copper is easily peelable, and combine the continuous " ion implanting+plating+figure of volume to volume
The design of transfer+etching+cutting " Making programme, can on a large scale make and bury electric capacity composite, meet package substrate pair from now on
Bury electric capacity slimming demand for development.
According to the first aspect of the invention there is provided a kind of electric capacity, it includes：High dielectric constant polymer composite layer；
Ion implanted layer, the ion implanted layer makes conductive material ion be injected into high-k polymerization at a high speed by ion injection method
Formed in thing composite layer；And metal level, it forms and is covered on the ion implanted layer.
Preferably, the high dielectric constant polymer composite layer includes fluoropolymer resin and high dielectric constant particle.
Preferably, the injection material of the ion implanted layer and high dielectric constant polymer composite layer formation doping knot
Structure, the doped structure forms multiple foundation piles under the surface of the high dielectric constant polymer composite layer.
Preferably, the electric capacity also includes conductor sedimentary, and the conductor sedimentary is covered on the ion implanted layer, and the gold
Category layer is covered on the conductor sedimentary, and the conductor sedimentary includes plasma deposited layers and/or magnetron sputtering deposition layer,
The plasma deposited layers make conductive material ion deposition by plasma deposition method and formed；Magnetron sputtering layer passes through
Magnetically controlled sputter method makes conductive material atomic deposition and formed.
Preferably, the plasma deposited layers and magnetron sputtering layer include one or more layers conductor material, each layer
Conductor material is formed by one or many plasma-deposited or magnetron sputtering processes.
Preferably, the material of the ion implanted layer includes：One kind in Ti, Cr, Ni, Cu, Ag, Au, V, Zr, Mo, Nb or
It is a variety of, or the one or more in binary, ternary and quaternary alloy between them.
Preferably, the material of the conductor sedimentary includes：One kind in Ti, Cr, Ni, Cu, Ag, Au, V, Zr, Mo, Nb or
It is a variety of, or the one or more in binary, ternary and quaternary alloy between them.
Preferably, the material of the metal level includes：By Al, Mn, Fe, Ti, Cr, Co, Ni, Cu, Ag, Au, V, Zr, Mo, Nb
In one or more, or one or more compositions in binary, ternary and quaternary alloy between them.
Preferably, the fluoropolymer resin include epoxy resin, it is BT resins, BMI, cyanate, polyethylene, poly-
Styrene, Kynoar, polyester, makrolon, polyphenylene sulfide, fire resistant polypropylene, poly- 2,6 naphthalene diacid second diester, polyamides
One or more in imines, polytetrafluoroethylene (PTFE), polyphenylene oxide.
Preferably, the high dielectric constant particle includes inorganic ceramic particle and/or conducting particles.
Preferably, the inorganic ceramic particle includes silica, barium titanate, strontium titanates, lead zirconate titanate, load lanthanium titanate, zirconium
One or more in lead plumbate lanthanum, strontium bismuth tantalate.
Preferably, the conducting particles include CNT, carbon black, graphite composite powder, Al, Al2O3, Ag, Ni in one kind or
It is a variety of.
Preferably, the percentage by weight that the high dielectric constant particle accounts for the high dielectric constant polymer composite layer is
10-90%。
Preferably, the percentage by weight that the high dielectric constant particle accounts for the high dielectric constant polymer composite layer is
More than 80%.
Preferably, the metal level is obtained by the one or more in plating, chemical plating, vacuum evaporation coating.
Preferably, the thickness of the high dielectric constant polymer composite layer is 8-25 μm.
Preferably, the electric capacity is the electric capacity of form of film.
According to the second aspect of the invention there is provided a kind of method for manufacturing the electric capacity according to the present invention, it includes following step
Suddenly：A) high dielectric constant particle and mixed with polymers are obtained into the high dielectric constant polymer composite layer；B) to this
High dielectric constant polymer composite carries out ion implanting to form ion implanted layer；And c) on the ion implanted layer
Metal is covered to form the metal level.
