Solder alloy for die bonding
10189119 · 2019-01-29
Assignee
Inventors
- Takeshi Asagi (Ichihara, JP)
- Susumu Mitani (Ichihara, JP)
- Hirohiko Watanabe (Kawasaki, JP)
- Masayoshi Shimoda (Kawasaki, JP)
Cpc classification
H05K3/3457
ELECTRICITY
H05K3/3463
ELECTRICITY
B23K35/26
PERFORMING OPERATIONS; TRANSPORTING
B23K35/264
PERFORMING OPERATIONS; TRANSPORTING
H01L2924/01322
ELECTRICITY
H01L2924/00012
ELECTRICITY
H01L2924/00
ELECTRICITY
B23K1/0016
PERFORMING OPERATIONS; TRANSPORTING
H01L2924/01322
ELECTRICITY
H01L2924/00
ELECTRICITY
International classification
B23K1/00
PERFORMING OPERATIONS; TRANSPORTING
B23K35/02
PERFORMING OPERATIONS; TRANSPORTING
B23K35/26
PERFORMING OPERATIONS; TRANSPORTING
Abstract
An object of the invention is to provide a lead-free solder for die bonding having a high heat resistance temperature and an improved wetting property. Provided are a solder alloy for die bonding which contains 0.05% by mass to 3.0% by mass of antimony and the remainder consisting of bismuth and inevitable impurities, and a solder alloy for die bonding which contains 0.01% by mass to 2.0% by mass of germanium and the remainder consisting of bismuth and inevitable impurities.
Claims
1. A solder alloy for die bonding consisting of bismuth, 0.05% by mass to 3.0% by mass of antimony, 0.01% by mass to 1.0% by mass of germanium and inevitable impurities.
2. A solder alloy for die bonding consisting of bismuth, 0.05% by mass to 3.0% by mass of antimony, 0.01% by mass to 0.1% by mass of nickel and inevitable impurities.
3. A solder alloy for die bonding consisting of bismuth, 0.05% by mass to 3.0% by mass of antimony, 0.01% by mass to 1.0% by mass of germanium, 0.01% by mass to 0.1% by mass of nickel and inevitable impurities.
4. A solder alloy for die bonding consisting of bismuth, 0.05% by mass to 3.0% by mass of antimony, 0.01% by mass to 1.0% by mass of germanium, 0.001% by mass to 0.1% by mass of phosphorus and inevitable impurities.
5. A solder alloy for die bonding consisting of bismuth, 0.05% by mass to 3.0% by mass of antimony, 0.01% by mass to 0.1% by mass of nickel, 0.001% by mass to 0.1% by mass of phosphorus and inevitable impurities.
6. A solder alloy for die bonding consisting of bismuth, 0.05% by mass to 3.0% by mass of antimony, 0.01% by mass to 1.0% by mass of germanium, 0.01% by mass to 0.1% by mass of nickel, 0.001% by mass to 0.1% by mass of phosphorus and inevitable impurities.
7. A solder alloy for die bonding consisting of bismuth, 0.01% by mass to 2.0% by mass of germanium and inevitable impurities.
8. A solder paste comprising: the solder alloy for die bonding according to claim 7 and a flux.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
(8) Embodiments of the present invention will be described below with reference to attached drawings. However, the present invention is not limited by the embodiments described below.
First Embodiment: A BiSb Binary Alloy
(9) According to the first embodiment of the present invention, a solder alloy for die bonding contains 0.05% by mass to 3.0% by mass of Sb, and the remainder consists of Bi and inevitable impurities. The inevitable impurities mainly include copper (Cu), Ni, zinc (Zn), iron (Fe), aluminium (Al), arsenic (As), cadmium (Cd), Ag, gold (Au), In, P, Pb, Sn, and the like. In particular, the solder alloy according to the present invention is characteristic in that it does not include Sn except for Sn contained in the inevitable impurities. This exclusion of Sn is intended to prevent the melting point of the solder alloy from being lowered due to the presence of a BiSn eutectic composition. In addition, the solder alloy according to the present invention is a lead-free solder alloy that does not include Pb.
