ALUMINUM BONDING WIRE FOR POWER SEMICONDUCTOR

Abstract

An aluminum wire with which, at the time of bonding a bonding wire for a power semiconductor, the wire is not detached from a wedge tool, and a long life is achieved in a power cycle test. The aluminum wire is made of an aluminum alloy having an aluminum purity of 99 mass % or more and contains, relative to a total amount of all elements of the aluminum alloy, a total of 0.01 mass % or more and 1 mass % or less of iron and silicon. In a lateral cross-section in a direction perpendicular to a wire axis of the aluminum wire, an orientation index of is 1 or more, an orientation index of is 1 or less, and an area ratio of precipitated particles is in a range of 0.02% or more to 2% or less.

Claims

1-12. (canceled)

13. An aluminum wire comprising an aluminum alloy having an aluminum purity of 99 mass % or more, the aluminum wire containing, relative to a total amount of the aluminum alloy, a total of 0.01 mass % or more and 1 mass % or less of iron and silicon, wherein in a lateral cross-section in a direction perpendicular to a wire axis of the aluminum wire, an orientation index of is 1 or more, an orientation index of is 1 or less, and an area ratio of precipitated particles is 0.02% or more and 2% or less.

14. The aluminum wire according to claim 13, wherein the aluminum alloy contains a total of 0.1 mass % or more and 1 mass % or less of iron and silicon relative to the total amount, and an area ratio of the precipitated particles is 0.1% or more and 2% or less.

15. The aluminum wire according to claim 13, further containing, relative to the total amount of the aluminum alloy, a total of 50 mass ppm or more and 800 mass ppm or less of at least one element of gallium and vanadium.

16. The aluminum wire according to any one of claim 13, wherein a residual resistance ratio represented by the following formula is 10 or more.
Residual resistance ratio=(electric resistance at room temperature of 300 K/(electric resistance in liquid helium at 4.2 K)(1)

17. The aluminum wire according to any one of claim 13, wherein an area ratio of the precipitated particles is 0.2% or more and 1.8% or less.

18. The aluminum wire according to any one of claim 13, wherein an aluminum purity of the aluminum alloy is 99.9 mass % or less.

19. The aluminum wire according to any one of claim 13, wherein an orientation index of the (111) is 1.3 or more.

20. The aluminum wire according to any one of claim 13, wherein an orientation index of the (200) is 0.6 or less.

21. The aluminum wire according to any one of claim 13, wherein a content ratio of iron and silicon in the aluminum alloy is 0.3 or more and 90 or less by mass ratio represented by iron/silicon.

22. The aluminum wire according to any one of claim 13, wherein a wire diameter thereof is 40 ?m or more and 700 ?m or less.

23. An aluminum wire manufacturing method comprising: a step of preparing an aluminum alloy material, the aluminum alloy material being an aluminum alloy having an aluminum purity of 99 mass % or more and containing, relative to a total amount of the aluminum alloy, a total of 0.01 mass % or more and 1 mass % or less of iron and silicon; and a step of performing wire drawing on the aluminum alloy material.

24. The aluminum wire manufacturing method according to claim 23, wherein the step of performing wire drawing comprises: an intermediate wire drawing step of obtaining an intermediate wire rod by performing wire drawing on the aluminum alloy material so as to have a wire diameter of 7 to 130 times a final wire diameter thereof; and a solution treatment step in which the intermediate wire rod is heated at 400? C. to 560? C. and then quenched, and the step of performing wire drawing is a step of performing wire drawing so as to obtain a final wire diameter of 40 ?m or more and 700 ?m or less.

25. A semiconductor device comprising: a semiconductor element having an electrode; and an aluminum wire connected to the electrode, the aluminum wire comprising an aluminum alloy having an aluminum purity of 99% by mass or more, and containing a total of 0.01% by mass or more and 1% by mass or less of iron and silicon relative to a total amount of the aluminum alloy, wherein in a lateral cross section in a direction perpendicular to a wire axis of the aluminum wire, an orientation index of is 1 or more, an orientation index of is 1 or less, and an area ratio of precipitated particles is 0.02% or more and 2% or less.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0039] FIG. 1 is a photograph of a cross-section of an aluminum wire of Example 12 which is taken with an FE-SEM at a magnification of 1000 times and binarized with image analysis so that areas where the brightness value is higher than the threshold are shown as white and areas where the brightness value is lower than the threshold are shown as black. The white part represents precipitated particles.

[0040] FIG. 2 is a photograph showing precipitated particles of an aluminum wire of Comparative Example 6 which is taken and binarized in the same manner as in FIG. 1.

[0041] FIG. 3 shows a photograph (left side) taken by enlarging a wedge tool portion of a wire in which the wedge tool become detached, and a normal photograph (right side) in which the wedge tool is not detached.

[0042] FIG. 4 shows bonding photographs of aluminum wires in a comparative example and an example.

[0043] FIG. 5 is a photograph showing a result of EBSD (electron backscatter diffraction pattern) measurement of crystal orientations in a cross-section perpendicular to the wire axial direction of an aluminum wire of an example. The result of the EBSD measurement is shown by color-coding specific crystal orientations in the respective crystal grains, which is shown in black and white shading in FIG. 5. The photograph of FIG. 5 shows wide variations in the shading, indicating large variations in the crystal orientations.

[0044] FIG. 6 is a cross-sectional view schematically showing a configuration of a semiconductor device according to an embodiment.

[0045] FIG. 7 is a cross-sectional view schematically showing a configuration of a semiconductor device according to another embodiment.

[0046] FIG. 8 is an enlarged view of an IV region of FIG. 6.

[0047] FIG. 9 is a cross-sectional view schematically showing a crack that has occurred in the semiconductor device and corresponding to FIG. 8.

[0048] FIG. 10 is a photograph partially showing the semiconductor device of the embodiment in which no crack has occurred.

[0049] FIG. 11 is a photograph partially showing the semiconductor device in which a crack has occurred.

DESCRIPTION OF EMBODIMENTS

[0050] Hereinafter, an aluminum wire of an embodiment of the present invention will be described. An aluminum wire of the present embodiment is an aluminum wire made of an aluminum alloy having an aluminum purity of 99 mass % or more and containing, relative to a total amount of the aluminum alloy, a total of 0.01 mass % or more and 1 mass % or less of iron and silicon, wherein in a lateral cross-section in a direction perpendicular to a wire axis of the aluminum wire, an orientation index of (111) is 1 or more, an orientation index of (200) is 1 or less, and an area ratio of precipitated particles is in a range of 0.02% or more and 2% or less. A detailed description will be given below of the history of trial and error until the present invention is obtained, a configuration of the aluminum wire of the present invention, and a manufacturing method thereof.

[0051] The present inventors experimentally produced many types of aluminum wires with different compositions by several different manufacturing methods. As a result of careful observation of a cross-sectional structure perpendicular to the wire axial direction of the prototype wire, there could be seen an overall fine crystal grain structure, an overall large crystal grain structure, and a crystal structure in which a large size of crystal grain and a small size of crystal grain partially coexist in the same cross-section. The fact that the crystal grains partially differ in size in the same cross-section suggests that the crystal grain structure cannot be an indicator of the properties of the entire aluminum wire. Further, it has been found that there are granular substances (herein referred to as precipitated particles) on these crystal grain structures. The precipitated particles will be described later.

[0052] The crystal orientations were measured by an EBSD (electron backscatter diffraction pattern) to see if there is any difference in the crystal orientations of the structure in which these crystal grains differ in size. In FIG. 5, shading in the crystal grains represents the difference in the crystal orientations. It can be understood from FIG. 5 that the crystal orientations differ depending on the part. This suggests that the state of some of the crystal orientations cannot be an indicator of the properties of the entire wire. In a wire drawing step, the way of processing changes along the longitudinal direction of the wire (wire axial direction). That is, practical uniformity is maintained, whereas strictly speaking, influences such as micro-vibration of the wire at the time of wire drawing using a die and frictional heat between the wire and the die may cause parts with different properties depending on the position in the longitudinal direction. Accordingly, the crystal orientations of the cross-section cannot be uniquely determined, and as a result, it has been found to be extremely difficult to uniquely express the properties of the entire aluminum wire by the crystal orientation ratio.

[0053] Thus, as a result of examination of an indicator capable of expressing the properties of the entire aluminum wire, an orientation index was determined as an indicator. The orientation index is a value obtained by dividing the diffraction intensity ratio of each crystal plane of the wire, that is, (diffraction intensity of each crystal plane/a sum of diffraction intensities of the respective crystal planes) by the diffraction intensity ratio of a non-oriented aluminum powder standard sample. By obtaining the orientation index, it can be quantitatively determined which crystal plane is preferentially oriented and which crystal plane is not preferentially oriented, that is, the tendency of preferential orientation of the crystal plane. The orientation index is expressed by a mathematical formula, i.e., the following Wilson's formula. The analysis intensity ratio of the standard sample of aluminum powder employed a value of the ICDD card (also called PDF, ASTM card, or JPCDS card) PDF No. 00-004-0787 (aluminum) provided by ICDD (International Centre for Diffraction Data, a non-profit scientific organization that handles powder diffraction data). A cross-section of the wire rod in the direction perpendicular to the wire axis is subjected to X-ray diffraction, and the diffraction intensity ratio of each crystal plane of the aluminum is used to determine an orientation index N of each crystal plane by means of the following Wilson's formula (1).

[00001]$\begin{array}{cc}\mathrm{Orientation}\mathrm{index}\left(N\right)=\frac{\left(\frac{\left(I/I\left(\mathrm{hkl}\right)\right)}{.Math.I/I\left(\mathrm{hkl}\right)}\right)}{\left(\frac{\mathrm{ICDD}I/I\left(\mathrm{hkl}\right)}{.Math.\mathrm{ICDD}I/I\left(\mathrm{hkl}\right)}\right)}& \left(1\right)\end{array}$

[0054] In the above formula (1), I/I(hkl) is the diffraction intensity ratio on the (hkl) plane of the sample, ICDD I/I(hkl) is the diffraction intensity ratio on the (hkl) plane of the ICDD card, and ?I/I(hkl) and ?ICDD I/I(hkl) are each a sum of the diffraction intensity ratios of all crystal planes. It should be noted that the diffraction intensity can be obtained from the area ratio of each peak.

[0055] Regarding the orientation index of the aluminum wire, forty aluminum wires were bundled and embedded in resin, and the lateral cross-section in the direction perpendicular to the wire axis was subjected to X-ray diffraction to measure the diffraction intensities of (111), (200), (220), (311), (222), and (400), then the orientation index of each of the crystal planes was obtained by means of the Wilson's formula. The orientation index is a value of a preferential orientation of a solid aluminum wire assembly, which is not affected by variations of, for example, a dual structure of a central portion and a peripheral portion of the individual aluminum wire. In addition, the orientation index is a value corrected to a comparison value with a standard sample and thus can indicate more objective orientation of the aluminum wire.

[0056] As a result of experimentally producing aluminum wires with various orientation indexes and measuring the orientation indexes through earnest studies, the present inventors discovered that an aluminum wire controlled such that the orientation index of (111) of a plane perpendicular to the wire axis is 1 or more and the orientation index of (200) is 1 or less is long life in the power cycle test.

[0057] It should be noted that as described above, a crystal orientation ratio is the similar indicator. The crystal orientation ratio is a value obtained by measuring the occupancy of crystal orientations in a two-dimensional plane obtained by cutting an aluminum wire at a certain area. As shown in FIG. 5, the crystal orientation ratio in the cross-section perpendicular to the wire axis depends on the cutting position of the aluminum wire, and even with the same composition and manufacturing condition, some of the crystal orientations are not oriented in a certain direction and have variations; accordingly, it is difficult to determine the objective properties of the aluminum wire only from the crystal orientation ratio.

[0058] The present inventors actually measured the crystal orientation ratio of each of samples in examples described later but could not obtain a correlation with the power cycle life. Wires having a crystal orientation ratio of <111> being as large as 50% or more roughly tend to have a long life, whereas there were wires having a long life of 200,000 cycles or more among wires having a crystal orientation ratio of <111> being as small as 20% range.

[0059] Next, precipitated particles will be described. The inventors experimentally produced many aluminum wires having different aluminum purities in various manufacturing steps and carefully observed a metal structure of a cross-section perpendicular to the wire axial direction; as a result, they discovered that precipitated particles on an aluminum-based matrix differ in shape, size, and number depending on the composition and manufacturing condition of each prototype wire.

[0060] Presuming that these precipitated particles have some relationship with long-term reliability and followability of the wire, the inventors analyzed a photograph of the precipitated particles taken with a SEM (scanning electron microscope reflection electron image) using image processing software and quantified a cross-sectional area of the precipitated particles on the image. Although the quantification method will be described in detail in the examples, the inventors discovered that the area ratio of the precipitated particles to the cross-section perpendicular to the wire axial direction correlates with the life in the power cycle test and the wire followability. That is, the inventors presumed that the area ratio of the precipitated particles varies depending on the combinations of different aluminum purities and wire manufacturing methods.

[0061] The inventors experimentally produced many wires having combinations of different orientation indexes and area ratios of the precipitated particles and diligently performed power cycle tests and tool detachment evaluation; as a result, they invented a wire that has long-term reliability under the following conditions and has followability which does not cause tool detachment.