Preferably, step a)-c are additionally included in) after following steps：D) pre-treatment, pad pasting, exposure, development, etching,
AOI is checked；And e) cut.
Preferably, volume to volume the electric capacity is continuously manufactured.
Condenser network plate is buried there is provided one kind according to the third aspect of the invention we, it includes：According to the electric capacity of the present invention；With
And the electric capacity is embedded to circuit base material therein.
According to the fourth aspect of the invention there is provided a kind of method for manufacturing and burying condenser network plate, it comprises the following steps：Root
The step of according to method of the invention；And condenser network plate will be buried in electric capacity lamination embedment circuit base material to obtain this.
Compared with prior art, beneficial effects of the present invention are as follows：
1. the present invention uses ion implantation technique, due to injecting the high-energy of metal ion, it may be implemented in dielectric constant content and reach
Metallization is realized on to more than 80% high dielectric constant polymer base material, there is higher peel off between obtained metal level and base material
Intensity.Compared with the magnetron sputtering method or pressing method of prior art, the electric capacity of more Large Copacity can be made.Made from magnetron sputtering method
Adhesion between metal level and base material is poor, leads to not realization and is reaching that more than 80% high dielectric is normal in dielectric constant content
Metallization is realized on number polymeric substrate.
2. the present invention uses ion implantation technique, pin hole quantity is reduced.If there is pin hole on electrode, in circuit board system
Pickling liquid may cause thin insulating medium also to have pin hole along the high Dk inorganic particles in pin-hole corrosion dielectric layer in journey, from
And make the easy leakage current of capacitor, insulation proof voltage hydraulic performance decline.If there is pin hole on electrode, the dielectric loss of capacitance material
Will increase.
Meanwhile, ion implantation technique of the invention also can solve the problem that the Bao Tonghe that covers of " high Dk composites ", and to cover copper easily peelable
Problem, expands the content range of the application kind quantity for burying electric capacity polymer composites and the application of high Dk particles.In circuit
Plate field, for 8-25 μm of medium thickness, it is not necessary to using being coated on copper foil or being laminated copper foil, directly in medium thickness 8-
25 μm of (composite " resin+high Dk particles ") ion implanting metal levels；It can avoid being laminated copper because high Dk granule contents are high
Paper tinsel peeling.
Laminating makes and buries capacitance process, when the composite of copper foil and high-content particle is laminated, be easily peeled off or
Foaming.For 8-25 μm of medium thickness, electric capacity is buried applied to field of circuit boards, it is general to be applied using " high Dk material resins "
On the thick copper foil for overlaying on RZ2-3 μm, then another thickness copper foil is carried out pressing and formed by dry, semi-solid preparation；Its two sides copper foil is
18th, 35 and 70 μm.
Sputtering method because sputtering particle energy is low, speed is low, produce many particle discrete areas or transmitting from target
Angle is larger, thus the particle onto composite base material is more, and the pin hole quantity of formation is more, cause the easy leakage current of capacitor,
Insulate proof voltage hydraulic performance decline.For semiconductor applications or high power capacity device, below 1 μm of medium thickness, using sputtering,
The methods such as CVD, spray coating are SiO2、BaTiO3Ceramics etc. " high Dk particles " (non-polymer resin) are directly sputtered or sprayed and apply
It is layed onto on copper foil.
3. the present invention can be advised greatly using continuous " ion implanting+plating+pattern transfer+etching+cutting " technology of volume to volume
Molding makees 10-25 μ m thicks, film morphology polymer composites and buries electric capacity, it is to avoid manufacturing process is because dielectric layer is excessively thin, mistake
It is crisp and bend or damaged, improve the machinability that circuit board making process buries electric capacity.
4. in the present invention, burying the thin copper design of the levels copper electrode of electric capacity and realizing, electrode during etching is improved
Area control precision, so as to improve the control accuracy of actual capacitance, also reduces in package substrate and buries electric capacity gross thickness,
Finally improve the reliability of semiconductor packages.
