WO2015068685A1 - Cu核ボール、はんだペースト、フォームはんだ、Cu核カラム及びはんだ継手 - Google Patents
Cu核ボール、はんだペースト、フォームはんだ、Cu核カラム及びはんだ継手 Download PDFInfo
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- WO2015068685A1 WO2015068685A1 PCT/JP2014/079214 JP2014079214W WO2015068685A1 WO 2015068685 A1 WO2015068685 A1 WO 2015068685A1 JP 2014079214 W JP2014079214 W JP 2014079214W WO 2015068685 A1 WO2015068685 A1 WO 2015068685A1
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
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- B23K35/302—Cu as the principal constituent
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
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- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
Definitions
- the present invention relates to a Cu core ball in which a Cu ball is coated with a solder alloy, a solder paste using the Cu core ball, a foam solder using the Cu core ball, a solder joint using the Cu core ball, a Cu core column, Cu
- the present invention relates to a solder joint using a nuclear column.
- BGA ball grid array
- An electronic component to which BGA is applied includes, for example, a semiconductor package.
- a semiconductor package a semiconductor chip having electrodes is sealed with a resin.
- Solder bumps are formed on the electrodes of the semiconductor chip. This solder bump is formed by joining a solder ball made of spherical solder or a solder column made of solder into a columnar shape to an electrode of a semiconductor chip.
- a semiconductor package using BGA is mounted on a printed circuit board by placing the solder bumps on the printed circuit board so that each solder bump contacts the conductive land of the printed circuit board, and the solder bumps and lands melted by heating are joined. Is done. Further, in order to meet the demand for further high-density mounting, three-dimensional high-density mounting in which semiconductor packages are stacked in the height direction has been studied.
- solder bumps using, for example, Cu core balls or Cu core columns, in which solder is coated on the surface of small diameter balls or columnar columns formed of a metal having a melting point higher than that of solder, such as Cu, have been studied. ing.
- a solder bump having a Cu ball or the like can support the semiconductor package with a Cu ball that does not melt at the melting point of the solder even when the weight of the semiconductor package is applied to the solder bump when the electronic component is mounted on the printed board. Therefore, the solder bump is not crushed by the weight of the semiconductor package.
- Patent Document 1 is cited.
- a solder bump manufactured using a solder ball, a solder column, a Cu core ball, or a Cu core column is required to have a strength against an impact such as a drop and a strength against expansion and contraction due to a temperature change called a heat cycle. .
- a solder ball made of a solder alloy containing Ag can have a predetermined strength for both drop strength and heat cycle.
- a solder alloy called low Ag in which the amount of Ag added is about 1.0% both the drop strength and the strength against the heat cycle can obtain a predetermined strength.
- An object of the present invention is to provide a drop strength and heat cycle strength equal to or higher than those of a solder ball or a solder column even in a Cu core ball. Solder paste, foam solder and solder joint, Cu core column, and solder joint using Cu core column.
- the solder made of the solder alloy not containing Ag is used. It was found that the drop strength is comparable to that of a ball or solder column, and the strength against heat cycle is improved.
- a Cu core ball comprising a core layer composed of Cu or a Cu alloy containing 50% or more of Cu and a solder layer composed of a solder alloy composed of Sn and Cu and covering the core layer.
- solder layer includes Cu in a range of 0.1% to 3.0%, and the balance is composed of Sn and impurities.
- a Cu nucleus column comprising a core layer composed of Cu or a Cu alloy containing 50% or more of Cu and a solder layer composed of a solder alloy composed of Sn and Cu and covering the core layer.
- solder layer includes Cu in a range of 0.1% to 3.0%, and the remainder is composed of Sn and impurities.
- the required strength can be obtained for both the drop strength and the heat cycle strength.
- a solder ball made of a solder alloy containing no Ag has a lower strength against heat cycles than a solder ball made of a solder alloy containing Ag.
- a solder alloy containing Ag is used.
- the strength against heat cycle is improved.
- the strength against heat cycle is improved as compared with a Cu core column made of a solder alloy containing Ag.
- the unit (ppm, ppb, and%) relating to the composition of the Cu core ball represents a ratio (mass ppm, mass ppb, and mass%) to mass unless otherwise specified.
- FIG. 1 is a cross-sectional view showing a schematic structure of a Cu core ball of the present embodiment.
- the Cu core ball 1 according to the present embodiment includes a Cu ball 2 and a solder layer 3 that covers the Cu ball.
- the solder layer 3 is made of an Ag-free solder alloy in which the addition amount of Cu is 0.1% or more and 3.0% or less, and the balance is Sn, and solder is plated by solder plating on the surface of the Cu balls 2. Layer 3 is formed.
- the Cu ball 2 is made of Cu or a Cu alloy containing 50% or more of Cu.
- a diffusion prevention layer 4 is formed between the Cu ball 2 and the solder layer 3.
- the diffusion prevention layer 4 is composed of one or more elements selected from Ni, Co, and the like, and prevents Cu constituting the Cu ball 2 from diffusing into the solder layer 3.
- the solder layer 3 is formed on the surface of the Cu ball 2 with a solder alloy having a composition not containing Ag, in which the addition amount of Cu is 0.1% or more and 3.0% or less and the balance is Sn.
- the object to be joined is a Cu-OSP substrate in which the surface of the Cu layer is prefluxed, or an electrolytic Ni / Au plated substrate in which the surface of the Cu layer is subjected to electrolytic Ni / Au plating
- the required strength can be obtained both for the strength against an impact such as a drop and the strength against expansion and contraction due to a temperature change called a heat cycle.
- solder ball made of a solder alloy containing no Ag is less resistant to heat cycles than a solder ball made of a solder alloy containing Ag.
- the solder layer 3 is formed of a solder alloy that does not contain Ag, but the required drop compared to a Cu core ball made of a solder alloy containing Ag. In addition to obtaining strength, strength against heat cycle is improved.
- the semiconductor package can be supported by the Cu ball that does not melt at the melting point of the solder alloy. Therefore, the solder bump is not crushed by the weight of the semiconductor package.
