CN105040106B - A kind of Cu6Sn5The preparation method of intermetallic compound monocrystalline seed - Google Patents
A kind of Cu6Sn5The preparation method of intermetallic compound monocrystalline seed Download PDFInfo
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Abstract
The present invention provides a kind of Cu6Sn5The preparation method of intermetallic compound monocrystalline seed, including with its (CuNi) with structural similarity6Sn5、(CuCo)6Sn5、(CuNiCo)6Sn5Deng the preparation method of other reciprocity intermetallic compound seeds, the method includes the selections of a) solder；B) solder pre-processes；C) monocrystalline seed is prepared by supersaturation melt；D) monocrystalline seed is processed.This method increases the preparation method in terms of the cost, efficiency and quality that prepare specific dimensions monocrystalline seed compared with the existing technology.
Description
Technical field
The invention belongs to field of material technology, in particular to a kind of Cu6Sn5Intermetallic compound and therewith have structure phase
Like (CuNi) of property6Sn5、(CuCo)6Sn5、(CuNiCo)6Sn5Deng the preparation side of other reciprocity intermetallic compound monocrystalline seeds
Method.
Background technique
Cu6Sn5Intermetallic compound is a kind of anisotropy metallic crystal with silvery white metallic luster, and fusing point is
688.15K, density are 8.270~8.448gcm-3, elasticity modulus is 85~125GPa, and hardness is 4.5~6.5GPa, conductance
Rate is 2.38~5.71 × 104Scm, thermal conductivity 0.341Wcm-1·K-1, thermal expansion coefficient is 12.2~16.3 × 10- 6K-1.In Electronic Packaging field, due to the extensive use of copper-based lead and tinbase interconnection solder, Cu6Sn5Intermetallic compound conduct
The main interconnection interface product formed after the forming of copper and tin metal metallurgy smelting is the main guarantor for realizing interconnection structure stabilization and electrically conducting
Card.Especially with electronic device towards miniaturization, integrated and high power direction development, it is desirable that interconnection package size is not
Break and reduce and packaging technology temperature remains unchanged, therefore interface C u6Sn5Generation volume account for interconnection solder joint entirety volume ratio general
It dramatically increases, or even is formed completely with Cu6Sn5Intermetallic compound solder joint based on phase.In view of Cu6Sn5Crystal has relatively strong
Anisotropy, c-axis direction conductivity with higher and a, b axis direction shear strength with higher, so if energy
It is enough formed at interconnection interface using c-axis be disposed vertically direction and a, b axis as the Cu of plane placement direction6Sn5Mono-crystalline structures, that
For realizing the target of the identical high reliability interconnection solder joint of mechanical and electric property in high-density packages system extremely
Favorably, the promotion of butt welding point bulk life time also has important practical value.
But, the interface C u that conventional tin-based solder and copper-based pad metallurgical reaction generate6Sn5Crystal grain orientation is completely random
's.Although there is document to show the copper-based pad of the monocrystalline of specific orientation for the Cu of formation large area specific orientation6Sn5Crystal grain has
Control action, but it is this difficult to realize really whole consistent in a manner of " the soft control " of crystal nucleation-length greatly core；Separately
Outside, even if realizing completely single-orientated Cu6Sn5Crystal grain layer, the grain boundary defects area between neighboring die can also become pad melt it is broken
Bad and cracking failure starting position, to jeopardize the reliability of solder joint.Therefore, how to obtain and matched with pad size and brilliant
Body is orientated controllable Cu6Sn5Monocrystalline seed has become the bottleneck of solder joint interconnection technique at this stage.
On the other hand, Cu6Sn5Intermetallic compound or a kind of important cathode material for lithium ion battery.In view of portable
Formula small-sized electronic product etc. to the requirement in terms of lithium battery energy density, power density, safety in utilization and cycle life,
Cu6Sn5The volume expansion during tin and lithium alloyage can largely be alleviated as lithium ion battery negative material,
With preferable cyclical stability, and Cu6Sn5The theoretical capacitance of storage of lithium ion battery negative material is up to 1900mAh
cm-3, therefore the material is of great significance to the innovation of cathode materials for lithium battery.