Brief description of the drawings
The present invention is specifically described below with reference to accompanying drawing and in conjunction with the embodiments, advantages of the present invention and implementation will more
Plus substantially, wherein, content shown in the drawings is only used for that the present invention is explained, without constituting any meaning to the present invention
Limitation in justice, accompanying drawing is only illustrative, not strictly drawn to scale.In all of the figs, identical reference number
Same or analogous part is represented, wherein：
Fig. 1 shows electric capacity according to embodiments of the present invention；
Fig. 2, which is shown, according to embodiments of the present invention buries condenser network plate；
Fig. 3 shows manufacture electric capacity according to embodiments of the present invention and the method for burying condenser network plate.
Reference number：
100 electric capacity
102 fluoropolymer resins
104 ion implanted layers
106 metal levels
108 high Dk particles
200 bury condenser network plate
202 fluoropolymer resins
204 ion implanted layers
206 metal levels
208 high Dk particles
210 circuit base materials
High Dk particles are mixed and are dried to obtain high dielectric constant polymer composite material film by 302 with fluoropolymer resin
304 pairs of high dielectric constant polymer composite material films carry out ion implanting to form ion implanted layer
306 in ion implanted layer overlying metal to form metal level
308 pre-treatments, pad pasting, exposure, development, etching, AOI are checked
310 cut to obtain electric capacity
312 will bury condenser network plate in electric capacity lamination embedment circuit base material to obtain.
Embodiment
The present invention relates to electric capacity, bury condenser network plate and its manufacture method.Electric capacity includes fluoropolymer resin and high Dk particles,
5 μm of gross thickness ＞；By liquid polymeric resins and high Dk particles mixing (skeletal support such as no glass material), make film and answer
Condensation material or high Dk particle weights content are in the composite of 10-90% scopes, and material has certain bending resistance, then passes through volume
Roll form is made " ion implanting, cover copper, dry film pre-treatment, pad pasting, exposure, development, etching, AOI check, cutting " flow sets
Meter, is fabricated to the electric capacity that buries comprising metal capacitance electrode, then be laminated in embedment multilayer circuit board.
I. ion implanting
Ion implanting can be realized by the following method：Using conductive material as target, under vacuum conditions, made by electric arc
Ionized with the conductive material made in target and produce ion.Then, the ion is made to accelerate under high-tension electric field and obtain very
High energy (such as 1-1000keV, such as 50keV, 100keV, 200keV, 500keV).The conductive material ion of high energy is then
The surface of high dielectric constant polymer composite is directly hit with very high speed, and is injected into high dielectric constant polymer
In the certain depth bounds of the lower face of composite.Answered in the conductive material ion injected with high dielectric constant polymer
Chemical bond (such as ionic bond or covalent bond) is formd between the molecule of condensation material, so as to constitute doped structure.Chemical bond is helped
In enhancing ion implanted layer and high dielectric constant polymer composite between adhesion so that ion implanted layer be not easy from
High dielectric constant polymer composite comes off.
Outer surface (or being upper surface) and the high dielectric constant polymer composite of thus obtained ion implanted layer
Surface be flush, and its inner surface (or being lower surface) is then deep into the inside of high dielectric constant polymer composite.
As a specific example, the ion of conductive material can be obtained during ion implanting 50-1000keV (such as 50keV, 100keV,
200keV, 300keV, 400keV, 500keV, 600keV, 700keV, 800keV, 900keV) energy, and can be injected into
High dielectric constant polymer composite lower face 1-500nm (such as 10nm, 20nm, 50nm, 100nm, 200nm,
300nm, 400nm) depth.
