CN102773624B - One-dimensional nano welding flux for micron/nanoscale welding and preparation method thereof - Google Patents

One-dimensional nano welding flux for micron/nanoscale welding and preparation method thereof Download PDF

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CN102773624B
CN102773624B CN201210150049.6A CN201210150049A CN102773624B CN 102773624 B CN102773624 B CN 102773624B CN 201210150049 A CN201210150049 A CN 201210150049A CN 102773624 B CN102773624 B CN 102773624B
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nano
electrode
scolder
welding
template
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CN102773624A (en
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彭勇
张宏
贝芙莉·尹格申
托尼·卡力斯
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Lanzhou University
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Lanzhou University
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Abstract

The invention discloses one-dimensional nano welding flux for micron/nanoscale welding and a preparation method of the one-dimensional nano welding flux for micron/nanoscale welding. The one-dimensional nano welding flux disclosed by the invention is a metal nanowire or an alloy nanowire, the diameter of which is 3-400 nanometers. The preparation method of the welding flux disclosed by the invention comprises the steps of: first, taking a microporous material which is 3-400 nanometers in pore diameter and dozens of nanometers to 150 microns in thickness as a moldboard; depositing corresponding metal wires or alloy wires in nanopores of the moldboard in a metal ion electrolyte corresponding to components of the prepared welding flux through an electrochemical method; then dissolving the moldboard material by a solution that dissolves the moldboard material but not dissolves alloy in the nanopores of the moldboard so that the metal nanowires or alloy wires in the nanopores of the moldboard are released and dispersed to the solution; and then cleaning and filtering various salt components in the system, and dispersing the metal nanowires or alloy wires in deionized water for future use.

Description

1-dimention nano scolder welding for micro-/ nano yardstick and preparation method thereof
technical field
The present invention relates to solder material field, especially relate to 1-dimention nano scolder for the welding of micro-/ nano yardstick and preparation method thereof.
background technology
Along with the deep development of current nano materials research, people can be easily prepare thousands upon thousands kinds of nano materials by various physics, chemistry or the way such as biological, but utilize single nano material or the nano-device element solder that modern welding technology but cannot directly be prepared these on nanoscale to arrive together, connect into various nano electron device, sensor, device, equipment and the instruments etc. with features and effect.Reason is that in modern welding technology, welding procedure soldering appliance used and scolder, much larger than nano material size, cannot thoroughly cover nano-weld parent, in size, completely also cannot mate.At present, modern welding technology, can be at nano-space by also famine of various nano-weld technology welded together to monomer material or the device cell etc. of nanoscale.This be also why to today nanosecond science and technology not as people's desired basic reason that drops on a large scale practical application before 10 years.
Much nanosecond science and technology research of present stage just uses simply as scanning probe microscopy technology, to upper growing technology, single or array nano material are put together the end of by, and this and the permanently effective tie-point of firm solid energy that is welded have essential distinction.Simply nano material is put together and can not form reliable, stable and long-life and really have the nano-device of actual use.Therefore, recent years, the research work that nano-weld is relevant has started to be subject to researcher's attention, becomes an emerging research branch in research in nanotechnology.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, can really promote research in nanotechnology and rise to from the research of nano material all sidedly the level of nanosecond science and technology.
At present, existing several nano-weld technology, as FIB welding, high-energy electron beam irradiation, Ultrasonic Radiation, laser weld and nanometer electricity solder technology, are found out the single micro-/ nano monomer of welding.Wherein, first three is planted solder technology and itself has determined its limitation by its technology.FIB welding intermediate ion bundle can cause material modification while injecting the nanometer parent that will weld or nano-pattern, as character changes such as thing phase, constituent structure; High-energy electron beam irradiation solder technology can only be under transmission electron microscope, to carry out and speed of welding is slow, exist a large amount of amorphous carbon to pollute at present, temporarily can only be used for scientific research; That Ultrasonic Radiation solder technology cannot be accomplished is micro-/receive zone location.Therefore,, in visible future, these three kinds of solder technology are difficult to can be really for nanosecond science and technology industrial production.Laser welding technology speed of welding is fast, is easy to realize automation, and production efficiency is high.But with regard to current technical merit, laser facula is at least micro-meter scale at present conventionally, laser energy can affect the irradiation zone beyond nano-weld point, causes that nano-device deforms or disabler, has a strong impact on the practical of it.
