CN102152018A - Carbon-nanotube-reinforced lead-free solder and preparation method thereof - Google Patents
Carbon-nanotube-reinforced lead-free solder and preparation method thereof Download PDFInfo
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- CN102152018A CN102152018A CN2011100491851A CN201110049185A CN102152018A CN 102152018 A CN102152018 A CN 102152018A CN 2011100491851 A CN2011100491851 A CN 2011100491851A CN 201110049185 A CN201110049185 A CN 201110049185A CN 102152018 A CN102152018 A CN 102152018A
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Abstract
The invention relates to a welding material and a method in the field of electronic packaging technique, and in particular relates to a carbon-nanotube-reinforced lead-free solder and a preparation method thereof. The electroless plating method is used to achieve the surface metallization of a carbon nanotube, and the metal can serve as the transition layer to improve the wettability between the carbon nanotube and a solder matrix, thereby improving the dispersion and the interface bonding strength of the carbon nanotube in the solder melt. Therefore, the carbon-nanotube-reinforced composite lead-free solder with excellent performance can be obtained.
Description
Technical field
The present invention relates to the method for a kind of welding material and technical field of electronic encapsulation, specifically, relate to a kind of CNT and strengthen lead-free solder and preparation method thereof.
Background technology
Tradition tin-kupper solder has good welding performance, be widely used in electronics industry for a long time, but plumbous meeting cause potential hazard to health and natural environment.Along with the development of electronics industry, solder joint is more and more littler in the super large-scale integration, and the mechanics that is born, electricity and calorifics load are more and more heavier, and is more and more higher to the requirement of scolder.The creep-resistant property of tradition tin-lead alloy is poor, can not satisfy the requirement of hyundai electronics industry.Therefore, the dual role of protecting environment and improving the electronic product quality is being undertaken in the development and application of lead-free solder.
Series alloys such as tin-copper, tin-silver-copper, tin-zinc are more typically arranged in the lead-free solder.But, up to the present still do not develop a kind of lead-free solder that can substitute traditional tin-kupper solder fully.A kind of feasible method that strengthens solder performance is to introduce second phase in conventional scolder, makes it become composite solder.CNT is becoming the good wild phase of conventional solder with its good mechanical, electricity and thermal property.Theoretical calculating shows that the mechanical property of CNT obviously is better than other crystal whisker materials, has very high axial strength and rigidity.Density that CNT is low and good structural stability make it have tempting application prospect in the composite solder field.But because CNT specific surface energy height, in the brazing metal matrix, be difficult for disperseing, and it is poor with the interfacial bonding property of scolder matrix, therefore how to bring into play the humidification of CNT in lead-free solder, preparing the excellent scolder of new generation good, environmental protection of performance is the major issue that electronics industry needs to be resolved hurrily.
Find through literature search prior art, Chinese patent " a kind of high wetting, antioxidizing leadless tin-base alloy " (application number: 200810121373.9, publication number: CN 101363088A), by being base material with tin, in base material, add other elements such as phosphorous, nickel and prepare lead-free solder, but the use of phosphorus can cause body eutrophication, polluted source, nickel is a heavy metal species, and is harmful.Chinese patent " nano-enhanced leadless solder and preparation method thereof " (application number: 200910306035.7, publication number: CN 101653877A), introduce a kind of CNT and strengthened Sn-Bi lead-free solder and preparation method thereof, this method adds the scolder matrix with CNT according to predetermined mass ratio, ball milling, compacting obtain blank, again the blank sintering are obtained lead-free solder.But its described ball grinding method is not easy even carbon nanotube is disperseed, and is easy to the structure of destroying carbon nanometer tube in the ball milling.Chinese patent " solder caps that nanotube strengthens, composing method and chip encapsulation and system " (application number: 200710170166.8, publication number: CN 101276796A), the CNT scolder of this method demonstrates high thermal conductivity and electric conductivity, as the little cap of scolder on the metal salient point, but the associativity of not surface treated CNT and matrix scolder is bad, influences the performance of composite solder.
Summary of the invention
The objective of the invention is to overcome weak point of the prior art, provide a kind of CNT to strengthen lead-free solder and preparation method thereof.The present invention utilizes the method for chemical plating, realize the surface metalation of CNT, utilize this layer metal as transition zone, improve the wellability between CNT and the scolder matrix, thereby improve dispersiveness and the interface bond strength of CNT in the scolder melt, obtain well behaved CNT and strengthen compound lead-free solder.