, can such as Injection Current, voltage, implantation dosage by controlling the various relevant parameters in ion implantation process
To adjust the depth that ion implanted layer is deep into high dielectric constant polymer composite inner, i.e. the interior table of ion implanted layer
Face depth residing below high dielectric constant polymer composite material surface.For example, the energy of injection ion is 5-
1000keV, the dosage of injection is 1.0 × 1012To 1.0 × 1018ions/cm2(it is highly preferred that implantation dosage is 1.0 × 1015Extremely
5.0×1016ions/cm2), so that the inner surface of ion implanted layer is located at the surface of high dielectric constant polymer composite
Lower section 5-50nm depth.In ion implantation process, can use and high dielectric constant polymer composite combination
Power stronger metal or alloy carries out ion implanting, for example can using Ti, Cr, Ni, Cu, Ag, Au, V, Zr, Mo, Nb, Al,
The metals such as Be, Co, Fe, Mg, Mn, Pt, Ta, W and binary between them, ternary or quaternary alloy (such as NiCr, TiCr,
VCr, CuCr, MoV, NiCrV, TiNiCrNb) in one or more as the target in ion implantation process, wherein, Ni,
Cr, Ti are preferred injection materials.In other words, the ion implanted layer of gained can by Ti, Cr, Ni, Cu, Ag, Au, V, Zr,
One or more compositions in Mo, Nb, Al, Be, Co, Fe, Mg, Mn, Pt, Ta, W, or the alloy group between these elements
Into.
In ion implantation process, conductive material ion is forcibly injected into high dielectric constant polymer with very high speed
The inside of composite, stable doped structure is formed with high dielectric constant polymer composite, normal equivalent in high dielectric
The lower face of number polymer composites forms large number of foundation pile.Due to the presence of foundation pile, and follow-up obtained gold
Category layer is connected with foundation pile, therefore, base material and the peel strength being subsequently formed between metal level thereon can reach 0.5N/mm with
On, even more than 0.8N/mm, up to such as 0.7-1.5N/mm.By comparison, in the case where conventional magnetron is sputtered, sputtering
The energy of particle is only up to several electron-volts, thus the particle can be deposited on substrate surface but not enter in base material
Portion, the adhesion between the conductor layer and substrate surface of gained is not high, only up to 0.5N/mm or so, hence it is evident that less than ion note
Enter.Moreover, the conductive material size for ion implanting is usually nanoscale, it is distributed during ion implanting than more uniform, and
And it is little to the incident angle difference of substrate surface.It is accordingly possible to ensure base material and being subsequently formed between metal level thereon
Composition surface there is relatively low surface roughness, for example, less than 0.4 μm, even as low as 0.001-0.1 μm (e.g., from about 0.02 μ
m).Therefore, in high frequency signal transmission, the loss of signal as caused by conductor layer can be significantly reduced, so as to further reduce whole
The body loss of signal.
Compared with laminating makes and buries electric capacity, it is easily peeled off or bubbles during lamination copper foil；Using ion implantation technique, solve
The Bao Tonghe that covers of " high dielectric constant polymer composite " covers the easily peelable problem of copper, expands and buries electric capacity polymer resin material
Application kind quantity and scope.
Compared with sputtering, ion implantation is that high energy ion is injected after high dielectric constant polymer composite material surface,
Stable doped structure is formed, it is square into multiple foundation piles under the surface, thus conductive ion implanted layer polymerize with high-k
Thing composite adhesion is more preferable, in circuit board making process (such as pad pasting, etching spray, live roller, carrying operation)
Under the stress extruding of impact or bending, metal copper layer forms entirety with polymeric material resistant to bending, and bending will not be run into easily
And fracture, peel off or bubble, machinability is more preferable.Layers of copper causes copper electrode out-of-flatness (equivalent to dielectric layer under folding s tress
Thickness change), local capacitance variation is unfavorable for electric capacity value stabilization and high-precision control.
High Dk inorganic ceramic materials in composite, are formed by high-temperature calcination, and material is harder and densification, sputter low energy
The ion for measuring low speed can not be preferably in connection；Compared with sputtering, ion implantation is that the ion implanting of high-energy high speed is arrived
Behind high Dk inorganic ceramic materials surface, form stable doped structure, it is square into multiple foundation piles under a surface, thus it is conductive from
Sub- implanted layer and base material adhesion are more preferable.Sputtering simultaneously is because energy is low, many particle discrete areas or hair produced from target
The angle penetrated is larger, thus the particle onto base material is more, and the pin hole quantity of formation is more.
