CN104599976B - Leadless welding alloy and its preparation method and application - Google Patents
Leadless welding alloy and its preparation method and application Download PDFInfo
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- CN104599976B CN104599976B CN201410817601.1A CN201410817601A CN104599976B CN 104599976 B CN104599976 B CN 104599976B CN 201410817601 A CN201410817601 A CN 201410817601A CN 104599976 B CN104599976 B CN 104599976B
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Abstract
The present invention relates to a kind of method for preparing leadless welding alloy, prepares metal I films in substrate first；Secondly metal II films are prepared in metal I film surfaces；Nano-silver layer finally is prepared in metal II film surfaces, obtains leadless welding alloy.Wherein, metal I is one kind in Cu, Ag, Bi, Zn, In or Ni, and metal II is Sn.The present invention also provides the Pb-free solder alloy prepared using the above method, including some metal film layers, and metal film layer is followed successively by metal I films, metal II films and nano-silver layer, and the thickness ratio of metal I films, metal II films, nano-silver layer is 1~100:1~100:0.01~0.1, the fusing point of leadless welding alloy is less than or equal to 180 DEG C.The leadless welding alloy prepared using the method for the present invention, its fusing point are less than or equal to 180 DEG C, electronic component is used with substrate and carry out reflow soldering at a lower temperature.
Description
Technical field
The present invention relates to solder alloy field, the leadless welding alloy such as specifically a kind of tin-copper and/or tin-silver-copper and its
Preparation method and application.
Background technology
In Electronic Packaging industry, due to tin-lead alloy have excellent wetability, weldability, electric conductivity, mechanical property and
The features such as cost is low, therefore as solder alloy the most frequently used in the sector.But the compound of lead and lead is pollution environment
Poisonous and harmful substance, in order to reduce the pollution to environment, countries in the world are all promoting the unleaded process of solder alloy in succession.
At present, the research for lead-free solder is concentrated mainly on Sn-Ag systems, Sn-Cu systems, Sn-Zn systems, Sn-Bi systems etc. two
The ternary alloy three-partalloys such as first alloy and Sn-Ag-Cu system, Sn-Zn-Bi systems.The most possible substitution lead-tin soldering unanimously generally acknowledged in the world
Material is Sn-Ag-Cu alloy series, and this alloy series are to add Cu on the basis of Sn-Ag systems alloy, is maintaining Sn-Ag
While the superperformances such as alloy strength height, good in oxidation resistance, melt temperature scope be big, its fusing point can also be reduced, and can subtract
Cu dissolving in few institute wlding material.
Present Sn-Ag-Cu eutectic composition is not decided uniformly also exactly.It is considered 96.5Sn- in Japan
3.0Ag-0.5Cu, the U.S. is considered 95.5Sn-3.9Ag-0.6Cu, and European Union is then 95.5Sn-3.8Ag-0.7Cu.It is various to match somebody with somebody
The fusing point of the Sn-Ag-Cu alloys of ratio is more or less the same, simply mechanical performance difference.
But use above-mentioned Sn-Ag-Cu and/or Sn-Cu as bonding solder have a problem that, i.e., welding temperature compared with
It is high.It is well known that high temperature on electronic component has many adverse effects, resistance, electric capacity, inductance, transformer in electronic equipment,
The heat of the components such as amplifier cannot distribute in time, be easy to cause cause thermal damage, influence the normal use of device.Cause
This, the control in encapsulation process to welding temperature just becomes extremely to be necessary, the height of welding temperature will influence electronics member device
The quality of part.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of relatively low leadless welding alloy of fusing point, its welding temperature phase
To relatively low so that electronic component can be completed to weld at a lower temperature with substrate.
The present invention provides a kind of method for preparing leadless welding alloy, comprises the following steps：
S1. metal I films are prepared in substrate；
S2. metal II films are prepared in the metal I film surfaces；
S3. nano-silver layer is prepared in the metal II film surfaces, obtains the leadless welding alloy.
Wherein, the metal I is one kind in Cu, Ag, Bi, Zn, In or Ni, and the metal II is Sn.It is i.e. described unleaded
Solder alloy can be Nano Silver-Sn-Cu, Nano Silver-Sn-Ag, Nano Silver-Sn-Bi, Nano Silver-Sn-Zn, Nano Silver-Sn-
In or Nano Silver-Sn-Ni.Preferably, the metal I is Cu, i.e., described leadless welding alloy is Nano Silver-Sn-Cu.
