JP2006216929A - Bonding wire for semiconductor device - Google Patents

Bonding wire for semiconductor device Download PDF

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Publication number
JP2006216929A
JP2006216929A JP2005193629A JP2005193629A JP2006216929A JP 2006216929 A JP2006216929 A JP 2006216929A JP 2005193629 A JP2005193629 A JP 2005193629A JP 2005193629 A JP2005193629 A JP 2005193629A JP 2006216929 A JP2006216929 A JP 2006216929A
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JP
Japan
Prior art keywords
wire
copper
skin layer
core
bonding
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2005193629A
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Japanese (ja)
Inventor
Tomohiro Uno
Yukihiro Yamamoto
智裕 宇野
幸弘 山本
Original Assignee
Nippon Steel Corp
新日本製鐵株式会社
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Filing date
Publication date
Priority to JP2005000637 priority Critical
Application filed by Nippon Steel Corp, 新日本製鐵株式会社 filed Critical Nippon Steel Corp
Priority to JP2005193629A priority patent/JP2006216929A/en
Priority claimed from KR1020077017936A external-priority patent/KR101016158B1/en
Publication of JP2006216929A publication Critical patent/JP2006216929A/en
Pending legal-status Critical Current

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    • HELECTRICITY
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    • H01L24/42Wire connectors; Manufacturing methods related thereto
    • H01L24/44Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
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    • H01L2224/02Bonding areas; Manufacturing methods related thereto
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Abstract

PROBLEM TO BE SOLVED: To provide a copper bonding wire for a semiconductor element having a low material cost and excellent bonding property, loop control, wire deformation, etc., for a semiconductor having a large diameter for power IC use or a low cost priority. The purpose is to provide.
A bonding wire having a core material mainly composed of copper and a skin layer of a conductive metal having a composition different from that of the core material on the core material, the copper in the wire radial direction within the skin layer. A bonding wire for a semiconductor device, wherein the copper concentration on the surface of the skin layer is 0.1 mol% or more.
[Selection figure] None

Description

  The present invention relates to a bonding wire for a semiconductor device used for connecting an electrode on a semiconductor element and a wiring of a circuit wiring board (lead frame, substrate, tape).

  Currently, fine wires (bonding wires) having a wire diameter of about 20 to 50 μm are mainly used as bonding wires for bonding between electrodes on semiconductor elements and external terminals. Bonding wires are generally joined by ultrasonic thermocompression bonding, and a general-purpose bonding apparatus, a capillary jig used for connecting the wires through the inside, or the like is used. After the wire tip is heated and melted by arc heat input and a ball is formed by surface tension, this ball portion is pressure bonded onto the electrode of the semiconductor element heated within the range of 150 to 300 ° C., and then directly The wire is bonded to the external lead side by ultrasonic pressure bonding.

  In recent years, the structure, materials, connection technology, etc. of semiconductor mounting have been diversified rapidly. For example, in the mounting structure, in addition to QFP (Quad Flat Packaging) using the current lead frame, a substrate, polyimide tape, etc. are used. New forms such as BGA (Ball Grid Array) and CSP (Chip Scale Packaging) have been put into practical use, and there is a demand for bonding wires with improved loop characteristics, bondability, mass production usability, and the like. In such wire connection technology, in addition to the current mainstream ball / wedge joints, wedge / wedge joints suitable for narrow pitches join the wires directly at two locations, so it is necessary to improve the jointability of fine wires. It is done.

  The materials to which bonding wires are bonded are diversified, and in addition to conventional Al alloys, Cu suitable for finer wiring has been put to practical use as wiring and electrode materials on silicon substrates. In addition, Ag plating, Pd plating, etc. are applied on the lead frame, and Cu wiring is applied on the resin substrate, tape, etc., and noble metal elements such as gold and alloys thereof are formed thereon. In many cases, a film is applied. It is required to improve the bondability of the wire and the reliability of the joint according to these various joining partners.

  As a material for the bonding wire, gold of high purity 4N (purity> 99.99 mass%) has been mainly used so far. However, since gold is expensive, a bonding wire of another kind of metal having a low material cost is desired.

  In the demand from the wire bonding technology, it is important to form a ball having good sphericity when forming the ball and obtain a sufficient bonding strength at the bonding portion between the ball portion and the electrode. Further, in order to cope with a decrease in the bonding temperature, thinning of the wire, etc., it is necessary to have a bonding strength, a tensile strength, and the like at a portion where the wire is wedge-connected to the wiring portion on the circuit wiring board.

  In the resin sealing process in which high-viscosity thermosetting epoxy resin is injected at high speed, the wire deforms and comes into contact with the adjacent wire, and further, while narrow pitch, long wire, and thinning are progressing, It is required to suppress even a little wire deformation during resin sealing. Although the deformation can be controlled to some extent by increasing the wire strength, it is difficult to put it to practical use unless problems such as loop control becomes difficult and the strength at the time of bonding decreases.

  As a wire characteristic that satisfies these requirements, loop control in the bonding process is easy, and bondability to the electrode part and lead part is improved, and excessive wire deformation in the resin sealing process after bonding is suppressed. It is desired to satisfy the overall characteristics.

  In order to increase material costs at low cost, excellent electrical conductivity, ball bonding, wedge bonding, and the like, a bonding wire using copper as a raw material has been developed, and Patent Document 1 is disclosed. However, copper bonding wires have problems in that the bonding strength is reduced due to the oxidation of the wire surface, and that the wire surface is easily corroded when sealed with a resin. This is also the reason why the practical application of copper bonding wires has not progressed.