If there is pin hole on copper electrode, pickling liquid may be along the height in pin-hole corrosion dielectric layer in circuit board process
Dk inorganic particles, cause thin insulating medium also to have pin hole, so that the easy leakage current of capacitor, insulation proof voltage hydraulic performance decline.
If there is pin hole on copper electrode, the dielectric loss of capacitance material also will increase.
II. plasma-deposited/magnetron sputtering
In addition to ion implanted layer, plasma deposited layers and/or magnetron sputtering layer can also be formed on the surface of base material.
Plasma deposited layers and/or magnetron sputtering layer are made up of conductive material, and can have 1-10000nm thickness, for example
For 100nm, 200nm, 500nm, 700nm, 1 μm, 2 μm, 5 μm, 7 μm or 10 μm etc..Plasma deposited layers and/or magnetic control splash
Penetrating the thickness of layer can set as desired by various deposition parameters are adjusted, for example, it can be set to be formed with this etc.
The sheet resistivity of the substrate of plasma deposition layer and/or magnetron sputtering layer is less than 200 Ω/, 100 Ω/, 80 Ω/, 50
Ω/, etc..In addition, as composition plasma deposited layers and/or magnetron sputtering layer conductive material, can use with from
Sub- implanted layer identical or different various metals, alloy, conductive oxide, conductive carbide, conductive organic matter etc., but not
It is limited to this.It can be selected to be used for plasma according to constituent and thickness of selected base material and ion implanted layer etc.
The conductive material of body deposition and/or magnetron sputtering.Preferably, entered using the metal or alloy being well combined with ion implanted layer
The plasma-deposited and/or magnetron sputtering of row, for example, can be used Ti, Cr, Ni, Cu, Ag, Au, V, Zr, Mo, Nb and they it
Between alloy in one or more, the alloy is, for example, NiCr, TiCr, VCr, CuCr, MoV, NiCrV, TiNiCrNb etc..And
And, plasma deposited layers and/or magnetron sputtering can also include being made up of identical or different material one or more layers.
III. electric capacity
Fig. 1 shows electric capacity 100 according to embodiments of the present invention, and it includes high dielectric constant polymer composite layer, ion
Implanted layer 104 and metal level 106, wherein high dielectric constant polymer composite layer include fluoropolymer resin 102, and (excellent is resistance to
Hot, mechanical property and machinability, cost are low) and high Dk particles 108 (excellent high Dk dielectric properties).High-k gathers
Compound composite material layer ensure that material while having excellent processability, low-dielectric loss and high Dk dielectric properties；And gather
Compound can be processed into film (8-25 μm of thickness), and the advantage of " thin dielectric layer " high-capacitance can be played to greatest extent, thus
With preferable application prospect.
High Dk particles 108 include inorganic ceramic particle and conducting particles；In inorganic ceramic particle, BaTiO3 is used as high dielectric
Ceramics and extensive use；Also the filling of conducting particles (CNT, carbon black, graphite composite powder or other metallics etc.) is had been reported that
To the material of polymer, the dielectric constant close to percolation threshold material abnormal can increase, but this kind of composite dielectric properties weight
Existing property is poor, the more difficult control of material Dk, Df stability.Fluoropolymer resin includes two kinds of " non-polar and polar "；Non-polar polymer
(such as PTFE, PPE) only produces induced dipole square under external electric field, and dielectric loss is low, substantially not by frequency and temperature change shadow
Ring, dielectric constant is relatively low (being less than 2.5)；Polar polymer can produce electron cloud displacement polarization, dipole under External Electrical Field
Orientation polarization and polar group polarization, dielectric loss are larger, are influenceed larger by frequency and temperature, dielectric constant is also larger, typically
3-10 or so.
In a word, various polymeric materials increase after high Dk fillers, and the increased amplitude of dielectric constant, dielectric loss respectively differs
A kind of sample, further-more it is desirable to make polymer composites with " high Dk dielectric constants, low-loss, be easily worked ".
