CN104105353B - A kind of manufacture method of high-precision ceramic circuit board - Google Patents
A kind of manufacture method of high-precision ceramic circuit board Download PDFInfo
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- CN104105353B CN104105353B CN201410314204.2A CN201410314204A CN104105353B CN 104105353 B CN104105353 B CN 104105353B CN 201410314204 A CN201410314204 A CN 201410314204A CN 104105353 B CN104105353 B CN 104105353B
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Abstract
The invention discloses a kind of manufacture method of high-precision ceramic circuit board, comprise the ceramic base plate surface being radiated at by laser and covering palladium ion solid film, control laser energy density and reach more than substrate modification threshold value, ceramic base plate surface is made to form V-type micro groove structure, in this microflute, palladium ion is reduced into atomic state and is at high temperature combined with oxygen atom and forms the high palladium oxide of chemical stability, and form firmly metallurgical binding with substrate, and substrate surface structures does not change in the LASER HEAT zone of influence, palladium ion is only reduced into Metal Palladium.By chemical cleaning step, the Metal Palladium in selective clearing heat affected area, leaves the activated centre of the palladium oxide in micro groove structure as catalytic chemistry plating reaction.Then implement chemical plating, high accuracy conducting wire can be obtained.This technology can prepare conducting wire fast on the surface of ceramic substrate, and to baseplate material without particular/special requirement, gained conducting wire precision is high, and good conductivity, adhesion is strong.
Description
Technical field
The invention belongs to conducting wire plate and make field, and Laser Surface Treatment field, relate to a kind of method making high accuracy conducting wire in ceramic material surfaces.Specifically, be the making for ceramic material surfaces conducting wire of Laser Surface Modification Technology, chemical cleaning technique and electroless plating technology.
Background technology
Along with popularizing rapidly of the electronics and information industries such as computer and the Internet, mobile communication, flat panel display, solar photovoltaic industry and energy-saving illumination industry, electric equipment products continues to future developments such as microminiaturization, flexibility, high integration, and closely-related Electronic Encapsulating Technology enters super-speed development period with it.Circuit board (Printed Circuit Board, i.e. PCB) is almost the core component of each electronic product indispensability, the various aspects involved by encapsulation technology, carries out nearly all on circuit boards or associated.After 20th century the mid-90 IC industry marches toward high-density packages, as a ring important in Electronic Encapsulating Technology, PCB manufacturing technology becomes the barrier hindering encapsulation performance and density to improve gradually.Therefore, electronics manufacturing high speed development is promoted in the urgent need to novel PCB manufacturing technology.
Up to the present, organic material especially epoxy resin material still occupies the overwhelming majority with cheap cost and ripe technique in PCB output, and organic printed circuit board of routine is subject to the restriction of heat dissipation and matched coefficients of thermal expansion two aspect, the requirement that semiconductor circuit integrated level improves constantly can not be met.Ceramic-like materials has good high frequency performance and electric property, and there is the performance that thermal conductivity is high, the organic substrate such as chemical stability and good heat stability does not possess, be the desirable encapsulating material of large scale integrated circuit of new generation and power electronics modules, therefore ceramic circuit board obtains and pays close attention to widely and develop rapidly.
Industrialization ceramic circuit board manufacturing technology mainly comprises screen printing technique, direct copper plating (DPC) technology and direct copper (DBC) technology three kinds both at home and abroad at present.Screen printing technique is widely used in High Temperature Co Fired Ceramic (HTCC) technology and LTCC (LTCC) technology, but uses the maximum line width resolution of the thick film circuit of this fabrication techniques to be about 60 μm.In addition, this technology metal paste used needs high temperature sintering ability and ceramic substrate to form good combination, and the Binder Phase in slurry is difficult to remove completely, can affect the electric property of wire.Like this, for more high accuracy, more high-density packages, this thick film technology is difficult to meet the demands.Direct copper (DBC) refers to that Copper Foil is at high temperature bonded directly to the technical method of ceramic base plate surface, and this technology is the ceramic surface metallization technology grown up based on aluminium oxide ceramics, afterwards again for aluminium nitride ceramics.Current direct copper (DBC) technique is difficult to make the substrate of copper layer thickness below 60 μm.In addition, be difficult to the space thoroughly avoiding remaining when fitting between Copper Foil and pottery therebetween, this will affect the performance of final conducting wire.Follow-up photoetching, etching process also can waste a large amount of metallic coppers, and these shortcomings all make the application of this technology be restricted.In recent years, direct copper plating (DPC) the technology part of based thin film process exploitation solve the problems referred to above, the method first on substrate sputtered with Ti or Cr as intermediate layer, then sputter Cu layer, then to be formed by plating thickening and photoetching process process.The method can realize high-precision wire producing, and is applied in microelectronics Packaging particularly high power, small size ceramic packaging substrate, but shortcoming needs expensive sputtering coating equipment and lithographic equipment, and complex process, production efficiency is lower.And above technology all can only realize on planar substrates, its process limitation makes them cannot realize accurate wiring on 3 D complex curved substrate, and this all limits the development and apply of ceramic PCB in Electronic Packaging field.