  Therefore, as a method for preventing the surface oxidation of the copper bonding wire, Patent Document 2 proposes a wire in which copper is coated with a noble metal such as gold, silver, platinum, palladium, nickel, cobalt, chromium, titanium, or a corrosion-resistant metal. Yes. Further, from the viewpoints of ball formability, prevention of deterioration of the plating solution, and the like, Patent Document 3 describes a core material mainly composed of copper, a dissimilar metal layer made of a metal other than copper formed on the core material, and There has been proposed a wire formed on the dissimilar metal layer and having a coating layer structure made of an oxidation-resistant metal having a melting point higher than that of copper.

JP-A-61-99645 JP-A-62-97360 JP 2004-64033 A

  As practical problems of the copper bonding wire, it can be mentioned that the surface of the wire is likely to be oxidized and the bonding strength is likely to be lowered. Therefore, as a means for preventing the surface oxidation of the copper bonding wire, it is possible to coat the wire surface with a noble metal or an oxidation resistant metal.

  The present inventors evaluated in consideration of needs such as high density, miniaturization, and thinning of semiconductor packaging, and the conventional multilayer copper wire having a structure in which the surface of the copper bonding wire is covered with a metal different from copper. In the following (hereinafter referred to as conventional multilayer copper wire), it has been found that many practical problems as described later remain.

  Conventionally, when a ball is formed at the tip of a multilayer copper wire, there is a problem that a flat ball deviated from a true sphere is formed, or an unmelted wire remains in the ball. If such an abnormal ball portion is bonded onto the electrode, it may cause problems such as a decrease in bonding strength and chip damage.

  When complex loop control is performed with conventional multilayer copper wires, the loop shape becomes unstable due to peeling at the interface between the coating layer and copper, etc., and adjacent wires cause electrical shorts in narrow pitch connections There is concern.

  Conventionally, when a multilayer copper wire is wedge-connected to an electrode such as a circuit board, the interface between the coating layer and the core material is peeled off, the coating layer is discharged from the wire-electrode joint, and the copper is directly joined Therefore, there is a concern that the bonding strength becomes unstable or decreases.

  As a factor for improving the problems of the conventional multilayer copper wire described above, it is conceivable to control the thickness of the coating layer. However, thickening the coating layer is expected to improve wedge connection, etc., but forming a thick coating layer by plating or vapor deposition causes problems in industrial production, such as reduced productivity and increased material costs. . Further, when the coating layer is thickened, the concentration of elements other than copper is increased in the melted ball portion, so that the ball portion is cured, and there is a problem that chip damage is caused at the time of ball bonding.

  On the other hand, if the coating layer of the conventional multilayer copper wire is only made thin, peeling at the interface between the coating layer and the core material occurs, and it becomes difficult to prevent oxidation and improve wedge connection.

  Therefore, in the present invention, the problems of the prior art as described above are solved, the ball section formability and bondability are improved, the loop controllability is good, the joint strength of wedge connection is increased, and the industrial productivity is improved. It is another object of the present invention to provide a bonding wire mainly composed of copper that is cheaper than gold wires.

The gist of the present invention for solving the above problems is as follows.
(1) A bonding wire having a core material mainly composed of copper and a conductive metal skin layer having a composition different from that of the core material on the core material, the copper wire being formed in the skin layer in the wire radial direction. A bonding wire for a semiconductor device having a concentration gradient and having a copper concentration on the surface of the skin layer of 0.1 mol% or more.
(2) A bonding wire having a core material mainly composed of copper and a skin layer of a conductive metal having a composition different from that of the core material on the core material, the copper wire being formed in the skin layer in the wire radial direction. A bonding wire for a semiconductor device comprising a concentration gradient and an intermetallic compound, wherein the copper concentration on the surface of the skin layer is 0.1 mol% or more.
(3) The bonding wire for a semiconductor device according to (1) or (2), wherein a main component of the skin layer is at least one selected from gold, palladium, platinum, silver, or nickel.
(4) The main component of the skin layer is one or more selected from gold, palladium, platinum or silver, and 1 to 300 mass in total of one or more selected from Ca, Sr, Be, Al or rare earth elements The bonding wire for a semiconductor device according to (1) or (2), which contains ppm.
(5) The bonding wire for a semiconductor device according to (1) or (2), wherein the core material containing copper as a main component contains 0.02 to 30% by mass in total of one or more of silver, tin, and zinc. .
(6) The semiconductor according to any one of (1) to (5), wherein the total amount of conductive metals other than copper constituting the skin layer is in the range of 0.02 to 10 mol% in terms of the content of the entire wire. Bonding wire for equipment.
(7) The bonding wire for a semiconductor device according to any one of (1) to (5), wherein copper is concentrated at a crystal grain boundary of the skin layer.

  The bonding wire for a semiconductor device of the present invention is low in material cost, excellent in ball bondability, wire bondability, etc., and in good loop formation, for narrow pitch thinning, and for thickening power IC applications. It becomes possible to provide a copper-based bonding wire that is also applicable.

  The bonding wire of the present invention is composed of a core material mainly composed of copper and a conductive metal skin layer having a composition different from that of the core material. However, the simple two-layer structure of the copper core material and the skin layer does not have sufficient ball formation, bondability, loop control, and the like, and may cause characteristic deterioration as compared with a single-layer copper wire. Therefore, in order to improve the characteristics comprehensively over the single layer copper wire, the skin layer of the present invention has a copper concentration gradient inside.

