TW200923142A - Sn-plated conductive material, method for making such material and electric conduction part - Google Patents

Abstract

This invention provides a Sn-plated conductive material which is a Sn-plated conductive material 1 having a Sn-plating layer 5 of Sn or alloy of Sn on a substrate 2 of a conductive metal. In a cross-section along the direction of the overlay of the substrate 2 and the Sn-plating layer 5, an Ag-Sn alloy layer 6 having Ag-Sn particles aggregated in the surface portion of the Sn-plating layer 5 is formed.

Description

200923142 • Nine, invention description: • [Technical field to which the invention belongs] "The present invention relates to a money-tin conductive material using a material as a semiconductor device and an electronic appliance, and a method of manufacturing the same, and using the mirror' Electrolytic parts such as terminals, connectors, lead frames, etc. formed by electrical materials. This patent application is based on the 2,7,7,7,7,,,,,,,,,,,,,,,,,, Japanese application, Japanese Patent Application No. 2008-185061 claims priority, and its contents are hereby incorporated. [Prior Art] Electrical Li Electronics ♦ Electrical parts are used in the composition of copper alloys, etc.: Tin-plated conductive material obtained from tin. In order to improve the reliability of production and the reliability of thousands of parts, it is required to produce a tin-plated conductive material with excellent resistance to whiskers (whisker). Produced., Cafés Substanees, (4); ^=, plus - does not require the absence of the wrong pure tin plating. But it is known that ^ is not attached to the tin-like part of the whisker. And producing tin at the same time 'will not lead When the tin-based tin ore is reflowed, the electro-mineral layer can partially inhibit the natural generation of tin whiskers. However, for example, ^3 is released, so the contact between the female terminal and the male terminal is stressed. The tin whisker is caused by the connector, and finally the electronic appliance: 320516 200923142. The reliability of the piece will be reduced. The method of suppressing the tin whisker can be electroplated by expensive and valuable resources, but the manufacturing cost will become Extremely high. ▲Materials' connector terminals for semiconductor lead frames and electronic components, in addition to their whisker resistance, are also required for thermal properties (safety of electrical contact resistance). Tin metal is easy to use in air. Oxidation, an emulsified film is often formed on the surface thereof. Therefore, the material on the opposite side of the 'moon shape' of the material whose coating material is coated with the tin-plated layer will damage the oxide film and the contact should be I: soft The tin metal is electrically connected thereby, which makes the reaction speed of the diffusion alloying of the known tin-bismuth metal fast, so that the alloying reaction between the element and the tin in the material will simultaneously make the film of the layer; especially In a high temperature environment, 'will promote the alloying reaction between tin and copper, ^ completely alloy the tin layer, thus exposing the copper-tin alloy layer to the electric ore layer: oxidation: ίί surface forms copper oxide in addition to the formation of tin oxide film Membrane. It can't be easily damaged when it comes into contact with the contralateral material, so it will change to 15 (the temperature required by TC is higher than J, which makes it more serious. Layer thickness: delay: ensure its reliability' It has become necessary to adopt a method of increasing the tin plating for a long time until the tin layer is completely alloyed.... In the case of the terminal, the increase is two;;;='in the _ joint force causes the electric ore layer deformation 1 ^ degree due to the mother movement The end of the resistance;: the pull of the force), so that the embedding of your sauce α έ 人口 population this day gray oh, its sliding resistance (insert burden. D 乍 性 I I , , 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 516 It is extremely difficult to produce it at the same time and it has a tin-plated material of #,^, which has resistance to day and day and heat resistance. Nearly (4) there is a tin-plated conductive material that is highly resistant to purity and resistance. For example, on the surface of the wind, the proposal of Μ 为 is to set up a copper layer between the copper plating layer and the tin plating layer of the inter-layer of the copper substrate, and to form a silver layer by reflow treatment. Layer.",

In the case of the copper substrate or the Fe alloy, the silver substrate is not plated with silver, and the silver-tin alloy layer is formed on the surface of the enamel. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2002-31-7295 [Patent Document 3] JP-A-2002-220682 (Invention) Problem) (But the tin-plated conductive material having the silver-tin alloy layer is formed into a silver-plated layer, and then formed into a silver-tin by reflow or diffusion annealing at a temperature at which the tin-tin layer is melted. The alloy causes the particles of the silver-tin alloy to be dispersed in the entire tin tin layer. Therefore, in order to improve the heat resistance, it is necessary to increase the pot silver content, so that the manufacturing cost of the tin-plated conductive material may be improved; In view of the foregoing, the researcher aims to provide a plating=conductive material and a manufacturing method thereof, and an energized part using the tin-plated conductive material, wherein the nickel-plated conductive material can reduce the amount of silver used, and thus can be manufactured at low cost. 'The heat resistance and the resistance to whisker formation can be improved. 7 320516 200923142 . (Means for Solving the Problem) - In order to solve this problem, the inventor of the inventor Yukishima & When the bamboo shoots form a thin silver layer on the tin-plated layer, the temperature at which the tin is melted is lower than the temperature at which the tin is melted, and the silver and tin are diffused into a 'surface layer to form a silver-tin alloy layer. The present invention in the tin-plated layer is based on the discovery of the founder in the tin conductive material comprising: a substrate having conductivity & R in the middle of the ^. ^ ^, formed in the mine a tin-plated layer composed of tin or a tin alloy on the soil material, and a silver-tin alloy layer formed by agglomerating silver on the surface layer portion of the tin-plated layer.... The tin-plated conductive material of the composition is composed of silver- Tin-particles condensed into silver-tin;: layer=partially forming the movement of tin atoms on the surface of the layer, inhibiting the tin ^' mouth, which prevents the presence of bond tins and inhibits the tin whisker into a tin-grained AgsSn metal The compound is formed by .. , and the conductive silver-tin particles are not in the direction along the substrate and the layer of the layer of the yttrium-iron layer, which is folded into the surface of the tin layer. Reducing the amount of silver used, still = because of the::, can be produced at low cost The silver-tin-i layer formed by the aggregation of silver and particles on the material layer has corrosion resistance, so that the oxidation is carried out, especially in the high, "production of φ Ά, the tin diffusion on the surface of the tin plating layer can be inhibited. The situation is "H ^ ^ m of the tin plating layer, between the silver of the rhyme _ tin particles will not expand

It is placed on the tin-plated layer and is present in the form of an island on the layer of 曰L 恳 恳 U m , , Dan ', 口 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日Turning to Aberdeen, because the silver-tin particles are made of 320516 8 200923142. The conductive AgsSn intermetallics make you _ layer completely alloyed and surface! It is generated, so even if the compound is electrically contacted between the silver and silver compounds. It can also be made by the sound of n-metal tin; ^ can be improved by the heat resistance of π, so there is no need to excessively increase the clock type i connection, not only can suppress the generation of tin whiskers, in the case of forming a rear-connected connection terminal, etc. It can also improve its insertion and removal. The substrate ' can be made of a material having at least a surface having electrical conductivity. 2. Composite materials such as copper alloys or F_Fe alloys. Among them, a material in which a conductive material is coated with conductivity =: = is preferred. ( (4) Copper and copper alloys with good characteristics. The average thickness of the preferred layer in the range of silver-tin combined with the above-mentioned silver-tin can be set.

In this case, the silver-tin alloy layer is flat.

V: Up and down::: Suppresses the generation of tin whiskers from the _ layer and the continents ^ Because of the tin smelting, its resistance to whisker formation and heat resistance. On the other hand, the contact resistance rises, and the silver can be discolored by vulcanization to cause electrical connection. V also prevents deterioration of solder wettability. It is not gold::: it is extremely thin. The micro-L::=: exists in the composition, but the silver-tin intermetallicization is formed. This is not formed; Γ: two: the state in which the sheet is dispersed on the surface. For example, the layer (silver-tin particles) of the yang: Dan, the child is the silver-tin alloy, the area of the adhesion area on the silver plated layer is 320516 200923142. And a copper plating layer formed on the substrate and the tin plating layer. It is also possible to form a layer of copper or a copper alloy and to make the chemical state of the surface of the substrate uniform by a copper plating layer, thereby improving the diffusion of the uniformity of the bond tin layer to the limit of the tin, which can be electricity Clock, electroless electric clock, replacement plating. A diffusion preventing layer for preventing diffusion may also be formed on the substrate. Soil ππτϋ京扩(4) 'Because the diffusion preventing layer can prevent the element and tin in the substrate from being r-', it can improve the bonding strength of the tin-conducting material to the thermal and ore" substrate. At the same time, the diffusion prevention is prevented. The element of the layer, if it is difficult to react with the element in the aforementioned substrate, for example, in the case where the substrate is composed of copper or a copper alloy, the diffusion preventing layer can be used, for example, Ni, .+

