Solder material, solder joint, and method of manufacturing the solder material

Abstract

Provided is a solder material which enables a growth of an oxide film to be inhibited. A solder ball which is a solder material is composed of a solder layer and a covering layer covering the solder layer. The solder layer is spherical and is composed of a metal material containing an alloy including Sn content of 40% and more. Otherwise the solder layer is composed of a metal material including Sn content of 100%. In the covering layer, a SnO film is formed outside the solder layer, and a SnO.sub.2 film is formed outside the SnO film. A thickness of the covering layer is preferably more than 0 nm and equal to or less than 4.5 nm. Additionally, a yellow chromaticity of the solder ball is preferably equal to or less than 5.7.

Claims

1. A solder material comprising: a solder layer composed of either a metal material containing an alloy including Sn content of 40% and more, or a metal material including Sn content of 100%; and a covering layer covering a surface of the solder layer, wherein the covering layer includes a SnO film which is formed outside the solder layer and a SnO.sub.2 film which is formed outside the SnO film, a thickness of the covering layer is more than 0 nm and equal to or less than 4.5 nm, a yellow chromaticity in L*a*b* color space is equal to or less than 5.7, the solder material is a solder ball having a diameter of 1 to 1000 m, and the solder ball is a sphere.

2. The solder material according to claim 1, wherein the solder layer comprises 0% or more and less than 4% of Ag, 0% or more and less than 1% of Cu, 0 ppm or more and less than 5 ppm of P, and 0 ppm or more and less than 20 ppm of Ge.

3. The solder material according to claim 1, wherein in order to make a contained amount of Sn equal to or more than 40%, (i) the solder layer contains a total amount of less than 1% of at least one element selected from the group consisting of Ni, Co, Fe, and Sb, or less than 1% of the respective elements and a total amount of less than 40% of at least one element selected from the group consisting of In and Bi, or less than 40% of either one of In and Bi and less than 20% of the other, or (ii) the solder layer contains a total amount of less than 1% of at least one element selected from the group consisting of Ni, Co, Fe, and Sb, or less than 1% of the respective elements, or a total amount of less than 40% of at least one element selected from the group consisting of In and Bi, or less than 40% of either one of In and Bi and less than 20% of the other.

4. The solder material according to claim 1, wherein an alpha dose to be radiated is equal to or less than 0.0200 cph/cm.sup.2.

5. A method of manufacturing a solder material which is a spherical solder ball having a diameter of 1 to 1000 m, wherein the method comprises: a solder-layer-forming step of forming a solder layer, wherein a solder layer composed of either a metal material containing an alloy including Sn content of 40% and more, or a metal material including Sn content of 100% is formed, and an oxide-film-forming step of forming a covering layer on a surface of the solder layer, wherein in the covering layer, a SnO film is formed outside the solder layer and a SnO.sub.2 film is formed outside the SnO film, a thickness of the covering layer is more than 0 nm and equal to or less than 4.5 nm, and yellow chromaticity in L*a*b* color space of a surface of the covering layer is equal to or less than 5.7.

6. The method of manufacturing the solder material according to claim 5, wherein in the oxide-film-forming step, O.sub.2Ar plasma is discharged on the surface of the solder layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a cross-sectional view of a solder ball as an example of a solder material according to the present embodiment for showing a schematic configuration thereof.

(2) FIG. 2A is a cross-sectional view for schematically showing a method of manufacturing a solder ball as an example of the solder material according to the present embodiment.

(3) FIG. 2B is a cross-sectional view for schematically showing the method of manufacturing the solder ball as the example of the solder material according to the present embodiment.

(4) FIG. 2C is a cross-sectional view for schematically showing the method of manufacturing the solder ball as the example of the solder material according to the present embodiment.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

(5) A solder material, a solder joint and a method of manufacturing the solder material according to the prevent invention will be described in detail hereinafter.

(6) <Configuration Example of Solder Material>

(7) FIG. 1 is a cross-sectional view of a solder ball as an example of a solder material according to the present embodiment for showing a schematic configuration thereof. In this specification, units (such as ppm, ppb, and %) relating to composition of the solder material represent ratios to mass of the solder material (mass ppm, mass ppb, and mass %), unless otherwise specified.

