Copper alloy wire for semiconductor device

Abstract

In a copper alloy wire for semiconductor devices, improvement of ball joint life under high temperature and high humidity environment is achieved. A copper alloy wire for semiconductor devices, characterized by containing 0.03 mass% or more and 3 mass% or less of at least one or more elements selected from Ni, Zn, Ga, Ge, Rh, In, Ir, and Pt (first elements) in total, and the remainder composed of Cu and inevitable impurities. By containing the predetermined amount of the first elements, generation of intermetallic compounds that are easily corroded under high temperature and high humidity environment is suppressed in the wire joint interface, and the ball joint life is improved.

Description

[0001] This application is a divisional application of an application with the application number 201780037612.X and the title "Copper alloy wire for semiconductor device" filed on December 17, 2018. TECHNICAL FIELD

[0002] The present application relates to a copper alloy wire for semiconductor device for connecting a circuit wiring substrate such as an electrode on a semiconductor element and an external lead wire. BACKGROUND

[0003] Currently, as a wire for semiconductor device for joining between an electrode on a semiconductor element and an external lead wire (hereinafter referred to as "wire"), a fine wire with a wire diameter of about 15 to 50 μm is mainly used. The joining method of the wire to the electrode of the semiconductor device is generally a ultrasonic wave and heat pressure bonding method, and a general joining device and a capillary jig that passes the wire through the inside thereof for connection are used. The joining process of the wire is as follows: the tip of the wire is heated and melted by arc heat input, and after a ball (FAB: Free Air Ball) is formed by surface tension, the ball portion (hereinafter referred to as "ball joining") is pressed and joined to the electrode of the semiconductor element heated to a range of 150 to 300°C, and then, after a wire arc is formed, the wire portion is pressed and joined (hereinafter referred to as "wedge joining") to the electrode on the external lead wire side, thereby completing. As the electrode on the semiconductor element as a joining object of the wire, an electrode structure in which an alloy mainly containing Al is formed on a Si substrate is used, and as the electrode on the external lead wire side, an electrode structure to which Ag plating or Pd plating is applied or the like is used.

[0004] So far, the material of the wire has been mainly gold (Au), but the substitution to copper (Cu) is progressing, centering on LSI use. On the other hand, in the background of the popularization of electric vehicles or hybrid vehicles in recent years, the demand for substitution from Au to Cu is also increasing in the use of in-vehicle equipment.

[0005] Regarding the copper wire, a copper wire using high-purity Cu (purity: 99.99 mass% or more) is proposed (for example, Patent Literature 1). In the case of using a copper wire, it is also required to have high joining reliability and stability of the wire arc in high-density mounting. The joining reliability evaluation is performed for the purpose of evaluating the life of the joint in the use environment of the actual semiconductor device. In general, for the joining reliability evaluation, a high-temperature storage test, a high-temperature high-humidity test are used. The high-temperature high-humidity test generally uses a test called PCT (Pressure Cooker Test) performed under conditions of a temperature of 121°C and a relative humidity of 100%.

[0006] In Patent Literature 2, a semiconductor copper alloy wire composed of a copper alloy containing Pd in a concentration range of 0.13 to 1.15 mass% is described. By adding Pd in the above concentration range, the high humidity heat reliability obtained by PCT test can be improved.

[0007] Prior Art Documents

[0008] Patent Literature

[0009] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 61-48543

[0010] Patent Literature 2: International Publication No. 2010 / 150814 SUMMARY

[0011] Problems to be Solved by the Invention

[0012] A semiconductor device for vehicle use is required to have a high bonding reliability in a high temperature and high humidity environment, compared to a general electronic device. In particular, the bonding life of a ball bonding portion in which a ball portion of a wire is bonded to an electrode becomes a major problem. Several methods for evaluating the bonding reliability in a high temperature and high humidity environment have been proposed, and as a representative evaluation method in recent years, HAST (Highly Accelerated Temperature and Humidity Stress Test) is used. HAST has features that moisture absorption of an evaluation package is uniform, and the reproducibility of evaluation results is high. In the case where HAST is used to evaluate the bonding reliability of a ball bonding portion, by exposing the ball bonding portion for evaluation to a high temperature and high humidity environment at a temperature of 130°C and a relative humidity of 85%, a change in resistance value of the bonding portion over time is measured, or a change in shear strength of the ball bonding portion over time is measured, thereby evaluating the bonding life of the ball bonding portion. Further, by applying a bias voltage, a more severe evaluation than PCT can be performed. Recently, a bonding life of 100 hours or more in HAST under such conditions has been required.

[0013] An object of the present application is to provide a semiconductor device bonding wire in which the bonding reliability of a ball bonding portion in a high temperature and high humidity environment is improved, and which is suitable for a semiconductor device for vehicle use. Specifically, the present application has found an optimum additive element for a copper alloy bonding wire and an optimum additive concentration thereof, which have sufficient bonding reliability even in a more severe evaluation method, i.e., HAST in which a bias voltage is applied.

[0014] Means for Solving the Problems

[0015] That is, the gist of the present application is as follows.

[0016] (1) A copper alloy wire for semiconductor devices, characterized by containing 0.03 mass% or more and 3 mass% or less in total of at least one or more elements selected from the group consisting of Ni, Zn, Ga, Ge, Rh, In, Ir, and Pt, with the remainder composed of Cu and unavoidable impurities.

[0017] (2) The copper alloy wire for semiconductor devices according to (1), characterized in that, when the wire diameter of the wire is taken as R (μm), the average crystal grain diameter (μm) in the core material cross section perpendicular to the wire axis of the copper alloy wire is:

[0018] 0.02 x R + 0.4 or more (1a)

[0019] 0.1 x R + 0.5 or less (1b).

[0020] (3) The copper alloy wire for semiconductor devices according to (1) or (2), characterized in that the average film thickness of copper oxide on the wire surface is in the range of 0.0005 to 0.02 μm.

[0021] (4) The copper alloy wire for semiconductor devices according to any one of (1) to (3), characterized in that the copper alloy wire further contains at least one or more elements selected from the group consisting of Ti, B, P, Mg, Ca, La, As, Te, and Se, each at 0.0001 to 0.050 mass% with respect to the entire wire.

[0022] (5) The copper alloy wire for semiconductor devices according to any one of (1) to (4), characterized in that the copper alloy wire further contains at least one or more elements selected from the group consisting of Ag and Au, in total at 0.0005 to 0.5 mass% with respect to the entire wire.

[0023] (6) The copper alloy wire for semiconductor devices according to any one of (1) to (5), characterized in that the copper alloy wire further contains Pd at 1.15 mass% or less.

[0024] (7) The copper alloy wire for semiconductor devices according to any one of (1) to (6), characterized in that the copper alloy wire contains two or more elements selected from the group consisting of Ni, Zn, Ga, Ge, Rh, In, Ir, and Pt.