Cr, M〇, W, M, Ti, Zr, v, Ta, Nb, etc.; or such alloys. The method for producing a tin-plated conductive material according to the present invention is the method for producing a tin-tin conductive material as described above, comprising: forming a tin-plated layer of a tin-plated layer composed of tin or a tin alloy on a conductive material; The forming step, the silver layer forming step of forming a silver layer composed of silver or a silver alloy on the tin plating layer, and the step of forming the silver layer are maintained at 1 Å. The silver-tin alloy layer forming step of the silver-tin alloy layer is formed by reacting the silver of the silver layer with the tin of the tin layer to form a temperature of not more than 100 C for more than 2 seconds. In the method for manufacturing a tin-plated conductive material, the silver-tin is reacted to form silver-tin particles (Α_metal. intermetallic compound) via silver-tin 10 320516 200923142. The alloy layer forming step, and the surface of the H tin layer forms silver. _ Tin particles are agglomerated into a silver-tin alloy layer. Since the temperature conditions in the silver-tin alloy layer forming step are grasped, the reaction between silver and tin can be promoted. Moreover, since the temperature condition of the silver-tin alloy layer forming step = is less than (10) t, it is possible to suppress excessive silver and tin = 2 = L (Ag3Sn intermetallic compound) dispersed throughout the cross section of the substrate and the ore. In the tin layer, silver-tin particles can be condensed on the surface of the tin plating layer. Before f is formed into (4), a step of forming a copper plating layer of a layer composed of copper or a copper alloy on the substrate may be provided. Step = =: the step of forming the copper layer by the key, and between the substrate and the layer of the tin layer: again =:, the ore, the layer, the chemical state of the surface of the substrate can be uniformly defined, the quality. Among them, the method of forming iron steel is not specifically for electroplating, electroless plating, or electroplating. The upper opening 'may also be a diffusion preventing layer forming step of the diffusion preventing layer which diffuses the elements in the substrate described above. / Day, price At this time, the layer shape can be prevented by diffusion, and the diffusion prevention layer can be formed. Borrowing =: tin sulphide diffuses from the substrate to the tin-plated layer, so the p-stop substrate is sturdy and the sputum 厗盥 π b knows that the tin-plated conductive material is resistant to j and the tin-plated layer is tight with the substrate. Sex. The diffusion prevention heat prevention is particularly limited, and may be, for example, a wet method of the wet method, a method of replacing the electric ore, a chemical conversion treatment (chromate treatment, etc.), an electric discharge clock, and a reduced ore method. The step of forming the mineralized copper layer in the form of the step 1 may be followed by a step of forming a diffusion preventing layer before the step of forming the copper plating layer 320516 11 200923142. In the silver layer forming step, the silver layer selected from the electric boat method, the electroless magnetic key method, the electric ore method and the steaming method may be formed to form the silver layer having a thickness of 〇 〇〇ι to 0·1 μηη. At this time, since the average thickness of the silver layer is 0.001 μm or more, silver and tin can be reacted to form a silver-tin alloy layer. On the other hand, since the average thickness of the two layers is less than Q1 μηη, all the silver in the formed silver θ can be reacted, and not only the residual silver can be suppressed from being discolored due to vulcanization, but also the electrical contact resistance can be improved, and the solder can be prevented. The degree of moisture is deteriorated. The formation is extremely thin (10) to. · 1-, so it is not a fine t aS-like connection, but presents money (4) the shape of the agglomerate of the wire = dispersed in the state of the tin-plated layer. The thickness of the silver layer formed by such unevenness. The tin-plated layer may also be present after the average area of the donor layer on the tin-plated layer. This reflow treatment is a melt treatment of heating to tin gold. In the above-mentioned tin plating layer forming step (the melting point of the reflow processing step of the preheating treatment and the formation of the (four) layer in the surface layer of the tin tin layer can be made by the reflow treatment to form the tin tin whisker. This prevents the internal stress from being caused by the internal substrate, as well as the layer of silver and the layer of silver-tin alloy. The energized parts of the present invention. The above-mentioned tin-plated conductive material 320516 12 200923142 is used to form the tin-plated conductive material 320516 12 200923142, and the above-mentioned tin-plated conductive material is used to constitute an electrical component such as a connector terminal, a dot, and a lead frame. It can improve the generation and heat resistance of these energized zero-resistance whiskers, and can provide high-reliability electric parts. The silver-tin alloy is widely distributed with tin-lead. The material material can be made into (the effect of the invention). The present invention forms a silver layer on the tin layer and reacts silver with tin, thereby forming silver which is formed by agglomerating silver-tin particles on the surface of the tin layer. _ Tin alloy layer, therefore, it is possible to provide a tin-based material which is excellent in whisker-forming property and heat resistance, a method for producing the same, and an energized component. [Embodiment] Hereinafter, a conductive material 1 of the i-th embodiment of the present invention will be described with reference to the accompanying drawings. It is the money tin conductive material of this embodiment! As shown in the rth diagram, the substrate 2 has a plating layer formed on the surface of the substrate 2, and a mineralized copper layer 4 formed on the surface of the key recording layer, and a mineral formed on the surface of the copper plating layer 4. The tin layer 5 and the silver-tin alloy layer 6 formed on the surface of the tin-plated layer 5. The base material 2 is made of a metal having conductivity. In the present embodiment, it is basically composed of various copper alloys, and an iron-based alloy may be used. The nickel-plated layer 3 is a diffusion preventing layer of an element of the substrate 2, which is composed of δ gold of nickel or nickel, and is formed on the surface of the substrate 2 by an electric clock method. The thickness of the clock recording layer 3 is set in the range of 0*01 to 1.0 μπί. The mineralized copper layer 4 is used as a diffusion preventing layer for alloying of nickel and tin, and is formed of a copper 'copper port' and formed on the surface of the mineral recording layer 3 by an electric ore method. Plating 320516 13 200923142 <The copper layer 4 has a function of preventing nickel of the nickel plating layer 3 from diffusing to the tin plating layer 5. The thickness of the copper plating layer 4 is set in the range of 〇丨 to 丨.〇. The tin-plated layer 5 is made of tin or a tin alloy and is formed by electroplating or electroless plating. The thickness of the tin-plated layer 5 is basically as long as the solder wettability is satisfied, and may be set within a range of 〇3 to 1 视 depending on the application. The tin-plated layer 5 is subjected to a reflow treatment (the molten portion) to be described later, and the stress inside the ore is released. The silver-tin alloy layer 6 is formed by agglomerating silver-tin particles on the surface layer portion of the tin-plated layer 5 in a cross section along the lamination direction of the substrate 2 and the tin-plated layer 5. Among them, the silver-tin particles are electrically conductive intermetallic compounds. The average thickness of the silver-tin alloy layer 6 is set in the range of 〇.〇〇2 to 〇 σ. The silver-tin alloy layer 6 is extremely thin due to its thickness. : 〇.2 μιη' is therefore not a fine crystalline continuous film, but is in a state in which particles or aggregates of the particles are uniformly dispersed in the tin-plated layer. The flow chart shown in Fig. 3 of Fig. 1 illustrates that the tin-conducting conductive material is formed on the surface of the substrate 2 via the core _ forming step S1). Next, a step of forming a copper plating layer by electroplating on the surface of the nickel plating layer 3 is carried out to form step S2). Thereafter, the tin-plated layer 5 is electroplated on the copper-plated layer 4 (the tin-plated layer forming step is magical). After the electrolysis is formed into the tin-plated layer 5 through the electric town, it is heated to the tin metal 320516 14 200923142 ... to make the tin material reflow treatment (reflow treatment step (4). At this time, the part of the copper plating layer 4 or All formed copper-tin alloy. , : times', as shown in Fig. 2, the electric ore method selected from the electric key, the electroless electric clock, the layering method, the clock method, and the rectification treatment of the tin tin &; forming a silver layer 7 of 〇.001 to 〇.1 叩 thick and composed of silver or a silver alloy (silver layer forming step S5). In the state in which the silver layer 7 is formed on the surface of the tin layer 5, The whole week is not more than 1〇〇t: the warm water bath is preserved, so that the silver of the silver layer 7 and the tin of the Lai layer 5 react with the tin-shaped Ug3Sn intermetallic compound), thus forming a silver-tin alloy= : Tin alloy layer forming step (6). At this time, all the silver of the silver layer 7 reacts with tin to form a silver-tin alloy, and therefore, the silver layer 7 does not remain. 2 operation can be made into the clock-tin conductive material of the present embodiment. The tin-plated material 1 is processed as shown in Fig. 4 to be used as the connector terminal 8 composed of the male and female contacts. It can be used not only for 00 but also for energized parts such as contacts and lead frames. In the plating material 丨 in the embodiment, since the silver-tin alloy layer 6 formed by the tin-particles (Ag3Sn intermetallic compound) condensed on the tin-plated layer 5::: is formed, the tin can be inhibited. In the layer 5, the tin is partially concentrated and the tin whisker is suppressed. In addition, the silver-tin particles must be grown into the tin whisker to increase the tin-resistance of the tin-based conductive material 1 due to the aggregation of the silver-tin particles (Ag3Sn intermetallic compound) on the surface of the plating. Therefore, even if the amount of silver used is reduced, the anti-crystal 320516 15 200923142 can be improved, and the tin-plated conductive material can be produced at low cost. • At 151 pm, even in the high-temperature use environment, even if the copper of the copper plating layer 4 diffuses to the mirror tin layer 5, the copper-tin alloy grows to the surface and oxidizes, and the silver of the silver-tin alloy layer 6 which is formed on the surface is formed. A tin particle (Ag3Sn intermetallic compound is also not easily oxidized. Therefore, the silver-tin alloy layer 6 can be electrically contacted, thereby improving the heat resistance of the tin-conducting conductive material i. Therefore, the resistance to strontium can be improved. Thinning the key tin layer 5 not only suppresses the generation of tin whiskers, but also forms a connection as shown in Fig. 4, which is as shown in Fig. 4, and inserts and pulls. The silver-tin alloy layer 6 has an average house sound command with a small η range. This can indeed suppress the generation of tin crystals from the core and its resistance to whisker formation and heat resistance, while preventing the silver-tin layer 6 from being fine enough to be The solder wettability is reduced. At the same time, because it can: use less silver 'so it can be made at low cost】 At the same time, because of the formation of == chain alloy composition between the substrate 2 and the tin-plated layer 5 The green material, or nickel, is thus prevented from being expanded by the nickel plating layer 3卞曰 丨 丨 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材On the right side, you have a shaft layer 4 as a nickel diffusion prevention. This hunting copper layer 4 prevents nickel from diffusing into the tin plating layer 5, and: the tin plating layer 5 is deteriorated in solder wettability. However, it is preventable that the Qianxi conductive material of the embodiment is formed by copper or copper on the nickel plating layer 3 by forming a lan layer of nickel layer 3 composed of nickel or a nickel alloy. The alloy is formed into a layer and the layer forming step y, the copper of the ore-bearing copper layer forms a mineral consisting of tin or tin alloy on the ore layer 4, a tin-tin layer formation step S3, and a tin-plated layer 5 At the pre-twisting point, the reflowing step S4 is performed, and the tin-plated θ / formed by the tin-plating layer forming step is composed of silver or a silver alloy. The silver layer of silver 7 is formed by the step of immersion and is maintained at _ or less (10). The tin of 5 seconds or more is reacted to form a silver-tin alloy layer 6 : The alloy layer is formed in the step S6. The tin HTci Γ π is caused by the silver-tin alloy layer forming step %#. The temperature condition is two or two: the silver and tin can be promoted, and the temperature condition of the silver-tin alloy layer is Since c is below, it can suppress excessive reaction of tin. Therefore, it is possible to prevent silver-tin particles (Ag3Sn intermetallicization person = dispersed in the cross section along the lamination direction of the substrate 2 and the tin-plated layer 5; the tin layer 5' The silver-tin particles can be condensed on the surface layer of the tin-plated layer 5. After that, the silver-tin alloy layer forming step can be performed after the /By=water contact, so that the furnace can be used without being used. Manufacture of tin-conducting conductive material 1. - Silver layer forming step S5 can be formed by the electro-mine method selected from the electric money method, the electroless electric key method and the Luo ore method to form a silver layer 7 of UG1 to G.1 μπι thick. Therefore, silver and tin can be promoted to form silver-tin particles, and not only the silver-tin alloy layer 6' can be formed but also all the silver in the silver layer 7 can be reacted, and the silver layer 7 can be prevented from remaining on the surface of the tin-plated layer 5. . Therefore, since silver is completely reacted in the silver layer 7, pure silver does not remain on the surface of the tin-plated layer 5, so that surface discoloration and electrical contact resistance can be prevented from rising. Since after the tin plating layer forming step S3, there is the tin plating layer 5 320516 17 200923142 •= the reflow processing step S4, the ferrite layer can be formed in the tin layer 5 in the step S3 via the reflow process. Internal stress prevents the tin whiskers from naturally occurring due to internal stresses. (4) Second, the human figure 5 shows the second embodiment of the present invention. In the conductive material U of the present embodiment, the substrate 12 is reinforced by a part and has a bell steel layer formed on the surface of the substrate 12; and plating is formed on the surface of the copper plating layer 14. The tin layer 15 and the silver-tin alloy layer 16 formed on the surface of the tin-plated layer 15. Substrate 12 is the same as the first! Similarly, the embodiment is basically composed of various copper alloys, but an iron-based alloy can also be used. The +mine copper layer is formed on the surface of the substrate 12 and is composed of copper or a copper alloy formed by electroplating or electroless phase. (4) Thickness of layer 14 is set within the range of U1. The electron system is composed of tin or a tin alloy and is formed by electrowinning or non-ferrous metal. The thickness of the paste 15 is basically as long as the degree of satisfaction is sufficient, and the tin can be set in the range of 0.3 to 10 (10) depending on the application; in the case of the second embodiment, the setting is in the practical case, and the layer 15 is partially localized. The necessary portion formed on the substrate 12 is heated to the tin-smelting purpose for the purpose of the internal stress of the tin layer 12: The temperature is known to be refluxed. The silver-tin alloy layer 16 is formed by agglomerating silver-tin particles on the surface layer of the tin-plated layer 15 along the substrate 12 and the tin layer 15; The average thickness of the silver-tin alloy layer 16 is set in the range of Q 〇〇 2 320516 18 200923142 . to 0. 2 μιη. 'law. The shape processing of the manufacturing part of the clock tin conductive material η will be described below with reference to Fig. 6 (the substrate processing step Tao / no tin plating layer is formed on the substrate 12 t (shading step s, l). The knife is cut into the *, and then the exposed clock of the substrate 12 is formed as a substrate, electricity, steps s, 2). The frying prevention layer (the copper plating layer is formed on the copper plating layer 15 by electroplating or electroless plating (tin plating formation step s, 3). The tin plating layer is formed on the surface of the tin tin layer 15 in accordance with the electromineral method, non-electrolysis The electroplating method selected from the electric clock, the factory's and the strip plating method forms a silver layer composed of silver or a silver alloy (the silver layer forming step s, 5) and then the tin layer. The surface of the 15 is formed with a silver layer, and the crucible is adjusted to a temperature above the HTC (10) C in a warm water bath, and then to 20 seconds, so that the silver layer of silver and "Temple tin particles" The formation of the reaction shape and the shape of the two Κ 〇 j j ' 形成 形成 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 银 θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ θ Silver-tin alloying is carried out in the form of a silver layer. The tin-tin conductive material 11 of the second embodiment thus formed is produced by the disk front crystal. The silver-tin alloy layer 16' suppresses tin. Implementing a tin-plated conductive material of the form, but the present invention does not deviate from the technology of the present invention by 320516 19 200923142 'month and $5& In the case of the above-mentioned range, the nickel-plated layer (the first embodiment) and the copper-bearing layer (the second embodiment) are formed. However, the present invention is not limited thereto, and a clock tin layer may be directly formed on the surface of the substrate. Further, the above description also exemplifies a substrate made of a metal conductive material, but the present invention is not limited thereto. It can be composed of a material coated with a non-metallic material and having conductivity. Specifically, for example, Cu-Ni-"Ling P-based copper alloy-based two-line copper alloy, sus, Fe_42 nickel alloy and other metal conductive surface "Non-bonded film or surface coating of semiconductor, glass and ceramic materials, non-metallic materials obtained from '5 vv electrical metal film." The whole, and ι'η form a step in the silver-tin alloy layer. It is indicated that the impregnation is in the temperature of the temperature: more than C is not reached (10). In the warm water bath for more than 2 seconds, Dan and Mingya are not limited to this, you can also use the means other than warm water bath, in the tin layer The surface is formed with silver sound #能_ holding 2 seconds two degrees above the irc, but the work will be silver The silver-tin particles are formed. The U-Ming Ming' is formed by an electric ore or an electroless electric clock. However, the present invention is not limited thereto, and may be used as a shovel anchor. Hot Dip) The method can be reflowed after forming the tin layer. - Also, as shown in Figure 6, the silver layer is formed without reflow treatment. It can be treated but it can be formed into a tin-plated layer and then reflowed. The above-mentioned § brothers do not ride the tin conductive village material 11 for heat treatment, but according to its ^ 20 320516 200923142 The temperature of the melting (for example, 12 Torr to 2 Torr (rc) is heat-treated. In the mode diagram of the present embodiment, a tin layer and a silver alloy layer are formed on the surface of the substrate - side. However, the present invention is not limited thereto, and may be formed on the entire substrate. Tin plating layer and silver-tin alloy layer. In the mode diagram of this embodiment, the formation of the tin-plated layer and the silver-tin alloy layer on the entire surface of the substrate is also described. However, the present invention is not limited thereto, and a tin-plated layer and silver may be partially formed. _ tin alloy layer. (Embodiment 1) The following describes the verification of the effectiveness of the present invention.

