CN103406685B - For the one-dimensional tin silver bielement nano solder of micro-/ nano welding - Google Patents
For the one-dimensional tin silver bielement nano solder of micro-/ nano welding Download PDFInfo
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Abstract
The present invention relates to solder material field, especially relate to the one-dimensional tin silver bielement nano solder for micro-/ nano welding.The present invention also discloses the welding procedure of this solder.For the one-dimensional tin silver bielement nano solder of micro-/ nano welding, 1-dimention nano solder is the alloy nano-wire of 3 nanometer ~ 400 nanometers containing the diameter of Sn, and the composition of described 1-dimention nano solder is Sn
yag
100-yalloy nano-wire, wherein 100 & gt; Y & gt; 0, its optimal components is 99 & gt; Y>=50.The alloy system of solder of the present invention has: fusing point is low, and electrical conductivity, thermal conductivity are good, and toxicity is low, without the need to inert gas shielding during use, welds parent wellability and diffusivity is good with majority.
Description
The invention belongs to the divisional application that application number is 201210150049.6, the applying date of original application is on May 16th, 2012, and denomination of invention is the 1-dimention nano solder and preparation method thereof for the welding of micro-/ nano yardstick.
Technical field
The present invention relates to solder material field, especially relate to the one-dimensional tin silver bielement nano solder for micro-/ nano welding.
Background technology
Along with the deep development of current nano materials research, people can easily pass through various physics, chemistry or the way such as biological and prepare thousands upon thousands kinds of nano materials, but the single nano material utilizing modern welding technology but cannot directly these be prepared on nanoscale or nano-device element solder are to together, connect into various there is features and effect nano electron device, sensor, device, equipment and instrument etc.Reason is that in modern welding technology, welding procedure soldering appliance used and solder, much larger than nano material size, cannot thoroughly cover nano-weld parent, size completely also cannot be mated.At present, modern welding technology, can at nano-space by various nano-weld technology also famine welded together to the monomer material of nanoscale or device cell etc.This is also why do not have the basic reason dropping into practical application on a large scale as desired before 10 years in people to nanosecond science and technology today.
Present stage many nanosecond science and technology research just uses as scanning probe microscopy technology simply, single or array nano material is put together to upper growing technology the end of by, and this tie-point permanently effective with the firm solid energy that is welded has essential distinction.Simply nano material is put together and can not form the nano-device that really there is actual use reliable, stable and long-life.Therefore, recent years, the research work that nano-weld is correlated with starts the attention receiving researcher, to become in research in nanotechnology an emerging research branch.Main research work comprises the preparation of nanotube-solder, the exploitation of nano-weld technology, nano-weld mechanism (as infiltrated and flooding mechanism between homogeneity, dissimilar materials) etc.It is that people research and develop and manufacture the multifunctional nano electronic sensor of many numerous and complicated and the basis of device and key technology guarantee.In a sense, its research and further developing, really can promote research in nanotechnology rises to nanosecond science and technology all sidedly level from the research of nano material.
At present, existing several nano-weld technology, as FIB welding, high-energy electron beam irradiation, Ultrasonic Radiation, laser weld and nanometer electricity solder technology, is found out the single micro-/ nano monomer of welding.Wherein, first three is planted solder technology and itself determines its limitation by its technology.FIB welding intermediate ion bundle can cause material modification, as the character such as thing phase, constituent structure change when injecting the nanometer parent or nano-pattern that will weld; High-energy electron beam irradiation solder technology can only be at present carry out under transmission electron microscope and speed of welding slow, there is a large amount of amorphous carbon and pollute, temporarily can only be used for scientific research; Ultrasonic Radiation solder technology cannot accomplish micro-/receive zone location.Therefore, in visible future, these three kinds of solder technology are difficult to can really for nanosecond science and technology industrial production.Laser welding technology speed of welding is fast, and be easy to realize automation, production efficiency is high.But just current technical merit, laser facula is at least micro-meter scale at present usually, and laser energy can affect the irradiation zone beyond nano-weld point, causes nano-device to deform or disabler, has a strong impact on the practical of it.