[0025] Effects of the Invention

[0026] According to the present invention, by containing at least one or more elements selected from the group consisting of Ni, Zn, Ga, Ge, Rh, In, Ir, and Pt, in total at 0.03 mass% or more and 3 mass% or less in the copper alloy wire for semiconductor devices, it is possible to improve the joint life of the ball joint portion under a high-temperature high-humidity environment, and to improve the joint reliability. DETAILED DESCRIPTION

[0027] First Element and Its Effect

[0028] The copper alloy wire for semiconductor devices (hereinafter, also simply referred to as "wire") of the present application is characterized by being formed by drawing a copper alloy containing, in total, 0.03 mass% or more and 3 mass% or less of at least one or more elements selected from the group consisting of Ni, Zn, Ga, Ge, Rh, In, Ir, and Pt (also referred to as "first element"), with the remainder being composed of Cu and unavoidable impurities. The wire of the present application is also referred to as "copper alloy wire" because it is an alloy in which copper is the main component. The copper alloy wire for semiconductor devices of the present application is a wire that does not have a coating layer in which a metal other than copper is the main component, and is also referred to as "bare Cu alloy wire". The wire of the present application can improve the joint reliability of the ball joint portion under a high-temperature high-humidity environment required for a device for vehicle use.

[0029] The encapsulation resin (epoxy resin) of the semiconductor device contains chlorine (Cl) in the molecular skeleton. Under a high-temperature high-humidity environment of 130°C and a relative humidity of 85% as the HAST evaluation condition, the Cl in the molecular skeleton is hydrolyzed and eluted as a chloride ion (Cl － ). In the case where the copper alloy wire is joined to an Al electrode, when the Cu / Al joint interface is placed under high temperature, Cu and Al diffuse into each other, and finally Cu9Al4 l4 , which is an intermetallic compound, is formed. Cu9Al4 l4 is easily corroded by halogens such as Cl, and the corrosion progresses due to the Cl eluted from the encapsulation resin, which is related to a decrease in joint reliability. Therefore, in the conventional copper alloy wire, the ball joint portion life in the HAST evaluation is insufficient.

[0030] To address this, the copper alloy wire of the present application contains, in total, 0.03 mass% or more of the first element (at least one or more elements selected from the group consisting of Ni, Zn, Ga, Ge, Rh, In, Ir, and Pt), and thus the ball joint portion life in the HAST evaluation is improved for the ball joint portion using the copper alloy wire. It is considered that when the first element is contained in total at 0.03 mass% or more, there is a tendency for the generation of the Cu9Al4 l4 intermetallic compound having the joint portion to be suppressed. It is considered that the first element present at the interface between Cu and Al in the ball joint portion improves the mutual diffusion suppression effect of Cu and Al, and as a result, the generation of Cu9Al4 l4 , which is easily corroded under a high-temperature high-humidity environment, is suppressed. Furthermore, the first element contained in the wire can also directly suppress the generation of Cu9Al4 l4The first element is considered to function as a barrier to hinder the movement of the corrosion-inducing halogen, to control the mutual diffusion of Cu and Al and the growth of intermetallic compounds, and the like.

[0031] Further, when a ball part is formed using a copper alloy wire containing a predetermined amount of the first element, and FAB is observed using a scanning electron microscope (SEM), a plurality of precipitates having a diameter of several tens of nm or so are seen on the surface of the FAB. When analyzed using energy dispersive X-ray spectroscopy (EDS), the first element is confirmed to be concentrated. From the above situation, the detailed mechanism is not clear, but it is considered that since the precipitates observed under the FAB exist on the joint interface between the ball part and the electrode, the joint reliability of the ball joint part under a high-temperature high-humidity environment having a temperature of 130°C and a relative humidity of 85% is significantly improved. It is apparent from the good results obtained in the HAST evaluation, which is a more severe condition than the PCT evaluation, that the wire of the present application can also obtain good results in the PCT evaluation.

[0032] From the viewpoint of improving the joint life of the ball joint part under a high-temperature high-humidity environment having a temperature of 130°C and a relative humidity of 85% and improving the joint reliability, the content (also referred to as the "concentration") of the first element in the wire is 0.03% by mass or more, preferably 0.050% by mass or more, more preferably 0.070% by mass or more, further preferably 0.090% by mass or more, 0.100% by mass or more, 0.150% by mass or more, or 0.200% by mass or more. When the concentration of the first element in the wire is 0.100% by mass or more, it is possible to respond to the requirement for more severe joint reliability.

[0033] On the other hand, from the viewpoint of obtaining a good FAB shape, from the viewpoint of suppressing the hardening of the wire to obtain good wedge bonding, the total of the concentration of the first element in the wire is 3 mass% or less, preferably 2.5 mass% or less, more preferably 2.0 mass% or less, further preferably 1.9 mass% or less, or 1.5 mass% or less. Furthermore, by thus regulating the upper limit of the content of the first element, the initial bonding strength with the Al electrode in low-temperature bonding is good, from the viewpoint of obtaining a long-term reliability in HAST testing, or a margin for mass production of a bonding wire that is excellent in bonding to substrates such as BGA (Ball Grid Array), CSP (Chip Size Package), and the like, tapes, and the like, and from the viewpoint of reducing chip damage, good results can be obtained. When the content of the first element exceeds 3.0 mass%, in order not to cause chip damage, ball bonding needs to be performed at a low load, the initial bonding strength with the electrode can decrease, and as a result, in some cases, HAST testing reliability can deteriorate. In the bonding wire of the present application, by setting the total of the content (concentration) of the first element to the above-mentioned preferable range, the reliability in HAST testing is further improved. For example, a bonding wire whose lifetime until the occurrence of a defect in HAST testing exceeds 250 hours can be achieved. This corresponds to a long-life of 1.5 times or more of the conventional Cu bonding wire in some cases, and use under severe environments can also be addressed.

[0034] From the viewpoint of achieving a copper alloy bonding wire that is significantly excellent in the bonding life of the ball bonding portion under a high-temperature high-humidity environment at a temperature of 130°C and a relative humidity of 85%, the Cu alloy bonding wire for a semiconductor device of the present application preferably contains two or more elements (first elements) selected from the group consisting of Ni, Zn, Ga, Ge, Rh, In, Ir, and Pt. Among these, as a combination of the first elements, combinations of Ni and Zn, Ni and Ga, Ni and Ge, Ni and In, Pt and Zn, Pt and Ga, Pt and Ge, Pt and In, Ir and Zn, Ir and Ge, Rh and Ga, Rh and In, Ni and Pt and Zn, Ni and Pt and Ga, Ni and Pt and Ge, Ni and Pt and In, Pt and Ir and Zn, Pt and Ir and Ga, Ir and Rh and Ge, Ir and Rh and In, and the like are preferable.

[0035] Average particle diameter of the bonding wire

[0036] The influence of the crystal grain diameter in the bonding wire on the quality of the wire was evaluated. As a result, it was ascertained that there is a preferable range of the average crystal grain diameter in the core material cross section perpendicular to the direction of the wire axis of the bonding wire, and when the wire diameter of the wire is R (μm), the average crystal grain diameter (μm) is

[0037] 0.02 x R + 0.4 or more (la)

[0038] 0.1 x R + 0.5 or less (lb)

[0039] In this case, the collapsed shape of the ball joint portion or the wedge joint property is particularly good.

