CN104105353A - Preparation method of high-accuracy ceramic printed circuit board - Google Patents
Preparation method of high-accuracy ceramic printed circuit board Download PDFInfo
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- CN104105353A CN104105353A CN201410314204.2A CN201410314204A CN104105353A CN 104105353 A CN104105353 A CN 104105353A CN 201410314204 A CN201410314204 A CN 201410314204A CN 104105353 A CN104105353 A CN 104105353A
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Abstract
The invention discloses a preparation method of a high-accuracy ceramic printed circuit board. The preparation method comprises the steps of radiating laser on the surface of a ceramic substrate covered with a palladium ion solid film, controlling the energy density of the laser to reach above a modified threshold of the substrate, allowing a V-shaped microgroove structure to be formed on the surface of the ceramic substrate, allowing a palladium ion in a microgroove to be reduced to an atom state, bonding the palladium ion with an oxygen atom at a high temperature to form palladium oxide with very high chemical stability, forming firm metallurgical bonding with the substrate, allowing the structure on the surface of the substrate in a heat affected zone of the laser not to be changed, and only allowing the palladium ion to be reduced to metal palladium. Metal palladium in the heat affected zone is selectively removed by the chemical cleaning step; palladium oxide in the microgroove structure is left as an active center of catalytic chemical plating reaction; and then a high-accuracy conducting circuit can be obtained by implementing chemical plating. According to the preparation method, the conducting circuit can be quickly prepared on the surface of the ceramic substrate; the preparation method has no special requirement for a material of the substrate; and the obtained conducting circuit is high in accuracy, good in conductivity and high in binding force.
Description
Technical field
The invention belongs to conducting wire plate and make field, and Laser Surface Treatment field, relate to a kind of method of making high accuracy conducting wire in ceramic material surfaces.Specifically, be Laser Surface Modification Technology, chemical cleaning technique and electroless plating technology the making for ceramic material surfaces conducting wire.
Background technology
Along with popularizing rapidly of the electronics and information industries such as computer and the Internet, mobile communication, flat panel display, 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 has entered super-speed development period with it.Circuit board (Printed Circuit Board, i.e. PCB) is almost the core component of each electronic product indispensability, and the various aspects that encapsulation technology is related are nearly all carried out or associated on circuit board.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 that hinders encapsulation performance and density raising gradually.Therefore, in the urgent need to novel PCB manufacturing technology, promote electronics manufacturing high speed development.
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 conventional organic printed circuit board is subject to the restriction of heat dissipation and matched coefficients of thermal expansion two aspects, can not meet the requirement that semiconductor circuit integrated level improves constantly.Ceramic-like materials has good high frequency performance and electric property, and the performance that have 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, so ceramic circuit board has obtained paying close attention to widely and developing rapidly.
At present both at home and abroad industrialization ceramic circuit board manufacturing technology is mainly to comprise three kinds of screen printing technique, direct copper plating (DPC) technology and direct copper (DBC) technology.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 μ m.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 high accuracy more, more for 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 growing 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 μ m.In addition, be difficult to the space of thoroughly avoiding residual between the two while fitting between Copper Foil and pottery, this will affect the performance of final conducting wire.Follow-up photoetching, etching process also can be wasted a large amount of metallic coppers, and these shortcomings all make the application of this technology be restricted.In recent years, the solution of the direct copper plating of based thin film process exploitation (DPC) technology part the problems referred to above, the method first on substrate sputtered with Ti or Cr as intermediate layer, sputter Cu layer then, the then thicken processing with photoetching process by platings and form.The method can realize high-precision wire producing, and particularly in high power, small size ceramic packaging substrate, is applied in microelectronics Packaging, but shortcoming is to need expensive sputtering coating equipment and lithographic equipment, complex process, and production efficiency is lower.And above technology all can only realize on planar substrates, its process limitation makes them cannot on 3 D complex curved substrate, realize accurate wiring, and this has all limited ceramic PCB in development and the application in Electronic Packaging field.
