TWI586448B - Raw copper wire for bonding wire and method for manufacturing raw copper wire for bonding wire - Google Patents
Raw copper wire for bonding wire and method for manufacturing raw copper wire for bonding wire Download PDFInfo
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Description
本發明係關於在製出線徑180μm以下的接合引線時所使用的接合引線用銅裸線及接合引線用銅裸線之製造方法。 The present invention relates to a method for producing a bare copper wire for a bonding wire and a bare copper wire for a bonding wire used for producing a bonding wire having a wire diameter of 180 μm or less.
本案係根據2011年7月22日在日本申請的日本特願2011-161036號主張優先權，在此沿用其內容。 The present application claims priority based on Japanese Patent Application No. 2011-161036, filed on Jan. 22, 2011, the entire disclosure of which is incorporated herein.
一般而言，在裝載有半導體元件的半導體裝置中，藉由上述接合引線來連接半導體元件與引線。以往，以接合引線而言，由拉延性及導電性等觀點來看，主要使用Au線。但是，由於Au昂貴，因此提供一種Cu製的接合引線，來作為代用該Au線的接合引線。 In general, in a semiconductor device in which a semiconductor element is mounted, a semiconductor element and a lead are connected by the above-described bonding wires. Conventionally, in the case of a bonding wire, an Au wire is mainly used from the viewpoints of drawability and conductivity. However, since Au is expensive, a bonding wire made of Cu is provided as a bonding wire for substituting the Au wire.
在此，Cu係比Au更硬，因此接合時形成在線材前端的球狀物會有破壞例如形成在Si半導體元件之表面的Al配線被膜之虞。此外，Cu由於延展比Au為更低，因此會有無法維持適當的線環形狀的問題。 Here, since the Cu system is harder than Au, the ball which forms the tip end of the wire at the time of joining may break the Al wiring film formed on the surface of the Si semiconductor element, for example. Further, since Cu has a lower ducting ratio than Au, there is a problem that an appropriate loop shape cannot be maintained.
因此，例如在專利文獻1、2係已提出一種使用純度為99.9999質量%以上之超高純度銅(6NCu)的Cu製接合引線。此外，在專利文獻3係已提供一種微量添加Ti、Zr、Hf、V、Cr及B的Cu製接合引線。 Therefore, for example, in Patent Documents 1 and 2, a bonding lead made of Cu using ultra-high purity copper (6NCu) having a purity of 99.9999% by mass or more has been proposed. Further, Patent Document 3 has provided a Cu-made bonding wire in which Ti, Zr, Hf, V, Cr, and B are added in a trace amount.
但是，如專利文獻1、2之記載所示，若使用純度為99.9999質量%以上的超高純度銅(6NCu)時，為了獲得 超高純度銅(6NCu)，必須進行精煉處理工程。因此，會有製造成本大幅增加的問題。 However, as described in Patent Documents 1 and 2, when ultrahigh purity copper (6NCu) having a purity of 99.9999% by mass or more is used, in order to obtain Ultra-high purity copper (6NCu) must be refined. Therefore, there is a problem that the manufacturing cost is greatly increased.
此外，在專利文獻3所記載的接合引線中，與Au相比，硬且延展性亦低。因此，以Au線的代用而言，特性不夠。 Further, in the bonding wire described in Patent Document 3, it is harder and more ductile than Au. Therefore, in terms of the substitution of the Au line, the characteristics are insufficient.
再者，近年來，圖求由Cu線所成之接合引線的細線化，對於接合引線用銅裸線，亦圖求不會發生斷線的加工性。 In addition, in recent years, the thinning of the bonding wires formed of the Cu wires has been obtained, and the bare copper wires for bonding the bonding wires have been shown to have no workability in which the wires are broken.
[專利文獻1]日本特開昭62-111455號公報 [Patent Document 1] Japanese Patent Laid-Open No. 62-111455
[專利文獻2]日本特開平04-247630號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 04-247630
[專利文獻3]日本特公平04-012623號公報 [Patent Document 3] Japanese Patent Publication No. 04-012623
本發明係鑑於前述情形而研創者，目的在提供一種硬度低、而且延展高、甚至加工性優異的接合引線用銅裸線及接合引線用銅裸線之製造方法。 The present invention has been made in view of the above circumstances, and an object of the invention is to provide a bare copper wire for a bonding wire and a bare copper wire for a bonding wire which are low in hardness, high in elongation, and excellent in workability.
為解決上述課題，本發明之一態樣之接合引線用銅裸線係用以形成線徑180μm以下的接合引線的銅裸線，其 中，裸線直徑為0.15mm以上、3.0mm以下，具有合計在0.0001質量%以上、0.01質量%以下的範圍含有選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的添加元素，且殘部為銅及不可避免雜質的組成，以EBSD法所被測定出之特殊粒界的長度L σ對全部結晶粒界的長度L的比率亦即特殊粒界比率(L σ/L)為50%以上。 In order to solve the above problems, a bare copper wire for a bonding wire according to an aspect of the present invention is a copper bare wire for forming a bonding wire having a wire diameter of 180 μm or less. In the meantime, the diameter of the bare wire is 0.15 mm or more and 3.0 mm or less, and the content is preferably 0.0001 mass% or more and 0.01 mass% or less, and is selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, Ti, and a rare earth element. One or more kinds of added elements, and the residual portion is a composition of copper and unavoidable impurities, and the ratio of the length L σ of the specific grain boundary measured by the EBSD method to the length L of all the crystal grain boundaries, that is, the specific grain boundary ratio ( L σ / L) is 50% or more.
在該接合引線用銅裸線中，具有合計在0.0001質量%以上、0.01質量%以下的範圍含有選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的添加元素，且殘部為銅及不可避免雜質的組成。因此，銅中所含有的S與上述元素起反應而形成化合物。藉此，S的影響會變小，可降低再結晶溫度，而且可降低硬度。 In the bare copper wire for a bonding wire, one or more selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, Ti, and a rare earth element are contained in a total amount of 0.0001% by mass or more and 0.01% by mass or less. The element is added and the residue is composed of copper and unavoidable impurities. Therefore, S contained in copper reacts with the above elements to form a compound. Thereby, the influence of S becomes small, the recrystallization temperature can be lowered, and the hardness can be lowered.
此外，以EBSD法所被測定出之特殊粒界的長度L σ對全部結晶粒界的長度L的比率亦即特殊粒界比率(L σ/L)為50%以上。因此，可在保持將硬度維持為較低的情況下，使延展及加工性提升。 Further, the ratio of the length L σ of the specific grain boundary measured by the EBSD method to the length L of all the crystal grain boundaries, that is, the specific grain boundary ratio (L σ/L) is 50% or more. Therefore, the elongation and the workability can be improved while keeping the hardness low.
其中，藉由使用電場放出型掃描電子顯微鏡的EBSD測定裝置，特定結晶粒界、特殊粒界，算出全部結晶粒界的長度L及特殊粒界的長度L σ。由該等長度，可得本態樣中的特殊粒界比率(L σ/L)。 In the EBSD measuring apparatus using an electric field emission type scanning electron microscope, the length L of the entire crystal grain boundary and the length L σ of the specific grain boundary were calculated for the specific crystal grain boundary and the specific grain boundary. From these lengths, the specific grain boundary ratio (L σ/L) in this aspect can be obtained.
結晶粒界係被定義為經二次元剖面觀察的結果，相鄰的2個結晶間的配向方位差為15°以上時的該結晶間的交界。 The crystal grain boundary is defined as a result of observation by a two-dimensional cross section, and the boundary between the crystals when the alignment misalignment between two adjacent crystals is 15 or more.