Fluoropolymer resin 102 includes epoxy resin epoxy, BT resin, BMI BMI, cyanate CE, polyethylene
(HDPE or LDPE), polystyrene PS, Kynoar PVDf, polyester PET, polycarbonate, polyphenylene thioether PPS, high temperature resistant
Polypropylene HTPP, poly- 2,6 naphthalene diacid second diester PEN, polyimides PI, polytetrafluoroethylene PTFE, polyphenylene oxide PPE etc.；Polymer
The solids weight content 10%-90% of resin.
High Dk particles 108 or filler include inorganic ceramic particle and conducting particles, and inorganic ceramic particle includes SiO2, metatitanic acid
Barium (BaTiO3), strontium titanates (SrTiO3), lead zirconate titanate Pb (ZrTi) O3(common name PZT), load lanthanium titanate (PbLaTiO), lead zirconates
Lanthanum (PbLaZrO) (common name PLZT), strontium bismuth tantalate (SrBi2Ta2O9) one kind of perofskite type oxide or several such as (common name SBT)
Plant mixture；The conducting particles nano-particle such as including CNT, and carbon black, graphite composite powder or Al, Al2O3, Ag, Ni metal
One or more of mixtures of particle etc..
Conductive material ion implanting is made to the surface of high dielectric constant polymer composite layer by ion injection method
Form ion implanted layer 104 down.Meanwhile, on ion implanted layer 104 formed metal level 106, its by plating, chemical plating,
One or more in the methods such as vacuum evaporation coating and obtains, to obtain the conductor layer with desired thickness and electrical conductivity.
Additionally, can also be on the surface of high dielectric constant polymer composite layer in addition to ion implanted layer
Conductor sedimentary is formed, conductor sedimentary is covered on ion implanted layer, and metal level is covered on conductor sedimentary, conductor
Sedimentary includes plasma deposited layers and/or magnetron sputtering deposition layer, and plasma deposited layers pass through plasma-deposited side
Method makes conductive material ion deposition and formed；Magnetron sputtering layer makes conductive material atomic deposition and shape by magnetically controlled sputter method
Into.
IV. condenser network plate is buried
Fig. 2 show it is according to embodiments of the present invention bury condenser network plate 200, it includes electric capacity and electric capacity embedment shown in Fig. 1
Circuit base material 210 therein.The electric capacity includes high dielectric constant polymer composite layer, ion implanted layer 204 and gold
Belong to layer 206, wherein high dielectric constant polymer composite layer includes fluoropolymer resin 202 and high Dk particles 208.
Electric capacity is embedded in package substrate or PCB, therefore need not weld to reduce inductance and source impedance, and solder joint
After reduction, solder joint failure phenomenon is reduced, and the reliability of wiring board or encapsulation also gets a promotion.On the other hand, Embedded capacitance device
The surface area of preciousness has been saved, plate suqare is reduced, has shortened circuit, the distance of capacitor element and chip chamber is reduced, has strengthened electrical resistance
Can, circuit board is progressively moved towards lightness and slimming.
V. electric capacity and the manufacture method of condenser network plate is buried
Fig. 3 shows manufacture electric capacity according to embodiments of the present invention and the method for burying condenser network plate, and it comprises the following steps：
Step 302：High Dk particles 108,208 are mixed with fluoropolymer resin 102,202 and are dried to obtain high-k and are polymerize
Thing composite；
Step 304：High dielectric constant polymer composite is carried out ion implanting to form ion implanted layer 104,204；
Step 306：In ion implanted layer 104,204 overlying metals to form metal level 106,206；
Step 308：Pre-treatment, pad pasting, exposure, development, etching, AOI are checked；
Step 310：Cut to obtain electric capacity 100；
Step 312：Electric capacity 100 is laminated in embedment circuit base material 210 and buries condenser network plate 200 to obtain.
In above-mentioned steps, high dielectric constant polymer composite is into form of film and rolled.Volume to volume is continuous
" ion implanting+cover copper+pattern transfer+etching+cutting " technology, 10-25 μ m thicks, film morphology polymer can be made on a large scale
The electric capacity of composite, it is to avoid manufacturing process because dielectric layer is excessively thin, it is excessively crisp and bend or damaged, improve circuit board making process
The machinability of electric capacity.
