TWI555102B - Method for manufacturing silver based wire containing gold-rich layer formed by solid phase reaction - Google Patents
Method for manufacturing silver based wire containing gold-rich layer formed by solid phase reaction Download PDFInfo
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- TWI555102B TWI555102B TW103119785A TW103119785A TWI555102B TW I555102 B TWI555102 B TW I555102B TW 103119785 A TW103119785 A TW 103119785A TW 103119785 A TW103119785 A TW 103119785A TW I555102 B TWI555102 B TW I555102B
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/42—Wire connectors; Manufacturing methods related thereto
- H01L24/43—Manufacturing methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/43—Manufacturing methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/45198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/45199—Material of the matrix
- H01L2224/452—Material of the matrix with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45238—Material of the matrix with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45239—Silver (Ag) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/45198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/45298—Fillers
- H01L2224/45299—Base material
- H01L2224/453—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45344—Gold (Au) as principal constituent
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Description
本發明係有關於一種含固相反應之富金層銀基導線製造方法，尤其是指一種有別於一般鍍層技術且適用於半導體封裝製程或人體生醫級晶片之銀基導線及其製造方法，在生醫級晶片之應用領域上係具有較高的細胞增長率，可有效達到優異的細胞相容性，是一種無鍍層表面熱誘發析出金合金層之銀基導線者。 The invention relates to a method for manufacturing a gold-rich wire containing a solid phase reaction, and particularly to a silver-based wire which is different from the general plating technology and is suitable for a semiconductor packaging process or a human medical grade wafer and a manufacturing method thereof. It has a high cell growth rate in the application field of biomedical grade wafers, and can effectively achieve excellent cell compatibility. It is a silver-based wire which is thermally induced to precipitate a gold alloy layer on a non-plated surface.
按，在半導體封裝製程中，係使用導線銲接方式將半導體晶片電性連接至封裝基板，以達到電力、訊號傳送、熱去除，以及電路保護等主要目的；在傳統的半導體封裝製程中，係使用金質導線之球接合方法將半導體晶片的鋁墊和封裝基板連接在一起，主要是由於金質導線具有優越的化學穩定性與導電性；然而，在半導體產業持續追求低成本的同時，金價的成本卻持續上升而居高不下，因此銀金合金導線的研究與發展遂逐步代替金質導線而成為半導體封裝製程之主流。 According to the semiconductor packaging process, the semiconductor wafer is electrically connected to the package substrate by wire bonding to achieve the main purposes of power, signal transmission, heat removal, and circuit protection; in the conventional semiconductor packaging process, the system is used. The ball bonding method of the gold wire connects the aluminum pad of the semiconductor wafer and the package substrate mainly because the gold wire has superior chemical stability and electrical conductivity; however, while the semiconductor industry continues to pursue low cost, the price of gold The cost has continued to rise and remains high. Therefore, the research and development of silver-gold alloy wires have gradually replaced gold wires and become the mainstream of semiconductor packaging processes.
由於銀質導線的成本相較於金質導線可降低約50%~70%，因而具有成本上的優勢，請參閱中國專利公開第CN101667566號之『一種銀 基覆金的鍵合絲線的製造方法』，其揭露一種以銀絲線為基材、表面覆有純金防氧化保護層的鍵合絲線產品，金係佔重量百分比之1.8%~10%，其餘為銀，其材料成本係不到純金鍵合絲線的1/3；然，銀質導線銲接至鋁墊時卻存在有可靠性的問題，主要是由於銀質導線與鋁墊的銲接面容易發生腐蝕或出現貼合不完全現象而嚴重削弱銲接之界面強度，此外，銀金屬與空氣中的二氧化硫反應具特有硫化現象亦嚴重影響產品之良率；再者，銀基材料僅具有抑菌功能而無細胞親和性，在生醫產品之應用方面受到侷限；由於合金線含金金屬可提升合金線之耐蝕性，含鈣金屬則可使合金線具有生物親和性，並可有效提升銀金合金在打線接合的可靠度；因此，銀金鈣合金導線遂被研發以解決上述之半導體封裝製程與提升生醫應用平台所遭遇的問題。 Since the cost of the silver wire can be reduced by about 50% to 70% compared with the gold wire, it has a cost advantage. Please refer to the Chinese Patent Publication No. CN101667566 A method for producing a gold-bonded bonding wire, which discloses a bonding wire product having a silver wire as a base material and a surface covered with a pure gold anti-oxidation protective layer, wherein the gold system accounts for 1.8% to 10% by weight, and the rest is Silver, the material cost is less than 1/3 of the pure gold bonding wire; however, there is a reliability problem when the silver wire is welded to the aluminum pad, mainly because the welding surface of the silver wire and the aluminum pad is prone to corrosion. Or the incompleteness of the bonding may seriously weaken the interface strength of the welding. In addition, the special vulcanization of the reaction between the silver metal and the sulfur dioxide in the air also seriously affects the yield of the product; in addition, the silver-based material has only the antibacterial function and no Cell affinity is limited in the application of biomedical products; since the alloy wire contains gold metal to improve the corrosion resistance of the alloy wire, the calcium-containing metal can make the alloy wire have bio-affinity, and can effectively improve the silver-gold alloy in the wire. The reliability of the joint; therefore, the silver-gold-calcium alloy wire 遂 was developed to solve the above-mentioned semiconductor packaging process and problems encountered in upgrading the biomedical application platform.