此外，特殊粒界係指作為在結晶學上根據CSL理論 (Kronberg et al：Trans.Met.Soc.AIME，185，501(1949))所被定義的Σ值滿足3≦Σ≦29的對應粒界，而且該對應粒界中的固有對應部位晶格方位缺陷Dq滿足Dq≦15°/Σ1/2(D.G.Brandon：Acta.Metallurgica.Vol.14，p.1479，(1966))的結晶粒界來加以定義。 In addition, the special grain boundary refers to a corresponding grain which satisfies 3≦Σ≦29 in the crystallographically defined Σ value according to the CSL theory (Kronberg et al: Trans. Met. Soc. AIME, 185, 501 (1949)). And the lattice orientation defect Dq of the intrinsic corresponding part in the corresponding grain boundary satisfies the crystal grain boundary of Dq≦15°/Σ 1/2 (DGBrandon:Acta.Metallurgica.Vol.14, p.1479, (1966)) To define it.
在本發明之一態樣之接合引線用銅裸線中，較佳為前述添加元素的含量合計為0.0003質量%以上、0.002質量%以下。 In the bare copper wire for a bonding wire according to an aspect of the invention, the total content of the additive element is preferably 0.0003 mass% or more and 0.002 mass% or less.
此時，可使再結晶溫度確實抑制為較低，且可降低硬度。 At this time, the recrystallization temperature can be surely suppressed to be low, and the hardness can be lowered.
此外，較佳為作為前述不可避免雜質的Fe、Pb、及S的含量為Fe：0.0001質量%以下、Pb：0.0001質量%以下、及S：0.005質量%以下。 Moreover, it is preferable that the content of Fe, Pb, and S as the unavoidable impurities is Fe: 0.0001% by mass or less, Pb: 0.0001% by mass or less, and S: 0.005% by mass or less.
藉由如前所述規定雜質的含量，可使再結晶溫度確實抑制為較低，且可降低硬度。 By specifying the content of the impurities as described above, the recrystallization temperature can be surely suppressed to be low, and the hardness can be lowered.
較佳為將前述接合引線用銅裸線100g在硝酸溶液加熱溶解所得的粒徑30μm以上的酸不溶解殘渣物的個數為1000個以下。 It is preferable that the number of acid-insoluble residues having a particle diameter of 30 μm or more obtained by heating and dissolving 100 g of the bare copper wire for bonding wires in a nitric acid solution is 1,000 or less.
此時，存在於接合引線用銅裸線的內部的酸不溶解殘渣物的粒徑小，而且個數少。因此，可抑制製造接合引線時的拉延加工時發生斷線。 At this time, the particle size of the acid-insoluble residue present in the bare copper wire for bonding leads is small and the number is small. Therefore, it is possible to suppress the occurrence of disconnection during the drawing process at the time of manufacturing the bonding wire.
較佳為將前述接合引線用銅裸線在硝酸溶液加熱溶解所得的酸不溶解殘渣物的量為0.00015質量%以下。 The amount of the acid-insoluble residue obtained by heating and dissolving the bare copper wire for the bonding wire in a nitric acid solution is preferably 0.00015 mass% or less.
此時，存在於接合引線用銅裸線的內部的酸不溶解殘 渣物的存在比率少。因此，可抑制製造接合引線時的拉延加工時發生斷線。 At this time, the acid existing in the bare copper wire for bonding leads does not dissolve. The slag has a low ratio of existence. Therefore, it is possible to suppress the occurrence of disconnection during the drawing process at the time of manufacturing the bonding wire.
本發明之一態樣之接合引線用銅裸線之製造方法係前述接合引線用銅裸線之製造方法，其具備有：銅熔融金屬生成工程，其係在純度99.99質量%以上、99.998質量%以下的銅原料添加選自Mg、Ca、sr、Ba、Ra、zr、Ti、及稀土類元素的1種以上的添加元素，生成銅熔融金屬；連續鑄造工程，其係將前述銅熔融金屬供給至帶輪式連續鑄造機，連續製出鑄塊；及連續壓延工程，其係將所被製出的鑄塊以初期溫度800℃以上的條件進行連續壓延。 A method for producing a bare copper wire for a bonding wire according to an aspect of the present invention is a method for producing a bare copper wire for a bonding wire, comprising: a copper molten metal forming process, wherein the purity is 99.99% by mass or more and 99.998% by mass The following copper raw material is added with one or more additive elements selected from the group consisting of Mg, Ca, sr, Ba, Ra, zr, Ti, and a rare earth element to form a copper molten metal; and a continuous casting process in which the copper molten metal is supplied To the wheeled continuous casting machine, the ingot is continuously produced; and the continuous rolling process is carried out by continuously rolling the ingot to be produced at an initial temperature of 800 ° C or higher.
藉由該接合引線用銅裸線之製造方法，使用純度99.99質量%以上、99.998質量%以下，所謂4NCu的銅原料。因此，與使用6NCu的情形相比，可大幅減低接合引線用銅裸線的製造成本。 A copper raw material having a purity of 99.99% by mass or more and 99.998% by mass or less, which is a so-called 4NCu, is used in the method for producing a bare copper wire for a bonding wire. Therefore, the manufacturing cost of the bare copper wire for bonding leads can be greatly reduced as compared with the case of using 6NCu.
另外具備有將所被製出的鑄塊以初期溫度800℃以上的條件進行連續壓延的連續壓延工程。因此，可將接合引線用銅裸線中的特殊粒界比率(L σ/L)形成為50%以上。 Further, a continuous rolling process in which the ingot to be produced is continuously rolled at an initial temperature of 800 ° C or higher is provided. Therefore, the specific grain boundary ratio (L σ / L) in the bare copper wire for bonding wires can be formed to be 50% or more.
此外，本發明之其他態樣之接合引線用銅裸線之製造方法係前述接合引線用銅裸線之製造方法，其具備有：銅熔融金屬生成工程，其係在純度99.99質量%以上、99.998質量%以下的銅原料添加選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的添加元素，生成銅熔融金屬；鑄造工程，其係對鑄模注入前述銅熔融金屬 而製出鑄塊；擠製工程，其係將所得的鑄塊以初期溫度800℃以上的條件進行擠製加工而製出擠製裸線；加工/退火工程，其係對所得的擠製裸線，反覆實施壓延加工或拉延加工的任一者、及退火；及輕壓下工程，其係以壓下率5%以上、25%以下進行壓延而形成為最終線徑0.15mm以上、3.0mm以下。 Further, a method for producing a bare copper wire for a bonding wire according to another aspect of the present invention is the method for producing a bare copper wire for a bonding wire, which is provided with a copper molten metal forming process, which is 99.99% by mass or more and 99.998. a copper raw material having a mass % or less is added with one or more additive elements selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, Ti, and a rare earth element to form a copper molten metal; and a casting process for injecting the copper into the mold Molten metal And the ingot is produced; the extrusion process is performed by extruding the obtained ingot at an initial temperature of 800 ° C or higher to produce an extruded bare wire; processing/annealing, which is performed by extruding the obtained bare The wire is repeatedly subjected to any of calendering or drawing, and annealing; and a soft reduction process is carried out by rolling at a reduction ratio of 5% or more and 25% or less to form a final wire diameter of 0.15 mm or more and 3.0. Below mm.
藉由該接合引線用銅裸線之製造方法，使用純度99.99質量%以上、99.998質量%以下，所謂4NCu的銅原料。因此，與使用6NCu的情形相比，可大幅減低接合引線用銅裸線的製造成本。 A copper raw material having a purity of 99.99% by mass or more and 99.998% by mass or less, which is a so-called 4NCu, is used in the method for producing a bare copper wire for a bonding wire. Therefore, the manufacturing cost of the bare copper wire for bonding leads can be greatly reduced as compared with the case of using 6NCu.