[0040] In measuring the crystal grain diameter, it is preferable to use the electron backscattered diffraction method (EBSD, Electron Backscattered Diffraction). For the grain diameter measurement, the arithmetic mean of the equivalent diameters (the diameters of a circle equivalent to the area of the crystal grains) of the crystal grains contained in the measurement region can be calculated by using the analysis software equipped with the device based on the measurement results of the EBSD method.

[0041] Average film thickness of copper oxide on the wire surface

[0042] In the present application, it is preferable to set the average film thickness of the copper oxide on the wire surface to a range of 0.0005 to 0.02 μm. In the copper alloy joint wire containing the first element in a total amount in a concentration range of 0.03 to 3 mass%, if the average film thickness of the copper oxide on the wire surface is in a range of 0.0005 to 0.02 μm, the effect of stably improving the HAST reliability at a mass production level can be further improved. When the film thickness of the copper oxide on the wire surface is thicker than 0.02 μm, the improvement effect of the HAST reliability of the ball joint portion of the joint wire composed of the copper alloy containing the first element can be deviated, and there is a tendency that the joint strength and the like after the HAST heating become unstable. This deviation of the HAST reliability can be more problematic in the joint wire having a wire diameter of 20 μm or less. Although there are still unknown points, it can be considered that the concentration distribution of the first element in the length direction or the depth direction from the wire surface becomes non-uniform, or the invading oxygen or the residual oxide inside the ball can hinder the improvement effect of the HAST reliability of the first element, and the like, as the main reason for the instability of the HAST reliability of the copper oxide on the surface of the copper alloy joint wire containing the first element. According to the copper alloy joint wire containing the first element, since the effect of delaying the surface oxidation can be obtained, it is easy to control the average film thickness of the copper oxide in a relatively thin range of 0.0005 to 0.02 μm. It is also confirmed that, in the copper alloy joint wire containing the first element in a total amount in a concentration range of 0.03 to 3 mass%, compared with high-purity copper, there is an effect of delaying the growth of the copper oxide film on the wire surface in a low temperature region of about 20 to 40°C.

[0043] Since the improvement effect of the HAST evaluation tends to be deviated, for example, when the number of evaluations is increased, as described above, when the average film thickness of the copper oxide on the wire surface exceeds 0.02 μm, the possibility that the improvement effect becomes unstable increases, and thus it is preferable that the upper limit of the average film thickness of the copper oxide on the wire surface be set to 0.02 μm. From the viewpoint of being able to reduce the deviation of the improvement effect, the average film thickness of the copper oxide on the wire surface is preferably 0.02 μm or less, more preferably 0.015 μm or less, and further preferably 0.013 μm or less. On the other hand, since special surface treatment, product management, and the like are required in order to stably suppress the average film thickness of the copper oxide on the wire surface to less than 0.0005 μm, a decrease in the joint property, an increase in cost, and the like are induced, and thus industrial application becomes difficult, and thus it is preferable that the lower limit of the average film thickness of the copper oxide on the wire surface be set to 0.0005 μm. For example, when the coating film of the rust preventive on the wire surface is thickened for the purpose of suppressing the average film thickness of the copper oxide to less than 0.0005 μm, there is a problem that the joint strength decreases and the continuous joint property decreases. In addition, since the guaranteed life of the atmospheric storage of the wire product is extremely shortened if the average film thickness of the copper oxide is suppressed to less than 0.0005 μm for the purpose of suppressing the average film thickness of the copper oxide, the operation in the mass production process of the wire bonding becomes difficult, and a problem of waste occurs, and thus the case is not tolerated in industry in some cases. From the viewpoint of being able to provide a joint wire that is suitable for industry, the average film thickness of the copper oxide on the wire surface is preferably 0.0005 μm or more, more preferably 0.0008 μm or more, and further preferably 0.001 μm or more.

[0044] Regarding the measurement of the average film thickness of the copper oxide on the wire surface, Auger spectroscopy, which is suitable for surface analysis, is effective, and it is desirable to use the average value of the film thickness of the copper oxide measured at the lowest 3 or more, and if possible, 5 or more random positions on the wire surface. The oxygen concentration is the ratio of the O concentration to the concentration of Cu, O, and metal elements in total. Since organic matter, which is a representative contaminant on the wire surface, is excluded, the amount of C is not included in the above-described concentration calculation. Since it is difficult to accurately find the absolute value of the film thickness of the copper oxide, it is desirable to calculate the film thickness of the copper oxide using the SiO2 conversion value generally used in Auger spectroscopy. In the present application, the oxygen concentration of 30 mass% is set as the boundary between the copper oxide and metallic copper. It is known that the main copper oxide is Cu2O and CuO, but since Cu2O is preferentially formed at low temperatures (25 to 500°C) on the surface of a copper alloy containing the first element, the oxygen concentration of 30 mass% is set as the boundary.

[0045]

[0046] ​The bonding wire of the present application preferably further contains 0.0001 to 0.050 mass% of at least one or more elements selected from Ti, B, P, Mg, Ca, La, As, Te, Se (also referred to as "second elements") with respect to the entire wire, respectively. Thereby, the collapse shape of the ball bonding portion required for high-density mounting, i.e., the circularity of the ball bonding portion shape can be improved. In addition, thereby, a better ball shape can be achieved. From the viewpoint of being able to improve the effect of making the pressing shape of the ball bonding portion circular, the content (concentration) of the second elements is preferably 0.0001 mass% or more, more preferably 0.0002 mass% or more, and further preferably 0.0003 mass% or more, in total. Furthermore, from the viewpoint of suppressing the hardening of the ball to suppress the damage to the chip at the time of ball bonding, the content of the second elements is preferably 0.050 mass% or less, more preferably 0.045 mass% or less, and further preferably 0.040 mass% or less. Furthermore, because by containing 0.0005 mass% or more of the second elements, respectively, an effect of reducing the occurrence of defects in the wedge bonding portion is obtained, it is more preferable. By adding the second elements, the work hardening of the wire at the time of wire deformation is alleviated, and the effect of promoting the wire deformation of the wedge bonding can be improved. Although the detailed mechanism is not clear, it is considered that the first elements are solid-solved in Cu, and the second elements are precipitated and segregated because the solid solubility in Cu is small, and thereby these elements complementarily act, and a more excellent effect on the wire deformation of the wedge bonding can be exerted.