The present invention realizes with following technical scheme: a kind of CNT strengthens lead-free solder and preparation method thereof, and it is characterized in that: this preparation method comprises the steps:
Step 1, the acidifying CNT;
Step 2, the sensitization activated carbon nano-tube;
Step 3, metallized carbon nanotubes;
Step 4 adds the fusion welding matrix with metallized carbon nanotubes, utilizes the melt paddling process to prepare CNT and strengthens lead-free solder.
In the step 1, the acid of described acidifying CNT is one or both mixing in sulfuric acid and the nitric acid; Described CNT is a multi-walled carbon nano-tubes, and its preparation method can be any one in the following method: arc discharge method, laser evaporation method, chemical vapour deposition technique.
In the step 2, it is to make the carbon nano tube surface of acidifying adsorb the material that one deck is reduced easily that the sensitization of described sensitization activated carbon nano-tube is handled, so that carry out activation processing, the sensitizer that uses is stannous chloride.
In the step 2, described activation processing is to cover the layer of precious metal that one deck has catalytic in carbon nano tube surface, and the activator that uses is palladium bichloride.
In the step 3, the metalized of described metallized carbon nanotubes is to use chemical plating method, cross on the activated carbon nano-tube surface and cover layer of metal, the described coat of metal can be silver, the gold and copper in a kind of.
In the step 4, described scolder matrix be in the following alloy series any one: tin-silver-copper, tin-indium-Yin, indium-Yin, Sn-Bi-Yin, tin-copper, tin-silver-copper-bismuth, Sn-Bi-Yin-indium, tin-zinc, tin-zinc-bismuth, Xi-Jin.
Compared with prior art, the present invention has following beneficial effect: (1) utilizes mechanics, electricity and the thermal property of CNT excellence, makes its wild phase as lead-free solder, reaches environmental protection, welds reliable requirement; (2) metallization processes destroying carbon nanometer tube original structure not improves the dispersiveness of CNT in melt; (3) surface metal plating layer improves the wellability between CNT and the scolder matrix, increases interface bond strength, gives full play to the humidification of CNT.
The specific embodiment
Below embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The present invention is achieved by the following technical solutions, and the present invention specifically comprises the steps:
Step 1, the sulfuric acid treatment CNT.CNT after the 2g annealing is placed in the 300ml high-concentration sulfuric acid, mixed liquor is put in ultrasonic 30min in the ultrasonic tank.Then solution is inserted reflux, stirring and refluxing 30min under 90 ℃ of temperature.With products therefrom repeatedly centrifugal to the solution pH value be 7.With the polyester film suction filtration of centrifugal product, 60 ℃ of oven dry, obtain the acidifying CNT at last with 1.2 μ m apertures.
Step 2, the sensitization activated carbon nano-tube.1g acidifying CNT is joined in the sensitizing solution (0.1M stannous chloride+0.2M hydrochloric acid), magnetic agitation 30min, extremely neutral with deionized water rinsing then; The sensitization CNT is joined activating solution (0.0025M palladium bichloride+0.25M hydrochloric acid), and magnetic agitation 30min obtains activated carbon nano-tube after the washing.
Step 3, carbon nano tube surface is silver-plated.Solution composition is: 10g/L silver nitrate+15ml/L ammoniacal liquor+40g/L natrium citricum.60 ℃ of reaction temperatures, solution pH value are 8.5, magnetic agitation time 1h.React the after washing that finishes,, obtain the CNT of electroplate at 70 ℃ of vacuum dryings.
Step 4 adds molten tin scolder matrix with the silver-plated CNT of 0.01g, and cooling forming behind the vigorous stirring 20min under nitrogen protection obtains CNT and strengthens tin-base lead-free solder.
Embodiment 2
Step 1, nitration mixture is handled CNT.CNT after the 3g annealing is placed (sulfuric acid: nitric acid=1: 3), with mixed liquor stirring at normal temperature 30min on agitator, be put in ultrasonic 30min in the ultrasonic tank again in the 300ml high concentration nitration mixture.Then solution is inserted reflux in 90 ℃ of stirring and refluxing 30min.The products therefrom centrifugal water is washed till neutrality, obtains the acidifying CNT.