Nanometer electricity solder technology is that electric current is introduced and caused the fusing of welding position nano-area and by welded together to nanometer parent or nano-pattern etc.Mainly contain at present two kinds of techniques.One is by nano-weld parent or nanostructured etc. by electric current, but this method has very large problem in the time of the metal wire for being less than 100 nanometers, due to reasons such as these little nanoscale material activity are high, surface tension is large, in the fusing of nanometer solder joint, nanostructured is also fused, cannot be welded together.Can only weld nano-weld parent or the nanostructured that can conduct electricity simultaneously.Another kind is, nanotube-solder is delivered to nano-weld position, then by electric current by and only melt 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, can immediately 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 conduction, can be widely used in homogeneity, dissimilar materials welding.The method of carrying nanotube-solder is mainly to use electron microscope in-situ nano robot, therefore can accurately locate.Along with further developing of nanometer robot, this solder technology very likely really becomes can be used for the solder technology that actual nano industrial is produced.
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 on a large scale the basic and key point of practical application, are the research fields that current research in nanotechnology must develop.It can by the physics by different, chemistry or the way such as biological prepares various single nano materials or nano-device unit just can be assembled into desired structure or pattern by nanometer robot, and further use various nano-weld technology to change them into multifunctional nano device, sensor or device truly, become the quantity expansion semiconductor technology of how much levels and Multi-functional special nano-device, sensor or device not prepared by chemical/biological self-assembling technique.Along with development and the maturation of this technology, can cannot use for the whole world is vast or contact semiconductor micro-/researcher of machining experiment chamber of receiving provides the multifunctional nano device that a low input but can prepare wide range of types more, the approach of sensor assembling.Simultaneously, because this utilization ESEM or transmission electron microscope are eyes, under vacuum environment, can be in real time, original position, dynamically by whole nanotube-solder fusing, the process whole process that soaks, cover, spread and solidify with nano-weld parent covers all at one glance and is presented in people at the moment, and can carry out to each process the analytical test of instant pattern, structure, composition, element distribution property, can help people to understand and grasp directly, intuitively nano-weld mechanism and mechanism.This has great significance for the vacuum welding technology of the construction of outer space space station and the emergent repairing of space flight instrument etc. for China.
Therefore, continuation research is used the nanotube-solder of the artificial instrument of electron microscope in-situ nano machine to be extremely important and is urgent.On the one hand, nanotube-solder will possess the basic demand of conventional solder as low fusion temperature, good mechanical property, solderability, wetability and stability.And on the other hand, prepared nanotube-solder will mate with welded nano material size, can weld and not damage nanometer part at nanoscale.But meet on the current technology, the nanotube-solder research of above-mentioned requirements seldom.
The document of report at present, modal nanotube-solder is made up of metal nanoparticle, comprise composite solder and pure nanotube-solder: composite solder is to be in micron-sized scolder, to add a certain amount of nano particle at traditional particle diameter, the mechanics of scolder and physical property are improved; The particle diameter of pure nanotube-solder is all nanoscale.This nanotube-solder preparation method who is made up of metal nanoparticle has two classes: one is processing method from top to bottom, comprises the method such as mechanical disintegration, 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.Finally make nanotube-solder by low-temperature sintering.But this scolder can only be used for micro-meter scale, can not be used for nanoscale and weld.Therefore, be not real " nanotube-solder ".
The disclosed nano metal particulate composition of for example Chinese invention patent application 200680022890.X disclosed " electromigration-resistant and comply with wire interconnects, nanotube-solder composition, the system of being made up of it and the method for assembly welding encapsulation " 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.The microelectronics Packaging that adopts reflowed nano-solder composition is also disclosed.A kind of method of assembling microelectronics Packaging comprises prepares wire interconnects template.Computing system comprises the nanotube-solder composition with wire interconnects coupling.
summary of the invention
The invention provides 1-dimention nano scolder for the welding of micro-/ nano yardstick and preparation method thereof, the present invention also discloses the welding procedure of 1-dimention nano scolder.
The present invention is to be metal nanometer line or the alloy nano-wire of 3 nanometer ~ 400 nanometers containing the diameter of Sn for the 1-dimention nano scolder of micro-/ nano yardstick welding.
The present invention is for the 1-dimention nano scolder of micro-/ nano yardstick welding, and described 1-dimention nano solder component is Sn xau 100-xalloy nano-wire, wherein: 95>=X>=20, its best composition is 95>=X>=50.