Further, the metal I films, the metal II films, the thickness ratio of the nano-silver layer are 1~100:1
~100:0.01~0.1, such as can be 1:1:0.01、1:1:0.1、1:100:0.01、1:100:0.1、100:1:0.01、
100:1:0.1、100:100:0.01、100:100:0.1 or 50:50:0.05 etc., here can not be exhaustive one by one.
Further, in S1 steps, before preparing the metal I films on the substrate, first on the substrate
Intermediate metal is prepared, then prepares the metal I films in the metal transfer layer surface.
Wherein, the substrate is electronic component to be welded, such as the substrate is chip to be welded.In the base
The intermediate metal is prepared using the method for magnetron sputtering on bottom.
Wherein, the intermediate metal can be Ti/Au intermediate metals, and the thickness ratio of Ti layers and Au layers is 1~10:
1~10；Can be Cr/Au intermediate metals, and the thickness ratio of Cr layers and Au layers is 1~10:1~10；Can be Ti/Ni/Au
Intermediate metal, and the thickness ratio of Ti layers, Ni layers, Au layers is 1~10:1~10:1~10；Can also be Cr/Ni/Au metal mistakes
Layer is crossed, and the thickness ratio of Cr layers, Ni layers, Au layers is 1~10:1~10:1~10.Any single gold in the intermediate metal
The thickness ratio for belonging to layer and metal I films in the leadless welding alloy is 1~10:10~1000.
Further, in S2 steps, before the metal I film surfaces prepare the metal II films, first in institute
State metal I film surfaces and prepare metal III films, then prepare the metal II films, institute in the metal III film surfaces
It is Ag or Zn to state metal III, it is preferable that the metal I is Cu, and the metal III is Ag, i.e., described leadless welding alloy is to receive
Meter Yin-Sn-Ag-Cu.
Further, the metal I films, the metal III films, the metal II films, the nano-silver layer
Thickness ratio is 1~100:0.01~1:1~100:0.01~0.1, such as can be 1:0.01:1:0.01、1:1:1:0.1、
100:0.01:100:0.1、100:0.5:100:0.01 or 50:0.05:50:0.05 etc., here can not be exhaustive one by one.
Further, the metal III films are prepared using the method for magnetron sputtering in the metal I film surfaces.
Further, prepare the method for the nano-silver layer using prepare Nano Silver method, chemical plating Nano Silver method or
Self-assembled nanometer silver method, the method that other can also be used routinely to prepare nano-silver layer, the structure of the nano-silver layer is single
Layer close-packed configuration or multilayer steps arrangement architecture, in the nano-silver layer Ag grain shape be dendroid, it is spherical or oval,
The grain spacing of the Ag is 0~5000nm, for example, can be 10nm, 20nm, 50nm, 80nm, 100nm, 500nm, 1000nm,
2000nm or 5000nm.
Preferably, Ag grain shape is spherical in the nano-silver layer, and the particle diameter of the Ag is 10~100nm,
Such as can be 10nm, 20nm, 50nm, 80nm or 100nm.
It should be noted that the Nano Silver refers to metallic particles diameter accomplishing nano level argent simple substance.Nanometer
From the point of view of the multilayer steps structure of silver layer refers to macroscopic view, nano-Ag particles stack up in layer.
Further, the metal I films are prepared, the method for metal II films is method commonly used in the art, such as can be with
For plating, the method for chemical plating.
Further, the fusing point of the leadless welding alloy is less than or equal to 180 DEG C.
Further, in the leadless welding alloy, quality of the metal I films in the leadless welding alloy
Percentage be 0.5%~0.8%, mass percent of the nano-silver layer in the leadless welding alloy be 3.0%~
4.0%, remaining composition is the metal II films.
Preferably, mass percent of the nano-silver layer in the leadless welding alloy is 0.3%~1.0%.
The present invention also provides a kind of leadless welding alloy prepared according to the above method, if the leadless welding alloy includes
Dry metal film layer, the metal film layer is followed successively by metal I films, metal II films and nano-silver layer, and the metal I is thin
Film, the metal II films, the thickness ratio of the nano-silver layer are 1~100:1~100:0.01~0.1, the Pb-free coating
Expect that the fusing point of alloy is less than or equal to 180 DEG C, wherein, the metal I is one kind in Cu, Ag, Bi, Zn, In or Ni, described
Metal II is Sn, it is preferable that the metal I is Cu.