First, as an example of the March electric boat using the Ni/Cu/Sn according to the first embodiment, W _· 〇% Ζη., Κ G/0, and Sn are represented as high-strength terminal materials. G. 5%, Si: G. 5% of the plate thickness of 0. 25 _ The copper plate of the copper plate is the base material 'forming a nickel layer, a copper layer, a tin layer, and then treating it, then on the layer A white silver layer was formed, and a test piece was produced by forming a silver-tin alloy layer in a warm water of 4 Gt. In the case of the example: a test piece in which no silver-tin alloy layer was formed. These test pieces were used to evaluate their resistance to whisker formation and heat resistance. The measurement of the generation of whiskers is performed by the external indenter method = the influence of external stress is investigated. The natural placement method is used. - The influence of the internal stress of the coating is based on the external indenter method. At the end, the load is 300 g at the end, and the acceleration is tested at room temperature for 12 hours. 21 320516 200923142 The state of generation of tin whiskers was confirmed by an electron microscope (SEM), and the whisker formation property was evaluated by the tin whisker length at the longest tin whisker. After the natural placement method was allowed to stand in the natural environment for more than 6 months, the state of the tin whiskers was confirmed by a sub-microscope (SEM), and the whisker formation property was evaluated by the tin whisker length at the most Z of the tin whiskers. ' The test for heat resistance is 16 (rcxl 000 hours, 1δ (Γ (: χΐ〇〇〇 hour heating test, and before and after the heating test according to JIS-C-5402, 蕤 from 4妓早鎞+ The beer is blocked by a 4-head contact resistance tester (f113-AU made by Yamazaki Seiko). The sliding load (1_) is used to measure the load change from 〇 to g - electrical contact resistance. II to 4 and comparison The evaluation results of the composition of the electric chain layer and the anti-crystallization of Examples 1 and 2 are shown in Table 1. In the evaluation of the anti-parent generation sweat, the evaluation results of the natural placement method are shown in the electrons of the test piece after electroplating in Example 1. The Μ Μ Β Β Β Β Β 。 。 。 - - - - - - - - - -