  Further, the productivity of the bonding wire process may be lower than the current mainstream gold bonding wire only with the copper concentration gradient. Therefore, for the first time, it has been found that it is effective to expose copper on the surface of the skin layer in order to improve the productivity to the same level or more as that of the gold bonding wire.

  That is, it is composed of a core material mainly composed of copper and a skin layer of a conductive metal having a composition different from that of the core material formed on the core material, for example, a skin layer mainly composed of a conductive metal other than copper. A bonding wire having a structure in which a copper concentration gradient is present inside the skin layer, and the copper concentration on the surface of the skin layer is 0.1 mol% or more.

  The conductive metal is a metal other than copper and is preferably a metal that is effective in preventing copper oxidation. The conductive metal is preferably at least one metal selected from gold, palladium, platinum, silver, and nickel. Among these, gold, palladium, platinum, and silver are preferable because they have high conductivity and can cope with high-speed semiconductor devices. In addition, gold has advantages in that it has many achievements in adhesion to the sealing resin, bondability to electrodes, etc., and quality control is easy. This is because silver is advantageous in that it is relatively inexpensive, has little surface oxidation, and provides good bonding properties with Ag plating frequently used on the surface of the frame. Palladium and platinum have the effect of stabilizing the ball shape.

  The skin layer is composed of a skin layer of copper and a conductive metal other than copper. The distribution of copper in the skin layer preferably has a copper concentration gradient, and improves the adhesion between the core material and the skin layer and the wedge bonding of the wire compared to the case where the copper layer is uniformly distributed throughout the layer. The improvement of sex can be improved at the same time. In addition, by having a copper concentration gradient inside the skin layer, it is possible to sufficiently improve the bondability even if the skin layer is thinned.As a result, the concentration of the conductive metal contained in the ball portion is reduced, The effect which suppresses hardening of a ball part is also acquired. On the other hand, when there is no uniform concentration gradient in which copper is evenly distributed in the skin layer, a number of required characteristics such as oxidation prevention, improvement in bondability, improvement in adhesion, and suppression of ball curing are simultaneously satisfied. Is difficult.

  As for the definition of the concentration gradient, it is desirable that the degree of concentration change in the depth direction is 5 mol% or more per 1 μm. If this change is exceeded, the improvement effect as the skin layer having the above-described concentration gradient can be expected, and the result of good reproducibility can be obtained in terms of the accuracy of quantitative analysis. However, the case where the element concentration in the wire locally fluctuates is distinguished from the case where it is unevenly distributed. Preferably, if it is 10 mol% or more per 1 μm, the production is easy. More preferably, if it is 20 mol% or more per 1 μm, a high effect of mutual use can be expected without impairing the different properties of the skin layer and the core material.

  This concentration gradient is desirably a region formed by diffusion of a conductive metal element and a copper element. This is because a layer formed by diffusion has many advantages such as low possibility of defects such as local peeling and cracks, and easy formation of continuous concentration changes. .

  The reason why the copper concentration on the surface of the skin layer is 0.1 mol% or more is that the skin layer and the core part are sufficiently dissolved to form a true ball part, the strength of the ball joint part is high, and the wedge bondability is high. It is because it is good. On the other hand, when copper does not exist on the surface even if the skin layer contains a concentration gradient, it is impossible to solve problems such as defective shape during ball formation, and problems that copper wires remain undissolved inside the copper balls. The copper concentration on the surface of the skin layer is more preferably 3 mol% or more. This is because if it is 3 mol% or more, a sufficient effect of increasing the joint strength of the wedge joint can be obtained. More preferably, if it is 10 mol% or more, the sphericity of the ball part is improved, and for example, even if a small ball part having a diameter of 2.5 times or less the wire diameter is formed, the sphericity is good. Because. Even more preferably, if it is 20 mol% or more, variation in ball diameter can be reduced by stabilizing arc discharge. The surface area here is an area from 0.001 μm to half the skin layer thickness in the depth direction from the outermost surface. This is because the depth at which stable quantitative analysis can be performed with an analysis technique such as Auger spectroscopy with high spatial resolution is about 0.001 μm, and the relationship between the Cu concentration on the surface and the characteristics is considered. This is because it has been confirmed that the Cu concentration up to half the depth of the skin layer is important in order to obtain the effect obtained. Preferably, it is desirable to treat the range from 0.001 μm to 0.002 μm from the outermost surface as the surface, and treat the concentration in that region as the above surface concentration. This is because the Cu concentration at a depth of up to 0.002 μm dominates the ball forming property.

  If the upper limit of the copper concentration on the surface of the skin layer is 90 mol% or less, the ball formability is good. Moreover, if it is 80 mol% or less, the effect which suppresses the surface oxidation of a wire is high, and the effect which suppresses characteristic deterioration is high even if it leaves in air | atmosphere. Furthermore, if it is 70 mol% or less, the higher effect which raises the intensity | strength at the time of wedge joining will be acquired.

  Regarding the copper concentration gradient, a change in which the copper concentration decreases from the core material side to the outermost surface side is preferable. By suppressing the copper concentration on the surface and increasing the copper concentration at the interface between the core material and the skin layer, it is possible to achieve both the suppression of the oxidation on the wire surface and the improvement in the adhesion between the core material and the skin layer. Wedge bondability, loop controllability, etc. can also be improved. In addition to the copper concentration gradient, the conductive metal desirably has a concentration gradient opposite to that of copper. This is because the mechanical strength and elastic modulus of the wire can be improved.