(8) A solder ball 1A according to the present embodiment is composed of a solder layer 2 and a covering layer 3 covering the solder layer 2. The solder layer 2 is spherical and is composed of alloy material comprising 0% or more and less than 4% of Ag, 0% or more and less than 1% of Cu, and 40% or more of Sn. Although, in general, oxidation resistance is improved by adding a predetermined amount of P or Ge, the oxidation resistance can be improved without adding these in the present invention. However, the effect of the present invention is not lost, even if an amount of less than 5 ppm of P or an amount of less than 20 ppm of Ge is added. Therefore, P or Ge may not be added, but in a case of adding them, an addition amount of P is less than 5 ppm and an addition amount of Ge is less than 20 ppm. Accordingly, the addition amount of P is 0 ppm or more and less than 5 ppm, and the addition amount of Ge is 0 ppm or more and less than 20 ppm.

(9) Moreover, in order to make a contained amount of Sn equal to or more than 40%, the solder layer contains a total amount of less than 1% of at least one element selected from a group of Ni, Co, Fe, and Sb, or less than 1% of the respective elements and a total amount of less than 40% of at least one element selected from a group of In and Bi, or less than 40% of either one of In and Bi and less than 20% of the other.

(10) Otherwise, the solder layer 2 contains a total amount of less than 1% of at least one element selected from a group of Ni, Co, Fe, and Sb, or less than 1% of the respective elements, or a total amount of less than 40% of at least one element selected from a group of In and Bi, or less than 40% of either one of In and Bi and less than 20% of the other.

(11) Furthermore, the solder layer 2 may contain a metal material including Sn content of 100%. In addition, an alpha dose radiated from the solder layer 2 is preferably equal to or less than 0.0200 cph/cm.sup.2.

(12) For the covering layer 3, a SnO film 3a is formed outside the solder layer 2, and a SnO.sub.2 film 3b is formed outside the SnO film 3a. For a layer of SnO film formed on the surface of the solder layer 2, its film thickness becomes thicker as time passes, according to any exposure of the solder ball 1A to the air. Additionally, when the film thickness becomes thick, the surface of the solder ball 1A turns yellow.

(13) Whereas, when the SnO.sub.2 film 3b is formed outside the SnO film 3a, the chemical reaction of Sn with O.sub.2 in the air is inhibited and the growth of the SnO film 3a and the SnO.sub.2 film 3b is respectively inhibited, and consequently the increase of the film thickness is inhibited. Moreover, turning yellow is inhibited by inhibiting the increase of the film thickness, and therefore, a predetermined silver-white color which is close to a hue of a metal material composing the solder layer 2 is maintained.

(14) A diameter of the solder ball 1A is preferably 1 to 1000 m. Also, a thickness of the covering layer 3 is preferably more than 0 nm (which means that 0 nm is not included) and equal to or less than 4.5 nm. When the thickness of the covering layer 3 exceeds 4.5 nm, it is difficult to remove the covering layer 3 by flux at the time of soldering and therefore the wettability gets worse.

(15) Moreover, the yellow chromaticity b* of the solder ball 1A is preferably equal to or less than 5.7. In managing the manufactured and stored solder ball 1A, there is an occasion when the yellow chromaticity is used. This is because a solder ball whose yellow chromaticity exceeds a predetermined value can be removed as unsuitable for use, from the fact that the yellow chromaticity is high and therefore the thickness of SnO film is thick.

(16) The brightness and the yellow chromaticity were determined from the color value L*a*b*, by measuring spectral transmittance according to Japanese Industrial Standards (JIS-Z 8722) color measuring methodreflection and transparent object color in D65 light source and 10 degree-sight, with the use of the CM-3500d2600d Spectrophotometer manufactured by Konica Minolta, INC.

(17) Additionally, the color value L*a*b* is as stipulated in Japanese Industrial Standards (JIS-Z 8729) color displaying methodL*a*b* color space, and L*U*V* color space.