另外具備有：對擠製裸線，反覆實施壓延加工或拉延加工的任一者、及退火的加工/退火工程；及以壓下率5%以上、25%以下進行壓延而形成為最終線徑0.15mm以上、3.0mm以下的輕壓下工程。因此，可將接合引線用銅裸線中的特殊粒界比率(L σ/L)形成為50%以上。 In addition, there is a method of performing a calendering process or a drawing process on an extruded bare wire, and an annealing/annealing process; and rolling at a reduction ratio of 5% or more and 25% or less to form a final line. Light reduction project with a diameter of 0.15mm or more and 3.0mm or less. Therefore, the specific grain boundary ratio (L σ / L) in the bare copper wire for bonding wires can be formed to be 50% or more.
藉由本發明之一態樣，可提供硬度低、而且延展高、甚至加工性優異的接合引線用銅裸線及接合引線用銅裸線之製造方法。 According to one aspect of the present invention, it is possible to provide a bare copper wire for a bonding wire and a bare copper wire for a bonding wire which have low hardness, high elongation, and excellent workability.
以下說明本發明之一實施形態之接合引線用銅裸線及接合引線用銅裸線之製造方法。 Hereinafter, a method of manufacturing a bare copper wire for a bonding wire and a bare copper wire for a bonding wire according to an embodiment of the present invention will be described.
本實施形態之接合引線用銅裸線係作為製造線徑180μm以下，更佳為線徑20μm以上、180μm以下的接合引線時的素材來使用。 The bare copper wire for the bonding wire of the present embodiment is used as a material for producing a bonding wire having a wire diameter of 180 μm or less, more preferably a wire diameter of 20 μm or more and 180 μm or less.
此外，本實施形態之接合引線用銅裸線的裸線直徑為0.15mm以上、3.0mm以下。 Further, the bare wire diameter of the bare copper wire for bonding wires of the present embodiment is 0.15 mm or more and 3.0 mm or less.
該接合引線用銅裸線係具有合計在0.0001質量%以上、0.01質量%以下的範圍含有選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的添加元素，殘部為銅及不可避免雜質的組成。較佳為選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的添加元素的含量合計為0.0003質量%以上、0.002質量%以下。 The copper bare wire for a bonding wire has a total of one or more additive elements selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, Ti, and a rare earth element in a total amount of 0.0001% by mass or more and 0.01% by mass or less. The residue is composed of copper and inevitable impurities. The total content of one or more additional elements selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, Ti, and a rare earth element is preferably 0.0003 mass% or more and 0.002 mass% or less.
此外，前述作為不可避免雜質的Fe、Pb、S的含量為Fe：0.0001質量%以下、Pb：0.0001質量%以下、S：0.005質量%以下。 Further, the content of Fe, Pb, and S as an unavoidable impurity is Fe: 0.0001% by mass or less, Pb: 0.0001% by mass or less, and S: 0.005% by mass or less.
在此，稀土類元素係指Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、及Lu。 Here, the rare earth element means Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
該接合引線用銅裸線的特殊粒界比率(L σ/L)為50%以上。在此，特殊粒界比率係特殊粒界的長度L σ對全部結晶粒界的長度L的比率。藉由使用電場放出型掃描電子顯微鏡的EBSD測定裝置，來特定結晶粒界、特殊粒界，而算出全部結晶粒界的長度L及特殊粒界的長度L σ。由該所算出的長度，獲得特殊粒界比率。亦即，本實施形態之接合引線用銅裸線係相較於一般的結晶粒界，特殊粒界存在更多。 The special grain boundary ratio (L σ/L) of the bare copper wire for bonding wires is 50% or more. Here, the specific grain boundary ratio is a ratio of the length L σ of the specific grain boundary to the length L of all the grain boundaries. By using an EBSD measuring apparatus of an electric field emission type scanning electron microscope, the crystal grain boundary and the specific grain boundary are specified, and the length L of the entire crystal grain boundary and the length L σ of the specific grain boundary are calculated. From the calculated length, a special grain boundary ratio is obtained. That is, the bare copper wire for the bonding wire of the present embodiment has more special grain boundaries than the general crystal grain boundary.
結晶粒界係被定義為經二次元剖面觀察的結果，相鄰的2個結晶間的配向方位差為15°以上時的該結晶間的交界。 The crystal grain boundary is defined as a result of observation by a two-dimensional cross section, and the boundary between the crystals when the alignment misalignment between two adjacent crystals is 15 or more.
此外，特殊粒界係指作為在結晶學上根據CSL理論(Kronberg et al：Trans.Met.Soc.AIME，185，501(1949))所被定義的Σ值滿足3≦Σ≦29的對應粒界，而且該對應粒界中的固有對應部位晶格方位缺陷Dq滿足Dq≦15°/Σ1/2(D.G.Brandon：Acta.Metallurgica.Vol.14，p.1479，(1966))的結晶粒界來加以定義。 In addition, the special grain boundary refers to a corresponding grain which satisfies 3≦Σ≦29 in the crystallographically defined Σ value according to the CSL theory (Kronberg et al: Trans. Met. Soc. AIME, 185, 501 (1949)). And the lattice orientation defect Dq of the intrinsic corresponding part in the corresponding grain boundary satisfies the crystal grain boundary of Dq≦15°/Σ 1/2 (DGBrandon:Acta.Metallurgica.Vol.14, p.1479, (1966)) To define it.
此外，將本實施形態之接合引線用銅裸線100g在硝酸溶液加熱溶解所得的粒徑30μm以上的酸不溶解殘渣物的個數為1000個以下。再者，上述酸不溶解殘渣物的存在比率為0.00015質量%以下。 In addition, the number of acid-insoluble residues having a particle diameter of 30 μm or more obtained by heating and dissolving 100 g of the bare copper wire for bonding wires of the present embodiment in a nitric acid solution is 1,000 or less. Further, the ratio of the acid insoluble residue is 0.00015% by mass or less.
酸不溶解殘渣物的評估係以如下所示的順序來實施。 The evaluation of the acid insoluble residue was carried out in the order shown below.
首先，由將表面洗淨後的接合引線用銅裸線，將預定量(100g)的試料進行取樣，於經加熱的硝酸溶液加熱溶解。在將熔解液冷卻至室溫後，以過濾器進行過濾來捕集殘渣物。 First, a predetermined amount (100 g) of a sample was sampled by a bare copper wire from a bonding wire obtained by washing the surface, and heated and dissolved in a heated nitric acid solution. After the molten solution was cooled to room temperature, it was filtered with a filter to collect the residue.
將捕集到殘渣物的過濾器進行秤量，來測定殘渣物的殘渣質量。接著，算出殘渣物的量(殘渣質量)對試料(接合引線用銅裸線)的量的比例(質量%)。藉由以上，來測定將接合引線用銅裸線在硝酸溶液加熱溶解所得的酸不溶解殘渣物的量(存在比率)。 The filter that has collected the residue is weighed to measure the residue quality of the residue. Next, the ratio (% by mass) of the amount of the residue (residue mass) to the amount of the sample (copper bare wire for bonding wires) was calculated. From the above, the amount (presence ratio) of the acid-insoluble residue obtained by heating and dissolving the bare copper wire for the bonding wire in a nitric acid solution was measured.
接著，藉由掃描型電子顯微鏡來觀察捕集到殘渣物的 過濾器，而對SEM照片進行攝影。將SEM照片進行畫像解析，且測定殘渣物的大小及個數。接著，求出粒徑30μm以上的殘渣物的個數。藉由以上，測定將接合引線用銅裸線100g在硝酸溶液加熱溶解所得的粒徑30μm以上的酸不溶解殘渣物的個數。 Next, the scanning electron microscope was used to observe the trapped residue. Filter and photograph SEM photos. The SEM photograph was subjected to image analysis, and the size and number of the residue were measured. Next, the number of the residue having a particle diameter of 30 μm or more was determined. In the above, the number of acid-insoluble residues having a particle diameter of 30 μm or more obtained by heating and dissolving 100 g of bare copper wire for bonding wires in a nitric acid solution was measured.