However, Cu at this stage6Sn5Lithium ion battery negative material is mainly the porous polycrystalline structure of electrochemical process synthesis, such as
The porous current collector/tin-base alloy/carbon nano-tube compound electric that Chinese patent CN10285131A is prepared by composite electroplating
Pole, the carbon-Cu for another example formed in Chinese patent CN103066252A by plating6Sn5Alloy electrode.Although these chemical syntheses
Porous C u6Sn5Structure has the advantage of large specific surface area, but its polycrystalline structure necessarily faces crystal boundary during circulating battery
Danger that is loose or even destroying fracture, therefore how to prepare the nanometer Cu of high specific surface area6Sn5Monocrystalline seed become its lithium from
The key difficulties of sub- cell negative electrode material application.
According to above-mentioned analysis, either in order to realize high performance interconnection solder joint, or it is negative in order to meet lithium ion battery
The cycle applications of pole material require to solve how to realize specific dimensions Cu6Sn5The preparation problem of monocrystalline seed.
Summary of the invention
The present invention solves the problems, such as of the existing technology by the following technical programs:
A kind of Cu6Sn5The preparation method of intermetallic compound monocrystalline seed, comprising: proeutectic is precipitated using supersaturated melt
Cu6Sn5The method of crystal grain prepares Cu6Sn5Monocrystalline filters out the Cu of appropriate size with quartz sieve later6Sn5Single grain, will
Its monocrystalline seed for sorting or being further cut into specific dimensions and demand.
Wherein supersaturated melt main component is tin copper, and may include a small amount of nickel, cobalt, silver, bismuth, rare earth element
Deng.The mass concentration or molar concentration range used for solder is as shown in table 1.
Certain density supersaturation is prepared by adding micrometer/nanometer copper powder in high temperature solution and being cooled to specific temperature
Melt.Finally according to melt concentration, reaction time and Cu6Sn5The reaction relation equation of growth size determines that quartzy sieve sieve takes
Cu6Sn5The Best Times of single grain.By the Cu of specific dimensions6Sn5Monocrystalline seed is classified according to application demand, is such as applied to weldering
The micron level monocrystalline seed of point interconnection aspect, is for another example applied to the Nano grade monocrystalline kind in terms of lithium ion battery negative material
Seed.
Table 1: supersaturated tin copper solder concentration
The preparation method includes: a) solder selection；B) solder pre-processes；C) monocrystalline kind is prepared by supersaturation melt
Seed；D) monocrystalline seed is processed.
A kind of Cu of the invention6Sn5The preparation method of intermetallic compound monocrystalline seed, specific steps include:
A), solder selects: tin-based solder appropriate is chosen, such as Sn, Sn-Ag, Sn-Bi, Sn-Cu, Sn-In, Sn-Pb, Sn-
The one or more of solder in Ag-Cu, Sn-Bi-Cu, Sn-In-Cu, Sn-Pb-Cu etc..
B), solder pre-processes: solder stick (block) sand for surface paper (such as 1200#) is polishing to no surface oxidation state；With
Cutting machine is cut to appropriate fritter；It is soaked in and fills hydrochloride alcohol or nitric acid alcohol melt (mass concentration is 1~10%)
Appropriate containers in, corrosive liquid is added according to the ratio of solder volume and corrosion melt 1:10, and is cleaned by ultrasonic 20min；It takes out
Solder fritter is placed on filling in the appropriate containers of distilled water, is cleaned by ultrasonic 20min again；After taking out again, use is cold
Wind quickly dries up spare.The step is mainly used for the oxide layer and organic pollutant that removal is attached to solder surface.