Or, the 1-dimention nano scolder for the welding of micro-/ nano yardstick of the present invention, the composition of described 1-dimention nano scolder is Sn yag 100-yalloy nano-wire, wherein 100>Y>0, its best composition is 99>Y>=50.
Or, the 1-dimention nano scolder for the welding of micro-/ nano yardstick of the present invention, the composition of described 1-dimention nano scolder is Sn mag ncu 100-m-nalloy nano-wire, wherein 100> (m or n) >0, m>n; Its best composition is m=96, n=3.5.
The preparation method of the 1-dimention nano scolder for the welding of micro-/ nano yardstick of the present invention, first be 3 ~ 400 nanometers with aperture, thickness is that the poromerics of 20 nanometer ~ 150 micron is template, with the prepared corresponding metal ion electrolyte of solder component in the nano-pore in template, deposit corresponding metal wire or alloy wire by electrochemical method, the solution that then can not dissolve the alloy in mould material nano-pore with dissolvable template material dissolves mould material, making to be arranged in the metal nanometer line of template nano-pore or alloy nano-wire discharges and is distributed to solution, again by cleaning and cross after the various salt components in the system of filtering out, metal nanometer line or alloy nano-wire are distributed in deionized water for subsequent use.
Described template is anodised aluminium.Carrying out first using the phosphoric acid of 0.01 ~ 1 mole every liter to remove the barrier layer on anodic oxidation aluminium formwork surface before electrochemical deposition operation, then at template surface deposition layer of copper or silver or gold or platinum or other any conducting metal as electrodes conduct layer; While carrying out electro-deposition operation, in two electrode systems take anodic oxidation aluminium formwork as negative electrode, with graphite electrode be anode, in three-electrode system take anodic oxidation aluminium formwork as working electrode, with platinum or gold or graphite electrode be to electrode, any normal electrode is as with reference to electrode, NaOH or copper chloride solution that the solution that dissolves template is, for example; The solution that dissolves template can be with the NaOH of 1 mole every liter (mol/L) or 2mol/L, or with 5 mol/L copper chloride solutions, can certainly use the sodium hydroxide solution of other concentration or the copper chloride solution of other concentration.
Described template is polycarbonate, should be first before electro-deposition operation at template surface deposition layer of copper or silver or gold or platinum or other any conducting metal as electrodes conduct layer, while carrying out electro-deposition operation, in two electrode systems take polycarbonate template as negative electrode, with graphite electrode be anode, in three-electrode system take polycarbonate template as working electrode, with platinum or gold or graphite electrode be to electrode, any normal electrode is as with reference to electrode, the solution that dissolves 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 1-dimention nano scolder for the welding of micro-/ nano yardstick: 1-dimention nano scolder is extracted with nanometer controller, be positioned over and need welding position; Nanometer controller is closely connected in 1-dimention nano scolder two ends, switches on power, and 1-dimention nano scolder electricity melts; Welding position is cooling, is connected into entirety.
The method that deposits electroplax conductive layer in above-mentioned scolder preparation method in template can be to electroplate, and can be also evaporation, or vacuum sputtering, or adopts other known ways.
The alloy system of scolder of the present invention has: fusing point is low; electrical conductivity, thermal conductivity are good; toxicity is low; when use without inert gas shielding; good with majority welding parent wellability and diffusivity; welding after welding position there is very high non-oxidizability, and conduction and heat conductivility good, the advantage that almost can forever keep.And scolder diameter of the present invention guaranteed the welding requirements at micron and nanoscale, but in the reality that is welded into of micro-meter scale or nanoscale.
Preparation method of the present invention can prepare diameter for number nanometers are to number Nanoalloy scolders, can guarantee that prepared scolder 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 scolder pattern;
Accompanying drawing 2 is one dimension Sn of the present invention 50au 50nano wire scolder pattern;
Accompanying drawing 3 is one dimension of the present invention Sillim nano wire scolder energy dispersive spectrum;
Accompanying drawing 4 is one dimension Sn of the present invention 18ag 2cu 80nano wire scolder 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 of use preparation of the present invention 99au 1nano wire scolder welds " people " font nano-pattern process of 50 nanometer diameter nanowires of gold compositions;
Nano-weld quality testing after the nanotube-solder welding homogeneous material that accompanying drawing 7 is use preparation of the present invention;
Accompanying drawing 8 is one-dimensional metal nano wire of the present invention---pure tin nano wire scolder pattern;
Accompanying drawing 9 is one-dimensional metal nano wire of the present invention---proof gold nano wire scolder pattern;
Accompanying drawing 10 is one dimension Sn of the present invention 96.5ag 3.5nano wire scolder pattern.