Nanometer electricity solder technology is introduced by electric current to cause the fusing of welding position nano-area and by welded together to nanometer parent or nano-pattern etc.Mainly contain two kinds of techniques at present.One is by nano-weld parent or nanostructured etc. by electric current, but this method has very large problem when the metal wire for being less than 100 nanometers, due to reasons such as these little nanometer sized materials activity are high, surface tension is large, while the fusing of nanometer solder joint, nanostructured is also fused, cannot be welded together.The nano-weld parent or nanostructured that can conduct electricity can only be welded simultaneously.Another kind is, nanotube-solder is delivered to nano-weld position, is then passed through by electric current and only melts nanotube-solder.Because electric current only passes through nanotube-solder, not by nano-weld parent or nanostructured, therefore can not damage or pollute nano-weld parent or nanostructured, immediately can carry out welding quality inspection and solder residue cleaning, whole process very fast, simply, totally.Meanwhile, solder joint is firm, solid, and nanotube-solder can choose at random because of nano-weld parent, and nano-weld parent or nanostructured, without the need to conduction, can be widely used in homogeneity, dissimilar materials welding.The method of conveying nanotube-solder mainly uses electron microscope in-situ nano robot, therefore can accurately locate.Along with further developing of nanometer robot, this solder technology very likely really becomes the solder technology that can be used for actual nano industrial and produce.
The preparation of nanotube-solder and solder technology are that research in nanotechnology can rise to nanosecond science and technology level, and really can be used for dropping into the basic of practical application and key point on a large scale, are the research fields that current research in nanotechnology must develop.It can by by different physics, chemistry or the way such as biological prepares various single nano material or nano-device unit just can be assembled into desired structure or pattern by nanometer robot, and they are changed into multifunctional nano device, sensor or device truly by the various nano-weld technology of use further, become Multi-functional special nano-device, sensor or device not prepared by the quantity of geometry level expansion semiconductor technology and chemical/biological self-assembling technique.Along with development and the maturation of this technology, cannot be able to use for the whole world is vast or contact semiconductor micro-/multifunctional nano device that the researcher that receives machining experiment room provides a low input but can prepare more wide range of types, sensor assembling approach.Simultaneously, because this technology uses ESEM or transmission electron microscope to be eyes, under vacuum conditions, can in real time, original position, dynamically whole nanotube-solder fusing, the process whole process that soaks, cover, spread and solidify with nano-weld parent are presented in people at the moment with covering all at one glance, and the analytical test of instant pattern, structure, composition, Elemental redistribution character can be carried out to each process, people can be helped to understand and grasp nano-weld mechanism and mechanism directly, intuitively.This is used for the construction of outer space space station and the space flight instrument vacuum welding technology of to repair etc. of meeting an urgent need for China and has great significance.
Therefore, continuing research uses the nanotube-solder of the artificial instrument of electron microscope in-situ nano machine to be extremely important and urgency.On the one hand, nanotube-solder will possess the basic demand of conventional solder as low fusion temperature, excellent mechanical property, solderability, wetability and stability.And on the other hand, prepared nanotube-solder will mate with welded nano material size, can carry out welding at nanoscale and not damage nanometer part.But on the current technology, meet the nanotube-solder research of above-mentioned requirements seldom.
The document of current report, modal nanotube-solder is made up of metal nanoparticle, comprise composite solder and pure nanotube-solder: composite solder is add a certain amount of nano particle in micron-sized solder at conventional particle size, the mechanics of solder and physical property are improved; The particle diameter of pure nanotube-solder is all nanoscale.This nanotube-solder preparation method be made up of metal nanoparticle has two classes: one is processing method from top to bottom, comprises the method such as mechanical crushing, electric spark blast; Another kind is processing method from bottom to top, comprises vapour deposition process, the precipitation method, sol-gal process, emblem emulsion method.Nanotube-solder is obtained finally by low-temperature sintering.But this solder can only be used for micro-meter scale, nanoscale can not be used for and weld.Therefore, be not real " nanotube-solder ".
Such as, nano-metal particles composition disclosed in Chinese invention patent application 200680022890.X disclosed " electromigration-resistant and the method complying with the encapsulation of wire interconnects, nano-solder composition, the system be made up of it and assembly welding " comprises first metal with about 50 nanometers or less particle size.Wire interconnects contacts with reflowed nano-solder, and has the metal or alloy composition identical with reflowed nano-solder.Also disclose the microelectronics Packaging adopting Reflowed nanosolder composition.A kind of method of assembling microelectronics Packaging comprises prepares wire interconnects template.Computing system comprises the nano-solder composition be coupled with wire interconnects.
Summary of the invention
The invention provides one-dimensional tin silver bielement nano solder welded for micro-/ nano and preparation method thereof, the present invention also discloses the welding procedure of this solder.
For the one-dimensional tin silver bielement nano solder of micro-/ nano welding, 1-dimention nano solder is the alloy nano-wire of 3 nanometer ~ 400 nanometers containing the diameter of Sn, and the composition of described 1-dimention nano solder is Sn
yag
100-yalloy nano-wire, wherein 100>Y>0, its optimal components is 99>Y>=50.