[0062] The aluminum wire having long-term reliability and followability which does not cause tool detachment is an aluminum wire having an aluminum purity of 99 mass % or more and containing iron and silicon with total of 0.01 mass % or more and 1 mass % or less of iron and silicon, wherein the cross-section perpendicular to the wire axial direction has an orientation index of (111) being 1 or more and an orientation index of (200) being 1 or less, and an area ratio of the precipitated particles is 0.02% or more and 2% or less with respect to the cross-section perpendicular to the wire axial direction. These configurations are intertwined with one another to form a synergistic effect, solving the two conflicting problems simultaneously. From the viewpoint of improving long-term reliability, the orientation index of (111) of the cross-section perpendicular to the wire axial direction of the aluminum wire is preferably 1.2 or more, more preferably 1.4 or more, and the orientation index of (200) is preferably 0.7 or less, more preferably 0.5 or less.

[0063] The precipitated particles are particles having a size (maximum particle length) of about 0.01 to 30 ?m in such as lump, ring, plate, needle, approximately spherical, and irregular shapes, which can be observed on an aluminum-based matrix. These particles are considered to include particles crystallized or precipitated during the manufacturing process and particles contained in the aluminum raw material. In addition, the precipitated particles are considered to include any one, two or more kinds of an alloy of aluminum and iron, an intermetallic compound, an alloy of aluminum, iron, and silicon, an intermetallic compound, and a precipitate of elemental silicon.

[0064] The area ratio of the precipitated particles can be controlled by the composition of the wire (a content ratio of iron to silicon), heat treatment temperature, time, timing of heat treatment, wire drawing conditions, and the like. It should be noted that the area ratio of the precipitated particles is a ratio of an area occupied by the precipitated particles to a cross-sectional area of a lateral cross-section perpendicular to the wire axis of the aluminum wire. The experimentally produced aluminum wire was measured to obtain the area ratio of the precipitated particles in the cross-section of each of the tip, the rear end, and the intermediate portion. The obtained values were almost the same regardless of the position in the wire, and the variations in the area ratio depending on the measurement part were smaller than those in the crystal orientation ratio. That is, this suggests that the area ratio of the precipitated particles in a certain cross-section perpendicular to the wire axis is representative of the area ratio of the entire wire. The area ratio of the precipitated particles can be calculated as follows. When a lateral cross-section perpendicular to the wire axis of an aluminum wire is analyzed using a SEM, the precipitated particles are displayed as pixels with a high brightness value due to the difference of the composition from the other region. The region other than the precipitated particles (in the aluminum matrix) is displayed with a low brightness value. This SEM image is binarized by determining a threshold of the brightness value (for example, 0.95) for separating the precipitated particles from the other region by means of a histogram or the like, and an area ratio of the region of the precipitated particles to the whole is calculated. It should be noted that the brightness value is a value normalized such that black is 0 and white is 1.

[0065] Although the mechanism that achieves both of the two conflicting properties in the above configurations is not necessarily clear, the content of iron and silicon and the area ratio of precipitated particles are greatly related to long-term reliability and followability of the wire, and it is difficult to achieve both of these properties when the content of iron and silicon is too little or too much.

[0066] In the aluminum wire of the present embodiment, the area ratio of the precipitated particles is in a range of 0.02% or more and 2% or less. From the viewpoint of improving followability, the area ratio of the precipitated particles is preferably 0.05% or more, more preferably 0.1% or more, even more preferably 0.2% or more. Furthermore, it is preferably 1% or less, more preferably 0.8% or less.

[0067] Controlling the orientation index and the area ratio of the precipitated particles brings a synergistic effect to the long life in the power cycle test (improvement of long-term reliability) and the aluminum wire detachment from the wedge tool. Further, the inventors examined many additive elements and found that containing, among those elements, in particular, both elements of iron (Fe) and silicon (Si) such that the total amount is 0.01 mass % or more and 1 mass % or less leads to a longer life and less chance of tool detachment, and further containing at least one element of gallium (Ga) and vanadium (V) such that the total is 50 mass ppm or more and 800 mass ppm or less leads to an increased residual resistance ratio and suppression of heat generation at the time of energization.

[0068] The aluminum wire of the present embodiment is made of an aluminum alloy having an aluminum purity (an amount of aluminum relative to the total amount of the aluminum wire) of 99 mass % or more. That is, the aluminum wire of the present embodiment has an aluminum purity of 99 mass % or more. Thus, the aluminum wire of the present embodiment has sufficient electric conductivity and exhibits good followability. An aluminum purity of the aluminum wire is preferably 99.9 mass % or less. An aluminum purity being 99.9 mass % or less allows to contain a sufficient amount of iron and silicon and further contain, as necessary, trace elements (gallium and vanadium) or trace elements (also referred to as additive elements, i.e., magnesium (Mg), copper (Cu), nickel (Ni), zinc (Zn), chromium (Cr), manganese (Mn), titanium (Ti), zirconium (Zr), tungsten (W), and scandium (Sc), which will be described later), thus improving long-term reliability of the aluminum wire.

[0069] Further, as described above, the aluminum wire of the present embodiment is made of an aluminum alloy containing a total of 0.01 mass % or more and 1 mass % or less of iron and silicon. That is, the aluminum wire of the present embodiment contains, relative to the total amount of the wire, a total of 0.01 mass % or less and 1 mass % of iron and silicon.

[0070] The aluminum wire of the present embodiment has a total amount of 0.01 mass % or more of iron and silicon and thus achieves a longer life than conventional aluminum wires. Moreover, when the total amount of iron and silicon exceeds 1 mass %, the area ratio of the precipitated particles becomes too large, which thus causes tool detachment. From the viewpoint of ease of achieving the long life, the total amount of iron and silicon is preferably 0.02 mass % or more, more preferably 0.05 mass % or more, more preferably 0.1 mass % or more, even more preferably 0.13 mass % or more. Furthermore, from the viewpoint of reducing tool detachment while achieving the long life, the total amount of iron and silicon is preferably 0.9 mass % or less, more preferably 0.8 mass % or less.

[0071] In the aluminum wire of the present embodiment, the amount of iron, relative to the total amount of the wire, is preferably 0.01 mass % or more, more preferably 0.03 mass % or more, even more preferably 0.05 mass % or more, particularly preferably 0.1 mass % or more, more particularly preferably 0.13 mass % or more. Further, the amount of iron, relative to the total amount of the wire, is preferably 0.95 mass % or less, more preferably 0.9 mass % or less. Further, the amount of silicon, relative to the total amount of the wire, is preferably 0.01 mass % or more, more preferably 0.05 mass % or more. The amount of silicon is preferably 0.5 mass % or less, more preferably 0.4 mass % or less. By combining the above preferred ranges of iron and silicon, the synergistic effect of iron and silicon makes it even easier to obtain long-term reliability of bonding and the effect of suppressing tool detachment.

[0072] In the aluminum wire of the present embodiment, the content ratio of iron and silicon is preferably 0.3 or more and 90 or less, more preferably 1.0 or more and 45 or less, by mass ratio represented by iron/silicon. The content ratio of iron and silicon within the above range makes is easy to control the precipitation amount of the precipitated particles and achieve both of followability of the wire and long-term reliability of bonding.

[0073] The aluminum wire of the present embodiment preferably contains at least one kind of gallium and vanadium, and in this case, the total amount of gallium and vanadium, relative to the total amount of the wire, is preferably 50 mass ppm or more. Although gallium and vanadium are not essential for the long life of the wire, containing at least one kind of these contributes to the long life of the wire. The upper limit of the content of at least one kind of gallium and vanadium is, though not particularly limited, about 1000 mass ppm, and containing 50 mass ppm or more of these makes it easy to obtain the effect of the further longer life, and the content of 800 mass ppm or less makes it easy to suppress the maximum temperature of the aluminum wire at the time of energization. The content of gallium and vanadium, relative to the total amount of the wire, may be 100 mass ppm or more or 150 mass ppm or more. The content of gallium and vanadium, relative to the total amount of the wire, may be 700 mass ppm or less or 600 mass ppm or less. Regarding the content of gallium and vanadium, when only either one of gallium and vanadium is contained in the wire, the amount of the one may be within the above range, and when both of gallium and vanadium is contained, the total amount of gallium and vanadium may be within the above range.

[0074] For example, when the maximum temperature at the time of energization is 150? C. in the case of using an aluminum wire having a purity of 99.99 mass %, the maximum temperature can be reduced to 160? C. or less if the content of gallium and vanadium is 800 mass ppm or less. That is, using an aluminum wire having a purity of 99.99 mass % as a criterion, the rising temperature caused by heat generation at the time of energization can be suppressed within about 10? C.

[0075] The aluminum wire of the present embodiment may contain one, two or more kinds of trace elements such as magnesium (Mg), copper (Cu), nickel (Ni), zinc (Zn), chromium (Cr), manganese (Mn), titanium (Ti), zirconium (Zr), tungsten (W), and scandium (Sc), in addition to iron, silicon, gallium, and vanadium. Regarding the content of a trace element(s), a total amount of iron, silicon, gallium, vanadium, and a trace element(s) is 1.0 mass % or less, which is preferably 0.1 mass % or more, relative to the entire wire.

[0076] The temperature rise caused by heat generation at energization as compared with the case of using the aluminum wire having a purity of 99.99 mass % described above increases as the residual resistance ratio increases. The residual resistance ratio is affected not only by the amount of impurities and the purity of aluminum but also by processing strain of the wire and the like and thus more accurately reflects the temperature rise caused by heat generation due to energization.

[0077] The temperature rise of 30? C. or more with the criterion described above also considerably affects members in contact with the wire. For example, an increase in the temperature of a sealing resin covering the wire increases the possibility in which an element in the resin that causes corrosion of the wire volatilizes and is released from the resin. To prevent corrosion of the wire, a sealing resin having heat resistance, a design for heat dissipation, and the like are required, which thus tends to lead to an increase in manufacturing cost and interfere with the degree of freedom in designing the power semiconductor.

[0078] The residual resistance ratio is expressed by the following formula by means of a numerical value representing a ratio of the electric resistance in liquid helium at 4.2 K (kelvin) and the electric resistance at room temperature of 300 K.

Residual resistance ratio=(electric resistance at room temperature)/(electric resistance in liquid helium)

[0079] The residual resistance ratio of the aluminum wire of the present embodiment is preferably 10 or more, more preferably 15 or more. When the residual resistance ratio is less than 10, the temperature rise due to heat generation at the time of energization is likely to be 30? C. or more with the criterion described above, which may adversely affect peripheral members of the wire.

[0080] The wire diameter of the aluminum wire of the present embodiment is typically 40 ?m or more and 700 ?m or less, which is preferably 70 ?m or more and 600 ?m or less, more preferably 100 ?m or more and 500 ?m or less. The cross-sectional shape of the aluminum wire is typically circular and additionally may be elliptical, oval, rectangular, or the like.

[0081] (Aluminum Wire Manufacturing Method)

[0082] Next, an example of an aluminum wire manufacturing method of the embodiment will be described. It should be noted that the aluminum wire manufacturing method is not limited to the manufacturing method shown below. It is desirable to adjust the conditions as appropriate in view of the weight of the aluminum wire to be manufactured and the processing capacity of the heat treatment furnace.

[0083] Iron and silicon are melted together in an aluminum having a high purity of 99 mass % or more to thereby prepare molten aluminum. The purity of high-purity aluminum used as a raw material may be 99.9 mass % or more or 99.99 mass % or more. A heating furnace such as an arc heating furnace, a high-frequency heating furnace, a resistance heating furnace, or a continuous casting furnace is used for melting. The molten aluminum in the heating furnace, though which may be melted in the atmosphere, may be melted while being maintained in a vacuum or an inert gas atmosphere such as argon or nitrogen, for the purpose of preventing incorporation of oxygen and hydrogen from the atmosphere. The molten material may be solidified by continuous casting from the heating furnace so as to have a predetermined wire diameter (diameter). Alternatively, the molten aluminum may be cast into a mold to make an ingot, and the ingot may be set in an extruder and subjected to extrusion molding so as to have a predetermined wire diameter.

[0084] The wire rod obtained by the above step is subjected to wire drawing so as to obtain an intermediate wire rod having a wire diameter of 5.0 mm. The wire diameter of the intermediate wire rod is typically 7 to 130 times the final wire diameter. Next, an intermediate heat treatment is performed on the wire after the wire drawing (intermediate wire rod) for heating at 400? C. to 560? C. for 60 minutes to 420 minutes and then a solution treatment is performed on the wire for quenching. The quenching speed is, for example, 20? C./second or more and 300? C./second or less, preferably 20? C./second or more and 100? C./second or less. Although the quenching speed may be a speed from the start of quenching to the end, more preferably, the cooling speed in the temperature range from 400? C. to 300? C. being within the above range makes it easier to obtain the above effects. The main purpose of the solution treatment is to dissolve elements other than aluminum into the aluminum matrix. After the solution treatment, wire drawing is performed so as to obtain a final wire diameter. In the wire drawing, the wire is passed through a plurality of cemented carbide dies or diamond dies in order so as to reduce the wire diameter of the wire stepwise.

[0085] The wire drawn to the final wire diameter is subjected to a final heat treatment. The final heat treatment mainly acts as relieving strain of a metal structure remaining inside the wire and adjusting the mechanical property and the like of the wire. However, since it may affect the area ratio of the precipitated particles, the temperature and treatment time of the final heat treatment are adjusted in view of these.

[0086] The intermediate heat treatment and the final heat treatment include a running heat treatment in which a wire is passed through a heating atmosphere heated to a predetermined temperature and heat-treated, and a batch heat treatment in which a wire is heated in a closed furnace. The final heat treatment in the present embodiment is preferably performed by the batch heat treatment at 200? C. or more and 340? C. or less for about 60 minutes.