320516 22 200923142 As shown in Fig. 7A and Fig. 7B, it was confirmed that a silver-tin alloy layer composed of fine particles of 1 Å to 50 nm or discontinuous sheets was formed on the surface of the tin plating layer. The silver-tin particles were determined to be AgsSn intermetallic compounds as measured by XRD (X-ray diffraction, x-ray diffraction), and were confirmed to have higher hardness and corrosion resistance than pure tin. It was also confirmed that the silver-tin oxide layer was not completely dispersed in the tin layer even if it was left at room temperature for a long period of time (for more than half a year), and was extremely stable. Thus, it was confirmed that the manufacturing method according to the present invention can produce a silver-tin alloy layer formed by agglomerating silver-tin particles on the surface layer portion of the mineral tin layer in a cross section along the lamination direction of the substrate and the tin-tin layer. Tin-plated conductive material. An example of the condition of whisker due to external stress, in the figure, the result of observing the electric dream η s s sem of the silver-tin alloy layer formed on the surface is not evaluated. In the evaluation of the electricity of Comparative Example 2, which was not formed into a silver-tin alloy layer

Observe the results. The surface of the present invention accounts for the female & sputum, two SEM, and the core-silver-tin alloy layer test, and does not cause a short circuit problem in the 7 /矣w m (10) needle (four) whiskers. Relatively in the general side, the money is more than $9 of the tin-plated layer (Comparative Example 2), which produces Huizhou needle-shaped impotence. In addition, the longest tin whisker has a short length of about 7 _, and in the comparative example, the inventive example 4 is more than π, and the Τ grows to a length of 62 um, so the invention can be seen. Extremely tin day..L effectively suppresses the generation of tin whiskers. As shown in the examples 1 to 4 in which silver-tin alloy reeds are formed, the longest length of tin whiskers is in accordance with the silver tin: the invention is less and slightly increased 'but the thickness of the short tin-gold layer is short. Reduce the fight. Another ancient hard 1 〇 _, while suppressing the tin crystal hair too much surface, in the formation of the silver-kick alloy layer of the comparative example 12 = 320516 23 200923142. Very long 22 _, 62 known to have problems with whiskers. In particular, from the present invention, the longest whisker length of the first example and the comparative example 1, the inventive example 4 and the comparative example 2, it was confirmed that the effect of suppressing the generation of whiskers was further improved in the case where the tin plating layer was thick. In terms of heat resistance, in the inventive examples j to 4, it was confirmed that the electrical contact resistance value of the silver-tin alloy layer formed on the surface was the same after the electroplating (initial), and was the same as the ruthenium examples 1, 2 However, there is a big difference in electrical conductivity after the heating test. In particular, in the case of the present invention in which a silver-tin alloy layer is formed on the surface, the electrical contact resistance value decreases as the thickness of the silver-tin alloy layer increases, that is, the heating test for 1000 hours is impossible. It was confirmed that it was larger than the initial value η' human L had excellent heat resistance. On the other hand, in the comparative example 2 of the unformed=connected layer, after the chest-hour heating test, the electric resistance value was greatly increased from the initial value, so that it was found that there was no heat resistance. At the same time, it is preferable to compare the thickness of the first embodiment of the present invention with the inventive example/, the tin layer to have a high heat resistance. Tin plating (Example 2) As the target of the i-heart 4 of the above-described i-th embodiment, it is used as a high-conductivity end θ ^ ρ.η Πης〇/, which is representative of ore-forming nickel. 々* ·4· steel alloy plate is the base material, the tin layer is 20%: tr money tin layer, and after reflow treatment, it is then immersed in the warm water for 10 seconds to make: kick Test piece of alloy layer. Use these tests = two non-formability and heat resistance. The evaluation method is as in the example! The piece is estimated to have its anti- whisker generation 320516 24 200923142 The present invention examples 5 to 7 盥 鲂 q q 士 a The composition of the plating layer in the 曰媢4 A we / the ninth example and the evaluation results of the resistance to whisker formation and heat resistance are shown in Table 2 [Table 2] No. Thickness Example 5 of the invention 0.4 Example 6 of the invention 0.4 Inventive Example 7 0.4 Comparative Example 3 0.4 Mineral layer β\Ά Forged copper layer βία Back bell tin layer flow silver layer whisker contact ^5ηΩ 50gf)|Long length Um 160°C xlOOOOh 180°C xlOOOh 0.3

In terms of its whisker resistance, the silver-tin alloy case "7" is formed and the silver-tin alloy layer is not formed. Comparative example 3 is more than -2::: must be - and is prominent, so it is known Inhibition of tin whisker generation = the aspect of the invention, the formation of silver on the surface, the alloy layer of the invention 歹 1 Even in the case of a long-time heating test, the average value of the method is greatly increased, so it is known that there is excellent = two In Comparative Example 3 of the silver-tin alloy layer, it was confirmed that the electrical contact resistance was greatly increased after the addendum 5 test. (Example 3) As the use of the aforementioned third 彳 every A 夕 杏 ^, w brother 1 The three-layer plating of Nl/Cu/Sn is a base material of Cu-Zn alloy with a thickness of 0.64 mm, which is a base material, forming a mineral nickel layer, a copper ore layer, and a tin-iron. Layer, and 320516 25 200923142. After the reflow treatment, a silver plating layer is formed on the tin-plated crucible, the four-winner, the meditation, and the main ϊ us, and at 40 ° C - / again / bei, buckle, The silver-tin alloy layer was formed and then y was used as the second test: in the comparative example t, no silver was formed: again = example 2. (4) Productivity and heat resistance. Evaluation method The evaluation results of the composition of the electric forging layer of +8 and the anti-sparitability and heat resistance of Example 8 and Comparative Example 4 of the present invention are shown in Table 3 [Table 3].

Copper 煳 mirror layer 4 PG example 5 2 0.80.8 reflow treatment + + no layer 艮 plating A 04 whisker most electrical contact resistance (ιηΩ 50sf) long length initial 160 ° C 180 ° C jum xlOOOOh xlOOOh 15 (0) 0.85 2.56 4.15 83(0) 0.89 20 or more and 20 or more are formed with silver-tin alloy, which is the case of 8th, which is more effective than the comparative example 4 which does not form silver-tin < gold layer. growing up. Into the eight: heat resistance aspect in the case of the unreformed reflow mirror tin... ^ In the case of a long-time heating test, it is confirmed that the film is electrically formed, and the electrical contact resistance is significantly increased. In the case of the invention δ in which the door force has a silver-tin alloy layer, even if the long-day:inter-heat test is performed, 7fR Af r-th -ί-τ> l- recognizes that the (four) touch resistance is greatly increased, The situation of stone _, . and tin θ, can also be used to improve long-term suffocation. (Example 4), an example of a two-layer key of a person who is a 1 Cu/Sn, as @320516 26 200923142 'The representative of the strength terminal material contains 0 53⁄4, .ηH Ζη: 1. 〇% , Sik . . . ^ The thickness of 0.25 mm copper alloy is extended from the copper layer, the mineral tin layer, and the back,,, and the $ plate as the substrate, forming a layer of gold and silver, and the temperature of the boots Immerse in water for IG seconds, making it /=====ΤΛ. In the comparative example, silver is not formed, and the alloy is slaughtered. The evaluation of the anti-whisker generation day and neck is evaluated by using the evaluation system of the above-mentioned examples 1 to 3, and the evaluation system is in the battle. (4). : The surface and cross section of the test piece of the present invention were observed by an electron microscope (FE-SEM). The results of the evaluation of the anti-crystal whisker and heat resistance of the electric ore layers in the inventive examples 9 to η and the comparative example 5 are shown in Table 4. - [Table 4] '----- Substrate thickness Nickel plating μπί Shovel layer μπί Reflow at the point μ® Whisker longest length μιη Electrical contact resistance (πιΩ 50gf) mm ^77 Jt Η 160°C 180 °C Inventive Example 0.25 *--:-- 0.3 1.1 ———_ ------ --~~-__„ xl20h xl20h Example of the invention + 0.01 —---- 7(0) 0. 77 1.21 1.31 10 0.25 0.3 1.1 + 〇. 06 5(0) —'-- Π 71 1.14 1.16 Example of the invention ------ 0.25 0 95 0.3 0 3 — ----—-- vJ. 1 1 1.1 1 1 + 4- 〇. 02 10(0) 0. 76 1.15 1.13 ------ 丄 "丄_U9 13.11 18.28