Step 2, the sensitization activated carbon nano-tube.1g acidifying CNT is joined in the sensitizing solution (0.1M stannous chloride+0.2M hydrochloric acid), magnetic agitation 30min, extremely neutral with deionized water rinsing then; The sensitization CNT is joined activating solution (0.0025M palladium bichloride+0.25M hydrochloric acid), and magnetic agitation 30min obtains activated carbon nano-tube after the washing.
Step 3, carbon nano tube surface copper facing.Electroplate liquid formulation is: 3g/L copper sulphate+20g/L disodium ethylene diamine tetraacetate+2g/L sodium sulphate+24.2g/L sodium acetate+20ml/L formaldehyde.60 ℃ of reaction temperatures, solution pH value are 10.5, magnetic agitation time 1h.React the after washing that finishes,, obtain the CNT of copper coating at 70 ℃ of vacuum dryings.
Step 4 is put into molten tin-spelter solder matrix with 0.005g coppered carbon nanotube, and cooling forming behind the vigorous stirring 15min under nitrogen protection obtains CNT and strengthens lead-free solder.
Embodiment 3
Step 1, the CNT after the nitric acid treatment annealing.The 2g CNT is placed in the high concentration nitric acid,, be put in ultrasonic 25min in the ultrasonic tank again mixed liquor stirring at normal temperature 20min.Then solution is inserted reflux in 80 ℃ of stirring and refluxing 60min.With products therefrom repeatedly centrifugal to the solution pH value be 7,60 ℃ of oven dry, obtain the acidifying CNT.
Step 2, the sensitization activated carbon nano-tube.1g acidifying CNT is joined in the sensitizing solution (0.1M stannous chloride+0.2M hydrochloric acid), magnetic agitation 30min, extremely neutral with deionized water rinsing then; The sensitization CNT is joined activating solution (0.0025M palladium bichloride+0.25M hydrochloric acid), and magnetic agitation 30min obtains activated carbon nano-tube after the washing.
Step 3, carbon nano tube surface is gold-plated.Electroplate liquid formulation is: 1g/L potassium auricyanide+6g/L potassium cyanide+6g/L potassium hydroxide+5.5g/L potassium borohydride+2.5g/L disodium ethylene diamine tetraacetate+25ml/L monoethanolamine.Room temperature magnetic agitation time 2h.React the after washing that finishes,, obtain the CNT of surface gold-plating at 60 ℃ of vacuum dryings.
Step 4 is put into molten tin-gold solder matrix with the gold-plated CNT of 0.005g, and cooling forming behind the vigorous stirring 20min under nitrogen protection obtains CNT and strengthens lead-free solder.
Claims (6)
1. a CNT strengthens lead-free solder and preparation method thereof, and it is characterized in that: this preparation method comprises the steps:
Step 1, the acidifying CNT;
Step 2, the sensitization activated carbon nano-tube;
Step 3, metallized carbon nanotubes;
Step 4 adds the fusion welding matrix with metallized carbon nanotubes, utilizes the melt paddling process to prepare CNT and strengthens lead-free solder.
2. CNT according to claim 1 strengthens lead-free solder and preparation method thereof, and it is characterized in that: in the step 1, the acid of described acidifying CNT is one or both mixing in sulfuric acid and the nitric acid; Described CNT is a multi-walled carbon nano-tubes, and its preparation method can be any one in the following method: arc discharge method, laser evaporation method, chemical vapour deposition technique.
3. CNT according to claim 1 strengthens lead-free solder and preparation method thereof, it is characterized in that: in the step 2, it is to make the carbon nano tube surface of acidifying adsorb the material that one deck is reduced easily that the sensitization of described sensitization activated carbon nano-tube is handled, so that carry out activation processing, the sensitizer that uses is stannous chloride.
4. CNT according to claim 1 strengthens lead-free solder and preparation method thereof, it is characterized in that: in the step 2, described activation processing is to cover the layer of precious metal that one deck has catalytic in carbon nano tube surface, and the activator that uses is palladium bichloride.
5. CNT according to claim 1 strengthens lead-free solder and preparation method thereof, it is characterized in that: in the step 3, the metalized of described metallized carbon nanotubes is to use chemical plating method, cross on the activated carbon nano-tube surface and to cover layer of metal, the described coat of metal can be silver, the gold and copper in a kind of.