The preparation method of the one-dimensional tin silver bielement nano solder for micro-/ nano welding of the present invention, first be 3 ~ 400 nanometers with aperture, thickness is the poromerics of 20 nanometer ~ 150 micron is template, in the nano-pore of template, corresponding metal wire or alloy wire is deposited by electrochemical method in the metal ion electrolyte corresponding to prepared solder component, mould material dissolves by the solution that then can not dissolve the alloy be in mould material nano-pore with dissolvable template material, make to be arranged in the metal nanometer line in templating nanoparticles hole or alloy nano-wire to discharge and be distributed to solution, again by after the various salt components in cleaning and removed by filtration system, metal nanometer line or alloy nano-wire are distributed in deionized water for subsequent use.
Described template is anodised aluminium.Before carrying out electrochemical deposition operation, first use the barrier layer on the phosphoric acid removing anodic oxidation aluminium formwork surface of 0.01 ~ 1 mole often liter, then deposit silver-colored or the golden or platinum of one deck copper or other any conducting metal as electrode conducting layer at template surface; When carrying out electro-deposition operation, be negative electrode with anodic oxidation aluminium formwork in two electrode systems, be anode with graphite electrode, be working electrode with anodic oxidation aluminium formwork in three-electrode system, with platinum gold or graphite electrode be to electrode, any normal electrode as with reference to electrode, the NaOH that the solution dissolving template is or copper chloride solution, such as; The solution dissolving template with the NaOH of 1 mole often liter (mol/L) or 2mol/L, or can use 5mol/L copper chloride solution, can certainly use the sodium hydroxide solution of other concentration or the copper chloride solution of other concentration.
Described template is polycarbonate, first silver-colored or the golden or platinum of one deck copper or other any conducting metal should be deposited as electrode conducting layer at template surface before electro-deposition operation, when carrying out electro-deposition operation, in two electrode systems with polycarbonate template for negative electrode, be anode with graphite electrode, in three-electrode system with polycarbonate template for working electrode, with platinum gold or graphite electrode be to electrode, any normal electrode is as reference electrode, the solution dissolving template is the organic solution of chloroform or other solubilized polycarbonate, such as methine chlorine or carrene or METHYLENE CHLORIDE or carbon tetrachloride or trichloro-ethylene or oxolane etc.
The welding procedure of the described one-dimensional tin silver bielement nano for the welding of micro-/ nano yardstick: 1-dimention nano solder nanometer controller is extracted, is positioned over and needs welding position; Nanometer controller is closely coupled to 1-dimention nano solder two ends, switches on power, and 1-dimention nano solder electricity melts; Welding position cools, and is connected into entirety.
The method depositing electroplax conductive layer in above-mentioned solder preparation method in template can be plating, also can be evaporation, or vacuum sputtering, or the way adopting other known.
The alloy system of solder of the present invention has: fusing point is low; electrical conductivity, thermal conductivity are good; toxicity is low; without the need to inert gas shielding during use; parent wellability is welded and diffusivity is good with majority; welding after welding position there is very high non-oxidizability, and conduction and heat conductivility excellent, the advantage that almost can forever keep.And solder diameter of the present invention ensure that the welding requirements at micron and nanoscale, but be welded into reality at micro-meter scale or nanoscale.
Preparation method of the present invention can prepare diameter for number nanometer is to number Nanoalloy solder, can ensure that prepared solder diameter is in micron and nanoscale requirement, and this point to be prior art cannot realize.
Accompanying drawing explanation
Accompanying drawing 1 is one dimension Sn of the present invention
78ag
22nano wire solder pattern;
Accompanying drawing 2 is one dimension Sn of the present invention
50au
50nano wire solder pattern;
Accompanying drawing 3 is one-dimensional tin nanowires of gold solder energy dispersive of the present invention spectrum;
Accompanying drawing 4 is one dimension Sn of the present invention
18ag
2cu
80nano wire solder pattern;
Accompanying drawing 5 is one dimension Sn of the present invention
18ag
2cu
80nano wire solder component research energy dispersive spectrum;
Accompanying drawing 6 is the Sn of 150 nanometer diameters using preparation of the present invention
99au
1nano wire solder welds " people " font nano-pattern process of 50 nanometer diameter nanowires of gold compositions;
Accompanying drawing 7 is the nano-weld quality testing after using the nanotube-solder of preparation of the present invention to weld homogeneous material;
Accompanying drawing 8 is one-dimensional metal nano wire of the present invention---pure tin nano wire solder pattern;
Accompanying drawing 9 is one-dimensional metal nano wire of the present invention---proof gold nano wire solder pattern;
Accompanying drawing 10 is one dimension Sn of the present invention
96.5ag
3.5nano wire solder pattern.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further elaborated.