(10)
(11) The solder alloy containing 0.05% by mass to 3.0% by mass of Sb and including the remainder constituted by Bi and inevitable impurities can be easily rolled and also has an excellent plastic workability. Further, by controlling the content of Sb within the above-described range, the wettability of the BiSb alloy can be significantly improved compared with the case of using Bi alone.
(12) More preferably, the content of Sb may be 0.05% by mass to 2.0% by mass, and yet more preferably, the content of Sb may be 1% by mass to 1.75% by mass. This is because if the content of Sb is controlled within these ranges, the alloy becomes most effective in terms of both the wettability and the workability.
(13) The solder alloy according to the present embodiment can be prepared by melting the stocks Bi and Sb in an electric furnace in accordance with an ordinary method. It is preferable to use materials with a purity of 99.99% by mass or higher as the materials.
(14) In addition, the solder alloy according to the present embodiment can be worked in the form of a plate-like preform material, a formed solder, or a solder paste prepared by powdering the materials and mixing the powder with a flux.
(15) If the solder alloy is to be provided in the form of a solder paste prepared by working the materials into the form of powder and mixing the powder with a flux, with respect to the particle size of the powdered solder, it is preferable to use a powdered solder of which the distribution of the particle size is in the range of 10 to 100 m, and more preferably, 20 to 50 m. For an average particle size, a powdered solder can be used of which the distribution of the particle size is in the range of 25 to 50 m, for example, by measurement carried out by using a common laser diffraction and scattering-type particle-size-distribution measuring apparatus.
(16) For the flux, a freely selected flux can be used, and in particular, a rosin based flux can be preferably used. In order to more effectively improve the wettability, it is especially preferable that the above-described solder paste be used in combination with a flux having a composition including a polymerized rosin of 45 to 55 mass parts, butyl carbitol of 41 to 51 mass parts, a cyclohexylamine HBr salt of 0.5 to 1 mass parts, adipic acid of 0.5 to 1 mass parts, and a hydrogenated castor oil of 2 to 4 mass parts. Alternatively, a flux having a composition including a mixed rosin of 45 to 55 mass parts (polymerized rosin:hydrogenated rosin=1:3), hexyl diglycol of 41 to 51 mass parts, 2,3-dibromo-1,4-butenediol of 0.5 to 5 mass parts, adipic acid of 0.5 to 1 mass parts, and a hydrogenated castor oil of 2 to 4 mass parts can be used. The mass ratio between the flux and the powdered solder is preferably 80:20 to 90:10, and more preferably 85:15 to 90:10.
(17) If the solder alloy is to be provided in the form of a formed solder, a member to be bonded can be bonded by first applying a flux similar to that described above onto the member and mounting the formed solder thereon under a specific temperature profile. The shape and the dimension of the formed solder is not limited to a specific shape or dimension, and the formed solder can have a shape and a dimension that are appropriate for a member to be bonded and commonly used by a person skilled in the art. For the volume of the flux, the flux can be used by such an amount that the volume thereof becomes the same as or about 1.2 times greater than that of the formed solder. Specifically, the temperature profile may include a preheating step for carrying out heating at 150 to 220 C., preferably at 170 to 200 C., for 100 to 130 seconds and a step for maintaining the temperature at 270 C. or higher for 40 to 120 seconds with a heating peak temperature at 350 C. or lower. By bonding the solder alloy according to the present invention in combination with a specific flux under the above-described temperature profile, the wettability of the solder alloy can be remarkably improved.
(18) If the solder alloy is to be provided in the form of a formed solder, the bonding can be carried out by using an active atmosphere such as a hydrogen atmosphere or a formic acid atmosphere. In this case, the alloy is heated up to the solidus temperature of Bi of 270 C. or higher, and the heating peak temperature is set to a temperature higher than the liquidus temperature of the alloy by 30 C. For the heating time, an excellent wettability can be obtained by maintaining the heated state for at least 60 seconds. For the heating peak temperature, it is not always necessary to carry out heating up to the liquidus temperature or higher, and if the component of the alloy is close to that of pure Bi, excellent bonding can be secured even under an active atmosphere by performing the heating at a temperature of around 270 C., which is the solidus temperature of pure Bi, +30 C.