Electronic product is eternal trend to high-performance, flexibility, extreme size (super large or extra small), low price future development, therefore how to realize the target that high accuracy, high efficiency, in enormous quantities, low-cost, the pollution-free researcher of creating of electronic product pursue.Above-mentioned requirements has proposed new technological challenge to PCB manufacturing process: the first, and require prepared conductive circuit pattern to meet under the prerequisite of electric property resolution higher; The second, can realize three-dimensional dimension processing, adapt to product design and user demand; The 3rd, can realize high efficiency, in enormous quantities, low-cost, low pollution manufacture.
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 direct-writing technology is arisen at the historic moment and is become next generation PC B and manufactures one of the most competitive technology in field.The manufacture that its adopts laser beam to assist conducting wire is a kind of noncontact, without pressure, without the direct patterned addition process manufacturing technology of material of mask.Compare traditional etching method, the method, without complicated figure conversion operation, has the advantages such as high accuracy, the high and low pollution of flexibility degree.This type of technology has attracted America and Europe, Japan and Korea S, China Taiwan, Hong Kong and the interior ground research interest of researchers in a large number, 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, on ceramic base plate surface, there are the printed circuit pattern of laser scanning and one to be melted by laser the conductive layer that the granular metal ball that forms and the common sintering of silver powder form, on conductive layer, have anti-solder ink and character silk printing.The method is by utilizing laser beam to make metal powder melt balling-up, be embedded in ceramic base plate surface and form firmly metallurgical binding, the conductive silver paste of subsequent coated plays the effect that connects conduction, in the middle of conductive layer and ceramic substrate, without any the low material of thermal conductivity, add, guaranteed that the ceramic circuit board of this invention has good radiating effect.But (0.5-5 μ m) is larger for the metal particle size of using in the method, and the mode depositing electrically conductive of follow-up use silk screen printing silver slurry, these technical characterstics make it be difficult to obtain meticulous conducting wire, 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 the mode of chemical plating, evaporation or sputter, and by its complete oxidation, form copper oxide as the presoma of laser activation.Re-use laser beam by the circuitous pattern ablation copper oxide of design in advance, its major part be vaporized, residue minority can catalytic chemistry the activated centre of plating stay ceramic surface, complete the activation of ceramic surface.By electroless plating technology, make the copper layer of laser ablation regioselectivity, re-use the copper oxide that dilute sulfuric acid or hydrochloric acid are removed not ablation, form final conducting wire.Compare printing conductive slurry, the metal level that electroless plating technology deposits possesses better electric property.But due to the existence of the LASER HEAT zone of influence, the laser facula minimum that the method is used is 10 μ m, and the width of the conducting wire making is for can only reach 20 μ m.In addition, the method need to be wasted a large amount of untapped metallic coppers, and this has limited its range of application.
Patent documentation CN103188877A discloses the method that the quick high flexibility of a kind of ceramic circuit-board is made, comprise the ceramic base plate surface that uses Ear Mucosa Treated by He Ne Laser Irradiation to contain active ion, make ceramic base plate surface generation chemical reaction separate out active material as the catalysis source of 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), LDS technology is general is applied to plastic base, its basic principle is in molding substrate process, active material to be mixed with baseplate material, utilize the substrate surface after moulding that is radiated at 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 class technology is to adopt the material with LDS performance, and longer to the cycle of final formation circuit board from initial molding substrate, die sinking somewhat expensive, is difficult to use in small lot batch manufacture.
Patent documentation CN203261570U has proposed a kind of ceramic laser metallization and metal-layer structure, this structure is by adopting pottery as baseplate material, replace traditional special specified material of LDS, utilize laser on this base material, to carry out two dimension or three-dimensional engraving, re-use chemical plating or electric plating method in internal shaping conducting wire, laser action region.The groove section configuration that this patent proposes laser engraving can be rectangle, trapezoidal and leg-of-mutton wherein a kind of, but does not point out the characteristic size of this shape, and what effect the groove of this class shape specifically has.