請參閱中華民國發明專利公開號第201001652號之『半導體封裝之含銀合金導線』，係揭露一種含銀合金導線，其所構成之族群為0.05%~5%的金、3ppm~5%的鈣，以及其餘的銀，然而上述專利並未述及任何合金線之製備方法，不僅無從得知金金屬如何形成於銀基線材中(目前銀線表面鍍金係被認為一種高污染之製程)，亦無法詳細述明如何將鈣金屬形成於銀金合金層之上；再者，目前已有技術使用塗佈(coating)的技術將鈣金屬鍍在覆蓋銀金屬層之金金屬層上，以達到降低導線斷裂風險與提高抗拉強度；然而，由於銀鈣合金線成分控制不易，而鈣與金亦無法接合，因此以塗佈之技術將鈣金屬鍍於含銀之金金屬層上之技術並無法有效達成，導致鈣金屬與金金屬層的接合度極差，製程上有剝離的疑慮，因此，以塗佈之技術將鈣金屬鍍於金金屬層上並無法達成；據此，為了有效確保銀金鈣 合金之導線在做為生醫級晶片導線使用時擁有良好的細胞相容性與結構穩定性，並在半導體封裝製程上可有效降低導線斷裂風險並提高抗拉強度，仍是現今本導體封裝製程或生醫級晶片用之銀基導線製造業者或研究人員需持續努力克服與解決之重要課題。 Please refer to the "Silver-Calloy Wire for Semiconductor Package" of the Republic of China Invention Patent No. 201001652, which discloses a silver-containing alloy wire composed of 0.05% to 5% gold and 3 ppm to 5% calcium. And the rest of the silver, however, the above patent does not describe any method of preparing the alloy wire, and it is not known how the gold metal is formed in the silver base material (the current gold plating on the silver wire is considered to be a highly polluting process), It is impossible to describe in detail how to form calcium metal on the silver-gold alloy layer; in addition, the prior art has used a coating technique to plate calcium metal on a gold metal layer covering the silver metal layer to reduce The risk of wire breakage and the improvement of tensile strength; however, because the composition of the silver-silver alloy wire is not easy to control, and calcium and gold cannot be joined, the technique of coating the calcium metal on the gold-containing metal layer by the coating technique cannot Effectively, the degree of bonding between the calcium metal and the gold metal layer is extremely poor, and there is a concern that the process is peeled off. Therefore, plating the calcium metal on the gold metal layer by the coating technique cannot be achieved; Gold silver calcium to ensure effective The alloy wire has good cell compatibility and structural stability when used as a biomedical grade wafer wire, and can effectively reduce the risk of wire breakage and increase the tensile strength in the semiconductor packaging process, which is still the current conductor packaging process. Manufacturers or researchers of silver-based wires used in biomedical wafers must continue to work hard to overcome and solve important problems.
今，發明人即是鑑於上述現有之銀基導線於實際實施使用時仍具有鈣金屬不易鍍上銀金合金導線，且鍍金製程不符合綠色訴求，以及塗佈厚度不均勻、無生物應用性與等諸多缺失，於是乃一本孜孜不倦之精神，並藉由其豐富專業知識及多年之實務經驗所輔佐，而加以改善，並據此研創出本發明。 Now, the inventor is that in view of the above-mentioned existing silver-based wires, the calcium metal is not easily plated with silver-gold alloy wires during the actual implementation, and the gold plating process does not conform to the green appeal, and the coating thickness is not uniform, and there is no biological application and the like. Many of the shortcomings are a tireless spirit, and are complemented by their rich professional knowledge and years of practical experience, and the invention has been developed accordingly.
本發明主要目的為提供一種含固相反應之富金層銀基導線製造方法，尤其是指一種有別於一般鍍層技術且適用於半導體封裝製程或人體生醫級晶片之銀基導線及其製造方法，在生醫級晶片之應用領域上係具有較高的細胞增長率，可有效達到優異的細胞相容性，是一種無鍍層表面熱誘發析出金合金層之銀基導線。 The main object of the present invention is to provide a method for manufacturing a gold-rich wire containing a solid phase reaction, and more particularly to a silver-based wire which is different from the general plating technology and is suitable for a semiconductor packaging process or a human medical grade wafer and its manufacture. The method has high cell growth rate in the application field of biomedical grade wafers, can effectively achieve excellent cell compatibility, and is a silver-based wire which is thermally induced to precipitate a gold alloy layer on a non-plated surface.
為了達到上述實施目的，本發明人提出一種含固相反應之富金層銀基導線製造方法，係至少包括下列步驟：首先，準備一含有鈣離子、鈦離子或鋯離子其中之一金屬離子之水溶液；再者，將奈米金粉加入水溶液內，奈米金粉係於水溶液中形成複數顆金粒子，利用水熱法將金屬離子吸附於金粒子表面，以形成奈米核殼複合金粒子；之後，過濾水溶液以獲得固相之奈米核殼複合金粒子；接續，將固相之奈米核殼複合金粒子置入一銀熔液內，攪拌均勻並靜置室溫冷卻以形成一銀基材，藉此，奈米核殼 複合金粒子係均勻分佈於銀基材；之後，進行二階段真空熱處理，使銀基材表面形成一富金合金層；最後，將銀基材進行抽線製程以形成含固相反應之富金層銀基導線。 In order to achieve the above-mentioned object, the present inventors propose a method for producing a gold-rich wire containing a solid phase reaction, which comprises at least the following steps: First, preparing a metal ion containing one of calcium ions, titanium ions or zirconium ions. In addition, the nano gold powder is added into the aqueous solution, and the nano gold powder is formed into a plurality of gold particles in the aqueous solution, and the metal ions are adsorbed on the surface of the gold particles by hydrothermal method to form nano core-shell composite gold particles; The aqueous solution is filtered to obtain a solid phase nano core-shell composite gold particle; subsequently, the solid phase nano core-shell composite gold particles are placed in a silver melt, stirred uniformly and allowed to stand at room temperature for cooling to form a silver base. Material, thereby, the nano core shell The composite gold particles are uniformly distributed on the silver substrate; after that, a two-stage vacuum heat treatment is performed to form a gold-rich alloy layer on the surface of the silver substrate; finally, the silver substrate is subjected to a drawing process to form a gold-rich reaction containing a solid phase reaction. Layer silver-based wire.