Electronic product is eternal trend to high-performance, flexibility, extreme dimensional (super large or extra small), low price future development, therefore how to realize the high accuracy of electronic product, high efficiency, in enormous quantities, low cost, the pollution-free target creating researcher and pursue.Above-mentioned requirements proposes new technological challenge to PCB manufacturing process: the first, and the resolution under the prerequisite meeting electric property of the conductive circuit pattern prepared by requirement is higher; The second, three-dimensional dimension processing can be realized, adapt to product design and user demand; 3rd, high efficiency, in enormous quantities, low cost, low stain manufacture can be realized.
After First laser was succeeded in developing in nineteen sixty, laser processing technology just develops rapidly with features such as its high accuracy, high-energy, high efficiency and is widely used in every subjects field.In conjunction with the demand of electronics manufacturing, laser writing technology arises at the historic moment and becomes next generation PC B and manufactures one of technology of field most competitiveness.Its adopts laser beam to assist the manufacture of conducting wire, is a kind of noncontact, without pressure, the direct patterned addition process manufacturing technology of material without mask.Compare conventional etch method, the method, without the need to the Graphic Exchanging operation of complexity, has the advantage such as high accuracy, the high and low pollution of flexibility degree.This type of technology has attracted the research interest of America and Europe, Japan and Korea S, China Taiwan, a large amount of researcher in Hong Kong and interior ground, is starting the revolution of a PCB manufacturing technology.
Patent documentation CN102271456B discloses a kind of thermal conductive ceramic base printed circuit board and preparation method thereof.The thermal conductive ceramic base printed circuit board of this invention includes a ceramic substrate, ceramic base plate surface there are the printed circuit pattern of laser scanning and one melted by laser the conductive layer that the granular metal ball that formed and silver powder sinter formation jointly, have anti-solder ink and character silk printing on the electrically conductive.The method melts balling-up by utilizing laser beam causes metallic powder, be embedded in ceramic base plate surface and form firmly metallurgical binding, the conductive silver paste of subsequent coated plays the effect connecting conduction, add without any the material that thermal conductivity is low in the middle of conductive layer and ceramic substrate, ensure that the ceramic circuit board of this invention has good radiating effect.But the metal particle size used in the method (0.5-5 μm) is larger, and the mode depositing electrically conductive of follow-up use silk screen printing silver slurry, these technical characterstics make it be difficult to obtain fine conductive circuit, and the Binder Phase in conductive silver paste can make the electric property of final conducting wire reduce, and is difficult to be applied to high-power component.
Patent documentation CN102762037A discloses a kind of manufacture method of ceramic circuit board, the method first on ceramic wafer surface with the whole plate copper layer of mode of chemical plating, evaporation or sputtering, and by its complete oxidation, form the presoma of copper oxide as laser activation.Re-use laser beam by the circuitous pattern ablation copper oxide designed in advance, its major part be vaporized, residue minority can catalytic chemistry plating activated centre stay ceramic surface, complete the activation of ceramic surface.Make laser ablated region optionally copper layer by electroless plating technology, re-use the copper oxide that dilute sulfuric acid or hydrochloric acid remove non-ablation, form final conducting wire.Compare printing electrocondution slurry, the metal level that electroless plating technology deposits possesses more excellent electric property.But due to the existence of the LASER HEAT zone of influence, the laser facula that the method uses is minimum is 10 μm, and the width of the conducting wire made is for can only reach 20 μm.In addition, the method needs to waste a large amount of untapped metallic copper, which has limited its range of application.
Patent documentation CN103188877A discloses the method that the quick high flexibility of a kind of ceramic circuit-board makes, comprise and use laser to irradiate the ceramic base plate surface containing active ion, make ceramic base plate surface generation chemical reaction separate out the catalysis source of active material as chemical plating, then form metal level by chemical plating.The method is similar to laser direct forming method (the Laser Direct Structuring of German LPKF D. O. O. exploitation, LDS), what LDS technology was general is applied to plastic base, its general principle is mixed with baseplate material by active material in molding substrate process, utilize the irradiation substrate surface after shaping of laser beam, the active material of irradiated area decomposes and has catalytic, then in conjunction with electroless plating technology plated metal.The shortcoming of this kind of technology to adopt the material with LDS performance, and the cycle from initial molding substrate to final formation circuit board is longer, and die sinking somewhat expensive, is difficult to use in small lot batch manufacture.
Patent documentation CN203261570U proposes the metallization of a kind of ceramic laser and metal-layer structure, this structure is by adopting pottery as baseplate material, replace traditional special specified material of LDS, utilize laser to carry out two dimension or three dimensional sculpture on the substrate, re-use chemical plating or electric plating method in internal shaping conducting wire, laser action region.The grooved section shape that this patent proposes laser engraving can be rectangle, trapezoidal and leg-of-mutton wherein one, but does not point out the characteristic size of this shape, and what effect the groove of this kind of shape specifically has.