[0047] <3rd Element and Its Effect>

[0048] The bonding wire of the present application preferably further contains 0.0005 to 0.5 mass% in total of at least one or more elements selected from Ag, Au (also referred to as "a third element"). In recent narrow pitch connections required for high density mounting, the deformed shape of the ball joint is important, and it is required to suppress the deformation into a petal shape, core deviation, and the like, and to make it circular. By adding the third element together with the first element, it is possible to easily make the ball deformation isotropic, and to improve the effect of making the pressed shape circular. As a result, it is confirmed that it is possible to sufficiently adapt to narrow pitch connections of 50 μm or less. If the content of the third element is 0.0005 mass% or more in total, the effect is more effectively exerted. From the viewpoint of being able to improve the effect of making the pressed shape of the ball joint circular, it is preferable that the content of the third element be 0.0005 mass% or more in total, more preferably 0.0007 mass% or more, and further preferably 0.001 mass% or more. Furthermore, from the viewpoint of obtaining a good FAB shape, it is preferable that the content of the third element be 0.5 mass% or less, more preferably 0.4 mass% or less, and further preferably 0.3 mass% or less. On the other hand, when the content of the third element exceeds 0.5 mass% in total, there is a risk that the FAB shape will deteriorate. When the bonding wire contains Au, the recrystallization temperature rises, and because dynamic recrystallization during wire drawing is prevented, the processing structure becomes uniform, and the crystal grain size after heat treatment becomes relatively uniform. As a result, the elongation at break of the wire is improved, and it is possible to form a stable wire arc at the time of joining. In the case of further containing Au, it is preferable to determine the content so that the total of the first element in the wire exceeds 0.1 mass%. The bonding wire of the present application can contain both the second element and the third element, or can contain the third element instead of the second element.

[0049] "Containing of Pd and its effects"

[0050] The bonding wire of the present application preferably further contains Pd in a range of 1.15 mass% or less. Thereby, the high humidity heat reliability of the ball joint portion can be further improved. It is considered that by containing Pd in the above concentration range in the bonding wire, Pd diffuses or solidifies to the joint interface, and by exerting an influence on the mutual diffusion of Cu and Al, the corrosion reaction of the Cu-Al based intermetallic compound grown on the joint interface of the ball joint portion is delayed. From the viewpoint of being able to significantly improve the HAST reliability, it is preferable that the content of Pd be 1.15 mass% or less, more preferably 1.0 mass% or less, and further preferably 0.9 mass% or less. On the other hand, when the Pd concentration exceeds 1.15 mass%, the room temperature strength, high temperature strength, and the like of the wire increase, and as a result, the occurrence of deviation in the arc shape of the wire, the reduction in wedge joint properties, and the like sometimes occur, so it is preferable that the upper limit of the Pd content be set to 1.15 mass%. The bonding wire of the present application can contain Pd together with the 2nd element and / or the 3rd element, or can contain Pd instead of either or both of the 2nd element and the 3rd element.

[0051] Method for manufacturing bonding wire

[0052] The outline of the method for manufacturing a bonding wire for a semiconductor device of the present application is described.

[0053] High purity copper having a copper purity of 4N to 6N (99.99 to 99.9999 mass%) is used, and a copper alloy containing the necessary concentration of additive elements is produced by melting. When melting is performed, an arc heating furnace, a high frequency heating furnace, a resistance heating furnace, or the like can be used. In order to prevent the mixing of gases such as O2, H2from the atmosphere, it is preferable to perform melting in a vacuum atmosphere or a non-active atmosphere such as Ar or N2. Then, slow cooling is performed in a furnace to produce a billet (ingot). In order to clean the surface of the billet, pickling and water washing are performed, and drying is performed. For the concentration analysis of the additive elements in copper, ICP (Inductively Coupled Plasma) analysis or the like is effective.

[0054] In this alloying, there are a method of directly adding high purity components, and a method of using a master alloy containing additive elements at a high concentration of about 1%. The method of using a master alloy is effective for uniformizing the distribution of elements because it contains at a low concentration. In the additive components of the present application, in the case where the 1st element is contained at a relatively high concentration of 0.5 mass% or more, high purity direct addition can be used, and in order to stably contain the 1st element and the 2nd element at a low concentration, the method of adding a master alloy is advantageous.

[0055] In the case where the bonding wire is made to contain the first element, the second element, the third element, and other elements, as described above, in addition to the method of making it contain these elements at the time of melting, even if the method of making the alloy element adhere to the surface of the bonding wire is employed, the effects of the present application described above can be exerted.

[0056] It is also possible to make the alloy component adhere to the surface of the wire at the middle of the wire manufacturing process so as to make it contain the alloy component. In this case, it can be inserted at some point of the wire manufacturing process, or it can be repeated a plurality of times. It can also be inserted in a plurality of processes. As the method of adhesion, it can be selected from (1) application of an aqueous solution, drying, heat treatment, (2) plating method (wet type), (3) evaporation method (dry type).

[0057] The copper alloy block manufactured is first processed to a large diameter by rolling, and then is thinned to the final wire diameter by wire drawing. In the rolling process, a groove type roll or swaging or the like is used. In the wire drawing process, a continuous wire drawing device capable of setting a plurality of diamond-coated dies is used. Heat treatment is performed at the middle stage of processing or at the final wire diameter as needed.

[0058] When the copper alloy bonding wire is made to contain the first element, the material strength (hardness) of the wire becomes high. Therefore, when the bonding wire is wire drawn, the reduction in area at the time of wire drawing is set to a low reduction in area of 5 to 8%. Further, in the heat treatment after wire drawing, because the hardness is still high, heat treatment is performed at a temperature of 700°C or higher in order to soften to a level that can be used as a bonding wire. Because it is a high heat treatment temperature, the average crystal grain diameter (μm) in the core material cross section is greater than (0.1 x R + 0.5) (R is the wire diameter (μm)), and the wedge bonding property can be slightly reduced. On the other hand, when the heat treatment temperature is lowered, as a result, the average crystal grain diameter (μm) in the core material cross section is less than (0.02 x R + 0.4), and the collapse shape of the ball bonding portion can be slightly reduced.

[0059] Therefore, in the present application, preferably, when performing drawing using a die, the area reduction ratio is set to 10% or more for more than half of the total number of dies, and further, the heat treatment temperature in the heat treatment after drawing is set to a lower temperature of 600°C or less. As a result, the average crystal grain size (μm) in the core material cross section in the direction perpendicular to the spool of the bonding wire can be set to an appropriate range (0.02 x R + 0.4 or more, 0.1 x R + 0.5 or less) (R is the wire diameter (μm)). By applying the latest drawing processing technology, designing the concentration of the nonionic surfactant contained in the lubricating liquid to be higher than ever before as the lubricating liquid, designing the approach angle of the die to be gentler than the approach angle of the die in the past as the die shape, setting the cooling water temperature of the die to be lower than ever before, and the like, by the synergistic effect of these, drawing processing with an area reduction ratio of 10% or more can be performed even though the copper alloy bonding wire is hardened by containing 0.03 mass% or more of the first element component in total.

[0060] As the manufacturing conditions for managing the average film thickness of the copper oxide on the wire surface at a mass production level in the range of 0.0005 to 0.02 μm, it is preferable to suppress oxidation in the wire manufacturing process. For controlling the formation of copper oxide in the heat treatment process, temperature (200 to 850°C), adjustment of the flow rate of the non-reactive gas in the heat treatment process (1 to 8 L / min), management of the oxygen concentration in the furnace, and the like are effective. For the oxygen concentration, it is effective to measure at the central portion of the furnace and adjust so that the concentration ranges from 0.1 to 6% by volume. As a method of controlling the oxygen concentration in the above range, it is possible to manage the prevention of atmospheric air from the outside from being drawn into the heat treatment furnace, and the like, by optimizing the above gas flow rate, changing the shape of the inlet and outlet of the furnace, and the like. Further, at a mass production level, it is desirable to also manage the drawing process, for example, by performing drying (blowing of warm air atmosphere of 40 to 60°C) before coiling the wire after the drawing process in water once, thereby actively removing moisture from the surface of the wire, managing the humidity of storage in the middle of the manufacturing process (relative humidity of 60% or less when stored for 2 days or more), and the like.