[0087] (Semiconductor Device)

[0088] Next, a configuration of a semiconductor device 100 using the aluminum wire of the embodiment will be described with reference to FIG. 6.

[0089] As shown in FIG. 6, the semiconductor device 100 includes a semiconductor element 1, a metal film 2, a wire 3, a circuit pattern 41, a metal pattern 42, an insulating member 43, a heat dissipating member 5, a bonding material 6, a case 7, a terminal 8, and a sealing material 9.

[0090] In the present embodiment, the semiconductor element 1 is, for example, a power semiconductor used for a semiconductor for power supply. Examples of the semiconductor element 1 include a metal oxide semiconductor field effect transistor (MOSFET), an IGBT, and the like.

[0091] The semiconductor element 1 is formed by laminating an electrode 11, a substrate portion 13, and a back surface electrode 12 in this order. The electrode 11 is, for example, an aluminum (Al)-silicon (Si) electrode, and the substrate portion 13 is, for example, a silicon (Si) substrate, a silicon carbide (SiC) substrate, a gallium nitride (GaN) substrate, or the like.

[0092] The metal film 2 is provided on a surface of the electrode 11 opposite to the substrate portion 13 so as to cover the surface of the electrode 11. The metal film 2 is a nickel (Ni) film, a copper (Cu) film, a titanium (Ti) film, a tungsten (W) film, or the like, and is a film formed by electroplating, electroless plating, vapor deposition, sputtering, or the like. The nickel (Ni) film includes a nickel (Ni) electroless plating film, which specifically includes an electroless nickel (Ni)-phosphorus (P) plating film, an electroless nickel (Ni)-boron (B) plating film, and the like. Other preferred aspects of the metal film 2 will be described later.

[0093] The wire 3 is made of the aluminum wire of the embodiment described above, and its configuration and properties are also as described above. The wire 3 is bonded to a surface of the metal film 2.

[0094] Next, a bonding structure of the metal film 2 and the wire 3 in the semiconductor device 100 of the embodiment shown in FIG. 6 will be described with reference to FIG. 8. FIG. 8 is an enlarged view schematically showing an IV region of FIG. 6 (the vicinity of a bonding interface of the metal film 2 and the wire 3). It should be noted that the sealing material 9 (see FIG. 6) is not described in FIG. 8.

[0095] The vicinity of the bonding interface of the wire 3 and the metal film 2 shown in FIG. 8 is referred to as a bonding portion 31. The bonding portion 31 is, for example, a range from the bonding interface of the wire 3 and the metal film 2 to a position advanced by one crystal grain to the inside of the wire 3.

[0096] Here, if the heat resistance of the aluminum wire is not sufficient, repeated start and stop of energization of the wire generates thermal stress in the vicinity of the bonding surface of the metal film and the wire in the bonding portion 31, which may cause metal fatigue in the aluminum wire. As a result, a crack may occur in the wire 3. FIG. 9 is a view schematically showing the bonding portion 31 in which a crack CR has occurred in the wire. Further, FIG. 10 is a photograph in the vicinity of the bonding portion 31 in which no crack has occurred in the wire, and FIG. 11 is a photograph showing a state in which the crack CR has advanced into the wire.

[0097] According to the aluminum wire of the embodiment described above, the wire can maintain heat resistance for a long period of time, so that repeated start and stop of energization of the wire causes no crack of the wire, and it is possible to maintain stable bonding of the bonding portion 31 for a long period of time. Further, combined with no failure in wedge bonding due to the good followability of the wire, it is possible to obtain long-term reliability of bonding (first bonding and second bonding).

[0098] In addition, since the wire can exhibit heat resistance for a long period of time, it is possible to obtain long-term stability of bonding regardless of the material of a bonding target (the electrode or the metal film). Furthermore, using the metal film 2 of the present embodiment allows to further improve the effect of the long-term stability, which is thus preferable.

[0099] When the hardness of a bonding target of the wire is lower than that of the wire, a crack that has occurred in the wire may spread to the bonding target and advance thereto. In contrast, when the bonding target is harder than the wire as in the metal film 2 of the present embodiment, even if a minute crack occurs in the wire, the crack does not advance to the bonding target, so that it is considered that crack expansion in the wire and the bonding target is suppressed and further long-term reliability of bonding is achieved.

[0100] For the metal film 2 as described above, an electroless nickel (Ni)-phosphorus (P) plating film, an electroless nickel (Ni)-boron (B) plating film, a nickel (Ni) film or a copper (Cu) film formed by electroplating, or a nickel (Ni) film, a copper (Cu) film, a titanium (Ti) film, or a tungsten (W) film formed by vapor deposition or sputtering is preferable. These metal films 2 have a crystal structure. Further, the purity of nickel (Ni) of the metal film 2 is high. This makes it possible to suppress cracking of the metal film 2 at the time of the heat treatment.

[0101] The metal film 2 is preferably an electroless nickel (Ni)-phosphorus (P) plating film that does not contain sulfur (S), from the viewpoint of cost, and the phosphorus content is preferably, relative to the total amount of the metal film 2, 8 mass % or less, more preferably 5 mass % or less. When the phosphorus content is 8 mass % or less, the metal film 2 has a crystal structure, so that the hardness of the metal film 2 increases, which makes it possible to suppress cracking of the metal film 2. In addition, since sulfur (S) is not contained, embrittlement of grain boundaries due to segregation of sulfur (S) at the grain boundaries is suppressed, which also makes it possible to suppress cracking of the metal film 2. From the above, heat resistance of the metal film 2 is improved.

[0102] Next, the other configuration of the semiconductor device 100 will be described. In the semiconductor device 100, a semiconductor circuit is formed by the semiconductor element 1, the wire 3, the terminal 8, the circuit pattern 41, and the metal pattern 42. The wire 3 is bent in the semiconductor device 100, and this bending portion is used to be bonded to each of the semiconductor element 1, the terminal 8, the circuit pattern 41, and the like.

[0103] The bonding material 6, the metal pattern 42, the insulating member 43, the circuit pattern 41, the bonding material 6, and the semiconductor element 1 are laminated in this order on a surface of the heat dissipating member 5 in the semiconductor device 100. The bonding material 6 is made of solder, silver (Ag), and the like for bonding the heat dissipating member 5 and the metal pattern 42 and bonding the circuit pattern 41 and the back surface electrode 12 of the semiconductor element 1. The insulating member 43 is an insulating substrate or the like.

[0104] The case 7 is formed by a ring-shaped housing having a space inside and is provided so as to surround an outer periphery of the heat dissipating member 5. The semiconductor element 1, the metal film 2, the wire 3, the circuit pattern 41, the metal pattern 42, the insulating member 43, the bonding material 6, and the sealing material 9, which are described above, are accommodated in the space inside the case 7.

[0105] The terminal 8 functions as a connection terminal with external equipment. The terminal 8 is provided on an upper surface of the case 7 and disposed such that one end portion thereof protrudes from the case 7 into the space inside the case 7 and the other end portion protrudes from the case 7 to a region outside the case 7. The sealing material 9 fills the space inside the case 7 so as to include the semiconductor element 1, the metal film 2, the wire 3, the circuit pattern 41, the metal pattern 42, the insulating member 43, and the bonding material 6. The sealing material 9 is a hardened material such as a gel-like sealing resin or a mold resin.

[0106] A semiconductor device 101 having a lead frame is shown in FIG. 7 as another embodiment of the semiconductor device. In FIG. 7, the same reference numerals are assigned to the configurations having the same functions as those of the semiconductor device 100 shown in FIG. 6, and a detailed description thereof will be omitted. The semiconductor device 101 shown in FIG. 7 has a lead frame LF, in addition to a semiconductor element 1, a metal film 2, a wire 3, an insulating member 43, a bonding material 6, and a sealing material 9. Since the semiconductor device 101 shown in FIG. 7 has the lead frame LF, the semiconductor device 101 does not have a case 7 but may be provided with the case 7. The lead frame LF is bonded on a surface of the insulating member 43 and has the same function as that of the circuit pattern 41 of the semiconductor device 100 shown in FIG. 6. It should be noted that although the lead frame LF and the insulating member 43 are bonded in FIG. 7, a metal plate (not shown) may be disposed between the lead frame LF and the insulating member 43.

[0107] The sealing material 9 is provided so as to include the semiconductor element 1, the metal film 2, the wire 3, the insulating member 43, the bonding material 6, and the lead frame LF. However, an end portion of the lead frame LF protrudes outside the sealing material 9, the lead frame LF forms electric circuits of the semiconductor element 1 and the wire 3, and the protruding end portion functions as a terminal 8 for connecting to external equipment of the semiconductor device 101.

[0108] Next, manufacturing methods of the semiconductor device 100 shown in FIG. 6 and the semiconductor device 101 shown in FIG. 7 will be described. First, the members that form the respective semiconductor devices 100 and 101 are prepared, laminated according to the configurations described above, and bonded to each other. Then, an end portion of the wire 3 is bonded to a surface of the metal film 2 by ultrasonic bonding or the like. Thereafter, the other end portion of the wire 3 is subjected to wedge bonding to an external electrode. The aluminum wire of the embodiment described above is used as the wire 3. Thereafter, a sealing resin is injected to the semiconductor device 100 and cured to form the sealing material 9. In the case of the semiconductor device 101, the lead frame on which the semiconductor element 1 and the like are mounted is placed in a mold, and a sealing resin is injected thereto and cured to form the sealing material 9.

EXAMPLES

[0109] Next, examples will be described. The present invention is not limited to the examples below.

[0110] A high-purity aluminum metal having a purity of 99.9 mass % or more was prepared. Iron and silicon were added in the amount described in Table 1. Further, gallium and vanadium were added as optional elements in the amount shown in Table 1. The aluminum alloy compositions of these examples are shown in Table 1. The alloy of each of these samples was melted in the atmosphere and then continuously cast to obtain a wire rod. The obtained wire rod was subjected to wire drawing so as to have an intermediate wire diameter of 5 mm, and this wire with the intermediate wire diameter of 5 mm was subjected to an intermediate heat treatment at 400? C. to 560? C. for 60 minutes. Immediately after the elapse of 60 minutes, it was quenched in water at a cooling speed of 25? C./second or more. Thereafter, the wire was subjected to wire drawing so as to have a final wire diameter of 400 ?m and lastly subjected to a final heat treatment in a batch furnace between 200? C. and 340? C. for 60 minutes. The aluminum wire that has completed the final heat treatment was rewound on a spool by a rewinding machine at intervals of about 300 m.

[0111] Next, the orientation index and the area ratio of precipitated particles of each of the samples of the examples were obtained.

[0112] (Measurement of Wire Orientation Index)

[0113] Sampling was performed at three positions of a tip portion, a rear end portion, and a periphery of the middle between the tip and the rear end (middle portion) of the sample wire rewound to about 300 m. Each sample were embedded in a resin such that each lateral cross-section in the direction perpendicular to the wire axis was exposed approximately perpendicular to the wire axis. This resin with the wire embedded therein was roughly polished with sandpaper so as to expose the lateral cross-section on the surface, then after finally being subjected to mirror-finishing by buffing, each part was measured with an X-ray diffractometer (SmartLab manufactured by Rigaku Corporation). A certain amount of wire cross-sectional area is required to obtain the intensity of X-ray diffraction, and thus only one sample having a wire diameter of 400 ?m may be insufficient in intensity. Accordingly, for each measurement, about forty wires were bundled to be brought into close contact with each other, embedded, polished, and subjected to X-ray diffraction.

[0114] It was performed under the analysis conditions as follows: an X-ray generating portion with a Cu anticathode, output 45 kV, and 200 mA; a semiconductor detector as a detecting portion; a parallel beam method (slit collimation) as an incident optical system; the incident side of the solar slit at 5? and the light receiving side at 5? as well; the incident side of the slit IS=1 mm; a longitudinal limit of 2 mm; and on the light receiving side, RS1=1 mm and RS2=2 mm. The scanning conditions were as follows: a scanning axis of 2 ?/?, continuous scanning as a scanning mode, a scanning range of 30 to 100?, a step width of 0.02?, and a scanning speed of 3?/minute.

[0115] Diffraction intensities (peak separation) of (111), (200), (220), (311), (222), and (400) of each sample were measured to obtain the respective orientation indexes by means of the Wilson's formula.

[0116] The orientation indexes of (111) and (200) indicating particularly characteristic tendencies in the examples are shown in Table 1 together with the alloy compositions. It should be noted that the orientation index described in Table 1 is the average value of three parts of the tip, the rear end, and the middle portion of the wire, each of which has five sample windings (five windings?three parts, that is, the average value of a total of fifteen parts). It should be noted that, as described above, the peripheral portion of each part is cut into forty pieces, and the forty pieces are bundled for measurement.

[0117] (Measurement of Area Ratio of Precipitated Particles)

[0118] Regarding grain diameters of precipitated particles at the tip portion, rear end portion, and intermediate portion of the wire having a final wire diameter of 400 ?m and obtained after the solution treatment, an image of the lateral cross-section in the direction perpendicular to the wire axis was taken with an FE-SEM (a field emission scanning electron microscope, JSM-7800F manufactured by JEOL) at an observation magnification of 400 times. However, only about each of four divisions of the slice section was included in the imaging range at the 400 magnifications; accordingly, an image of the wire cross-section was taken in four divisions, and the taken images were pasted together to obtain the area occupied by the precipitated particles relative to the entire slice section. It was performed under the SEM imaging conditions in which the accelerating voltage was set to 5 kV, the working distance (W.D.) was set to 10 mm, and a reflection electron image (BED-C) was selected. In the image analysis, the brightness value of the taken SEM image was normalized in a range of 0 to 1 and binarized with a threshold of 0.95, and e areas with a brightness value higher than the threshold was defined as precipitated particles.