Patent documentation CN103781285A proposes a kind of in two-dimentional or the surperficial making of three dimensional ceramic material and reparation electric line universal method, the method is covered with the ion of special metal or the ceramic material surfaces of complex ion in advance by utilizing laser beam irradiation, make ceramic surface produce catalytic activity, then implement chemical plating and obtain conducting wire.The method can be standby or repair the conducting wire of various complexity, to baseplate material without particular/special requirement in the surperficial fast direct grounded system of multiple ceramic substrate (comprise plane with three-dimensional).Although the width of single track wire can be adjusted in the method by the defocusing amount of control laser beam, sweep speed and laser power, but the heat effect that laser beam irradiation produces when substrate surface is difficult to avoid, metal ion in heat affected area, hot spot edge or complex ion can produce decomposition equally, in the process of chemical plating, all can the deposition of catalyticing metal particle in laser irradiation region and heat affected area.In addition, chemical plating process has the characteristic of metal isotropic deposition, and the width while thickness increases of the plain conductor on two dimensional surface too increases.The acting in conjunction of both can cause the final conductor width be shaped much larger than the width in laser irradiation region.
Generally speaking, the persursor material that above method adopts is different, but is mostly adopt laser irradiation substrate, makes substrate surface produce the activated centre with catalytic capability, then deposits the plain conductor of high conductivity in conjunction with electroless plating technology.The process of laser modified ceramic base plate surface utilizes the high-energy of laser beam presoma is decomposed and produces catalytic activity, and this is wherein main inducing with heat effect.In the process of chemical plating, the deposition of the position energy catalyticing metal particle be only modified.Therefore, the width of modification area and edge quality determine the fine degree of final formed conductor.In order to obtain meticulousr plain conductor, researchers are devoted to by adopting the laser beam of the shorter ultraviolet-deep ultraviolet wave band of wavelength or optimizing optical system parameters to obtain less spot diameter, or the ultra-short pulse laser bundle adopting heat affected area less, but these methods all fundamentally can not solve the generation of heat affected area, laser facula edge, in heat affected area, the decomposition of presoma can make the width expansion of modification area.On the other hand, the Energy distribution of normally used laser beam is uneven, for axisymmetric Gaussian Profile, so only have the energy in laser spot center region just can reach the decomposition threshold of presoma, and the presoma near decomposition threshold can not fully decompose, subsequent chemistry can be caused to be plated to, and the plain conductor edge of shape is sparse, burr is more, and this all can affect final packaging density.In addition, known as this area, in plating process, the deposition of metal is the process of isotropic, and the plain conductor of substrate surface also can to lateral growth while thickening, and this also can make the final conductor width be shaped obviously be greater than laser action peak width.Therefore, the laser processing technology of high flexibility is also difficult to realize industrial applications in ceramic circuit board manufacture field.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of manufacture method of high-precision ceramic circuit board, the method adopts Laser Surface Modification Technology, chemical cleaning technique and electroless plating technology to combine at ceramic base plate surface, selectivity is good, eliminate the impact of the LASER HEAT zone of influence on subsequent chemistry plated deposition metal, conducting wire live width be meticulous, edge quality good, with ceramic substrate binding ability excellent.
For achieving the above object, the ceramic circuit board manufacturing method that the present invention proposes, the steps include:
1st step adopts laser beam irradiation to be coated with the ceramic substrate of palladium ion solid film, makes the laser irradiation region of ceramic base plate surface form micro groove structure; Palladium ion in this micro groove structure is reduced into atomic state, is at high temperature combined with oxygen atom and forms palladium oxide particle, and mixes with ceramic material, melts, solidifies, and forms firmly metallurgical binding; And the palladium ion in heat affected area is only reduced into Metal Palladium particle;
2nd step utilizes wang aqueous solution to carry out chemical cleaning, optionally removes the Metal Palladium particle in heat affected area, leaves the activated centre of the palladium oxide particle in described micro groove structure as catalytic chemistry plating reaction;
3rd step implements chemical plating, conducting metal particles is only deposited in micro groove structure, obtains the ceramic circuit board that conductor width is narrower.
