TW201222691A - Solder ball for semiconductor packaging and electronic member - Google Patents

Abstract

The present invention provides a solder ball for semiconductor packaging and electronic member having the solder ball and a solder ball for semiconductor packaging that assures sufficient thermal fatigue characteristics even if the solder ball, which has been used in recent years, has a diameter of 250 μm or less, and electronic member having the solder ball. The solder ball for semiconductor mounting and electronic member having the solder ball have a main body formed primarily of Sn and containing 0.1 - 2.5% by mass Ag, 0.1 - 1.5% by mass Cu and one or more of Mg, Al, and Zn in a total of 0.0001 - 0.005% by mass, characterized in that there is a non-crystalline phase with a thickness of 1 - 50 nm on the surface of the solder ball, and the non-crystalline phase contains one or more of Mg, Al, and Zn as well as O and Sn.

Description

201222691 IV. Designated representative map: (1) The representative representative of the case is: None. (1) A brief description of the symbol of the representative figure: None. V. The present invention is a chemical formula for the invention of the invention. The present invention relates to a solder ball for semiconductor packaging and an electronic component using the solder ball. [Prior Art] Electronic components are packaged on a printed circuit board or the like. The electronic component temporarily bonds the solder ball for semiconductor encapsulation (hereinafter referred to as "solder ball") to the electronic component between the printed circuit board and the like, and then heats the entire printed circuit board to smear the solder ball 1 The board is cooled to room temperature to cure the solder balls to ensure that the solid solder joints are packaged in a so-called reflow process. / } When the electronic device is disposed of, the adverse effects on the environment are kept to a minimum. The solder alloy used as the electronic device connection material is required to be error-free. As a result, the solder composition of the aforementioned solder ball which is widely used is generally a Sn-Ag (tin-silver) eutectic composition (Ag: 35 mass%, such as the rest), and, for example, a licensed document! Before the contents disclosed in Patent Document 2 were before 201222691, the composition of the periphery of the .Ag eutectic was added as the material of (4). In addition, a ΓΓ3Υ 5 solder ball is mainly used in the solder ball for the BGA (hU "Η ^ 3 spherical gate array" which has been rapidly increased in recent times. 〃 同样 同样 同样 = = 器 器 器 器 器 施加 施加The current is the cause, and the heat is generated in the section 11. The above-mentioned zen ball is a material that is different from the resin substrate, and the thermal expansion coefficient is different. The solder ball becomes in a thermal fatigue environment (4). Cracking progress for cracks: the resistance to the electronic signal input and output of the ball is caused by: / In addition, with the miniaturization of the electronic type of electronic equipment in recent years: =: plus: labor == solder joint The joint area continues to shrink, and the hot-wrinkle solder 2 is more important. The conventional sphere size, that is, the surface of the joint of the straight ball of the main ball <5 nn ' (4), the case of the solder ball and the electrode The composition becomes a state in which a part of the oxide layer remains in the joint interface even if it is not completely removed in the oxygen θ-back mechanism existing on the surface of the solder, and it is not a problem between the solder ball and the electrode. For thermal fatigue characteristics Caused by bad:; strong; this milk is guaranteed to be a straightforward a3_raJ^sn_Ag_euMf characteristic, not to ensure that the surface of the solder ball is removed at 3-4 mass, ... the strength of the 'between' and the concentration of Ag will cause the solder to be considered When the intermetallic compound called AgsSn is precipitated by the enhanced concentration, the hardening of the solder ball is hardened by the hardening of the solder ball, and the external solder ball becomes difficult to change, even if it is accompanied by thermal fatigue, a negative t, accompanied by thermal fatigue. The variable is also small, which can delay the cracking of the inside of the solder ball. Also, in the solder ball, it is required to ensure the wettability at the time of soldering. The low melting point of the solder can be ensured at the low temperature. Package: The surface quality of the solder ball that can be correctly imaged by the solder ball is mounted, or: Ensure that the fall of the fault is not caused even if the electronic machine Is accidentally falls: [Prior Art] [Special License] (Special License 1) [Problems to be Solved by the Invention] In the solder for electronic components mainly composed of Sn, Ag, and Cu, the present invention is disclosed in Japanese Laid-Open Patent Publication No. 2003-1481 (Patent Document 2). When the diameter of the solder ball in the ball is, for example, a conventional #3〇〇" m or more, the aforementioned thermal fatigue characteristic can be ensured to the extent of the score, whereas the aforementioned thermal fatigue characteristic of the diameter of 25 Mm under the recent years cannot be ensured sufficiently. The degree of the problem is a very serious problem. And the ball. Therefore, in the present invention, the solder ball for the semiconductor package is provided with the electronic member thereof, and the solder having a diameter of 250 Mm or less can ensure sufficient thermal fatigue characteristics. Solder balls for semiconductor encapsulation and electronic components using the same. [Means for Solving the Problem] 201222691 The means for solving the above problems are as follows. According to the patent application scope, the semiconductor package is based on Sn, and the person A n uses the ball, the long mass m g 2·5 mass%, C".