'Compared to the fact that silver was not formed _ at the same time, it was confirmed that the growth of whiskers was suppressed even in Comparative Example 5 of the inventive Example 9 to U-kick alloy layer in which the silver-tin alloy layer was formed. 320516 27 200923142 ‘Two layers of Cu/Sn reflow tin plating' also inhibits the generation of tin whiskers. Flag tin aspect #not formed as a general two-layer reflow tin plating =-: two: layer comparison example 5 'due to the fact that copper is gradually diffused from the material, and the crucible is heated during the short period of I20 small crucible 'It is also true that the electrical contact resistance is obviously two, s + g + a, 4 rises, and the conductivity is significantly deteriorated. On the other hand, in the example of the present invention in which the silver-tin alloy layer was formed, it was not confirmed that the electrical contact resistance was greatly increased even when the same addition of the alkali metal was performed, and therefore it was confirmed that the heat resistance was remarkably improved. The figure shows the surface of the sample of the present invention (4) after the heating test of the 12 〇 3 shoud, and the section of the Τ Τ Τ 。 为其. From the surface of - ρ 之 之 ' ' ' ' 锡 锡 锡 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因 ' ' ' ' ' ' ' ' ' ' ..., the moon is sure, tin is changed from Cu6Sn5 to Cu3Sn through copper-tin alloying, and finally it is not affected by sodium sister eight. 70 Wang Hao is CU3Sn, but Ag3Sn block is also affected by copper-tin alloying. Spit A 0, which is directly in the surface layer and is stable in the island. The oxidation resistance is stronger than that of the copper-tin alloy. Therefore, it is important to reduce the conductivity of the surface of the material during the high temperature. That is, ^ = lower 'tin The composition is completely changed to Sn〇2/Cu3Sn, and there is a channel Γ/particle on the surface, and it can be safely electrically contacted with the opposite side. Therefore, Example 5) is used as a two-layer plating using Cu/Sn. The sound #/ , terminal 桠 - another yoke example, as a representative of the high conductive material # contains Mg: 〇. 7%, p of the copper alloy plate as the substrate, re-service copper layer: fine = 320516 200923142 After the treatment, 'the forged silver layer was formed on the tin-plated layer, and then -crushed for 10 seconds' to form a silver-tin alloy layer to make a test: dip in warm water. The effects of the tin-thickness film thickness were examined, and the thin ruthenium was set. Further, in the case of Comparative Example 6, no silver-tin-yield was formed: (4) sheets. ^ Add a slice of the mineral layer formed on the tin layer. The test piece of the residual silver plating layer on the gold layer was compared. Silver-tin composites were evaluated using these tests to determine their anti-spinning method as in Example 4. And 纟χί?η and heat resistance. Evaluation structure. The crystallization of these test pieces was evaluated by the coffee maker in the composition of 曰=months 12 to U and the plating layers of the comparative examples 6 and 7; 5 the results of the evaluation of the anti-study and the evaluation of the (4) nature and the results thereof As shown in Figure 1 of Figure 1. XRD test [Table 5] Thickness ------- Money copper layer cell μιπ Inventive example 0.6 μτ [Inventive Example 3 0.6 0.3 Inventive Example 4 0.6 0.3 jjj ΎΓ' ΎΓ' "tbSrT" ΤΓ' Zhong Xi Layer μιπ reflux treatment of silver layer μιπ 0.04

19(0)0.3 Tc〇y pm wmM. (Initial 160°C xl20h '- 180°C xl20h 0. 77 1.37 ----- 4.80 0.78 1.20 3.79 0. 78 1.59 --- - 5.98 0. 79 18.49 20 In the above |jU5 20 or more and 20 or more, the ratios of the inventive examples 12 to 14 and the comparative examples are silver, and the alloy layer 6 can suppress the whisker formation 320516 29 200923142 - long. In the case where the tin plating layer is thin, it is possible to suppress tin. In the heat resistance, the comparative example β 2 :::: tin layer in which the silver-tin alloy layer is not formed is completely changed to copper_tin after a short-time heating test. Alloy: • Deterioration ==Electrification: farther than the initial rise, and confirmed that its conductivity is significant on the one hand, in the case of the invention of the present invention in which the silver-tin alloy layer is formed, even if the tin-plated layer is completely changed to copper-tin alloy , still I method J = rise °, that is, the present invention can improve the _ sex even when the tin layer is etched, and the f 10 figure shows that the invention is made in 2 phantom 4 and comparative example 7, fixed sound The result of analysis by x-ray diffraction. For the Γ/1: crystal structure, the scale of the vertical axis intensity is matched with -= silver gossip wave degree adjustment. In the present invention examples 12 to 1 Nothing is observed in 4: silver metal peaks. Therefore, it can be seen that the diffusion rate and reactivity of the two r gp tin metal in the form of Ag3sn intermetallic compound are high, so when the key step is completed, it has completely changed into silver-tin. Alloy. Another 'in Comparative Example 7 because the mineral silver layer is very thick, under normal conditions, Yifa Wang silver-tin alloying, and confirmed that the surface of the tin tin layer remains pure silver metal layer. As shown in Table 5 In Comparative Example 7 in which the thickness of the silver plating layer was the effect of the tin whisker, the silver of the surface was vulcanized or oxidized in the heat resistance test, and it was confirmed that the electrical contact resistance was deteriorated. (Example 6) = Using a single layer bond The tin layer embodiment is made of a high-strength terminal material and contains a sheet thickness of Ni.2 0g/, 7 ι. (10) The copper joint i board is used as a substrate to form a tin-plated layer, and is carried out 320516 200923142 • After the reflow treatment, Ψ ^ ^ 1 π ίί ^ is now formed on the tin-plated layer, and the silver layer is forged and then collapsed in 4 (the warm water of TC) to form silver-tin in the case of A test piece was prepared from the 丄 丄 σ layer. In the case of the pregnancy, no silver-tin ya-a was formed. A test piece of the layer. The test piece was used to evaluate its k whisker formation property and resistance to 埶. 5 / The test method was as in Example 4, Example 15 of the present invention and Comparative Example 8 η±^η^ ^ A The composition of the electric money layer and its resistance to crystal [Table 6]