[0119] Further, in the image analysis, pixels adjacent to each other in eight neighbors in the region on the image recognized as particles were calculated as one particle. The eight neighbors mean eight directions around a center that predetermined region recognized as particles, its up, down, left, and right, and rotated each of them 45?, and a region in contact with the predetermined region in any of these eight directions is defined as one particle.

[0120] Next, the ratio of the entire cross-section perpendicular to the wire axial direction to the cross-sectional area was expressed as a percentage. The area ratio of the precipitated particles was substantially the same in all of the tip portion, rear end portion, and intermediate portion of the wire. The area ratio of the precipitated particles in each of the examples is shown in Table 1. Precipitated particles of Example 12 are shown in FIG. 1, and precipitated particles of Comparative Example 6 described later are shown in FIG. 2. However, FIGS. 1 and 2 are photographs obtained by, with the image analysis, binarizing images taken at a magnification of 1000 times so that the precipitated particles can be identified more easily. The areas in white show precipitated particles.

TABLE-US-00001 TABLE 1 WIRE PROPERTIES AREA WIRE COMPOSITIONS RATIO OF Fe + Ga + PRECIPITATED WIRE EVALUATION Al Si V OTHERS ORIENTATION PARTICLES TOOL HEAT MASS MASS MASS MASS INDEX PERCENTAGE LIFE DETACH- GENER- OVERALL No. % % ppm ppm (111) (200) % TEST MENT ATION EVALUATION EXAMPLES 1 90.09 0.9 52 48 1.78 0.43 1.9 S A S EXCELLENT 2 99.09 0.9 52 48 1.23 0.75 1.8 S A S EXCELLENT 3 99.09 0.9 52 48 1.25 0.62 1.6 S A S EXCELLENT 4 99.09 0.9 52 48 1.31 0.81 1.3 S A S EXCELLENT 5 99.09 0.9 52 48 1.62 0.12 1.7 S A S EXCELLENT 6 99.09 0.9 52 48 1.9 0.22 1 S A S EXCELLENT 7 99.09 0.9 52 48 1.35 0.69 1.5 S A S EXCELLENT 8 99.09 0.9 52 48 1.95 0.29 1.7 S A S EXCELLENT 9 99.8 0.11 785 115 1.82 0.32 1.2 S A S EXCELLENT 10 99.8 0.11 785 115 1.32 0.56 1 S A S EXCELLENT 11 99.8 0.11 785 115 1.51 0.54 1.3 S A S EXCELLENT 12 99.8 0.11 785 115 1.47 0.55 0.3 S A S EXCELLENT 13 99.8 0.11 785 115 1.77 0.28 0.9 S A S EXCELLENT 14 99.8 0.11 785 115 1.66 0.45 0.2 S A S EXCELLENT 15 99.8 0.11 785 115 1.34 0.97 0.5 S A S EXCELLENT 16 99.8 0.11 785 115 1.66 0.43 0.6 S A S EXCELLENT 17 99.44 0.55 46 54 1.81 0.55 0.5 A A S GOOD 18 99.44 0.55 46 54 1.33 0.86 1.6 A A S GOOD 19 99.44 0.55 46 54 1.23 0.68 1.8 A A S GOOD 20 99.44 0.55 46 54 1.1 0.74 0.6 A A S GOOD 21 99.44 0.55 46 54 1.67 0.29 1.3 A A S GOOD 22 99.44 0.55 46 54 1.51 0.44 1 A A S GOOD 23 99.44 0.55 46 54 1.33 0.57 0.8 A A S GOOD 24 99.44 0.55 46 54 1.56 0.4 1.1 A A S GOOD 25 99.28 0.63 820 80 1.39 0.48 1.4 S A A GOOD 26 99.28 0.63 820 80 1.1 0.88 1.5 S A A GOOD 27 99.28 0.63 820 80 1.32 0.66 1.7 S A A GOOD 28 99.28 0.63 820 80 1.45 0.71 1.5 S A A GOOD 29 99.28 0.63 820 80 1.88 0.07 1.8 S A A GOOD 30 99.28 0.63 820 80 1.64 0.21 1.4 S A A GOOD 31 99.28 0.63 820 80 1.32 0.65 1.3 S A A GOOD 32 99.28 0.63 820 80 1.99 0.55 0.9 S A A GOOD

[0121] (Tool Detachment Evaluation 1)

[0122] Next, each sample in which a wire diameter of the aluminum wire is 400 ?m was bonded to an aluminum plate using an ultrasonic bonding device (a wire bonder, ASTERION, manufactured by K&S) so that the distance between the first bonding and the second bonding was 5 mm. The second bonding portion was bent to the side horizontally with respect to the wire axial direction at a target angle of 45? (see FIG. 4, in which in the lower left photograph, it was bent at only about 30?). The bonding conditions were set such that the ultrasonic energy and the pressure were optimal for each sample. It should be noted that a bond tool, model number 127591-16 manufactured by Kulicke & Soffa, was used, and the dimensions of the alligator for gripping the wire were a frontage (inner diameter) of 0.5 mm, a height of 0.2 mm, and a length of 1.0 mm.

[0123] For each sample, whether a failure of tool detachment has occurred was determined by observing the state of the wire at the second bonding part. Each sample was subjected to the bonding 30 times (a combination of the first bonding and the second bonding is regarded as 1 time), and a wire that caused a bonding failure or had even one contact mark with a tool that made a one-sided contact therewith as shown in the lower left of FIG. 4 was graded fail and rated as C. As in the lower right of FIG. 4, if the bonding was normally made, it was graded pass and rated as A, which was shown in Table 1 as a tool detachment evaluation.

[0124] The two upper and lower photographs on the right side of FIG. 4 were obtained from Example 1. The upper right figure shows the wire after the first bonding by ultrasonic waves, and the lower right figure shows the wire obtained by being bent to the side at 45? horizontally with respect to the longitudinal direction of the wire after the first bonding and then subjected to the second bonding. As apparent from both of the photographs, it can be seen that the bonding was normally performed without any contact mark or the like.

[0125] (Power Cycle Test Evaluation)

[0126] Each sample in which a wire diameter of the aluminum wire is 400 ?m was bonded to a power chip in which nickel was metallized on an aluminum alloy electrode on the surface (a metal film was formed on the surface), using an ultrasonic bonding device (a wire bonder, REB09, manufactured by Ultrasonic Engineering). In the bonding conditions, the ultrasonic energy and the pressure were set such that the wire width after bonding was 500 ?m for each sample. The current, the energization time, and the cooling time were set such that a maximum temperature of the power chip was 150? C. and a minimum temperature thereof was 50? C., that is, ?T=100? C., then a power cycle test was performed. It was performed for about 20 seconds per one cycle in which the energization time at this time was about 7 seconds and the energization stop time was about 13 seconds.

[0127] The number of cycles in which the potential difference between the front and back electrodes of the power chip at the time of energization increased by 5% from the initial value was defined as a life in the power cycle test. A sample with a life of 200,000 cycles or more was regarded as having a life equal to or more than the target and denoted by S. A sample with a life of 100,000 cycles or more and less than 200,000 cycles was regarded as a target level and denoted by A. A sample with a life of 50,000 cycles or more and less than 100,000 cycles was regarded as a passing mark and denoted by B. A sample with a life of less than 50,000 cycles was regarded as fail and denoted by C. Table 1 shows the evaluation of the power cycle test of the aluminum wire in each example.

[0128] (Measurement 1 of Residual Resistance Ratio) (Heat Generation)

[0129] The residual resistance ratio (RRR) is expressed by the ratio of the electric resistance in liquid helium at 4.2 K (kelvin) and the electric resistance at room temperature of 300 K. The manufactured aluminum wire was cut into a length of 15 cm and measured the electric resistance. All of the electric resistances were measured by a four-terminal method, and after each electric resistance was measured, the ratio of the electric resistances was calculated. It should be noted that since the residual resistance ratio is proportional to the temperature rise at the time of energization, if a residual resistance value was 10 or more and less than 15, which allows to suppress the temperature rise so as to be less than 30? C. from the maximum temperature of the aluminum wire having a purity of 99.99 mass % described above, so it was denoted by A. If a residual resistance value is 15 or more, which allows to suppress the temperature rise so as to be 10? C. or less, so it was denoted by S in the sense that it is even better, in the column of the wire evaluation in Table 1. Further, a temperature rise of 30? C. or more was graded fail and evaluated as C.

[0130] (Overall Evaluation 1)

[0131] A sample in which the above three evaluations were two S and one A was determined as Excellent in the overall evaluation in the sense that it is superior. A sample with one S and two A was determined as Good in the overall evaluation in the sense that it is good. A sample with the other evaluation combination and no C was determined as Fair in the overall evaluation in the sense that it is a passing mark. A sample with even one C was determined as Poor in the overall evaluation in the sense that it is fail. Then each evaluation was described in Table 1.

[0132] Next, aluminum wires of Example 33 and the subsequent examples having a final wire diameter of 400 ?m were obtained in the same manner as in Example 1, except that the composition of the aluminum wire was adjusted as shown in Tables 2 to 13, and the manufacturing conditions such as the intermediate wire diameter, intermediate heat treatment conditions, and final heat treatment conditions were adjusted within the range of the above embodiment. For these aluminum wires, the orientation index and the area ratio of the precipitated particles were measured in the same manner as in Example 1, then the wire properties were evaluated. It should be noted that for Example 33 and the subsequent examples, the criteria of tool detachment evaluation, heat generation (residual resistance ratio) evaluation, and overall evaluation were set more specifically than those for Examples 1 to 32 described above, as in the following Tool Detachment Evaluation 2, Measurement 2 of Residual Resistance Ratio, and Overall Evaluation 2. The notation of - in each table indicates that it is less than the lower limit of measurement.

[0133] (Tool Detachment Evaluation 2)

[0134] The tool detachment test was performed in the same manner as in Tool Detachment Evaluation 1 described above, and the evaluation was as follows. Whether a failure of tool detachment has occurred was determined by observing the state of the wire at the second bonding part. Each sample was subjected to the bonding 100 times (a combination of the first bonding and the second bonding is regarded as 1 time), and tool detachment was evaluated as follows: a wire that caused a bonding failure or had four or more contact marks with a tool that made a one-sided contact therewith as shown in the lower left of FIG. 4 was graded fail and rated as C, a wire having two to three contact marks is desired to be slightly improved but has no practical problem so that rated as B, a wire having one contact mark is very excellent and thus was graded pass so that rated as A, and a wire having no contact mark at all was rated as S.

[0135] (Measurement 2 of Residual Resistance Ratio) (Heat Generation)

[0136] The residual resistance ratio (RRR) test was performed in the same manner as in Measurement 1 of Residual Resistance Ratio described above, and the evaluation criteria were changed as follows. The residual resistance ratio is proportional to the temperature rise at the time of energization. A residual resistance value being 15 or more it allows to suppress the temperature rise so as to be 10? C. or less from the maximum temperature which the aluminum wire having a purity of 99.99 mass % described above is assumed to reach, so that was evaluated as S in the sense that it is very excellent. A case that the temperature rise can be suppressed exceeding 10? C. so as to be 20? C. or less was evaluated as A. A case that the temperature rise can be suppressed exceeding 20? C. so as to be less than 30? C. was evaluated as B. A case that a temperature rise to 30? C. or more was graded fail and thus evaluated as C.

[0137] (Overall Evaluation 2)

[0138] A sample in which S was one or more and the other was S or A in the above three evaluations was determined as Excellent in the overall evaluation in the sense that it is superior, a sample with a total of two or more of A and S was determined as Good in the overall evaluation in the sense that it is good, a sample with two or more B and no C was determined as Fair in the overall evaluation in the sense that it is a passing mark, and a sample with even one C was determined as Poor in the overall evaluation in the sense that it is fail, then each evaluation was described in the table.

[0139] Specific combinations for each evaluation (in any order) are as follows. [0140] Excellent: SSS, SSA, SAA [0141] Good: SAB, SSB, AAB, AAA [0142] Fair: SBB, ABB, BBB [0143] Poor: a case of having even one C

[0144] The above results are shown in Tables 2 to 13 together with the compositions.