如上所述的含固相反應之富金層銀基導線製造方法，其中金屬離子為鈣離子時，水溶液係為添加硝酸鈣、醋酸鈣、磷酸鈣或碳酸鈣等其中之一種。 The method for producing a gold-rich wire containing a solid phase reaction containing a solid phase reaction, wherein the metal ion is calcium ion, the aqueous solution is one of adding calcium nitrate, calcium acetate, calcium phosphate or calcium carbonate.
如上所述的含固相反應之富金層銀基導線製造方法，其中水熱法係將水溶液加熱至沸騰，使金屬離子吸附於金粒子表面，以形成奈米核殼複合金粒子。 The method for producing a gold-rich wire containing a solid phase reaction as described above, wherein the hydrothermal method heats the aqueous solution to boiling, so that metal ions are adsorbed on the surface of the gold particles to form nano core-shell composite gold particles.
如上所述的含固相反應之富金層銀基導線製造方法，其中二階段真空熱處理係於真空環境下先進行700℃~800℃之溫度熱處理30~90分鐘後，再以425℃~520℃之溫度熱處理30~60分鐘。 The method for manufacturing a gold-rich wire containing a solid phase reaction containing a solid phase reaction as described above, wherein the two-stage vacuum heat treatment is performed in a vacuum environment at a temperature of 700 ° C to 800 ° C for 30 to 90 minutes, and then at 425 ° C to 520 Heat treatment at °C for 30 to 60 minutes.
如上所述的含固相反應之富金層銀基導線製造方法，其中富金合金層係為AgAu7Ca2與AgAu9Ca2，或AgAuTi與AgAuTi2，或AgAuZr與AgAuZr2等其中之一種。 The method for producing a gold-rich wire containing a solid phase reaction according to the above, wherein the gold-rich alloy layer is AgAu7Ca2 and AgAu9Ca2, or AgAuTi and AgAuTi2, or AgAuZr and AgAuZr2.
此外，本發明另提供一種含固相反應之富金層銀基導線，係以上述實施例之方法製備而成。 In addition, the present invention further provides a gold-rich wire containing a solid phase reaction, which is prepared by the method of the above embodiment.
如上所述的含固相反應之富金層銀基導線，其中含固相反應之富金層銀基導線係具有至少90%之細胞增長率。 The solid-phase-reacted gold-rich layer-containing silver-based wire as described above, wherein the solid-phase-reactive gold-rich layer silver-based wire system has a cell growth rate of at least 90%.
如上所述的含固相反應之富金層銀基導線，其中含固相反應之富金層銀基導線係與血漿反應，不生鈣鹽層。 The solid-phase-reacted gold-rich layer-containing silver-based wire as described above, wherein the gold-rich wire-based layer containing the solid phase reaction reacts with the plasma, and does not form a calcium salt layer.
藉此，本發明之含固相反應之富金層銀基導線製造方法係藉 由將鈣、鈦或鋯等金屬離子吸附並晶出於金粉之奈米核殼複合金粒子上，並熔進高溫之銀熔液內，繼續以真空連續爐進行有效之二階段真空熱處理方法，即於真空環境下先進行700℃~800℃之溫度熱處理30~90分鐘後，再以425℃~520℃之溫度熱處理30~60分鐘，以製備具有富金合金層之銀基線材，當應用於生醫級晶片之導線時，具有較高的細胞增長率，可有效達到優異的細胞相容性，是一種無鍍層表面熱誘發析出金合金層之銀基導線；此外，本發明之含固相反應之富金層銀基導線製造方法係藉由水熱法將鈣、鈦或鋯金屬離子以氧化方式吸附於金粉之奈米核殼複合金粒子上，可有效解決使用塗佈技術而不易將相關金屬層鍍上金金屬層與厚度不均勻之缺點，不僅解決鍍層剝離的問題，亦可達到製備銀金鈣、銀金鈦或銀金鋯等精細線之目標；最後，本發明之含固相反應之富金層銀基導線製造方法係藉由人工體液模擬人體血漿之體溫37℃浸置96小時的試驗，可有效與血漿反應而不生成絕緣體之鈣鹽層，有效達到以本發明之含固相反應之富金層銀基導線做為人體內之生醫級晶片傳導時，防止鈣鹽層造成短路而無法有效傳遞訊號的缺點。 Thereby, the method for manufacturing a gold-rich wire containing a solid phase reaction containing a solid phase reaction is A two-stage vacuum heat treatment method in which a metal ion such as calcium, titanium or zirconium is adsorbed and crystallized on the nano-core composite gold particles of the gold powder and melted into the high-temperature silver melt, and then continuously dried in a vacuum continuous furnace. That is, after heat treatment at 700 ° C to 800 ° C for 30 to 90 minutes in a vacuum environment, heat treatment at a temperature of 425 ° C to 520 ° C for 30 to 60 minutes to prepare a silver base material having a gold-rich alloy layer, when applied When the wire of the medical grade wafer is used, it has a high cell growth rate and can effectively achieve excellent cell compatibility, and is a silver-based wire which thermally induces a gold alloy layer on the surface of the uncoated layer; in addition, the solid content of the present invention The phase-reacted gold-rich silver-based wire manufacturing method is characterized in that the calcium, titanium or zirconium metal ions are adsorbed on the gold nano-core composite gold particles by hydrothermal method, which can effectively solve the problem of using coating technology. The disadvantage of plating the relevant metal layer with the gold metal layer and uneven thickness not only solves the problem of peeling of the plating layer, but also achieves the goal of preparing fine lines such as silver gold calcium, silver gold titanium or silver gold zirconium; finally, the present invention contains Solid Phase The silver-based wire manufacturing method of the gold-rich layer is simulated by artificial body fluid to simulate the body temperature of human plasma at 37 ° C for 96 hours, and can effectively react with plasma without forming a calcium salt layer of the insulator, thereby effectively achieving the inclusion of the present invention. The solid-phase reaction of the gold-rich silver-based wire is used as a medical-grade wafer in the human body to prevent the calcium salt layer from causing a short circuit and the inability to effectively transmit signals.