The evaluation results of the enthalpy and heat resistance are shown in Table 6. f Gold: 8 = layer of the invention Example 15' is more resistant to the growth of whiskers than Comparative Example 8 in which the silver-tin alloy layer is not formed. After the present invention in which the silver-tin alloy layer was formed, it was not confirmed that the electrical contact resistance was greatly increased n = the comparative example of the hot-working tin alloy layer, and after the heating test, it was confirmed by the copper expansion of 4 The electrical contact resistance increases significantly. Soil (Example 7) The average surface hardness of each electric ore sample was determined using a microhardness tester (Shimadzu: win w low weight measurement of the test examples 1 to 15 and comparative examples! to 8). 'Inventive example of the formation of a silver-tin alloy layer formed by a heart-shaped embodiment ^ 320516 31 200923142 • 15 is about 70 Hv, which is about 4 在 in the form of your sister into the eighth a. $成银- Comparative example of tin η layer! To 8 - character ^ 占真5 endure The surface of the tin tin layer is composed of hard Ag3Sn intermetallicization: 40% silver-tin alloy layer, with the effect of surface hardening of the tin tin layer In the south hardness silver, the alloy layer is pressed into the surface of the iron-tin layer, thereby suppressing the generation of tin whiskers and the growth of dots, π. A, and at the same time, the tin-forming material of the present invention having the silver-tin δ gold layer is The terminal, the ^ _ ^ Gan 4勹 and the shape of the moon, due to the surface hardening can make the insertion resistance less, so there is improvement in the cooperation (Example 8) 2 As shown in the figure shown in the figure, after the substrate is processed into the predetermined shape of the part, it is re-entered: All = Silver is not formed by applying reflow treatment to the tin-plated layer - I::fT confirms that the effectiveness of the present invention is indeed represented by the lead frame material, and the copper alloy containing mZn:0.m, P.0.li has a thickness of 0.125 _ On the tin-plated layer, a 'shaped copper layer, a m-heart is formed into a silver layer, and a silver and an alloy layer are formed in a warm water of 4 〇t to produce a test piece. The comparative example" does not form silver, and the alloy layer is formed. Test piece. The thickness of the tin layer in j, in order to make the difference in whisker more obvious, and set the 疋 is known not to carry out reflow treatment, the range (2 to 4 μπ within 2 β 曰U will take intense Comparative Example 10 of film thickness, on tin-plated reed: into: silver-tin particles in a dispersed state, after the silver layer was cut, and then the temperature of the money tin layer 320516 32 200923142 was (10) t χ 8 seconds) At the reflow point, these test pieces were used to evaluate the resistance to whisker formation and _ sex into 4 pieces. The evaluation method of the crystal 贞 ,, in order to investigate the I of the plating layer, placed in a natural placement method for 6 months. The heat resistance evaluation method is as follows: ^, +, 夕+, 仃 electron microscopic view _ under the heating test method. At the same time by == :=^ Surface and cross-section, and comparative examples = anti-must formation:: to 18 and the composition of the electroplated layers of Comparative Examples 9 and 10 and the results are shown in Table 7. Observe the results of the present invention, as shown in Figure 11A. Show, the observation section is wide 2:: As shown in the figure, the results of the section of Comparative Example 1 are observed as the first, - the mouth is as shown in the 13th and 13th, and the comparative example 9 is set to 2; The result of the surface is as shown in the l3c and 帛1汕:, the thickness of the substrate, the copper layer, the wrought tin layer, ------: ΜΜ, the whisker, the most knee, the day, the μΐ, the μπί μπί, the long length Ππί Initial 160°C x12〇h 180°C Of\L· Example 6 0.125 0.3 2.6 0.03 12(0) —~— 0.43 0.72 χΐό〇η 0.75 Umbrella goods example 7 士 nominal ΡΡΪ 0.125 0.3 2.6 0.05 (0) 0.41 0.66 -___ 0. 59 mouths Example 8 Comparative Example 9 0.125 0.125 0.3 0 3 2.6 2 6 0.01 (0) 〇. 46 ---- 0.77 0.88 Compare ST 10 —---- 0.125 0.3 2.6 0.09 84( 68) 26(0) 〇. 56 0.49 r~X70~~ 9.47 |T28~ ~-- 13.12 ----1 320516 33 200923142 As shown in Figure 11A and Figure 11β, it can be confirmed that it is crystallized from coarse tin = The surface of the tin layer formed Coated with silver - tin particles. Special: Nissan = silver _ tin alloy layer, after more than two months and then observe its profile 22nd part of the raw part of the condensation and diffusion to the inside of the tin layer diffusion phenomenon, + sexual and physical stability. _, it was confirmed that copper and tin diffusion occurred at room temperature, and a copper-tin intermetallic compound was partially formed. As a comparison, Figure 12 shows a photograph of the section of Comparative Example 1 in the case of the previous mine. It can be seen that after the silver plating is carried out: the case of returning to j is the silver-tin particles originally formed on the surface of the silver layer, which is promoted by the two 'dishes, and the m is scattered toward the tinned layer. On the surface of the tin plating layer, almost no silver-tin particles exist. κ An example of the situation in which whiskers are generated by the internal stress of the electric clock layer. The 13th and 帛13β diagrams show the natural placement of the sample of the inventive example 16 as shown in Fig. 13C and *13D. Example 9 The state of the surface after 6 months of natural placement. It is generally known that a tin plating layer having a film thickness of 2 to 4 μm which is not reflowed, due to the internal stress of the plating layer, causes tin whiskers to be generated only after 2 to 3 Å. Therefore, in the case of Comparative Example 9 in which the silver-tin alloy layer was not formed on the surface of the tin-plated layer, it was confirmed that the film was formed by a large amount of needle-shaped tin whiskers, and the growth was long enough to be about Μ 叩. In contrast, the surface of the money tin layer is formed with silver, and the alloy layer is in the form of the case: in the case of Example 16, even after a period of 6 months, the surface condition, such as the initial state after the electric ore, is almost impossible to confirm. Tin whiskers are produced, which are confirmed to have excellent whisker formation resistance. Table 7 shows the results of evaluation of the productivity and heat resistance of Examples 16 to 18 and Comparative Examples 9 and 1 of the present invention, which are resistant to crystal 320516 34 200923142. The inventive examples 16 to 1δ are formed on the surface of the eight tin-plated layer to form a silver-tin alloy layer, and after the heat is placed for 6 months, the lifted ball s bears the tin whisker generation, and it is confirmed that there is ~ "Inhibition of the effect of whisker whiskers. In terms of heat resistance, the tin-stained car ^, the surface of the temple layer formed with silver-tin alloy layer of the native example 16 to 18, the IK s + in the twist test On the other hand, in Comparative Example 9 in which a silver-tin alloy layer was formed in Fushun, it was confirmed that the electrical contact resistance was greatly increased after the heating test. In Comparative Example 1G, since the tin whiskers were not naturally generated due to the release of the stress of the electro-recording, since the entire reflow treatment was performed, the copper-tin alloying was promoted, and the electrical contact resistance after the heating test was confirmed. The rise (deterioration of conductivity) is improved. (Embodiment 9) As an example of a three-layer electric clock using Ni/Cu/Sn, as a representative of the lead frame material, Fe: 2.4%, ζ .η: G i3%, p·· 〇^ The thickness of the plate is 0.15, and the copper alloy plate is used as the substrate to form a nickel-plated layer and a plated steel. , tin plating layer, silver plating layer, and dipping in 4 (rc of warm water for 1 〇 second, so that a silver-tin alloy layer should be formed to prepare a test piece. In Comparative Example 11, no silver-tin alloy layer was formed. Test pieces. The test pieces were used to evaluate their whisker formation resistance and heat resistance. The heat resistance evaluation method was as in Examples 1 to 3, and the evaluation method of the whisker resistance was as in Example 7. ^ Silver was formed on the surface of the tin plating layer. - The results of the evaluation of the composition of the present invention and the composition of the electroplated layer of the repellent 11 and its resistance to whisker formation and heat resistance are shown in Table 8. 320516 35 200923142 [Table 8] T---丨丨 — Substrate thickness 1 ------ Mineral layer copper plating layer | Tin tin layer silver plating layer 1 whisker longest length μιη ——-- Contact resistance Ο π Ω 50gf) The invention ^ leg leg μ ~ ~ ---- μιη μηι m Initial 160°C vi onvi 180°C Example 19 Comparative Example 0.15 0.3 0.3 2.6 0.03 (0) 〇. 45 Αΐώυη 1.23 xiZUn 1.76 11 0.15 0.3 0.3 - 2.6 — (76) ----- -— _ 0.61 6. 67 8.13 In the case of the invention, in the case of the alloy 2, the tin-tin alloy layer of the invention was found to have no tin whisker in the form of a tummy, and no silver-tin was formed. The comparison of the layers 乂^ in the surface state, the tin (4) also becomes larger. The U1 towel is placed at room temperature in the case of the present invention in which the silver-tin alloy layer is formed, that is, the case of the small corona heating test. In addition, the electric contact resistance has risen sharply. In the comparative example where the silver-tin alloy layer is not formed, the electrical contact resistance can be found to rise sharply after the heating test. (Embodiment 10) r As a material for the use of Cu/Sn 2 layers of electricity, the material represented by Cr:0.w'Sn: "%, Zn::::= 0. 127 mm of copper Full plate; y ^ plate 厗 silver layer, and immersed in 4 (TC warm water 1 〇 and 甘 甘 甘 镀 、 、 、 镀 镀 、 、 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘 甘In the comparative example 12, an invisible test piece was prepared. Using these test pieces, the hardness resistance and the anti-day of the gold layer were evaluated, and the formation and heat resistance at the point and day of the day were evaluated. The method is as in Example 7. The composition of the inventive example 2 () and the comparative example 丨 2 of the present invention for forming a silver-tin alloy layer 320516 36 200923142 The composition of the layer and the evaluation results of the resistance to whisker formation and heat resistance are shown in Table g. 7JT 0 [Table 9] Substrate thick steel layer Iron tin layer Forged whiskers The longest length μπι Touch resistance (πιΩ 50gf) Too much degree Mm μπι μπί Initial 160°C xl20h 180°C x120h Set % Example 20 0.15 0.5 2.6 0. 03 (〇) 0. 52 1.11 1.54 Factory. Right 1 !! J 12 0.15 0.5 2.6 - (41) 0.65 4.44 6.59 - In the inventive example 20 in which a silver-tin alloy layer is formed on the surface of the tin plating layer, Placed in the coffee In the state of comparison, in the case of the silver-tin alloy layer, the tin whisker is enlarged even if it is placed at room temperature, and the tin whisker becomes large. In the case of the alloy layer of the invention of Example 20, even in the case of adding 120 τ to the case of L, it was not confirmed that the electrical contact resistance was large in the comparative example 12 in which the silver-tin alloy layer was not formed, and the heating test was possible. It was found that the electrical contact resistance was greatly increased. (Example 11) An example of electroplating using a two-layer plating of Cu/Sn, which is represented by a lead frame = Ni: 42% of a plate thickness 〇.127 _ of an iron alloy Plate water: A copper plating layer, a tin plating layer, a silver plating layer is formed, and a test piece is formed by forming a silver-tin alloy layer at a temperature of 40 ° / / / for 10 seconds. • H': In the example, a test piece which does not form a silver-tin alloy layer is produced. Using these sheets, it is estimated that it is resistant to whisker formation and heat resistance. The heat and resistance to whiskers 37 320516 200923142 § § estimation method as implemented Example 7. The evaluation results of the electroformability and heat resistance of Examples 21 and Comparative Example 13 of the present invention are as shown in the table and their anti-spinning agents [Table 10] Initial indication: Electrical contact resistance 160°C x120h 180°C xl20h 1.55 ~ΤΓ29~ 1.89 20 or more substrate thickness ram mineral copper layer μιη mineral tin layer μιη iron silver layer Mm invention example 21 0.25 0.5 2.6 〇. 03 Comparative Example 13 h 0.25 0.5 2.6 ---- The longest length of whiskers. m In the comparative example in which no silver-tin alloy layer was formed on the surface of the tin layer, there was a large expansion (four) number in the iron alloy substrate and the layer. Confirmation; Needle-shaped tin whiskers grow. In contrast, in the case 21 of the invention in which the tin layer i°-Kun, the Japanese coat has a silver-tin/layer, even after 6 months, the mediator + ' ^ ^ ^ a ^ Gu Yue ' can also It was confirmed that small tin whiskers were confirmed, but it was confirmed that the whisker formation resistance was improved. In terms of heat resistance, after the heating test of the invention No. 21 in which silver was formed on the surface of the tin-tin layer, electrical contact was not confirmed, and the resistance was greatly increased. On the other hand, in the comparative U in which the silver-tin alloy layer was not formed, it was confirmed that the electrical contact resistance was greatly increased after the heating test. (Embodiment 12) The following description evaluates the results of welding and the degree of durability of the tin-plated conductive material of the present invention. The evaluation of the wettability of the solder was carried out in accordance with JIS-C_0050 using a dynamic wetness measuring machine (manufactured by RHESCA Co., LTD., WET-6000) and evaluated according to Wetting Balance Test 320516 38 200923142. Specifically, after immersing in the rosin flux for 2 seconds, it is immersed to a depth of 2 mm for 10 seconds at a speed of 10 mm/sec in a fresh tank at a predetermined temperature, and then measured for maximum wetting stress and wetting. The time when the stress is 0 (zero crossing time). The shorter the zero crossing time, the better the solder wettability. Let's assume that the current Sn-Ph糸.what is used; 4·Xi/Fat Tt, “In the case of 糸红科, it is indicated that the solder bath temperature is set to be body and 使用 using eutectic solder (eutectic dot fiber) Estimate the temperature of 23 (the result of the evaluation of TC.... 2 province t the first implementation of the above (4) nickel plated Cu / Su cu-Ni-Si Ren Quan Xi / factory as the representative of the South strength terminal material Sl 5 gold plate thickness 0.25 _ copper alloy 柘 材料 ru ru ru ru ru ru 及 及 及 及 及 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 电 Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu ώ, the plate thickness of 0.4〇mm copper alloy shovel tin π, and, - 曰 tin plating layer, and after reflow treatment, and then form the same film thickness on the tin plating layer lt; The water is immersed for 10 seconds, and the silver layer of the yttrium bond is made at 4 (the temperature of the TC is made in /, / (the test piece is made of tin alloy layer. The strip is cut to a width of 10 nun, the test of 曰The test piece was immersed in the solder bath with zero time and maximum wetness. The measurement results are shown in Table 11. ", and then the average value was measured. The measurement was 320516 39 200923142 [ Table 11] Material thickness (mm) Inventive Example 22 Cu-Ni-Si 0.25 Inventive Example 23 Cii-Mg-P 0.4 Comparative Example 4 Cu-Ni-Si 0.25 Comparative Example 5 Cu-Mg-P 0.4 • Surface J Layer μπι tin layer μιη 1.2 0.3