Beneficial effect of the present invention is by realizing selective metallization in conjunction with chemical cleaning and electroless plating technology at ceramic base plate surface at employing laser surface modification.Be coated with the ceramic substrate of palladium ion solid film by laser beam irradiation, make laser irradiation region form V-type micro groove structure.Palladium ion in this laser irradiation region is reduced into atomic state, and form the palladium oxide particle that chemical stability is high, and in heat affected area, temperature is lower, substrate surface structures is not changed, and palladium ion is only reduced into Metal Palladium particle.Metal Palladium is utilized very easily to be dissolved in wang aqueous solution, and palladium oxide is insoluble in this basic chemical property of chloroazotic acid, by adding chemical cleaning step before chemical plating, optionally remove the Metal Palladium particle in heat affected area, leave the activated centre of the palladium oxide in micro groove structure as catalytic chemistry plating reaction.In the plated journey of subsequent chemistry, only have in micro groove structure the deposition having metallic particles, eliminate the impact that the LASER HEAT zone of influence is plated subsequent chemistry, significantly reduce the width of formed conductor.Making under identical laser technical parameters, obtaining meticulousr wire live width by adding chemical cleaning step.On the other hand, this micro groove structure to limit in plating process plain conductor to the growth of side direction.In electroless plating reaction; metallic particles is only deposited in micro groove structure, and constantly fills microflute, forms conducting wire; it reduce the impact of metallic particles meeting isotropic growth in plating process, to obtain, conductor width is narrower, the better ceramic circuit board of edge quality.Therefore, the width of the conducting wire prepared by the present invention depends mainly on the diameter of laser facula, and there is not the restriction of the LASER HEAT zone of influence, reliability is high, can meet the requirement of high-density packages.In addition, use nonmetallic palladium oxide as the catalytic active center of chemical plating in the present invention.Due to the soluble metallic copper of salpeter solution, and indissoluble solution palladium oxide, therefore when conducting wire disconnects or Pad off time, with the whole conducting wire of Nitric acid etching, then chemical plating can be implemented, directly realize the reparation of conducting wire.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the embodiment of the inventive method.
Fig. 2 is the optical amplifier figure after embodiment 1 sample making completes.
Fig. 3 is the optical amplifier figure after comparative example 1 sample making completes.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.It should be noted that at this, the explanation for these execution modes understands the present invention for helping, but does not form limitation of the invention.In addition, if below in described each execution mode of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Manufacture method in ceramic base plate surface high accuracy conducting wire provided by the invention, its concrete steps comprise:
(1) preset presoma: ceramic substrate entirety be immersed in the solution containing palladium ion, soak time does not make particular requirement, is generally 5-30min, then takes out drying; Or adopt the mode such as spraying, a painting this solution to be preset in the position of line pattern to be processed on substrate, then dry; Immersion or preset temperature are between the boiling point of solvent for use in room temperature to solution;
The shape of ceramic substrate comprises two dimensional surface and any three-dimensional curve, and the ceramic substrate material adopted comprises aluminium oxide, aluminium nitride, carborundum, beryllium oxide, silicon nitride, glass/ceramic composite material (LTCC) etc.
The solution of palladium ion can be the solution of at least one composition of the palladium salt such as palladium, palladium bichloride, palladium nitrate, and solution concentration is generally 0.01-1mol/L.
(2) laser modified ceramic surface:
Ceramic base plate surface modification comprises structurally-modified and composition modification.By CAD Software on Drawing conductive circuit pattern, utilize laser beam according to the line pattern designed in advance, by controlling the parameters such as Laser output average power, pulse repetition frequency, sweep speed, defocusing amount, trace interval and scanning pass, ceramic surface is processed, control laser energy density and reach more than modification threshold value, make most of material generating gasification in irradiation zone, the material of remaining fusing solidifies again, and ceramic surface forms micro groove structure, completing substrate surface structurally-modified.Now, in heat affected area, temperature is lower, and do not reach modification threshold value, substrate surface structures does not change.Presoma palladium ion in microflute is directly reduced to atomic state and is at high temperature combined with oxygen atom forms palladium oxide particle, mixes, melts, solidifies and form firmly metallurgical binding, make the modification of substrate surface generation composition with ceramic material.And the palladium ion in heat affected area is only reduced into Metal Palladium particle is attached to ceramic grain surface.This step needs to control suitable laser energy density, and when laser energy density is too low, ceramic surface cannot produce structurally-modified, and the Metal Palladium in laser irradiation region also cannot be oxidized into palladium oxide.The ablation of laser energy density too high then substrate surface is serious, and the fragility remelted layer thickness in laser irradiation region increases, and the binding ability of the coat of metal and ceramic substrate is declined.
Time laser modified, control to export energy density and reach more than modification threshold value, by high-frequency high-velocity scanning.The lasing light emitter used is pulse laser, and the output wavelength of laser can at infrared, visible ray or ultraviolet band.Laser output average power is usually at 1-100w, and corresponding sweep speed generally selects 10-1000mm/s, and the width of single-channel scanning line is 10-30 μm.When adopting wavelength to be 355nm ps pulsed laser and ns pulsed laser source, when Laser output average power is 1-10w, pulse repetition frequency is 100kHz, and sweep speed is 50-500mm/s, and now laser facula is minimum can reach 10 μm.When adopting wavelength to be 1064nm ps pulsed laser and ns pulsed laser source, when Laser output average power is 10-50w, pulse repetition frequency is 50kHz, and sweep speed is 100-1000mm/s, and now laser facula is minimum can reach 20 μm.Be conducive to obtaining meticulousr laser irradiation region to obtain less spot diameter by the laser beam or optimizing optical system parameters that adopt the shorter ultraviolet-deep ultraviolet wave band of wavelength, but when laser modified, still be difficult to the generation avoiding heat affected area, hot spot edge, in heat affected area, the decomposition of presoma can make the width expansion of modification area.