VI. embodiment 1
Substrate component：Epoxy resin is 20%, BaTiO3For 80%
Resin thickness：15 microns
Dielectric constant：20, far below the 35 of prior art similar material
Dielectric loss factor：0.009, far below the 0.014 of prior art similar material.
Ion implanting nickel is carried out to base material first, plasma-deposited nickel-copper is carried out afterwards（10-90）Alloy, is made gold
Belong to layer, so as to obtain capacitor.The static capacity of final obtained electric capacity：35, performance exceeds conventional capacitive more than 50%.
VII. embodiment 2
Substrate component：PI resins are that 15%, high-k filler is 85%
Resin thickness：10 microns
Dielectric constant：15, far below the 40 of prior art similar material
Dielectric loss factor：0.010, far below the 0.029 of prior art similar material.
Ion implanting nickel-chromium alloy is carried out to base material first, magnetron sputtering deposition nickel is carried out afterwards, magnetic control is carried out afterwards and is splashed
Deposition copper is penetrated, metal level is made, so as to obtain capacitor.The static capacity of final obtained electric capacity：25, performance is beyond common electricity
Hold more than 80%.
VIII. embodiment 3
Substrate component：Epoxy resin is that 15%, high-k filler is 85%
Resin thickness：20 microns
Dielectric constant：15, far below the 40 of prior art similar material
Dielectric loss factor：0.010, far below the 0.047 of prior art similar material.
Ion implanting nickel-chromium alloy is carried out to base material first, magnetron sputtering deposition nickel is carried out afterwards, magnetic control is carried out afterwards and is splashed
Deposition copper is penetrated, metal level is made, so as to obtain capacitor.The static capacity of final obtained electric capacity：30, performance is beyond common electricity
Hold more than 90%.
IX. conclusion
Metal is realized on the high dielectric constant polymer base material that more than 80% is reached present invention can be implemented in dielectric constant granule content
Change, have between obtained metal level and base material compared with high-peeling strength., can compared with the magnetron sputtering method or pressing method of prior art
The electric capacity of more Large Copacity is made.Adhesion made from magnetron sputtering method between metal level and base material is poor, leads to not realize
Reached in dielectric constant granule content and realize metallization on more than 80% high dielectric constant polymer base material.
Although the present invention has been described in detail together with only a limited number of embodiment, it should be readily understood that
It is that the present invention is not restricted to this disclosed embodiment.And on the contrary, the present invention can change with including not describing before but
It is any number of change, replacement, replacement or the equivalent arrangements matched with the spirit and scope of the present invention.Although in addition, description
Various embodiments of the present invention, it is to be understood that the aspect of the present invention may include only one in the embodiment of description
A bit.Therefore, the present invention will be not seen as limited by the foregoing description, but only be limited by the scope of claim.
Claims (22)
1. a kind of electric capacity, it includes：
High dielectric constant polymer composite layer；
Ion implanted layer, it is normal that the ion implanted layer makes conductive material ion inject paramount dielectric at a high speed by ion injection method
Formed in number polymer composite layer；And
Metal level, it forms and is covered on the ion implanted layer.
2. electric capacity according to claim 1, it is characterised in that the high dielectric constant polymer composite layer includes poly-
Polymer resin and high dielectric constant particle.
3. electric capacity according to claim 1, it is characterised in that the injection material of the ion implanted layer and the high dielectric
Biospecific polymer composite layer formation doped structure, the doped structure is in the high dielectric constant polymer composite layer
Surface under form multiple foundation piles.
4. electric capacity according to claim 1, it is characterised in that the electric capacity also includes conductor sedimentary, the conductor sinks
Lamination is covered on the ion implanted layer, and the metal level is covered on the conductor sedimentary, the conductor deposition
Layer includes plasma deposited layers and/or magnetron sputtering deposition layer, and the plasma deposited layers pass through plasma-deposited side
Method makes conductive material ion deposition and formed；The magnetron sputtering layer conductive material atomic deposition is made by magnetically controlled sputter method and
Formed.