Second Embodiment: A BiGe Binary Alloy
(19) According to the second embodiment of the present invention, a solder alloy for die bonding contains 0.01% by mass to 2.0% by mass of Ge, and the remainder consists of Bi and inevitable impurities. The solder alloy according to the second embodiment also is a lead-free solder alloy which does not include Sn or Pb except for Sn or Pb contained in the inevitable impurities.
(20)
(21) More preferably, the solder alloy according to the present embodiment may contain 0.01% by mass to 1.0% by mass of Ge. This is intended to achieve an excellent plastic workability, which can be achieved if the load of Ge is 1% by mass or lower.
(22) More preferably, the solder alloy according to the present embodiment may contain 0.01% by mass to 0.2% by mass of Ge. If the load of Ge is 0.2% by mass or smaller, the amount of the precipitate becomes small in terms of the alloy structure, which thereby suppresses increase of flaws and decrease of the strength that may occur due to crystallization of the precipitate. Further, by adding Ge, growth of a primary crystal of Bi is suppressed and the particle size of the primary crystal becomes fine. Because the primary crystal is refined as described above, it is considered that brittle failures, which may occur due to cleavage uniquely occurring in Bi, can be suppressed. The primary crystal may be expected to be further refined by using a material that contains more Ge; however, flaws may increase and the strength of the alloy may decrease in this case due to crystallization of the precipitate. In addition, if a material to be added having a high Ge content in which the primary crystal of Bi is more refined is used, then the workability may considerably degrade because the strength becomes high. Therefore, it is useful if the load of Ge be 0.01% by mass to 0.2% by mass as described above.
(23) Yet more preferably, the material may contain 0.01% by mass to 0.1% by mass of Ge. In the present embodiment, the heating peak temperature for bonding is preferably a temperature higher than the liquidus temperature of the material by about 30 C. It is advantageous that the load of Ge be 0.1% by mass or smaller because in this case, the liquidus temperature increases by a level as small as 2 C. to 3 C., and thus, it is possible to set conditions for bonding that use low heat energy without requiring excessive heating. The primary crystal may be expected to be further refined by using a material that contain more Ge as described above; however, if the load of Ge is 0.2% by mass, for example, then the liquidus temperature increases by about 10 C., and thus it becomes necessary to carry out the heating at a higher temperature. Accordingly, it is more preferable that the load of Ge be 0.1% by mass or lower. Most electronic parts are constituted by resins such as epoxy resin, metals, and the like. Although many materials have been improved in terms of the heat resistance temperature in recent years, resins generally have a heat resistance temperature ranging from 280 to 300 C., and considering the reliability of resins, if the bonding is to be performed in the temperature region of about 300 C., it is necessary to very deliberately determine the heating conditions for the bonding. Should the liquidus temperature to rise by about 10 C. in this temperature region, there arises a threat of the bonding temperature exceeding the heat resistance temperature of the resin. From these points of view, it is preferable that the solder alloy according to the present embodiment be a solder alloy which has a composition capable of realizing a low liquidus temperature and improving the bonding characteristics of the alloy by suppressing generation of oxides and by refining of the structure, and it is especially suitable if the load of Ge be 0.01% by mass to 0.1% by mass as described above.
(24) The solder alloy according to the present embodiment also can be prepared by melting the stock Bi and Ge in an electric furnace in accordance with an ordinary method, and it is preferable to use materials with a purity of 99.99% by mass or higher as the materials.
(25) The solder alloy according to the present embodiment constituted by a BiGe binary alloy can be provided in the form of a solder paste by working the solder alloy into powder and mixing the powder with a flux. By mixing the solder alloy with a flux, the wettability can be expected to further improve. The particle size of the powdered solder, the type of the flux, and the suitable composition of the flux in this case are the same as those described above in the first embodiment. In addition, the method of use and the bonding method in the case in which the solder alloy is to be provided in the form of a formed solder are the same as those described above in the first embodiment.