Patent documentation CN103781285A has proposed a kind of in two dimension or the making of three-dimensional ceramic material surface and the universal method of repairing electric line, the method is by utilizing laser beam irradiation to be covered with in advance the ceramic material surfaces of ion or the complex ion of special metal, make ceramic surface produce catalytic activity, then implement chemical plating and obtain conducting wire.The method is can be in the surperficial fast direct grounded system of multiple ceramic substrate (comprise plane with three-dimensional) standby or repair the conducting wire of various complexity, to baseplate material without specific (special) requirements.Although can adjust by controlling defocusing amount, sweep speed and the laser power of laser beam the width of single track wire in the method, but the heat effect that laser beam irradiation produces when substrate surface is difficult to avoid, metal ion or complex ion in heat affected area, hot spot edge can produce decomposition equally, in the process of chemical plating, deposition that all can 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 when thickness increases of the plain conductor on two dimensional surface has also increased.The two acting in conjunction meeting causes the final conductor width being shaped much larger than the width in laser irradiation region.
Generally speaking, the persursor material that above method adopts is different, but is mostly to adopt laser irradiation substrate, makes substrate surface produce the activated centre with catalytic capability, then in conjunction with electroless plating technology, deposits the plain conductor of high conductivity.The process of laser modified ceramic base plate surface is to utilize the high-energy of laser beam presoma is decomposed and produce catalytic activity, and this wherein take heat effect as main inducing.In the process of chemical plating, the deposition of the position energy catalyticing metal particle being only modified.Therefore, the width of modification area and edge quality have determined 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 less ultra-short pulse laser bundle in employing heat affected area, but these methods all can not fundamentally solve the generation of heat affected area, laser facula edge, in heat affected area, the decomposition of presoma can make the width of modification area expand.On the other hand, the Energy distribution of normally used laser beam is inhomogeneous, for axisymmetric Gaussian Profile, so only have the energy in laser spot center region just can reach the decomposition threshold of presoma, and near the presoma of decomposition threshold can not fully decompose, can cause subsequent chemistry to be plated to that the plain conductor edge of shape is sparse, burr is more, this all can affect final packaging density.In addition, known as this area, in chemical plating process, the deposition of metal is the process of isotropic, and the plain conductor of substrate surface also can be to lateral growth when thickening, and this also can make the final conductor width being 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, eliminated the impact of the LASER HEAT zone of influence on subsequent chemistry plated deposition metal, conducting wire live width is meticulous, edge quality good, with ceramic substrate binding ability good.
For achieving the above object, the ceramic circuit board manufacturing method that the present invention proposes, the steps include:
The 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 mix, melt, solidify with ceramic material, forms firmly metallurgical binding; And palladium ion in heat affected area is only reduced into Metal Palladium particle;
The 2nd step utilizes wang aqueous solution to carry out chemical cleaning, has optionally removed the Metal Palladium particle in heat affected area, leaves the palladium oxide particle activated centre that plating is reacted as catalytic chemistry in described micro groove structure;
The 3rd step is implemented chemical plating, and conducting metal particles is only deposited in micro groove structure, obtains the narrower ceramic circuit board of conductor width.