  From the standpoints of productivity and quality stability, it is preferable that the concentration gradient in the epidermis layer changes continuously. That is, the degree of the gradient of the concentration gradient is not necessarily constant in the epidermis layer, and may change continuously. For example, good characteristics can be obtained even when the gradient of concentration change at the interface between the skin layer and the core or near the outermost surface is different from the inside of the skin layer or when the concentration changes exponentially.

  In the region near the outermost surface of the skin layer, having a region where the copper concentration increases from the inside toward the surface side is also an effective concentration gradient. This is because the arc concentration at the time of ball formation is stabilized by the high copper concentration on the outermost surface, the shape and size of the ball can be stabilized, and the copper concentration in a slightly deeper direction from the outermost surface is kept low, thereby reducing the wedge. This is because sufficient bondability can be secured. When combined with the internal concentration gradient described above, when the change in copper concentration is viewed from the surface to the inside of the epidermis, the concentration decreases (negative concentration gradient), or the concentration increases (positive concentration gradient). ).

  In the structure of the skin layer, an alloy layer having a constant copper concentration is formed in the vicinity of the surface, and the characteristics may be improved by including a concentration gradient in the inner skin layer. This is because, in a region where the copper concentration on the surface is constant, the effect of stabilizing the arc discharge and stabilizing the shape, dimensions, etc. of the ball is obtained. The region in the vicinity of the surface here is a region having a depth from 0.003 to 0.01 μm immediately below the surface region described above.

  By forming the Cu oxide thinly on the surface of the skin layer, the adhesion with the sealing resin can be improved. The thickness of the Cu oxide is preferably 0.005 μm or less. This is because when it exceeds 0.005 μm, the wedge bonding strength of the wire under severe conditions such as low temperature is reduced.

  As mentioned above, about the skin layer formed on the core which has copper as a main component, it is desirable that it is a skin layer which consists of an alloy layer or a diffusion layer containing copper and a conductive metal.

  Here, the boundary between the skin layer and the core material is a region where the detected concentration of the conductive metal constituting the skin layer is 5 mol% or more. This is based on the fact that the effect of improving the characteristics can be expected from the structure of the skin layer of the present invention, and the conductive metal concentration often changes continuously for the expression of characteristics. The accuracy of quantitative analysis and the like were comprehensively determined, and the region where the concentration of the conductive metal was 5 mol% or more was determined. Preferably, in the region of 10 mol% or more, the accuracy of quantitative analysis is improved, and the measurement becomes simpler.

  In the case of the above-described skin layer, if the bonding metal has a total conductive metal concentration in the range of 0.02 to 10 mol% in the entire wire, in addition to improving the wedge bondability, the bondability of the ball portion is ensured. be able to. By controlling the conductive metal concentration in the entire wire, it is possible to reduce the damage to the ball structure and the diffusion of the bonding interface due to the solid solution of the conductive metal. Conceivable. On the other hand, it is difficult to keep the conductive metal concentration in the entire wire low by simply configuring the skin layer with only the conductive metal and reducing the layer thickness. When the total conductive metal concentration in the entire wire is less than 0.01 mol%, it is difficult to satisfy the wedge bondability, loop control, etc., and if it exceeds 10 mol%, chip damage becomes a problem or irregularities occur. It becomes a problem that the ball pressure bonding shape becomes unstable due to the above. Preferably, when the conductive metal concentration is in the range of 0.03 to 2 mol%, the effect of reducing damage to the chip during joining of large-diameter balls is enhanced. More preferably, if it is in the range of 0.04 to 0.8 mol%, the effect of stabilizing the crimped shape of the small ball is enhanced.

  The thickness of the skin layer is preferably 0.03 μm or more. If it is 0.03 μm or more, it can be uniformly formed on the entire wire, there are few surface irregularities, and there are no problems such as peeling of the skin layer, so that sufficient effects such as oxidation suppression and bonding properties can be obtained, This is because the loop shape is also stabilized. Further, the upper limit of the thickness is desirably 70% or less of the wire diameter, has high industrial mass productivity, and can sufficiently cope with quality control and the like. As for the lower limit of the thickness, preferably 0.1 μm or more, the effect of suppressing oxidation when exposed to high temperature is enhanced, and more preferably 0.2 μm or more, quality can be assured because it can be analyzed relatively easily. There are many advantages such as being easy. At one upper limit, it is easy to form a concentration-change layer uniformly within 50% of the wire diameter, and more preferably within 30% of the wire diameter, the increase in electrical resistance is reduced. There are advantages such as being suppressed.

  With regard to the distribution of the elements that make up the skin layer, a bonding wire in which copper is concentrated at the crystal grain boundary should provide a product with high industrial productivity while maintaining the overall use performance. Can do. Concentration of copper is preferably 5% or more of the average concentration in the region of about 0.01 μm of the grain boundary. In the plating method, vapor deposition method, etc., which is a method for forming the skin layer or the surface layer described later, a phenomenon that copper is likely to concentrate at the grain boundary is likely to occur, and the control of the manufacturing conditions is complicated to avoid it, On the other hand, we confirmed that the effect of crystal grain boundaries was almost negligible in wedge bondability, loop control, ball formation, etc., so a structure in which copper is concentrated at the crystal grain boundaries can improve productivity, yield, etc. It is possible to improve and provide a relatively inexpensive wire.