C), monocrystalline seed is prepared by supersaturated melt: solder fritter is placed in the silica crucible etc. cleaned up and is added
It heats in pond, with having gas protecting function and solder fritter is heated to its fusing by the heating device with accurate temperature controlling, is protected
Shield gas is mainly nitrogen (can also use the inert gases such as argon gas or helium)；Continuous heating melt is to 300~600 degrees Celsius；It will
A certain amount of Nano/micron copper powder (mass concentration 1.24%-39.12%) is added in the solder (can also be dense containing quality
Degree is 0-5% other elements, and other elements are nickel, cobalt, silver, bismuth or rare earth element, such as micro-/ nano nickel or cobalt powder, Ag, Bi, dilute
Earth elements), under nitrogen atmosphere mechanical stirring and keep the temperature (1~10h) until addition element be completely dissolved；Molten solder is slow
20~50 DEG C of solder liquidus curve or more are cooled to, held for some time (soaking time and required Cu6Sn5Crystallite dimension is related,
Typical soaking time such as 0.1h~10h；It is detailed in the crystallite dimension controlling curve and governing equation then provided)；Use specific dimensions
Quartzy filter screen (such as 1~100 μm) sieve take precipitation product in solder；Products therefrom is soaked in and fills hydrochloride alcohol or nitre
In the appropriate containers of sour alcohol melt (mass concentration 10~20%), according to the ratio for impregnating product and corrosive liquid volume ratio 1:10
Etchant solution is added, and is cleaned by ultrasonic 10 minutes (the remaining solder that this step is used for the attachment of wash products surface)；Product is taken out,
It is placed on filling in the appropriate containers of distilled water, is cleaned by ultrasonic 10min again；Product is taken out again and is quickly blown with cold wind
It is dry；Product is carried out to more careful size classes with the quartzy filter screen (such as 500nm~100 μm) of specific dimensions, is collected standby
With.The product is Cu6Sn5Monocrystalline (Fig. 1).
D), monocrystalline seed is processed: by gained Cu6Sn5Monocrystalline is arranged in parallel according to long axis direction, by 10~20 monocrystal rods
Stack it is in a row process together, in order to be loaded；In Cu6Sn5The outermost of monocrystal rod increase by two pieces of iron plates (thickness 0.5~
1mm), in order to the clamping of monocrystal rod；Monocrystalline, 0.1~0.5A of operating current are cut by the way of low-speed WEDM；Cutting
When can be according to parallel Cu6Sn5Monocrystalline long axis direction obtains and Cu6Sn5The parallel section (such as Fig. 2 a) of (10-10) crystal face, can also
According to vertical Cu6Sn5Monocrystalline long axis direction obtains and Cu6Sn5(0002) the parallel section of crystal face (such as Fig. 2 b)；After cutting
Product, which is put into alcohol melt, is cleaned by ultrasonic 1min, cold wind drying.The result is Cu6Sn5Monocrystalline seed.The cutting technique side
Method can preferably realize the Cu of specific dimensions specific orientation6Sn5The preparation of monocrystalline seed, the ratio especially in terms of processing speed
1-10 times is improved using the Precision Machinings efficiency such as femto-second laser, effective machining yield is up to 60% or more.
The most important inventive point of the present invention is to rely on theoretical model design and realize specific dimensions Cu6Sn5The efficient system of monocrystalline
It is standby.Concentration and reaction time of this method by the supersaturated melt of adjusting, can be effectively controlled specified particle diameter Cu6Sn5The generation of monocrystalline
Probability reduces difficulty of processing to reduce subsequent cutting processing number, improves stock utilization and yield rate.
The present invention establishes by theory deduction and improves specific dimensions Cu6Sn5The acquisition probability model of six side's bar-like single crystals,
And the correctness of the model is confirmed by many experiments.It is as follows that theoretical model shifts process onto:
Due to Cu6Sn5The initial nucleated time of crystal grain is shorter (being less than 1s), so this time can be ignored；And after forming core
By the growth of adjoint crystal grain, at this time if Cu6Sn5The growth of six square rod of phase is controlled by interfacial reaction, then liquid/solid two-phase
The migration rate v at interfaceL→ηIt can indicate are as follows:
η in formula --- Cu6Sn5Phase
L --- solder liquid phase
κ --- accommodation coefficient, κ=10 when rough interfaces-2, κ=10 when smooth interface-4(dimensionless)；
DL--- diffusion coefficient (m of the Cu in Sn2·s-1)；
λ——Cu6Sn5The interplanar distance (m) of phase；
ΔG——Cu6Sn5Driving force needed for phase grain growth (J).