Further, the gold being arranged between metal I films and metal II films is also included in the leadless welding alloy
Belong to III films, and the metal I films, the metal III films, the metal II films, the thickness ratio of the nano-silver layer
It is worth for 1~100:0.01~1:1~100:0.01~0.1, wherein, the metal III is Ag or Zn, it is preferable that the metal
III is Ag.
The present invention also provides a kind of application of the leadless welding alloy prepared according to the above method, the leadless welding alloy
For welding electronic component and substrate, the method for welding comprises the following steps：
S1. metal I films are prepared on the electronic component surface to be welded；
S2. metal II films are prepared in the metal I film surfaces；
S3. nano-silver layer is prepared in the metal II film surfaces, obtains the leadless welding alloy；
S4. fuse the leadless welding alloy using reflow method under conditions of less than or equal to 200 DEG C, by institute
Electronic component is stated with the substrate to weld together.For example, returned under conditions of 200 DEG C, 195 DEG C, 190 DEG C or 180 DEG C
Stream.
Wherein, the metal I is one kind in Cu, Ag, Bi, Zn, In or Ni, and the metal II is Sn.It is i.e. described unleaded
Solder alloy can be Nano Silver-Sn-Cu, Nano Silver-Sn-Ag, Nano Silver-Sn-Bi, Nano Silver-Sn-Zn, Nano Silver-Sn-
In or Nano Silver-Sn-Ni.Preferably, the metal I is Cu, i.e., described leadless welding alloy is Nano Silver-Sn-Cu.
Wherein, the electronic component for example can be chip, and the substrate for example can be printed circuit board (PCB), described time
Fluid welding method is the conventional technology of electronic manufacturing field.
Further, the metal I films, the metal II films, the thickness ratio of the nano-silver layer are 1~100:1
~100:0.01~0.1, such as can be 1:1:0.01、1:1:0.1、1:100:0.01、1:100:0.1、100:1:0.01、
100:1:0.1、100:100:0.01、100:100:0.1 or 50:50:0.05 etc., here can not be exhaustive one by one.
Further, in S1 steps, before the electronic component surface prepares the metal I films, first in institute
State electronic component surface and prepare intermediate metal, then prepare the metal I films in the metal transfer layer surface.
Wherein, the intermediate metal is prepared using the method for magnetron sputtering on the substrate.
Wherein, the intermediate metal can be Ti/Au intermediate metals, and the thickness ratio of Ti layers and Au layers is 1~10:
1~10；Can be Cr/Au intermediate metals, and the thickness ratio of Cr layers and Au layers is 1~10:1~10；Can be Ti/Ni/Au
Intermediate metal, and the thickness ratio of Ti layers, Ni layers, Au layers is 1~10:1~10:1~10；Can also be Cr/Ni/Au metal mistakes
Layer is crossed, and the thickness ratio of Cr layers, Ni layers, Au layers is 1~10:1~10:1~10.Any single gold in the intermediate metal
The thickness ratio for belonging to layer and metal I films in the leadless welding alloy is 1~10:10~1000.
Further, in S2 steps, before the metal I film surfaces prepare the metal II films, first in institute
State metal I film surfaces and prepare metal III films, then prepare the metal II films, institute in the metal III film surfaces
It is Ag or Zn to state metal III, it is preferable that the metal I is Cu, and the metal III is Ag, i.e., described leadless welding alloy is to receive
Meter Yin-Sn-Ag-Cu.
Further, the metal I films, the metal III films, the metal II films, the nano-silver layer
Thickness ratio is 1~100:0.01~1:1~100:0.01~0.1, such as can be 1:0.01:1:0.01、1:1:1:0.1、
100:0.01:100:0.1、100:0.5:100:0.01 or 50:0.05:50:0.05 etc., here can not be exhaustive one by one.
Further, the metal III films are prepared using the method for magnetron sputtering in the metal I film surfaces.
Compared with prior art, the present invention adds Nano Silver in leadless welding alloy so that Pb-free solder alloy melts
Point is reduced to less than 180 DEG C, so that electronic component can use the Pb-free solder alloy in relatively low temperature with substrate
Lower carry out reflow soldering.Weld at a lower temperature, the influence to the various electronic components in electronic equipment is smaller, ensures
The quality of each component.Further, since alloy crystalline particle size, therefore nano silver material can be obviously reduced in addition Nano Silver
Addition also improve the wetability of leadless welding alloy, the reliability of welding is enhanced, compared to nano mattisolda and/or general
Logical Sn-Ag-Cu solders, reduce cost.