  Concentration analysis of the skin layer is effective by analyzing the surface of the wire while digging in the depth direction by sputtering or the like, or by line analysis or point analysis at the wire cross section. The former is effective when the skin layer is thin, but if it is thick, it takes too much measurement time. Analysis of the latter cross section is effective when the skin layer is thick, and it is advantageous that the concentration distribution over the entire cross section, reproducibility confirmation in several places, etc. are relatively easy. When the skin layer is thin, the accuracy decreases. It is also possible to measure by increasing the thickness of the diffusion layer by obliquely polishing the wire. In the cross section, line analysis is relatively simple. However, if you want to improve the accuracy of the analysis, it is also effective to narrow the analysis interval of the line analysis or perform point analysis focusing on the area to be observed near the interface. . EPMA, EDX, Auger spectroscopic analysis, a transmission electron microscope (TEM), etc. can be utilized in the analysis apparatus used for these concentration analyses. Further, for the investigation of the average composition, etc., it is possible to dissolve in acid or the like stepwise from the surface portion, and obtain the composition of the dissolution site from the concentration contained in the solution.

It is also effective that the skin layer contains an intermetallic compound phase mainly composed of copper and a conductive metal in addition to the concentration gradient. That is, it is composed of a core material mainly composed of copper and a skin layer of a conductive metal. Inside the skin layer, a portion having a concentration gradient of copper and an intermetallic compound having copper and a conductive metal are 1 Excellent characteristics can be obtained with a bonding wire having a copper concentration of 0.1 mol% or more on the surface of the skin layer. By including the intermetallic compound phase in the skin layer, the mechanical properties such as the strength and elastic modulus of the wire are increased, which is effective in improving the linearity of the loop and suppressing the flow of the wire during sealing. The intermetallic compound phase is mainly composed of copper and conductive metal, and it is desirable that the total concentration thereof is 80 mol% or more. However, even if the alloying element contained in the core material and the skin layer is partially contained I do not care. For example, the intermetallic compound phase formed when the conductive metal is gold, palladium, platinum or the like is CuAu 3 , CuAu, Cu 3 Au, Cu 3 Pd, CuPd, Cu 3 Pt, CuPt, CuPt 3 , CuPt 7. Etc. are candidates, and these intermetallic compound phases are formed in the skin layer or the skin layer / core material interface, and are effective in improving the characteristics. The thickness of these intermetallic compound phases is preferably from 0.001 μm to half the thickness of the skin layer.

  When the skin main metal forming the skin layer is gold, palladium, platinum, silver, or copper, it further contains at least one of Ca, Sr, Be, Al, and rare earth elements in a total amount of 1 to 300 ppm by mass. Thus, since the strength, structure, and plastic deformation resistance of the skin layer can be adjusted, the effect of controlling the deformation of the wire and the electrode material (Ag, Au, Pd, etc.) at the time of wedge bonding can be promoted. It has been found that when the above-mentioned skin main metal has a concentration gradient, the effect of adding these elements is highly effective. Furthermore, since Ca, Sr, Be, Al, and rare earth elements have a concentration gradient, a higher effect can be obtained.

  When the core material mainly composed of copper contains one or more of silver, tin, or zinc in a total amount of 0.02 to 30% by mass, the wire strength and the like increase, so that the loop in the long span is increased. It becomes possible to increase the linearity or to suppress the wire deformation at the time of resin sealing and to cope with the narrow pitch fine line. Normally, when the wire strength decreases, the wedge bondability often decreases, but the addition of the above elements can achieve both strength increase and improved wedge bondability, providing a wire suitable for high-density mounting. It becomes possible to do.

  In producing the wire of the present invention, a step of forming a core material and a skin layer, and a concentration gradient in the skin layer of copper element and a heat treatment step exposed to the outermost surface are required.

  Methods for forming the skin layer on the surface of the copper core include plating, vapor deposition, and melting. As the plating method, either electrolytic plating or electroless plating can be used. Electrolytic plating called strike plating or flash plating has a high plating speed and good adhesion to the substrate. Solutions used for electroless plating are classified into substitutional type and reduction type. If the film is thin, substitutional plating alone is sufficient, but when forming a thick film, reduction type plating is used after substitutional plating. It is effective to apply stepwise. The electroless method is simple and easy to use, but requires more time than the electrolysis method.

  In the vapor deposition method, physical adsorption such as sputtering, ion plating, and vacuum deposition, and chemical adsorption such as plasma CVD can be used. All of them are dry-type, and cleaning after film formation is unnecessary, and there is no concern about surface contamination during cleaning.

  Regarding the stage of plating or vapor deposition, either the method of forming a conductive metal film with a target wire diameter or the method of forming a film on a thick core material and then drawing multiple times to the target wire diameter Is also effective. In the former film formation with the final diameter, manufacturing, quality control and the like are simple, and the latter film formation and wire drawing are advantageous in improving the adhesion between the film and the core material. As a specific example of each forming method, a method of forming a film while continuously sweeping a wire into an electrolytic plating solution on a copper wire of a target wire diameter, or thick copper in an electrolytic or electroless plating bath For example, a method of drawing the wire to reach the final diameter after immersing the wire to form a film is possible.