Beneficial effect of the present invention is by adopting laser surface modification to realize selective metallization in conjunction with chemical cleaning and electroless plating technology at ceramic base plate surface.By laser beam irradiation, be coated with the ceramic substrate of palladium ion solid film, make laser irradiation region form V-type micro groove structure.Palladium ion in this laser irradiation region is reduced into atomic state, form the high palladium oxide particle of chemical stability, and in heat affected area, temperature is lower, and substrate surface structure is not changed, and palladium ion is only reduced into Metal Palladium particle.Utilize Metal Palladium to be very easily dissolved in wang aqueous solution, and palladium oxide is insoluble in this basic chemical property of chloroazotic acid, by added chemical cleaning step before chemical plating, optionally remove the Metal Palladium particle in heat affected area, left the palladium oxide activated centre that plating is reacted as catalytic chemistry in micro groove structure.In subsequent chemistry plating process, only have the deposition that has metallic particles in micro groove structure, eliminated the impact of the LASER HEAT zone of influence on subsequent chemistry plating, significantly reduced the width of formed conductor.Make under identical laser technical parameters, by adding chemical cleaning step to obtain meticulousr wire live width.On the other hand, this micro groove structure has limited in chemical 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; this has reduced the impact of metallic particles meeting isotropic growth in chemical plating process, and to obtain, conductor width is narrower, the better ceramic circuit board of edge quality.Therefore, the width of the conducting wire that the present invention is prepared depends mainly on the diameter of laser facula, does not have the restriction of the LASER HEAT zone of influence, and reliability is high, can meet the requirement of high-density packages.In addition, in the present invention, use nonmetallic palladium oxide as the catalytic active center of chemical plating.Due to the soluble metallic copper of salpeter solution, and indissoluble solution palladium oxide, therefore when conducting wire disconnection or Pad off, can be with the whole conducting wires of Nitric acid etching, then implement chemical plating, 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.At this, it should be noted that, for the explanation of these execution modes, be used for helping to understand the present invention, but do not form limitation of the invention.In addition,, in each execution mode of described the present invention, involved technical characterictic just can not combine mutually as long as do not form each other conflict.
Manufacture method in ceramic base plate surface high accuracy conducting wire provided by the invention, its concrete steps comprise:
(1) preset presoma: ceramic substrate integral body is immersed in the solution containing palladium ion, and soak time is not made particular requirement, is generally 5-30min, then takes out dry; Or adopt the modes such as spraying, a painting this solution to be preset in to the position of line pattern to be processed on substrate, then dry; Soak or preset temperature is room temperature between the boiling point of solvent for use in solution;
The shape of ceramic substrate comprises two dimensional surface and any three-dimensional curve, and the ceramic substrate material adopting 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 designing 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, more than control laser energy density reaches 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, does not reach modification threshold value, and substrate surface structure does not change.Presoma palladium ion in microflute is become atomic state and is at high temperature combined with oxygen atom by direct-reduction to form palladium oxide particle, mixes, melts, solidifies and form firmly metallurgical binding with ceramic material, makes the modification of substrate surface generation composition.And being only reduced into Metal Palladium particle, palladium ion in heat affected area is attached to ceramic grain surface.This step need to be controlled suitable laser energy density, and too low when laser energy density, ceramic surface cannot produce structurally-modified, and the Metal Palladium in laser irradiation region also cannot be oxidized into palladium oxide.The ablation of the too high substrate surface of laser energy density 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.
When laser modified, more than control output energy density reaches modification threshold value, by high-frequency high-velocity scanning.The lasing light emitter using is pulse laser, and the output wavelength of laser can be at infrared, visible ray or ultraviolet band.Laser output average power is conventionally at 1-100w, and corresponding sweep speed is generally selected 10-1000mm/s, and the width of single-channel scanning line is 10-30 μ m.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 minimum can reach 10 μ m.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 minimum can reach 20 μ m.By adopting laser beam or the optimizing optical system parameters of the shorter ultraviolet-deep ultraviolet wave band of wavelength to be conducive to obtain meticulousr laser irradiation region to obtain less spot diameter, but when laser modified, still be difficult to avoid the generation of heat affected area, hot spot edge, in heat affected area, the decomposition of presoma can make the width of modification area expand.
Line pattern does not now have conductive capability, but as the catalytic activation center of subsequent chemistry depositing process.
(3) chemical cleaning: the ceramic substrate after laser treatment is soaked in rare wang aqueous solution, and 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, without the presoma palladium ion of laser irradiation and the Metal Palladium particle in the LASER HEAT zone of influence, be completely removed, stay and in microflute, be insoluble in the palladium oxide particle of wang aqueous solution as the catalytic active center of subsequent chemistry plating reaction.Ultrasonic wave can be used as the supplementary means of cleaning.