Accompanying drawing 1(a) be the Sn synthesized with homemade porous anodic alumina template
78ag
22nano wire solder ESEM (SEM) shape appearance figure, nanowire diameter is 50 nanometers, and length is about 50 microns; B Sn that () synthesizes by commercial polycarbonate template
78ag
22nano wire solder ESEM (SEM) shape appearance figure, nanowire diameter is 80 nanometers, and length is about 10 microns; (c) single Sn
78ag
22nano wire solder transmission electron microscope (TEM) shape appearance figure; (d) many Sn
78ag
22nano wire solder scanning transmission electron microscope (STEM) shape appearance figure.
Accompanying drawing 2 is one dimension Sn of the present invention
50au
50nano wire solder pattern: the Sn that (a) synthesizes with homemade porous anodic alumina template
50au
50nano wire solder ESEM (SEM) shape appearance figure, nanowire diameter is 45 nanometers, and length is about 15 microns.B Sn that () synthesizes by commercial polycarbonate template
30au
70nano wire solder transmission electron microscope (TEM) shape appearance figure, nanowire diameter is 80 nanometers, and length is about 10 microns.
Accompanying drawing 3 is one-dimensional tin nanowires of gold solder energy dispersive spectrum of the present invention: (a) quantitative analysis results is Sn:Au=50:50 solder spectrogram; B () quantitative analysis results is Sn:Au=30:70 solder spectrogram; C () quantitative analysis results is Sn:Au=95:5 solder spectrogram; D () quantitative analysis results is Sn:Au=90:10 solder spectrogram.
Accompanying drawing 4 is one dimension Sn of the present invention
18ag
2cu
80nano wire solder pattern: the Sn that (a) synthesizes by commercial polycarbonate template
18ag
2cu
80nano wire solder ESEM (SEM) shape appearance figure, nanowire diameter is 80 nanometers, and length is about 10 microns.B Sn that () synthesizes with homemade porous anodic alumina template
50au
50nano wire solder transmission electron microscope (SEM) shape appearance figure, nanowire diameter is 70 nanometers, and length is about 7 microns.
Accompanying drawing 5 is one dimension Sn of the present invention
18ag
2cu
80nano wire solder component research energy dispersive spectrum, quantitative analysis results is Sn:Ag:Cu=18:2:80.
Accompanying drawing 6 is the Sn of 150 nanometer diameters using preparation of the present invention
99au
1nano wire solder welds " people " font nano-pattern process of 50 nanometer diameter nanowires of gold compositions: (a) uses nanometer manipulation device to extract 55 nm of gold nano wires, assemble " people " font nano-pattern ESEM (SEM) figure be not connected; B () nanometer controller extracts single 150 nanometer Sn99Au1 nano wire solders and is positioned over position to be welded, and nano-probe is closely held on 1-dimention nano solder two ends SEM and schemes; C () is communicated with power supply, Sn99Au1 nano wire solder is melted by 120% maximum electric current and the rapid electrical of bearing, after melting nanotube-solder cooled and solidified, discrete " people " word is welded into the overall SEM figure of high conductivity.
Accompanying drawing 7 is the nano-weld quality testing after using the nanotube-solder of preparation of the present invention to weld homogeneous material: (a), and (b) homogeneity parent nanowires of gold is welded together; (c), (d), (e) is real-time, welded in place means of spot welds quality mechanics intensity detection; F () transmission electron microscope nano-weld point is micro-/and micro-nano structure detects.
Accompanying drawing 8 is pure tin nano wire solder pattern, (a): stereoscan photograph; (b): scanning transmission electron microscope photo; (c): x-ray electron energy dispersion spectrum measurement result, is shown as pure tin composition.
Accompanying drawing 9 is proof gold nano wire solder pattern, (a): stereoscan photograph; (b): transmission electron microscope photo; (c): x-ray electron energy dispersion spectrum measurement result, is shown as proof gold composition; (d): nanowires of gold is positioned over the nano-pattern of having arranged position to be welded as solder; (e): after energising, position to be welded is soldered to stereoscan photograph together.
Accompanying drawing 10 is Sn96.5Ag3.5 nano wire solder pattern, (a): stereoscan photograph; (b): transmission electron microscope photo; (c): x-ray electron energy dispersion spectrum measurement result, is shown as Sn96.5Ag3.5 composition.