Line pattern does not now have conductive capability, but as the catalytic activation center of subsequent chemistry depositing process.
(3) chemical cleaning: be soaked in rare wang aqueous solution by the ceramic substrate after laser treatment, soak time is generally 1-5min, then takes out and repeatedly cleans with deionized water.Because Metal Palladium is very easily dissolved in wang aqueous solution, and palladium oxide is insoluble in this basic chemical property of chloroazotic acid, after chemical cleaning, be completely removed without the Metal Palladium particle in the presoma palladium ion of laser irradiation and the LASER HEAT zone of influence, leave in microflute the palladium oxide particle that the is insoluble in wang aqueous solution catalytic active center as subsequent chemistry plating reaction.Ultrasonic wave can as the supplementary means of cleaning.
Chloroazotic acid is the mixed acid that a kind of nitric acid and hydrochloric acid configure according to volume ratio 1: 3, and rare chloroazotic acid used in this step is the wang aqueous solution of volume fraction 5-50%.
(4) chemical plating forms conductive metal layer: the ceramic substrate after laser activation and chemical cleaning is placed in chemical plating fluid and implements chemical plating, implement electroless copper, silver, nickel, platinum, palladium, tin, zinc, chromium, gold or its combination at activating area, obtain conducting wire.Chemical plating process adopts conventional chemical depositing process, and first adopt electroless copper as the conductive layer of circuit board, thickness of coating can regulate according to requirements within the scope of 1-10 μm.Follow-up according to the concrete environment for use of device and performance requirement chemical nickel plating, thickness of coating 0.3-3 μm, its effect avoids layers of copper to be oxidized, and promotes anti-wear performance.Chemical gilding again, it act as anti-oxidant, thickness of coating 0.01-1 μm.Because non-activated baseplate material does not have platability, therefore only could plated metal layers of copper in the position of " implantation " above-mentioned palladium oxide particulate.
The formula of the chemical plating fluid adopted is the common prescription in chemical plating field.The such as formula of chemical copper plating solution used: CuSO
45H
2o10g/L, EDTA2Na30g/L, formaldehyde 15ml/L, sodium potassium tartrate tetrahydrate 40g/L, α, α ' bipyridine 10mg/L, potassium ferrocyanide 100mg/L, polyethylene glycol 10mg/L, temperature 40-50 DEG C, pH value 12.1-12.9; The formula of chemical nickel-plating solution: nickelous sulfate 25g/L, sodium hypophosphite 25g/L, sodium acetate 20g/L, acetic acid 15g/L, thiocarbamide 10mg/L, temperature 82-86 DEG C, pH value is 4.2-4.5; The formula of chemical gilding solution: gold sodium sulfide 2g/L, sodium sulfite 15g/L, sodium thiosulfate 12.5g/L, borax 10g/L, temperature 75 DEG C, pH value is 7.0.
Shown in Fig. 1 (a-d), the solution containing palladium ion is preset in substrate 1 surface, after drying, forms uniform solid film 2 at substrate surface; Laser beam 3 is utilized to carry out laser irradiation process on substrate 1 surface, V-type micro groove structure is formed at laser spot center, in micro groove structure, palladium ion is reduced and is at high temperature combined with oxygen atom, form palladium oxide particle 4, the palladium ion in the LASER HEAT zone of influence is directly reduced to Metal Palladium particle 5 and is attached to ceramic grain surface; By chemical cleaning step, the Metal Palladium particle 5 in heat affected area and the solid film 2 in non-irradiation zone are completely removed, and leave palladium oxide particle 4 in microflute as catalytic active center; Particles filled in microflute by electroless-deposited metal, form conducting wire 6.
The inventive method is used for the making of ceramic base plate surface high accuracy conducting wire Laser Surface Modification Technology, chemical cleaning technique and electroless plating technology.The defects such as gained wire line precision is high, edge quality good, good conductivity, pore-free, crackle.Binding ability between coating and substrate is evaluated by pulling method, stretches in unit are after welded wire with stretching-machine perpendicular to substrate, until coating peels off substrate completely.Coating prepared by the inventive method and the bond strength between substrate can reach more than 35MPa, close to the ultimate tensile strength of conventional tin-lead solder, can meet the instructions for use of electronics manufacturing completely.
In further detail the present invention is described below by embodiment, but following examples are only illustrative, protection scope of the present invention is not by the restriction of these embodiments.
Embodiment 1
(1) be immersed in 1mol/L palladium solution by 96% alumina ceramic plate entirety, soaking temperature is room temperature, and soak time is 5 minutes, takes out dry.