6. CNT according to claim 1 strengthens lead-free solder and preparation method thereof, it is characterized in that: in the step 4, described scolder matrix be in the following alloy series any one: tin-silver-copper, tin-indium-Yin, indium-Yin, Sn-Bi-Yin, tin-copper, tin-silver-copper-bismuth, Sn-Bi-Yin-indium, tin-zinc, tin-zinc-bismuth, Xi-Jin.
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Cited By (10)
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| CN102593710A (en) * | 2012-03-21 | 2012-07-18 | 中国工程物理研究院应用电子学研究所 | Packaging method for semiconductor laser |
| CN102581504A (en) * | 2012-03-23 | 2012-07-18 | 天津大学 | Graphene reinforced lead-free solder and preparation method thereof |
| CN103602850A (en) * | 2013-11-13 | 2014-02-26 | 青岛科技大学 | High-conductivity carbon nano tube metal-based composite material |
| CN104416296A (en) * | 2013-09-03 | 2015-03-18 | 天津大学 | Method and application for improving electromigration resistance of interconnection welding spots of welding fluxes |
| CN104668812A (en) * | 2015-03-20 | 2015-06-03 | 郑州机械研究所 | Process for preparing ultra-thin brazing fillers by chemical plating and electric plating |
| CN107058784A (en) * | 2017-01-12 | 2017-08-18 | 哈尔滨工业大学 | Preparation method for the CNTs Sn solder with composite material of tin-coated welding strip |
| CN109411376A (en) * | 2018-11-02 | 2019-03-01 | 武汉天马微电子有限公司 | A kind of display panel manufacturing method and display panel |
| CN111151909A (en) * | 2020-01-03 | 2020-05-15 | 苏州优诺电子材料科技有限公司 | Carbon nano tube modified low-temperature solder and preparation method thereof |
| CN116713635A (en) * | 2023-08-08 | 2023-09-08 | 江西兆驰半导体有限公司 | Solder paste preparation method, solder paste and application of solder paste in LED chip packaging |
| CN116810210A (en) * | 2023-05-26 | 2023-09-29 | 齐齐哈尔大学 | Composite brazing filler metal and preparation method and application thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593710A (en) * | 2012-03-21 | 2012-07-18 | 中国工程物理研究院应用电子学研究所 | Packaging method for semiconductor laser |
| CN102581504A (en) * | 2012-03-23 | 2012-07-18 | 天津大学 | Graphene reinforced lead-free solder and preparation method thereof |
| CN102581504B (en) * | 2012-03-23 | 2014-07-30 | 天津大学 | Graphene reinforced lead-free solder and preparation method thereof |
| CN104416296A (en) * | 2013-09-03 | 2015-03-18 | 天津大学 | Method and application for improving electromigration resistance of interconnection welding spots of welding fluxes |
| CN103602850A (en) * | 2013-11-13 | 2014-02-26 | 青岛科技大学 | High-conductivity carbon nano tube metal-based composite material |
| CN104668812B (en) * | 2015-03-20 | 2016-08-17 | 郑州机械研究所 | The technique that ultra-thin solder is prepared in chemical plating and plating |
| CN104668812A (en) * | 2015-03-20 | 2015-06-03 | 郑州机械研究所 | Process for preparing ultra-thin brazing fillers by chemical plating and electric plating |
| CN107058784A (en) * | 2017-01-12 | 2017-08-18 | 哈尔滨工业大学 | Preparation method for the CNTs Sn solder with composite material of tin-coated welding strip |
| CN109411376A (en) * | 2018-11-02 | 2019-03-01 | 武汉天马微电子有限公司 | A kind of display panel manufacturing method and display panel |
| CN111151909A (en) * | 2020-01-03 | 2020-05-15 | 苏州优诺电子材料科技有限公司 | Carbon nano tube modified low-temperature solder and preparation method thereof |
| CN111151909B (en) * | 2020-01-03 | 2021-10-29 | 苏州优诺电子材料科技有限公司 | Carbon nano tube modified low-temperature solder and preparation method thereof |
| CN116810210A (en) * | 2023-05-26 | 2023-09-29 | 齐齐哈尔大学 | Composite brazing filler metal and preparation method and application thereof |
| CN116810210B (en) * | 2023-05-26 | 2024-04-09 | 齐齐哈尔大学 | Method for preparing composite solder |
| CN116713635A (en) * | 2023-08-08 | 2023-09-08 | 江西兆驰半导体有限公司 | Solder paste preparation method, solder paste and application of solder paste in LED chip packaging |
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Application publication date: 20110817 |