5. electric capacity according to claim 4, it is characterised in that the plasma deposited layers and magnetron sputtering layer are
Including one or more layers conductor material, each layer conductor material passes through one or many described plasma-deposited or magnetic controls
Sputter procedure is formed.
6. the electric capacity according to any one of claim 1-5, it is characterised in that the material of the ion implanted layer includes：
In one or more in Ti, Cr, Ni, Cu, Ag, Au, V, Zr, Mo, Nb, or binary, ternary and quaternary alloy between them
One or more.
7. the electric capacity according to claim 4 or 5, it is characterised in that the material of the conductor sedimentary includes：Ti、Cr、
One kind in one or more in Ni, Cu, Ag, Au, V, Zr, Mo, Nb, or binary, ternary and quaternary alloy between them
Or it is a variety of.
8. the electric capacity according to any one of claim 1-5, it is characterised in that the material of the metal level includes：By Al,
One or more in Mn, Fe, Ti, Cr, Co, Ni, Cu, Ag, Au, V, Zr, Mo, Nb, or binary, ternary and four between them
One or more compositions in first alloy.
9. electric capacity according to claim 2, it is characterised in that the fluoropolymer resin includes epoxy resin, BT resins, double
Maleimide, cyanate, polyethylene, polystyrene, Kynoar, polyester, makrolon, polyphenylene sulfide, high temperature resistant are gathered
One or more in propylene, poly- 2,6 naphthalene diacid second diester, polyimides, polytetrafluoroethylene (PTFE), polyphenylene oxide.
10. electric capacity according to claim 2, it is characterised in that the high dielectric constant particle includes inorganic ceramic particle
And/or conducting particles.
11. electric capacity according to claim 10, it is characterised in that the inorganic ceramic particle includes silica, metatitanic acid
One or more in barium, strontium titanates, lead zirconate titanate, load lanthanium titanate, lead zirconates lanthanum, strontium bismuth tantalate.
12. electric capacity according to claim 10, it is characterised in that the conducting particles includes CNT, carbon black, graphite
Powder, Al, Al2O3, one or more in Ag, Ni.
13. electric capacity according to claim 2, it is characterised in that the high dielectric constant particle accounts for the high-k
The percentage by weight of polymer composite layer is 10-90%.
14. electric capacity according to claim 2, it is characterised in that the high dielectric constant particle accounts for the high-k
The percentage by weight of polymer composite layer is more than 80%.
15. the electric capacity according to any one of claim 1-5, it is characterised in that the metal level passes through plating, chemistry
Plating, the one or more in vacuum evaporation coating and obtain.
16. the electric capacity according to any one of claim 1-5, it is characterised in that the high dielectric constant polymer is combined
The thickness of material layer is 8-25 μm.
17. the electric capacity according to any one of claim 1-5, it is characterised in that the electric capacity is the electric capacity of form of film.
18. a kind of method for manufacturing the electric capacity according to any one of claim 1-17, it comprises the following steps：
A) high dielectric constant particle and mixed with polymers are obtained into the high dielectric constant polymer composite layer；
B) the high dielectric constant polymer composite is carried out ion implanting to form ion implanted layer；And
C) in the ion implanted layer overlying metal to form the metal level.
19. method according to claim 18, it is characterised in that be additionally included in step a)-c) after following steps：
D) pre-treatment, pad pasting, exposure, development, etching, AOI are checked；And
E) cut.
20. the method according to claim 18 or 19, it is characterised in that continuously manufacture the electric capacity to volume to volume.
21. one kind buries condenser network plate, it includes：
Electric capacity according to any one of claim 1-17；And
The electric capacity is embedded to circuit base material therein.
22. a kind of manufacture the method for burying condenser network plate, it comprises the following steps：
The step of method according to any one of claim 18-20；And
Electric capacity lamination is embedded in circuit base material to bury condenser network plate described in acquisition.
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| CN110708867A (en) * | 2019-11-15 | 2020-01-17 | 广州兴森快捷电路科技有限公司 | PCB (printed Circuit Board) voltage-resistant test module and test method |
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