[0061] Example

[0062] Hereinafter, a bonding wire according to an embodiment of the present application will be described with reference to the example.

[0063] (Sample)

[0064] First, the sample production method will be described. As the raw material of the core material, a raw material having a purity of 99.99 mass% or more (6N (a raw material having a concentration of 99.9999 mass% or more) was used in this example) and the remainder consisting of inevitable impurities was used. As the first element, the second element, the third element, and Pd, a raw material having a purity of 99 mass% or more and the remainder consisting of inevitable impurities was used. The alloy elements of the first element, the second element, the third element, and Pd, which are the added elements to the core material, were adjusted so that the composition of the wire or the core material becomes the target composition. As for the addition of each element, it can be adjusted as a single body, but in the case of a single body, in which the melting point is high or the added amount is extremely small, a Cu master alloy containing the added elements can be prepared in advance and adjusted to the target added amount.

[0065] For the copper alloy, production was performed by continuous casting so as to have a wire diameter of several mm. For the obtained several mm alloy, drawing was performed to produce a wire of φ 0.3 to 1.4 mm. For the drawing, a commercially available lubricating liquid was used, and the drawing speed was set to 20 to 150 m / min. Except for a part of the examples, drawing was performed using a die having a reduction ratio of 10 to 21% for more than half of the total number of dies after pickling treatment using hydrochloric acid or the like for the purpose of removing the oxide film on the surface of the wire, and further, heat treatment was performed at 200 to 600°C once to three times in the middle, thereby processing to a diameter of 20 μm or a diameter of 18 μm. After the processing, heat treatment was performed so that the final breaking elongation reached about 5 to 15%. The heat treatment method was performed while continuously sweeping the wire, or while flowing N2 or Ar gas. The wire feeding speed was set to 10 to 90 m / min, the heat treatment temperature was set to 350 to 600°C, and the heat treatment time was set to 1 to 10 seconds. As for the production method of Examples 6, 10, 11, 23, 55, 56, 62, and 77, in Examples 11 and 56, the heat treatment temperature was set to a lower temperature of 300°C or less, and in Examples 6, 10, 55, 62, and 77, the heat treatment temperature was set to a higher temperature of 700°C or more.

[0066] (Evaluation method)

[0067] [Element content]

[0068] As for the content of each alloy element in the wire, analysis was performed using an ICP emission spectroscopy analyzer.

[0069] [Crystal grain diameter]

[0070] For the crystal grain size, evaluation was performed using the EBSD method. For the analysis of the EBSD measurement data, a dedicated software (OIM Analysis, manufactured by TSL Solution) was used. The crystal grain size is the result of arithmetically averaging the equivalent diameters (the diameters of a circle equivalent to the area of the crystal grains) of the crystal grains contained in the measurement region.

[0071] [average film thickness of copper oxide]

[0072] For the measurement of the average film thickness of copper oxide on the wire surface, the average value of the film thickness of copper oxide measured at three or more of the lowest points of random positions on the wire surface was used by performing depth analysis by Auger spectroscopy. The measurement was performed in the depth direction while sputtering with Ar ions, and the unit of the depth was expressed in terms of SiO2. The interface between copper oxide and metallic copper was set to an oxygen concentration of 30 mass%. Here, the so-called oxygen concentration was the ratio of the oxygen concentration to the concentration of the total of Cu, oxygen, and metallic elements. For the measurement, a SAM-670 (manufactured by PHI, FE type) was used, the acceleration voltage of the electron beam was set to 5 kV, the measurement region was set to 10 nA, and the measurement was performed with an acceleration voltage of 3 kV and a sputtering speed of 11 nm / min by Ar ion sputtering. The measurement results of the average film thickness of copper oxide are described in the column of "average film thickness of copper oxide" in each table.

[0073] [HAST]

[0074] For the joining reliability of the ball joint portion under a high-temperature high-humidity environment or a high-temperature environment, a sample for joining reliability evaluation was prepared, HAST evaluation was performed, and the joining life of the ball joint portion was determined. For the electrode formed of an alloy of Al-1.0% Si-0.5% Cu having a film thickness of 0.8 μm on a Si substrate on a general metal frame, a ball joint was formed using a commercially available wire bonder, and sealing was performed using a commercially available epoxy resin, thereby preparing a sample for joining reliability evaluation. For the ball, a N2+5% H2 gas was flowed at a flow rate of 0.4 to 0.6 L / min, and the size was set to a range of φ 33 to 34 μm.

[0075] For the HAST evaluation, the prepared sample for joining reliability evaluation was exposed to a high-temperature high-humidity environment at a temperature of 130°C and a relative humidity of 85% using an unsaturated pressure cooker tester, and a bias of 7 V was applied. For the joining life of the ball joint portion, a shear test of the ball joint portion was performed every 48 hours, and the time at which the shear strength became 1 / 2 of the initial shear strength was adopted. The shear test after the high-temperature high-humidity test was performed after the ball joint portion was exposed by removing the resin by acid treatment.

[0076] The shear tester used in the HAST evaluation was a tester manufactured by DAGE. The value of the shear strength was the average of the values measured at 10 randomly selected ball joints. In the above evaluation, if the joint life was less than 96 hours, it was judged to be a problem in practice and marked with an X mark, if it was 96 hours or more and less than 144 hours, it was judged to be slightly problematic although it could be used in practice and marked with a Δ mark, if it was 144 hours or more and less than 192 hours, it was judged to be not problematic in practice and marked with an O mark, and if it was 192 hours or more, it was judged to be excellent and marked with a mark, and recorded in the column of "HAST" in each table. Only X was unqualified, and the others were qualified.

[0077] [FAB shape]

[0078] In the evaluation of the ball formation of the ball portion (FAB shape), the balls before joining were sampled and observed, and the presence or absence of bubbles on the ball surface and the presence or absence of deformation of the ball of the original perfect sphere were determined. In any of the above cases, it was judged to be defective. For the ball formation, in order to suppress oxidation during the melting process, it was performed while blowing N2 gas at a flow rate of 0.5 L / min. The diameter of the ball was set to 1.7 times the wire diameter. 50 balls were observed for one condition. For the observation, SEM was used. In the evaluation of the ball formation, in the case where 5 or more defects occurred, it was judged to be problematic and marked with an X mark, if the defects were 3 to 4, it was judged to be slightly problematic although it could be used in practice and marked with a Δ mark, in the case where the defects were 1 to 2, it was judged to be not problematic and marked with an O mark, and in the case where no defects occurred, it was judged to be excellent and marked with a mark, and recorded in the column of "FAB shape" in each table. Only X was unqualified, and the others were qualified.