接著，說明本實施形態之接合引線用銅裸線之製造方法。 Next, a method of manufacturing a bare copper wire for a bonding wire according to the present embodiment will be described.
特殊粒界的全特殊粒界長度L σ對結晶粒界的全結晶粒界長度L的比率(L σ/L)為50%以上的接合引線用銅裸線，係藉由連續鑄造壓延方法或鑄塊的擠製加工方法來製造。 a copper bare wire for a bonding lead having a ratio of a total grain boundary length L σ of a specific grain boundary to a total grain boundary length L of a grain boundary (L σ/L) of 50% or more, by a continuous casting calendering method or The ingot is extruded to be manufactured.
在本實施形態中，係以使用圖1所示之連續鑄造壓延裝置10之例來進行說明。 In the present embodiment, an example in which the continuous casting rolling apparatus 10 shown in Fig. 1 is used will be described.
圖1所示之連續鑄造壓延裝置10係具有：熔解爐11、保持爐12、鑄造導管13、帶輪式連續鑄造機30、連續壓延裝置15、及盤捲器18。 The continuous casting and rolling apparatus 10 shown in Fig. 1 has a melting furnace 11, a holding furnace 12, a casting duct 13, a pulley type continuous casting machine 30, a continuous rolling apparatus 15, and a coiler 18.
在本實施形態中，使用具有圓筒形爐本體的豎爐作為熔解爐11。在爐本體的下部係以圓周方向配備有複數個燃燒器(圖示省略)，而且朝上下方向配備成多段狀。接著，由爐本體的上部被裝入作為原料的電性銅。藉由前述燃燒器的燃燒，電性銅被熔解，而連續性製造銅熔融金屬。 In the present embodiment, a shaft furnace having a cylindrical furnace body is used as the melting furnace 11. A plurality of burners (not shown) are provided in the lower portion of the furnace body in the circumferential direction, and are arranged in a plurality of stages in the vertical direction. Next, electrical copper as a raw material was placed in the upper portion of the furnace body. By the burning of the burner described above, the electrical copper is melted to continuously produce the copper molten metal.
保持爐12係將在熔解爐11所被製造的純銅熔融金屬，在以預定溫度保持的狀態下暫時貯留，且將一定量的銅 熔融金屬送至鑄造導管13。 The holding furnace 12 temporarily stores the pure copper molten metal produced in the melting furnace 11 while being held at a predetermined temperature, and a certain amount of copper is held. The molten metal is sent to the casting conduit 13.
鑄造導管13係將由保持爐12所被輸送的銅熔融金屬，移送至被配置在帶輪式連續鑄造機30的上方的漏斗20。該鑄造導管13係以例如Ar等惰性氣體或還原性氣體予以密封。其中，在該鑄造導管13係設有藉由惰性氣體來攪拌銅熔融金屬的攪拌手段(未圖示)。 The cast conduit 13 transfers the copper molten metal conveyed by the holding furnace 12 to the funnel 20 disposed above the pulley continuous casting machine 30. The cast conduit 13 is sealed with an inert gas such as Ar or a reducing gas. Among these, the casting conduit 13 is provided with a stirring means (not shown) for stirring the copper molten metal by an inert gas.
在漏斗20設有對所被移送的銅熔融金屬添加元素的元素添加手段21。此外，在漏斗20的銅熔融金屬的流動方向終端側配置有澆注噴嘴22。透過該澆注噴嘴22而對帶輪式連續鑄造機30供給漏斗20內的銅熔融金屬。 The funnel 20 is provided with an element adding means 21 for adding a copper molten metal element to be transferred. Further, a pouring nozzle 22 is disposed on the terminal side of the flow direction of the copper molten metal of the funnel 20. The copper continuous metal in the funnel 20 is supplied to the pulley continuous casting machine 30 through the pouring nozzle 22.
帶輪式連續鑄造機30係具有：在外周面形成有溝槽的鑄造輪31、及以接觸該鑄造輪31之外周面的一部分的方式進行繞周圍移動的無端環帶32。在形成於前述溝槽與無端環帶32之間的空間，注入透過澆注噴嘴22所被供給的銅熔融金屬來進行冷卻，連續鑄造棒狀鑄塊40。 The pulley type continuous casting machine 30 has an endless belt 32 that moves around the circumference of the casting wheel 31 having a groove formed on the outer circumferential surface thereof and a part of the outer circumferential surface of the casting wheel 31. The copper molten metal supplied through the pouring nozzle 22 is injected into the space formed between the groove and the endless endless belt 32 to be cooled, and the rod-shaped ingot 40 is continuously cast.
接著，該帶輪式連續鑄造機30係與連續壓延裝置15相連結。該連續壓延裝置15係將由帶輪式連續鑄造機30所被製出的棒狀鑄塊40進行連續壓延，而製出預定外徑的銅線材50。由連續壓延裝置15所被製出的銅線材50係透過洗淨冷卻裝置16及探傷器17而被捲繞在盤捲器18。 Next, the pulley type continuous casting machine 30 is coupled to the continuous rolling device 15. The continuous rolling apparatus 15 continuously rolls the rod-shaped ingot 40 produced by the pulley type continuous casting machine 30 to produce a copper wire 50 having a predetermined outer diameter. The copper wire 50 produced by the continuous rolling device 15 is wound around the coiler 18 through the cleaning and cooling device 16 and the flaw detector 17.
接著，使用圖1、圖2，說明使用該帶輪式連續鑄造機30之接合引線用銅裸線之製造方法。 Next, a method of manufacturing a bare copper wire for a bonding wire using the pulley type continuous casting machine 30 will be described with reference to Figs. 1 and 2 .
首先，在熔解爐11投入純度99.99質量%以上、 99.998質量%以下的銅原料(所謂4NCu)進行熔解而得銅熔融金屬(熔解工程S01)。在該熔解工程S01中，係調整豎爐的複數燃燒器的空燃比而將熔解爐11的內部形成為還原氣體環境。 First, the purity of the melting furnace 11 is 99.99% by mass or more. A copper raw material (so-called 4NCu) of 99.998 mass% or less is melted to obtain a copper molten metal (melting engineering S01). In the melting process S01, the air-fuel ratio of the complex burner of the shaft furnace is adjusted to form the inside of the melting furnace 11 as a reducing gas atmosphere.
藉由熔解爐11所得的銅熔融金屬係透過保持爐12及鑄造導管13而被移送至漏斗20。 The copper molten metal obtained by the melting furnace 11 is transferred to the funnel 20 through the holding furnace 12 and the casting conduit 13.
在此，通過以惰性氣體或還原性氣體予以密封的鑄造導管13的銅熔融金屬係藉由前述攪拌手段予以攪拌。藉此，促進銅熔融金屬與惰性氣體或還原性氣體的反應。 Here, the copper molten metal of the casting conduit 13 sealed with an inert gas or a reducing gas is stirred by the stirring means. Thereby, the reaction of the copper molten metal with the inert gas or the reducing gas is promoted.
接著，藉由元素添加手段(裝置)21，在漏斗20內的銅熔融金屬，連續添加選自Mg、Ca、sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的元素(元素添加工程S02)。藉此，生成選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的元素的含量合計被調整為0.0001質量%以上、0.01質量%以下，更佳為被調整為0.0003質量%以上、0.002質量%以下的銅熔融金屬。 Next, one or more elements selected from the group consisting of Mg, Ca, sr, Ba, Ra, Zr, Ti, and a rare earth element are continuously added to the copper molten metal in the funnel 20 by the element adding means (device) 21 ( Element added project S02). In this way, the total content of one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, Ti, and a rare earth element is adjusted to be 0.0001% by mass or more and 0.01% by mass or less, and more preferably The copper molten metal is adjusted to 0.0003 mass% or more and 0.002 mass% or less.