Among the Mg, A1, and Zn, a solder alloy having a thickness of 1% or more of 2 or more layers is formed, and the amorphous phase of the solder ball having a thickness of 1 to 5 is formed. The amorphous phase contains one or two or more kinds of Zn, and ruthenium and the like. In addition, the "main body" is 9% by mass or more. According to the second aspect of the patent application, the solder ball for semiconductor encapsulation contains "Ag" as the main component of Sn, and includes Ag 0·1 to U mass%, and Cu 〇1 to 1 0 among i or more than two or more. 0001% by mass of a solder alloy, wherein M of the solder ball has an amorphous phase having a thickness of 1 to 5 nm, and the amorphous phase contains i or more than two or more of g, A1, and zn. And as well as. According to the third aspect of the patent application, the solder ball for semiconductor package is characterized in that it is in the first or second range of the patent range, and the Ag alloy concentration of the solder alloy is 〇·5 to 1.9% by mass. The solder ball for semiconductor package according to the fourth aspect of the patent application is characterized in that it is included in any of items 1 to 3 of the patent application, and further includes Bi(叙)〇_〇1 to 5 mass%. According to the solder ball for semiconductor package of claim 5, the basin is characterized in that in the claims 1 to 4, the solder alloy further contains S Ni (4), p (phosphorus), and Sb (recorded (钸). , u (class), c〇 (phantom, Fe (iron) and bismuth (indium), i or more than two or more 〇〇〇〇5 201222691 〇. 5 mass%. According to the scope of application of the sixth item of the electronic The electronic component of the member is characterized in that the four-knife of the solder joint portion uses the solder balls of the first to fifth cases of the patent application range. The semiconductor package described in the above section [Effect of the invention] As described above, the present invention is used. The ball and the electric component for the semiconductor package can ensure sufficient thermal fatigue characteristics even when the solder ball having the diameter of 250 " m or less is formed. σ [Embodiment] The results of the intensive research of the present inventors It is known that even if the concentration of red is increased to delay the development of cracks inside the solder ball, the conventional idea is to use a solder ball having a diameter of 250" or less, and the reason why the thermal fatigue characteristics are not sufficient can be ensured. Oxidation of the solder ball surface The excess growth of the layer, and this phenomenon will become significant when the solder balls after shipment are stored for several months. This is because (1) the surface area of the solder balls per unit volume in the diameter of 25 to below is inevitably increased. After the time passes, the surface of the solder ball is oxidized, and the oxide layer on the surface of the ball is grown thickly to the extent that the flux cannot be completely removed during the reflow process. The oxide remains at the bonding interface between the solder ball and the electrode after the reflow. (7) The bonding area between the electrode and the solder ball is inevitably small at a diameter of 2...m or less, and even if only a small amount of oxide remains, the proportion per joint area becomes a considerable amount, and the diameter is less than 250 #πι. Even if the solder ball is in a small fatigue count, the bonding strength between the solder balls 6 201222691 and the electrodes is lowered, and as a result, the thermal fatigue characteristics, the inventors concentrate on the results of the research, and:: The excessive growth of the layer, if Table φ of the ball: gasification 7η ^ φ ΛΛ 〇 ^ For 3 ^ Mg, ΑΙ and the species or more than 2, and 0 and ~ of the amorphous phase with a thickness of i ~ (10) Formed, it was found that even after the shipment (four) balls were stored for several months, the thickness of the solder ball oxide layer was kept as thin as the thickness when shipped. (In addition, the surface of the solder ball In terms of the area from the solder = surface to the depth -), the oxide layer can be removed without problems in the reflow process. The above effect 'oxidizes only the crystalline layer in the oxide layer. In the case of tin composition, since the tin oxide reacts with oxygen contained in the atmosphere over time: the thickness of the long emulsion layer increases, and conversely, the amorphous phase is not so long as time passes. Reacts with oxygen in the atmosphere, the thickness of the oxide layer does not increase several times. It is considered that there is a grain boundary between the crystalline tin oxide and the inside. The oxygen in the milk can diffuse along the grain boundary of the tin oxide to the inside. In contrast, the amorphous phase described above does not have a grain boundary, so it is difficult to diffuse oxygen in the atmosphere. In order to obtain the above effect, the amorphous phase is preferably formed by the thickness of the bismuth. However, when the amorphous phase is less than 1 nm, it is difficult to obtain a k-like effect. On the other hand, even if the amorphous phase exceeds the thickness of 5 Onm, the same effect as described above can be obtained. Considering the production method described later, in order to achieve the thickness, the surface of the solder ball must be quenched at a relatively constant cooling rate, and the thickness of the oxide layer should be uniform. It is preferable to control the thickness to a predetermined thickness, and it is industrially difficult. The thickness of the amorphous phase is 30 nm or less, and the thickness control of the oxide layer can be more accurately performed. The amorphous phase is not necessarily 201222691 疋The surface of the solder ball is covered on the surface of the solder ball. The fine crystal tin oxide may be present at the same time. Here, 'di tin or micro-occupies more than 30% of the total oxide layer. The amorphous phase needs to be two. When the amorphous phase is less than the thickness of the entire oxide layer, the result is an effect. In addition, the oxide layer of the inhibitory effect phase which grows in the (iv) vapor layer does not contain one or more of Mg and A1. σ ά ς @ λ has the quality phase among the Α1 and Ζη, in the case of the main and the 0 composition, even if it is amorphous: the f-time oxide layer becomes thicker and has no effect of suppressing the growth of the layer. So, in order to get the inclusion and the Zn in the Zn Species or above 'and the smashing of 〇 and Sri, 4 2 kinds ^ and medium, the step-by-step makes the quality «good. This is the test of the addition of 〇·000 1~ 〇 shoulder layer, by Mg;;; And ζ = in the cold state, the formation of amorphous oxygen, in the case of Mg, A1 and Zn, 9 or more of the rare type, if the total amount is less than 〇. 〇〇〇一负里/〇, the formation of 曰-like oxidation cannot be obtained. The effect of the layer of material α is non-ruthenium or Ζ 会 is violently oxidized, and the ball is "two mass% or more, and A1 is not spherical, and it is not preferable. In addition, even if Mg or ϋ 7 U is added, g A1 or Ζη does not define "a total of 9 filaments containing Mg, Al, and yttrium, and 2 or more species, and an amorphous phase of yttrium and Sn. According to the added concentration, the gentleman & n # ” — /,,,,, Daytime, or microcrystalline oxide. For τ, the amorphous phase is indeed obtained, and Μ should be controlled by the addition concentration of the raw material S by the input or Ζη. In the case of ...: 'η 3, the oxygen concentration is good', specifically, the raw material Sn is 8 201222691: the concentration of °. 3 to "double the most effective oxygen concentration in the concentration of n qJ and s, when the solder ball is not filled with Zn and will form a crystal, because it does not contain Mg, A1 or the oxygen contained in the ball, s· On the other hand, when it is excessively added beyond the welding U ^ port, the _, or Μ 2 〇 3 or Ζ 〇 〇 of the gentleman S zh crystallization will form: :: quality, or slightly the main body added as # _ s is preferable In the case of Mg Majia, this is because the fear of being a polygon is more than w... In order to deform the ball described in the ', 乂, even if it is added to the upper limit 〇〇〇5 t θ %, In contrast, since Α1, ::! is easily oxidized, it is added to the upper limit 〇. - Ζ Ζ M M M “ “ “ “ “ “ J J The right is caused by a small amount of pattern on the surface of the ball to deform the ball into a polygonal shape for some reason in an environment susceptible to oxidation. Such oxidation traces on the surface of the sphere can be used, for example, FE_SEM (Fieid)

Emission-Scanning Electron Microscope >i## ^ # ^ ^ High-resolution electron microscope observation, such as electron microscopy in Lah or tungsten-made SEM (scanning electron microscope) Concentration of 'the above traces of oxidation is difficult to observe. The identification of the amorphous phase is based on a transmission electron microscope (TEM;

Transmission Electron Microscope) diffraction pattern and TEM-mounted energy scattering X-ray spectrometry (EDX; energy dispersive x-ray spectrometry) 'The thickness of the amorphous phase is just described TEM, or Oujie The electronic analysis method (AES, AugerElectron Spectroscopy) has good accuracy and is excellent in performance. Further, the inventors of the present invention have further studied the results of the above-mentioned study, and it is known that the idea of "increasing the concentration of Ag to delay the crack development in the inside of the solder ball" is not applied to the solder ball having a diameter of 250 / zm or less. There is another reason why the thermal fatigue characteristics have reached a sufficient level. This is because, in general, the relationship between the "thermal deformation amount and the deformation amount + the size of the ball" is iL, but the deformation amount is determined by the difference in thermal expansion coefficient of the device constituent material #, which is almost constant, and relatively 35 The amount of deformation becomes smaller as the size becomes smaller. For example, if the diameter of the solder ball is 25G", the thermal deformation amount is larger than the direct control of the solder ball at 3GG/zm or less. (1) The diameter of the solder ball is 3〇〇. # m Above: Does not exceed the deformation of the solder ball, so the damage occurs in the solder ball. (2) The diameter of the solder ball is 25 〇/im or less: - The hard ball breaks the soft ball at the joint interface because it exceeds the deformation of the solder ball because No more than the deformation of the solder ball breaks the J in the solder ball. That is to say, in the case of (1), in order to make the amount of thermal deformation of the hard solder ball or the soft material ball in the range of deformation of the solder "hard soldering