- the soft error is that the stored content may be rewritten when ⁇ rays enter a memory cell of a semiconductor integrated circuit (hereinafter referred to as “IC”).
- ⁇ rays are emitted by ⁇ decay of radioactive isotopes such as U, Th, 210 Po and the like contained as impurities in the solder alloy. Accordingly, solder alloys having a composition that can realize low ⁇ rays have been developed.
- the Cu core ball 1 if the Cu ball 2 is covered with the solder layer 3 and the solder alloy constituting the solder layer 3 can realize low ⁇ rays, the ⁇ rays emitted from the Cu balls 2 can be shielded. However, even with the Cu ball 2, a composition capable of realizing low ⁇ rays is required.
- Cu core ball 1 if the sphericity indicating how close to the true sphere is low, the fluidity at the time of mounting and the uniformity of the solder amount are lowered when the solder bump is formed. . For this reason, Cu core ball 1 with high sphericity is desired.
- the composition of the solder layer 3 is a lead-free solder alloy containing Sn as a main component, and is a Sn—Cu alloy from the viewpoint of strength against impact such as dropping and strength against heat cycle.
- the thickness of the solder layer 3 is not particularly limited, but is preferably 100 ⁇ m (one side) or less. Generally, it may be 1 to 50 ⁇ m.
- the solder layer 3 is formed by flowing a Cu ball 2 or a plating solution. Due to the flow of the plating solution, elements of Pb, Bi, and Po form salts in the plating solution and precipitate. Once a precipitate that is a salt is formed, it is stably present in the plating solution. Therefore, in the Cu core ball 1 according to the present invention, precipitates are not taken into the solder layer 3, the content of radioactive elements contained in the solder layer 3 can be reduced, and the ⁇ dose of the Cu core ball 1 itself is reduced. It becomes possible.
- U and Th are radioactive elements, and it is necessary to suppress their contents in order to suppress soft errors.
- the U and Th contents need to be 5 ppb or less in order to make the ⁇ dose of the solder layer 3 0.0200 cph / cm 2 or less. Further, from the viewpoint of suppressing soft errors in current or future high-density mounting, the contents of U and Th are preferably 2 ppb or less, respectively.
- the ⁇ dose of the Cu core ball 1 according to the present invention is 0.0200 cph / cm 2 or less. This is an ⁇ dose that does not cause a soft error in high-density mounting of electronic components.
- the ⁇ dose of the Cu core ball 1 according to the present invention is achieved when the ⁇ dose of the solder layer 3 constituting the Cu core ball 1 is 0.0200 cph / cm 2 or less. Further, the ⁇ dose of the Cu core ball 1 can also be achieved when the ⁇ dose of the Cu ball 2 is 0.0200 cph / cm 2 or less, as will be described later.
- the Cu core ball 1 according to the present invention is formed at a temperature of 100 ° C. at the highest, it is unlikely that the content of radioactive elements is reduced by vaporization of radioactive elements such as U, Th, 210 Po, Bi and Pb.
- radioactive elements such as U, Th, 210 Po, Bi and Pb.
- U, Th, Pb, Bi, and 210 Po are precipitated by forming a salt in the plating solution.
- the precipitated salt is electrically neutral and does not enter the solder plating film even if the plating solution is flowing.
- the Cu core ball 1 according to the present invention since the Cu core ball 1 according to the present invention is covered with such a solder layer 3, it exhibits a low ⁇ dose.
- the ⁇ dose is preferably 0.0020 cph / cm 2 or less, and more preferably 0.0010 cph / cm 2 or less, from the viewpoint of suppressing soft errors in further high-density mounting.
- the lower limit of the amount of impurities is not particularly limited.
- the upper limit is preferably 1000 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, and particularly preferably 10 ppm or less from the viewpoint of reducing the ⁇ dose.
- the total amount of impurities in the solder layer 3 is the total content of impurities other than Sn and Cu in the solder layer 3.
- the contents of Bi and Pb are small.
- Bi and Pb contain trace amounts of 210 Bi and 210 Pb, which are radioisotopes, respectively. Therefore, it is considered that the ⁇ dose of the solder layer 3 can be remarkably reduced by reducing the contents of Bi and Pb.
- the contents of Bi and Pb in the solder layer 3 are each preferably 15 ppm or less, more preferably 10 ppm or less, and particularly preferably 0 ppm each.
- composition, ⁇ dose, and sphericity of the Cu ball 2 constituting the Cu core ball 1 according to the present invention will be described in detail.
- the Cu ball 2 constituting the Cu core ball 1 according to the present invention does not melt at the soldering temperature when the Cu core ball 1 is used for a solder bump, it is possible to suppress variations in the height of the solder joint. Therefore, it is preferable that the Cu ball 2 has a high sphericity and a small variation in diameter. Further, as described above, it is preferable that the ⁇ dose of the Cu ball 2 is also low like the solder layer 3. The preferred embodiment of the Cu ball 2 is described below.
- U and Th are radioisotopes, and it is necessary to suppress their contents in order to suppress soft errors.
- the contents of U and Th are required to be 5 ppb or less in order to make the ⁇ dose of the Cu ball 2 0.0200 cph / cm 2 or less. Further, from the viewpoint of suppressing soft errors in current or future high-density mounting, the contents of U and Th are preferably 2 ppb or less, respectively.
- Cu ball purity 99.9% to 99.995%
- Cu ball 2 has a purity of 3N or more and 4N5 or less. That is, the Cu ball 2 has an impurity element content of 50 ppm or more.
- the purity of a metal material such as Cu is 99% 2N, 99.9% 3N, 99.99% 4N, and 99.999% 5N. 4N5 indicates that the purity of the metal material is 99.995%.
- the Cu material formed into small pieces of a predetermined shape is melted by heating, and the molten Cu becomes spherical due to surface tension, which solidifies to become the Cu ball 2.
- the molten Cu solidifies from the liquid state, crystal grains grow in the spherical molten Cu.
- the impurity elements serve as crystal nuclei and growth of crystal grains is suppressed. Accordingly, the spherical molten Cu becomes a Cu ball 2 having a high sphericity due to the fine crystal grains whose growth is suppressed.
