EP3867005A1 - Bleifreie lötlegierung und verwendung einer solchen legierung - Google Patents
Bleifreie lötlegierung und verwendung einer solchen legierungInfo
- Publication number
- EP3867005A1 EP3867005A1 EP19797182.3A EP19797182A EP3867005A1 EP 3867005 A1 EP3867005 A1 EP 3867005A1 EP 19797182 A EP19797182 A EP 19797182A EP 3867005 A1 EP3867005 A1 EP 3867005A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- alloy
- copper
- tin
- antimony
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 82
- 239000000956 alloy Substances 0.000 title claims abstract description 82
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 60
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 25
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000005476 soldering Methods 0.000 claims description 13
- 238000005219 brazing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000009736 wetting Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PQIJHIWFHSVPMH-UHFFFAOYSA-N [Cu].[Ag].[Sn] Chemical compound [Cu].[Ag].[Sn] PQIJHIWFHSVPMH-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000969 tin-silver-copper Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
Definitions
- the present invention relates to a solder alloy composition which is free of lead.
- solder alloy comprising lead which has a high melting point of approximately 300 ° C. Due to regulatory constraints, such lead-based alloys can no longer be used.
- a tin-silver-copper alloy is better known by its English abbreviation "SAC alloy”.
- SAC alloy an SAC305 alloy is known, comprising approximately 3% by mass of silver and approximately 0.5% by mass of copper, the melting temperature of which is between 217 ° C. and 220 ° C.
- Such an SAC305 alloy has lower performance than a lead alloy for operating temperatures above 150 ° C. However, such operating temperatures are frequently reached in the petroleum, aeronautical, automotive or other fields. In addition, such an SAC305 alloy is not very robust to thermal shocks between -40 ° C and + 150 ° C. We are therefore looking for an alloy that does not melt below 200 ° C or ideally 230 ° C and is as reliable in terms of thermal cycling, electrical and thermal conductivity and mechanical resistance as the leaded alloy.
- An object of the invention is therefore to provide a brazing alloy with good reliability for use in a variety of welding processes, such as wave soldering, reflow soldering, dip soldering, wire brazing and selective soldering. .
- the invention relates to a lead-free solder alloy having a composition comprising:
- Cu copper
- the alloy comprises:
- the alloy comprises:
- such a brazing alloy has melting temperatures and phase diagrams which are optimal for implementing a reflow process.
- a conventional SAC alloy i.e. a Tin-Silver-Copper alloy
- the mechanical resistance is increased by more than 50%
- the wetting performance is increased and the thermal conductivity is increased.
- the cost of an alloy according to the invention is reduced significantly, preferably by around 50%.
- the thermal conductivity greater than 60W.nr 1 .K 1 , preferably between 60W.nr 1 K 1 and 65W.nr 1 K 1 .
- the wettability is less than 25 °.
- the alloy comprises only tin (Sn), antimony (Sb) and copper (Cu).
- the alloy comprises:
- the alloy comprises 90% -92% by weight of tin (Sn).
- the alloy comprises 7% -8% by weight of antimony (Sb).
- the alloy comprises 1% -2% by weight of copper (Cu).
- the alloy comprising:
- the alloy comprising:
- the invention also relates to a composite alloy for brazing comprising a brazing alloy as presented above and 5% -25% by weight of silver or copper particles.
- the composite alloy for brazing consists only of an alloy of brazing and particles of silver or copper.
- Such a composite alloy of solder improves the thermal and electrical conductivity.
- the silver or copper particles have dimensions between 1 and 30 micrometers.
- the invention also relates to the use of an alloy as presented above for a process for remelting electronic components.
- the invention also relates to the use of an alloy as presented above for soldering a housing of electronic components and / or a surface mounting device (SMD) to a substrate, the alloy being applied in the form of a paste.
- SMD surface mounting device
- a brazing alloy is proposed for wave soldering, for selective soldering and in particular for a method of soldering electronic components by reflow.
- Such an alloy can also be used for the manufacture or connection of electronic components, in particular, semiconductors.
- a lead-free solder alloy having a composition comprising:
- a melting range between 220 ° C. and 340 ° C. is obtained.