The ball can make the solder ball more difficult. # sm A is difficult to shape in the ruler. As a result, the deformation of the inside of the solder ball can be delayed, and the thermal fatigue characteristics are relatively 'relatively' (2). The solder ball is straight 彳 a 250 is 250 # m or less, because the horse uses a hard solder ball, the θ θ ",, double $ will exceed the range of solder deformation degree ¥ material ball can not be fully deformed to the temple ^ The amount of thermal deformation of the Τ, therefore, the insufficient part of the deformation becomes the burden of the joint interface, and the crack does not become inside the solder ball' to the joint interface. AA as wins because the intermetallic compounds that are brittle at the joint interface grow thickly, and grow in the cracks at the joint interface. 4 Cracks (for example, when the glass collapses, it becomes bad. When the glass breaks) Development, thermal fatigue characteristics 10 201222691 "m: two sample months: the result of intensive research, in the environment of the diameter of the solder ball is 25 °: two: the sample will have a large amount of thermal deformation, Xiao Xizhi's ideas are different When the concentration of the right solder alloy is less than 2.5% by mass, it is found that by softening the solder ball, the amount of thermal deformation rapidly increases with the diameter of the solder ball by the solder ball itself. After the receipt, the shear stress can be prevented from acting at the joint interface, and the breaking mode of the cracking of the inside of the solder ball which is the same as that of the q q nn 、 、 、 、 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (4) Although the amount exceeds the range of the degree of deformation of the solder, (4) the thermal fatigue characteristics become poor due to the development of the crack to the joint interface, and the harder solder ball can be soldered when the amount of thermal deformation does not exceed the range of the degree of deformation of the solder. In a state in which it is difficult to deform, the development of the solder ball (4) is delayed, and the thermal fatigue characteristics are improved. That is to say, it can be said that a large thermal deformation amount occurs when the diameter of the solder ball is 25 〇. The focus of the improvement of the thermal fatigue characteristics in the environment is to harden the solder in the range of the amount of thermal deformation that does not exceed the range of the deformation of the weld # high in the solder. On the other hand, when the concentration of Ag exceeds 2 5% by mass, the hardness of the solder becomes too hard, and the crack at the time of the thermal fatigue test progresses to the above-mentioned brittle intermetallic compound, resulting in extremely short thermal fatigue life.

When the concentration of Ag is less than 0.1% by mass, the melting point of the solder ball is as high as 234 ° C. Therefore, it is necessary to increase the reflow temperature of one of the manufacturing conditions, resulting in an increase in production cost. Not on the ground. 5质量百分比。 The average concentration of the 5% of the 5%. Preferably, in the case of a diameter of 25 Å/zm or less, when the concentration of Ag is 0.5 to 2.5% by mass, it is industrially applicable to low reflux 11 201222691, so it is preferable to remove A. When 〇·9~2. 2% by mass, good thermal fatigue characteristics 操作 operate under the condition of “low back”, which can be balanced at the same time. Further, in order to ensure the (four) properties of the solder balls, Gu% is preferable. On the other hand, when the concentration of rbu is less than 0.1% by mass, the effect of the sample cannot be obtained, and when the concentration of Cu is more than 1.5% by mass, the ball becomes easy to gas. The limit is 1.5% by mass. However, it is preferable that when the concentration of Cu is 〇1 to 曰•1·2, the mass is 30% or more, and even if the content of Cu is 30 ppm or more, the raw material of c 3 'mother is used as the raw material. It is also better to avoid the problem of oxidation, and better r ^ ^ avoiding rolling

The effect of Cu is further improved when the concentration of Cu is 0.% by mass. That is to say, 'the solution to the above problem is in the case where the diameter of the solder ball is 250" or less, and the species is taken by Srl a, . ^ η π , as the main body, which contains 2.5% by mass of 〇. 5% by mass of Cu, 7 of 7 tannins, and 1 of 9 kinds of formulas 〇. 〇〇〇1~ " The solder composed of the solder alloy of % is found on the surface of the solder ball, and .10, 韭曰" - an amorphous phase with a thickness of 1 to 5 〇 nm, and a non-daily enamel layer containing Mg, A1, and 7. Another, or one or two of Zn

For 〇 and Sn, it is better to use a semiconductor package ball that is characterized by a U. The diameter of the solder ball is! 8〇 "The size of the case below m is reduced. In the case of thermal fatigue test, the straight 彳1e J of 4 is used to make the shape variable and the amount of the ball Θ deformation: ^ (4) is the same degree 'causing heat deformation ball The size) becomes larger. Therefore, since the fatigue test is the same condition, the influence of your tolerance on the material becomes more extreme, and when 敎D, the crack starts to the brittle intermetallic compound. The upper limit of the development of the silver-enriched 12 201222691 degree will be reduced. The inventor of this case concentrates on the results of the results of the 100-up, 18 〇... % is better. That is, when the concentration of the solder core exceeds 5% by mass, it is found that the hardness is excessive: the frying stress at the time of the two fatigue cannot be welded by the deformation of the solder ball itself, so the crack cannot be transferred to the inside of the solder ball. The development becomes a break to the development of the joint brittle phase. ★ 1 scoop type, the thermal fatigue characteristics are easily deteriorated. That is, at a diameter of 100... The appropriate "concentration. "~"Quality" and the situation under 1.9% by mass. Also in the case of a straight 栌m or less, Ag's helmet nc 18U//g, when the degree is 0.5 to 1.9% by mass, It is suitable for low reflow temperature, and it is better to prevent it. In the case of Ag concentration of 0 5~1 η/0, the softening of the solder alloy is at a low reflow temperature. The result of the intensive research by the inventors of the two excellent cases, the advancement of the solder ball in the solder ball is greatly improved by the invention in this case. Under the 〇〇1 ..., the fatigue characteristics will be more fruitful, and vice versa詈〇 / 天天 ^ 士 ^ 的 效 罝 的 的 的 的 的 的 的 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Bi 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料 焊料2~5皙吾〇/ n The main reason is better to make the thermal fatigue characteristics of B i ϊ%. He 幵A fruit will be extremely improved and this phenomenon is based on the total of two or more Mg and a 〇〇〇〇1~〇〇〇/n towel 1 kind or image, even if it is in the solder ball that does not satisfy this & m 0 solder ball Bl 0.01 13 201222691 ~ 5 mass %, there is no significant increase in thermal fatigue characteristics. Reasons "The interaction between h and such as, A1 or with: = because 当 because when the concentration is added, can be ag, AI or Zn is suitable for excessive oxidation, fruit = surface formation of an amorphous layer 'concomitant inhibition ^ by solid solution; βΐ is mostly composed of solder such as neutralization). On the other hand, when the concentration of the solid solution S η is less than the above range, it is difficult to form an amorphous layer on the surface, and oxidation is added to make solid solution strengthening difficult to be expected. When the susceptibility is more than 0.005 mass%, due to the concentrated oxidation of A g or Zn, the ball is formed by the formation of Mg, AI, or Zn, and the shape of the agonist is formed into a polygonal shape. The convex fatigue, the thermal fatigue characteristics become bad and not as described above, in order to prevent the failure of the electronic machine, the electronic machine does not malfunction when accidentally falling, and the solder surface is not able to fall. HS, Si An m ^.1. » Two and Lv, resistance to falling eve by placing the test piece on the height of the test piece and falling again, making a drop of ^1 from 30~100" change $1# and confirming the solder joints The resistance is not estimated. The drop resistance can be