Chloroazotic acid is the mixed acid that a kind of nitric acid and hydrochloric acid form according to volume ratio configuration in 1: 3, and in this step, rare chloroazotic acid used 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 to chemical plating fluid and implements chemical plating, at activating area, implement electroless copper, silver, nickel, platinum, palladium, tin, zinc, chromium, gold or its combination, obtain conducting wire.Chemical plating is processed and is adopted conventional chemical depositing process, first adopts electroless copper as the conductive layer of circuit board, and thickness of coating can regulate according to requirements within the scope of 1-10 μ m.Follow-up according to the concrete environment for use of device and performance requirement chemical nickel plating, thickness of coating 0.3-3 μ m, its effect is to avoid the oxidation of copper layer, promotes anti-wear performance.Chemical gilding again, it act as anti-oxidant, thickness of coating 0.01-1 μ m.Because non-activated baseplate material does not have platability, therefore only could plated metal copper layer in the position of " implantation " above-mentioned palladium oxide particulate.
The formula of the chemical plating fluid adopting is the common prescription in chemical plating field.The formula of chemical copper plating solution used: CuSO for example
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 ℃, 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 ℃, 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, 75 ℃ of temperature, pH value is 7.0.
Shown in Fig. 1 (a-d), the solution containing palladium ion is preset in to substrate 1 surface, after being dried, at substrate surface, forms uniform solid film 2; On substrate 1 surface, utilize laser beam 3 to carry out laser irradiation processing, at laser spot center, form V-type micro groove structure, 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 become Metal Palladium particle 5 to be attached to ceramic grain surface by direct-reduction; By chemical cleaning step, the solid film 2 in the Metal Palladium particle 5 in heat affected area and not irradiation zone is completely removed, and leaves palladium oxide particle 4 in microflute as catalytic active center; By electroless deposition metallic particles, be filled in microflute, form conducting wire 6.
The inventive method is the making for ceramic base plate surface high accuracy conducting wire Laser Surface Modification Technology, chemical cleaning technique and electroless plating technology.Gained wire line precision is high, edge quality good, good conductivity, pore-free, defects i.e.cracks.Binding ability between coating and substrate is evaluated by pulling method, stretches, until coating is peeled off substrate completely in unit are after welded wire with stretching-machine perpendicular to substrate.More than the coating that the inventive method is prepared and the bond strength between substrate can reach 35MPa, approach the ultimate tensile strength of conventional tin-lead solder, can meet the instructions for use of electronics manufacturing completely.
Below by embodiment, the present invention is described in further detail, but following examples are only illustrative, protection scope of the present invention is not subject to the restriction of these embodiment.
Embodiment 1
(1) 96% alumina ceramic plate integral body is immersed in 1mol/L palladium solution, soaking temperature is room temperature, and soak time is 5 minutes, takes out dry.
(2) adopt ultraviolet ps pulsed laser and ns pulsed laser to carry out modification to being coated with the alumina ceramic plate of palladium film.It is 10W that lasing light emitter adopts peak power output, and pulse duration is 20-40ns, and pulse repetition frequency is 25-100kHz, the ultraviolet pulse Nd:YVO that wavelength is 355nm
4laser.This potsherd is placed on three-shaft linkage numerically controlled machine, by negative pressure adsorption equipment, fixes.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, sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width approximately 15 μ m, and the degree of depth is the micro groove structure of approximately 15 μ m.In micro groove structure, palladium is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of microflute both sides approximately 10 μ m, palladium is directly decomposed into 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 to (volume fraction: 50%) in rare wang aqueous solution, after 2 minutes, take out and use deionized water rinsing, now without the palladium film in laser irradiation region and the Metal Palladium particle in the LASER HEAT zone of influence, be all completely removed, substrate surface only leaves the palladium oxide in micro groove structure.By this step, remove the catalytic active center in the LASER HEAT zone of influence, significantly dwindled the area of catalysis region.