- the impurity element include Sn, Sb, Bi, Zn, Fe, Al, As, Ag, In, Cd, Cu, Pb, Au, P, S, U, and Th.
- the lower limit of purity is not particularly limited, it is preferably 3N or more from the viewpoint of suppressing the ⁇ dose and suppressing deterioration of electrical conduction and thermal conductivity of the Cu ball 2 due to a decrease in purity. That is, the content of impurity elements in the Cu ball 2 excluding Cu is preferably less than 1000 ppm.
- ⁇ dose 0.0200 cph / cm 2 or less
- the ⁇ dose of Cu ball 2 is 0.0200 cph / cm 2 or less. This is an ⁇ dose that does not cause a soft error in high-density mounting of electronic components.
- the ⁇ dose is preferably 0.0020 cph / cm 2 or less, and more preferably 0.0010 cph / cm 2 or less, from the viewpoint of suppressing soft errors in further high-density mounting.
- the content of either Pb or Bi, or the total content of Pb and Bi is 1 ppm or more.
- impurity elements contained in the Cu ball 2 Sn, Sb, Bi, Zn, Fe, Al, As, Ag In, Cd, Cu, Pb, Au, P, S, U, Th, etc. are conceivable, but the Cu ball 2 constituting the Cu core ball 1 according to the present invention is either Pb or Bi among the impurity elements.
- Such a content, or the total content of Pb and Bi is preferably 1 ppm or more as an impurity element.
- 210 Pb is changed to 210 Bi by decay beta
- 210 Bi is changed to 210 Po by decay beta
- 210 Po is changed to 206 Pb by decay alpha.
- the content of either the impurity element Pb or Bi, or the content of Pb and Bi is as low as possible.
- the content ratio of 210 Pb contained in Pb and 210 Bi contained in Bi is low. Therefore, if the content of Pb and Bi is reduced to some extent, it is considered that 210 Pb and 210 Bi are sufficiently removed to such an extent that the ⁇ dose can be reduced to the aforementioned range.
- the content of the impurity element is high as described above.
- the Cu ball 2 preferably has a Pb or Bi content, or a total content of Pb and Bi of 1 ppm or more.
- the content of either Pb or Bi, or the total content of Pb and Bi is more preferably 10 ppm or more.
- the upper limit is not limited as long as the ⁇ dose can be reduced, but from the viewpoint of suppressing deterioration of the electrical conductivity of the Cu ball 2, the content of either Pb or Bi, or the total of Pb and Bi is more preferable. Is less than 1000 ppm.
- the content of Pb is more preferably 10 ppm to 50 ppm, and the content of Bi is more preferably 10 ppm to 50 ppm.
- the sphericity of the Cu ball 0.95 or more
- the shape of the Cu ball 2 is preferably 0.95 or more from the viewpoint of controlling the standoff height.
- the sphericity of the Cu ball 2 is less than 0.95, the Cu ball has an indefinite shape, so that bumps with non-uniform height are formed at the time of bump formation, and the possibility of occurrence of poor bonding is increased.
- the sphericity is more preferably 0.990 or more. In the present invention, the sphericity represents a deviation from the sphere.
- the sphericity is obtained by various methods such as a least square center method (LSC method), a minimum region center method (MZC method), a maximum inscribed center method (MIC method), and a minimum circumscribed center method (MCC method).
- LSC method least square center method
- MZC method minimum region center method
- MIC method maximum inscribed center method
- MCC method minimum circumscribed center method
- the sphericity is an arithmetic average value calculated when the diameter of each of the 500 Cu balls 2 is divided by the major axis, and the closer the value is to the upper limit of 1.00, the closer to the true sphere.
- the length of the major axis and the length of the diameter mean a length measured by an ultra quick vision, ULTRA QV350-PRO measuring device manufactured by Mitutoyo Corporation.
- the diameter of the Cu ball 2 is preferably 1 to 1000 ⁇ m. Within this range, spherical Cu balls 2 can be manufactured stably, and connection short-circuiting when the terminals are at a narrow pitch can be suppressed.
- the Cu core ball 1 is used for a solder paste in which a solder powder, a Cu core ball 1 and a flux are kneaded.
- the “Cu core ball” may be referred to as “Cu core powder”.
- Cu core powder is an aggregate of a large number of Cu core balls 1 having the above-mentioned characteristics. For example, it is distinguished from a single Cu core ball in the form of use, such as being blended as a powder in a solder paste. Similarly, when used for the formation of solder bumps, it is normally treated as an aggregate, so that the “Cu core powder” used in such a form is distinguished from a single Cu core ball.
- the diameter of the Cu core ball is generally 1 to 300 ⁇ m.
- the Cu core ball 1 according to the present invention is used for foam solder in which the Cu core ball 1 is dispersed in the solder.
- a solder alloy having a composition of Sn-3Ag-0.5Cu each numerical value is% by mass
- the present invention is not limited to this solder alloy.
- the Cu core ball 1 according to the present invention is used for a solder joint of an electronic component.
- the present invention may also be applied to the form of columns, pillars, and pellets having Cu as a nucleus.
- the Cu material used as a material is placed on a heat-resistant plate which is a heat-resistant plate such as ceramic, and is heated together with the heat-resistant plate in a furnace.
- the heat-resistant plate is provided with a number of circular grooves whose bottoms are hemispherical.
- the diameter and depth of the groove are appropriately set according to the particle diameter of the Cu ball. For example, the diameter is 0.8 mm and the depth is 0.88 mm.
- chip-shaped Cu material hereinafter referred to as “chip material” obtained by cutting the Cu thin wire is put into the groove of the heat-resistant plate one by one.
- the heat-resistant plate in which the chip material is put in the groove is heated to 1100 to 1300 ° C. in a furnace filled with ammonia decomposition gas and subjected to heat treatment for 30 to 60 minutes. At this time, if the furnace temperature becomes equal to or higher than the melting point of Cu, the chip material melts and becomes spherical. Then, the inside of a furnace is cooled and the Cu ball
- a molten Cu droplet is dropped from an orifice provided at the bottom of the crucible, and this droplet is cooled to form a Cu ball 2 or thermal plasma is Cu-cut.