- the alloy comprises: - 88% -94% by weight of tin (Sn),
- the alloy comprises:
- Such a brazing alloy has a melting point which is between 220 ° C and 310 ° C and has very good properties in the mechanical, electrical and wetting fields. In addition, the absence of lead makes it possible to comply with the new environmental standards.
- the alloy comprises:
- a melting range between 220 ° C. and 300 ° C. is obtained.
- the alloy comprises:
- the alloy consists of:
- a melting range between 220 ° C. and 250 ° C. is obtained.
- the alloy consists of:
- the alloy comprises:
- the alloy comprises:
- Such a brazing alloy has melting temperatures and phase diagrams which are optimal for implementing a reflow process.
- a conventional SAC alloy i.e. a Tin-Silver-Copper alloy
- the mechanical resistance is increased by more than 50%
- the wetting performance is increased and the thermal conductivity is increased.
- the cost of an alloy according to the invention is reduced significantly, preferably on the order of 50%.
- the alloy according to the invention was produced in quartz tubes closed under vacuum to avoid the phenomenon of oxidation, then in alumina crucibles. Elements of high purity, Sn (99.949%), Sb (99.76%) and Cu (99.99%) were introduced and mixed after weighing in the crucibles, then placed in a resistance oven at a temperature of 370 ° C.
- XRF X-ray fluorescence
- EDS dispersive dispersion spectrometry
- SEM scanning electron microscope
- the high energy X-ray diffraction ring method was also used at the European Synchrotron Radiation Facility (ESRF) in Grenoble.
- ESRF European Synchrotron Radiation Facility
- the DSC analyzes then made it possible to determine the solidus and liquidus temperatures as well as the enthalpy of fusion from samples with a mass of approximately 50 mg in 30 ⁇ l cylindrical aluminum crucibles.
- the test cycle includes two heating and cooling periods between 20 ° C and 350 ° C with a speed of 5 ° C / min.
- the alloy has good resistance to thermal shock between -40 ° C and + 150 ° C.
- the wettability measurements were carried out with a wetting balance. To implement this method, a rectangular plate of a substrate is immersed in the molten solder having a defined depth and the force is measured during the test.
- the procedure for preparing each sample before the test consists of cleaning / degreasing with acetone followed by a chemical attack with a 2% aqueous solution of nitric acid, rinsing with distilled water and d '' immersion in a flow of CA (activated rosin) (ECOFREC TM CMA 185 from Inventec).
- the ability of a liquid to spread over a surface is characterized by the angle between the surface of the substrate and a droplet deposited on the surface. The smaller the angle, the better the wettability. If the wettability is greater than 90 °, the wettability is zero. According to the invention, the wetting angle is closed at 20 ° in our case (between 25 ° and 35 ° for the SAC305).
- the alloy was prepared in the form of cylindrical test pieces for the tensile tests (according to ISO 6892) which were directly cast in a stainless steel mold.
- the thermal conductivity was measured by the hot disc method.
- a spiral nickel sensor is placed between two cylindrical samples of the alloy to be measured. These samples, 10 mm high and 35 mm in diameter, must have a flat face to improve contact with the sensor. This sensor fulfills a first heating function and a second measurement function. For this type of measurement, the sample size is directly linked to the expected conductivity of the sample.
- the tensile tests were carried out with a tensile testing machine equipped with a load sensor of 5 kN and a strain gauge of 25 mm, with a strain rate of 3.10-2 s-1 (0.75 mm / min).
- the mechanical properties were determined by three tensile tests at microhardness at room temperature.
- the microhardness was measured with a Vickers indenter under a load of 10 N for 10 seconds.
- the average value is around 23HV instead of 6HV and 18HV for Tin and SAC 05, respectively.
- the mechanical behavior is similar to that of SAC305, without hardening.
- the maximum elongation is less than 35%, preferably of the order of 34%, the maximum elongation being of the order of 38% for a conventional SAC alloy.
- the mechanical strength of the alloy according to the invention is greater than 60 MPa, preferably of the order of 70 MPa, which is greater than that of a conventional SAC alloy which is of the order of 50 MPa.
- the thermal conductivity l which is one of the predominant parameters of a soldering alloy in microelectronics, since it guarantees good dissipation of the heat induced by the current, has been determined by the heating disc method.
- the thermal conductivity greater than BOW.m- i .K 1 , preferably between 60W. m- l .K 1 and 65W. m- i .K 1 .