  A diffusion heat treatment by heating is effective as the step of exposing the copper concentration gradient and the outermost surface of the copper in the skin layer using the skin layer and the core material formed by the above method. This is a heat treatment for promoting mutual diffusion between copper and a conductive metal at the interface between the skin layer and the core material. The method of performing heat treatment while continuously sweeping the wire is excellent in productivity and quality stability. However, simply heating the wire does not control the distribution of copper on and within the skin layer. Even if the processing strain relief annealing used in normal wire manufacturing is applied as it is, loop control becomes unstable due to a decrease in adhesion between the skin layer and the core material, or wire scraps accumulate inside the capillary and clog. It is difficult to completely solve problems such as the occurrence of oxidization and the oxidation of copper exposed on the surface to decrease the bonding strength. Therefore, it is important to control the temperature, speed, time, etc. of the heat treatment.

As a preferred heat treatment method, the heat treatment is performed while continuously sweeping the wire, and the temperature in the furnace is not constant, which is a general heat treatment. It becomes easy to mass-produce a wire having an outer skin layer and a core material. Specific examples include a method of introducing a temperature gradient locally and a method of changing the temperature in the furnace. In order to suppress the surface oxidation of the wire, it is also effective to heat while flowing an inert gas such as N 2 or Ar into the furnace.

  In the temperature gradient method, a positive temperature gradient near the furnace inlet (temperature rises with respect to the wire sweep direction), a stable temperature range, and a negative temperature gradient near the furnace outlet (temperature falls with respect to the wire sweep direction) Etc.), it is effective to incline the temperature in a plurality of regions. This improves adhesion without causing separation of the skin layer and core material in the vicinity of the furnace inlet, promotes diffusion of copper and conductive metal in a stable temperature region, and forms a desired concentration gradient, Further, by suppressing excessive oxidation of copper on the surface in the vicinity of the furnace outlet, it is possible to improve the bondability and loop controllability of the obtained wire. In order to obtain such an effect, it is desirable to provide a temperature gradient at the entrance / exit of 10 ° C./cm or more.

  In the method of changing the temperature, it is also effective to create a temperature distribution by dividing the furnace into a plurality of regions and performing different temperature control in each region. For example, the inside of the furnace is divided into three or more locations, temperature control is performed independently, and both ends of the furnace are set to a temperature lower than that of the central portion, so that the same improvement effect as in the case of the temperature gradient can be obtained. Moreover, in order to suppress the surface oxidation of a wire, the joint strength of a wedge-joint part can be increased by setting both ends of the furnace or the outlet side to a low temperature at which the oxidation rate of copper is low.

  Heat treatment with such a temperature gradient or temperature distribution is desirably performed at the final wire diameter in terms of productivity. On the other hand, by performing wire drawing after the heat treatment, the surface oxide film is removed at a low temperature. The effect of reducing wire scraping inside the capillary can be obtained by improving the bondability and further using wire drawing and strain relief annealing.

  In addition, the melting method is a technique in which either the skin layer or the core material is melted and cast, and it is excellent in productivity by drawing after connecting the skin layer and the core material with a large diameter of about 1 to 50 mm. Compared to plating and vapor deposition methods, the alloy component design of the skin layer is easy, and there are advantages such as easy improvement of properties such as strength and bondability. In a specific process, a melted conductive metal is cast around a prefabricated core wire to form a skin layer, and a prefabricated conductive metal hollow cylinder is used, and a melted copper is formed in the center portion thereof. Or it is divided into the method of forming a core wire by casting a copper alloy. Preferably, it is easier to stably form a copper concentration gradient or the like in the skin layer by casting a copper core into the latter hollow cylinder. Here, if a small amount of copper is contained in the skin layer prepared in advance, the copper concentration on the surface of the skin layer can be easily controlled. Further, in the melting method, it is possible to omit the heat treatment work for diffusing Cu in the skin layer, but further improvement in characteristics can be expected by performing the heat treatment to adjust the Cu distribution in the skin layer. .

  Further, when such a molten metal is used, at least one of the core wire and the skin layer can be manufactured by continuous casting. By this continuous casting method, the process is simplified as compared with the above casting method, and the wire diameter can be reduced to improve the productivity.

  Examples will be described below.

  As the raw material of the bonding wire, the copper used for the core material is a high-purity material having a purity of about 99.99% by mass or more, and the purity of 99.9% by mass is used for Au, Pt, Pd, Ni, and Ag materials on the outer periphery. % Of raw materials were prepared.

  In order to form a copper layer thinned to a certain wire diameter and to form a different metal layer on the surface of the wire, electrolytic plating, electroless plating, vapor deposition, melting, etc. are performed to form a concentration gradient. Therefore, heat treatment was performed. The case of forming the skin layer with the final wire diameter and the method of forming the skin layer with a certain wire diameter and then further thinning to the final wire diameter by wire drawing were utilized. As the electrolytic plating solution and the electroless plating solution, a plating solution commercially available for semiconductor applications was used, and the sputtering method was used for vapor deposition. A wire having a diameter of about 50 to 200 μm is prepared in advance, and the wire surface is coated by vapor deposition, plating, etc., drawn to a final diameter of 15 to 25 μm, and finally the processing strain is removed to obtain an elongation value of 4 to 10%. Heat treatment was applied so as to be within a range. As needed, after wire drawing to a wire diameter of 30 to 100 μm, diffusion heat treatment was performed, and then wire drawing was further performed.

  When utilizing the melting method, a method of casting a molten metal around a core wire prepared in advance and a method of casting molten copper or a copper alloy in the central portion of a hollow cylinder prepared in advance were employed. The diameter of the core wire was about 3 to 8 mm, and the diameter of the outer peripheral portion was about 5 to 10 mm. Thereafter, forging, roll rolling, die drawing, and the like and heat treatment were performed to produce a wire.