Brief description of the drawings
Fig. 1 is the structural representation of the leadless welding alloy of embodiment one.
Fig. 2 is the structural arrangement schematic diagram of nano-silver layer in embodiment one.
Fig. 3 is the structural representation of the leadless welding alloy of embodiment two.
Fig. 4 is the structural arrangement schematic diagram of nano-silver layer in embodiment two.
Embodiment
Below by specific embodiment, the present invention is described in detail, it should be appreciated that these specific embodiment parties
Formula is only used for enumerating the present invention, not forms any type of any restriction to the real protection scope of the present invention.
Preparation example one prepares Nano Silver-Sn-Cu Pb-free solder alloys
(1) Ti/Au intermediate metals 2 are prepared using the method for magnetron sputtering on the surface of chip 1 of cleaning, wherein Ti layers with
The thickness of Au layers is 0.1~1 μm；
(2) electric plating method is used to prepare thickness as 1~100 μm of Cu films 3 on the surface of Ti/Au intermediate metals 2；
(3) electric plating method is used to prepare thickness as 1~100 μm of Sn films 4 on the surface of Cu films 3；
(4) use electric plating method to prepare thickness as 0.01~0.1 μm of nano-silver layer on the surface of Sn films 4, obtain
Leadless welding alloy Nano Silver-Sn-Cu.
Its structure of leadless welding alloy made from the present embodiment is as shown in figure 1, wherein, nano-silver layer is in leadless welding alloy
In mass percent be that mass percents of 0.1%, the Sn in leadless welding alloy is 99.2%, Cu in leadless welding alloy
In mass percent be 0.7%.Ag grain shape is spherical, particle diameter 50nm in nano-silver layer, and grain spacing is
50nm, nano-silver layer are packed mono-layer structure, and its structural arrangement is as shown in Figure 2.
Preparation example two prepares Nano Silver-Sn-Ag-Cu Pb-free solder alloys
(1) Cr/Ni/Au intermediate metals 2, wherein Cr are prepared using the method for magnetron sputtering on the surface of chip 1 of cleaning
The thickness of layer, Ni layers and Au layers is 1~3 μm；
(2) electric plating method is used to prepare thickness as 1~100 μm of Cu films on the surface of Cr/Ni/Au intermediate metals 2
3；
(3) method of magnetron sputtering is used to prepare thickness as 0.05 μm of simple substance Ag layers 6 on the surface of Cu films 3；
(4) electric plating method is used to prepare thickness as 1~100 μm of Sn films 4 on the surface of simple substance silver layer 6；
(5) method of chemical plating Nano Silver is used to prepare thickness as 0.01~0.1 μm of Nano Silver on the surface of Sn films 4
Layer, obtains leadless welding alloy Nano Silver-Sn-Ag-Cu.
Its structure of leadless welding alloy made from the present embodiment is as shown in figure 3, wherein, nano-silver layer is in leadless welding alloy
In mass percent be that mass percents of 1.0%, the Sn in leadless welding alloy is 98.2%, Cu in leadless welding alloy
In mass percent be 0.8%.Ag grain shape is ellipse in nano-silver layer, and nano-silver layer is multilayer steps structure,
Its structure is as shown in Figure 4.
The welding chip of embodiment one and printed circuit board (PCB)
Make using reflow method the leadless welding alloy fusion in preparation example one under conditions of 200 DEG C, and then by core
Piece and printed circuit plate weld.
The welding chip of embodiment two and printed circuit board (PCB)
Make using reflow method the leadless welding alloy fusion in preparation example two under conditions of 200 DEG C, and then by core
Piece and printed circuit plate weld.
Performance test
Performance test is carried out with printed circuit board (PCB) to the chip using reflow soldering process welding.
| Reflow Soldering temperature (DEG C) | Whether successfully burn-on | Shearing force testing (GPa) | |
| Embodiment 1 | 200 | It is | 4.5 |
| Embodiment 2 | 200 | It is | 6.1 |
Shearing force testing result shows, chip and printed circuit board (PCB) can be successfully realized using embodiments of the present invention
Welding.