- An average value of 63.60 W. m- i .K 1 with a standard deviation of 0.05 W. m- i .K 1 was obtained by three measurements carried out on the same sample.
- the alloy can be used in wave soldering, selective soldering, dip soldering, as part of wire, for placement of CMS and for applications dough-in-dough.
- the alloy is packaged in the form of bars, preforms, ingots, powder, solder paste or solder cream.
- the alloy according to the invention with silver or copper particles having a dimension between 1 and 30 micrometers in order to form a composite alloy.
- silver or copper particles are added in an amount of 5 to 25% by weight of the mixture.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1859695A FR3087368B1 (fr) | 2018-10-19 | 2018-10-19 | Alliage de brasure sans plomb et utilisation d'un tel alliage |
| PCT/EP2019/078210 WO2020079147A1 (fr) | 2018-10-19 | 2019-10-17 | Alliage de brasure sans plomb et utilisation d'un tel alliage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3867005A1 true EP3867005A1 (de) | 2021-08-25 |
Family
ID=65494362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19797182.3A Pending EP3867005A1 (de) | 2018-10-19 | 2019-10-17 | Bleifreie lötlegierung und verwendung einer solchen legierung |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP3867005A1 (de) |
| CN (1) | CN112969549A (de) |
| FR (1) | FR3087368B1 (de) |
| WO (1) | WO2020079147A1 (de) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4758407A (en) * | 1987-06-29 | 1988-07-19 | J.W. Harris Company | Pb-free, tin base solder composition |
| WO1997012718A1 (en) * | 1995-10-06 | 1997-04-10 | Brown University Research Foundation | Soldering methods and compositions |
| JP2005122970A (ja) * | 2003-10-15 | 2005-05-12 | Matsushita Electric Ind Co Ltd | 管球 |
| DE102005059544A1 (de) * | 2005-12-13 | 2007-06-14 | Ecka Granulate Gmbh & Co. Kg | Sn-haltige hochbelastbare Materialzusammensetzung; Verfahren zur Herstellung einer hochbelastbaren Beschichtung und deren Verwendung |
| JP5285079B2 (ja) * | 2008-10-24 | 2013-09-11 | 三菱電機株式会社 | はんだ合金および半導体装置 |
| WO2010113833A1 (ja) * | 2009-03-30 | 2010-10-07 | 荒川化学工業株式会社 | 鉛フリーはんだ用フラックス組成物及び鉛フリーはんだ組成物 |
| JP5463845B2 (ja) | 2009-10-15 | 2014-04-09 | 三菱電機株式会社 | 電力半導体装置とその製造方法 |
| CN102441743B (zh) * | 2011-06-28 | 2013-04-17 | 力创(台山)电子科技有限公司 | 一种铜铝合金复合管专用焊环 |
| JP6118249B2 (ja) * | 2011-06-29 | 2017-04-19 | 株式会社日本スペリア社 | 信頼性が向上したはんだ接合部の製造方法 |
| JP6767506B2 (ja) * | 2016-05-06 | 2020-10-14 | アルファ・アセンブリー・ソリューションズ・インコーポレイテッドＡｌｐｈａ Ａｓｓｅｍｂｌｙ Ｓｏｌｕｔｉｏｎｓ Ｉｎｃ． | 高信頼性鉛フリーはんだ合金 |
| JP6810915B2 (ja) * | 2017-03-17 | 2021-01-13 | 富士電機株式会社 | はんだ材 |
| CN107322178A (zh) * | 2017-06-23 | 2017-11-07 | 哈尔滨理工大学 | 一种用于功率器件封装的新型钎料 |
-
2018
- 2018-10-19 FR FR1859695A patent/FR3087368B1/fr active Active
-
2019
- 2019-10-17 CN CN201980068590.2A patent/CN112969549A/zh active Pending
- 2019-10-17 WO PCT/EP2019/078210 patent/WO2020079147A1/fr unknown
- 2019-10-17 EP EP19797182.3A patent/EP3867005A1/de active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN112969549A (zh) | 2021-06-15 |
| WO2020079147A1 (fr) | 2020-04-23 |
| FR3087368A1 (fr) | 2020-04-24 |
| FR3087368B1 (fr) | 2020-10-30 |
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