(2) ultraviolet ps pulsed laser and ns pulsed laser is adopted to carry out modification to the alumina ceramic plate being coated with palladium film.Lasing light emitter adopts peak power output to be 10W, and pulse duration is 20-40ns, and pulse repetition frequency is 25-100kHz, and wavelength is the ultraviolet pulse Nd:YVO of 355nm
4laser.This potsherd is placed on three-shaft linkage numerically controlled machine, is fixed by negative pressure adsorption equipment.Laser beam is by surperficial according to predetermined line pattern scanning substrate after beam expanding lens, scanning galvanometer and f-theta lens.During laser surface modification, control laser energy density more than ceramic modified threshold value.When laser output power is 2W, (now the power density of laser is 1.13 × 10
6w/cm
2), pulse repetition frequency is 100kHz, and sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width about 15 μm, and the degree of depth is the micro groove structure of about 15 μm.In micro groove structure, palladium is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of about 10 μm, microflute both sides, palladium Direct Resolution is Metal Palladium with the form of palladium oxide.After laser activation, the Metal Palladium of ceramic surface and the particle of palladium oxide do not have conductive capability, but exist with " isolated island " form, as the catalytic active center of subsequent chemistry plating.
(3) next this potsherd is soaked in (volume fraction: 50%) in rare wang aqueous solution, take out and use deionized water rinsing after 2 minutes, now all be completely removed without the Metal Palladium particle in the palladium film in laser irradiation region and the LASER HEAT zone of influence, substrate surface only leaves the palladium oxide in micro groove structure.Eliminate the catalytic active center in the LASER HEAT zone of influence by this step, significantly reduce the area of catalysis region.
(4) after this, aforesaid substrate is put into chemical copper plating solution, take out after 20 minutes, only there is the deposition of metallic copper at the microflute position of laser ablation, and copper conductor width is about 15 μm.The conducting wire resistivity finally obtained is about 5 × 10
-5Ω cm, conducting wire surface uniform is fine and close, flawless.(as shown in Figure 2)
Embodiment 2
(1) be immersed in 0.5mol/L palladium chloride solution by 99% alumina ceramic plate entirety, soaking temperature is room temperature, and soak time is 5 minutes, takes out dry.
(2) ps pulsed laser and ns pulsed laser is adopted to carry out modification to the alumina ceramic plate being coated with palladium bichloride film.Lasing light emitter adopts peak power output to be 50W, and pulse duration is 120ns, and pulse repetition frequency is 50kHz, and wavelength is the pulse optical fiber of 1064nm.This potsherd is placed on three-shaft linkage numerically controlled machine, is fixed by negative pressure adsorption equipment.Laser beam is by surperficial according to predetermined line pattern scanning substrate after beam expanding lens, scanning galvanometer and f-theta lens.During laser surface modification, control laser energy density more than ceramic modified threshold value.When laser output power is 10.8W, (now the power density of laser is 1.13 × 10
6w/cm
2), pulse repetition frequency is 50kHz, and sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width about 25 μm, and the degree of depth is the micro groove structure of about 10 μm.In micro groove structure, palladium bichloride is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of about 15 μm, microflute both sides, palladium bichloride Direct Resolution is Metal Palladium with the form of palladium oxide.After laser activation, the Metal Palladium of ceramic surface and the particle of palladium oxide do not have conductive capability, but exist with " isolated island " form, as the catalytic active center of subsequent chemistry plating.
(3) next this potsherd is soaked in (volume fraction: 50%) in rare wang aqueous solution, take out and use deionized water rinsing after 5 minutes, now all be completely removed without the Metal Palladium particle in the palladium bichloride film in laser irradiation region and the LASER HEAT zone of influence, substrate surface only leaves the palladium oxide in micro groove structure.Eliminate the catalytic active center in the LASER HEAT zone of influence by this step, significantly reduce the area of catalysis region.
(4) after this, aforesaid substrate is put into chemical copper plating solution, take out after 20 minutes, only there is the deposition of metallic copper at the microflute position of laser ablation, and copper conductor width is about 25 μm.Implement chemical nickel plating process again, take out after 5 minutes, the conducting wire resistivity finally obtained is about 8 × 10
-5Ω cm, conducting wire surface uniform is fine and close, flawless.
Embodiment 3
(1) aqueous solution containing 0.1mol/L palladium bichloride is coated in the position of line pattern designed by alumimium nitride ceramic sheet surface, and natural drying.