Embodiment 1-Sn
78ag
22the preparation of nano wire solder
1a) the selecting of template: adopt aperture to be 3 ~ 400 nanometers, thickness is the anodised aluminium of 10 nanometer ~ 150 micron is template, this aluminium oxide can use commercial product, and have any problem can prepare voluntarily if purchase commercial Woelm Alumina, concrete preparation method has report in the prior art.
1b) the preparation of electroplate liquid: 0.18mol/L stannous methanesulfonate+0.001mol/L silver iodide+0.60mol/L potassium pyrophosphate+2.0mol/L KI+0.4mol/L triethanolamine+5g/L ascorbic acid+1g/L hydroquinones.
1c) electrochemical deposition:
Use and crossed the polycarbonate template of electrode (electrode can be any as any conducting metals such as copper, silver, gold, platinum) or porous anodic alumina template (removing barrier layer) is negative electrode, graphite electrode is anode, under-14V sedimentation potential, deposit 45 minutes, preparing tin silver proportioning components is the Sn of 78:22
78ag
22alloy nano-wire solder.
The Theil indices of end product is by changing stannous methanesulfonate and silver iodide relative concentration, or change electrochemical deposition current potential (or current density) realizes.Nanowire length changed by the electrochemical deposition time.
1d) the collection of goods:
Polycarbonate template chloroform containing tinbase nano wire in its hole formed plating dissolves, and tinbase nano wire is distributed in chloroform automatically.Further use be less than made nanowire diameter porous anodic alumina films filtration devices, wash the Merlon dissolved, cleaned tinbase nano wire can discretely be deposited or again be distributed in pure chloroform to retain to solid-state reservation in the substrates such as silicon chip and deposit, and uses for next step nano-weld.
The tinbase nano wire using anodic oxidation aluminium formwork to prepare adopts 0.1mol/L to 5mol/L copper chloride solution to dissolve 12 hours, treat that anodic oxidation aluminium formwork dissolves, the porous polycarbonate film filter being less than made nanowire diameter is used to filter, wash copper chloride and aluminate, cleaned tinbase nano wire can discretely be deposited or again be distributed in pure chloroform to retain to solid-state reservation in the substrates such as silicon chip and deposit, and uses for next step nano-weld.
After tinbase nano wire is distributed to the aqueous solution, visual sample aequum in concrete use, gets 30 microliters Solution Dispersions to silicon chip.About there is hundreds of thousands to arrive millions of nano wires at the silicon chip of 1cm × 1cm area, nano wire discrete quantities can be controlled by needs.
1e) the sign of goods
The Sn of preparation
78ag
22the pattern of nano wire solder, crystal structure and chemical composition/component utilize SEM (SEM) (Hitachi S-4800, Japan) and the several functions of high resolution transmission electron microscopy (HRTEM) (TecnaiTMG2F30, FEI, USA) carried out measurement & characterization.That Fig. 1 shows is representational Sn
78ag
22nano wire solder pattern result of study.Nano wire in Fig. 1 uses homemade anodic oxidation aluminium formwork to synthesize, and wherein anodic oxidation aluminium formwork is thoroughly cleared up, Sn
78ag
22nanometer line length is on gold electrode substrate, and on golden substrate, each bright spot is a nanowire growth point.In Fig. 1 a, nanowire diameter is 50 nanometers, and length is about 50 microns.Nanowire diameter, length dimension are even.That Fig. 1 b shows is the Sn be distributed on silicon chip
78ag
22nano wire, the commercial polycarbonate template of nano wire is prepared from, and nanowire diameter is 80 nanometers, and length is about 10 microns.That Fig. 1 c shows is single Sn
78ag
22nano wire solder transmission electron microscope (TEM) shape appearance figure.Fig. 1 d is many Sn
78ag
22nano wire solder scanning transmission electron microscope (STEM) shape appearance figure.As can be seen from the figure nanowire diameter, length dimension are evenly, but nano wire presents taper shape, top end diameter 80 nanometer, and bottom end diameter 170 nanometer, embodies the shape of polycarbonate template hole own.