- a metal is heated to 1000 ° C. or more and granulated.
- the Cu balls 2 thus granulated may be reheated at a temperature of 800 to 1000 ° C. for 30 to 60 minutes.
- the Cu material as a raw material of the Cu ball 2 may be heat-treated at 800 to 1000 ° C. before the Cu ball 2 is granulated.
- the Cu material that is the raw material of the Cu ball 2 for example, pellets, wires, pillars, and the like can be used.
- the purity of the Cu material may be 99.9 to 99.99% from the viewpoint of not reducing the purity of the Cu ball too much.
- the heat treatment described above may not be performed, and the molten Cu holding temperature may be lowered to about 1000 ° C. as in the conventional case.
- the above-described heat treatment may be omitted or changed as appropriate according to the purity of the Cu material and the ⁇ dose.
- these Cu balls can be reused as raw materials, and the ⁇ dose can be further reduced.
- solder layer 3 on the Cu ball 2 by flowing the Cu ball 2 or the plating solution produced as described above, it is connected to a known electrolytic plating method such as barrel plating or a plating tank.
- a pump generates high-speed turbulent flow in the plating solution in the plating tank, and a plating film is formed on the Cu balls 2 by the turbulent flow of the plating solution.
- the solution is stirred at high speed and a plating film is formed on the Cu balls 2 by the turbulent flow of the plating solution.
- a Cu ball with a diameter of 100 ⁇ m is coated with Ni plating with a film thickness of 2 ⁇ m (one side), and further an 18 ⁇ m Sn—Cu solder plating film is formed on the Ni plating to form a Cu core ball with a diameter of about 140 ⁇ m. explain.
- the Sn—Cu-containing plating solution according to an embodiment of the present invention contains Sn and Cu as essential components as a sulfonic acid and a metal component in a medium mainly composed of water.
- the metal component is present as Sn ions (Sn 2+ and / or Sn 4+ ) and Cu ions (Cu + / Cu 2+ ) in the plating solution.
- the plating solution is obtained by mixing a plating mother solution mainly composed of water and sulfonic acids and a metal compound, and preferably contains an organic complexing agent for the stability of metal ions.
- Examples of the metal compound in the plating solution include the following.
- Specific examples of the Sn compound include tin salts of organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, p-phenolsulfonic acid, tin sulfate, tin oxide, tin nitrate, tin chloride, bromide.
- the 1st Sn compound of these is mentioned. These Sn compounds can be used individually by 1 type or in mixture of 2 or more types.
- Cu compound copper salts of the above organic sulfonic acids, copper sulfate, copper oxide, copper nitrate, copper chloride, copper bromide, copper iodide, copper phosphate, copper pyrophosphate, copper acetate, copper formate, copper citrate , Copper gluconate, copper tartrate, copper lactate, copper succinate, copper sulfamate, copper borofluoride, copper silicofluoride and the like.
- These Cu compounds can be used individually by 1 type or in mixture of 2 or more types.
- the amount of each metal in the plating solution is 0.05 to 2 mol / L, preferably 0.25 to 1 mol / L as Sn 2+ , and 0.002 to 0.02 mol / L, preferably 0.003, as Cu. -0.01 mol / L.
- the amount of Sn 2+ may be adjusted in the present invention.
- the deposition amount of a desired solder plating is estimated by the following formula (1) according to Faraday's law of electrolysis, the amount of electricity is calculated, and an electric current is passed through the plating solution so that the calculated amount of electricity is obtained. And plating while flowing the plating solution.
- the capacity of the plating tank can be determined according to the total amount of Cu balls and plating solution.
- w is the amount of electrolytic deposition (g)
- I is the current (A)
- t is the energization time (seconds)
- M is the atomic weight of the deposited element (118.71 in the case of Sn)
- Z is The valence (divalent in the case of Sn)
- F is the Faraday constant (96500 coulomb)
- Q is represented by (I ⁇ sec)
- the plating is performed while flowing the Cu ball and the plating solution, but the method of flowing is not particularly limited.
- Cu ball and plating solution can be caused to flow by rotation of the barrel as in the barrel electrolytic plating method.
- the Cu core ball according to the present invention can be obtained by drying in the air or N 2 atmosphere.
- a Cu core ball having a solder layer formed of a solder alloy containing no Ag, a Cu core ball having a solder layer formed of a solder alloy containing Ag, a solder ball formed of a solder alloy containing no Ag, and Ag A solder ball formed of a solder alloy containing, and a drop strength test for measuring strength against impact such as dropping and a heat cycle test for measuring strength against expansion and contraction due to heat cycle were performed.
- Example 1 a Cu core ball 1 having a diameter of 300 ⁇ m was prepared as a Cu core ball 1 as shown in FIG.
- a diffusion preventing layer 4 having a thickness of 2 ⁇ m on one side was formed of Ni on a Cu ball 2 having a diameter of 250 ⁇ m, and a solder layer 3 was formed of a Sn—Cu alloy.
- the composition of the Sn—Cu alloy was Sn—0.7Cu, and the amount of Cu added to the solder layer 3 was 0.7%.
- a Cu core ball having a solder layer formed of a Sn—Ag—Cu alloy was prepared.
- the composition of the Sn-Ag-Cu alloy was Sn-1.0Ag-0.7Cu.
- solder balls were made of Sn—Cu alloy having the same composition as in Example 1.
- solder balls were made of an Sn—Ag—Cu alloy having the same composition as Comparative Example 1.
- the heat cycle test was performed by bonding 15 semiconductor package substrates (PKG) onto one printed wiring board (PCB) using the Cu core balls and solder balls of the above-described examples and comparative examples.
- a substrate was created.
- As the printed wiring board a Cu-OSP substrate having a size of 174 mm ⁇ 120 mm and a thickness of 0.8 mm, in which the surface of the Cu layer was prefluxed, was used.