(2) ultraviolet ps pulsed laser and ns pulsed laser is adopted to carry out modification to the alumina ceramic plate being coated with palladium bichloride film.Lasing light emitter adopts peak power output to be 10W, and pulse duration is 20-40ns, and pulse repetition frequency is 25-100kHz, and wavelength is the ultraviolet pulse Nd:YVO of 355nm
4laser.This potsherd is placed on three-shaft linkage numerically controlled machine, is fixed by negative pressure adsorption equipment.Laser beam is by surperficial according to predetermined line pattern scanning substrate after beam expanding lens, scanning galvanometer and f-theta lens.During laser surface modification, control laser energy density more than ceramic modified threshold value.When laser output power is 0.8W, (now the power density of laser is 1.02 × 10
6w/cm
2), pulse repetition frequency is 100kHz, and sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width about 10 μm, and the degree of depth is the micro groove structure of about 6 μm.In micro groove structure, palladium bichloride is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of about 5 μm, microflute both sides, palladium bichloride Direct Resolution is Metal Palladium with the form of palladium oxide.After laser activation, the Metal Palladium of ceramic surface and the particle of palladium oxide do not have conductive capability, but exist with " isolated island " form, as the catalytic active center of subsequent chemistry plating.
(3) next this potsherd is soaked in (volume fraction: 20%) in rare wang aqueous solution, take out and use deionized water rinsing after 10 minutes, now all be completely removed without the Metal Palladium particle in the palladium bichloride film in laser irradiation region and the LASER HEAT zone of influence, substrate surface only leaves the palladium oxide in micro groove structure.Eliminate the catalytic active center in the LASER HEAT zone of influence by this step, significantly reduce the area of catalysis region.
(4) after this, aforesaid substrate is put into chemical copper plating solution, take out after 20 minutes, only there is the deposition of metallic copper at the microflute position of laser ablation, and copper conductor width is about 10 μm.The conducting wire resistivity finally obtained is about 5 × 10
-5Ω cm, conducting wire surface uniform is fine and close, flawless.
Comparative example 1
This comparative example and embodiment 1 contrast, and the impact not using chemical cleaning on wire live width is described, it comprises the following steps:
(1) be immersed in 1mol/L palladium solution by 96% alumina ceramic plate entirety, soaking temperature is room temperature, and soak time is 5 minutes, takes out dry.
(2) ultraviolet ps pulsed laser and ns pulsed laser is adopted to carry out modification to the alumina ceramic plate being coated with palladium film.Lasing light emitter adopts peak power output to be 10W, and pulse duration is 20-40ns, and pulse repetition frequency is 25-100kHz, and wavelength is the ultraviolet pulse Nd:YVO of 355nm
4laser.This potsherd is placed on three-shaft linkage numerically controlled machine, is fixed by negative pressure adsorption equipment.Laser beam is by surperficial according to predetermined line pattern scanning substrate after beam expanding lens, scanning galvanometer and f-theta lens.During laser surface modification, control laser energy density more than ceramic modified threshold value.When laser output power is 2W, (now the power density of laser is 1.13 × 10
6w/cm
2), pulse repetition frequency is 100kHz, and sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width about 15 μm, and the degree of depth is the micro groove structure of about 15 μm.In micro groove structure, palladium is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of about 10 μm, microflute both sides, palladium Direct Resolution is Metal Palladium with the form of palladium oxide.After laser activation, the Metal Palladium of ceramic surface and the particle of palladium oxide do not have conductive capability, but exist with " isolated island " form, as the catalytic active center of subsequent chemistry plating.
(3) next this potsherd is soaked in deionized water, supersonic wave cleaning machine is adopted to clean 5 minutes, palladium film now without laser irradiation region is completely removed, and substrate surface leaves the palladium oxide in micro groove structure and the Metal Palladium in heat affected area.
(4) after this, aforesaid substrate is put into chemical copper plating solution, take out after 20 minutes, all have the deposition of metallic copper in the microflute position of laser ablation and heat affected area, copper conductor width is about 40 μm.The conducting wire resistivity finally obtained is about 5 × 10
-5Ω cm, conducting wire surface uniform is fine and close, flawless.(as shown in Figure 3)
In comparative example, metallic copper all has deposition in the microflute position and heat affected area of laser ablation, and metallic copper can only be deposited on the microflute position of laser ablation in embodiment, illustrate that chemical cleaning step effectively eliminates the catalytic active center in heat affected area, significantly improve the precision of subsequent conductive circuit, the encapsulation requirement of current high-power small size electronic device can be met.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment and accompanying drawing.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.
Claims (8)
1. a manufacture method for ceramic electrical circuit, the method adopts laser surface modification to realize selective metallization in conjunction with chemical cleaning and chemical plating at ceramic base plate surface, specifically comprises the steps:
1st step adopts laser beam irradiation to be coated with the ceramic substrate of palladium ion solid film, makes the laser irradiation region of ceramic base plate surface form micro groove structure; Palladium ion in this micro groove structure is reduced into atomic state, is at high temperature combined with oxygen atom and forms palladium oxide particle, and mixes with ceramic material, melts, solidifies, and forms firmly metallurgical binding; And the palladium ion in heat affected area is only reduced into Metal Palladium particle;
2nd step utilizes wang aqueous solution to carry out chemical cleaning, to remove the palladium ion solid film at non-irradiation position, and the Metal Palladium particle optionally removed in heat affected area, leave the activated centre of the palladium oxide particle in described micro groove structure as catalytic chemistry plating reaction, eliminate the impact of heat affected area on chemical plating at microflute edge, and this micro groove structure to limit in plating process plain conductor to the growth of side direction;
3rd step implements chemical plating, and conducting metal particles is only deposited in micro groove structure, obtains that conductor width is narrower, the better ceramic circuit board of binding ability.