(S1)‧‧‧步驟一 (S1)‧‧‧Step one
(S2)‧‧‧步驟二 (S2)‧‧‧Step 2
(S3)‧‧‧步驟三 (S3) ‧ ‧ Step 3
(S4)‧‧‧步驟四 (S4)‧‧‧Step four
(S5)‧‧‧步驟五 (S5) ‧ ‧ step five
(S6)‧‧‧步驟六 (S6) ‧‧‧Step six
第一圖：本發明含固相反應之富金層銀基導線製造方法之步驟流程圖 First: Flow chart of the steps of the method for manufacturing a gold-rich wire containing a solid phase reaction in a solid phase reaction
第二圖：本發明含固相反應之富金層銀基導線製造方法之未經熱處理之銀基導線顯微鏡照片電子圖 The second figure: the electron micrograph of the unheated silver-based wire of the silver-based wire manufacturing method of the solid phase reaction-containing gold-rich wire of the present invention
第三圖：本發明含固相反應之富金層銀基導線製造方法其一較佳實施例之經熱處理之銀金鈣導線顯微鏡照片電子圖 The third figure: the electron-phase photograph of the heat-treated silver-gold-calcium wire of a preferred embodiment of the method for producing a gold-rich wire containing a solid phase reaction
本發明之目的及其結構功能上的優點，將依據以下圖面所示之結構，配合具體實施例予以說明，俾使審查委員能對本發明有更深入且具體之瞭解。 The object of the present invention and its structural and functional advantages will be explained in conjunction with the specific embodiments according to the structure shown in the following drawings, so that the reviewing committee can have a more in-depth and specific understanding of the present invention.
首先，請參閱第一圖所示，為本發明含固相反應之富金層銀基導線製造方法之步驟流程圖，其製造方法係主要包括有如下步驟：步驟一(S1)：準備一含有鈣離子、鈦離子或鋯離子等其中之一種金屬離子之水溶液；在本發明其一較佳實施例中，當金屬離子為鈣離子時，水溶液係為添加硝酸鈣[Ca(NO3)2]、醋酸鈣[Ca(C2H3O2)2]、磷酸鈣[Ca3(PO4)2]或碳酸鈣(CaCO3)等其中之一種化合物；此外，鈦和鋯等金屬離子亦可經由將硝酸鈦、醋酸鈦、磷酸鈦、碳酸鈦或硝酸鋯、醋酸鋯、磷酸鋯、碳酸鋯等其中之一種化合物添加於水溶液獲得；步驟二(S2)：將奈米金粉加入水溶液內，奈米金粉係於水溶液中形成複數顆金粒子，利用水熱法將金屬離子吸附於金粒子表面，以形成奈米核殼複合金粒子；在本發明其一較佳實施例中，水熱法又稱為水蒸汽法，係將水溶液加熱至沸騰100℃之溫度，則金屬離子會吸附於金粒子表面，以形成奈米核殼複合金粒子；步驟三(S3)：過濾水溶液以獲得固相之奈米核殼複合金粒子；在本發明其一較佳實施例中，固態之奈米核殼複合金粒子係為一種純金外覆金鈣材質的奈米顆粒；步驟四(S4)：將固相之奈米核殼複合金粒子置入一銀熔液內，攪拌均勻並靜置室溫冷卻以形成一銀基材，藉此，奈米核殼複合金粒 子係均勻分佈於銀基材；在本發明其一較佳實施例中，銀熔液之溫度係為1100℃；步驟五(S5)：進行二階段真空熱處理，使銀基材表面形成一富金合金層；真空熱處理條件係將含奈米核殼複合金粒子之銀熔液置入一真空連續爐內，於真空環境下先進行700℃~800℃之溫度熱處理30~90分鐘後，再以425℃~520℃之溫度熱處理30~60分鐘完成銀基材；在本發明其一較佳實施例中，含銀、鈣之富金合金層係經過第一階段之真空熱處理條件730℃，60分鐘與第二階段之真空熱處理條件425℃，30分鐘後完成；此外，富金合金層係為AgAu7Ca2與AgAu9Ca2，或AgAuTi與AgAuTi2，或AgAuZr與AgAuZr2等其中之一種；以及步驟六(S6)：將銀基材進行抽線製程以形成含固相反應之富金層銀基導線；在本發明其一較佳實施例中，銀基材進行抽線製程後係可獲得直徑約20微米(μm)之可應用於生醫級晶片與半導體封裝製程之銀金鈣精細線。 First, please refer to the first figure, which is a flow chart of the steps of the method for manufacturing a gold-rich wire containing a solid phase reaction containing a solid phase reaction, and the manufacturing method thereof mainly comprises the following steps: Step 1 (S1): preparing a containing An aqueous solution of one of metal ions such as calcium ions, titanium ions or zirconium ions; in a preferred embodiment of the invention, when the metal ions are calcium ions, the aqueous solution is added with calcium nitrate [Ca(NO3)2], a compound such as calcium acetate [Ca(C2H3O2)2], calcium phosphate [Ca3(PO4)2] or calcium carbonate (CaCO3); in addition, metal ions such as titanium and zirconium may also pass titanium nitrate, titanium acetate, phosphoric acid One of titanium, titanium carbonate or zirconium nitrate, zirconium acetate, zirconium phosphate, zirconium carbonate, etc. is added to the aqueous solution; step two (S2): the nano gold powder is added to the aqueous solution, and the nano gold powder is formed in the aqueous solution to form a plurality of The gold particles adsorb the metal ions on the surface of the gold particles by hydrothermal method to form nano core-shell composite gold particles; in a preferred embodiment of the present invention, the hydrothermal method is also called the water vapor method, and the aqueous solution is Heat to a temperature of boiling 100 ° C Degree, metal ions are adsorbed on the surface of the gold particles to form nano core-shell composite gold particles; Step 3 (S3): filtering the aqueous solution to obtain solid phase nano core-shell composite gold particles; In the embodiment, the solid nano-core-shell composite gold particle is a pure gold-coated gold-calcium nanoparticle; step 4 (S4): placing the solid phase nano-core composite gold particle into a silver melt Inside, stir evenly and let stand at room temperature to cool to form a silver substrate, whereby the nano core-shell composite gold particles The daughter system is evenly distributed on the silver substrate; in a preferred embodiment of the invention, the temperature of the silver melt is 1100 ° C; Step 5 (S5): performing a two-stage vacuum heat treatment to form a rich surface of the silver substrate The gold alloy layer; the vacuum heat treatment condition is that the silver melt containing the nano core-shell composite gold particles is placed in a vacuum continuous furnace, and the temperature is heat-treated at 700 ° C to 800 ° C for 30 to 90 minutes in a vacuum environment, and then The silver substrate is heat-treated at a temperature of 425 ° C to 520 ° C for 30 to 60 minutes. In a preferred embodiment of the present invention, the gold-rich alloy layer containing silver and calcium is subjected to a vacuum heat treatment condition of 730 ° C in the first stage. 60 minutes and the second stage of the vacuum heat treatment conditions 425 ° C, completed after 30 minutes; in addition, the gold-rich alloy layer is AgAu7Ca2 and AgAu9Ca2, or AgAuTi and AgAuTi2, or AgAuZr and AgAuZr2, etc.; and step six (S6) : The silver substrate is subjected to a wire drawing process to form a gold-rich wire containing a solid phase reaction; in a preferred embodiment of the invention, the silver substrate is subjected to a wire drawing process to obtain a diameter of about 20 micrometers ( Μm) can be applied to biomedical wafers and semi-conductors Packaging process of silver fine gold wires calcium.