Reflow treatment, plating, μπι, average zero crossing time, sec, average maximum wetting stress, mN 0. 04 0.48 6. 60 0.04 0.69 6.29 _ ~ 0.89 6.28 uo 6.15 Example 22, particle composition of the right-out layer formed on the surface of the tin layer. For comparison, confirm the comparison example of the average zero point and the time interval = layer. "See the value of the wettability" π: = (melting point 峨) particle composition of the silver layer ==,,, tin (hyun point 232C The time for integration has grown. This is similar to the reaction of the silver 'tin (four) material. Tin is relatively flat compared to Comparative Example 1/2; the thickness of the tin layer is doubled. In contrast, in Example 22 of the thickness of the tin-plated layer and the comparative gold layer, the silver-tin-bonding of Comparative Example 14 was "doubled." Thus, it can be seen that for the solder _ shadow, the layer-to-layer tin plating The film thickness is small. '艮~锡合(Example 13) It is assumed that the use of the error-free zinc tin with a small environmental burden is described using 320516 40 200923142 , Sn-3% Αε^~〇ς〇/ ^ . Evaluate 11 materials ((4) 2_, fresh trough set temperature in order to obtain such as Sn, pb 曰 (4), in the case of using error-free solder, for Sain activity and /, the degree of wetness of the day (zero point and time) ), preparation of Cao temperature::activatlng nux) pre-treatment ^ deliberate to 250 c, in this example, is the front and rear of the wetness of the front, by the results of the pre-test:, _] -=. The evaluation condition of the solder wettability is the same as that of the embodiment 12. ^ is a CU-Mg~P which is a representative of the high-conductivity terminal material by using the Ni/Cu/Sn 3-layer electric ore of the above-mentioned embodiment! Alloy: "·40_ of the copper alloy plate as the substrate, forming a mineral nickel layer, a copper layer, a layer, and after reflow treatment, and then on the tin plating layer A test layer was formed by forming a silver layer of 膜 〇 δ _ film thickness and dipping it in warm water of 45 t for 1 sec second to form a silver-tin alloy layer. The evaluation of solder wetness is the same as the actual one. The evaluation results are shown in the table. ———————- Comparative Example 1 fi ------ ϊ ϊ TT=? violent thickness coffee 1 π λ nickel plating layer μιη mineral copper layer μιη tin plating layer μπι reflow treatment μιη average zero crossing time sec ^ Inventive Example U. 4 0· 3 0.2 1.0 -------- —L__ —---- 3.95 24 — Tai Lu Day only warehouse! 1 0.4 0.3 0.2 1.0 + 0. 01 3. 60 t Xi 1J 0.4 —------- _ 0.3 0.2 1.0 + 0. 02 3.10 'aj 26 '^rz--- BH -/sil 0.4 I· 0.3 0.2 1.0 + 0. 04 2.85 27 ~~ Tai Kung B-day, ϊ 0.4 0.3 0.2 1.0 + 0.06 2. 88 0.4 0.3 0.2 1.0 + 0. 08 2.93 320516 41 200923142 Due to the lead-free soldering, the average zero point and the time of the whole crystal fresh material are high, the composition of the silver - kick all + = ...long, but the surface formed by the silver-tin micro-time average is less than the average zero point of the unwrapped 27 and the ratio of the _ sexual layer of the error-free solder is short, so it is known, so its suitability Preferably, the copper solder is the same element tin =:=, the possibility of the silver-tin alloy layer of the present invention is generally reflowed (four) is the average of the low solder temperature, and the invention has the silver-tin alloy. Layer of tinned conductive material Parent lines and short time of the ore with the thickness of the silver layer, initially a substantial reduction bubble L 'square Π A 25 λ λ r r. Μιη about the minimum value and stability. This is considered to be caused by the eutectic point composition (Uat% Ag-232 °C) of the I (four) layer and the Sn-3% Ag_G solder joint age close to the silver tin crystal ruthenium. (Example 14) I: "In order to verify the theory of the tin-resistant whisker-forming mechanism of the tin-plated conductive material of the present invention", the stress of the tin-plated layer before and after the silver-mine is measured and analyzed. The results are described below. The measurement was performed by a micro-focus ray ray stress measuring device (manufactured by Rigaku Corporation, PspC/MSF, 40 kV/30 mA, CrKa). The peak intensity of each predicted tin crystal surface was calculated by the S i η2 Φ method. The stress of the film. For the determination of the tin crystal surface of the tin plating layer for stress calculation, according to the crystal state of tin before and after the heat treatment, the tin (312) surface is selected in the reflow_tin plating, and the tin (440) is selected in the general tin plating. 42 320516 200923142 As a substrate using a reflow-tin plating "alloy thickness of 0.64 = H, with C_-p alloy and layer, copper plating layer, each forming a film thickness i 〇 ~ plate as a substrate" to form nickel plating Tin layer, after reflow treatment, _, h5 _, 2.G _ coating thickness (10) ^ (four) ^ ^ ' and then formed on each (four) tin layer, © v v, sub, main m • (10) mineral layer 'And at 40 ΐ :::, to form a silver-tin alloy layer to make a test tin film test. Each is shown. “The stress grading results are shown in Table 13 and Figure 15 [Table 13]