Sb'Ce, U, CG, Fe and; in (4), there is a diffusion between the constituent elements of the electrode containing Nl, 卜·5 t * ^ ^ 1 ^tf °·〇〇05^ "When the fruit has 1 疋It will hinder the formation of Sn and the inter-personalized characters, and the thickness of the σ phase in the joint interface can be reduced, and the electronic device can be accidentally dropped by the occurrence and development of thin intermetallic compound cracks. , η Even if it is transmitted to the joint interface, 'Kurui knows the exhibition, it can be broken. The quantity can not fully achieve the above effect. The other 3! Less than Q._5 quality, because the content exceeds 14 201222691 • 0_5 mass% of the melting point of the solder ball It will rise rapidly and is not industrially good. The identification method of the composition of the solder ball is not particularly limited, but for example, EDX, electronic microprobe analysis (EPMA; Electr〇n pr〇be Micr〇)

Analyzer), AES, secondary ion mass spectrometry (SIMS; Sec〇ndaq - microprobe Mass Spectrometer), Inductively Coupled Plasma (ICP), Glow Discharge Spectral Mass Spectrometry (GD-MASS; Glow Discharge Mass) Spectrometry, X-ray Fluorescence Spectr〇 (XRF) methods are excellent in performance and high in accuracy. A method of manufacturing a solder ball can be obtained by dissolving and heating a solder master alloy in which a mixed additive element is heated in a crucible or a mold, and then solidifying it to obtain a predetermined concentration. However, depending on the atmosphere at which the solder master alloy is melted, the added element is oxidized and is no longer contained in the solder. Here, in the process of melting the solder master alloy, for example, a method in which the atmosphere around the solder is an atmosphere of oxygen partial pressure 〇1 to 1 〇〇Pa, or a low pressure non-oxidation using 〇.1 to 1 0 1 300Pa. The atmosphere method can suppress oxidation of an additive element in the solder ball, and as a result, an additive element can be surely contained in the solder alloy. It can be used as a non-oxidizing atmosphere such as an inert gas such as nitrogen, argon or helium or a gas having a reducing action such as C0 or hydrogen. The rationale is that oxygen can be removed from the solder alloy if these atmospheres are used. However, when the pressure of a specific oxygen partial pressure atmosphere or a non-oxidizing atmosphere is lower than 〇1 Pa, a trace amount of an additive element in the solder is vaporized from the solder, and the concentration of π-doped in the solder ball becomes irregular. On the other hand, when the partial pressure of oxygen exceeds the pressure of helium, a considerable amount of oxygen remains in the atmosphere, and the above-mentioned = 15 201222691 is found. Since m 300Pa is the average atmospheric pressure, and the pressure of the non-oxidizing atmosphere exceeds l〇1 300Pa. Non-oxidizing atmosphere leaks ^ ... μθ „ The risk of addition outside the field increases. : In the case of the second-material master alloy refining process, the mold is sealed and the internal and external gases are isolated, and the performance is rich and better. When 0 and Sn are formed on the surface of the solder ball, in the process of manufacturing the solder ball, the cooling rate at which the molten solder alloy is solidified and spheroidized after being solidified is as fast as possible. important. Specifically, it is preferable that the cold portion speed is i 〇 (rc/sec or more, preferably (4). Second or more (four), the amorphous f phase can be formed thickly and stably, so that it is preferable. The cooling rate is preferable because the solder alloy which is solidified by the cold gas during the cooling process is simple, but it is also possible to use a method in which the solidified solder alloy is dropped into water to be water-cooled. However, the cold portion exceeding the load/second is used. At the time of speed, although an amorphous phase exceeding 5 〇 nm can be formed, a large amount of cold gas is necessary in this case, which is a cause of cost increase, which is not industrially preferable. The shape of the solder ball of the present invention is not limited, The spherical solder alloy is transferred to the joint portion to form a protrusion shape, and the protrusion is further encapsulated on another electrode, etc., which is industrially preferable. The solder ball of the present invention is other than the aforementioned BGA. Even when used as a semiconductor device connection terminal having a package form called CSP (Chip Scale Package) or FC (F1 lp Chip, flip chip), it has been found that the effective H embodiment is effective. In the case where the solder ball is used as a connection terminal of these semiconductor splits, for example, after an organic substance such as a flux or a solder paste is applied to an electrode on a printed circuit board in advance, 16 201222691 'solder balls and electrodes are arranged. An electronic component can be obtained by forming a strong solder joint portion by the above-described reflow method. The electronic component of the present embodiment includes the electronic component of the solder ball of the BGA, cSp, and % of the present embodiment, or includes After the flux and the solder paste are previously applied to the electrodes of the printed circuit board, the electronic component is placed on the electrode. 'The electronic component is further encapsulated on the printed circuit board by firmly connecting the tantalum by the reflow method described above. Further, a flexible circuit tape called TAB (Tape Automated Bonding) π, a metal wire called a lead frame may be used instead of the printed circuit board. The preferred embodiment of the invention, however, the present invention can solve the following problems which have been remarkable in recent years by appropriate changes. The problem related to reflow is that the strength of the solder is more dependent on the granular alloy phase precipitated in the solder than the parent phase Sn, and the strength is high when the fine coarse alloy phase exists in many cases. However, the granular alloy phase is not rich in heat. If most of the returning materials are carried out, the granular alloy phase will be coarsened and the number will be reduced due to the exposure in the high temperature environment exceeding the melting temperature, although the diameter of the solder ball is 3 〇〇" It is not particularly considered as a problem. However, when the diameter of the solder ball is 25 〇 or less, and most of the reflow is performed, the solder cannot ensure the necessary strength for the above reasons, and the solder is excessively deformed when subjected to stress. In the case of a bad situation, it may be short-circuited or broken. For the solution of this defect, it is preferable to add ^^ at the same time in the invention of the present invention. This is because the simultaneous addition of ^^ and Ni can refine the coarse Cu in the solder during the reflow of most of the reflows (Sn5 is refined, even if 17 201222691 is more: the backflow will be coarsened) The total number of fine-grained alloy phases present in the solder is reduced, and the reduced amount of the fraction can be precipitated and hardened by the fine CueSn5, and the strength of the itch ball is prevented from being lowered. Although the reason of the autumn 1 has not been solved' However, it is considered that the Cu in the coarse and large n5 is replaced by Ni, and when fine (c Ni) ns is formed, Mg acts as a catalyst to assist in the replacement, and the effect is not sufficient. Two topics are 'related to electrode stripping. In recent years, the structure of the thunder pole has been transformed from a conventional CU electrode or a CU/Nl/Au electrode to C^/Pd/Au (copper/nickel/Ji/Gold). Even if such an electrode is used, the diffusion between the solder and the electrode does not proceed when the reflow is 1 to 2 times, so that the layered growth of the brittle alloy phase at the solder/electrode interface can be avoided, but the multi-gap is performed. When the mouth W is 'cannot ignore the influence of the aforementioned diffusion, the electric surface Metallographic layering grows and electrode peeling occurs. In the worst case, :: 2 is broken. This tendency is especially found in Cu/N1/Pd/Au electroporation. The neck should suppress the peeling of this electrode, although it is suppressed. The layered growth of the alloy phase of the solder/electrode boundary can also be changed to the nA brittleness MU Nl in the furnace. In the invention of the solder/electrode boundary, the interdiffusion of the interface at the same time will become sluggish, so that The thickness of the brittle alloy phase is thinned, and the shape thereof is also smoothed and it is possible. 'Although the effect of adding Ni alone may be found, but it is not necessary to make the thickness of the brittle alloy phase thin, as described above. "And [being better. The reason is because, because Nl shows the function of interdiffusion at the time of welding; the interfacial diffusion of the extreme interface delays the interdiffusion, Mg such as 18 201222691 media can help N1 as a diffusion barrier function. [Examples] The raw material in which the additive element of the present embodiment is added to the main wound is placed in a graphite crucible and heated in a high-frequency melting furnace to be melted, followed by cooling to obtain a solder alloy, and the original method is determined by a combustion method. The concentration of oxygen contained in Sn is shown in Tables 1 and 2, and the heating temperature is 3 〇〇t. Thereafter, the solder alloy is made into a wire having a wire diameter of 20 " m, and the wire is cut into 26·1 mm and 9 · The length of 72_ is heated in a high-frequency melting furnace under a fixed volume. Melting, and then the cold part to obtain solder balls with diameters of 250 /zm and 180 // πι respectively. The reheating temperature is 35 (TC. The atmosphere in the high-frequency dissolving furnace is nitrogen, and the partial pressure of oxygen is about 100 Pa. In addition, when the solder ball is manufactured, the solder which cools the cooling process by cold gas can increase the cooling rate to 300^/sec. The composition of each solder ball. Identification by icp analysis, these values are shown in Tables 1-5. The melting point of each solder ball is differentially scanned by thermal analysis (DSC,