此外，本發明另提供一種含固相反應之富金層銀基導線，係以上述實施例之方法製備而成，亦即以上述方法製備而成之含固相反應之富金層銀基導線係為直徑20μm且具有富金合金層之銀基導線；再者，本發明之含固相反應之富金層銀基導線係具有至少90%之細胞增長率(cell relative growth rate，簡稱RGR)，亦即本發明之含固相反應之富金層銀基導線具有優異的細胞相容性；在與血漿反應的試驗中，係具有不生成鈣鹽層之特點，其中本發明之含固相反應之富金層銀基導線與血漿反應試驗係以人工體液模擬血漿，將本發明之含固相反應之富金層銀基導線浸置於模擬 人體溫度37℃之人工體液中持續96小時後而不生成鈣鹽層，即適合於生醫級晶片導線之應用。 In addition, the present invention further provides a gold-rich wire containing a solid phase reaction, which is prepared by the method of the above embodiment, that is, a gold-rich wire containing a solid phase reaction and containing a solid phase reaction. A silver-based wire having a diameter of 20 μm and having a gold-rich alloy layer; further, the solid-phase-reactive gold-rich silver-based wire system of the present invention has a cell growth rate (RGR) of at least 90%. That is, the solid-phase-reactive gold-rich silver-based wire of the present invention has excellent cytocompatibility; in the test for reacting with plasma, it has the characteristic of not forming a calcium salt layer, wherein the solid phase containing the present invention The reaction-rich gold-rich layer of silver-based wire and plasma reaction test simulates plasma with artificial body fluid, and immerses the gold-rich wire of the solid phase reaction-containing gold-rich wire of the present invention in a simulation. The artificial body fluid with a body temperature of 37 ° C does not form a calcium salt layer after 96 hours, which is suitable for the application of biomedical grade wafer wires.
再者，本發明係透過下列數個表格所列之複數個實驗例以證實本發明之功效；首先，本發明其一較佳實施例係準備一添加有硝酸鈣、醋酸鈣、磷酸鈣或碳酸鈣等其中之一種化合物之含有鈣離子之水溶液；接續，將奈米金粉加入含有鈣離子之水溶液中，並以100℃之水熱法加熱水溶液使鈣金屬離子吸附於金粒子表面，以形成奈米核殼複合金粒子；再者，過濾水溶液以獲得固相之奈米核殼複合金粒子；之後，將固相之奈米核殼複合金粒子置入一銀熔液內，攪拌均勻並靜置室溫冷卻以形成一銀基材，藉此，奈米核殼複合金粒子係均勻分佈於銀基材；接續，進行真空熱處理，使銀基材表面形成一含銀、鈣之富金合金層(AgAu7Ca2與AgAu9Ca2)；於此同時，本發明人係嘗試各種不同的熱處理方式以找到合適之真空熱處理條件並獲取最佳之參數值；最後，再將含銀、鈣之富金合金層之銀基材進行抽線製程以形成20μm的含固相反應之富金層銀基導線；如下表所示之實驗結果，係未經任何真空熱處理條件所獲得的各項數據，其中，不論鈣含量之重量百分比(wt.%)為何，無真空熱處理步驟即未生成表面奈米金鈣合金層，且七天細胞增長率(RGR)之實驗數值係介於82%~87%之間，結果顯示無真空熱處理之銀基導線與細胞之相容性低，無法達到標準值之90%以上，該含固相反應之富金層銀基導線之外觀請參閱第二圖所示，為本發明含固相反應之富金層銀基導線製造方法之未經熱處理之銀基導線顯微鏡照片電子圖。 Furthermore, the present invention demonstrates the efficacy of the present invention by a plurality of experimental examples listed in the following tables; first, a preferred embodiment of the present invention prepares an addition of calcium nitrate, calcium acetate, calcium phosphate or carbonic acid. An aqueous solution containing calcium ions of one of calcium and the like; subsequently, the nano gold powder is added to an aqueous solution containing calcium ions, and the aqueous solution is heated by a hydrothermal method at 100 ° C to adsorb calcium metal ions on the surface of the gold particles to form a naphthalene. The rice core shell composite gold particles; further, the aqueous solution is filtered to obtain a solid phase nano core shell composite gold particle; after that, the solid phase nano core shell composite gold particles are placed in a silver melt, stirred uniformly and statically Cooling at room temperature to form a silver substrate, whereby the nano-core-shell composite gold particles are uniformly distributed on the silver substrate; and subsequently, vacuum heat treatment is performed to form a gold-rich alloy containing silver and calcium on the surface of the silver substrate. Layer (AgAu7Ca2 and AgAu9Ca2); at the same time, the inventors tried various heat treatment methods to find suitable vacuum heat treatment conditions and obtain the best parameter values; finally, silver and calcium were added. The silver substrate of the gold alloy layer is subjected to a wire drawing process to form a 20 μm silver-rich wire containing a solid phase reaction rich gold layer; the experimental results shown in the following table are the data obtained without any vacuum heat treatment conditions, wherein Regardless of the weight percentage (wt.%) of the calcium content, the surface nano-calcium alloy layer is not formed without the vacuum heat treatment step, and the experimental value of the seven-day cell growth rate (RGR) is between 82% and 87%. The results show that the silver-based wire without vacuum heat treatment has low compatibility with cells and cannot reach more than 90% of the standard value. The appearance of the solid-phase-reacted gold-rich wire of the gold-rich layer is shown in the second figure. The electron micrograph of the unheated silver-based wire of the method for producing a gold-rich wire containing a solid phase reaction in a solid phase reaction.