TABLE-US-00002 TABLE 2 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn O 33 99.03 0.92 0.6 0.32 1.9 401 300 101 100 10 30 5 15 34 99.47 0.48 0.39 0.09 4.3 450 320 130 100 10 30 5 15 35 99.75 0.19 0.15 0.04 3.6 510 320 190 100 10 30 5 15 36 99.13 0.85 0.67 0.18 3.7 105 56 49 110 10 13 30 5 15 37 99.55 0.43 0.39 0.04 9.8 120 100 20 105 10 10 30 5 10 38 99.80 0.17 0.12 0.05 2.4 152 100 52 100 10 5 30 5 10 39 99.10 0.88 0.51 0.37 1.4 68 30 36 110 20 5 30 5 10 40 99.57 0.41 0.32 0.09 3.6 90 70 20 110 20 5 30 5 10 41 99.83 0.15 0.11 0.04 2.6 77 67 10 125 30 5 30 5 15 42 99.39 0.55 0.45 0.1 4.5 444 400 44 125 30 5 30 5 15 43 99.56 0.39 0.3 0.09 3.3 422 400 22 120 25 5 30 5 15 44 99.75 0.18 0.1 0.08 1.3 621 600 21 120 25 5 30 5 15 45 99.32 0.66 0.6 0.06 10.0 112 100 12 135 40 5 30 5 15 46 99.75 0.22 0.2 0.02 10.0 130 100 30 125 40 5 30 5 5 47 99.77 0.19 0.11 0.08 1.4 300 250 50 115 30 5 30 5 5 48 99.41 0.57 0.34 0.23 1.5 66 50 16 100 15 5 30 5 5 49 99.05 0.33 0.23 0.1 2.3 78 40 38 100 15 5 30 5 5 50 99.96 0.02 0.01 0.01 1.0 99 50 49 105 20 5 30 5 5 51 99.12 0.02 0.8 0.02 40.0 449 400 49 105 20 5 30 5 5 52 99.85 0.24 0.21 0.03 7.0 980 950 30 110 15 5 30 5 5 53 99.76 0.17 0.15 0.02 7.5 567 450 117 95 5 30 5 5 54 99.08 0.88 0.87 0.01 87.0 258 240 18 105 5 30 5 15 55 99.61 0.35 0.3 0.05 0.0 298 200 98 105 5 30 5 15 AREA RATIO OF WIRE EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 33 10 10 20 1.52 0.01 1.97 S B B FAIR 34 10 10 20 1.57 0.02 0.93 S A B GOOD 35 10 10 20 1.8 0.03 0.42 A S A EXCELLENT 36 10 10 20 1.87 0.04 1.78 S B B FAIR 37 10 10 20 1.78 0.02 0.96 S A A EXCELLENT 38 10 10 20 1.67 0.03 0.31 B S S GOOD 39 10 10 20 1.56 0.05 1.72 S B B FAIR 40 10 10 20 1.53 0.06 0.86 A A S EXCELLENT 41 10 10 20 1.92 0.08 0.35 B S S GOOD 42 10 10 20 1.43 0.07 1.12 S B B FAIR 43 10 10 20 1.41 0.03 0.9 A S A EXCELLENT 44 10 10 20 1.4 0.03 0.44 B S A GOOD 45 10 10 20 1.48 0.01 1.36 A B B FAIR 46 10 10 20 1.25 0.01 0.5 B S S GOOD 47 10 10 20 1.29 0.02 0.44 B S S GOOD 48 10 10 20 1.35 0.02 1.18 A B A GOOD 49 10 10 20 1.44 0.03 0.73 B S S GOOD 50 10 10 20 1.42 0.06 0.02 B S S GOOD 51 10 10 20 1.01 0.05 1.73 A B B FAIR 52 10 20 20 1.18 0.01 0.56 B S B FAIR 53 10 20 20 1.17 0.02 0.42 B S A GOOD 54 10 20 20 1.12 0.02 1.87 A B B FAIR 55 10 20 20 1.11 0.04 0.88 B S S GOOD

TABLE-US-00003 TABLE 3 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 56 99.84 0.12 0.1 0.02 5.0 320 240 80 105 5 30 5 15 57 95.13 0.86 0.2 0.58 0.3 110 5 5 30 5 15 58 95.73 0.25 0.1 0.15 0.7 66 40 26 130 20 5 30 10 15 59 99.64 0.14 0.12 0.02 6.0 96 50 46 110 15 5 30 10 60 99.20 0.75 0.5 0.25 2.0 411 300 111 115 15 10 30 10 61 99.63 0.3 0.2 0.1 2.0 578 400 178 130 30 10 30 10 62 99.72 0.17 0.12 0.05 2.4 990 50 940 133 30 10 30 10 3 63 99.39 0.58 0.56 0.02 28.0 159 100 59 138 35 10 30 10 3 64 99.63 0.34 0.33 0.01 33.0 200 100 100 138 35 10 30 10 3 65 99.77 0.19 0.12 0.07 1.7 280 200 80 139 36 10 30 10 3 66 99.47 0.51 0.4 0.11 3.6 78 50 28 143 40 10 30 10 3 67 99.51 0.47 0.4 0.07 5.7 48 30 18 126 23 10 30 10 3 68 99.78 0.2 0.1 0.1 1.0 89 80 9 141 23 10 30 10 3 15 69 99.28 0.85 0.6 0.05 12.0 589 400 189 138 20 10 30 10 3 15 70 99.51 0.4 0.3 0.1 3.0 767 600 167 140 17 15 30 10 3 15 71 99.78 0.17 0.1 0.07 1.4 407 300 107 142 19 15 30 10 3 15 72 99.09 0.88 0.8 0.08 10.0 129 100 29 124 21 15 10 10 3 15 73 99.61 0.35 0.3 0.05 6.0 289 200 89 114 11 15 10 10 3 15 74 99.80 0.16 0.1 0.06 1.7 222 200 22 137 39 15 10 10 3 10 75 99.38 0.6 0.55 0.05 11.0 41 30 11 132 34 15 10 10 3 10 AREA RATIO OF WIRE EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 56 10 20 20 1 0.05 0.3 B S S GOOD 57 10 20 20 1.08 0.08 1.72 B B B FAIR 58 10 20 20 1.19 0.09 0.55 B S S GOOD 59 10 20 20 1.16 0.03 0.38 B S S GOOD 60 10 20 20 1.52 0.4 1.57 S B B FAIR 61 10 20 20 1.67 0.32 0.78 A S A EXCELLENT 62 10 20 20 1.69 0.15 0.42 A S B GOOD 63 10 20 20 1.65 0.23 1.13 S B B FAIR 64 10 20 20 1.55 0.19 0.8 A S S EXCELLENT 65 10 20 20 1.98 0.44 0.43 B S S GOOD 66 10 20 20 1.88 0.32 1.06 A B A GOOD 67 10 20 20 1.9 0.21 1 B A S GOOD 68 10 20 20 1.6 0.23 0.6 B S S GOOD 69 10 20 20 1.3 0.34 1.33 S B B FAIR 70 10 20 20 1.32 0.44 0.82 A S A EXCELLENT 71 10 20 20 1.34 0.47 0.56 B S A GOOD 72 10 20 20 1.42 0.48 1.77 S B B FAIR 73 10 20 20 1.41 0.12 0.72 B S S GOOD 74 10 20 20 1.47 0.34 0.32 B S S GOOD 75 10 20 20 1.32 0.33 1.27 B B A FAIR

TABLE-US-00004 TABLE 4 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 76 99.54 0.44 0.43 0.01 43.0 75 60 15 137 39 15 10 10 3 10 77 99.82 0.16 0.1 0.06 1.7 8 123 20 15 10 10 3 15 78 99.42 0.52 0.02 25.0 479 400 79 139 36 15 10 10 3 15 79 99.67 0.25 0.2 0.05 4.0 675 500 175 120 12 20 10 10 3 15 80 99.78 0.12 0.1 0.02 5.0 835 500 335 120 12 20 10 10 3 15 81 99.08 0.9 0.78 0.12 6.5 108 60 48 142 34 20 10 10 3 15 82 99.65 0.31 0.23 0.08 2.9 267 200 67 147 39 20 10 10 3 15 83 99.78 0.18 0.12 0.06 2.0 300 200 100 145 37 20 10 10 3 15 84 0.66 0.55 0.11 5.0 67 50 17 128 20 20 10 10 3 15 85 99.61 0.37 0.32 0.05 6.4 78 50 28 128 20 20 10 10 3 15 86 99.82 0.16 0.12 0.04 3.0 98 50 48 118 5 25 10 10 3 15 87 99.17 0.77 0.67 0.1 6.7 467 300 167 118 5 25 10 10 3 15 88 99.57 0.35 0.33 0.02 18.5 500 166 128 5 25 10 10 10 3 15 89 99.77 0.14 0.12 0.02 6.0 742 400 342 128 5 25 10 10 10 3 15 90 99.45 0.52 0.43 0.09 4.8 123 100 23 133 5 30 10 10 10 3 15 91 99.55 0.42 0.3 0.12 2.5 187 100 87 133 5 30 10 10 10 3 15 92 99.78 0.13 0.12 0.06 2.0 273 200 78 133 5 30 10 10 10 3 15 93 99.39 0.59 0.43 0.16 2.7 40 26 150 35 10 10 10 10 10 15 94 99.76 0.22 0.2 0.02 10.0 77 50 27 147 32 10 10 10 10 10 15 95 99.80 0.18 0.15 0.03 5.0 97 70 27 125 10 10 10 10 10 10 15 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 76 10 20 20 1.36 0.48 0.92 B A S GOOD 77 10 20 20 1.39 0.41 0.4 B S S GOOD 78 10 20 20 1.11 0.31 1.03 A B B FAIR 79 10 20 20 1.16 0.17 0.52 B S A GOOD 80 10 20 20 1.18 0.2 0.32 B S B FAIR 81 10 20 20 1.17 0.21 1.76 A B B FAIR 82 10 20 20 1.12 0.22 0.68 B S S GOOD 83 10 20 20 1.07 0.3 0.35 B S S GOOD 84 10 20 20 1.17 0.31 1.33 B B A FAIR 85 10 20 20 1.12 0.4 0.71 B S S GOOD 86 10 20 20 1.15 0.43 0.38 B S S GOOD 87 10 20 20 1.62 0.52 1.54 S B B FAIR 88 10 20 20 1.65 0.62 0.71 A S A EXCELLENT 89 10 20 20 1.72 0.6 0.32 A S A EXCELLENT 90 10 20 20 1.82 0.67 1.06 S B B FAIR 91 10 20 20 1.66 0.8 0.83 S A A EXCELLENT 92 10 20 20 1.52 0.31 0.41 B S S GOOD 93 10 20 20 1.53 0.57 1.22 A B A GOOD 94 10 20 20 1.68 0.62 0.45 B S S GOOD 95 10 20 20 1.55 0.91 0.37 B S S GOOD indicates data missing or illegible when filed

TABLE-US-00005 TABLE 5 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 96 99.40 0.55 0.52 0.03 17.3 403 300 103 125 10 10 10 10 10 10 15 97 99.45 0.48 0.45 0.03 15.0 572 300 272 127 12 10 10 10 10 10 15 98 99.73 0.19 0.18 0.01 18.0 656 300 356 122 12 5 10 10 10 10 15 99 99.46 0.52 0.48 0.04 12.0 120 70 50 123 13 5 10 10 10 10 15 100 99.07 0.3 0.21 2.3 200 100 100 126 16 5 10 10 10 10 15 101 99.77 0.18 0.18 0.02 8.0 388 300 88 134 34 5 10 10 10 15 102 99.18 0.8 0.77 0.03 25.7 67 50 17 130 30 5 10 10 10 15 103 99.05 0.33 0.3 0.03 10.0 70 50 20 128 28 5 10 10 10 15 104 99.86 0.12 0.1 0.02 5.0 99 50 49 133 5 15 10 10 15 105 99.34 0.6 0.5 0.1 5.0 423 300 123 131 5 15 10 10 15 106 99.56 0.37 0.3 0.07 4.3 567 300 267 131 26 5 15 10 10 15 107 99.72 0.19 0.17 0.02 8.5 766 400 366 143 28 5 10 15 10 10 15 108 99.30 0.67 0.55 0.12 4.6 150 100 50 137 22 5 10 15 10 10 15 109 99.52 0.44 0.34 0.1 3.4 300 250 50 137 22 5 10 15 10 10 15 110 99.81 0.15 0.1 0.05 2.0 250 200 50 149 34 5 10 15 10 10 15 111 99.11 0.88 0.72 0.16 4.5 134 19 5 10 15 10 10 15 112 99.67 0.31 0.3 0.01 30.0 78 40 38 133 18 5 10 15 10 10 15 113 99.87 0.11 0.1 0.01 10.0 96 50 46 137 27 10 15 10 10 15 114 99.38 0.56 0.43 0.13 3.3 478 400 78 142 27 10 15 10 10 15 115 99.71 0.22 0.2 0.02 10.0 507 300 207 145 30 10 15 10 10 15 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 96 10 20 20 1.45 0.92 1.12 S B B FAIR 97 10 20 20 1.32 0.99 0.97 A S A EXCELLENT 98 10 20 20 1.3 0.55 0.4 B S A GOOD 99 10 20 20 1.38 0.71 1.05 A B B FAIR 100 10 20 20 1.41 0.77 0.62 B S S GOOD 101 10 20 20 1.28 0.82 0.41 B S S GOOD 102 10 20 20 1.3 0.81 A B A GOOD 103 10 20 20 1.37 0.61 B S S GOOD 104 10 20 20 1.42 0.66 0.23 B S S GOOD 105 10 20 20 1.07 0.68 1.21 B B B FAIR 106 10 20 20 1.12 0.69 0.76 B S A GOOD 107 10 20 20 1.05 0.81 0.43 B S A GOOD 108 10 20 20 1.09 0.9 1.33 B B A FAIR 109 10 20 20 1.12 0.92 0.87 B A A GOOD 110 10 20 20 1.17 0.95 0.31 B S S GOOD 111 10 20 20 1.19 0.66 1.89 B B B FAIR 112 10 20 20 1.16 0.7 0.67 B S S GOOD 113 10 20 20 1.2 0.71 0.23 B S S GOOD 114 15 20 20 1.52 0.01 1.21 S B B FAIR 115 15 20 20 1.59 0.02 A S A EXCELLENT indicates data missing or illegible when filed