(4) after this, aforesaid substrate is put into chemical copper plating solution, after 20 minutes, take out, only there is the deposition of metallic copper at the microflute position of laser ablation, and copper conductor width is about 15 μ m.The conducting wire resistivity finally obtaining is about 5 * 10
-5Ω cm, conducting wire surface uniform is fine and close, flawless.(as shown in Figure 2)
Embodiment 2
(1) 99% alumina ceramic plate integral body is immersed in 0.5mol/L palladium chloride solution, soaking temperature is room temperature, and soak time is 5 minutes, takes out dry.
(2) adopt ps pulsed laser and ns pulsed laser to carry out modification to being coated with the alumina ceramic plate of palladium bichloride film.It is 50W that lasing light emitter adopts peak power output, and pulse duration is 120ns, and pulse repetition frequency is 50kHz, the pulse optical fiber that wavelength is 1064nm.This potsherd is placed on three-shaft linkage numerically controlled machine, by negative pressure adsorption equipment, fixes.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, sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width approximately 25 μ m, and the degree of depth is the micro groove structure of approximately 10 μ m.In micro groove structure, palladium bichloride is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of microflute both sides approximately 15 μ m, palladium bichloride is directly decomposed into 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 to (volume fraction: 50%) in rare wang aqueous solution, after 5 minutes, take out and use deionized water rinsing, now without the palladium bichloride film in laser irradiation region and the Metal Palladium particle in the LASER HEAT zone of influence, be all completely removed, substrate surface only leaves the palladium oxide in micro groove structure.By this step, remove the catalytic active center in the LASER HEAT zone of influence, significantly dwindled the area of catalysis region.
(4) after this, aforesaid substrate is put into chemical copper plating solution, after 20 minutes, take out, only there is the deposition of metallic copper at the microflute position of laser ablation, and copper conductor width is about 25 μ m.Implement chemical nickel plating again and process, after 5 minutes, take out, the conducting wire resistivity finally obtaining is about 8 * 10
-5Ω cm, conducting wire surface uniform is fine and close, flawless.
Embodiment 3
(1) aqueous solution that contains 0.1mol/L palladium bichloride is coated in to the position of the designed line pattern in alumimium nitride ceramic sheet surface, and natural drying.
(2) adopt ultraviolet ps pulsed laser and ns pulsed laser to carry out modification to being coated with the alumina ceramic plate of palladium bichloride film.It is 10W that lasing light emitter adopts peak power output, and pulse duration is 20-40ns, and pulse repetition frequency is 25-100kHz, the ultraviolet pulse Nd:YVO that wavelength is 355nm
4laser.This potsherd is placed on three-shaft linkage numerically controlled machine, by negative pressure adsorption equipment, fixes.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, sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width approximately 10 μ m, and the degree of depth is the micro groove structure of approximately 6 μ m.In micro groove structure, palladium bichloride is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of microflute both sides approximately 5 μ m, palladium bichloride is directly decomposed into 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 to (volume fraction: 20%) in rare wang aqueous solution, after 10 minutes, take out and use deionized water rinsing, now without the palladium bichloride film in laser irradiation region and the Metal Palladium particle in the LASER HEAT zone of influence, be all completely removed, substrate surface only leaves the palladium oxide in micro groove structure.By this step, remove the catalytic active center in the LASER HEAT zone of influence, significantly dwindled the area of catalysis region.
(4) after this, aforesaid substrate is put into chemical copper plating solution, after 20 minutes, take out, only there is the deposition of metallic copper at the microflute position of laser ablation, and copper conductor width is about 10 μ m.The conducting wire resistivity finally obtaining is about 5 * 10
-5Ω cm, conducting wire surface uniform is fine and close, flawless.
Comparative example 1
This comparative example contrasts with embodiment 1, illustrates and does not use the impact of chemical cleaning on wire live width, and it comprises the following steps:
(1) 96% alumina ceramic plate integral body is immersed in 1mol/L palladium solution, soaking temperature is room temperature, and soak time is 5 minutes, takes out dry.