此外，當第二階段真空熱處理之溫度參數提升為290℃、熱處理時間為30分鐘時，下表係表示本發明其一較佳實施例之含固相反應之富金層銀基導線的實驗數據，其中於「形成鈣化銀金熱擴散區」欄位中標示為「NO」者係代表此銀金鈣混合比例之含固相反應之富金層銀基導線結構不穩定，無法有效形成可用之含固相反應之富金層銀基導線；再者，本組實驗亦加入與血漿混合之人工體液浸置實驗，實驗之設置係使用人工體液模擬人體內之血漿，將本發明之含固相反應之富金層銀基導線浸置於模擬人體體溫37℃之人工體液內96小時，以測量本發明之含固相反應之富金層銀基導線與血漿的反應狀況，其中在「人工體液浸置實驗37C-96hr」欄位內顯示為「NG」者係代表與血漿反應會生成絕緣體之鈣鹽層，而導致以本發明之含固相反應之富金層銀基導線做為人體內之生醫級晶片傳導時阻抗會提高，而無法有效傳遞訊號，進而造成生醫級晶片無作用；由下表數據顯示，當鈣含量小於或等於0.32wt.%，無法有效形成鈣化銀金熱擴散區而導致銀基導線之結構不穩定，而當鈣含量小於或等於0.11wt.%時，於人工體 液浸置試驗中會生成鈣鹽層而使連接之生醫級晶片無作用。 In addition, when the temperature parameter of the second-stage vacuum heat treatment is raised to 290 ° C and the heat treatment time is 30 minutes, the following table shows the experimental data of the solid-phase-reactive gold-rich layer-containing silver-based wire according to a preferred embodiment of the present invention. Among them, the "NO" in the field of "Formation of Calcium Silver Gold Thermal Diffusion Zone" indicates that the silver-rich wire containing solid phase reaction of the silver-calcium mixed ratio is unstable and cannot be effectively formed. A gold-rich wire containing a solid phase reaction; in addition, this experiment also incorporates an artificial body fluid immersion test mixed with plasma. The experiment is performed by using artificial body fluid to simulate plasma in the human body, and the solid phase containing the present invention. The gold-rich wire of the reaction-rich gold layer was immersed in an artificial body fluid simulating human body temperature of 37 ° C for 96 hours to measure the reaction state of the solid-phase reaction-rich gold-rich silver-based wire and plasma of the present invention, wherein "artificial body fluid" The "NG" in the field of immersion test 37C-96hr" represents a calcium salt layer which reacts with plasma to form an insulator, resulting in the use of the solid phase reaction-rich gold-based silver-based wire of the present invention as a human body. It When the medical grade wafer is conducted, the impedance will increase, and the signal will not be transmitted effectively, which will cause the biomedical grade wafer to have no effect. The data in the following table shows that when the calcium content is less than or equal to 0.32 wt.%, the calcified silver gold thermal diffusion region cannot be effectively formed. The structure of the silver-based wire is unstable, and when the calcium content is less than or equal to 0.11 wt.%, the artificial body In the liquid immersion test, a calcium salt layer is formed to make the connected medical grade wafer ineffective.
再者，當第二階段真空熱處理之溫度參數再提升至425℃、熱處理時間同樣為30分鐘時，下表亦表示本發明其一較佳實施例之銀金鈣銀基導線的實驗數據，其中在細胞增長率與人工體液浸置實驗中，不論鈣含量之重量百分比為何，亦即當鈣含量之重量百分比從0.06wt.%~0.58wt.%，本發明之含固相反應之富金層銀基導線的細胞增長率皆可達到標準值之90%以上，而與血漿之反應亦不會生成鈣鹽層，可有效達到生醫級晶片之應用；再者，此真空熱處理之條件亦可完全形成13奈米(nm)以上之鈣化銀金熱擴散區，顯示本發明之含固相反應之富金層銀基導線可處於穩定之結構狀態。 Furthermore, when the temperature parameter of the second-stage vacuum heat treatment is further increased to 425 ° C and the heat treatment time is also 30 minutes, the following table also shows experimental data of a silver-gold-silver-silver-based wire according to a preferred embodiment of the present invention, wherein In the cell growth rate and artificial body liquid immersion test, regardless of the weight percentage of the calcium content, that is, when the weight percentage of the calcium content is from 0.06 wt.% to 0.58 wt.%, the solid phase reaction-rich gold layer of the present invention The cell growth rate of silver-based wires can reach more than 90% of the standard value, and the reaction with plasma does not produce a calcium salt layer, which can effectively achieve the application of biomedical grade wafers; in addition, the conditions of the vacuum heat treatment can also be The calcified silver gold thermal diffusion region of 13 nm or more is completely formed, and it is shown that the solid-phase-reactive gold-rich layer-containing silver-based wire of the present invention can be in a stable structural state.