Embodiment 2-Sn
xau
ythe preparation of nano wire solder
2a) the selecting of template:
The same
2b) the preparation of electroplate liquid:
Two kinds of electroplate liquids can use:
Electroplate liquid 1:100g/L tri-ammonium citrate+5g/L chlorauride+9g/L stannic chloride+60g/L sodium sulfite+10g/L gelatin+5g/L ascorbic acid
Electroplate liquid 2:0.5mol/L stannic chloride+5g/L chlorauride+10g/L gelatin+5g/L ascorbic acid+0.01mol/L hydrochloric acid
2c) electrochemical deposition:
Use commercial electrochemical workstation, adopt three-electrode system, use and crossed the polycarbonate template of electrode (electrode can be any as any conducting metals such as copper, silver, gold, platinum) or porous anodic alumina template (removing barrier layer) is working electrode, Ag/AgCl or Hg/HgCl
2electrode is reference electrode, and platinum electrode is to electrode, compares reference electrode-1800mV sedimentation potential, uses one of above-mentioned two kinds of electroplate liquids, deposits 45 minutes or 1 hour, and preparation Sillim proportioning components is the Sn of 50:50
50au
50alloy nano-wire solder.The Theil indices of end-product is by changing stannic chloride and chlorauride relative concentration, or change electrochemical deposition current potential (or current density) realizes.Nanowire length changed by the electrochemical deposition time.
2d) the collection of goods:
The same with above-mentioned tin nano silver wire solder collection mode.
2e) the sign of goods
Fig. 2 shows Sillim's nano wire solder pattern result of study prepared by above-mentioned three-electrode system.Fig. 2 a is nano wire solder ESEM (SEM) shape appearance figure of homemade porous anodic alumina template synthesis, and diameter is 45 nanometers, and length is about 15 microns.Composition result of study shows Sillim's ratio for 50:50(is as shown in 3a).Fig. 2 b is the nano wire solder transmission electron microscope shape appearance figure synthesized by commercial polycarbonate template, and be directly 80 nanometers, length is about 10 microns.Composition result of study show Sillim's ratio be 70:30(as shown in Figure 3 b).Meanwhile, also prepared Sillim's nano wire solder of other proportioning components, it is 95:5 nano wire solder energy dispersive spectrum experimental result that Fig. 3 c is depicted as Sillim's ratio, and it is 90:10 nano wire solder energy dispersive spectrum experimental result that Fig. 3 d is depicted as Sillim's ratio.Results of elemental analyses adopts electron energy loss spectroscopy (EELS) investigative technique to obtain confirmation further.
Embodiment 3-Sn
18ag
2cu
80the preparation of nano wire solder
3a) the selecting of template:
The same
3b) the preparation of electroplate liquid:
0.18mol/L stannous methanesulfonate+0.001mol/L silver iodide+0.5mol/L copper nitrate+0.60mol/L potassium pyrophosphate+2.0mol/L KI+0.4mol/L triethanolamine+5g/L ascorbic acid+1g/L hydroquinones.
3c) electrochemical deposition:
Use commercial electrochemical workstation, adopt three-electrode system, use and crossed the polycarbonate template of electrode (electrode can be any as any conducting metals such as copper, silver, gold, platinum) or porous anodic alumina template (removing barrier layer) is working electrode, Ag/AgCl or Hg/HgCl
2electrode is reference electrode, and platinum electrode is to electrode, compares reference electrode-1800mV sedimentation potential, uses one of above-mentioned two kinds of electroplate liquids, deposits 45 minutes or 1 hour, and preparing SAC gold proportioning components is the Sn of 18:2:80
18ag
2cu
80alloy nano-wire solder.The SAC content of end-product by changing stannous methanesulfonate, relative concentration between silver iodide and copper nitrate, or change electrochemical deposition current potential (or current density) and realize.Nanowire length changed by the electrochemical deposition time.
3d) the collection of goods:
The same with above-mentioned SAC nano wire solder collection mode.
3e) the sign of goods
Sillim's nano wire solder pattern result of study that Fig. 4 is prepared by above-mentioned three-electrode system.Fig. 4 a is nano wire solder ESEM (SEM) shape appearance figure synthesized by commercial polycarbonate template, and diameter is 80 nanometers, and length is about 10 microns.Fig. 4 b is nano wire solder transmission electron microscope (TEM) shape appearance figure synthesized with homemade porous anodic alumina template, and diameter is 70 nanometers, and length is about 7 microns.The ratio of Fig. 5 composition result of study display SAC pantogen subnumber is 18:2:80.