Third Embodiment: A BiSbGe Ternary Alloy
(26) According to the third embodiment of the present invention, a solder alloy for die bonding contains 0.05% by mass to 3.0% by mass of Sb and 0.01% by mass to 1.0% by mass of Ge, and the remainder consists of Bi and inevitable impurities. By adding Sb and Ge by the load in the above-described ranges, bonding can be performed at a high melting point of 270 to 345 C. while maintaining the solidus temperature of a metal of Bi at 260 C. or higher, and thereby the workability can be improved to a level at which the alloy can be worked as a solder alloy. In addition, the wettability of the alloy can be improved compared with the case of using the metal of Bi alone.
(27) It is more preferable that the solder alloy according to the present embodiment contain 0.05% by mass to 1.0% by mass of Sb and further contain 0.01% by mass to 0.2% by mass of Ge and if the remainder consist of Bi and inevitable impurities. By adding Sb and Ge by the load in the above-described ranges, a more excellent wettability can be achieved. In addition, the alloy can be allowed to have a metal structure in which no precipitation occurs, and thereby the working characteristic can be further improved.
(28) Note that in the ternary solder alloy according to the present embodiment, the loads of Sb and Ge can be limited to the loads described above in the first and the second embodiments as the more preferable ranges, and the advantages described above are maintained in this case.
(29) The solder alloy according to the present embodiment can be prepared by melting the stocks of a base metal constituted by a BiGe material and a base metal constituted by a BiSb material in an electric furnace.
(30) The solder alloy according to the present embodiment can be also worked in the form of a plate-like preform material, a formed solder, or a solder paste prepared by powdering the solder alloy and mixing the powdered solder with a flux. If the solder alloy is used as a solder paste, the particle size of the powdered solder, the type of the flux, and the suitable composition of the flux are the same as those described above in the first embodiment. In addition, the method of use and the bonding method in the case in which the solder alloy is provided in the form of a formed solder are the same as those described above in the first embodiment.
Fourth Embodiment: A BiSbGeNi Quaternary Alloy
(31) According to the fourth embodiment of the present invention, a solder alloy for die bonding contains 0.05% by mass to 3.0% by mass of Sb, 0.01% by mass to 1.0% by mass of Ge, and 0.01% by mass to 0.1% by mass of Ni, and the remainder consists of Bi and inevitable impurities.
(32) Further, it is more preferable that the solder alloy according to the present embodiment contain 0.05% by mass to 1.0% by mass of Sb, 0.01% by mass to 0.2% by mass of Ge, and 0.01% by mass to 0.1% by mass of Ni and that the remainder consist of Bi and inevitable impurities.
(33) By adding Ni by the load in the above-described range, not only can the advantages of the compositions described above in the first to the third embodiments be obtained, but also excessive generation of Bi.sub.3Ni that may be locally crystallized can be suppressed and also degradation of the bondability and the reliability can be prevented. In addition, the present embodiment is advantageous because the heat resistance of the solder alloy can be improved due to the heat resistance characteristic that Ni per se includes.
(34) The solder alloy according to the present embodiment can be prepared by melting the stocks of a base metal constituted by a BiGe material, a base metal constituted by a BiSb material, and a base metal constituted by a BiNi material in an electric furnace. In addition, the solder alloy according to the present embodiment can be also worked in the form of a plate-like preform material, a formed solder, or a solder paste prepared by powdering the solder alloy and mixing the powdered solder with a flux. If the solder alloy is used as a solder paste, the particle size of the powdered solder, the type of the flux, and the suitable composition of the flux are the same as those described above in the first embodiment. In addition, the method of use and the bonding method in the case in which the solder alloy is provided in the form of a formed solder are the same as those described above in the first embodiment.
(35) Further, Ni can be added by the load of 0.01% by mass to 0.1% by mass not only to the quaternary composition specifically described above but also to all the compositions of the first, the second, and the third embodiments described herein, which is advantageous for all the above compositions in order to improve the heat resistance and the bondability and also advantageous in order to achieve the effect of suppressing substances that may be crystallized in an excessive amount.