TABLE-US-00006 TABLE 6 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 116 99.74 0.16 0.12 0.04 3.0 815 500 315 148 33 10 15 10 10 15 117 99.27 0.7 0.6 0.1 6.0 130 100 30 128 23 15 10 10 15 118 99.67 0.3 0.23 0.07 3.3 189 100 89 129 29 15 10 5 15 119 99.85 0.11 0.1 0.01 10.0 298 260 38 128 15 10 5 15 120 98.98 1 0.1 9.0 55 39 16 113 13 15 10 5 15 121 99.54 0.44 0.32 0.12 2.7 89 56 33 128 23 15 10 5 15 122 99.84 0.14 0.12 0.02 6.0 67 55 12 132 22 10 15 10 5 15 123 98.94 0.99 0.88 0.11 8.0 567 500 67 137 27 10 15 10 5 15 124 99.44 0.48 0.45 0.03 15.0 700 300 400 120 10 10 15 10 5 15 125 99.73 0.18 0.1 0.08 1.3 789 580 209 16 10 15 10 5 15 126 99.09 0.88 0.85 0.03 28.3 145 100 45 115 5 10 15 10 5 15 127 99.75 0.22 0.2 0.02 10.0 156 120 36 120 10 10 15 10 5 15 128 99.83 0.14 0.12 0.02 8.0 178 100 78 160 40 10 10 15 10 5 15 129 0.70 0.02 39.0 67 30 37 155 35 10 10 15 10 5 15 130 99.65 0.33 0.3 0.03 10.0 89 40 49 153 33 10 10 15 10 5 15 131 99.81 0.17 0.15 0.02 7.5 99 50 49 138 28 10 15 10 5 15 132 0.67 0.6 0.07 8.6 409 300 109 139 29 10 15 10 5 15 133 99.54 0.39 0.32 0.07 4.6 578 400 178 119 29 10 15 10 5 15 134 99.79 0.12 0.1 0.02 5.0 798 600 198 111 21 10 15 10 5 15 135 99.32 0.53 0.13 4.1 129 100 29 115 20 15 15 10 5 15 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 116 15 20 20 1.62 0.02 0.33 A S B GOOD 117 15 20 20 1.77 0.04 1.42 S B B FAIR 118 15 20 20 1.84 0.01 0.65 A S S EXCELLENT 119 15 20 20 1.96 0.05 0.21 B S S GOOD 120 15 20 20 1.56 0.06 1.99 S B B FAIR 121 15 20 20 1.55 0.07 0.92 A A S EXCELLENT 122 15 20 20 1.79 0.07 0.27 B S S GOOD 123 15 20 20 1.32 0.08 1.96 S B B FAIR 124 15 20 20 1.37 0.09 0.92 A A B GOOD 125 15 20 20 1.39 0.03 0.43 B S A GOOD 126 15 20 20 1.32 0.04 1.77 S B B FAIR 127 15 20 20 1.37 0.05 0.43 B S S GOOD 128 15 20 20 1.25 0.05 0.32 B S S GOOD 129 15 20 20 1.45 0.03 1.62 A B A GOOD 130 15 20 20 1.44 0.02 0.86 B S S GOOD 131 15 20 20 1.41 0.02 0.44 B S S GOOD 132 15 20 20 1.1 0.01 1 A B B FAIR 133 15 20 1.19 0.05 0.88 B S A GOOD 134 15 20 1.15 0.05 0.32 B S A GOOD 135 15 20 1.12 0.06 1.3 A B B FAIR indicates data missing or illegible when filed

TABLE-US-00007 TABLE 7 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 136 99.51 0.45 0.44 0.01 44.0 245 200 45 111 16 15 15 10 5 15 137 99.78 0.18 0.16 0.02 8.0 300 200 100 108 23 15 10 5 5 15 138 99.30 0.69 0.6 0.09 6.7 38 30 3 106 21 15 10 5 5 15 139 99.70 0.28 0.23 0.05 4.6 76 70 6 111 21 15 10 5 5 15 140 99.86 0.12 0.1 0.02 5.0 88 60 28 110 20 15 10 5 5 15 141 99.39 0.55 0.44 0.11 4.0 450 400 50 122 32 15 10 5 5 15 142 99.55 0.38 0.32 0.06 5.3 545 300 245 128 38 15 10 5 5 15 143 99.72 0.19 0.12 0.07 1.7 768 800 166 38 15 10 5 5 15 144 99.39 0.59 0.43 0.18 2.7 120 100 20 123 38 15 10 5 15 145 99.67 0.29 0.21 0.06 2.6 266 100 168 125 40 15 10 5 15 146 99.84 0.11 0.1 0.01 10.0 345 300 45 125 40 15 10 5 15 147 99.22 0.76 0.73 0.03 24.3 78 60 18 107 32 10 10 5 15 148 99.61 0.37 0.3 0.07 4.3 95 60 35 91 16 10 10 5 15 149 99.81 0.17 0.15 0.02 7.5 68 50 18 28 10 10 5 15 150 99.39 0.55 0.5 0.05 10.0 466 450 16 91 26 10 5 15 151 99.47 0.45 0.4 0.05 8.0 700 500 200 86 21 10 5 15 152 99.81 0.12 0.1 0.02 5.0 578 500 78 88 20 10 3 5 15 153 99.21 0.77 0.7 0.07 10.0 123 100 23 88 20 10 3 5 15 154 99.48 0.49 0.43 0.06 7.2 222 200 22 90 17 10 3 5 15 155 99.76 0.2 0.16 0.04 4.0 302 250 52 17 10 3 5 15 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 136 15 20 1.17 0.06 1.1 B A A GOOD 137 15 20 1.14 0.07 0.36 B S S GOOD 138 15 20 1.16 0.08 1.39 B B A FAIR 139 15 5 20 1.13 0.08 0.57 B S S GOOD 140 15 5 20 1.18 0.02 0.24 B S S GOOD 141 15 5 20 1.52 0.12 1.2 S B B FAIR 142 15 5 20 1.67 0.17 0.82 A S A EXCELLENT 143 15 5 20 1.72 0.18 0.4 A S A EXCELLENT 144 15 5 20 1.8 0.2 1.22 S B B FAIR 145 15 5 20 1.81 0.23 0.67 A S S EXCELLENT 146 15 5 20 1.85 0.24 0.22 B S S GOOD 147 15 20 1.82 0.29 1.47 A B A GOOD 148 15 20 1.71 0.28 0.93 B S S GOOD 149 15 20 1.68 0.28 0.43 B S S GOOD 150 15 20 1.43 0.4 1.03 S B B FAIR 151 15 20 1.48 0.43 1.02 A A B GOOD 152 15 20 1.42 0.42 0.24 B S A GOOD 153 15 20 1.44 0.44 1.55 A B B FAIR 154 15 5 20 1.41 0.47 0.99 A A A GOOD 155 15 5 15 1.42 0.49 0.43 B S S GOOD indicates data missing or illegible when filed

TABLE-US-00008 TABLE 8 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 156 99.31 0.67 0.65 0.02 32.5 66 50 16 89 21 10 3 5 15 157 99.65 0.33 0.3 0.03 10.0 89 70 19 78 15 10 3 5 15 158 99.84 0.14 0.1 0.04 2.5 96 70 26 93 30 10 3 5 15 159 99.16 0.79 0.75 0.04 18.8 402 300 102 98 30 10 3 5 15 160 99.70 0.24 0.2 0.04 5.0 521 300 221 97 29 10 3 5 15 161 99.74 0.19 0.1 0.09 1.1 634 400 234 102 29 10 3 5 20 162 99.47 0.51 0.34 0.17 2.0 111 100 11 102 29 10 3 5 20 163 99.63 0.34 0.23 0.11 2.1 234 200 34 98 30 10 3 5 20 164 99.81 0.15 0.11 0.04 2.8 300 200 100 20 10 3 5 20 165 99.21 0.77 0.7 0.07 10.0 98 70 28 88 20 10 3 5 20 166 99.65 0.33 0.3 0.03 10.0 76 50 26 87 15 10 3 5 20 167 99.80 0.19 0.12 0.07 1.7 67 40 27 83 10 10 3 5 20 168 99.19 0.76 0.55 0.21 2.6 428 300 128 83 10 10 3 5 20 169 0.45 0.23 0.22 1.0 571 300 271 78 10 10 3 5 15 170 99.77 0.10 0.12 0.04 3.0 862 500 162 63 10 3 15 171 99.08 0.9 0.56 0.34 1.6 159 100 59 53 10 3 15 172 99.53 0.44 0.34 0.1 3.4 234 100 134 70 10 10 15 173 99.77 0.19 0.13 0.06 2.2 350 200 150 80 20 10 15 174 99.40 0.58 0.5 0.08 50 20 90 10 20 10 15 175 99.59 0.39 0.32 0.07 4.6 95 50 45 125 10 20 10 45 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 156 15 5 15 1.49 0.42 1.33 A B A GOOD 157 15 15 1.37 0.35 0.67 B S S GOOD 158 15 5 15 1.32 0.3 0.32 B S S GOOD 159 15 5 15 1.03 0.32 1.52 A B B FAIR 160 15 5 15 1.09 0.34 0.51 B S A GOOD 161 15 5 15 1.12 0.22 0.41 B S A GOOD 162 15 5 15 1.18 0.25 1.02 A B B FAIR 163 15 15 1.19 0.3 0.87 B S S GOOD 164 15 15 1.15 0.25 0.32 B S S GOOD 165 15 15 1.14 0.28 1.55 B B A FAIR 166 15 15 1.16 0.42 0.65 B S S GOOD 167 15 5 15 1.12 0.45 0.38 B S S GOOD 168 15 5 15 1.6 0.59 1.52 S B B FAIR 169 15 5 15 1.67 0.81 0.92 A S A EXCELLENT 170 15 5 15 1.65 0.87 0.38 A S A EXCELLENT 171 15 5 15 1.71 0.87 1.7 S B B FAIR 172 15 5 15 1.88 0.67 0.92 S A A EXCELLENT 173 15 5 15 1.96 0.91 0.31 B S S GOOD 174 15 5 15 1.9 0.95 1.22 A B A GOOD 175 15 10 15 1.6 0.9 0.86 B S S GOOD indicates data missing or illegible when filed

TABLE-US-00009 TABLE 9 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 176 99.84 0.14 0.1 0.04 2.5 64 50 14 130 10 5 20 10 45 177 99.42 0.52 0.5 0.02 25.0 490 400 90 134 11 5 20 10 3 45 178 99.63 0.3 0.23 0.07 3.3 567 400 167 135 12 5 20 10 3 45 179 99.78 0.11 0.1 0.01 10.0 970 900 70 139 16 5 20 10 3 45 180 99.22 0.75 0.74 0.01 74.0 122 100 22 139 18 5 20 10 3 45 181 99.65 0.31 0.3 0.01 30.0 234 200 34 145 17 5 20 15 3 45 182 99.76 0.19 0.1 0.09 1.1 345 300 45 132 29 5 20 15 3 20 183 99.18 0.8 0.75 0.05 15.0 47 20 21 132 29 5 20 15 3 20 184 99.86 0.32 0.23 0.09 2.6 67 40 27 131 28 5 20 15 3 20 185 99.85 0.13 0.1 0.03 3.3 80 40 40 143 30 5 20 15 10 3 20 186 99.17 0.77 0.7 0.07 10.0 404 300 104 151 33 5 20 20 10 3 20 187 99.68 0.25 0.23 0.02 11.5 560 500 60 153 35 5 20 20 10 3 20 188 99.73 0.18 0.15 0.03 5.0 777 500 277 153 40 5 20 15 10 3 20 189 99.18 0.79 0.76 0.03 25.3 134 100 34 153 40 5 20 15 10 3 20 190 99.48 0.48 0.44 0.04 11.0 289 200 89 123 20 5 20 10 5 3 20 191 99.76 0.19 0.13 0.06 2.2 389 200 109 120 25 5 20 10 5 3 20 192 99.99 0.99 0.6 0.19 4.2 40 30 18 128 25 5 20 10 5 3 20 193 99.52 0.46 0.32 0.14 2.3 78 30 48 123 25 5 20 5 5 3 20 194 99.80 0.18 0.17 0.01 17.0 98 50 48 119 21 5 20 5 5 3 20 195 99.40 0.55 0.5 0.05 10.0 421 300 121 119 21 5 20 5 5 3 20 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 176 15 10 15 1.55 0.55 0.32 B S S GOOD 177 15 10 15 1.32 0.59 1.06 S B B FAIR 178 15 10 15 1.34 0.6 0.77 A S A EXCELLENT 179 15 10 15 1.44 0.77 0.32 B S B FAIR 180 15 10 15 1.45 0.71 1.68 A B B FAIR 181 15 10 15 1.37 0.73 0.85 B S S GOOD 182 15 10 15 1.33 0.72 0.41 B S S GOOD 183 15 10 15 1.27 0.73 1.64 B B A FAIR 184 15 10 15 1.22 0.78 0.93 B S S GOOD 185 15 10 15 1.3 0.86 0.3 B S S GOOD 186 15 10 15 1.1 0.81 1.44 A B B FAIR 187 15 10 15 1.17 0.82 0.45 B S A GOOD 188 15 10 15 1.12 0.80 0.38 B S A GOOD 189 15 10 15 1.16 0.92 1.6 A B B FAIR 190 15 10 15 1.18 0.97 0.97 B A A GOOD 191 15 10 15 1.15 0.91 0.41 B S S GOOD 192 15 10 15 1.14 0.57 1.95 B B B FAIR 193 15 10 15 1.06 0.82 0.95 B A S GOOD 194 15 10 15 1.08 0.66 0.44 B S S GOOD 195 15 10 15 1.52 0.02 1.12 S B B FAIR