[0079] [Wedge joint property]

[0080] In the evaluation of the wedge joint property of the wire joint, 1000 joints were made on the lead wire portion of the lead frame, and the occurrence frequency of peeling of the joint was determined. The lead frame used was a Fe-42 at% Ni alloy lead frame on which plating of Ag of 1 to 3 μm was performed. In this evaluation, a more stringent joint condition than usual was assumed, and the joint stage temperature was set to 150°C, which was lower than the general set temperature range. In the above evaluation, in the case where 11 or more defects occurred, it was judged to be problematic and marked with an X mark, if the defects were 6 to 10, it was judged to be slightly problematic although it could be used in practice and marked with a Δ mark, in the case where the defects were 1 to 5, it was judged to be not problematic and marked with an O mark, and in the case where no defects occurred, it was judged to be excellent and marked with a mark, and recorded in the column of "Wedge joint property" in each table. Only X was unqualified, and the others were qualified.

[0081] [Collapsing shape]

[0082] For the evaluation of the collapse shape of the ball joint, the ball joint being joined was observed from directly above, and the regularity of the circle was determined. The joining object was an electrode of an alloy of Al-0.5% Cu having a thickness of 1.0 μm formed on a Si substrate. For the observation, an optical microscope was used, and 200 places were observed for one condition. The ball joint having an elliptical shape with a large deviation from a regular circle, and the ball joint having a deformed shape with anisotropy were determined to be poor in the collapse shape of the ball joint. In the above evaluation, in the case where 6 or more were poor, it was determined to be problematic and marked with an X mark, in the case where 4 to 5 were poor, it was determined to be slightly problematic although it was practical and marked with a Δ mark, in the case where 1 to 3 were poor, it was determined to be not problematic and marked with an O mark, and in the case where all were good in the regularity of the circle, it was determined to be particularly excellent and marked with a mark, and recorded in the column of "Collapse shape" in each table.

[0083] [Table 1]

[0084]

[0085] [Table 2]

[0086]

[0087] [Table 3]

[0088]

[0089] [Table 4]

[0090]

[0091] [Table 5]

[0092]

[0093] [Table 6]

[0094]

[0095] (Evaluation results)

[0096] As shown in Tables 1 and 2, it was confirmed that the copper alloy wire relating to Examples 1 to 103 in which the total concentration of the first element was 0.03 to 3.0 mass% was good in the ball joint reliability in the HAST test under a high-temperature high-humidity environment at a temperature of 130°C and a relative humidity of 85%.

[0097] Further, the wire surface relating to Examples 1 to 103 in which the average film thickness of copper oxide was in the range of 0.0005 to 0.02 μm was good in the HAST evaluation results.

[0098] In addition, in the wire bonds of Embodiments 1 to 5, 7 to 9, 12 to 22, 24 to 54, 57 to 61, 63 to 69, 71 to 76, 78 to 103 in which the area reduction rate at the time of wire drawing in more than half of the total number of molds in the wire bond was set to 10% or more and the heat treatment temperature in the heat treatment after wire drawing was set to a low temperature of 600°C or less, the average crystal grain diameter (μm) in the core material cross section in the direction perpendicular to the wire axis of the wire bond was in the range of 0.02 x R + 0.4 or more and 0.1 x R + 0.5 or less (R is the wire diameter (μm) of the wire). Here, the evaluation results of Embodiments 7 to 14 in which the content of the first element was 0.8 to 1.0 mass% were compared, and in the wire bonds in which the average crystal grain diameter was in the above range (Embodiments 7 to 9, Embodiments 12 to 14), the wedge joint property and the collapse shape of the ball joint portion were good compared to the wire bonds in which the average crystal grain diameter was outside the above range (Embodiments 10, 11). From this result, it was found that when the average crystal grain diameter (μm) in the core material cross section in the direction perpendicular to the wire axis of the wire bond was in the range of 0.02 x R + 0.4 or more and 0.1 x R + 0.5 or less (R is the wire diameter (μm) of the wire), the wedge joint property and the collapse shape of the ball joint portion became good.

[0099] In Embodiment 11, because the heat treatment temperature was set to a low temperature of 300°C or less, the average crystal grain diameter was less than the lower limit of the preferable range, and the wedge joint property was "Δ", so the result was slightly reduced.

[0100] In Embodiment 10, because the heat treatment temperature was set to a high temperature of 700°C or more, the average crystal grain diameter exceeded the upper limit of the preferable range, and as a result, in Embodiment 10, the collapse shape was "Δ", so the result was slightly reduced.

[0101] In the wire bonds of Embodiments 24 to 43 in which two or more kinds of first elements were contained, the result of the HAST test was further good compared to the wire bonds of Embodiments 7 to 14 in which only one kind of first element was contained and the content was the same degree. From this result, it was found that in the wire bonds in which two or more kinds of first elements were contained, the ball joint portion reliability in the HAST test in a high-temperature high-humidity environment in which the temperature was 130°C and the relative humidity was 85% became further good.

[0102] In the wire bonds of Embodiments 44 to 66 in which the second element was further contained at 0.0001 to 0.050 mass% each, the collapse shape of the ball joint portion was good.

[0103] In the wire bonds according to Embodiments 67 to 92 further containing 0.0005 to 0.5 mass% in total of at least one or more elements selected from Ag, Au (3rd element) in the wire bonds according to Embodiments, the collapse shape of the ball bonding portion is good.

[0104] It was confirmed that in the wire bonds according to Embodiments 93 to 103 further containing 1.15 mass% or less of Pd in the wire bonds according to Embodiments, the ball bonding portion reliability is further improved in the HAST test under a high-temperature high-humidity environment of 130°C and 85% relative humidity.

[0105] In the wire bonds according to Embodiments 75, 76, 84, 85, 90 to 92 further containing 0.0001 to 0.050 mass% of the 2nd element and 0.0005 to 0.07 mass% in total of at least one or more elements selected from Ag, Au (3rd element) in addition to the 1st element in the wire bonds according to Embodiments, as the HAST evaluation results, the desired results of good wedge bonding and good collapse shape of the ball bonding portion were obtained. Among them, the HAST evaluation results were particularly good in Embodiments 75 and 76 containing two or more 1st elements.

[0106] Further, in the wire bonds according to Embodiments 98 to 99 further containing 0.0001 to 0.050 mass% of the 2nd element and 1.15 mass% or less of Pd in addition to the 1st element in the wire bonds according to Embodiments, the desired results of further good HAST evaluation results and good FAB shape, wedge bonding, and collapse shape of the ball bonding portion were obtained.

[0107] On the other hand, in the wire bonds of Comparative Examples 3 and 4 in which the total concentration of the 1st element is less than 0.03 mass% in the wire bonds of Comparative Examples, the ball bonding portion reliability was not obtained in the HAST test, and in the wire bonds of Comparative Examples 1, 2, 5, and 6 in which the total concentration of the 1st element is more than 3 mass%, the FAB shape and wedge bonding were poor.