此外，下表係表示同樣的鈣、金重量百分比含量於同樣的真空熱處理條件下，不同的參數特性，例如打線成球性、打線接合密度、熔斷電流密度，以及界面金屬間化合物厚度等，其中打線成球性係為一種積體電路封裝產業的製程之一，是一種高壓放電的球形接合打線技術，又稱為放電結球(electronic flame off，簡稱EFO)，由下表中顯示，不論鈣含量之重量百分比為何，其打線成球性皆可過關；此外，當鈣含量大於0.46wt.%時，其打線接合強度係呈現下降的趨勢，此表示在半導體封裝製程時，其接合之強度不足，無法有效當作積體電路封裝之導線使用；再者，請一併參閱第三圖所示，為本發明含固相反應之富金層銀基導線製造方法其一較佳實施例之經熱處理之銀金鈣導線顯微鏡照片電子圖，其中熱處理係於真空環境下先進行730℃之溫度熱處理60分鐘後，再以425℃之溫度熱處理30分鐘完成，與第二圖之未經熱處理之顯微鏡照片電子圖比較得知，經過熱處理可生成富金合金層，經過拉線製程後，此富金合金層會包覆在導線之外側，因此，含固相反應之富金層銀基導線之外側會較為平整，而內部銀 質導線的區域亦會存在有鈣金屬離子。 In addition, the following table shows the same calcium and gold weight percentage content under the same vacuum heat treatment conditions, different parameter characteristics, such as wire spheroidality, wire bonding density, fusing current density, and interface intermetallic compound thickness, etc. The ball-forming system is one of the processes of the integrated circuit packaging industry. It is a high-voltage discharge ball bonding wire bonding technology, also known as electronic flame off (EFO), which is shown in the table below, regardless of calcium content. The weight percentage of the wire can be passed through; in addition, when the calcium content is more than 0.46 wt.%, the wire bonding strength tends to decrease, which indicates that the bonding strength is insufficient in the semiconductor packaging process. It can not be effectively used as a conductor of the integrated circuit package; further, please refer to the third figure, which is a heat treatment of a preferred embodiment of the method for manufacturing a gold-rich wire containing a solid phase reaction. Electron micrograph of the silver-gold-calcium wire microscope, in which the heat treatment is performed in a vacuum environment at a temperature of 730 ° C for 60 minutes, followed by 42 The heat treatment at a temperature of 5 ° C is completed for 30 minutes. Compared with the electronic image of the unheated micrograph of the second figure, it is known that a gold-rich alloy layer can be formed by heat treatment. After the wire drawing process, the gold-rich alloy layer is coated. Outside the wire, therefore, the outer side of the gold-rich wire containing the solid phase reaction will be flatter, while the inner silver Calcium metal ions are also present in the area of the conductor.
因此，由上述四個表格的不同真空熱處理條件之實驗數據顯示，若以100%的總組成成份之重量百分比計算，本發明其一較佳實施例之含固相反應之富金層銀基導線係至少包括有0.06wt.%~0.39wt.%的鈣含量、3.2wt.%的金含量，以及剩餘重量百分比的銀含量，含固相反應之富金層銀基導線係具有至少90%之細胞增長率(RGR)，並且與血漿反應，係具有不生成鈣鹽層之特點。 Therefore, the experimental data of the different vacuum heat treatment conditions of the above four tables show that the solid phase reaction-rich gold-rich layer silver-based wire according to a preferred embodiment of the present invention is calculated by weight percentage of 100% of the total composition. The system comprises at least a calcium content of 0.06 wt.% to 0.39 wt.%, a gold content of 3.2 wt.%, and a silver content of the remaining weight percentage, and the gold-rich wire containing the solid phase reaction has at least 90% The cell growth rate (RGR), and reacts with plasma, is characterized by the absence of a calcium salt layer.
此外，在本發明其二較佳實施例中，首先，係準備一添加有硝酸鈦、醋酸鈦、磷酸鈦或碳酸鈦等其中之一種化合物之含有鈦離子之水溶液；接續，將金粉加入含有鈦離子之水溶液中，以100℃之水熱法加熱水溶液使鈦金屬離子吸附於金粒子表面，以形成奈米核殼複合金粒子；再者，過濾水溶液以獲得固相之奈米核殼複合金粒子；之後，將固相之奈米核殼複合金粒子置入銀熔液內，攪拌均勻並靜置室溫冷卻以形成一銀基材，藉 此，奈米核殼複合金粒子係均勻分佈於銀基材；接續，進行真空熱處理，使銀基材表面形成一含銀、鈦之富金合金層(AgAuTi與AgAuTi2)；最後，再將含銀、鈦之富金合金層之銀基材進行抽線製程以形成20μm的含固相反應之富金層銀基導線；下表係表示在二階段真空熱處理條件為730℃，60分鐘與465℃，30分鐘下之含固相反應之富金層銀基導線實驗結果，由數據顯示，含固相反應之富金層銀基導線係至少包括有0.12wt.%~0.85wt.%的鈦含量、2.8wt.%的金含量，以及剩餘重量百分比的銀含量，含固相反應之富金層銀基導線係具有90%以上之細胞增長率(RGR)，亦即擁有優異的細胞相容性，並且與血漿反應，亦具備有不生成鈦鹽層之特點。 In addition, in the second preferred embodiment of the present invention, first, an aqueous solution containing titanium ions added with one of titanium nitrate, titanium acetate, titanium phosphate or titanium carbonate is prepared; and then, the gold powder is added to the titanium-containing solution. In the aqueous solution of ions, the aqueous solution is heated by a hydrothermal method at 100 ° C to adsorb titanium metal ions on the surface of the gold particles to form nano core-shell composite gold particles; further, the aqueous solution is filtered to obtain a solid phase nano core-shell composite gold. Particles; after that, the solid phase nano-core shell composite gold particles are placed in the silver melt, stirred uniformly and allowed to stand at room temperature to cool to form a silver substrate, Therefore, the nano core-shell composite gold particles are uniformly distributed on the silver substrate; and subsequently, vacuum heat treatment is performed to form a gold-rich alloy layer containing silver and titanium (AgAuTi and AgAuTi2) on the surface of the silver substrate; finally, The silver substrate of the silver-titanium rich gold alloy layer is subjected to a wire drawing process to form a 20 μm silver-rich wire containing a solid phase reaction rich gold layer; the following table shows that the two-stage vacuum heat treatment condition is 730 ° C, 60 minutes and 465 °C, the results of the silver-based wire of the gold-rich layer containing solid phase reaction at 30 minutes, the data show that the gold-rich wire containing the solid phase reaction contains at least 0.12wt.%~0.85wt.% of titanium. The content, the gold content of 2.8 wt.%, and the silver content of the remaining weight percentage, the silver-rich wire-based system containing the solid phase reaction has a cell growth rate (RGR) of more than 90%, that is, excellent cell compatibility Sexually, and reacted with plasma, it also has the characteristics of not forming a titanium salt layer.