- a semiconductor package substrate a Cu-OSP substrate having a size of 12 ⁇ 12 mm was used.
- the drop strength test was performed by joining three semiconductor package substrates on one printed wiring board using the Cu core balls and solder balls of the above-described examples and comparative examples.
- a Cu-OSP substrate having a size of 30 ⁇ 120 mm and a thickness of 0.8 mm, in which the surface of the Cu layer was prefluxed, was used.
- a Cu-OSP substrate was used as the semiconductor package substrate.
- the semiconductor package substrate used for the heat cycle test and the drop strength test is formed with a resist film having a film thickness of 15 ⁇ m, and an opening having an opening diameter of 240 ⁇ m is formed in the resist film.
- Cu core balls or solder balls were joined.
- the peak temperature was 245 ° C. in an N 2 atmosphere, preheating was performed at 140 to 160 ° C. for 20 seconds, and main heating was performed at 220 ° C. or more for 40 seconds.
- the semiconductor package substrate to which the Cu core ball or the solder ball was bonded in this way was mounted on a printed wiring board for a heat cycle test and a printed wiring board for a drop strength test.
- the printed wiring board was printed with solder paste having a solder alloy composition of Sn-3.0Ag-0.5Cu for both heat cycle test and drop strength test, with a thickness of 100 ⁇ m and a diameter of 240 ⁇ m.
- substrate with which the Cu core ball or solder ball of the comparative example was joined was connected to the printed wiring board with the reflow furnace.
- the peak temperature was 245 ° C. in the atmosphere, preheating was performed at 140 to 160 ° C. for 70 seconds, and main heating was performed at 220 ° C. or more for 40 seconds.
- both ends of the substrate were fixed using a dedicated jig at a position where the created evaluation substrate was lifted 10 mm from the pedestal.
- a dedicated jig at a position where the created evaluation substrate was lifted 10 mm from the pedestal.
- an impact with an acceleration of 1500 G was repeatedly applied, and the time when the initial resistance value increased 1.5 times was regarded as a break, and the number of drops was recorded.
- the resistance of the prepared evaluation board was constantly measured by a series circuit. 15 cycles on a printed wiring board are considered when the resistance value exceeds 15 ⁇ as one cycle with the heat and thermal shock equipment TSA101LA made by ESPEC being held for 10 minutes each at -40 ° C and + 125 ° C. The number of thermal fatigue cycles when all the solder joints of the package substrate were destroyed was recorded. For each composition, 10 sets of evaluation substrates were prepared and tested 10 times, and the average value was used as the result.
- Table 1 shows the test results when the semiconductor package substrate is a Cu-OSP substrate in which the surface of the Cu layer is prefluxed.
- the semiconductor package substrate is a Cu-OSP substrate in which the surface of the Cu layer is prefluxed, as shown in Table 1, in the Cu core ball of Example 1 in which the solder layer is formed of an Sn-Cu alloy, While the drop strength was improved, the required strength over heat cycle was over 1500 times.
- the Cu core ball of Comparative Example 1 in which the solder layer is formed of an Sn-Ag-Cu alloy can obtain a predetermined strength, but a decrease in strength with respect to the heat cycle. was seen.
- the drop strength was improved in the solder ball of Comparative Example 2 formed of an Sn-Cu alloy, but a decrease in strength was observed with respect to the heat cycle.
- the solder ball of Comparative Example 3 formed of Sn—Ag—Cu alloy, required values were obtained for both drop strength and heat cycle strength.
- the drop strength test and the heat cycle test were performed in the range of 0.1% or more and 3.0% or less of the addition amount of Cu in the solder layer.
- the drop strength and the heat cycle were measured.
- the strength against a value more than required was obtained.
- the amount of Cu added is about 3.0%, the melting point of the solder alloy increases. Therefore, the amount of Cu added to the solder layer formed of the Sn—Cu alloy is preferably 0.1% or more and 2.0% or less.
- ⁇ Measurement of ⁇ dose> a Cu ball having a high sphericity was prepared, and the ⁇ dose of the Cu core ball having a solder layer formed on the surface of the Cu ball was measured.
- the measurement method of sphericity is described in detail below.
- the sphericity was measured with a CNC image measurement system.
- the apparatus is an Ultra Quick Vision, ULTRA QV350-PRO manufactured by Mitutoyo Corporation.
- ⁇ ⁇ dose The measurement method of ⁇ dose is as follows. For measuring the ⁇ dose, an ⁇ ray measuring device of a gas flow proportional counter was used. The measurement sample is a 300 mm ⁇ 300 mm flat shallow container in which Cu balls are spread. This measurement sample was placed in an ⁇ -ray measuring apparatus and allowed to stand for 24 hours in a PR-10 gas flow, and then the ⁇ dose was measured.
- the PR-10 gas (90% argon—10% methane) used for the measurement was obtained after 3 weeks or more had passed since the gas cylinder was filled with the PR-10 gas.
- the use of a cylinder that has passed for more than 3 weeks follows the guidelines of the ⁇ ray measurement method established by JEDEC (Joint Electron Engineering Engineering) so that no ⁇ ray is generated by radon in the atmosphere entering the gas cylinder. It is.
- Table 2 shows the elemental analysis results and ⁇ dose of the produced Cu balls.
- the sphericity of the Cu balls using Cu pellets having a purity of 99.9% and Cu wires having a purity of 99.995% or less showed 0.990 or more.
- the sphericity of Cu balls using a Cu plate having a purity exceeding 99.995% was less than 0.95. For this reason, in the following Examples and Comparative Examples, Cu core balls were produced using Cu balls produced with 99.995% or less of Cu wire.
- a Cu solder ball of Example 2 was prepared by forming a Sn solder plating film under the following conditions for a Cu ball manufactured with a Cu wire having a purity of 99.995% or less.
- the Cu core ball of Example 2 was plated using the following plating solution with an electric charge of about 0.17 coulomb so that a 250 ⁇ m diameter Cu ball was coated with a 50 ⁇ m thick solder layer (one side). Went. When the cross section of the Cu core ball coated with the solder plating film was observed with an SEM photograph, the film thickness was about 50 ⁇ m. After the treatment, it was dried in the air to obtain a Cu core ball.