TABLE-US-00010 TABLE 10 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 196 99.63 0.3 0.2 0.1 2.0 587 300 267 115 17 5 20 5 5 3 20 197 99.81 0.11 0.1 0.01 10.0 656 300 356 115 17 5 20 5 5 3 20 198 99.17 0.81 0.75 0.06 12.5 134 100 34 115 17 5 20 5 5 3 20 199 99.65 0.31 0.3 0.01 30.0 278 200 123 20 10 20 5 5 3 20 200 99.78 0.17 0.12 0.05 2.4 345 200 145 30 10 20 5 5 3 20 201 99.01 0.97 0.7 0.27 2.6 47 40 7 153 30 10 20 5 5 3 20 202 99.62 0.36 0.32 0.04 8.0 45 30 15 153 30 10 20 5 5 3 20 203 99.84 0.14 0.1 0.04 2.5 67 30 37 30 10 20 5 5 3 20 204 99.23 0.71 0.6 0.11 5.5 456 400 56 23 10 20 5 10 3 20 205 99.69 0.25 0.2 0.05 4.0 477 400 77 165 27 10 20 5 10 3 20 206 99.73 0.2 0.14 0.06 2.3 400 89 165 27 10 20 5 10 3 20 207 99.40 0.55 0.5 0.05 10.0 356 300 56 152 27 10 20 5 10 5 20 208 99.65 0.3 0.28 0.02 14.0 321 300 21 159 19 20 20 5 10 5 20 209 99.63 0.12 0.1 0.02 5.0 302 200 102 152 17 20 20 5 10 5 20 210 99.39 0.59 0.56 0.03 18.7 76 40 36 156 21 20 20 5 10 5 20 211 99.59 0.39 0.34 0.05 6.8 87 50 37 156 21 20 20 5 10 5 20 212 99.79 0.18 0.12 0.06 2.0 95 50 45 160 40 20 20 5 10 5 20 213 99.42 0.51 0.45 0.06 7.5 506 400 106 180 40 20 20 5 10 5 20 214 99.70 0.22 0.2 0.02 10.0 654 400 254 175 35 20 20 5 10 5 20 215 99.70 0.15 0.1 0.05 2.0 721 400 321 160 35 20 20 5 10 5 20 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 196 15 10 15 1.57 0.02 0.67 A S A EXCELLENT 197 15 10 15 1.59 0.03 0.23 A S A EXCELLENT 198 15 10 15 1.65 0.04 1.78 S B B FAIR 199 15 10 15 1.76 0.04 0.62 A S S EXCELLENT 200 15 15 10 15 1.77 0.05 0.33 B S S GOOD 201 15 20 10 15 1.76 0.04 1.95 A B B FAIR 202 15 20 10 15 1.85 0.01 0.72 B S S GOOD 203 15 15 10 15 1.82 0.01 0.34 B S S GOOD 204 15 15 10 15 1.42 0.02 1.44 S B B FAIR 205 15 30 10 15 1.41 0.05 0.67 A S A EXCELLENT 206 15 30 10 15 1.4 0.07 0.63 B S A GOOD 207 15 15 10 15 1.38 0.07 1.12 A B B FAIR 208 15 20 10 15 1.28 0.08 0.72 B S S GOOD 209 15 15 10 15 1.32 0.07 0.16 B S S GOOD 210 15 15 10 15 1.33 0.05 1.23 A B A GOOD 211 15 15 10 15 1.42 0.04 0.82 B S S GOOD 212 15 20 10 15 1.47 0.04 0.27 B S S GOOD 213 15 20 10 15 1.1 0.03 1.04 A B B FAIR 214 15 20 10 15 1.18 0.03 0.38 B S A GOOD 215 10 20 20 15 1.17 0.02 0.42 B S A GOOD indicates data missing or illegible when filed

TABLE-US-00011 TABLE 11 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 216 99.10 0.87 0.78 0.09 8.7 135 100 35 170 35 10 20 5 10 5 20 217 99.50 0.47 0.45 0.02 22.5 146 100 46 181 36 10 20 5 10 10 20 218 99.77 0.19 0.17 0.02 8.5 187 100 67 187 37 10 20 10 10 10 20 219 99.32 0.65 0.64 0.01 84.0 87 70 17 194 37 12 20 10 10 10 20 220 99.57 0.3 0.23 0.07 3.3 95 80 15 197 40 12 20 10 10 10 20 221 99.83 0.15 0.1 0.05 2.0 75 50 25 167 25 12 20 10 10 10 20 222 99.04 0.88 0.8 0.08 10.0 590 400 190 174 25 19 20 10 10 10 20 223 99.61 0.32 0.23 0.09 2.6 521 400 121 177 25 17 20 10 10 10 20 224 99.75 0.18 0.12 0.06 2.0 555 400 155 165 20 10 20 10 10 10 20 225 99.20 0.75 0.7 0.05 14.0 300 200 100 160 20 5 20 10 10 10 20 226 99.57 0.38 0.23 0.15 1.6 310 200 110 163 20 3 20 10 10 10 20 227 99.81 0.14 0.11 0.03 3.7 324 200 124 163 20 3 20 10 10 10 20 228 99.47 0.51 0.43 0.08 5.4 37 50 37 163 20 3 20 10 10 10 20 229 99.52 0.45 0.44 0.01 44.0 95 50 45 168 20 3 20 10 10 10 20 230 99.79 0.19 0.14 0.05 2.8 59 40 19 167 20 2 20 10 10 10 20 231 99.35 0.58 0.43 0.15 2.9 578 300 278 147 15 2 20 10 10 10 20 232 99.63 0.31 0.25 0.06 4.2 501 300 201 147 15 2 20 10 10 10 20 233 99.79 0.15 0.1 0.05 2.0 480 300 180 153 16 2 20 10 10 10 20 234 99.17 0.8 0.75 0.05 15.0 111 100 11 168 17 21 20 10 10 10 20 235 99.51 0.46 0.43 0.03 14.3 178 100 78 147 17 20 10 10 10 20 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 216 10 20 20 15 1.12 0.01 1.83 A B B FAIR 217 10 25 20 15 1.16 0.01 0.99 B A A GOOD 218 10 25 20 15 1.19 0.04 0.55 B S S GOOD 219 10 30 20 15 1.15 0.03 1.27 B B A FAIR 220 10 30 20 15 1.12 0.03 0.67 B S S GOOD 221 10 15 20 15 1.19 0.05 0.35 B S S GOOD 222 10 15 20 15 1.53 0.23 1.77 S B B FAIR 223 10 20 20 15 1.58 0.3 0.65 A S A EXCELLENT 224 10 20 20 15 1.61 0.32 0.35 A S A EXCELLENT 225 10 20 20 15 1.65 0.33 1.55 S B B FAIR 226 10 25 20 15 1.62 0.4 0.73 A S S EXCELLENT 227 10 25 20 15 1.72 0.49 0.32 B S S GOOD 228 10 25 20 15 1.78 0.42 1.01 A B A GOOD 229 10 30 20 15 1.78 0.41 0.95 A A S EXCELLENT 230 10 30 20 15 1.82 0.46 0.47 B S S GOOD 231 10 15 20 15 1.23 0.33 1.23 S B B FAIR 232 10 15 20 15 1.29 0.31 0.51 A S A EXCELLENT 233 10 20 20 15 1.28 0.35 0.4 B S A GOOD 234 10 15 20 15 1.26 0.14 1.55 A B B FAIR 235 10 15 20 15 1.25 0.15 0.72 A A A GOOD

TABLE-US-00012 TABLE 12 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 236 99.78 0.18 0.15 0.03 5.0 200 100 100 183 18 20 20 10 10 10 20 237 99.98 0.99 0.77 0.22 3.5 87 30 57 171 26 20 10 10 10 20 238 99.76 0.22 0.15 0.07 2.1 67 40 27 181 26 10 20 10 10 10 20 239 99.87 0.11 0.1 0.01 10.0 44 40 4 158 13 10 20 10 10 10 20 240 99.24 0.7 0.65 0.05 13.0 451 400 51 163 13 10 20 15 10 10 20 241 99.46 0.46 0.4 0.08 6.7 598 400 198 163 13 10 20 15 10 10 20 242 99.77 0.14 0.1 0.04 2.5 700 400 300 160 20 5 20 15 10 10 20 243 99.15 0.81 0.77 0.04 19.3 198 100 98 160 20 5 20 15 10 10 20 244 99.51 0.45 0.4 0.05 8.0 267 100 167 155 20 5 20 15 10 10 20 245 99.77 0.18 0.17 0.01 17.0 350 200 150 163 23 5 20 15 10 10 20 246 99.11 0.87 0.83 0.04 20.8 51 30 21 162 27 5 20 15 10 10 20 247 99.76 0.22 0.2 0.02 10.0 86 30 36 162 27 5 20 15 10 10 20 248 99.81 0.17 0.1 0.07 1.4 78 30 48 165 30 5 20 15 10 10 20 249 99.42 0.52 0.5 0.02 25.0 402 300 102 165 33 5 20 15 10 10 20 250 99.59 0.33 0.32 0.01 32.0 598 300 298 162 27 5 20 15 10 10 20 251 99.78 0.15 0.1 0.05 2.0 752 400 352 150 15 5 20 15 10 10 20 252 99.31 0.66 0.4 0.26 1.5 123 100 23 165 15 5 20 15 10 10 20 253 99.73 0.24 0.2 0.04 5.0 149 100 49 160 15 20 15 10 10 20 254 99.82 0.14 0.13 0.01 13.0 267 100 187 160 15 20 15 10 10 20 255 99.43 0.55 0.54 0.01 54.0 48 30 18 165 20 20 15 10 10 20 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 236 10 30 20 15 1.24 0.12 0.43 B S S GOOD 237 10 30 20 15 1.23 0.23 1.99 A B B FAIR 238 10 30 20 15 1.32 0.35 0.43 B S S GOOD 239 10 20 20 15 1.33 0.36 0.24 B S S GOOD 240 10 20 20 15 1.1 0.39 1.32 A B B FAIR 241 10 20 20 15 1.12 0.4 0.93 A A B GOOD 242 10 15 20 15 1.12 0.41 0.28 B S A GOOD 243 10 15 20 15 1.13 1.63 A B B FAIR 244 10 15 15 15 1.19 0.45 0.91 B A A GOOD 245 10 20 15 15 1.16 0.41 0.42 B S S GOOD 246 10 20 15 10 1.12 0.45 1.70 B B B FAIR 247 10 20 15 10 1.12 0.48 0.5 B S S GOOD 248 10 20 15 10 1.11 0.47 0.33 B S S GOOD 249 10 20 15 10 1.52 0.52 1.00 S B B FAIR 250 15 15 15 10 1.62 0.55 0.75 A S A EXCELLENT 251 15 15 15 10 1.72 0.66 0.13 A S A EXCELLENT 252 15 30 15 10 1.77 0.68 1.32 S B B FAIR 253 15 30 15 10 1.75 0.69 0.28 A S S EXCELLENT 254 15 30 15 10 1.98 0.99 0.29 B S S GOOD 255 15 30 15 10 1.75 0.91 1.22 B B A FAIR indicates data missing or illegible when filed

TABLE-US-00013 TABLE 13 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS EXAMPLE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 256 99.66 0.32 0.3 0.02 15.0 89 40 49 150 20 20 15 10 10 20 257 99.93 0.05 0.03 0.02 1.5 67 50 17 150 20 20 15 10 10 20 258 99.05 0.89 0.78 0.11 7.1 421 400 21 140 10 20 15 10 10 20 259 99.55 0.38 0.3 0.08 3.8 562 400 145 10 20 15 10 10 20 260 0.12 0.1 0.02 5.0 671 400 271 145 10 20 15 10 10 20 261 99.01 0.95 0.7 0.25 2.8 298 200 98 140 5 20 15 10 10 20 262 99.48 0.48 0.32 0.16 2.0 211 100 111 140 5 20 15 10 10 20 263 99.01 0.14 0.1 0.04 2.5 319 150 169 140 5 20 15 10 10 20 264 99.20 0.76 0.76 0.02 38.0 86 40 26 145 5 20 15 10 10 30 265 99.61 0.37 0.32 0.05 6.4 78 40 38 145 5 20 15 10 10 30 266 99.79 0.19 0.13 0.06 2.2 90 50 40 140 20 15 10 10 30 267 99.03 0.89 0.76 0.13 5.8 689 500 189 140 20 15 10 10 30 268 99.47 0.45 0.32 0.13 2.5 651 500 151 150 10 20 15 10 10 30 269 99.73 0.18 0.13 0.05 2.6 710 500 210 150 10 20 15 10 10 30 270 99.36 0.61 0.43 2.4 120 80 40 150 30 10 20 15 10 10 30 271 99.66 0.31 0.2 0.11 1.8 198 100 98 150 30 10 20 15 10 10 30 272 99.80 0.17 0.13 0.04 3.3 155 100 55 144 32 2 20 15 10 10 30 273 99.02 0.94 0.02 47.0 67 40 27 145 33 2 20 15 10 10 30 274 99.73 0.25 0.2 0.05 4.0 60 50 10 152 40 2 20 15 10 10 30 275 99.82 0.10 0.12 0.04 3.0 58 40 18 152 40 2 20 15 10 10 30 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT EXAMPLE DETAILS INDEX PARTICLES GENER- OVERALL No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 256 15 15 15 10 1.65 0.92 0.52 B S S GOOD 257 15 15 15 10 1.78 0.78 0.07 B S S GOOD 258 15 15 15 10 1.34 0.88 1.8 S B B FAIR 259 15 20 15 10 1.32 0.80 0.59 A S A EXCELLENT 260 15 20 15 10 1.32 0.78 0.32 B S A GOOD 261 15 20 15 10 1.29 1.9 S B B FAIR 262 15 20 15 10 1.27 0.52 0.8 A A A GOOD 263 15 20 15 10 1.26 0.55 0.33 B S S GOOD 264 15 15 15 10 1.24 0.57 1.67 A B A GOOD 265 15 15 15 10 1.44 0.64 0.76 B S S GOOD 266 15 15 15 10 1.42 0.68 0.32 B S S GOOD 267 30 15 10 1.1 0.7 1.77 A B B FAIR 268 30 15 10 1.12 0.71 0.86 A A B GOOD 269 30 15 10 1.11 0.77 0.38 B S A GOOD 270 15 10 1.1 0.8 1.23 A B B FAIR 271 15 10 1.12 0.82 0.47 B S S GOOD 272 15 10 1.18 0.85 0.45 B S S GOOD 273 15 10 1.19 0.88 1.93 B B B FAIR 274 15 10 1.14 0.81 0.53 B S S GOOD 275 15 10 1.18 0.87 0.6 B S S GOOD indicates data missing or illegible when filed

[0145] It should be noted that details of the elements contained in the aluminum wires of the examples shown in Table 1 are shown in Table 14.