如上所示被調整成分的銅熔融金屬係透過澆注噴嘴22而被供給至帶輪式連續鑄造機30，連續製出棒狀鑄塊40(連續鑄造工程S03)。在此，在連續鑄造工程S03中，形成在鑄造輪31的溝槽與無端環帶32之間的空間呈梯形狀。因此，製出剖面呈大致梯形狀的棒狀鑄塊40。 The copper molten metal to which the component is adjusted as described above is supplied to the pulley type continuous casting machine 30 through the pouring nozzle 22, and the rod-shaped ingot 40 is continuously produced (continuous casting process S03). Here, in the continuous casting process S03, the space formed between the groove of the casting wheel 31 and the endless endless belt 32 has a trapezoidal shape. Therefore, a rod-shaped ingot 40 having a substantially trapezoidal shape in cross section is produced.
該棒狀鑄塊40係被供給至連續壓延裝置15來施行滾筒壓延加工，製出預定外徑(在本實施形態中為直徑8mm)的銅線材50(連續壓延工程S04)。在該連續壓延 工程S04中，係在400~900℃的範圍實施壓延。在本實施形態中，係將壓延的初期溫度設為800℃以上。壓延的初期溫度較佳為800℃以上、1050℃以下。 The rod-shaped ingot 40 is supplied to the continuous rolling device 15 to perform roll calendering, and a copper wire 50 having a predetermined outer diameter (in the present embodiment, a diameter of 8 mm) is produced (continuous rolling process S04). In this continuous rolling In the project S04, rolling is performed in the range of 400 to 900 °C. In the present embodiment, the initial temperature of rolling is set to 800 ° C or higher. The initial temperature of rolling is preferably 800 ° C or more and 1050 ° C or less.
由連續壓延裝置15所被製出的銅線材50係透過洗淨冷卻裝置16及探傷器17而被捲繞在盤捲器18。洗淨冷卻裝置16係以酒精等洗淨劑來洗淨由連續壓延裝置15所被製出的銅線材50的表面，並且進行冷卻。此外，探傷器17係探查由洗淨冷卻裝置16所被輸送的銅線材50的損傷。 The copper wire 50 produced by the continuous rolling device 15 is wound around the coiler 18 through the cleaning and cooling device 16 and the flaw detector 17. The washing and cooling device 16 cleans the surface of the copper wire 50 produced by the continuous rolling device 15 with a detergent such as alcohol, and cools it. Further, the flaw detector 17 detects the damage of the copper wire 50 conveyed by the cleaning and cooling device 16.
接著，對所得的銅線材50實施拉延加工，形成為最終線徑0.15mm以上、3.0mm以下(在本實施形態中為直徑0.9mm)(拉延加工工程S05)。 Next, the obtained copper wire 50 is subjected to drawing processing to have a final wire diameter of 0.15 mm or more and 3.0 mm or less (in the present embodiment, a diameter of 0.9 mm) (drawing processing S05).
接著，在上述拉延加工工程S05之後，以150℃以上、250℃以下進行再結晶化熱處理(最終熱處理工程S06)。在本實施形態中，以220℃實施2小時的氣體環境熱處理。 Next, after the drawing process S05, the recrystallization heat treatment (final heat treatment process S06) is performed at 150 ° C or more and 250 ° C or less. In the present embodiment, the gas environmental heat treatment was performed at 220 ° C for 2 hours.
藉由如上所示之順序，製出本實施形態之接合引線用銅裸線。 The bare copper wire for bonding leads of the present embodiment is produced by the procedure as described above.
本實施形態之接合引線用銅裸線係另外施行引伸加工而形成為直徑180μm以下的細線，作為接合引線來使用。 In the bare copper wire for a bonding wire of the present embodiment, a thin wire having a diameter of 180 μm or less is formed by extension processing, and used as a bonding wire.
藉由具有如上所示之特徵之本實施形態之接合引線用銅裸線，具有合計在0.0001質量%以上、0.01質量%以下的範圍含有選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土 類元素的1種以上的添加元素，且殘部為銅及不可避免雜質的組成。更佳為上述添加元素的含量的合計為0.0003質量%以上、0.002質量%以下。因此，銅中所含有的S與上述添加元素形成化合物。因此，由於S的影響變小，因此可降低再結晶溫度，而且可降低硬度。 The bare copper wire for a bonding wire of the present embodiment having the above-described characteristics has a total content of 0.0001% by mass or more and 0.01% by mass or less, and is selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, and Ti. And rare earth One or more additional elements of the class element, and the residue is a composition of copper and unavoidable impurities. More preferably, the total content of the above-mentioned additive elements is 0.0003 mass% or more and 0.002 mass% or less. Therefore, S contained in copper forms a compound with the above-mentioned additive element. Therefore, since the influence of S becomes small, the recrystallization temperature can be lowered and the hardness can be lowered.
此外，本實施形態之接合引線用銅裸線的特殊粒界比率(L σ/L)為50%以上。其中，藉由使用電場放出型掃描電子顯微鏡的EBSD測定裝置，特定結晶粒界、特殊粒界，而算出全部結晶粒界的長度L及特殊粒界的長度L σ。接著，由該所算出的長度，獲得特殊粒界比率。若該特殊粒界比率高時，組織全體的結晶粒界的整合性會提升，錯位排列不易蓄積。因此，可在維持硬度為較低的情況下使延展及加工性提升。 Further, the special grain boundary ratio (L σ / L) of the bare copper wire for bonding wires of the present embodiment is 50% or more. Among them, the length L of the entire crystal grain boundary and the length L σ of the specific grain boundary were calculated by using an EBSD measuring apparatus using an electric field emission type scanning electron microscope to specify a crystal grain boundary and a specific grain boundary. Next, from the calculated length, a special grain boundary ratio is obtained. When the specific grain boundary ratio is high, the integration of the crystal grain boundaries of the entire structure is improved, and the misalignment arrangement is less likely to accumulate. Therefore, the elongation and the workability can be improved while maintaining the hardness to be low.
此外，將本實施形態之接合引線用銅裸線100g在硝酸溶液加熱溶解所得的粒徑30μm以上的酸不溶解殘渣物的個數為1000個以下。再者，酸不溶解殘渣物的量(存在比率)為0.00015質量%以下。 In addition, the number of acid-insoluble residues having a particle diameter of 30 μm or more obtained by heating and dissolving 100 g of the bare copper wire for bonding wires of the present embodiment in a nitric acid solution is 1,000 or less. Further, the amount (presence ratio) of the acid-insoluble residue is 0.00015% by mass or less.
如上所示，酸不溶解殘渣物的粒徑小，而且個數少，甚至其存在比率亦受到抑制。因此，可抑制將接合引線用銅裸線朝接合引線拉延加工時的斷線。 As described above, the particle size of the acid-insoluble residue is small, and the number is small, and even the ratio of its existence is suppressed. Therefore, it is possible to suppress the disconnection when the bare copper wire for the bonding wire is drawn toward the bonding wire.
此外，藉由本實施形態之接合引線用銅裸線之製造方法，使用純度99.99質量%以上、99.998質量%以下，所謂4Ncu的銅原料。因此，與使用6Ncu的情形相比，可大幅減低接合引線用銅裸線的製造成本。 In the method for producing a bare copper wire for a bonding wire of the present embodiment, a copper material having a purity of 99.99% by mass or more and 99.998% by mass or less is used. Therefore, the manufacturing cost of the bare copper wire for bonding leads can be greatly reduced as compared with the case of using 6Ncu.
另外具備有：使用帶輪式連續鑄造機30連續製出棒狀鑄塊40的連續鑄造工程S03、及將所被製出的棒狀鑄塊40以初期溫度800℃以上的條件進行連續壓延的連續壓延工程S04。因此，可將所被製出的接合引線用銅裸線的特殊粒界比率(L σ/L)形成為50%以上。 Further, the continuous casting process S03 in which the rod-shaped ingot 40 is continuously produced by the pulley type continuous casting machine 30 and the rod-shaped ingot 40 produced are continuously rolled at an initial temperature of 800 ° C or higher. Continuous rolling engineering S04. Therefore, the specific grain boundary ratio (L σ / L) of the bare copper wire for the bonding wire to be produced can be made 50% or more.