- the solder plating solution was prepared as follows. The entire volume of a 54% by weight methanesulfonic acid aqueous solution was placed in 1/3 of the water required for adjusting the plating solution in the stirring vessel, and used as groundwater. Next, acetylcysteine, which is an example of a mercaptan compound as a complexing agent, was added and confirmed to be dissolved, and then 2,2 ′ ⁇ -dithiodianiline, which was an example of an aromatic amino compound as another complexing agent, was added. When it became a light blue gel-like liquid, stannous methanesulfonate was quickly added.
- ⁇ -naphthol polyethoxylate (EO 10 mol) 3 g / L as an example of a surfactant was added, and the preparation of the plating solution was completed.
- a plating solution having a methanesulfonic acid concentration of 2.64 mol / L and a tin ion concentration of 0.337 mol / L in the plating solution was prepared.
- the stannous methanesulfonate used in this example was prepared using the following Sn sheet material as a raw material.
- the ⁇ dose of the Sn sheet material was measured in the same manner as the Cu ball except that the Sn sheet material was laid on a 300 mm ⁇ 300 mm flat shallow container.
- the ⁇ dose of the Cu core ball was measured in the same manner as the Cu ball described above.
- the sphericity of the Cu core ball was also measured under the same conditions as the Cu ball. These measurement results are shown in Table 3. As a comparative example, the ⁇ dose of the Sn sheet material was measured.
- the Sn sheet material was used to form a solder layer with a Sn—Cu alloy on a Cu ball.
- the alpha dose was less than 0.0010 cph / cm 2 .
- the Cu core ball of Example 2 was proved to reduce the ⁇ dose by forming a solder plating film by a plating method.
- the Cu core ball according to the present invention has been described above, but the shape of the present invention is not limited to the ball shape as long as the object of preventing the solder bumps from being crushed by the weight of the semiconductor package can be achieved. It can also be applied to Cu core columns. Specifically, a column body in which upper and lower surfaces in direct contact with a substrate such as a cylinder, a triangular column, or a quadrangular column are configured with three or more sides may be applied.
- the Cu column serving as the nucleus can be formed by a known method, and the plating covering the surface of the Cu column can also be formed by the method used for the Cu core ball described above.
- FIG. 2 is a side sectional view showing a schematic structure of the Cu nucleus column of the present embodiment
- FIG. 3 is a plan sectional view showing a schematic structure of the Cu nucleus column of the present embodiment.
- the Cu core column 5 of the present embodiment includes a Cu column 6 and a solder layer 7 that covers the Cu column 6.
- the diameters of the top and bottom surfaces of the Cu column 6 constituting the Cu core column 5 according to the present invention are preferably 1 to 1000 ⁇ m, more preferably 1 to 300 ⁇ m, even more preferably 1 to 200 ⁇ m, particularly when used for fine pitch. Most preferred is 1 to 100 ⁇ m.
- the height L of the Cu column 6 is preferably 1 to 3000 ⁇ m, particularly preferably 1 to 300 ⁇ m, more preferably 1 to 200 ⁇ m, and most preferably 1 to 100 ⁇ m when used for fine pitch. . When the diameter and height L of the Cu column 6 are within the above ranges, mounting with a narrow pitch between the terminals is possible, so that connection short-circuiting can be suppressed and the semiconductor package can be miniaturized and highly integrated. be able to.
- preferable conditions such as purity, ⁇ dose, impurities contained in the Cu column 6 constituting the Cu core column 5 according to the present invention are the same as those of the Cu ball 2 according to the present invention. is there.
- the sphericity is not required in the Cu column 6, it is not necessary that the purity is 4N5 or less, that is, the impurity element content is 50 ppm or more.
- the ⁇ dose can be reduced, it is not necessary to reduce the impurity content to the utmost. If the U and Th contents are reduced to a predetermined value or less in order to reduce the ⁇ dose, Pb or Bi Therefore, it is not necessary to reduce the content of Pb or Bi to the limit. Even if the impurity content is not reduced to the limit, the drop strength and heat cycle strength are not affected.
- solder composition a solder composition having a high degree of purity
- ⁇ dose a solder composition having a high degree of purity
- impurities contained in the solder layer 7 constituting the Cu core column 5 according to the present invention are the same as the conditions of the solder layer 3 according to the present invention.
- preferable conditions such as the ⁇ dose of the Cu core column 5 according to the present invention are the same as the conditions of the Cu core ball 1 according to the present invention.
- a diffusion prevention layer 8 may be formed between the Cu column 6 and the solder layer 7.
- the diffusion prevention layer 8 is composed of one or more elements selected from Ni, Co, or the like, and prevents Cu constituting the Cu column 6 from diffusing into the solder layer 7.
- the Cu core column 5 according to the present invention can also be used as a through-silicon via (TSV) for connecting electrodes between stacked semiconductor chips.
- TSV is manufactured by drilling holes in silicon, forming an insulating layer in the hole, and then forming through conductors in that order, polishing the top and bottom surfaces of silicon and exposing the through conductors on the top and bottom surfaces.
- the through conductor is conventionally formed by filling a hole with Cu or the like by a plating method. In this method, the entire surface of silicon is immersed in a plating solution. There is a risk of adsorption and moisture absorption.
- the Cu core column 5 according to the present invention can be directly inserted into a hole formed in silicon in the height direction and used as a through conductor.
- the Cu core column 5 may be bonded with a solder material such as a solder paste.
- the Cu core column 5 may be bonded only with flux. Thereby, defects such as impurity adsorption and moisture absorption can be prevented, and the manufacturing cost and time can be reduced by omitting the plating step.
- the above-described Cu core column 5 according to the present invention can obtain a drop strength equal to or higher than that of a solder column and a strength against a heat cycle.