Claims

1. A copper alloy wire for semiconductor devices, characterized by comprising: a total of 0.1 mass% or more and 3 mass% or less of one or more first elements selected from Zn, Ga, Ge, In, and Ir, 0.0001 mass% or more and 0.050 mass% or less of one or more elements selected from P and Mg, respectively, the remainder being composed of Cu and unavoidable impurities, the copper alloy wire for semiconductor devices being a bare Cu alloy wire, when the wire diameter of the wire is set to R (μm), the average crystal grain diameter (μm) in the core material cross section of the copper alloy wire in the direction perpendicular to the wire axis is: 0.02 x R + 0.4 or more (1a) 0.1 x R + 0.5 or less (1b).

2. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: a total of 2.5 mass% or less of one or more first elements selected from Zn, Ga, Ge, In, and Ir is contained.

3. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: a total of 2.0 mass% or less of one or more first elements selected from Zn, Ga, Ge, In, and Ir is contained.

4. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: 0.0003 mass% or more of one or more elements selected from P and Mg is contained, respectively.

5. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: 0.0005 mass% or more of one or more elements selected from P and Mg is contained, respectively.

6. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: 0.040 mass% or less of one or more elements selected from P and Mg is contained, respectively.

7. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: the copper alloy wire further contains one or more elements selected from Ti, B, Ca, La, As, Te, and Se at 0.0001 mass% or more and 0.050 mass% or less with respect to the entire wire, respectively.

8. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: the average film thickness of copper oxide on the wire surface is in the range of 0.0005 μm or more and 0.02 μm or less.

9. The copper alloy wire for semiconductor devices according to claim 8, characterized in that: the average film thickness of copper oxide on the wire surface is 0.0008 μm or more.

10. The copper alloy wire for semiconductor devices according to claim 8, characterized in that: the average film thickness of copper oxide on the wire surface is 0.001 μm or more.

11. The copper alloy wire for semiconductor devices according to claim 8, characterized in that: the average film thickness of copper oxide on the wire surface is 0.015 μm or less.

12. The copper alloy wire for semiconductor devices according to claim 8, characterized in that: the average film thickness of copper oxide on the wire surface is 0.013 μm or less.

13. The copper alloy wire for semiconductor devices according to claim 1, characterized in that: The above copper alloy wire further contains 0.0005% by mass or more and 0.5% by mass or less in total of one or more elements selected from Ag, Au, with respect to the entire wire.

14. The copper alloy wire for semiconductor devices according to claim 13, characterized in that, The above copper alloy wire further contains 0.0007% by mass or more of one or more elements selected from Ag, Au, with respect to the entire wire.

15. The copper alloy wire for semiconductor devices according to claim 13, characterized in that, The above copper alloy wire further contains 0.001% by mass or more of one or more elements selected from Ag, Au, with respect to the entire wire.

16. The copper alloy wire for semiconductor devices according to claim 13, characterized in that, The above copper alloy wire further contains 0.4% by mass or less of one or more elements selected from Ag, Au, with respect to the entire wire.

17. The copper alloy wire for semiconductor devices according to claim 13, characterized in that, The above copper alloy wire further contains 0.3% by mass or less of one or more elements selected from Ag, Au, with respect to the entire wire.

18. The copper alloy wire for semiconductor devices according to claim 7, characterized in that, The above copper alloy wire further contains 0.0005% by mass or more and 0.5% by mass or less in total of one or more elements selected from Ag, Au, with respect to the entire wire.

19. The copper alloy wire for semiconductor devices according to claim 18, characterized in that, The above copper alloy wire further contains 0.0007% by mass or more of one or more elements selected from Ag, Au, with respect to the entire wire.

20. The copper alloy wire for semiconductor devices according to claim 18, characterized in that, The above copper alloy wire further contains 0.001% by mass or more of one or more elements selected from Ag, Au, with respect to the entire wire.

21. The copper alloy wire for semiconductor devices according to claim 18, characterized in that, The above copper alloy wire further contains 0.4% by mass or less of one or more elements selected from Ag, Au, with respect to the entire wire.

22. The copper alloy wire for semiconductor devices according to claim 18, characterized in that, The above copper alloy wire further contains 0.3% by mass or less of one or more elements selected from Ag, Au, with respect to the entire wire.

23. The copper alloy wire for semiconductor devices according to claim 1, characterized in that, The above copper alloy wire further contains 1.15% by mass or less of Pd.

24. The copper alloy wire for semiconductor devices according to claim 23, characterized in that, The above copper alloy wire further contains 1.0% by mass or less of Pd.

25. The copper alloy wire for semiconductor devices according to claim 23, characterized in that, The above copper alloy wire further contains 0.9% by mass or less of Pd.

26. The copper alloy wire for semiconductor devices according to claim 7, characterized in that, The above copper alloy wire further contains 1.15 mass% or less of Pd.

27. The copper alloy wire for semiconductor devices according to claim 26, wherein The above copper alloy wire further contains 1.0 mass% or less of Pd.

28. The copper alloy wire for semiconductor devices according to claim 26, wherein The above copper alloy wire further contains 0.9 mass% or less of Pd.

29. The copper alloy wire for semiconductor devices according to claim 13, wherein The above copper alloy wire further contains 1.15 mass% or less of Pd.

30. The copper alloy wire for semiconductor devices according to claim 29, wherein The above copper alloy wire further contains 1.0 mass% or less of Pd.

31. The copper alloy wire for semiconductor devices according to claim 29, wherein The above copper alloy wire further contains 0.9 mass% or less of Pd.

32. The copper alloy wire for semiconductor devices according to claim 18, wherein The above copper alloy wire further contains 1.15 mass% or less of Pd.

33. The copper alloy wire for semiconductor devices according to claim 32, wherein The above copper alloy wire further contains 1.0 mass% or less of Pd.

34. The copper alloy wire for semiconductor devices according to claim 32, wherein The above copper alloy wire further contains 0.9 mass% or less of Pd.

35. The copper alloy wire for semiconductor devices according to claim 1, wherein The above copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

36. The copper alloy wire for semiconductor devices according to claim 7, wherein The above copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

37. The copper alloy wire for semiconductor devices according to claim 13, wherein The above copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

38. The copper alloy wire for semiconductor devices according to claim 18, wherein The above copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

39. The copper alloy wire for semiconductor devices according to claim 23, wherein The above copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

40. The copper alloy wire for semiconductor devices according to claim 26, wherein The above copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

41. The copper alloy wire for semiconductor devices according to claim 29, wherein The above copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

42. The copper alloy wire for semiconductor devices according to claim 32, wherein The above copper alloy wire contains 2 or more elements selected from Zn, Ga, Ge, In, and Ir.

43. A copper alloy wire for semiconductor devices, characterized by comprising: 1 or more first elements selected from Zn, Ga, Ge, In, and Ir in total of 0.05 mass% or more, 1 or more elements selected from Rh and Pt in total of 0.03 mass% or more, and the total of the above first elements and the above elements is 3 mass% or less, the remainder is composed of Cu and inevitable impurities, the above copper alloy wire for semiconductor devices is a bare Cu alloy wire, when the wire diameter of the wire is R (μm), the average crystal grain diameter (μm) in the core material cross section perpendicular to the direction of the wire axis of the above copper alloy wire is: 0.02 x R + 0.4 or more (1a) 0.1 x R + 0.5 or less (1b).

44. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more first elements selected from Zn, Ga, Ge, In, and Ir in total of 0.070 mass% or more.

45. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more first elements selected from Zn, Ga, Ge, In, and Ir in total of 0.090 mass% or more.

46. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more first elements selected from Zn, Ga, Ge, In, and Ir in total of 0.100 mass% or more.

47. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more first elements selected from Zn, Ga, Ge, In, and Ir in total of 2.5 mass% or less.

48. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more first elements selected from Zn, Ga, Ge, In, and Ir in total of 2.0 mass% or less.

49. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more elements selected from Rh and Pt in total of 0.050 mass% or more.

50. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more elements selected from Rh and Pt in total of 0.070 mass% or more.

51. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more elements selected from Rh and Pt in total of 0.100 mass% or more.

52. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more elements selected from Rh and Pt in total of 2.5 mass% or less.

53. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: 1 or more elements selected from Rh and Pt in total of 2.0 mass% or less.

54. The copper alloy wire for semiconductor devices according to claim 43, characterized in that: The above copper alloy wire further contains 0.0001 to 0.050% by mass of one or more elements selected from Ti, B, P, Mg, Ca, La, As, Te, and Se.

55. The copper alloy wire for semiconductor devices according to claim 54, wherein The above copper alloy wire further contains 0.0003% by mass or more of one or more elements selected from Ti, B, P, Mg, Ca, La, As, Te, and Se.

56. The copper alloy wire for semiconductor devices according to claim 54, wherein The above copper alloy wire further contains 0.0005% by mass or more of one or more elements selected from Ti, B, P, Mg, Ca, La, As, Te, and Se.

57. The copper alloy wire for semiconductor devices according to claim 54, wherein The above copper alloy wire further contains 0.040% by mass or less of one or more elements selected from Ti, B, P, Mg, Ca, La, As, Te, and Se.

58. The copper alloy wire for semiconductor devices according to claim 43, wherein The average film thickness of copper oxide on the surface of the wire is in the range of 0.0005 μm or more and 0.02 μm or less.

59. The copper alloy wire for semiconductor devices according to claim 58, wherein The average film thickness of copper oxide on the surface of the wire is 0.0008 μm or more.

60. The copper alloy wire for semiconductor devices according to claim 58, wherein The average film thickness of copper oxide on the surface of the wire is 0.001 μm or more.

61. The copper alloy wire for semiconductor devices according to claim 58, wherein The average film thickness of copper oxide on the surface of the wire is 0.015 μm or less.

62. The copper alloy wire for semiconductor devices according to claim 58, wherein The average film thickness of copper oxide on the surface of the wire is 0.013 μm or less.

63. The copper alloy wire for semiconductor devices according to claim 43, wherein The above copper alloy wire further contains 0.0005 to 0.5% by mass in total of one or more elements selected from Ag and Au.

64. The copper alloy wire for semiconductor devices according to claim 63, wherein The above copper alloy wire further contains 0.0007% by mass or more of one or more elements selected from Ag and Au.

65. The copper alloy wire for semiconductor devices according to claim 63, wherein The above copper alloy wire further contains 0.001% by mass or more of one or more elements selected from Ag and Au.

66. The copper alloy wire for semiconductor devices according to claim 63, wherein The above copper alloy wire further contains 0.4 mass% or less in total of one or more elements selected from Ag, Au, with respect to the entire wire.

67. The copper alloy wire for semiconductor devices according to claim 63, wherein The above copper alloy wire further contains 0.3 mass% or less in total of one or more elements selected from Ag, Au, with respect to the entire wire.

68. The copper alloy wire for semiconductor devices according to claim 54, wherein The above copper alloy wire further contains 0.0005 mass% or more and 0.5 mass% or less in total of one or more elements selected from Ag, Au, with respect to the entire wire.

69. The copper alloy wire for semiconductor devices according to claim 68, wherein The above copper alloy wire further contains 0.0007 mass% or more of one or more elements selected from Ag, Au, with respect to the entire wire.

70. The copper alloy wire for semiconductor devices according to claim 68, wherein The above copper alloy wire further contains 0.001 mass% or more of one or more elements selected from Ag, Au, with respect to the entire wire.

71. The copper alloy wire for semiconductor devices according to claim 68, wherein The above copper alloy wire further contains 0.4 mass% or less in total of one or more elements selected from Ag, Au, with respect to the entire wire.

72. The copper alloy wire for semiconductor devices according to claim 68, wherein The above copper alloy wire further contains 0.3 mass% or less in total of one or more elements selected from Ag, Au, with respect to the entire wire.

73. The copper alloy wire for semiconductor devices according to claim 43, wherein The above copper alloy wire further contains 1.15 mass% or less of Pd.

74. The copper alloy wire for semiconductor devices according to claim 73, wherein The above copper alloy wire further contains 1.0 mass% or less of Pd.

75. The copper alloy wire for semiconductor devices according to claim 73, wherein The above copper alloy wire further contains 0.9 mass% or less of Pd.

76. The copper alloy wire for semiconductor devices according to claim 54, wherein The above copper alloy wire further contains 1.15 mass% or less of Pd.

77. The copper alloy wire for semiconductor devices according to claim 76, wherein The above copper alloy wire further contains 1.0 mass% or less of Pd.

78. The copper alloy wire for semiconductor devices according to claim 76, wherein The above copper alloy wire further contains 0.9 mass% or less of Pd.

79. The copper alloy wire bond for semiconductor applications of claim 63 wherein, The above copper alloy wire further contains 1.15 mass% or less of Pd.

80. The copper alloy wire bond for semiconductor devices of claim 79 wherein, The above copper alloy wire further contains 1.0 mass% or less of Pd.

81. The copper alloy wire bond for semiconductor applications of claim 79 wherein, The above copper alloy wire further contains 0.9 mass% or less of Pd.

82. The copper alloy wire bond for semiconductor applications of claim 68 wherein, The above copper alloy wire further contains 1.15 mass% or less of Pd.

83. The copper alloy wire bond for semiconductor devices of claim 82 wherein, The above-mentioned copper alloy wire further contains 1.0 mass% or less of Pd.

84. The copper alloy wire bond for semiconductor devices of claim 82 wherein, The above-mentioned copper alloy wire further contains 0.9 mass% or less of Pd.

85. The copper alloy wire bond for semiconductor applications of claim 43 wherein, The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

86. The copper alloy wire bond for semiconductor applications of claim 54, wherein The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

87. The copper alloy wire bond for semiconductor applications of claim 63 wherein, The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

88. The copper alloy wire bond for semiconductor devices of claim 68 wherein, The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

89. The copper alloy wire bond for semiconductor applications of claim 73 wherein, The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

90. The copper alloy wire bond for semiconductor applications of claim 76, wherein The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

91. The copper alloy wire bond for semiconductor applications of claim 79 wherein, The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

92. The copper alloy wire bond for semiconductor devices of claim 82 wherein, The above-mentioned copper alloy wire contains 2 or more kinds of elements selected from Zn, Ga, Ge, In, and Ir.

Images