The specific embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further elaborated.
Accompanying drawing 1(a) be with the synthetic Sn of homemade porous anodic alumina template 78ag 22nano wire scolder ESEM (SEM) shape appearance figure, nanowire diameter is 50 nanometers, length is about 50 microns; (b) with the synthetic Sn of commercial polycarbonate template 78ag 22nano wire scolder ESEM (SEM) shape appearance figure, nanowire diameter is 80 nanometers, length is about 10 microns; (c) single Sn 78ag 22nano wire scolder transmission electron microscope (TEM) shape appearance figure; (d) many Sn 78ag 22nano wire scolder scanning transmission electron microscope (STEM) shape appearance figure.
Accompanying drawing 2 is one dimension Sn of the present invention 50au 50nano wire scolder pattern: (a) with the synthetic Sn of homemade porous anodic alumina template 50au 50nano wire scolder ESEM (SEM) shape appearance figure, nanowire diameter is 45 nanometers, length is about 15 microns.(b) with the synthetic Sn of commercial polycarbonate template 30au 70nano wire scolder transmission electron microscope (TEM) shape appearance figure, nanowire diameter is 80 nanometers, length is about 10 microns.
Accompanying drawing 3 is one dimension of the present invention Sillim nano wire scolder energy dispersive spectrum: (a) quantitative analysis results is Sn:Au=50:50 scolder spectrogram; (b) quantitative analysis results is Sn:Au=30:70 scolder spectrogram; (c) quantitative analysis results is Sn:Au=95:5 scolder spectrogram; (d) quantitative analysis results is Sn:Au=90:10 scolder spectrogram.
Accompanying drawing 4 is one dimension Sn of the present invention 18ag 2cu 80nano wire scolder pattern: (a) with the synthetic Sn of commercial polycarbonate template 18ag 2cu 80nano wire scolder ESEM (SEM) shape appearance figure, nanowire diameter is 80 nanometers, length is about 10 microns.(b) with the synthetic Sn of homemade porous anodic alumina template 50au 50nano wire scolder transmission electron microscope (SEM) shape appearance figure, nanowire diameter is 70 nanometers, 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 of use preparation of the present invention 99au 1nano wire scolder welds " people " font nano-pattern process of 50 nanometer diameter nanowires of gold compositions: (a) use nanometer manipulation device to extract 55 nm of gold nano wires, assemble " people " font nano-pattern ESEM (SEM) figure not being connected; (b) nanometer controller extracts single 150 nanometer Sn99Au1 nano wire scolders and is positioned over position to be welded, and nano-probe is closely held on to 1-dimention nano scolder two ends SEM figure; (c) be communicated with power supply, make Sn99Au1 nano wire scolder bear electric current by 120% maximum and electricity melting fast, after melting nanotube-solder cooled and solidified, discrete " people " word is welded into high conductivity entirety SEM figure.
Nano-weld quality testing after the nanotube-solder welding homogeneous material that accompanying drawing 7 is use preparation of the present invention: (a), (b) homogeneity parent nanowires of gold is welded together; (c), (d), (e) real-time, original position pad welding quality mechanical strength detects; (f) transmission electron microscope nano-weld point micro-/micro-nano structure detect.
Accompanying drawing 8 is pure tin nano wire scolder 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 scolder 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 arranging position to be welded as scolder; (e): after energising, position to be welded is soldered to stereoscan photograph together.
Accompanying drawing 10 is Sn96.5Ag3.5 nano wire scolder 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 scolder
1a) selecting of template: adopting aperture is 3 ~ 400 nanometers, thickness is that the anodised aluminium of 10 nanometer ~ 150 micron is template, this aluminium oxide can use commercial product, has any problem and can prepare voluntarily if purchase commercial Woelm Alumina, and concrete preparation method has report in the prior art.
1b) the preparation of electroplate liquid: 0.18 mol/L triethanolamine+5, mol/L KI+0.4, mol/L potassium pyrophosphate+2.0, mol/L stannous methanesulfonate+0.001mol/L silver iodide+0.60 g/L ascorbic acid+1g/L hydroquinones.