In Comparative Examples 17-19, since the small tensile stress (positive value) was released due to the swelling of the tin film, the thickness of the film was changed to become the surface, and it was confirmed that the core buckle of the present invention in which the silver-tin alloy layer was formed was confirmed. Both have a tensile stress greater than that of the comparison of the examples of the 17th to the 19th, and the tin/silver effect is greater than the ratio of 320516 43 200923142 IS: two t: force layer. The tensile stress is presumed to be caused by the growth of silver precipitated in plating ·=: or by alloying of silver (4) into a plane ^. This tensile stress initially decreases as the film thickness increases to 0·^"1 or more as the film thickness of the silver-tin alloy layer increases. It is speculated that this is caused by the decrease in m's planar growth of m's Ag3sn. That is, in order to obtain the maximum tensile stress, a silver alloy alloy of appropriate thickness must be formed. '', (Example 15) Next, as an example of using the tin-coated tin other than the second embodiment, the copper alloy plate of the thickness of the u-Fe-P alloy G. 15 is used as a substrate. After 'respectively, the thin tin layer of tin whiskers (3 and thick mirrors: layer U5 form a layer of 矿5 _ ore) and is immersed in warm water of C for 1G seconds. A silver-tin alloy layer was formed. In the comparative example, a bond tin test piece was formed which did not form a silver-tin alloy layer. = The stress was measured in three test pieces. The evaluation results are shown in Table 1 and Figure 1 [Table 14] __Processing plating _ μπι stress MPa stress difference $ Mpa — 0.05 75.33 32.99 — 0.05 83.59 33. 66 Γ〇Γ〇5 86. 50 30.36 one 42. 34 one~~~----- - 49. 93 — 56.14 - ※The stress difference is 320516 44 200923142. There is no big twist on the effect of twisting and smashing; and the conditions of the mine conditions and additives are 37, 38, 39. 2::: Implementation as described In Example 14, it was confirmed that the present invention confirmed that the tensile stress was greater than::=: 20, 21, and 22. In the case, the stretched shore was opened, and the difference was different in application. The thickness of the film produced by silver in the tin of the tin-like tin is increased and increased, but the amount of the female silk is also increased by the thickness of the tin-plated film, which is approximately the same value. -Γ Λ· '. The increase in stress is determined by # Ρ ° 'relative to the (four) layer of the tensile ore, the same as the silver: r degree. This tensile stress is estimated and reflowed with respect to tin crystal == tin alloying However, in order to basically, the driving force is / membrane Μ has been carried out various studies, and the stress of the 疋 疋 犋 itself is dependent on the copper-tin alloy shrinkage stress, and the local mechanical properties are increased due to external terminals. Should: and the difference between the thermal expansion rate of the film and the substrate generated by the heat: where the suppression of whisker caused by external stress should be ^

V = _. The reason for the tin generation of the tin-preventing conductive material in the present invention will be described below. ^ - It is generally believed that the pure mineral tin is considered to be, in the case of reintroduction, the local stress of the external indenter, or in the absence of reflow, the internal stress of the copper -: alloy, the application of the tin film The stress is reduced, so the tin is squeezed to produce whiskers. On the other hand, the tin-conducting conductive material of the present invention is subjected to alloying with silver-tin of mirror silver to cause tensile stress on the tin film. This tensile stress is considered to cancel the external compressive stress applied from the outside or the internal contraction stress caused by the copper-tin alloying of the electric layer itself, thereby suppressing the generation of tin whisker. At the same time, the surface Ag3Sn particles are considered to be able to disperse and relax the stress of the chisel portion by the agglomeration and migration of the tin particle ring 320516 45 200923142. At the same time, Ag3Sn-particles are also considered to hinder the movement and migration of tin atoms, so that the formation and growth of acicular tin whiskers of a single crystal are physically suppressed. (Industrial Applicability) Therefore, the present invention can provide a tin-conducting conductive material which can reduce the amount of silver used and can be manufactured at low cost, and can improve its heat resistance and whisker-forming property, and a method for producing the same, and use the same. An energized part of tin-plated conductive material. BRIEF DESCRIPTION OF THE DRAWINGS I Fig. 1 is an explanatory view showing a tin-plated conductive material of a third embodiment of the present invention. Fig. 2 is an explanatory view showing a state in which the tin-plated conductive material shown in the figure is before the silver-tin alloy forming step. Fig. 3 is a flow chart showing the steps of the method of manufacturing the tin-plated conductive material shown in the second drawing. Fig. 4 is an explanatory view showing the use of a connector terminal of a key tin conductive material shown in Fig. 1. Fig. 5 is an explanatory view showing a tin-plated conductive material according to a second embodiment of the present invention. Fig. 6 is a flow chart showing the steps of the method for producing the remaining tin-conducting electrically conductive material according to the second embodiment of the present invention. f ? A is an electron micrograph of the surface after plating of Example 1 of the present invention. The fβ map is an electron micrograph of the post-electrode profile of Example 1 of the present invention. Fig. 8A is a photograph of the whisker evaluation due to external stress in Example 4 of the present invention. 320516 46 200923142 Fig. 8B is a photograph of the surface of the whisker evaluation test of Comparative Example 2 due to external stress. Fig. 9A is an illustration of the invention of Example 9 to 18〇. Electron micrograph of the surface after heat resistance test for 12 hours. Fig. 9B is a diagram of Example 9 of the present invention. Electron micrograph of the cross section after the heat resistance test was carried out for 12 hours. Fig. 10 is a graph showing the results of XRD measurement of the inventive examples 12 to 14 and comparative example 7 after electroplating. Photograph 11A is an electron microscope photograph of the surface of the invention of Example 16 after electrodiagnosis. Fig. 11B is an electron microscope of the cross section of the inventive example 16 after electroplating. Fig. 12 is a photograph of a cross section of the crucible after reflow treatment. Fig. 13A is a SEM photograph of Example 16 of the present invention after natural placement for 6 months. I The first ruling picture is a natural SEM photograph of Example 16 of the present invention. SEM 24 to 27 solder on the SEM moon surface of the surface after month of the month. Fig. 13C is a comparative example 9 in which 6 photographs were placed naturally. Fig. 13D is a comparative example 9 in which 6 photographs are naturally placed. Fig. 14 is a graph showing the results of the wetness evaluation of Comparative Example 16 and the present invention. Fig. 15 is a graph showing the results of stress measurement of Comparative Examples 至7 to 19, Examples of the present invention μ to 320516 47 200923142. Fig. 16 is a graph showing the results of stress measurement of Comparative Examples 20 to 22 and Inventive Examples 37 to 39. [Main component symbol description] 1 Tin-tin conductive material 2 Substrate 3 Nickel-plated layer 4 Copper-plated layer 5 Tin-plated layer 6 Silver-tin alloy layer 7 Silver layer 8 Connector terminal (power supply zero.) 8 A male terminal 8B Female terminal 11 Tin-plated conductive material 12 Substrate 14 Copper-plated layer 15 Tin-plated layer 16 Silver-tin alloy layer 48 320516

Claims (1)

200923142, the scope of application for patents · · Tin-plated conductive materials, including: having a base material formed on the conductive material, and using tin as a base material and formed of tin or tin alloy In the surface layer of the above-mentioned lang layer 2. As the patented scope, the tin-plated conductive material of the item, the average thickness of the #中银-tin alloy layer is set in Ο.ΟοΓ^ο'μη^::. Dry of μ® 3. 4. 5. =: Patent No. or Item 2 of the tin-tin conductive material, in: open; formed between the aforementioned substrate and the aforementioned tin-tin layer and consists of copper or copper: rabbit heart The clock is made of copper. Or (4) the conductive material of the second item (4), which is diffused on the H material and seems to prevent the tin-plated conductive material of the third item in the above-mentioned substrate, which has a shape diffusion: A method for producing a material for preventing the diffusion of an element in the substrate, U. Patent Application No. 1 or 2, and a method for producing a tin-plated conductive material, comprising: a base having conductivity a tin plating layer forming step of forming a tin plating layer formed of tin or a tin alloy, forming a silver layer formed of silver or a silver alloy on the tin layer, and a state in which the mother layer is formed by the element Stay at 1〇. 〇The above is not 49 320516 200923142 Da Loot: The temperature is more than 2 seconds. The tin of the tin layer reacts to form the silver of the second and the other plating formation steps. A method for producing a silver-tin alloy layer of the silver-tin alloy layer of the silver-tin alloy layer, in the sixth aspect of the present invention, is provided before the formation of the mineral tin layer, and is formed by plating the copper or copper alloy. The copper plating layer of the copper layer forms an Ai step. 8. = The method for manufacturing the tin-plated conductive material of claim 6 of the patent specification, ^ having the element before the formation step of the layer 4, the sound is used to prevent the element in the substrate The diffusion prevention layer of the diffusion prevents the layer formation step. (2) The method for producing a tin-plated conductive material according to item 7 of the patent scope, the second substrate, before the step of forming the copper plating layer, the substrate; the diffusion preventing layer for preventing diffusion of elements in the substrate The diffusion preventing layer forming step. please! The manufacturing method of the tin-conducting conductive material of the sixth item of the benefit range, the silver layer forming step is an electric forging method selected according to the electro-mine method, the electroless electron microscope/positive replacement electric money method and the steaming method. 11 'from the above thickness of GQG1 to α.1μΠ12 of the aforementioned silver layer. The method for producing a tin-plated conductive material according to item 6 of the patent application is a reflow treatment step of heat-treating the tin-plated e-side after the step of forming the tantalum-chain tin layer. 12) The method for manufacturing a conductive material according to item 6 of the sixth aspect of the patent application, wherein the tin layer 320516 200923142 and the silver-tin alloy layer are formed after the base portion is processed into a predetermined shape. _ 13. —Electrically energized parts, using tin-plated conductive materials in the first or second patent application. 51 320516