(18) Moreover, although a form of the solder material is spherical in the present executed examples, a cylindrical form, a square pole or any other form may be available. In addition, an alpha dose radiated from the solder ball 1A is also preferably equal to or less than 0.0200 cph/cm.sup.2.

(19) <Examples of Manufacturing Method of Solder Material>

(20) FIGS. 2A, 2B and 2C are cross-sectional views for schematically showing a method of manufacturing the solder ball as an example of the solder material according to the present embodiment.

(21) At a solder-layer-forming step, as shown in FIG. 2A, a spherical solder layer 2 is formed with either a metal material containing an alloy including Sn content of 40% and more, or a metal material including Sn content of 100%, as described above. At the solder-layer-forming step, in the present executed examples, a dropping method is used, wherein melted metal material is dropped and cured to sphere.

(22) At an oxide-film-forming step, as shown in FIG. 2C, the SnO.sub.2 film 3b is formed on the surface of the SnO film 3a generated by exposing the surface of the solder layer 2 to the air as shown in FIG. 2B. A publicly known method can be used as a method of forming an oxide film. A vapor deposition method, a sputtering method, a plasma discharge method and the like are enumerated, for example. In the present executed examples, the oxide-film-forming step is substantiated by using an atmospheric pressure plasma apparatus with the plasma discharge method. In the plasma discharge method, high density of O.sub.2Ar plasma is discharged during the process where the melted metal material is dropped and cured to sphere.

(23) By manufacturing methods mentioned above, the solder ball 1A is manufactured, wherein the covering layer 3 is formed on the surface of the solder layer 2 having a predetermined diameter. The thickness of the covering layer 3a is more than 0 nm and equal to or less than 4.5 nm, and the SnO film 3a is formed outside the solder layer 2 and the SnO.sub.2 film 3b is formed outside the SnO film 3a. Furthermore, the yellow chromaticity of the solder ball 1A is equal to or less than 5.66.

Executed Examples

(24) Metal balls each corresponding to the solder layer 2 were manufactured with metal material containing 3% of Ag, 0.5% of Cu, and Sn as the balance by the dropping method. A solder ball in each of the executed examples was generated by forming a film corresponding to the covering layer 3 on each of the metal balls by the plasma discharge method. In the plasma discharge method, high density of O.sub.2Ar plasma was discharged during the process where the melted metal material is dropped and cured to sphere.

(25) As comparison examples, solder balls in each of which a SnO layer was formed on the surface thereof by natural oxidation were generated.

(26) Each of the solder balls in the executed example and the comparison example was heated at the temperature of 200 degrees C. and the result of the observation of an oxidation behavior thereof was shown at yellow chromaticity b* value in Table 1.

(27) TABLE-US-00001 TABLE 1 Elapsed Time (min) 0 10 15 30 60 90 Yellow Chromaticity b* 3.24 3.90 4.60 5.66 10.18 15.98 in Executed example Yellow Chromaticity b* 3.63 10.21 13.15 18.79 24.32 25.35 in Comparison example

(28) As shown in Table 1, it has been proved that the yellow chromaticity b* value rises rapidly for the solder ball in the comparison example, whereas, according to the qualitative analysis by SERA (Sequential Electrochemical Reduction Analysis), for the solder ball in the executed example, the growth of the oxide film thickness is inhibited, because a SnO layer is formed outside the solder layer containing Sn as a main component, and a SnO.sub.2 layer is formed outside the SnO layer.

(29) Moreover, in order to separate the oxidation step from the heating test step in the comparison example, for reference, a one-minute heating was conducted with the temperature of 200 degrees C. and then another heating was conducted after cooling. However, the yellow chromaticity b* value rose rapidly similarly to the one before separating the steps.

(30) Next, by FE-AES (Field Emission Auger Electron Spectroscopy), the quantitative analysis was performed on an oxide film thickness of each of the solder ball in the executed example 1 which had been heated at the temperature of 200 degrees C. for 15 minutes and the solder ball in the executed example 2 which had been heated at the temperature of 200 degrees C. for 30 minutes, as the solder ball in the executed example mentioned above. Also, the qualitative analysis thereof was performed by SERA, in order to confirm that a component of the formed oxide film is an oxide of Sn (SnO and SnO.sub.2).