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Abstract
Description
(1)Cu、あるいは、Cuを50%以上含むCu合金で構成される核層と、SnとCuからなるはんだ合金で構成され、核層を被覆するはんだ層とを備えたCu核ボール。
U及びThは放射性元素であり、ソフトエラーを抑制するにはこれらの含有量を抑える必要がある。U及びThの含有量は、はんだ層3のα線量を0.0200cph/cm2以下とするため、各々5ppb以下にする必要がある。また、現在または将来の高密度実装でのソフトエラーを抑制する観点から、U及びThの含有量は、好ましくは、各々2ppb以下である。
本発明に係るCu核ボール1のα線量は0.0200cph/cm2以下である。これは、電子部品の高密度実装においてソフトエラーが問題にならない程度のα線量である。本発明に係るCu核ボール1のα線量は、Cu核ボール1を構成するはんだ層3のα線量が0.0200cph/cm2以下であることにより達成される。また、Cu核ボール1のα線量は、後述するように、Cuボール2のα線量が0.0200cph/cm2以下であることによっても達成される。
前述のようにU及びThは放射性同位元素であり、ソフトエラーを抑制するにはこれらの含有量を抑える必要がある。U及びThの含有量は、Cuボール2のα線量を0.0200cph/cm2以下とするため、各々5ppb以下にする必要がある。また、現在または将来の高密度実装でのソフトエラーを抑制する観点から、U及びThの含有量は、好ましくは、各々2ppb以下である。
Cuボール2は純度が3N以上4N5以下である。つまり、Cuボール2は不純物元素の含有量が50ppm以上である。ここで、Cu等の金属材料の純度は、99%を2N、99.9%を3N、99.99%を4N、99.999%を5Nとする。4N5とは、金属材料の純度が99.995%であることを示す。
Cuボール2のα線量は0.0200cph/cm2以下である。これは、電子部品の高密度実装においてソフトエラーが問題にならない程度のα線量である。本発明では、Cuボール2を製造するために通常行っている工程に加え再度加熱処理を施している。このため、Cu材にわずかに残存する210Poが揮発し、Cu材と比較してCuボール2の方がより一層低いα線量を示す。α線量は、更なる高密度実装でのソフトエラーを抑制する観点から、好ましくは0.0020cph/cm2以下であり、より好ましくは0.0010cph/cm2以下である。
Cuボール2に含まれる不純物元素としては、Sn、Sb、Bi、Zn、Fe、Al、As、Ag、In、Cd、Cu、Pb、Au、P、S、U、Thなどが考えられるが、本発明に係るCu核ボール1を構成するCuボール2は、不純物元素の中でも特にPbまたはBiのいずれかの含有量、あるいは、Pb及びBiの合計の含有量が1ppm以上不純物元素として含有することが好ましい。本発明では、α線量を低減する上でPbまたはBiのいずれかの含有量、あるいは、Pb及びBiの含有量を極限まで低減する必要がない。
これは以下の理由による。
Cuボール2の形状は、スタンドオフ高さを制御する観点から真球度は0.95以上であることが好ましい。Cuボール2の真球度が0.95未満であると、Cuボールが不定形状になるため、バンプ形成時に高さが不均一なバンプが形成され、接合不良が発生する可能性が高まる。真球度は、より好ましくは0.990以上である。本発明において、真球度とは真球からのずれを表す。真球度は、例えば、最小二乗中心法(LSC法)、最小領域中心法(MZC法)、最大内接中心法(MIC法)、最小外接中心法(MCC法)など種々の方法で求められる。詳しくは、真球度とは、500個の各Cuボール2の直径を長径で割った際に算出される算術平均値であり、値が上限である1.00に近いほど真球に近いことを表す。本発明での長径の長さ、および直径の長さとは、ミツトヨ社製のウルトラクイックビジョン、ULTRA QV350-PRO測定装置によって測定された長さをいう。
Cuボール2の直径は1~1000μmであることが好ましい。この範囲にあると、球状のCuボール2を安定して製造でき、また、端子間が狭ピッチである場合の接続短絡を抑制することができる。
材料となるCu材はセラミックのような耐熱性の板である耐熱板に置かれ、耐熱板とともに炉中で加熱される。耐熱板には底部が半球状となった多数の円形の溝が設けられている。溝の直径や深さは、Cuボールの粒径に応じて適宜設定されており、例えば、直径が0.8mmであり、深さが0.88mmである。また、Cu細線が切断されて得られたチップ形状のCu材(以下、「チップ材」という。)は、耐熱板の溝内に一個ずつ投入される。
Sn化合物の具体例としては、メタンスルホン酸、エタンスルホン酸、2-プロパノールスルホン酸、p-フェノールスルホン酸などの有機スルホン酸の錫塩、硫酸錫、酸化錫、硝酸錫、塩化錫、臭化錫、ヨウ化錫、リン酸錫、ピロリン酸錫、酢酸錫、ギ酸錫、クエン酸錫、グルコン酸錫、酒石酸錫、乳酸錫、コハク酸錫、スルファミン酸錫、ホウフッ化錫、ケイフッ化錫などの第一Sn化合物が挙げられる。これらのSn化合物は、一種単独又は二種以上混合して用いることができる。
Agを含まないはんだ合金ではんだ層が形成されたCu核ボールと、Agを含むはんだ合金ではんだ層が形成されたCu核ボールと、Agを含まないはんだ合金で形成されたはんだボールと、Agを含むはんだ合金で形成されたはんだボールを作成し、落下等の衝撃に対する強度を測定する落下強度試験と、ヒートサイクルによる伸縮に対する強度を測定するヒートサイクル試験を行った。
次に、真球度が高いCuボールを作製し、このCuボールの表面にはんだ層を形成したCu核ボールのα線量を測定した。
真球度が高いCuボールの作製条件を調査した。純度が99.9%のCuペレット、純度が99.995%以下のCuワイヤー、及び純度が99.995%を超えるCu板を準備した。各々をるつぼの中に投入した後、るつぼの温度を1200℃に昇温し、45分間加熱処理を行い、るつぼ底部に設けたオリフィスから溶融Cuの液滴を滴下し、液滴を冷却してCuボールを造粒した。これにより平均粒径が250μmのCuボールを作製した。作製したCuボールの元素分析結果及び真球度を表3に示す。
以下に、真球度の測定方法を詳述する。真球度はCNC画像測定システムで測定された。装置は、ミツトヨ社製のウルトラクイックビジョン、ULTRA QV350-PROである。
α線量の測定方法は以下の通りである。α線量の測定にはガスフロー比例計数器のα線測定装置を用いた。測定サンプルは300mm×300mmの平面浅底容器にCuボールを敷き詰めたものである。この測定サンプルをα線測定装置内に入れ、PR-10ガスフローにて24時間放置した後、α線量を測定した。