When Reflow Soldering temperature is higher than more than 20 DEG C of solder alloy fusing point, solder alloy just can be melted fully and well
Matrix surface is spread over, efficiently accomplishes welding.During due in performance test, using Reflow Soldering temperature as 200 DEG C, you can success is real
Now weld, it follows that the fusing point of the leadless welding alloy prepared in the present invention is less than or equal to 180 DEG C.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
Other various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
All any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (8)
- A kind of 1. method for preparing leadless welding alloy, it is characterised in that comprise the following steps：S1, metal I films are prepared in substrate；S2, in the metal I film surfaces prepare metal II films；S3, the metal II film surfaces prepare nano-silver layer, obtain the leadless welding alloy；The leadless welding alloy Fusing point be less than or equal to 180 DEG C；The structure of the nano-silver layer is packed mono-layer structure or multilayer steps arrangement architecture, institute The grain shape of Ag in nano-silver layer is stated as dendroid, spherical or oval；The Nano Silver refers to do metallic particles diameter To nano level argent simple substance；Wherein, the metal I is one kind in Cu, Ag, Bi, Zn, In or Ni, and the metal II is Sn；The metal I films, The metal II films, the thickness ratio of the nano-silver layer are 1~100:1~100:0.01~0.1.
- 2. according to the method for claim 1, it is characterised in that：In S2 steps, described in metal I film surfaces preparation Before metal II films, metal III films are prepared in the metal I film surfaces first, then in the metal III film tables Face prepares the metal II films, and the metal III is Ag or Zn.
- 3. according to the method for claim 2, it is characterised in that：The metal I films, the metal III films, the gold Belong to II films, the thickness ratio of the nano-silver layer is 1~100:0.01~1:1~100:0.01~0.1.
- 4. method according to claim 1 or 2, it is characterised in that：In S1 steps, the metal is prepared on the substrate Before I films, intermediate metal is prepared on the substrate first, then prepare the metal in the metal transfer layer surface I films.
- 5. according to the method for claim 1, it is characterised in that：The method for preparing the nano-silver layer is electroplating nano silver side Method, chemical plating Nano Silver method or self-assembled nanometer silver method, the structure of the nano-silver layer is packed mono-layer structure or multilayer Step arrangement architecture, in the nano-silver layer Ag grain shape be dendroid, it is spherical or oval.
- A kind of 6. leadless welding alloy, it is characterised in that：The leadless welding alloy includes some metal film layers, the metal Film layer is followed successively by metal I films, metal II films and nano-silver layer, and the metal I films, the metal II films, institute The thickness ratio for stating nano-silver layer is 1~100:1~100:0.01~0.1, the fusing point of the leadless welding alloy be less than or Equal to 180 DEG C, wherein, the metal I is one kind in Cu, Ag, Bi, Zn, In or Ni, and the metal II is Sn；It is described unleaded The fusing point of solder alloy is less than or equal to 180 DEG C；The structure of the nano-silver layer is that packed mono-layer structure or multilayer steps are arranged Array structure, in the nano-silver layer Ag grain shape be dendroid, it is spherical or oval；The Nano Silver refers to metal Grain diameter accomplishes nano level argent simple substance.
- 7. leadless welding alloy according to claim 6, it is characterised in that：Also include setting in the leadless welding alloy Metal III films between metal I films and metal II films, and it is the metal I films, the metal III films, described Metal II films, the thickness ratio of the nano-silver layer are 1~100:0.01~1:1~100:0.01~0.1, wherein, it is described Metal III is Ag or Zn.
- 8. a kind of application of leadless welding alloy prepared by method according to any one of claim 1 to 5, its feature exist In：The leadless welding alloy is used for welding electronic component and substrate, and the method for welding comprises the following steps：S1, on the electronic component surface to be welded prepare metal I films；S2, in the metal I film surfaces prepare metal II films；S3, the metal II film surfaces prepare nano-silver layer, obtain the leadless welding alloy；The knot of the nano-silver layer Structure is packed mono-layer structure or multilayer steps arrangement architecture, in the nano-silver layer Ag grain shape be dendroid, it is spherical or Ellipse；The Nano Silver refers to metallic particles diameter accomplishing nano level argent simple substance；S4, fuse the leadless welding alloy using reflow method under conditions of less than or equal to 200 DEG C, by the electricity Sub- component welds together with the substrate；Wherein, the metal I is one kind in Cu, Ag, Bi, Zn, In or Ni, and the metal II is Sn.
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| CN103151430A (en) * | 2011-12-06 | 2013-06-12 | 北京大学深圳研究生院 | Preparation method of achieving low-temperature metal interface connection of light-emitting diode (LED) with nanometer metal granules |
| CN103377956A (en) * | 2012-04-26 | 2013-10-30 | 亚太优势微系统股份有限公司 | Method for bonding package structure and substrate |
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