(2) adopt ultraviolet ps pulsed laser and ns pulsed laser to carry out modification to being coated with the alumina ceramic plate of palladium film.It is 10W that lasing light emitter adopts peak power output, and pulse duration is 20-40ns, and pulse repetition frequency is 25-100kHz, the ultraviolet pulse Nd:YVO that wavelength is 355nm
4laser.This potsherd is placed on three-shaft linkage numerically controlled machine, by negative pressure adsorption equipment, fixes.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, sweep speed is 50mm/s, controls laser focal plane at substrate surface.Now substrate surface forms width approximately 15 μ m, and the degree of depth is the micro groove structure of approximately 15 μ m.In micro groove structure, palladium is decomposed into Metal Palladium and by high-temperature oxydation, exist, and in the heat affected area of microflute both sides approximately 10 μ m, palladium is directly decomposed into 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 to deionized water, adopts supersonic wave cleaning machine to clean 5 minutes, now the palladium film without laser irradiation region is completely removed, and substrate surface leaves 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, after 20 minutes, take out, all have the deposition of metallic copper in the microflute position of laser ablation and heat affected area, copper conductor width is about 40 μ m.The conducting wire resistivity finally obtaining 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 of laser ablation and heat affected area, and in embodiment, metallic copper can only be deposited on the microflute position of laser ablation, illustrate that chemical cleaning step effectively removed the catalytic active center in heat affected area, significantly improve the precision of follow-up conducting wire, can meet the encapsulation requirement of current high-power small size electronic device.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment and accompanying drawing.So every, do not depart from the equivalence completing under spirit disclosed in this invention or revise, all falling into the scope of protection of the invention.
Claims (8)
1. a manufacture method for ceramic electrical circuit, the method comprises the steps:
The 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 mix, melt, solidify with ceramic material, forms firmly metallurgical binding; And palladium ion in heat affected area is only reduced into Metal Palladium particle;
The 2nd step utilizes wang aqueous solution to carry out chemical cleaning, has optionally removed the Metal Palladium particle in heat affected area, leaves the palladium oxide particle activated centre that plating is reacted as catalytic chemistry in described micro groove structure;
The 3rd step is implemented chemical plating, and conducting metal particles is only deposited in micro groove structure, obtains the narrower ceramic circuit board of conductor width.
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 integral body is immersed in the solution containing palladium ion, then takes out dry;
The described solution containing palladium ion is that concentration is the palladium salting liquid of 0.01-1mol/L;
The shape of ceramic substrate comprises two dimensional surface and any three-dimensional curve, and the ceramic substrate material adopting 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 painting mode the solution containing palladium ion to be preset in to the position of line pattern to be processed on ceramic substrate, then dry;
The described solution containing palladium ion is that concentration is the palladium salting liquid of 0.01-1mol/L;
The shape of ceramic substrate comprises two dimensional surface and any three-dimensional curve, and the ceramic substrate material adopting comprises aluminium oxide, aluminium nitride, carborundum, beryllium oxide, silicon nitride, or glass and ceramic composite.
4. according to the manufacture method of the ceramic electrical circuit described in claim 1,2 or 3, it is characterized in that, the concentration of volume percent of described wang aqueous solution is 5-50%.
5. according to the manufacture method of the ceramic electrical circuit described in claim 1,2 or 3, it is characterized in that, in the 1st step, described laser beam is the pulse laser of wavelength 248-1064nm.
6. according to the manufacture method of the ceramic electrical circuit described in claim 1,2 or 3, it 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 μ m.
7. according to the manufacture method of the ceramic electrical circuit described in claim 1,2 or 3, it is characterized in that, in the 1st step, adopting wavelength is 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 minimum reaches 10 μ m.
8. according to the manufacture method of the ceramic electrical circuit described in claim 1,2 or 3, it is characterized in that, in the 1st step, when adopting wavelength, it 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 minimum reaches 20 μ m.
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| CN105848422A (en) * | 2016-06-08 | 2016-08-10 | 上海安费诺永亿通讯电子有限公司 | Circuit fabrication method |
| CN108558413A (en) * | 2018-07-02 | 2018-09-21 | 上海安费诺永亿通讯电子有限公司 | A kind of preparation method of ceramic base electronic circuit |
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