1-dimention nano solder is used for actual nano-space welding example
Example 1: actual homogeneity welding
The 1-dimention nano solder prepared in the present invention has been actually used in the welding of nano-space nano-pattern, prototype electronic device.The Sn of 150 nanometer diameters is used shown in Fig. 6
99au
1nano wire solder welds " people " font nano-pattern process of 50 nanometer diameter nanowires of gold compositions.Be dispersed in two 55 nm of gold nano wires on silicon chip by the gripping of nanometer manipulation device, clean silicon chip be assembled into and do not connect into overall " people " word pattern (as shown in Figure 6 a).That prepares in the present invention is about 1.5 microns, the special one dimension Sn of diameter 150 nanometer
99au
1nano wire solder is extracted by nanometer controller subsequently, is positioned over and needs welding position.Two nanometer controller nano-probes are closely coupled to 1-dimention nano solder two ends (shown in Fig. 6 b), switch on power, make Sn
99au
1nano wire solder is melted by 120% maximum electric current and the rapid electrical of bearing, and as fig. 6 c discrete " people " word is welded into high conductivity entirety after melting nanotube-solder cooled and solidified.
The 1-dimention nano solder prepared in the present invention is also actually used in heterojunction nanowire welding.
Welding quality can use that nanometer controller carries out in real time immediately, original position, image conversion detect.
Welding quality also can be detected by in-situ mechanical measurement.After homogeneity parent nanowires of gold that what Fig. 7 showed is is welded together, uses nanometer controller to carry out nanometer solder joint in-situ mechanical character immediately and to measure and pad is transferred in transmission electron microscope and carried out the careful example detected for micro-/micro-nano structure further.The pad mechanical stretch intensity that measurement result shows nanowires of gold in Fig. 7 is greater than 110MPa, and Young's modulus is greater than 75GPa, and micro-/micro-nano structure research display pad thoroughly fuses into one, and forms twin.
This kind be by electron microscope in-situ nano executor (or claim, nanometer robot) 1-dimention nano solder is delivered to micro-/ nano welding position, then electric current is welded together by mother metal by also only melting nanotube-solder, because electric current only passes through nanotube-solder, not by micro-/ nano welding parent or micro/nano structure, therefore can not damage or pollute micro-/ nano welding parent or micro/nano structure.Also immediately can carry out welding quality inspection and solder residue cleaning, whole process very fast, simply, totally.Meanwhile, solder joint is firm, solid, and nanotube-solder can choose at random because micro-/ nano welds parent, and micro-/ nano welding parent or nanostructured, without the need to conduction, can be widely used in homogeneity, dissimilar materials welding.Except two practical embodiments of above-mentioned displaying, the nano wire that the 1-dimention nano solder system of the different components prepared in the present invention, component, Sillim, Xi Yin and SAC have successfully achieved gold, platinum, copper, nickel-cadmium, cobalt platinum multilayer, ferronickel Multilayered Nanowires not of the same race by nanometer controller technology in this on nano-space is welded into Multi-functional special nano-sensor and electronic device, and they is welded on integrated circuit plate electrode.
But solder of the present invention is not only limited to the nanotube-solder of these three kinds of components, any one dimension tinbase nanotube-solder can be used.Welding parent is not only limited to this six kinds of parents, can be the simple substance of any micro-/ nano yardstick, alloy or multiple layer metal, circuit board electrode.
Claims (6)
1. for the one-dimensional tin silver bielement nano solder of micro-/ nano welding, it is characterized in that: 1-dimention nano solder is the alloy nano-wire of 3 nanometer ~ 400 nanometers containing the diameter of Sn, and the composition of described 1-dimention nano solder is Sn
yag
100-yalloy nano-wire, wherein 100>Y>0.
2. the one-dimensional tin silver bielement nano solder for micro-/ nano welding according to claim 1, is characterized in that: 99>Y >=50.
3. the preparation method of the one-dimensional tin silver bielement nano solder for micro-/ nano welding described in claim 1 or 2, it is characterized in that: be first 3 ~ 400 nanometers with aperture, thickness is the poromerics of 10 nanometer ~ 150 micron is template, in the nano-pore of template, corresponding metal wire or alloy wire is deposited by electrochemical method in the metal ion electrolyte corresponding to prepared solder component, mould material dissolves by the solution that then can not dissolve the alloy be in mould material nano-pore with dissolvable template material, make to be arranged in the metal nanometer line in templating nanoparticles hole or alloy nano-wire to discharge and be distributed to solution, again by after the various salt components in cleaning and removed by filtration system, metal nanometer line or alloy nano-wire are distributed in deionized water.
4. the preparation method of the one-dimensional tin silver bielement nano solder for micro-/ nano welding according to claim 3, it is characterized in that: described template is anodised aluminium, first remove the barrier layer on anodic oxidation aluminium formwork surface before carrying out electrochemical deposition operation, and deposit silver-colored or the golden or platinum of one deck copper or other any conducting metal as electrode conducting layer at template surface; When carrying out electro-deposition operation, taking anodic oxidation aluminium formwork as negative electrode in two electrode systems, is anode with graphite electrode, is working electrode in three-electrode system with anodic oxidation aluminium formwork, with platinum gold or graphite electrode be to electrode, any normal electrode as reference electrode; The solution dissolving template is NaOH or copper chloride solution.