Regarding the heat treatment of the wire of the example of the present invention, the wire was heated while continuously sweeping. A method of introducing a temperature gradient locally, a method of changing the temperature in the furnace, and the like were used. This temperature difference was set in the range of 30 to 200 ° C., and the temperature distribution, the wire sweep speed, etc. were optimized and adjusted so that the tensile elongation was around 4%. In the atmosphere of the heat treatment, in addition to the air, an inert gas such as N 2 or Ar was used for the purpose of suppressing oxidation. Regarding the heat treatment process of the comparative example, when the plated layer was formed after the heat treatment was performed on the drawn Cu wire (Comparative Examples 2, 5 to 9), the heat treatment was performed after the drawing, and after the formation of the plated layer, 2 Samples were prepared in the case of repeated application (Comparative Examples 3 and 4).

  The tensile strength and elastic modulus of the wire were obtained by carrying out a tensile test of five wires having a length of 10 cm and calculating the average value.

  Depth analysis by AES was used to measure the film thickness on the wire surface, and surface analysis and line analysis by AES, EPMA, etc. were performed to observe element distribution such as concentration of crystal grain boundaries. The conductive metal concentration in the wire was measured by ICP analysis, ICP mass spectrometry or the like. When the copper concentration is higher by 5% or more in the vicinity of the crystal grain boundary of the skin layer, it is indicated by ◯, and when it is less than that, it is indicated without concentration.

For connection of the bonding wire, a commercially available automatic wire bonder was used to perform ball / wedge bonding. A ball (initial ball diameter: 35 to 50 μm) was produced at the tip of the wire by arc discharge, and it was joined to the electrode film on the silicon substrate, and the other end of the wire was wedge joined to the lead terminal. In order to suppress oxidation during ball melting, discharging was performed while N 2 gas was blown onto the tip of the wire.

  As a bonding partner, an Al alloy film (Al-1% Si-0.5% Cu film, Al-0.5% Cu film) having a thickness of 1 μm, which is a material of an electrode film on a silicon substrate, was used. On the other hand, a lead frame whose surface was Ag-plated (thickness: 1 to 4 μm) or a resin substrate having an electrode structure of Au plating / Ni plating / Cu was used as a partner for wedge bonding.

  Regarding the loop shape stability in the bonding process, two types of bonding samples with a wire length of 3 mm and 5 mm were prepared, and 500 wires were observed with a projector, and the linearity of the wire, variation in loop height, etc. were observed. Judged. The condition with a long wire length of 5 mm is a stricter evaluation. If the wire length is 3 mm and there are 5 or more defects such as linearity and loop height, it is judged that there is a problem and is indicated by x, the wire length is 3 mm, 2 to 4 defects, and the wire length is 5 mm. In the case where the number of defects is 5 or more, it is determined that improvement is necessary, and is represented by a Δ mark. Since the loop shape is relatively good, it is indicated by a circle, and when the wire length is 5 mm and the number of defects is 1 or less, the loop shape is determined to be stable and is indicated by an ◎. As one of the causes of defects, the adhesion between the interface between the core wire and the outer peripheral portion is not sufficient, and the characteristic variation in the cross section is assumed.

  Measurement of wire flow (resin flow) at the time of resin sealing is performed using a soft X-ray non-destructive inspection device after preparing a bonding sample with a wire length of 5 mm and sealing with a commercially available epoxy resin. The amount of flow in this part was measured, and the average value divided by the span length of the wire (percentage) was taken as the wire deformation rate at the time of sealing. If this wire deformation rate is 6% or more, it is judged as defective, and if it is 4% or more and less than 6%, improvement is necessary. Is marked as o, and if it is less than 2.5%, the wire deformation is excellently reduced, and is marked as o.

  In the observation of the initial ball shape, 20 balls before bonding were observed to determine whether the shape was a true sphere or whether the dimensional accuracy was good. If there are two or more abnormally shaped balls, the mark is bad because it is defective, and the number of irregular shapes is two or less. If there are 2 to 4 misalignments, it is judged that there is no major problem in practical use. If the misalignment is less than 1 and the dimensional accuracy is good, the ball formation is good. Indicated.

  In determining the bonded shape of the press-bonded ball portion, 500 bonded balls were observed to evaluate the roundness of the shape, dimensional accuracy, and the like. The conditions for the ball crimp diameter to be in the range of 2 to 3 times the wire diameter were selected. If there are 5 or more defective ball shapes such as anisotropy and ellipse with a large deviation from the perfect circle, it is judged as defective, x mark, 2 to 4 defective ball shapes, or petal-shaped ball crimping part If the number of outer peripheral parts is 8 or more, improvement is necessary. Therefore, Δ mark, less than 1 defective ball shape, and 3 to 7 petal-like deformations, it is determined that there is no problem in practical use. Since it is good if the number of petal-like deformations is 2 or less, it is indicated by ◎.

  With respect to the bonding strength of the ball bonding portion, 40 breaking loads (shear strength) were measured by a shear test method in which the jig was moved in parallel 2 μm above the aluminum electrode to read the shear breaking strength. The absolute value of the shear strength can be easily increased or decreased by changing the joining conditions or the like, but the variation in the shear strength is closely related to the stability of the ball deformation and is important from the viewpoint of mass productivity. If the standard deviation of the shear strength is 14.7 mN or more, it is necessary to improve the variation. Therefore, if it is 7.8 to 14.7 mN, there is no practical problem. If so, it is indicated by ◎ because it is stable.