以上說明本發明之實施形態，惟本發明並非限定於此，可在未脫離本發明之技術思想的範圍內作適當變更。 The embodiment of the present invention has been described above, but the present invention is not limited thereto, and may be appropriately modified without departing from the spirit of the invention.
在本實施形態中，係形成為使用帶輪式連續鑄造機來製造接合引線用銅裸線者來進行說明，但是並非限定於此。 In the present embodiment, the description is made to manufacture a bare copper wire for a bonding wire using a pulley type continuous casting machine, but the invention is not limited thereto.
例如，亦可如圖3所示，藉由實施銅熔融金屬生成工程S11、鑄造工程S12、熱間擠製工程S13、加工/退火工程S14、及輕壓下工程S15，製出特殊粒界比率(L σ/L)為50%以上的接合引線用銅裸線。 For example, as shown in FIG. 3, a special grain boundary ratio can be produced by implementing a copper molten metal forming process S11, a casting process S12, a hot extrusion process S13, a processing/annealing process S14, and a soft reduction engineering S15. (L σ / L) is a bare copper wire for bonding leads of 50% or more.
在銅熔融金屬生成工程S11中，係在純度99.99質量%以上、99.998質量%以下的銅原料(所謂4NCu)，添加選自Mg、Ca、Sr、Ba、Ra、Zr、Ti、及稀土類元素的1種以上的添加元素而得銅熔融金屬。 In the copper molten metal formation project S11, a copper raw material (so-called 4NCu) having a purity of 99.99% by mass or more and 99.998% by mass or less is added to a material selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Zr, Ti, and rare earth elements. A copper molten metal is obtained by adding one or more kinds of elements.
在鑄造工程S12中，係對鑄模澆注銅熔融金屬而得直徑200mm~400mm的鑄塊。 In the casting process S12, a copper molten metal is cast into a mold to obtain an ingot having a diameter of 200 mm to 400 mm.
在熱間擠製工程S13中，係將鑄塊以初期溫度800℃以上的條件進行擠製加工，而得擠製裸線。擠製加工的初期溫度較佳為800℃以上、1050℃以下。 In the hot extrusion process S13, the ingot is extruded at an initial temperature of 800 ° C or higher, and the bare wire is extruded. The initial temperature of the extrusion processing is preferably 800 ° C or more and 1050 ° C or less.
在加工/退火工程S14中，係對擠製裸線反覆實施壓 延加工或拉延加工的任一者、及退火。退火係在每次剖面減少率為80%以上時即實施。 In the processing/annealing project S14, the pressing of the extruded bare wire is repeated. Any of the processing or drawing processes, and annealing. The annealing is performed every time the reduction rate of the profile is 80% or more.
在輕壓下工程S15中，係以壓下率5%以上、25%以下進行壓延，形成為最終線徑0.15mm以上、3.0mm以下。 In the soft reduction work S15, rolling is performed at a reduction ratio of 5% or more and 25% or less, and the final wire diameter is 0.15 mm or more and 3.0 mm or less.
以下說明針對前述本實施形態之接合引線用銅裸線進行評估後的評估試驗結果。 The evaluation test results after evaluation of the bare copper wire for bonding wires of the present embodiment described above will be described below.
藉由圖2的流程圖所示方法，製出本發明例1~5及比較例1、2的接合引線用銅裸線。詳言之，在4Ncu添加表1記載的添加元素而得銅熔融金屬。對帶輪式連續鑄造機澆注銅熔融金屬來進行連續鑄造壓延。另外實施拉延加工及最終熱處理，製出直徑0.9mm的接合引線用銅裸線。 The bare copper wires for bonding leads of Examples 1 to 5 and Comparative Examples 1 and 2 of the present invention were produced by the method shown in the flow chart of Fig. 2 . In detail, the additive element described in Table 1 was added to 4Ncu to obtain a copper molten metal. Continuous casting calendering is carried out by casting a copper molten metal into a wheeled continuous casting machine. Further, a drawing process and a final heat treatment were carried out to produce a copper bare wire for a bonding wire having a diameter of 0.9 mm.
藉由圖3的流程圖所示方法，製出本發明例6~10及比較例3、4的接合引線用銅裸線。詳言之，在4NCu添加表1記載的添加元素而得銅熔融金屬。使用銅熔融金屬而製出直徑240mm的鑄塊。將該鑄塊以800℃進行熱間擠製加工而製出直徑8mm的擠製裸線。對該擠製裸線反覆進行壓延與退火而製出線徑1mm的銅裸線。之後，對該銅裸線實施壓延率10%的壓延。接著，以220℃進行最終熱處理，製出直徑0.9mm的接合引線用銅裸線。 The copper bare wires for bonding wires of Examples 6 to 10 and Comparative Examples 3 and 4 of the present invention were produced by the method shown in the flow chart of Fig. 3 . In detail, the additive element described in Table 1 was added to 4NCu to obtain a copper molten metal. An ingot having a diameter of 240 mm was produced using copper molten metal. The ingot was subjected to hot extrusion processing at 800 ° C to produce an extruded bare wire having a diameter of 8 mm. The extruded bare wire was repeatedly rolled and annealed to produce a bare copper wire having a wire diameter of 1 mm. Thereafter, the copper bare wire was subjected to rolling at a rolling ratio of 10%. Next, the final heat treatment was carried out at 220 ° C to produce a copper bare wire for a bonding wire having a diameter of 0.9 mm.
藉由以下方法，製出習知例的接合引線用銅裸線。首先，在4NCu添加0.0030質量%的Zr而得銅熔融金屬。使用銅熔融金屬而製出直徑240mm的鑄塊。將該鑄塊以800℃進行熱間擠製加工而製出直徑8mm的擠製裸線。對該擠製裸線實施拉延加工。接著，以220℃進行最終熱處理，製出直徑0.9mm的接合引線用銅裸線。 A bare copper wire for a bonding wire of a conventional example is produced by the following method. First, 0.0030% by mass of Zr was added to 4NCu to obtain a copper molten metal. An ingot having a diameter of 240 mm was produced using copper molten metal. The ingot was subjected to hot extrusion processing at 800 ° C to produce an extruded bare wire having a diameter of 8 mm. The extruded bare wire is subjected to drawing processing. Next, the final heat treatment was carried out at 220 ° C to produce a copper bare wire for a bonding wire having a diameter of 0.9 mm.
此外，對所得本發明例1~10、比較例1~4、及習知例的接合引線用銅裸線，實施拉延加工而製出直徑180μm的接合引線。 Further, the bare copper wires for the bonding wires obtained in the inventive examples 1 to 10, the comparative examples 1 to 4, and the conventional examples were subjected to drawing processing to produce bonding wires having a diameter of 180 μm.
針對所得的本發明例1~10、比較例1~4、及習知例的接合引線用銅裸線，藉由以下方法來測定特殊粒界比率(L σ/L)。 The specific grain boundary ratio (L σ / L) was measured by the following method for the obtained bare copper wires for bonding wires of the inventive examples 1 to 10, the comparative examples 1 to 4, and the conventional examples.
針對各試料，使用耐水研磨紙及鑽石磨粒來進行機械研磨。接著，使用膠質氧化矽溶液來進行最終研磨。 For each sample, mechanical polishing was performed using water-resistant abrasive paper and diamond abrasive grains. Next, the final pulverization is carried out using a colloidal cerium oxide solution.