1c) electrochemical deposition:
Polycarbonate template or porous anodic alumina template (having removed barrier layer) that electrode (electrode can be any conducting metal as any in copper, silver, gold, platinum etc.) has been crossed in use are negative electrode, graphite electrode is anode, under-14V sedimentation potential, deposit 45 minutes, prepare the Sn that tin silver proportioning components is 78:22 78ag 22alloy nano-wire scolder.
The tin content of end product can pass through to change stannous methanesulfonate and silver iodide relative concentration, or change electrochemical deposition current potential (or current density) is realized.Nanowire length can change by the electrochemical deposition time.
1d) the collection of goods:
The polycarbonate template chloroform that its hole of electroplating formation is contained to tinbase nano wire dissolves, and tinbase nano wire is distributed in chloroform automatically.Further use the porous anodic alumina films filter that is less than made nanowire diameter to filter, wash the Merlon dissolving, cleaned tinbase nano wire can be discrete deposited or is again distributed in pure chloroform to solid-state reservation in the substrates such as silicon chip and retains and deposit, and uses for next step nano-weld.
Use tinbase nano wire prepared by anodic oxidation aluminium formwork to adopt 0.1mol/L to dissolve 12 hours to 5mol/L copper chloride solution, treat that anodic oxidation aluminium formwork dissolves, the porous polycarbonate film filter that use is less than made nanowire diameter filters, washes copper chloride and aluminate, cleaned tinbase nano wire can be discrete deposited or is again distributed in pure chloroform to solid-state reservation in the substrates such as silicon chip and retains and deposit, and uses for next step nano-weld.
Tinbase nano wire is distributed to after the aqueous solution, and visual sample aequum in concrete use, gets 30 microlitre left and right Solution Dispersions to silicon chip.Approximately there is hundreds of thousands to arrive millions of nano wires at the silicon chip of 1cm × 1cm area, can be controlled by needs nano wire and disperse quantity.
1e) the sign of goods
The Sn of preparation 78ag 22the pattern of nano wire scolder, crystal structure and chemical composition/component are utilized SEM (SEM) (Hitachi S-4800, Japan) and the several functions of high resolution transmission electron microscopy (HRTEM) (TecnaiTM G2 F30, FEI, USA) carried out measurement & characterization.That Fig. 1 shows is representational Sn 78ag 22nano wire scolder pattern result of study.Nano wire in Fig. 1 uses homemade anodic oxidation aluminium formwork synthetic, 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 being distributed on silicon chip 78ag 22nano wire, nano wire is prepared from by commercial polycarbonate template, and nanowire diameter is 80 nanometers, and length is about 10 microns.That Fig. 1 c shows is single Sn 78ag 22nano wire scolder transmission electron microscope (TEM) shape appearance figure.Fig. 1 d is many Sn 78ag 22nano wire scolder scanning transmission electron microscope (STEM) shape appearance figure.As can be seen from the figure nanowire diameter, length dimension are even, but nano wire presents taper shape, top end diameter 80 nanometers, and bottom place diameter 170 nanometers, have embodied the shape of polycarbonate template hole own.
Embodiment 2-Sn xau ythe preparation of nano wire scolder
2a) selecting of template:
The same
2b) the preparation of electroplate liquid:
Two kinds of electroplate liquids can use:
Electroplate liquid 1:100 g/L tri-g/L gelatin+5, g/L sodium sulfite+10, g/L stannic chloride+60, g/L chlorauride+9, ammonium citrate+5 g/L ascorbic acid
G/L ascorbic acid+0.01, g/L gelatin+5, g/L chlorauride+10, electroplate liquid 2:0.5 mol/L stannic chloride+5 mol/L hydrochloric acid
2c) electrochemical deposition:
Use commercial electrochemical workstation, adopt three-electrode system, polycarbonate template or porous anodic alumina template (having removed barrier layer) that electrode (electrode can be any conducting metal as any in copper, silver, gold, platinum etc.) has been crossed in use are 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, the Sn that preparation Sillim proportioning components is 50:50 50au 50alloy nano-wire scolder.The tin content of end-product can pass through to change stannic chloride and chlorauride relative concentration, or change electrochemical deposition current potential (or current density) is realized.Nanowire length can change by the electrochemical deposition time.
2d) the collection of goods:
The same with above-mentioned tin nano silver wire scolder collection mode.