作製したCuボールの元素分析結果、α線量を表2に示す。
Claims (12)
- Cu、あるいは、Cuを50%以上含むCu合金で構成される核層と、
SnとCuからなるはんだ合金で構成され、前記核層を被覆するはんだ層と
を備えたことを特徴とするCu核ボール。 - 前記はんだ層は、Cuを0.1%以上3.0%以下で含み、残部がSnと不純物から構成される
ことを特徴とする請求項1に記載のCu核ボール。 - Ni及びCoから選択される1元素以上からなる層で被覆された上記核層が、上記はんだ層で被覆される
ことを特徴とする請求項2に記載のCu核ボール。 - α線量が0.0200cph/cm2以下である
ことを特徴とする請求項3に記載のCu核ボール。 - 請求項1~4のいずれか1項に記載のCu核ボールを使用した
ことを特徴とするはんだペースト。 - 請求項1~4のいずれか1項に記載のCu核ボールを使用した
ことを特徴とするフォームはんだ。 - 請求項1~4のいずれか1項に記載のCu核ボールを使用した
ことを特徴とするはんだ継手。 - Cu、あるいは、Cuを50%以上含むCu合金で構成される核層と、
SnとCuからなるはんだ合金で構成され、前記核層を被覆するはんだ層と
を備えたことを特徴とするCu核カラム。 - 前記はんだ層は、Cuを0.1%以上3.0%以下で含み、残部がSnと不純物から構成される
ことを特徴とする請求項8に記載のCu核カラム。 - Ni及びCoから選択される1元素以上からなる層で被覆された上記核層が、上記はんだ層で被覆される
ことを特徴とする請求項9に記載のCu核カラム。 - α線量が0.0200cph/cm2以下である
ことを特徴とする請求項10に記載のCu核カラム。 - 請求項8~11のいずれか1項に記載のCu核カラムを使用した
ことを特徴とするはんだ継手。
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EP14860167.7A EP3067151B1 (en) | 2013-11-05 | 2014-11-04 | Copper core ball, solder paste, formed solder, and solder joint |
CN201480072248.7A CN105873716B (zh) | 2013-11-05 | 2014-11-04 | Cu芯球、焊膏、成形焊料和钎焊接头 |
JP2015546641A JP5967316B2 (ja) | 2013-11-05 | 2014-11-04 | Cu核ボール、はんだペースト、フォームはんだ及びはんだ継手 |
KR1020167014464A KR101858884B1 (ko) | 2013-11-05 | 2014-11-04 | Cu 핵 볼, 땜납 페이스트, 폼 땜납 및 납땜 조인트 |
US15/034,194 US10322472B2 (en) | 2013-11-05 | 2014-11-04 | Cu core ball, solder paste, formed solder, Cu core column, and solder joint |
TW103138311A TWI612633B (zh) | 2013-11-05 | 2014-11-05 | 銅核球、焊膏、泡沫焊、銅核柱以及焊接接頭 |
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CN107690699A (zh) * | 2015-05-21 | 2018-02-13 | 高通股份有限公司 | 具有焊接到管芯或基板的重分布层的高纵横比互连的集成电路封装及对应制造方法 |
KR20180088440A (ko) * | 2015-12-01 | 2018-08-03 | 미쓰비시 마테리알 가부시키가이샤 | 솔더 분말 및 이 분말을 사용한 솔더용 페이스트의 조제 방법 |
KR102180860B1 (ko) * | 2015-12-01 | 2020-11-19 | 미쓰비시 마테리알 가부시키가이샤 | 솔더 분말 및 이 분말을 사용한 솔더용 페이스트의 조제 방법 |
JP6217836B1 (ja) * | 2016-12-07 | 2017-10-25 | 千住金属工業株式会社 | 核材料および半導体パッケージおよびバンプ電極の形成方法 |
CN108172523A (zh) * | 2016-12-07 | 2018-06-15 | 千住金属工业株式会社 | 芯材料和半导体封装体和凸块电极的形成方法 |
US10381319B2 (en) | 2016-12-07 | 2019-08-13 | Senju Metal Industry Co., Ltd. | Core material, semiconductor package, and forming method of bump electrode |
JP6376266B1 (ja) * | 2017-10-24 | 2018-08-22 | 千住金属工業株式会社 | 核材料およびはんだ継手およびバンプ電極の形成方法 |
KR20190045846A (ko) * | 2017-10-24 | 2019-05-03 | 센주긴조쿠고교 가부시키가이샤 | 핵재료 및 납땜 이음 및 범프 전극의 형성 방법 |
KR101983510B1 (ko) | 2017-10-24 | 2019-05-28 | 센주긴조쿠고교 가부시키가이샤 | 핵재료 및 납땜 이음 및 범프 전극의 형성 방법 |
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JPWO2015068685A1 (ja) | 2017-03-09 |
JP5967316B2 (ja) | 2016-08-24 |
US10322472B2 (en) | 2019-06-18 |
KR101858884B1 (ko) | 2018-05-16 |
TW201537710A (zh) | 2015-10-01 |
US20160368105A1 (en) | 2016-12-22 |
CN105873716B (zh) | 2018-11-09 |
EP3067151B1 (en) | 2018-08-08 |
EP3067151A4 (en) | 2017-07-19 |
CN105873716A (zh) | 2016-08-17 |
KR20160079079A (ko) | 2016-07-05 |
EP3067151A1 (en) | 2016-09-14 |
TWI612633B (zh) | 2018-01-21 |
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