TABLE-US-00014 TABLE 14 EESSENTIAL ELEMENTS OPTIONAL ELEMENTS EXAMPLE (MASS %) (MASS ppm) TRACE ELEMENTS (MASS ppm) No. Al Fe + Si Fe Si Ga + V Ga V Mg Cu Ni Zn Cr Mn Ti Zr W Sc OTHERS TOTAL 1 99.09 0.9 0.8 0.1 52 37 15 10 10 5 10 13 48 9 99.80 0.11 0.1 0.01 785 385 400 15 5 15 5 5 5 10 5 15 15 20 115 17 99.44 0.55 0.5 0.05 46 32 14 10 10 10 5 5 5 9 54 25 99.28 0.63 0.6 0.03 820 500 320 10 12 5 5 5 10 5 10 18 80

[0146] Next, comparative examples will be described. An aluminum metal having a purity of 99.9 mass % or more was prepared in the same manner as in the examples, and Fe, Si, Ga, and V were added so as to have the compositions shown in Table 15. Comparative Examples 1 to 4 are wires having the same composition as Example 17 but are wires prepared by changing the manufacturing conditions such as heat treatment temperature or time at the intermediate wire diameter and the final wire diameter, a processing rate from each wire diameter to the next wire diameter, a cooling speed after the intermediate heat treatment, and an area reduction rate of each die. Further, Comparative Examples 5 and 6 differ from the examples in the composition itself. The measurement methods of the orientation indexes, the area ratios of the precipitated particles, and the residual resistance ratios (heat generation) of the aluminum wires of these comparative examples were also performed in the same manner as in Example 1, and the measurement results were summarized in Table 15.

[0147] Regarding the area ratio of the precipitated particles, an image taken at a magnification of 400 times in the same manner as in the examples was binarized into precipitated particles (a high brightness value in white) and other than the precipitated particles (a low brightness value in black) based on a brightness value threshold of 0.95, to obtain the area ratio of the precipitated particles. FIG. 2 shows precipitated particles of the aluminum wire of Comparative Example 6, and the area ratio was 3.2% as shown in Table 15. Although the area ratio is obtained from a photograph taken at a magnification of 400 times, FIG. 2 is a photograph after binarization processing which was taken at a magnification of 1000 times so that the precipitated particles can be easily distinguished.

TABLE-US-00015 TABLE 15 WIRE PROPERTIES AREA WIRE COMPOSITIONS RATIO OF WIRE EVALUATION Al Fe + Si Ga + V OTHERS ORIENTATION PRECIPITATED TOOL HEAT OVERALL MASS MASS MASS MASS INDEX PARTICLES LIFE DETACH- GENER- EVALU- No. % % ppm ppm (111) (200) PERCENTAGE % TEST MENT ATION ATION COMPAR- 1 99.44 0.55 46 54 1.9 0.4 2.2 A C A POOR ATIVE 2 99.44 0.55 46 54 0.8 1.3 1.8 C A A POOR EXAMPLES 3 99.44 0.55 46 54 0.5 1.2 1.7 C A A POOR 4 99.44 0.55 46 54 1.8 0.4 2.3 A C A POOR 5 99.94 0.03 280 20 1.5 0.6 0.06 C A A POOR 6 98.89 1.1 60 40 1.3 0.8 3.2 S C C POOR

[0148] Further, the aluminum wire of Comparative Example 1 was examined for wire detachment from a wedge tool. Separately, a wire similar to the aluminum wire of Comparative Example 1 was prepared, bent to the side at 30? horizontally with respect to the longitudinal direction of the wire after the first bonding, and subjected to the second bonding; as a result, as in the lower left photograph of FIG. 4 described above, wire detachment from the wedge tool occurred, and the wire was bonded in a state of making a one-sided contact. The bonding conditions were set such that the ultrasonic energy and the pressure were optimal for each sample. The upper left of FIG. 4 shows the wire after the first bonding by means of ultrasonic waves, and as described above, the wire on the left side of the upper left photograph was obliquely cut, and the wire on the right side could not be bonded to the substrate and caused a bonding failure.

[0149] Further, in the same manner as in the examples, Table 15 shows the results of the life measurement of the power cycle test, the tool detachment test, the heat generation evaluation test, and the overall evaluation for Comparative Examples 1 to 6.

[0150] Next, details of the other elements contained in the aluminum wires of the comparative examples shown in Table 15 are shown together in Table 16.

TABLE-US-00016 TABLE 16 EESSENTIAL ELEMENTS OPTIONAL ELEMENTS COMPARATIVE (MASS %) (MASS ppm) TRACE ELEMENTS (MASS ppm) EXAMPLE No. Al Fe + Si Fe Si Ga + V Ga V Mg Cu Ni Zn Cr Mn Ti Zr W Sc OTHERS TOTAL 1 99.44 0.55 0.5 0.05 46 32 14 8 8 5 5 15 5 8 54 5 99.94 0.03 0.02 0.01 280 200 80 5 5 5 5 20 6 98.89 1.1 0.8 0.3 60 40 20 10 5 5 5 5 5 5 40

[0151] Further, aluminum wires of Comparative Example 7 and the subsequent comparative examples were obtained in the same manner as in Example 33 described above, except that an aluminum metal having a purity of 99.9 mass % or more was prepared, elements other than aluminum (Fe, Si, Ga, and V) were added so as to have the compositions shown in Tables 17 and 18, and the manufacturing conditions such as heat treatment conditions were changed. For these aluminum wires of Comparative Example 7 and the subsequent comparative examples, each of the properties was evaluated in the same manner as in the examples. The results are shown in Tables 17 and 18. It should be noted that the comparative examples shown in Tables 17 and 18 used the criteria of Tool Detachment Evaluation 2, Measurement 2 of Residual Resistance Ratio, and Overall Evaluation 2 for the tool detachment, the residual resistance ratio, and the overall evaluation, respectively.

TABLE-US-00017 TABLE 17 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS COMPARATIVE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS EXAMPLE No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 7 98.76 1.2 1 0.2 5.0 243 100 143 130 30 20 10 5 30 8 98.89 1.1 1 0.1 10.0 19 10 9 125 30 10 10 5 5 30 9 99.90 0.008 0.007 0.001 7.0 820 600 220 120 25 10 10 5 5 30 10 98.68 1.22 1 0.22 4.5 888 600 288 115 25 10 10 5 5 30 11 99.51 0.48 0.34 0.12 2.8 178 100 78 115 25 15 10 5 30 12 99.91 0.06 0.03 0.03 1.0 201 100 101 115 30 15 10 30 13 98.81 1.15 1.1 0.05 22.0 305 200 105 132 32 10 15 10 5 30 14 99.73 0.26 0.23 0.03 7.7 132 32 10 15 10 5 30 15 98.67 1.31 1.1 0.21 5.2 40 20 20 122 22 10 15 10 5 30 16 99.45 0.44 0.3 0.14 2.1 960 600 360 117 17 10 15 10 5 30 17 98.72 1.18 1.1 0.08 13.8 867 600 267 115 10 10 15 10 30 18 98.76 1.23 1.2 0.03 40.0 12 10 2 115 5 15 10 30 19 98.66 1.32 1.3 0.02 65.0 23 10 13 170 15 15 30 10 5 30 20 98.40 1.5 1.2 0.3 4.0 789 700 89 173 18 15 30 10 5 30 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT COMPARATIVE DETAILS INDEX PARTICLES GENER- OVERALL EXAMPLE No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 7 5 20 10 1.3 0.23 2.34 S C C POOR 8 5 20 10 1.35 0.43 2.21 A C C POOR 9 5 20 10 1.44 0.34 0.03 C S A POOR 10 20 10 1.42 0.24 2.23 S C C POOR 11 20 10 0.2 0.22 0.91 C A A POOR 12 20 10 0.81 0.39 0.12 C S S POOR 13 20 10 0.62 0.27 2.2 C C C POOR 14 20 10 0.52 0.22 0.52 C S S POOR 15 20 10 0.97 0.32 2.6 C C C POOR 16 20 10 0.9 0.35 0.89 C A B POOR 17 10 20 10 0.89 0.37 2.37 C C C POOR 18 10 15 20 10 1.44 1.2 2.4 A C C POOR 19 15 20 20 10 0.71 2.21 2.61 C C C POOR 20 15 20 20 10 0.6 1.8 2.89 C C C POOR

TABLE-US-00018 TABLE 18 TRACE Al Fe + Si Fe/Si Ga + V ELEMENTS COMPARATIVE (MASS (MASS DETAILS MASS (MASS DETAILS (MASS DETAILS EXAMPLE No. %) %) Fe Si RATIO ppm) Ga V ppm) Mg Cu Ni Zn Cr Mn Ti 21 99.95 0.005 0.001 5.0 278 150 128 181 21 15 30 10 5 5 30 22 98.06 1.12 1.11 0.01 111.0 19 10 9 150 30 5 10 5 5 30 23 99.89 0.008 0.003 0.005 0.6 870 700 170 132 32 5 10 5 5 30 24 99.54 0.45 0.4 0.05 8.0 150 35 5 10 10 5 30 25 98.69 1.29 1.2 0.00 13.3 40 10 30 142 32 5 10 10 30 26 98.90 1.08 1.04 0.04 26.0 31 20 11 145 10 5 10 10 10 30 27 99.50 0.48 0.4 0.08 5.0 124 100 24 115 30 10 5 10 10 10 28 98.46 1.6 1.4 0.1 14.0 287 160 127 90 10 10 5 10 10 5 29 98.75 1.23 1.2 0.03 40.0 47 30 17 110 30 10 10 10 5 30 98.62 1.33 1.3 0.03 43.3 355 300 55 145 40 10 10 10 10 10 10 31 99.42 0.48 0.43 0.05 8.6 865 750 115 90 25 10 10 10 10 32 98.55 1.38 1.35 0.07 135.0 810 750 60 90 25 10 10 10 10 33 99.88 0.09 0.05 0.04 1.3 150 100 50 139 19 5 5 10 10 5 30 34 98.88 1.1 0.6 0.5 1.2 100 50 50 105 25 10 10 5 5 5 10 35 99.07 0.9 0.8 0.1 8.0 200 100 100 150 20 5 5 5 5 10 30 38 99.97 0.02 0.01 0.01 1.0 50 30 20 75 10 5 5 5 5 5 5 AREA WIRE RATIO OF EVALUATION ORIENTATION PRECIPITATED HEAT COMPARATIVE DETAILS INDEX PARTICLES GENER- OVERALL EXAMPLE No. Zr W Sc OTHERS 111 200 PERCENTAGE % LIFE TOOL ATION EVALUATION 21 15 20 20 10 1.26 0.22 0.01 C S S POOR 22 15 20 20 10 1.3 0.37 2.2 A C C POOR 23 15 20 10 1.32 0.47 0.01 C S A POOR 24 15 20 20 0.77 0.22 0.87 C A S POOR 25 15 20 20 0.92 0.26 2.5 C C C POOR 26 30 20 20 0.82 2.2 2.11 C C C POOR 27 10 10 20 0.61 0.24 0.98 C A A POOR 28 10 10 20 0.71 0.33 2.97 C C C POOR 29 5 10 10 20 1.46 0.35 2.45 A C C POOR 30 5 10 10 20 0.82 0.4 2.05 C C C POOR 31 5 10 10 0.82 0.22 0.95 C A B POOR 32 5 10 10 0.93 0.4 2.7 C C C POOR 33 15 20 20 1.34 1.23 0.17 C S S POOR 34 15 10 10 1.23 0.95 1.9 C S S POOR 35 10 20 20 20 1.33 0.82 2.1 A C C POOR 38 5 20 5 5 1.1 0.92 0.01 C S S POOR indicates data missing or illegible when filed

[0152] None of the aluminum wires of the comparative examples shown in Tables 15, 17, and 18 passed in all of the evaluations and was graded poor in the overall evaluation. In addition, the range of the variations of each data was narrow, and the variations depending on the measurement part were small. That is, this suggests that measurement data of any cross-section perpendicular to the wire axial direction may be considered as a value indicating the entire wire.

[0153] From the above, by controlling the orientation index and the area ratio of the precipitated particles, the aluminum wire for a power semiconductor according to the embodiment could simultaneously solve an object of having followability for lateral bending and causing no wire detachment from a wedge tool and an object of achieving a long life in a power cycle test.

[0154] The aluminum wire for a power semiconductor according to the present invention can greatly contribute to the development of the power electronics industry, the automobile industry, the electric railroads, the electric power industry, and the like.