However, it is contemplated that tin atom is many fastly in the interstitial diffusion rate of liquid phase self-diffusion speed ratio copper atom, so copper
The diffusion rate of atom, which may become, restricts Cu6Sn5The major obstacle of grain growth.Therefore according to the diffusion flux of copper
Equilibrium condition: if the copper unit time reaches the mass flux M ' at interfaceArrivedNot less than interface with speed vL→ηGrowth institute
The mass flux M ' neededneeded, then this interfacial reaction is controlled by interface growth；If the copper unit time reaches
The mass flux at interface is less than interface with speed vL→ηMass flux required for growing, then this interfacial reaction is by copper coin
Element diffusion control.So as to obtain following formula:
Surface area (the m of S in formula --- solid liquid interface2)；
dV——Cu6Sn5Volume change (the m of phase3)；
ρ——Cu6Sn5Cu atomic concentration in the solder of phase front end is distributed (at%m-1)。
By above 4 groups of formula, reaction time and Cu under a certain concentration can be obtained6Sn5Grain growth size it is accurate
Relationship, and then the Cu of single particle size can be improved6Sn5The generating probability of monocrystalline.
The technology of preparing applies also for preparation and Cu6Sn5The monocrystalline of the reciprocity intermetallic compounds such as the similar nickel of structure, cobalt
Seed, such as (CuNi)6Sn5、(CuCo)6Sn5、(CuNiCo)6Sn5Monocrystalline seed.Specific method is will to be containing mass concentration
0-5% other elements, other elements are nickel, cobalt, silver, bismuth or rare earth element, if nickel, cobalt micrometer/nanometer powder are (such as addition solder matter
Amount concentration 0~5%) it is mixed into micrometer/nanometer copper powder, and molten solder is dissolved in subsequent heating process.
The present invention further provides a kind of cathode material for lithium ion battery, which is characterized in that contains the aforementioned preparation side
The Cu that method is prepared6Sn5、(CuNi)6Sn5、(CuCo)6Sn5、(CuNiCo)6Sn5Equal intermetallic compounds monocrystalline seed.
Wherein, term wt% is mass percent, at% atomic percentage.
The present invention compared with the existing technology the advantages of and beneficial effect be:
1 present invention fully takes into account the pass in melt between crystal growth and the supply of element quality from model foundation
System, so that the accuracy of theoretical model prediction be greatly improved.And then experiment is effectively instructed by theoretical calculation, from
And the growth time of specific dimensions partial size is accurately obtained, it improves efficiency and yield.
The supersaturated melt deposition method that 2 present invention apply prepares single crystal process simple operations conveniently, and it is high-efficient to obtain product
And it is at low cost, in addition, the simple environmental pollution of cleaning process is less.
Monocrystalline excellent quality that 3 present invention obtain and it is easy to save for a long time, in addition cutting technique efficiency swashs higher than femtosecond
The processing of light device, and stock utilization can reach 60% using solder quality.
Detailed description of the invention
Cu before the screening of attached drawing 16Sn5Monocrystalline
Cu after the cutting of attached drawing 26Sn5Monocrystalline: it (a) is cut along parallel long axis direction；(b) it is cut along vertical long axis.
3 tin copper binary phase diagraml of attached drawing
Attached drawing 4 (a) Cu6Sn5Six side's monocrystal rod shape appearance figures；(b) correlation XRD diffracting spectrum, wherein red is six side's monocrystal rods
Spectral line and blue for grinding after powder XRD spectral line；(c)Cu6Sn5The Kikuchi style map of grain surface.
The correlation of six square rod sizes and time under 5 Interface Control growth conditions of attached drawing
Attached drawing 6 spreads (a) half-breadth of supply amount and demand and six square rods under control condition in the copper unit time
Degree and (b) relationship between half length.
Attached drawing 7 (a) copper supplies the size of six square rods and the correlation of time under mechanism control；(b) fitting obtains
Diameters of axle ratio curve and experimental measurements comparison.
Cu of 8 partial size of attached drawing at 0.8~1 μm6Sn5Monocrystalline cathode material for lithium ion battery
(CuNi) of 9 partial size of attached drawing at 180 μm6Sn5Monocrystalline micron bar
Specific embodiment
The invention will be further described with embodiment with reference to the accompanying drawings of the specification:
The Cu of 1 20~40 micron grain size of embodiment6Sn5The preparation of intermetallic compound monocrystalline seed
30g copper nano is added in 1kg Sn0.7wt%Cu eutectic solder, in 350 DEG C of mechanical stirrings and is kept the temperature for 24 hours
To guarantee that copper nano sufficiently dissolves；Solder melt is cooled to 250 DEG C and heat preservation 10h；With 20 μm of quartzy sieves from solder
Leaching solid phase, by it in ice quenching-in water；The hydrochloride alcohol melt of gained solid phase mass concentration 10% is cleaned by ultrasonic
10min, the solder of removal surface attachment, and products therefrom wash with distilled water；It is weeded out with 40 μm of quartzy sieves and does not meet size
It is required that bulky grain, the powder collection of size will be met.