Scanning Calorimetry), the values are shown in the table. The amorphous phase was measured by TEM & EDX, and the elements identified in the amorphous f phase are shown in Table 2. Further, the thickness of the amorphous phase and the total tin oxide was measured by TM, and the occupancy ratio of the amorphous phase tin oxide in the total tin oxide was calculated. The values are shown in Tables 1 and 2. In addition, the degree of oxidation of the surface of the solder ball was observed at a magnification of 10,000 times using FE, M, and EDX. At this time, if the surface of the weld 2 has a polygonal deformation, it is represented by X in Tables 1 and 2. If only a slight deformation is observed, it is represented by Δ, and the right side of the King is not aware of such deformation. Said. As a printed circuit board for encapsulating solder balls, a size of 40 is used for 19 201222691 SOnnnxi, the electrode is 〇·3 coffee pitch, and the surface of the electrode is a. A water-soluble flux is applied to the substrate, followed by a solder ball/two object. : ' Degrees are maintained in a 25-generation reflow oven, cooling (4) front palpitations 2 = soldering on (4). Further, the bumps are bonded to the semiconductor lead in the same manner to obtain a printed circuit board/solder bump/semiconductor agricultural structure = part. Further, the aforementioned semiconductor device is 8 horns, such as pins, and the electrodes are Cu. Further, several levels of the test piece were repeatedly heated and cooled four times in a reflow furnace after obtaining an electronic component having a printed circuit board/solder bump. The test piece subjected to this test was re-displayed in Table 6, and the same test was carried out only for the test 'Cu/Ni/Au electrode and Cu/Ni/Pd/Au t electrode. The thermal fatigue characteristics were evaluated by a TCT test (temperature cycle test; Thermal Test). At this time, the ambient temperature of the test piece is changed from -4〇t to +125艽, and the test piece is taken out from the TCT test device every 25 times, and the conduction test is performed. When the resistance value exceeds the initial value by 2 times It is considered to be bad. The number of occurrences of the initial failure is shown in Tables i and 2 as the TCT life. The thermal fatigue characteristic at the time of direct operation at 250/zm is that if the number of initial failures is good at 5 turns or more, the thermal fatigue characteristics at a diameter of 180 #m are good if the number of initial failures is more than 300 times. . The financial system is evaluated based on the JESEC (Solid State Technology Association) standard JESD22-B111. At this time, the continuity of the test piece was confirmed every time it was dropped, and the conduction was considered to be a failure when it exceeded twice the initial value. Number of rounds of initial failures 20 201222691 The impact life of the drop is shown in Tables 4 and 5. The measurement of the tensile strength was carried out only on the test piece which was subjected to the above-mentioned multiple reflow test. At this time, using a commercially available tensile strength measuring machine (Dage24〇〇pc), the tensile test was carried out at a test speed of 30 0 /zm/sec, and the closed pressure of the test piece was 1 psi, and the holding time during the measurement was measured. The maximum tensile strength of (2 seconds) was obtained as a value of tensile strength at 50 points, which is shown in Table 6. Diameter 250" "If the tensile strength after repeated reflow tests is __ to observe the surface of the microscope, then #家.不八•,- ώ诅 忒 忒 之 之 之 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极%μ日丨, if it is less than 4 o'clock, ", 彳Show by X, observe & enter 'do'..., use the standard without special problems, Λ g 兀王, and have persuaded to make thousands of △ If you don't see it, you can see it by 〇. The thermal fatigue characteristics of "peeling 25 〇" m planted in Table 6: 21 201222691 [Table 1 -1 ] ^喵^资 〇 〇 〇 〇 〇 ο o o 〇

V 〇 〇

V 〇 〇 o 〇 〇 〇 〇 ο v 〇 〇

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OS § -9 -elns- oe οε οε οε

OS 09 oe 09 oe 〇g 09 oe oe oe oe 05 09 οε 09 οε 0·° 09 Cao) 羿輙 羿輙 - ? - oe - 〇ζ ? - - °e 〇g (p) Step on tf

LZZ 933 -3 ιττ -3 δ -3 δ ezz -3 ezz zzz -3 -3 εζζ -3 ζττ S3

OH s3 δ °°ΙΛΓ0=8 a v*o=s uNo=s °°ΙΛΙ .o=s °°JAro=s miato=s °°s Wes lv°=s lv*o£s lvd=s uNo= s uNo(us U2t>=s

1V-IAT0=S

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Ms"=s lv°=s lv"=s lv"=s uz*o=s

UN"=S uno£s si 500.0 500.0 i.° —0.0 ei.o Ζ.910Ό -000.0 oso.o

0S00O 500.0 0-00.0 ioo soo.o soo.o —0Ό 800.0 eei δ 3.0 10 oi.o 0S000 108Ό 018.0 osoo

CZ 0 500.0 500.0 050.0 o—.o 0 500.0 io.o 0 0 500.0 050.0 oi.o 0 io.o 0 10 050.0 §0.0 0 0 500.0 0 io.o io.o ο— oso.o 0 °°Σ 500.0 00.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

I 3.1 ΓΙ •l •1 ΓΙ cs #妹

#H #砘 资 s^ 61-> shame e-in 遂驷 22 201222691 [Table 1 -2 ]