(31) In addition, for the reason why FE-AES was used for the quantitative analysis, it is easier for analyses by FE-AES to show a definite value in order to discuss a specific oxide film thickness as quantitative analysis, whereas the analysis value by SERA varies widely, although it is possible to conduct the qualitative analysis by SERA. The thickness of the oxide film was measured by an apparatus and conditions described hereinafter. Moreover, a measured value of the oxide film thickness was obtained by S.sub.iO.sub.2 conversion.

(32) Measuring apparatus: scanning FE-Auger Electron Spectroscopic Analyzer manufactured by ULVAC-PHI, Inc.

(33) Measuring conditions: 10 kV of Beam Voltage; 10 nA of Sample Current (The measuring method of sputtered depth by using an Ar ion gun is based on ISO/TR 15969)

(34) The measurement results of the oxide film thickness and the yellow chromaticity respectively are shown in Table 2.

(35) TABLE-US-00002 TABLE 2 Elapsed Yellow Time (min) Chromaticity b* Film Thickness (nm) EXECUTED 15 4.60 2.6 EXAMPLE 1 EXECUTED 30 5.66 4.1 EXAMPLE 2

(36) As shown in Table 2, it has been proved that the thickness of the oxide film is inhibited so to be 5 nm or less, and the thickness of the covering layer is preferably equal to or less than 4.5 nm. In addition, it has been proved that the yellow chromaticity is inhibited so to be 10 or less, and the yellow chromaticity is preferably equal to or less than 5.7 according to the result of Table 2.

(37) Next, storage ability and wettability were verified in each of the solder balls in the executed examples and the comparison examples mentioned above, with the film thickness and yellow chromaticity thereof being changed and formed.

(38) For each of the solder balls in the executed examples, the film thickness thereof was equal to or less than 4.5 nm. The film thickness was 2.6 nm for the solder ball in the executed example 1, the film thickness was 4.1 nm for the solder ball in the executed example 2, and the film thickness was 1.5 nm for the solder ball in the executed example 3, respectively.

(39) Also, for each of the solder balls in the executed examples, the yellow chromaticity thereof was equal to or less than 5.7. The yellow chromaticity was 4.60 for the solder ball in the executed example 1, the yellow chromaticity was 5.66 for the solder ball in the executed example 2, and the yellow chromaticity was 3.90 for the solder ball in the executed example 3, respectively.

(40) Meanwhile, for each of the solder balls in the comparison examples, the film thickness was equal to or more than 10 nm and the yellow chromaticity was equal to or more than 10. The yellow chromaticity was 10.21 for the solder ball in the comparison example 1, and the yellow chromaticity was 13.15 for the solder ball in the comparison example 2, respectively.

(41) The verification result is shown in Table 3.

(42) TABLE-US-00003 TABLE 3 Film Thickness Yellow Storage (nm) Chromaticity b* Ability Wettability EXECUTED 2.6 4.60 EXAMPLE 1 EXECUTED 4.1 5.66 EXAMPLE 2 EXECUTED 1.5 3.90 EXAMPLE 3 COMPARISON >10 10.21 X X EXAMPLE 1 COMPARISON >10 13.15 X X EXAMPLE 2

(43) As shown in Table 3, the predetermined conditions of both the storage ability and the wettability were met for each of the solder balls in the executed examples 1 through 3, whereas the predetermined conditions of both the storage ability and the wettability were not met for each of the solder balls in the comparison examples.

(44) Accordingly, it has been proved that both of the storage ability and the wettability are improved for the solder ball whose covering layer thickness is more than 0 nm and equal to or less than 4.5 nm, and the yellow chromaticity b* is equal to or less than 5.7.

(45) In addition, the solder material according to the present invention can be applied to a solder joint of electronic components, by being electrically joined to an electrode with solder paste.

DESCRIPTION OF CODES

(46) 1A Solder Ball 2 Solder Layer 3 Covering Layer 3a SnO Layer 3b SnO.sub.2 Layer