Experimentation more than brief analysis is as follows.30g copper powder is added to 1kg Sn1.3at%Cu eutectic solder and (has incited somebody to action
Mass concentration is scaled atomic concentration) in melt, it will theoretically obtain the solder melt that copper atom concentration is 6.5at%.By copper
(Fig. 3) known to tin binary phase diagraml, the concentration are precisely 342 DEG C of copper and tins saturation solder concentration, thus when solder heat to 350 DEG C and
After long agitation and heat preservation, theoretically copper nano can melt completely.Then, when temperature is reduced to 250 DEG C, solder is molten
The saturation solubility of copper will decrease to 2.3at% in liquid, and solder melt will become the supersaturated melt of copper at this time, that is to say, that
Cu6Sn5The supercooling of temperature needed for phase homogeneous nucleation and constitutional supercooling condition have met, therefore theoretically separate from the solder
Solid phase out should be Cu6Sn5Phase, and be Cu6Sn5Phase homogeneous nucleation and pass through the resulting product of steady-state growth.
Fig. 4 a is 20~40 μm of Cu6Sn5The typical pattern of intermetallic compound monocrystalline seed.By X-ray energy dispersion
Spectrum analysis (EDS) finds the stoichiometric number of such club shaped structure close to Cu6Sn5, and pass through subsequent X-ray diffraction spectrum analysis
(XRD) this conclusion is also further demonstrated.Obviously, the solid phase separated from the melt can be determined as Cu6Sn5Xiang Jing
Grain.This crystal grain has six side's Rod-like shapes, and each side is bright and clean flat.It is worth noting that this six square rods shape
The top of monocrystal is quasi- scallop shape.In addition, having hollow structure in some barred bodies.
It is found (such as Fig. 4 b) according to the further analysis of X-ray diffraction spectrum, the surface of this six sides monocrystal rod exists apparent
Preferred orientation, and main Surface Texture is (10-10) (11-20), (21-31) and (30-30).Fig. 4 c is dissipated by energy back
Penetrate six square rod side Kikuchi styles of diffraction experiment (EBSD) acquisition.According to Kikuchi pattern design it was determined that six square rod shape lists
Brilliant side is { 10-10 } or { 11-20 } two kinds of family of crystal planes.In conjunction with XRD and EBSD analysis result it was determined that six square rod shapes
Side should be the crystal face that those may be constructed complete hexagonal prisms structure, i.e., { 10-10 } or { 11-20 } family of crystal planes (and has same
One crystal zone axis [0001]), and the top surface of six square rod shapes should be vertical with side or close vertical surface, i.e., (0002) crystal face and
Its nearly parallel crystal face.Additionally by analysis of statistical results, the Cu being made of { 10-10 } crystal face6Sn5Six square rod shape single grain ratios
Be made of { 11-20 } crystal face it is more, it can be considered that six side's bar-like single crystals along long axis direction be horizontally arranged top surface be (10-
10) crystal face, and long axis vertical section is (0002) crystal face.
The Cu that embodiment 2 is obtained by process above parameter6Sn5The construction method of growth size Controlling model:
The foundation of the model is mainly for raising specific dimensions Cu6Sn5The acquisition probability of six side's bar-like single crystals reduces heating
Time improves monocrystalline and obtains efficiency.
Due to Cu6Sn5The grain nucleation time is shorter (being less than 1s), so this time can be ignored.If Cu6Sn5Xiang Liufang
The growth of stick is controlled by interfacial reaction, then Cu6Sn5The boundary of crystal grain side { 10-10 } and top surface (0002) at 250 DEG C
Face mobility can be expressed as
When what Fig. 5 was indicated is the six square rod half widths (X or r) integrated according to mobility and half length (Y) and growth
Between relation curve (red and black curve).Due to the relationship of geometry, dome radius r(0002)It also needs equal to side
Half width X{10-10}, therefore six square rod growth curves of Interface Control should indicate for blue and red curve, and size control
Shown in equation processed such as formula (7) and (8).