Oxidation 1 V0 <〇〇〇〇〇〇〇〇〇〇<〇〇< 〇〇〇〇〇〇〇X 命h 5 650 〇mv〇jn Ρί ο ΙΛ) Pi 〇R 〇Ο R ο JQ ITi 450 JO 1 Η φπζ -41 ^ *瓌沄沄沄§ § 沄s ο 〇〇s 毋 Zhao 3; < (nm) ΓΟ inch - — CS mm inch \〇ο 〇〇s JiL. Melting point / VP (N CS m rN (N (N O t t ON ON &N; N \ \ (N σ \ fS 〇 (N σ\ (Ν OS (Ν ο (Ν ON < N Ο (Ν ON ( N s Ρ Ν Ν 4 4 4 4 4 4 4 4 4 4 £ (Λ 〇" io' 居Λ ' ' ' 碟 end ML· *nt> ώ (3⁄4 ώ i / -V *6- ♦) s SS 0.0033 S s 〇〇ο 沄o S 0.0007 5 S 〇 ο Ο ο o 〇 〇〇oo 〇〇〇ο ο ο o S ο 8 〇〇o ο o 〇oo 〇〇ο ο ώ o 〇ο Ο 〇〇o S o ο ο 承Ξ F; 沄ο oo 〇o 〇ooo 〇〇ο ο i ο 8 8 ο Ο 〇〇 oo ο o ο ο ο 〇〇 < 0.0001 ο 0.0001 〇o 〇oo 0.0001 0.0010 0.0050 ο ο ο 0.0001 〇0.0001 ο Ο 〇〇o /—Ν ο 5 oso 〇o 沄Ξ 〇〇ο ο ο ο 8 〇o 〇ooo 〇〇ο ο ο oooo ο ο 〇〇o φΐ ο ο d 〇o 〇ooo 〇ο a «η *T) (N CN m <nm »n »n ιη Ό W-) W-) vi (Ν ο UJ d 〇md W) CN (Ν (N 00 o (N rs CN (N r4 cs fN CN (N (N Η ίΝ (Ν <Ν <Ν ( Ν fN CN CN fN CN (Ν (Ν rs (N m (Ν ο m 5 (N 5)) The conical cone conical is invited to shun the eagle while the sister Ms Η Η Ms ν〇<Ν rs 00 ΓΝ OS (N m fN IT) ν〇m Ρ; 00 ΓΟ Ο one CN m 5 5 5 5 ¥ 4<? 镩 粲嚭 粲嚭 AS f®: Debate t: -Ο OJ aJ 23 201222691 Thermal fatigue characteristics of diameter 180 μm: [Table 2-1] ν§ 〇〇〇〇〇 〇〇〇〇<〇〇<1〇〇〇〇〇〇〇〇<]〇〇<1 峨令*峨b £- /*~s S 〇Ο mm jn r^is Tf < η ro m ο JQ ΓΟ m ο tj- JO ro 〇8 to 8 8 Tf m 8 inches in mm ο to jn m 〇ο to ¥^^ g mg WW 沄沄s δ 沄s 沄s 沄s S *瓌cm S -CN CO wear <Ν *Q m 沄 to ν〇- o fN *Q m 沄m Tt ML· /«—V . . (Ν (Ν <N fN id <N Ν s (Ν S (N Ν Ν (Ν (N (Ν Ώ (Ν <N fQ <N « (N s (Ν S (Ν ίΝ s (Ν s CN <Ν S (Ν s (N <Ν <NS (N fN s (Ν < Ν < Ν Σ < CN Σ <<< c5 CN 〇B οί) < Σ Σ Σ <<< c£ 〇Β -δ- mg 〇〇d 〇ο o' dd 1 〇ΰ O' O' 〇o' O' o" 〇d Σ Σ Room (5 (5 ΕΛ cS cS ( 3⁄4 (3⁄4 5ι (3⁄4 (3⁄4?: °Λ (3⁄4 3ι ΕΛ (3⁄4 (3⁄4 ό °„ • LU- ΕΛ άό i 00 ΕΛ φ| SS m " 〇ο 8 gm !〇o OS (Λ 8 i § δ I 8 ο s 8 s 8 8 8 8 i 8 8 B 8 ss 8 8 8 8 8 ο ο 〇 〇Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο 5 8 ο ο o ο ο 〇 ο os 8 8 8 8 8 8 oo oo Ο oo S 8 oo 8 5 g O o Ο 〇ο o ο d 〇ο 〇〇沄ο ο 〇Q o Ο < ο ooo ο ο o ο IS ο o Ο o ο 8 ο oo 8 i 8 ο o 〇S ο o ο 〇ο ο o Ο oo ο /-Ν 5 8 oo ο 8 5 8 0 1 8 ο 〇ο o ο o ϊ 5 8 5 8 5 8 o 8 8 Ο oo ο o 〇 5 8 ΐ ΐ ο Ο ο o Ο ο ο O ο oo ο ο 5 5 m O ir 〇 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 〇ο ο 5 rn »n Ο) O) Ο) Ο) Os Os ο On Ό\ ON Ο) Q) Os ο po ρ pp ρ p ρ ρ ρ (S invites # invites the male cone to wander around the male cone Visit the umbrella male and female umbrella sister sister H. sister sister ON mm ν~» »/Ί $ ssss ο § $ ο 雀雀4ϋ 餐省省ΐΚ Κ ⁄ 43⁄4 ΐΚ {(4) 24 201222691 [Table 2-2]