接著，藉由EBSB測定裝置(HITACHI公司製S4300-SEM、EDAX/TSL公司製OIM Data Collection)、及解析軟體(EDAX/TSL公司製OIM Data Analysis ver.5.2)，特定結晶粒界、特殊粒界，算出全部結晶粒界的長度L及特殊粒界的長度L σ。藉此，進行平均結晶粒徑及特殊粒界長度比率的解析。測定方法的詳細內容如以下所示。 Next, specific crystal grain boundaries and special grain boundaries were determined by an EBSB measuring device (S4300-SEM manufactured by HITACHI Co., Ltd., OIM Data Collection manufactured by EDAX/TSL Co., Ltd.) and analytical software (OIM Data Analysis ver. 5.2 manufactured by EDAX/TSL Co., Ltd.). The length L of all the crystal grain boundaries and the length L σ of the special grain boundaries were calculated. Thereby, the analysis of the average crystal grain size and the specific grain boundary length ratio was performed. The details of the measurement method are as follows.
首先，使用掃描型電子顯微鏡，對試料表面的測定範 圍內的各個測定點照射電子線，使電子線以2次元掃描至試料表面。藉由利用後方散射電子線繞射所為之方位解析，將鄰接的測定點間的方位差為15°以上的測定點間設為結晶粒界。 First, using a scanning electron microscope, the measurement of the surface of the sample Each measurement point in the circumference is irradiated with an electron beam, and the electron beam is scanned to the surface of the sample in 2 dimensions. By using the azimuth analysis by the backscattered electron beam diffraction, the measurement point between the adjacent measurement points having an azimuth difference of 15 or more is defined as a crystal grain boundary.
測定出測定範圍中的結晶粒界的全粒界長度(全部結晶粒界的長度)L。此外，決定鄰接的結晶粒的界面為特殊粒界的結晶粒界的位置，並且測定出特殊粒界的全粒界長度(全部特殊粒界的長度)L σ。接著，求出上述所測定出的特殊粒界的長度L σ對結晶粒界的全粒界長度L的比率L σ/L，設為特殊粒界比率(L σ/L)。 The total grain boundary length (length of all crystal grain boundaries) L of the crystal grain boundaries in the measurement range was measured. Further, the interface of the adjacent crystal grains is determined as the position of the grain boundary of the special grain boundary, and the total grain boundary length (the length of all the special grain boundaries) L σ of the specific grain boundary is measured. Next, the ratio L σ/L of the length L σ of the measured specific grain boundary to the total grain boundary length L of the crystal grain boundary is determined as a specific grain boundary ratio (L σ/L).
接著，針對由本發明例1~10、比較例1~4、及習知例的接合引線用銅裸線、及該等接合引線用銅裸線所製出的接合引線，測定硬度。 Next, the hardness of the bonding wires prepared by the bare copper wires for bonding wires of the inventive examples 1 to 10, the comparative examples 1 to 4, and the conventional examples, and the bare copper wires for the bonding wires were measured.
其中，硬度試驗係使用AKASHI製的微小維克氏試驗機MVK-700，依據JIS Z 2241來實施。 Among them, the hardness test was carried out in accordance with JIS Z 2241 using a micro Vickers tester MVK-700 manufactured by AKASHI.
接著，針對由本發明例1~10、比較例1~4、及習知例的接合引線用銅裸線、及該等接合引線用銅裸線所製出的接合引線，使用AKASHI製的AMSLER式縱型拉伸試驗機來實施拉伸試驗，而對延展進行評估。 Next, the AMSLER type manufactured by AKASHI was used for the bonding wires made of the bare copper wires for bonding wires of the inventive examples 1 to 10, the comparative examples 1 to 4, and the conventional examples, and the bare copper wires for the bonding wires. A tensile test was performed on a longitudinal tensile tester to evaluate the elongation.
對所得的本發明例1~10、比較例1~4、及習知例的接合引線用銅裸線另外施行拉延加工，製作出直徑為87μm、50μm、或20μm的線材。對拉延加工時的斷線次數進行評估。 The obtained bare copper wires for bonding wires of the inventive examples 1 to 10, the comparative examples 1 to 4, and the conventional examples were subjected to drawing processing to prepare wires having a diameter of 87 μm, 50 μm, or 20 μm. The number of disconnections during drawing processing was evaluated.
關於接合引線用裸線的特殊粒界比率(L σ/L)、硬度、及延展、接合引線的硬度及延展、以及拉延加工時的斷線次數，將所評估的結果顯示於表1。 The results of the evaluation are shown in Table 1 regarding the specific grain boundary ratio (L σ/L) of the bare wire for bonding leads, the hardness, and the elongation, the hardness and elongation of the bonding wires, and the number of wire breaks during the drawing process.
在本發明例1~10中確認出特殊粒界比率(L σ/L)為50%以上。另一方面，在比較例1~4及習知例中，特殊粒界比率(L σ/L)為未達50%。若將本發明例6~10與習知例作對比，確認出在對具有最終線徑的裸線實施最終熱處理之前，實施壓延率10%的加工，藉此可使特殊粒界比率(L σ/L)增加。 In the inventive examples 1 to 10, it was confirmed that the specific grain boundary ratio (L σ / L) was 50% or more. On the other hand, in Comparative Examples 1 to 4 and the conventional examples, the specific grain boundary ratio (L σ / L) was less than 50%. Comparing Examples 6 to 10 of the present invention with a conventional example, it was confirmed that a processing of a rolling ratio of 10% was carried out before the final heat treatment of the bare wire having the final wire diameter, whereby a special grain boundary ratio (L σ ) was obtained. /L) increase.
在特殊粒界比率(L σ/L)為50%以上的本發明例1~10中，確認在線徑180μm的接合引線的狀態下，硬度低為40Hv以下。 In the inventive examples 1 to 10 in which the specific grain boundary ratio (L σ/L) was 50% or more, the hardness of the bonding wire having a wire diameter of 180 μm was confirmed to be 40 Hv or less.
此外，在本發明例1~10中，與比較例相比，確認拉延時的斷線受到抑制，而可拉延至細徑為止。 Further, in the inventive examples 1 to 10, as compared with the comparative example, it was confirmed that the disconnection of the pull-delay was suppressed, and it was possible to stretch until the small diameter.
接著，使用本發明例1~10的接合引線用銅裸線，來評估酸不溶解殘渣物的殘渣量與粒度分布。 Next, using the bare copper wire for bonding wires of Examples 1 to 10 of the present invention, the amount of residue and the particle size distribution of the acid-insoluble residue were evaluated.
將試料以硝酸進行蝕刻處理，將附著在表面的雜質去除。接著，秤量100g的試料。將該試料在硝酸溶液加熱溶解。加熱溫度係設為60℃。反覆進行該作業。 The sample was etched with nitric acid to remove impurities adhering to the surface. Next, weigh 100 g of the sample. The sample was dissolved by heating in a nitric acid solution. The heating temperature was set to 60 °C. Repeat the job.
接著，冷卻至室溫，接著以過濾器進行過濾來捕集殘渣。 Then, it was cooled to room temperature, and then filtered by a filter to collect a residue.
在此，係使用聚碳酸酯過濾器(孔徑0.4μm)來進行過濾。將捕集到殘渣物的聚碳酸酯過濾器在清淨室內精密秤量，測定出殘渣物的殘渣質量。 Here, filtration was carried out using a polycarbonate filter (pore size 0.4 μm). The polycarbonate filter that collected the residue was accurately weighed in a clean room, and the residue quality of the residue was measured.