Fifth Embodiment: A BiSbGeP Quaternary Alloy and a BiSbGeNiP Quinary Alloy
(36) According to the fifth embodiment of the present invention, a solder alloy for die bonding contains 0.05% by mass to 3.0% by mass of Sb, 0.01% by mass to 1.0% by mass of Ge, and 0.001% by mass to 0.1% by mass of P, and the remainder consists of Bi and inevitable impurities. It is more preferable that the solder alloy according to the present embodiment contain 0.05% by mass to 1.0% by mass of Sb, 0.01% by mass to 0.2% by mass of Ge, and 0.001% by mass to 0.1% by mass of P and if the remainder consist of Bi and inevitable impurities. The content of P is more preferably 0.001% by mass to 0.05% by mass. This is because if the content of P is 0.05% by mass or higher, a phase rich in P may be generated and thereby degradation of the impact strength may occur in some cases. In addition, as illustrated in a diagram of a BiP binary phase (not shown), it is considered that only an extremely small amount of P acts on Bi. Accordingly, the more suitable load is 0.001% by mass to 0.05% by mass.
(37) Alternatively, the solder alloy according to the present embodiment is a quinary solder alloy for die bonding containing 0.05% by mass to 3.0% by mass of Sb, 0.01% by mass to 1.0% by mass of Ge, 0.01% by mass to 0.1% by mass of Ni, and 0.001% by mass to 0.1% by mass of P, and the remainder consists of Bi and inevitable impurities. It is more preferable that the solder alloy according to the present embodiment contain 0.05% by mass to 1.0% by mass of Sb, 0.01% by mass to 0.2% by mass of Ge, 0.01% by mass to 0.1% by mass of Ni, and 0.001% by mass to 0.1% by mass of P and that the remainder consist of Bi and inevitable impurities. In addition, in the quinary solder alloy for die bonding described above also, it is preferable that the content of P be 0.001% by mass to 0.05% by mass due to the same reasons as described above.
(38) By adding P by the load in the range described above, oxidation of Bi can be prevented, and thereby the bondability can be improved. In addition, the present embodiment is advantageous also in the point that it improves the workability in preparing a powdered alloy by working the solder alloy.
(39) The solder alloy according to the present embodiment can be prepared by melting the stocks of a base metal constituted by a BiGe material, a base metal constituted by a BiSb material, and a base metal constituted by a BiP material, and optionally the stocks of a base metal constituted by a BiNi material, in an electric furnace. In addition, the solder alloy according to the present embodiment can be also worked in the form of a plate-like preform material, a formed solder, or a solder paste prepared by powdering the solder alloy and mixing the powdered solder with a flux. If the solder alloy is used as a solder paste, the particle size of the powdered solder, the type of the flux, and the suitable composition of the flux are the same as those described above in the first embodiment. In addition, the method of use and the bonding method in the case in which the solder alloy is provided in the form of a formed solder are the same as those described above in the first embodiment.
(40) Further, P can be added by the load of 0.001% by mass to 0.1% by mass, preferably by the load of 0.001% by mass to 0.05% by mass, not only to the quaternary composition and the quinary composition specifically described above, but also to all the compositions of the first, the second, and the third embodiments described herein, which is advantageous for all the above compositions in order to suppress oxidation and improve the workability characteristics in working the solder alloy into powder while maintaining the characteristics such as the temperature characteristics, the workability, and the wettability at the same time.
EXAMPLES
(41) (1) Influence on the Wettability Applied Due to the Presence of the Elements Added to a Bi-Based Alloy (Formed Solder)
(42) The wetting and spreading property in the case in which Ge and Sb were added to Bi as additive elements was measured. In the bonding, a 6.0t 0.2 mm formed solder was used, the flux was applied onto an Ni-coated plate by using a 6.5t 0.2 mm metal mask, and the formed solder was mounted thereon to perform the soldering by reflow soldering. In this process, the preheating was carried out at 170 to 200 C. for 120 seconds, and the reflow soldering was carried out at the primary heating peak temperature of 300 C. under the temperature profile in which the temperature was maintained at 270 C. or higher for 50 seconds. With respect to the method of preparing the flux used in the process, 50 mass parts of a polymerized rosin, 46 mass parts of butyl carbitol, 0.5 mass parts of a cyclohexylamine HBr salt, 0.5 mass parts of adipic acid, and 3 mass parts of a hydrogenated castor oil were charged into a container, and the mixture was heated and melted at 150 C.