According to formula (8), the growth length of six square rods will reach 2cm after 10h, measurement knot of this value much larger than experiment
Fruit.In view of the interstitial diffusion rate of the liquid phase self-diffusion speed ratio copper atom of tin atom at 250 DEG C is many fastly, so copper atom
Diffusion rate may become restrict Cu6Sn5The mutually major obstacle of growth.Therefore according to formula (2)-(4), we can be into
One step determines Cu6Sn5Equilibrium relation between grain growth and elements fed.
What Fig. 6 a and 6b were respectively indicated be spread supply amount under control condition in the copper unit time and demand with
Relationship between the half width of six square rods and half length.Obviously, red copper demand curve and blue copper are supplied
Curve is measured in X{10-10}=42.8 μm and Y(0002)Intersected when=669nm.This means that either length direction is still
The growth of width direction, six square rods is always controlled in the incipient stage by interfacial reaction, and when the dimensional growth of six square rods to one
The supply amount for determining copper after degree will be less than needed for its growth, and at this time grain growth will be spread by copper and control.
In order to obtain specific six square rods growth kinetics model, both the above growth control mechanism is subjected to unification, is built
Vertical copper supplies Mechanism Model.When supply abundance, interfacial reaction is by interfacial reaction mechanism control.Copper atom supply
When inadequate, interfacial reaction is controlled by diffusion.So as to obtain following formula:
Fig. 7 a is the size of six square rods and the correlation of time under copper supply mechanism control.React initial 41s
Interior is the formation for closing on nucleus.After 41s, the sizes of six square rods by its growth of interfacial reaction mechanism control, at this time due to
The supply amount of the limited copper of the size of six square rods is sufficient for needed for its growth.After growth time reaches 349s, six square rods
Dome at copper supply amount start to be unable to satisfy needed for interface growth, dome surface starts the diffusion machine by copper at this time
Its growth of system control.When growth time reaches 22764s, the width direction of six square rods also starts the flooding mechanism by copper
Control, is at the same time the restrictive condition for meeting geometry, dome surface can also adjust therewith.Therefore, six square rods
There are two kinds of growth phases in the direction of the width in size and the relationship of growth time, and three kinds of growth steps are presented in the longitudinal direction
Section.
It is worth noting that, the maximum value of the half width of six square rods and half length is 58.3 μm and 440 μm respectively after 10h,
This coincide good with the result that Germicidal efficacy arrives.In addition, comparing the diameters of axle ratio curve of theory deduction and six square rods of experiment measurement
Diameters of axle ratio data (such as Fig. 7 b) are it can be found that also very much like between the two.Theoretically there is the maximum diameters of axle ratio hair of six square rods
Raw and maximum diameters of axle ratio is 96.7 X=872nm at, and finally stable diameters of axle ratio is close to 7.54.
Heating time is adjusted according to process above parameter it is found that can get a large amount of width when heating 2.96~5.9h is 20
~40 μm, six side's bar-like single crystal Cu that length is 200~1000 μm6Sn5Crystal grain (probability density 77.4%).It is this to pass through building
Governing equation is so that it is determined that Cu6Sn5The method of grain growth size, when reaction needed for crystal growth not only can be significantly reduced
Between, while can also be improved the number for obtaining single size crystal grain, reduce subsequent wire cutting number.It finally, can be by simple
A step cutting, realize interconnection window be 20~40 μm three-dimensional high-density encapsulate solder joint application.
The Cu of 3 0.8~1 micron grain size of embodiment6Sn5The preparation of monocrystalline cathode material for lithium ion battery
30g copper nano is added in 1kg Sn0.7wt%Cu eutectic solder, in 350 DEG C of mechanical stirrings and is kept the temperature for 24 hours
To guarantee that copper nano sufficiently dissolves；Solder melt is cooled to 250 DEG C and 7.09~8.86min of heat preservation；With 0.5 μm of quartz sieve
Net leaching solid phase from solder, by it in ice quenching-in water；The hydrochloride alcohol melt of gained solid phase mass concentration 10% is surpassed
Sound cleans 10min, the solder of removal surface attachment, and products therefrom wash with distilled water；It is weeded out and is not met with 1 μm of quartzy sieve
The bulky grain that size requires, will meet the powder collection of size.Gains as shown in figure 8, be length at 20~80 μm and
Cu of the diameter at 0.8~1 μm6Sn5Crystal grain.