2e) the sign of goods
Fig. 2 shows Sillim's nano wire scolder pattern result of study of preparing by above-mentioned three-electrode system.Fig. 2 a is synthetic nano wire scolder ESEM (SEM) shape appearance figure of homemade porous anodic alumina template, and diameter is 45 nanometers, and length is about 15 microns.Composition result of study shows that Sillim's ratio is that 50:50(is as shown in 3a).Fig. 2 b is the nano wire scolder transmission electron microscope shape appearance figure synthetic by commercial polycarbonate template, is directly 80 nanometers, and length is about 10 microns.Composition result of study show Sillim ratio be 70:30(as shown in Figure 3 b).Meanwhile, also prepared Sillim's nano wire scolder of other proportioning components, it is 95:5 nano wire scolder energy dispersive spectrum experimental result that Fig. 3 c is depicted as Sillim's ratio, and it is 90:10 nano wire scolder energy dispersive spectrum experimental result that Fig. 3 d is depicted as Sillim's ratio.Results of elemental analyses further adopts electron energy loss spectroscopy (EELS) investigative technique to obtain confirmation.
Embodiment 3-Sn 18ag 2cu 80the preparation of nano wire scolder
3a) selecting of template:
The same
3b) the preparation of electroplate liquid:
0.18 g/L ascorbic acid+1, mol/L triethanolamine+5, mol/L KI+0.4, mol/L potassium pyrophosphate+2.0, mol/L copper nitrate+0.60, mol/L silver iodide+0.5, mol/L stannous methanesulfonate+0.001 g/L hydroquinones.
3c) electrochemical deposition:
Use commercial electrochemical workstation, adopt three-electrode system, polycarbonate template or porous anodic alumina template (having removed barrier layer) that electrode (electrode can be any conducting metal as any in copper, silver, gold, platinum etc.) has been crossed in use are 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, prepares the Sn that SAC gold proportioning components is 18:2:80 18ag 2cu 80alloy nano-wire scolder.The SAC content of end-product can pass through to change relative concentration between stannous methanesulfonate, silver iodide and copper nitrate, or change electrochemical deposition current potential (or current density) is realized.Nanowire length can change by the electrochemical deposition time.
3d) the collection of goods:
The same with above-mentioned SAC nano wire scolder collection mode.
3e) the sign of goods
Sillim's nano wire scolder pattern result of study that Fig. 4 prepares by above-mentioned three-electrode system.Fig. 4 a is nano wire scolder ESEM (SEM) shape appearance figure synthetic by commercial polycarbonate template, and diameter is 80 nanometers, and length is about 10 microns.Fig. 4 b is nano wire scolder transmission electron microscope (TEM) shape appearance figure synthetic with homemade porous anodic alumina template, and diameter is 70 nanometers, and length is about 7 microns.Fig. 5 composition result of study shows that the ratio of SAC pantogen subnumber is 18:2:80.
1-dimention nano scolder is for actual nano-space welding example
Example 1: actual homogeneity welding
The 1-dimention nano scolder of preparing in the present invention has been actually used in the welding of nano-space nano-pattern, prototype electronic device.Shown in Fig. 6, use the Sn of 150 nanometer diameters 99au 1nano wire scolder 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, on clean silicon chip, be assembled into " people " word pattern (as shown in Figure 6 a) that does not connect into entirety.That in the present invention, prepares is about 1.5 microns, the special one dimension Sn of diameter 150 nanometer 99au 1nano wire scolder is extracted by nanometer controller subsequently, is positioned over and needs welding position.Two nanometer controller nano-probes are closely connected in 1-dimention nano scolder two ends (shown in Fig. 6 b), switch on power, and make Sn 99au 1nano wire scolder bears electric current by 120% maximum and electricity melting fast, after melting nanotube-solder cooled and solidified, as shown in Fig. 6 c, discrete " people " word is welded into high conductivity entirety.
The 1-dimention nano scolder of preparing in the present invention is also actually used in heterojunction nanowire welding.
Welding quality can be used that nanometer controller carries out in real time immediately, original position, image conversion detect.
Welding quality also can detect by in-situ mechanical measurement.After homogeneity parent nanowires of gold that what Fig. 7 showed is is welded together, use immediately nanometer controller to carry out that nanometer solder joint in-situ mechanical character is measured and pad is transferred to and in transmission electron microscope, further carried out the careful example detecting for micro-/micro-nano structure.Measurement result shows that the pad mechanical stretch intensity of nanowires of gold in Fig. 7 is greater than 110MPa, and Young's modulus is greater than 75GPa, and micro-/micro-nano structure studies show that pad thoroughly fuses into one, and forms twin.