  In order to evaluate damage to the silicon substrate immediately below the ball joint, the ball joint and the electrode film were removed with aqua regia, and then cracks, minute pit holes, etc. on the silicon substrate were observed with a light microscope, SEM, or the like. When 500 or more joints are observed and 3 or more cracks of 5 μm or more are observed, it is judged that chip damage is a problem and is represented by Δ, and 1 to 3 cracks are generated or about 1 μm. If two or more pit holes are recognized, chip damage is a concern, but there is no problem in practical use. Therefore, it is marked with a circle and no cracks are generated. Since it is good, it is indicated by ◎.

  Judgment of wedge bondability for bonding wires to the lead side makes bonding difficult at lower temperatures. Therefore, 1000 pieces of bonding are performed at a stage temperature of 220 ° C. and 180 ° C. The deformation shape, etc. were investigated. When there are two or more complete peels at the joint at 220 ° C, X mark, less than two at 220 ° C, and improvement when partial peel near the wire breakage occurs △ mark, there is no defect at 220 ° C, and when complete peeling at 180 ° C is 1 or less, ○ mark, no complete peeling at 180 ° C, and partial peeling is less than 3 In some cases, it is indicated by ◎.

  In the measurement of the pull strength of the wedge joint, a pull test was performed in the vicinity of the wedge joint with a sample having a wire length of 3 mm in order to determine the adhesion at the joint interface, and the average value of 20 pieces was obtained.

  Tables 1, 3, and 4 show the evaluation results of the copper bonding wires according to the present invention, and Table 2 shows a comparative example.

  The bonding wires according to the first claim are Examples 1 to 25, the bonding wires according to the second claim are Examples 5, 7, 19, and 23, and the bonding wires according to the third claim are Examples 1. The bonding wires according to the fourth claim are Examples 26 to 34, the bonding wires according to the fifth claim are Examples 35 to 45, and the bonding wires according to the sixth claim are Examples 1 to 45, Seventh. The bonding wires according to the claims correspond to Examples 2 to 7, 9 to 19, 21 to 24, 26 to 31, 33, 34, 36 to 41, and 43 to 45. Table 2 shows the results of bonding wires that do not fall under the claims of this application.

  A part of the evaluation results will be described for representative examples of each claim.

  The bonding wires of Examples 1 to 25 have a concentration gradient of copper inside the skin layer according to the present invention, and the copper concentration on the surface is 0.1 mol% or more. It was confirmed that the shape and wedge bondability were good. It became clear that the Cu wire which formed the film | membrane of elements other than copper of Comparative Examples 1-9 on the surface is not enough, and these characteristics are improved in Examples 1-25.

  In Examples 1 to 45, the concentration of the additive element in the entire wire is 0.01 to 10 mol% in total, so that chip damage was reduced, whereas the concentration was more than 10 mol%. 4 and 7, many chip damages were observed.

  The bonding wires of Examples 5, 7, 19, and 23 have a copper concentration gradient, copper and an intermetallic compound inside the skin layer according to the present invention, and the copper concentration on the surface is 0.1 mol% or more. As a result, the wire strength was increased, and the wire deformation during resin sealing was reduced.

  The bonding wires of Examples 26 to 34 are wedge-bondable by containing gold, palladium, or platinum as a main component of the skin layer according to the present invention and containing Ca, Sr, Be, Al, or a rare earth element. Had improved.

  The bonding wires according to Examples 35 to 45 are wires that ensure sufficient wedge bondability while the core material according to the present invention is made of a copper alloy containing at least one of silver, tin, or zinc. The effect of increasing the strength and suppressing the wire flow during resin sealing was improved.

  The bonding wires of Examples 2 to 7, 9 to 19, 21 to 24, 26 to 31, 33, 34, 36 to 41, and 43 to 45 are concentrated in the grain boundary of the skin layer according to the present invention. As the ball diameter and loop shape were stabilized, the variation was reduced, and the overall yield of the wire manufacturing process was improved by 5% or more on average.

Claims (7)

  1.   A bonding wire having a core material mainly composed of copper and a conductive metal skin layer having a composition different from that of the core material on the core material, the copper concentration gradient in the wire radial direction in the skin layer A bonding wire for a semiconductor device, wherein the surface layer has a copper concentration of 0.1 mol% or more.
  2.   A bonding wire having a core material mainly composed of copper, and a conductive metal skin layer having a composition different from that of the core material on the core material, and a copper concentration gradient in the wire radial direction in the skin layer. A bonding wire for a semiconductor device, comprising an intermetallic compound, wherein the surface layer has a copper concentration of 0.1 mol% or more.
  3.   The bonding wire for a semiconductor device according to claim 1 or 2, wherein a main component of the skin layer is one or more selected from gold, palladium, platinum, silver, or nickel.
  4.   The main component of the skin layer is at least one selected from gold, palladium, platinum or silver, and contains 1 to 300 mass ppm in total of at least one selected from Ca, Sr, Be, Al or rare earth elements. The bonding wire for a semiconductor device according to claim 1 or 2.
  5.   3. The bonding wire for a semiconductor device according to claim 1, wherein the core containing copper as a main component contains 0.02 to 30 mass% in total of one or more of silver, tin, and zinc.
  6.   6. The bonding wire for a semiconductor device according to claim 1, wherein the total amount of the conductive metals other than copper constituting the skin layer is in a range of 0.02 to 10 mol% in terms of the content of the entire wire.
  7.   The bonding wire for a semiconductor device according to claim 1, wherein copper is concentrated in a crystal grain boundary of the skin layer.
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