此外，測定酸不溶解殘渣物的粒度分布。藉由掃描型 電子顯微鏡來觀察捕集到前述殘渣物的過濾器，對SEM畫像進行攝影。將畫像取入個人電腦，以畫像解析用軟體(WinRoof軟體)將畫像進行2值化處理的解析。接著，測定殘渣物的投影面積，算出具有與該投影面積為相同面積的圓的直徑(圓等效直徑)。使用該圓等效直徑作為殘渣物的粒徑。測定殘渣物的大小(圓等效直徑)及個數。其中，由本發明例1之資料作成粒度分布的圖表。將其結果顯示於圖4。 Further, the particle size distribution of the acid insoluble residue was measured. Scanning type The filter that captured the residue was observed by an electron microscope, and the SEM image was photographed. The image is taken into a personal computer, and the image analysis software (WinRoof software) is used to perform binarization processing. Next, the projected area of the residue is measured, and the diameter (circle equivalent diameter) of the circle having the same area as the projected area is calculated. The equivalent diameter of the circle is used as the particle size of the residue. The size (circle equivalent diameter) and the number of residues were measured. Among them, a graph of particle size distribution was prepared from the data of Example 1 of the present invention. The result is shown in Fig. 4.
WinRoof軟體的畫像解析結果，確認出將本發明例1~10的試料(接合引線用銅裸線)100g在硝酸溶液加熱溶解時，粒徑30μm以上的酸不溶解殘渣物的個數均為1000個以下。此外，以上述方法測定殘渣物的殘渣質量的結果，確認出本發明例1~10的試料中的酸不溶解殘渣物的質量比為0.00015質量%以下。 As a result of the image analysis of the WinRoof software, it was confirmed that the number of the acid-insoluble residue of the particle diameter of 30 μm or more was 1000 when 100 g of the sample (brown bare wire for bonding wires) of the inventive examples 1 to 10 was dissolved in a nitric acid solution. Below. In addition, as a result of measuring the mass of the residue of the residue by the above method, it was confirmed that the mass ratio of the acid-insoluble residue in the samples of Examples 1 to 10 of the present invention was 0.00015% by mass or less.
本實施形態之接合引線用銅裸線係硬度低，而且延展高，甚至加工性優異。因此，本實施形態之銅裸線係可適於使用在取代Au線所使用的Cu接合引線的製造工程。 The bare copper wire for a bonding wire of the present embodiment has low hardness, high elongation, and excellent workability. Therefore, the bare copper wire of the present embodiment can be suitably used for the manufacturing process of the Cu bonding wire used in place of the Au wire.
10‧‧‧連續鑄造壓延裝置 10‧‧‧Continuous casting calender
11‧‧‧熔解爐 11‧‧‧ melting furnace
12‧‧‧保持爐 12‧‧‧ Keep the furnace
13‧‧‧鑄造導管 13‧‧‧ cast conduit
15‧‧‧連續壓延裝置 15‧‧‧Continuous calendering device
16‧‧‧洗淨冷卻裝置 16‧‧‧Washing cooling device
17‧‧‧探傷器 17‧‧‧Detector
18‧‧‧盤捲器 18‧‧‧ coiler
20‧‧‧漏斗 20‧‧‧ funnel
21‧‧‧元素添加手段 21‧‧‧ elemental means
22‧‧‧澆注噴嘴 22‧‧‧ pouring nozzle
30‧‧‧帶輪式連續鑄造機 30‧‧‧wheeled continuous casting machine
31‧‧‧鑄造輪 31‧‧‧ casting wheel
32‧‧‧無端環帶 32‧‧‧ Endless belt
40‧‧‧棒狀鑄塊 40‧‧‧ rod ingot
50‧‧‧銅線材 50‧‧‧ copper wire
圖1係製造本發明之一實施形態之接合引線用銅裸線時所使用的連續鑄造壓延裝置的說明圖。 Fig. 1 is an explanatory view showing a continuous casting rolling apparatus used for producing a bare copper wire for bonding a lead wire according to an embodiment of the present invention.
圖2係本發明之一實施形態之接合引線用銅裸線之製 造方法的流程圖。 2 is a system for manufacturing a bare copper wire for a bonding wire according to an embodiment of the present invention; Flow chart of the method.
圖3係本發明之其他實施形態之接合引線用銅裸線之製造方法的流程圖。 Fig. 3 is a flow chart showing a method of manufacturing a bare copper wire for bonding leads according to another embodiment of the present invention.
圖4係顯示本發明例1中的酸不溶解殘渣物的評估結果的圖表。 Fig. 4 is a graph showing the results of evaluation of the acid-insoluble residue in Example 1 of the present invention.
Claims (9)
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| JP6175932B2 (en) * | 2013-06-24 | 2017-08-09 | 三菱マテリアル株式会社 | Drawing copper wire, drawing copper wire manufacturing method and cable |
| KR101519075B1 (en) * | 2013-12-03 | 2015-05-21 | (주)신동 | Electromagnetic wave shielding Fe-Cu wire, rod and Manufacturing method for the same |
| JP6056876B2 (en) | 2015-01-07 | 2017-01-11 | 三菱マテリアル株式会社 | Superconducting stabilizer |
| JP6299802B2 (en) | 2016-04-06 | 2018-03-28 | 三菱マテリアル株式会社 | Superconducting stabilizer, superconducting wire and superconducting coil |
| JP6299803B2 (en) * | 2016-04-06 | 2018-03-28 | 三菱マテリアル株式会社 | Superconducting wire and superconducting coil |
| CN106119597A (en) * | 2016-08-30 | 2016-11-16 | 芜湖楚江合金铜材有限公司 | The different in nature copper wires of a kind of environment-friendly and high-performance and processing technique thereof |
| CN106947881A (en) * | 2017-05-05 | 2017-07-14 | 三门峡宏鑫有色金属有限公司 | Multielement rare earth high conductivity Cu alloy material and preparation method thereof |
| JP6642763B2 (en) * | 2017-10-30 | 2020-02-12 | 三菱マテリアル株式会社 | Superconducting stabilizer, superconducting wire and superconducting coil |
| CN111656501B (en) * | 2018-01-30 | 2024-10-01 | 拓自达电线株式会社 | Bonding wire |
| CN111661953A (en) * | 2020-06-16 | 2020-09-15 | 包头稀土研究院 | Method for separating fluorine and phosphorus in mixed rare earth alkaline wastewater and application |
| JP2022103567A (en) | 2020-12-28 | 2022-07-08 | 日立金属株式会社 | Rough drawing wire production method and rough drawing wire production device |
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| US4676827A (en) * | 1985-03-27 | 1987-06-30 | Mitsubishi Kinzoku Kabushiki Kaisha | Wire for bonding a semiconductor device and process for producing the same |
| CN1924049A (en) * | 2005-09-02 | 2007-03-07 | 日立电线株式会社 | Copper alloy material and method of making same |
| WO2011086978A1 (en) * | 2010-01-12 | 2011-07-21 | 三菱マテリアル株式会社 | Phosphorous-containing copper anode for electrolytic copper plating, method for manufacturing same, and electrolytic copper plating method |
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| JPS63286212A (en) * | 1987-05-16 | 1988-11-22 | Sumitomo Electric Ind Ltd | Manufacture of metal wire for wiring of semiconductor |
| JPH02207541A (en) * | 1989-02-07 | 1990-08-17 | Sumitomo Electric Ind Ltd | Manufacture of semiconductor element connection wire |
| JP5396939B2 (en) * | 2009-03-16 | 2014-01-22 | 三菱マテリアル株式会社 | Rough drawn copper wire manufacturing method, rough drawn copper wire manufacturing apparatus, and rough drawn copper wire |
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| US4676827A (en) * | 1985-03-27 | 1987-06-30 | Mitsubishi Kinzoku Kabushiki Kaisha | Wire for bonding a semiconductor device and process for producing the same |
| CN1924049A (en) * | 2005-09-02 | 2007-03-07 | 日立电线株式会社 | Copper alloy material and method of making same |
| WO2011086978A1 (en) * | 2010-01-12 | 2011-07-21 | 三菱マテリアル株式会社 | Phosphorous-containing copper anode for electrolytic copper plating, method for manufacturing same, and electrolytic copper plating method |
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| WO2013015154A1 (en) | 2013-01-31 |
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| JP5344070B2 (en) | 2013-11-20 |
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