Cu of the embodiment 4 containing elements such as Ni, Co6Sn5The preparation of intermetallic compound monocrystalline seed
Cu6Sn5There are a solid-state phase changes between 186~189 DEG C for intermetallic compound, i.e., by the solid matter of high temperature state six
Square structure η-Cu6Sn5(P63/ mmc) it is changed into the monocline η '-Cu of cold state6Sn5(C2/c), and along with lattice structure
Change Cu6Sn52.15% volume expansion will occur for phase structure cell.In view of the volume of interior 2% or more generation during service is swollen
It is swollen that serious problem of stress concentration will be generated to interface, so if the generation of this solid-state phase changes will be likely to Cu6Sn5Monocrystalline
The reliability of seed poses a serious threat.
It is reported according to California, USA university Los Angeles branch school K.N.Tu et al., η-in the interconnection interface of quenching state
Cu6Sn5It can retain at room temperature for a long time.Univ Helsinki Finland T.Laurila et al. is also confirmed that since interconnection solder joint is cold
But the limitation of time, η-Cu6Sn5To η '-Cu6Sn5Solid-state phase changes usually because transformation time deficiency due to be difficult to fully achieve, from
And lead to interface C u at room temperature6Sn5Crystal grain is made of two kinds of lattice structures.In addition, according to X ray diffracting spectrum in Fig. 4 b
As a result, it was confirmed that six side's bar-like single crystal Cu that this technology is prepared6Sn5Crystal grain is implicitly present in η-Cu6Sn5Phase structure.
According to the study found that adding nickel in right amount, cobalt element can effectively improve η-Cu6Sn5Structural reliability, to eliminate
Because of Cu6Sn5Monocrystalline seed interfacial failure caused by solid-state phase changes occurs.Therefore, this technology need to only adjust in the single crystal preparation stage and add
Enter the type of nano powder, that is, add a small amount of nickel, the one or two of cobalt element (mass ratio 0~5%) can effectively prepare containing
The Cu of nickel, cobalt element6Sn5Reciprocity intermetallic compound.
34.17 grams of nickel nano powders are added in the pure Sn solder of 1kg, in 350 degrees Celsius of mechanical stirrings and keep the temperature 24 hours
To guarantee that copper nano sufficiently dissolves；Solder melt is cooled to 250 degrees Celsius and 29.5~32.1h of heat preservation；With 150 microns of stones
English sieve leaching solid phase from solder, by it in ice quenching-in water；Gained solid phase is melted with the hydrochloride alcohol of mass concentration 10%
Liquid is cleaned by ultrasonic 10 minutes, the solder of removal surface attachment, and products therefrom wash with distilled water；With 180 micron quartz sieves
The bulky grain for not meeting size requirement is weeded out, the powder collection of size will be met.
Fig. 9 is (CuNi) of 150~180 μm of partial sizes of this technology preparation6Sn5Reciprocity intermetallic compound as shown in the figure should
Structure is still six side's club shaped structures, with Cu6Sn5Bar-like single crystal is slightly coarse compared to its surface.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (2)
1. a kind of Cu6Sn5The preparation method of intermetallic compound monocrystalline seed, the monocrystalline are specific dimensions Cu6Sn5Six square rod shapes
Monocrystalline, which is characterized in that
Improve specific dimensions Cu6Sn5Six side's bar-like single crystal acquisition probabilities pass through following model realization,
Cu6Sn5The growth of six square rods is controlled by interfacial reaction, the migration rate v of liquid/solid two-phase interfaceL→ηIt indicates are as follows:
η in formula --- Cu6Sn5Phase
L --- solder liquid phase
κ --- accommodation coefficient, κ=10 when rough interfaces-2, κ=10 when smooth interface-4, dimensionless；
DL--- diffusion coefficient of the Cu in Sn, unit: m2·s-1；
λ——Cu6Sn5The interplanar distance of phase, unit: m；
ΔG——Cu6Sn5Driving force needed for phase grain growth, unit: J；
Obtaining specific method by the model includes: that proeutectic Cu is precipitated using supersaturated melt6Sn5The method of crystal grain prepares Cu6Sn5