2. the manufacture method of ceramic electrical circuit according to claim 1, is characterized in that, in the 1st step, described palladium ion solid film adopts following method to obtain:
Ceramic substrate entirety is immersed in the solution containing palladium ion, then takes out drying;
The palladium salting liquid of the described solution containing palladium ion to be concentration be 0.01-1mol/L;
The shape of ceramic substrate comprises two dimensional surface and any three-dimensional curve, and the ceramic substrate material adopted comprises aluminium oxide, aluminium nitride, carborundum, beryllium oxide, silicon nitride, or glass and ceramic composite.
3. the manufacture method of ceramic electrical circuit according to claim 1, is characterized in that, in the 1st step, described palladium ion solid film adopts following method to obtain:
Adopt spraying or drip the position that the solution containing palladium ion is preset in line pattern to be processed on ceramic substrate by painting mode, then dry;
The palladium salting liquid of the described solution containing palladium ion to be concentration be 0.01-1mol/L;
The shape of ceramic substrate comprises two dimensional surface and any three-dimensional curve, and the ceramic substrate material adopted comprises aluminium oxide, aluminium nitride, carborundum, beryllium oxide, silicon nitride, or glass and ceramic composite.
4. the manufacture method of the ceramic electrical circuit according to claim 1,2 or 3, is characterized in that, the concentration of volume percent of described wang aqueous solution is 5-50%.
5. the manufacture method of the ceramic electrical circuit according to claim 1,2 or 3, is characterized in that, in the 1st step, described laser beam is the pulse laser of wavelength 248-1064nm.
6. the manufacture method of the ceramic electrical circuit according to claim 1,2 or 3, is characterized in that, in the 1st step, Laser output average power is 1-100w, and the sweep speed of laser beam is between 10-1000m/s, and the width of single-channel scanning line is 10-30 μm.
7. the manufacture method of the ceramic electrical circuit according to claim 1,2 or 3, it is characterized in that, in 1st step, wavelength is adopted to be 355nm ps pulsed laser and ns pulsed laser source, when Laser output average power is 1-10w, pulse repetition frequency is 100kHz, and sweep speed is 50-500mm/s, and laser facula is minimum reaches 10 μm.
8. the manufacture method of the ceramic electrical circuit according to claim 1,2 or 3, it is characterized in that, in 1st step, when employing wavelength is 1064nm ps pulsed laser and ns pulsed laser source, when Laser output average power is 10-50w, pulse repetition frequency is 50kHz, and sweep speed is 100-1000mm/s, and laser facula is minimum reaches 20 μm.
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| CN105371119A (en) * | 2015-11-24 | 2016-03-02 | 苏州威恩斯光电科技有限公司 | LED lamp and manufacturing method thereof |
| CN105848422B (en) * | 2016-06-08 | 2017-03-22 | 上海安费诺永亿通讯电子有限公司 | Circuit fabrication method |
| EP3417982A1 (en) * | 2017-06-21 | 2018-12-26 | Heraeus Deutschland GmbH & Co. KG | Laser cutting of metal-ceramic substrates |
| TWI687531B (en) * | 2018-01-26 | 2020-03-11 | 謝孟修 | Ceramic printed circuit board and method of making the same |
| CN110136911A (en) * | 2018-02-02 | 2019-08-16 | 盈成科技有限公司 | Loop construction and preparation method thereof |
| CN108558413B (en) * | 2018-07-02 | 2021-05-18 | 上海安费诺永亿通讯电子有限公司 | Preparation method of ceramic-based electronic circuit |
| CN111515543A (en) * | 2019-01-16 | 2020-08-11 | 福士瑞精密工业(郑州)有限公司 | Laser degumming method and device |
| CN112552079B (en) * | 2019-09-26 | 2023-09-12 | 航天特种材料及工艺技术研究所 | Metallized ceramic matrix composite material and curved surface metallization method |
| CN110972406B (en) * | 2019-12-04 | 2020-07-28 | 广东工业大学 | Repair method for fine line |
| CN111613888B (en) * | 2020-06-02 | 2021-10-08 | 华中科技大学 | Integrated conformal manufacturing method of multilayer interconnected three-dimensional circuit |
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| CN1763245B (en) * | 2004-10-21 | 2010-12-29 | 阿尔卑斯电气株式会社 | Plating substrate, electroless plating method, and circuit forming method using the same |
| CN102776492A (en) * | 2011-05-13 | 2012-11-14 | 比亚迪股份有限公司 | Selective metallization method of surface of ceramic, and ceramic and its application |
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