This kind is (or to claim by electron microscope in-situ nano executor, nanometer robot) 1-dimention nano scolder 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, do not weld parent or micro/nano structure by micro-/ nano, therefore can not damage or pollute micro-/ nano welding parent or micro/nano structure.Also can immediately 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 conduction, can be widely used in homogeneity, dissimilar materials welding.Except two practical embodiments of above-mentioned displaying, the different components of preparing in the present invention, 1-dimention nano solder system, Sillim, Xi Yin and the SAC of component have successfully been realized gold, platinum, copper, nickel-cadmium, cobalt platinum multilayer, ferronickel Multilayered Nanowires nano wire not of the same race by nanometer controller technology in this and have been welded into Multi-functional special nano-sensor and electronic device, and they are welded on integrated circuit plate electrode on nano-space.
But scolder of the present invention is not only limited to the nanotube-solder of these three kinds of components, can use any one dimension tinbase nanotube-solder.Welding parent is not only limited to this six kinds of parents, can be simple substance, alloy or multiple layer metal, the circuit board electrode of any micro-/ nano yardstick.

Claims (5)

1. for the 1-dimention nano scolder of micro-/ nano yardstick welding, it is characterized in that: 1-dimention nano scolder is to be the alloy nano-wire of 3 nanometer ~ 400 nanometers containing the diameter of Sn, and described 1-dimention nano solder component is Sn xau 100-xalloy nano-wire, wherein: 95>=X>=50.
2. the preparation method of the 1-dimention nano scolder for the welding of micro-/ nano yardstick claimed in claim 1, it is characterized in that: be first 3 ~ 400 nanometers with aperture, thickness is that the poromerics of 10 nanometer ~ 150 micron is template, with the prepared corresponding metal ion electrolyte of solder component in the nano-pore in template, deposit corresponding alloy wire by electrochemical method, the solution that then can not dissolve the alloy in mould material nano-pore with dissolvable template material dissolves mould material, the alloy nano-wire that makes to be arranged in template nano-pore discharges and is distributed to solution, again by cleaning and cross after the various salt components in the system of filtering out, alloy nano-wire is distributed in deionized water.
3. the preparation method of the 1-dimention nano scolder for the welding of micro-/ nano yardstick claimed in claim 2, it is characterized in that: described template is anodised aluminium, carry out first removing before electrochemical deposition operation the barrier layer on anodic oxidation aluminium formwork surface, and at template surface deposition layer of copper or silver or gold or platinum or other any conducting metal as electrodes conduct layer; In the time carrying out electro-deposition operation, in two electrode systems take anodic oxidation aluminium formwork as negative electrode, with graphite electrode be anode, in three-electrode system take anodic oxidation aluminium formwork as working electrode, with platinum or gold or graphite electrode be to electrode, any normal electrode is as with reference to electrode; The solution that dissolves template is NaOH or copper chloride solution.
4. the preparation method of the 1-dimention nano scolder for the welding of micro-/ nano yardstick claimed in claim 2, it is characterized in that: described template is polycarbonate, carry out before electrochemical deposition operation first at template surface deposition layer of copper or silver or gold or platinum or other any conducting metal as electrodes conduct layer, while carrying out electro-deposition operation, in two electrode systems take polycarbonate template as negative electrode, with graphite electrode be anode, in three-electrode system take polycarbonate template as working electrode, with platinum or gold or graphite electrode be to electrode, any normal electrode is as with reference to electrode, the solution that dissolves template is the organic solution of chloroform or other solubilized polycarbonate.
5. a welding procedure, utilizes the 1-dimention nano scolder for the welding of micro-/ nano yardstick described in claim 1, it is characterized in that: 1-dimention nano scolder nanometer controller is extracted, be positioned over and need welding position; Nanometer controller is closely connected in 1-dimention nano scolder two ends, switches on power, and 1-dimention nano scolder electricity melts; Welding position is cooling, is connected into entirety.
CN201210150049.6A 2011-11-02 2012-05-16 One-dimensional nano welding flux for micron/nanoscale welding and preparation method thereof Expired - Fee Related CN102773624B (en)

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