5. the preparation method of the one-dimensional tin silver bielement nano solder for micro-/ nano welding according to claim 3, it is characterized in that: described template is polycarbonate, to carry out before electrochemical deposition operation first depositing silver-colored or the golden or platinum of one deck copper or other any conducting metal as electrode conducting layer at template surface, when carrying out electro-deposition operation, in two electrode systems with polycarbonate template for negative electrode, be anode with graphite electrode, in three-electrode system with polycarbonate template for working electrode, with platinum gold or graphite electrode be to electrode, any normal electrode is as reference electrode, the solution dissolving template is the organic solution of chloroform or other solubilized polycarbonate.
6. the welding procedure of the one-dimensional tin silver bielement nano solder for micro-/ nano welding described in claim 1 or 2, is characterized in that: extracted by 1-dimention nano solder nanometer controller, be positioned over and need welding position; Nanometer controller is closely coupled to 1-dimention nano solder two ends, switches on power, and 1-dimention nano solder electricity melts; Welding position cools, and is connected into entirety.
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| CN201310249805.5A CN103406685B (en) | 2011-11-02 | 2012-05-16 | For the one-dimensional tin silver bielement nano solder of micro-/ nano welding |
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| CNPCT/CN2011/001845 | 2011-11-02 | ||
| CN2011001845 | 2011-11-02 | ||
| CN201310249805.5A CN103406685B (en) | 2011-11-02 | 2012-05-16 | For the one-dimensional tin silver bielement nano solder of micro-/ nano welding |
| CN201210150049.6A CN102773624B (en) | 2011-11-02 | 2012-05-16 | One-dimensional nano welding flux for micron/nanoscale welding and preparation method thereof |
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| CN201310250546.8A Expired - Fee Related CN103358047B (en) | 2011-11-02 | 2012-05-16 | For the one-dimensional tin silver-bearing copper ternary nano solder of micro-/ nano yardstick welding |
| CN201310249805.5A Expired - Fee Related CN103406685B (en) | 2011-11-02 | 2012-05-16 | For the one-dimensional tin silver bielement nano solder of micro-/ nano welding |
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| CN201310250546.8A Expired - Fee Related CN103358047B (en) | 2011-11-02 | 2012-05-16 | For the one-dimensional tin silver-bearing copper ternary nano solder of micro-/ nano yardstick welding |
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| CN103215575A (en) * | 2013-04-26 | 2013-07-24 | 中国矿业大学(北京) | Novel welding method for metal nanowire |
| CN103624388B (en) * | 2013-11-13 | 2015-09-30 | 中国科学院合肥物质科学研究院 | A kind of welding method of the monodimension nanometer material based on electroluminescent heating effect |
| CN103706959B (en) * | 2013-11-27 | 2016-08-17 | 中国科学院合肥物质科学研究院 | A kind of for single nanometer materials welding help solder and welding method thereof |
| CN106868538B (en) * | 2015-12-13 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of Carbon dioxide electrochemical reduction electrode, preparation method and applications |
| CN107680949B (en) * | 2017-09-08 | 2019-12-17 | 苏州汉尔信电子科技有限公司 | preparation method and packaging method of low-temperature nano tin paste |
| CN109834406B (en) * | 2017-11-27 | 2022-01-18 | 财团法人金属工业研究发展中心 | Light metal joining method and joining filler therefor |
| CN111224091B (en) * | 2018-11-27 | 2021-08-31 | 中国科学院大连化学物理研究所 | Metal lithium wire and preparation method thereof |
| CN111996560A (en) * | 2020-07-10 | 2020-11-27 | 深圳先进技术研究院 | Metal wire preparation method, metal wire and clamp |
| CN112067643A (en) * | 2020-09-08 | 2020-12-11 | 宁波江丰电子材料股份有限公司 | Sample preparation method for SEM detection of welding diffusion layer of high-purity aluminum target assembly |
| CN112222672A (en) * | 2020-10-09 | 2021-01-15 | 哈尔滨工业大学（深圳） | Composite material for low-temperature packaging, preparation method thereof and packaging method |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103358047A (en) | 2013-10-23 |
| CN103406685A (en) | 2013-11-27 |
| CN102773624A (en) | 2012-11-14 |
| CN102773624B (en) | 2014-05-14 |
| CN103358047B (en) | 2016-04-20 |
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