25 201222691 Thermal fatigue characteristics of diameter 2 5 0 // m: [Table 3] Composition (% by mass) Melting point TCT life Sn Ag Cu Mg A1 Zn Bi (°C) (back) Example 87 Remaining 0.1 1.2 0.0010 0 0 0.0100 227 675 Example 88 Remaining 0.1 1.2 0.0010 0 0 1.0000 227 705 Example 89 Remaining 0.1 1.2 0.0010 0 0 2.0000 227 735 Example 90 Remaining 0.1 1.2 0.0010 0 0 3.0000 227 755 Example 91 Remaining 0.1 1.2 0.0010 0 0 5.0000 227 775 Example 92 Remaining 1.2 1.2 0.0010 0 0 0.0100 220 775 Example 93 Remaining 1.2 1.2 0.0010 0 0 1.0000 220 805 Example W Remaining 1.2 1.2 0.0010 0 0 2.0000 220 835 Example 95 Remaining 1.2 1.2 0.0010 0 0 3.0000 220 855 Example 96 Remaining 1.2 1.2 0.0010 0 0 5.0000 220 875 Example 97 Remaining 2.0 1.0 0.0010 0 0 0.0100 223 825 Example 98 Remaining 2.0 1.0 0.0010 0 0 1.0000 223 855 Example 99 Remaining 2.0 1.0 0.0010 0 0 2.0000 223 885 Example 1 〇 rest 2.0 1.0 0.0010 0 0 3.0000 223 905 Example 101 Remaining 2.0 1.0 0.0010 0 0 5.0000 223 925 Example 〇 2 Remaining 2.2 0.5 0.0010 0 0 0.0100 2 19 850 Example 103 Remaining 2.2 0.5 0.0010 0 0 1.0000 219 880 Example 丨〇 4 Remaining 2.2 0.5 0.0010 0 0 2.0000 219 910 Example 105 Remaining 2.2 0.5 0.0010 0 0 3.0000 219 930 Example 106 Remaining 2.2 0.5 0.0010 0 0 5.0000 219 950 Example 107 Remaining 2.0 1.0 0 0.0010 0 0.0100 223 800 Example 108 Remaining 2.0 1.0 0 0.0010 0 1.0000 223 830 Example] 09 Remaining 2.0 1.0 0 0.0010 0 2.0000 223 860 Example 110 Remaining 2.0 1.0 0 0.0010 0 3.0000 223 880 Example 111 Remaining 2.0 1.0 0 0.0010 0 5.0000 223 900 Example 112 Remaining 2.0 1.0 0.0000 0 0.0010 0.0100 223 800 Example 113 Remaining 2.0 1.0 0.0000 0 0.0010 1.0000 223 830 Example 114 Remaining 2.0 1.0 0.0000 0 0.0010 2.0000 223 860 Implementation Example 115 Remaining 2.0 1.0 0.0000 0 0.0010 3.0000 223 880 Example 116 Remaining 2.0 1.0 0.0000 0 0.0010 5.0000 223 900 Comparative Example 9 Remaining 0.1 1.2 0 0 0 0.0010 227 475 Comparative Example 1 〇 Remaining 0.1 1.2 0 0 0 6.0000 227 475 Comparative Example The remaining 1.2 0.5 0 0 0 1.0000 221 475 Comparative Example 12 The remaining 1.2 0.5 0 0 0.0060 1.0000 221 425 Diameter drop resistance of 2 5 0 // m: 26 201222691 • [Table 4_ 1 ] © h 〇VJ NO 〇Ο Ο O s Ο 〇〇Ο ο 〇〇Ρ m <N <N m < N ΓΜ ΓΟ ίΝ fN <N <N <N <N m fN ίΝ m <N rvj r<·) fN fN N PM m <N iN m <N fS ίΝ r^> fN &lt ;N <N <N sm ίΝ <Ν rn (Ν iS r<-i ΓΑ <S fn fN (N m fM <N r*-i (N ίΝ ΓΟ (N <N r〇ίΝ j Γ〇 Ν 〇 Ο 〇 Ο 〇 〇 Ο 〇 〇 〇 〇 Ο oo oo Ο oo Ο Ο oo Ο ο ο ο ο Ο ο Ο ο ο oooooo Ο o Ο o ο ο ο ooo »〇8 ο ο ο ο S ο ο S «ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο So Vi ooo 0. Ο ο ο ο ο o Oooosoo »n c> oo ο o ο o ο ο ο oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο o o o o ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο oooooo 8 ο 8 ο ο ο ο ο δ fN fN <Ν (Ν <Ν ΓΜ fN (N (N rs (N fN fN Ν Ν Ν Ν Ν Ν Ν N N Ν N N N N N N N N N N N N N N N N N N N N N N <Ν(Ν Ο (Ν ο (Ν ο CN ο r^i Ο <Ν o fN o iN o fN S o (N o (N ο (Ν o (NS o (N ο (Ν ο (Ν ο (Ν o fs o <N o fS ο (Ν Ο (Ν S ο 5^ 雄 迤 迤 * * * 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 (N rs *n fN v〇rs 0 0 ίΝ Ον ΓΊ (Ν mm *Τί m ο m 06 m 〇\ Γ^ι ο 苳5 II AS) ¥? «? •uO Ag 4ϋ Αά νς» Ag as; (k (four) Vi {(4) 2Ί 201222691 Falling impact Lifetime (back) Ο s ο $ s ο s S s ο ο g § 00 Melting Point/<*S rn (N rN m (N (N NN f (Ν Ν Ν Ν Ν CM (Ν m (N (N m fN (Ν 230 230 Ν Ν 〇 00 00 fS (Ν fN <Ν composition (% by mass) 〇〇〇Ο 0.0005 0.0050 0.0500 0.5000 〇0.0500 ο ο Ο ο Ο 〇o ο ο ίϊ 0.0005 : 0.0050 0.0500 0.5000 o ο ο ο 0.0001 ο ο ο Ο ο Ο oo ο ο ooo Ο o ο ο ο o ο 0.1000 0.1000 ο ο ο oo ο ο J3 ooo ο o ο ο ο o 0.0500 0.1000 0.1000 ο ο ο oo ο ο ooo Ο o ο ο ο o 0.0500 0.1000 0.1000 ο ο ο oo ο ο 泛 ooo Ο o ο ο ο o 0.3000 0.1000 0.1000 ο ο ο oo ο ο CL. ooo Ο o ο ο ο 0.0002 ο 0.1000 0.1000 ο ο ο oo ο ο 少ooo Ο o ο ο ο 0.0002 0.0500 ο ο ο ο ο o o ο ο oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo Oo ο ο 〇〇Σ 0.0010 , 0.0010 0.0010 0.0010 0.0010 0.0010 0.0010 0.0010 0.0010 0.0010 0.0010 0.0010 0.0001 0.0010 0.0050 oo ο ο a <N <N (N ίΝ (N ίΝ <Ν (N (Ν fS ιη ιη 卜o Ir( 00 N N N N N N N (Ν (Ν o ο (Ν remaining | rest | remaining 1 remaining remaining rest remaining rest remaining 1 remaining 1 remaining 1 remaining remaining 1 remaining remaining 1 remaining remaining embodiment 141 1 embodiment 142 1 embodiment 丨 43 embodiment 丨44 Example 145 Example 146 1 Example 147 1 Example 丨 48 1 Example 丨 49 Example 150 Example 丨 51 Example 152 Example 31 Example 32 1 Example 33 Comparative Example 5 Comparative Example 6 Comparison 洌7 Comparative Example 8 28 201222691 Sex drop resistance m ο 8 -< Straight 5 Table <*4iL ^ % 0 Bud V) ON ο *η s Ο ο R ο s ο ο Ο s ο ο 8 ο R Ν 0. ΓΛ (N (Ν Ν ^ r^> (Ν fvi cn sr^i fN rj m CM CS m (Ν 04 ro fS (N (Ν (Ν m <N (Ν <N ίΝ (Ν fN rj N m CN (Ν cn <Ν fN <Ν (Ν <Ν (Ν fN CN <N rsj (Ν ίΝ m ΓΊ <N CM m Ν Ν; N <N (N composition (% by mass) Ξ o ο 〇Ο £ O O 〇Ο £ O O 〇Ο £ O O O 〇Ο £ O O 〇Ο O O O O O O O O O O O O O O O ο ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Oo ο o ο ο ο ο o 0.0005 0.0050 0.0500 0.5000 oo ο oo ο o οο ο ο ο oo ο o ο 0.0005 0.0050 0.05 (8) 0.5000 ο ο ο ο oo oo oo ο o C- ο ο ο ο o 0.0005 | 0.0500 0.5000 ο ο ο o ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο oo oo oo ο o < ο ο ο ο oo ο o ο ο ο ο o ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Ον Ο 〇\ ο OS Ο On 〇〇 \ o Ο Ο On 〇Os 〇ΟΝ ο Os 〇 逛 逛 锥 逛 逛 逛 迤 迤 14 14 14 14 14 c c c c c c c c c c 49 49 49 49 49 49 49 49 49 49 49 49 49 Example 155 Embodiment 丨 56 1 Embodiment 157 1 Embodiment 158 | Embodiment 丨 59 Embodiment 1 60 1 Embodiment 161 1 Embodiment 丨 62 1 Embodiment 163 Embodiment 164 1 Embodiment 165 1 Example 丨 66 1 Implementation Example 167 1 Embodiment 168 1 Embodiment 丨 69 Embodiment 丨 70 Embodiment 丨 71 1 Embodiment 丨 72 | Embodiment 丨 73 Embodiment 174 1 Embodiment 175 29 201222691 z © 〇ο ο 〇s 〇\ (Ν Os o jn ^Τ) ο m (N (N ΓΛ (Ν <Ν rn (N (N (N (N <N m &lt ;Ν <Ν m (Ν Ν ro Ν (Ν rs (Ν ΓΛ (N <N (N (N o (N Os ON On <N m (N 00 卜<N Ν Ν (Ν φή 颜• Oso Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Oso 1 ο ο 〇〇 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο oo oooooooodoooosoooo ο ο ρ ρ ρ ρ ρ ο ρ ρ ρ ρ pp pp pp pp o ui o ο ο Ό ο ο 〇〇 〇〇 〇 \ \ \ ο as \ O O O O O O O O O O O O O O O O O 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Ms 迤迤 cone Ms 逛锥ο 运00 On gg (Ν 00 5 镩m 00 s Ώ ν〇oo 5 £S «? jn 丧JO 鸯»n 湓Jj v〇-Ο 卜录00 兹 30 201222691 diameter 250 The tensile strength and peeling after several reflow tests at am: [Table 6]