Monocrystalline filters out the Cu of appropriate size with quartz sieve later6Sn5Single grain is sorted or is further cut into specific ruler
The monocrystalline seed of very little and demand, the preparation method include: a) solder selection: choose tin-based solder below, Sn, Sn-Ag,
One of Sn-Bi, Sn-Cu, Sn-In, Sn-Pb, Sn-Ag-Cu, Sn-Bi-Cu, Sn-In-Cu, Sn-Pb-Cu；
B) solder pre-processes: step a) solder stick or block sand for surface paper are polishing to no surface oxidation state；It will with cutting machine
It is cut into fritter；It is soaked in and fills in the container that mass concentration is 1~10% hydrochloride alcohol solution or nital, press
It is that hydrochloride alcohol solution is added in 1:10 or nitric acid alcohol is molten according to solder volume and hydrochloride alcohol solution or nital ratio
Liquid, and it is cleaned by ultrasonic 20min；Solder fritter is taken out, is placed on filling in the container of distilled water, be cleaned by ultrasonic again
20min；After taking out again, quickly dried up with cold wind spare；
C) monocrystalline seed is prepared by supersaturation melt, step b) solder fritter is placed in adding for the silica crucible cleaned up
It heats in pond, with having gas protecting function and solder fritter is heated to its fusing by the heating device with accurate temperature controlling, is protected
Shield gas is the inert gas of nitrogen, argon gas or helium；Continuous heating melt is to 300~600 degrees Celsius；According to tin, copper and its
The mass concentration ratio of his element is 60.88%-98.76%:1.24%-39.12%:0-5%, by Micron Copper Powder and other elements
It is added in the solder, other elements are nickel, cobalt, silver, bismuth or rare earth element, under nitrogen atmosphere mechanical stirring and heat preservation 1
~10h is described that molten solder is slowly cooled to 250 DEG C until addition element is completely dissolved, and held for some time 0.1h~
10h；The precipitation product in solder is taken with the quartz filtering mesh screen of 1~100 μ m in size；
D) monocrystalline seed is processed: by Cu obtained by step c)6Sn5Monocrystalline is arranged in parallel according to long axis direction, by 10~20 monocrystal rods
Stack it is in a row process together, in order to be loaded；In Cu6Sn5The outermost of monocrystal rod increase by two pieces of 0.5~1mm of thickness iron plates with
Convenient for the clamping of monocrystal rod；Monocrystalline, 0.1~0.5A of operating current are cut by the way of low-speed WEDM；When cutting according to
Parallel Cu6Sn5Monocrystalline long axis direction obtains and Cu6Sn5The parallel section of crystal face, also according to vertical Cu6Sn5Monocrystalline long axis direction obtains
And Cu6Sn5The parallel section of crystal face；Product after cutting is put into alcoholic solution and is cleaned by ultrasonic 1min, cold wind drying.
2. a kind of Cu according to claim 16Sn5The preparation method of intermetallic compound monocrystalline seed, which is characterized in that institute
State step c) be precipitated product after further products therefrom is soaked in fill mass concentration be 10~20% hydrochloride alcohol solutions or
It in the container of nitric acid alcohol, is added, and is cleaned by ultrasonic 10 minutes according to immersion product and liquor capacity ratio 1:10；Product is taken out,
It is placed on filling in the container of distilled water, is cleaned by ultrasonic 10min again；Product is taken out again and is quickly dried up with cold wind；
Product is carried out to more careful size classes with the quartzy filter screen of size 500nm~100 μm, is collected spare.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4896422A (en) * | 1972-03-10 | 1973-12-10 | ||
| KR920007930B1 (en) * | 1989-11-30 | 1992-09-19 | 삼성전기 주식회사 | Process for removing copper in the molten solder |
| CN101896310A (en) * | 2007-10-19 | 2010-11-24 | 日本斯倍利亚社股份有限公司 | Solder joint |
-
2015
- 2015-06-10 CN CN201510317525.2A patent/CN105040106B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4896422A (en) * | 1972-03-10 | 1973-12-10 | ||
| KR920007930B1 (en) * | 1989-11-30 | 1992-09-19 | 삼성전기 주식회사 | Process for removing copper in the molten solder |
| CN101896310A (en) * | 2007-10-19 | 2010-11-24 | 日本斯倍利亚社股份有限公司 | Solder joint |
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