(43) The wetting and spreading property was measured as a rate of spread by using a method compliant with JIS Z3197:1999 and calculated in accordance with the following expression.
Rate of spread (%)=(diameter obtained by regarding the solder as a sphereheight of the spread solder)/diameter obtained by regarding the solder as a sphere100
(44) The wettability of Bi-based formed solders will be illustrated in Table 1 and
(45) TABLE-US-00001 TABLE 1 Composition of Wettability solder alloy and rate [% by mass] of spread Workability Structure Sample Bi Ge Sb [%] of rolling of alloy Comparative 100 80.2 Rough Example 1 Example 1 Remainder 0.01 84.1 Rough Example 2 Remainder 0.2 84.1 Rough Example 3 Remainder 0.5 84.0 Rough and a small amount of precipitate Example 4 Remainder 1 83.5 Rough and a small amount of precipitate Example 5 Remainder 2 80.7 Rough and a large amount of precipitate Comparative Remainder 3 x Rough and a Example 2 large amount of precipitate Example 6 Remainder 0.05 84.1 Rough Example 7 Remainder 0.5 87.4 Rough Example 8 Remainder 1 88.4 Rough Example 9 Remainder 1.5 88.0 Rough Example 10 Remainder 2 87.1 Rough Example 11 Remainder 3 85.5 Rough Comparative Remainder 4 83.3 Fine Example 4 Comparative Remainder 5 80.9 Fine Example 5 Comparative Remainder 7.5 x Extremely Example 3 fine Example 12 Remainder 0.01 0.05 84.6 Rough Example 13 Remainder 0.2 1 88.2 Rough Example 14 Remainder 1 3 84.9 Rough and a small amount of precipitate
(46) (2) Influence on the Wettability Applied Due to the Presence of the Elements Added to a Bi-Based Alloy (Solder Paste)
(47) A powder of a solder in which Ge and Sb were added to Bi was prepared, and the wettability of the solder paste was evaluated. The above-described flux and the solder powder (particle size: 25 to 45 m) were charged into a container at the mass ratio of 11:89, and the mixture was stirred to prepare the solder paste. The solder paste was applied onto a Ni-coated plate and a Cu plate by using a 6.5t 0.2 mm metal mask and the reflow soldering was carried out under the profile described above.
(48)
(49) As can be known from
(50) (3) Influence on the Alloy Structure and the Workability Applied Due to the Presence of the Elements Added to a Bi-Based Alloy
(51) A formed solder constituted by the Bi-based alloy was worked by hot rolling at the temperature ranging from 100 C. to the melting point. The rollability of the formed solder is shown in Table 1. In Table 1, (circle) indicates that the workability of the solder alloy was excellent, (triangle) simply indicates that the solder alloy was workable, and x (cross) indicates that the solder alloy was not workable.
(52) In the cases in which Sb was added, the solder alloy was rollable up to the addition of Sb by the load of 5% by mass; however, the difficulty of the rolling became high for the range in excess of addition of Sb by the load of 3% by mass. Referring to the structure photographs illustrated in
(53) In the case in which Ge was loaded, the solder alloy was rollable up to an addition of Ge by the load of 2% by mass; however, the difficulty of the rolling became high for the range of the load of Ge by 1% by mass or more. It was considered that this occurred because, as illustrated in the structure photographs shown in
INDUSTRIAL APPLICABILITY
(54) The solder alloy according to the present invention is used generally for electronic devices in portions of a semiconductor chip and the like to be bonded by die bonding. Specifically, the solder alloy according to the present invention is suitably used for bonding of packaged components such as integrated circuits (ICs). In addition, the solder alloy according to the present invention is suitably used for die bonding of portions of components in which high heat is generated, e.g., power semiconductor devices such as light-emitting diodes (LEDs) or power diodes, and further for die bonding of portions of internal bonding of an IC devices of electronic devices in general. In addition, the solder alloy according to the present invention can be applied to products such as illumination components that use the LEDs described above, drive circuits of inverter devices, power conversion devices such as power modules, and the like.