As shown in Table 1, according to the present embodiment, even a small-diameter solder ball having a diameter of 25 〇 # ^ can obtain good thermal fatigue characteristics of 5 turns or more. Further, as shown in Table 2, according to the present embodiment, even a small-diameter solder ball having a diameter of 18 0 #m can obtain good thermal fatigue characteristics of 3 〇 or more. Further, as shown in Table 3, according to the present embodiment, even if the diameter #m is small, the solder ball can obtain good thermal fatigue characteristics. _ 5 is also shown in Table 4. According to this embodiment, even if you are a straight worker, you can get 90 or more good resistances. Falling down. According to the present embodiment, even if it is as large as a diameter, it is possible to obtain a good profit of 90 or more. Further, as shown in Table 5, a small diameter solder ball of 18 〇 #m is inferior. 31 201222691 In addition, as shown in Table 6, according to the embodiment in which N i and Mg are simultaneously added, a good tensile strength and a peeling interface can be obtained even if a plurality of reflow tests are performed. [Simple description of the diagram] None. [Main component symbol description] None. 32

Claims (1)

201222691 VII. Patent application scope · 1. - Solder balls for semiconductor packaging Ag 〇. 1~2 5皙旦. / r η 1 u horse body, containing "middle! kind or two:" ~. ^% by mass 'and "and alloy formation, characterized by a ten 〇 0001 〇 005 005 mass % of solder on the surface of the solder ball, having a thickness of the amorphous phase containing mZn among the phases 'front 0 and Sn. One or more of them, and 2. A solder ball for semiconductor encapsulation, which is ^01 to 1 〇 and which is mainly composed of Sn and contains 2.3% by mass '. ".1~u quality", and "! One type of Zn? 丨 丨 及 及 及 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 0001 Contains ^8^ among or ...: phase' then 0 and Sn. ! 4 Z or more, and 3. as claimed in the scope of the patent! _ 2 item ball, the towel of the aforementioned solder alloy conductor package welding "application Patent range 〖to 3 items: 匕5~1.9.... The solder ball is mounted, and the semiconductor package described in the above item further contains BiO.Ol to 5% by mass. 5. If you apply for a patent range! Up to four items of solder soldering ^, the semiconductor seal of the item, /, the solder alloy further contains Ni, p, Sb, c a, C 〇, Fe and In, e, mass%. work…. t U. 0005~〇. 5 member 6 - an electronic component, which is an electron having a solder joint 33 201222691, characterized in that at least a part of the solder joint is used according to any one of claim 1 Solder balls for semiconductor packaging. 34 201222691 IV. Designated representative map: (1) The representative representative of the case is: None. (1) A brief description of the symbol of the representative figure: None. V. The present invention is a chemical formula for the invention of the invention. The present invention relates to a solder ball for semiconductor packaging and an electronic component using the solder ball. [Prior Art] Electronic components are packaged on a printed circuit board or the like. The electronic component temporarily bonds the solder ball for semiconductor encapsulation (hereinafter referred to as "solder ball") to the electronic component between the printed circuit board and the like, and then heats the entire printed circuit board to smear the solder ball 1 The board is cooled to room temperature to cure the solder balls to ensure that the solid solder joints are packaged in a so-called reflow process. / } When the electronic device is disposed of, the adverse effects on the environment are kept to a minimum. The solder alloy used as the electronic device connection material is required to be error-free. As a result, the solder composition of the aforementioned solder ball which is widely used is generally a Sn-Ag (tin-silver) eutectic composition (Ag: 35 mass%, such as the rest), and, for example, a licensed document! The contents disclosed in Patent Document 2 are amended at 2 201222691 17th, February 15th, 2011. Replacement page VII. Patent application scope: 1. A semiconductor package material ball, which is based on Sn and contains Ag 0.1^2.5 Cu 0-1^1.5 f*%, Mg. A1 A Zn is formed by one or more kinds of a total of q. A G. GG5 mass% solder alloy is formed, and the surface of the solder ball has a thickness. The amorphous phase of 5 〇 nm, the amorphous phase described above contains one or more of Mg and Zn, and bismuth and Sn. 2_ A semiconductor package material ball, the mn is the main body, containing z I 9 mass % ' Cu 〇 · 1~1. 〇 mass%, and one or more of Mg, A1 and n. Nflni The amount of solder σ gold in the range of 0.00〇1 to 0.005 mass% is also characterized by: the surface of the solder ball, and the amorphous phase of the right-handed phase contains a Μ/amorphous phase, the former 0 and the like. There are one or two or more of Mg and A^zn, and the solder ball for semiconductor sealing F described in claim 1 or 2 of the patent range, J: φ, +, L, 卞 魃 魃The Ag alloy concentration of the solder alloy is 0.5 to 1.9% by mass. The semi-conductor of the range of the ball is the second one. The third is Bi〇.01~5 mass%. Second application: The solder for semiconductor package described in item 3 of the patent scope further contains Bi〇.01 to 5% by mass. The ball 6 6 = the range of the semiconductor package described in the first or second item, or two or more kinds of total 〇.〇〇〇5 to 〇 5 mass%. In the case of the solder ball for semiconductor package described in claim 3, the solder alloy further contains Ni, P, Sb, Ce, La, Co, Fe. And one or more of In and 〇. 0005~〇. 5 mass%. 8. The solder ball for semiconductor package according to claim 4, wherein the solder alloy further contains Ni, p, Sb, Ce, ^, h, 9. an electronic component, characterized in that: the solder joint At least one of the jg sheets, Fe and Ιη, at least one of the parts, or a total of 〇· 0005~〇·5 mass%. The tanner ball for semiconductor packaging described in the above. It is an electronic component with a solder joint, and a small part of the material is required to be patented.