再者，在本發明其三較佳實施例中，首先，係準備一添加有硝酸鋯、醋酸鋯、磷酸鋯或碳酸鋯等其中之一種化合物之含有鋯離子之水溶液；接續，將金粉加入含有鋯離子之水溶液中，以100℃之水熱法加熱水溶液使鋯金屬離子吸附於金粒子表面，以形成奈米核殼複合金粒子；再者，過濾水溶液以獲得固相之奈米核殼複合金粒子；之後，將固相之奈米核殼複合金粒子置入銀熔液內，攪拌均勻並靜置室溫冷卻以形成一銀基材，藉此，奈米核殼複合金粒子係均勻分佈於銀基材；接續，進行真空熱處理，使銀基材表面形成一含銀、鋯之富金合金層(AgAuZr與AgAuZr2)；最後，再將含銀、鋯之富金合金層之銀基材進行抽線製程以形成20μm的含固相反 應之富金層銀基導線；下表係表示在真空熱處理條件為730℃，60分鐘與520℃，60分鐘下之含固相反應之富金層銀基導線實驗結果，由數據顯示，此含固相反應之富金層銀基導線係至少包括有0.09wt.%~0.72wt.%的鋯含量、4.1wt.%的金含量，以及剩餘重量百分比的銀含量，含固相反應之富金層銀基導線係具有90%以上之細胞增長率(RGR)，亦即擁有優異的細胞相容性，並且與血漿反應，亦具備有不生成鋯鹽層之特點。 Furthermore, in the third preferred embodiment of the present invention, first, an aqueous solution containing zirconium ions added with one of zirconium nitrate, zirconium acetate, zirconium phosphate or zirconium carbonate is prepared; and then, the gold powder is added to contain In the aqueous solution of zirconium ions, the aqueous solution is heated by hydrothermal method at 100 ° C to adsorb zirconium metal ions on the surface of the gold particles to form nano core-shell composite gold particles; further, the aqueous solution is filtered to obtain a solid phase nano core-shell composite. Gold particles; after that, the solid phase nano core-shell composite gold particles are placed in the silver melt, stirred uniformly and allowed to stand at room temperature to cool to form a silver substrate, whereby the nano core-shell composite gold particles are uniform Distributed on the silver substrate; followed by vacuum heat treatment to form a gold-rich alloy layer containing silver and zirconium (AgAuZr and AgAuZr2) on the surface of the silver substrate; finally, silver-based alloy layer containing silver and zirconium The material is subjected to a drawing process to form a 20 μm solid opposite The gold-rich wire of the rich gold layer; the following table shows the experimental results of the gold-rich wire containing the solid phase reaction in the vacuum heat treatment condition of 730 ° C, 60 minutes and 520 ° C, 60 minutes, as shown by the data, The gold-rich wire containing solid phase reaction contains at least 0.09 wt.% to 0.72 wt.% of zirconium content, 4.1 wt.% of gold content, and residual weight percentage of silver content, containing solid phase reaction rich The gold-based silver-based wire system has a cell growth rate (RGR) of more than 90%, that is, it has excellent cell compatibility, and reacts with plasma, and has the characteristic of not forming a zirconium salt layer.
上述之實施說明可知，本發明之銀基導線及其製造方法與現有技術相較之下，本發明具有以下優點： The above description of the invention shows that the silver-based wire of the present invention and the method of manufacturing the same have the following advantages compared with the prior art:
1.本發明之含固相反應之富金層銀基導線製造方法係藉由將鈣、鈦或鋯等金屬離子吸附並晶出於金粉之奈米核殼複合金粒子上，並熔進高溫之銀熔液內，繼續以真空連續爐進行有效之二階段真空熱處理方法，即於真空環境下先進行700℃~800℃之溫度熱處理30~90分鐘後，再以425℃~520℃之溫度熱處理30~60分鐘，以製備具有富金合金層之銀基線材，當應用於生醫級晶片之導線時，具有較高的細胞增長率，可有效達到優異的細胞相容性，是一種無鍍層表面熱誘發析出金合金層之銀基導線。 1. The method for producing a gold-rich wire containing a solid phase reaction containing a solid phase reaction is carried out by adsorbing and crystallizing a metal ion such as calcium, titanium or zirconium onto a nano-core composite gold particle of a gold powder and melting it into a high temperature. In the silver melt, the effective two-stage vacuum heat treatment method is continued in a vacuum continuous furnace, that is, the temperature is heat-treated at 700 ° C to 800 ° C for 30 to 90 minutes in a vacuum environment, and then at a temperature of 425 ° C to 520 ° C. Heat treatment for 30 to 60 minutes to prepare a silver base material with a gold-rich alloy layer. When applied to a wire of a biomedical grade wafer, it has a high cell growth rate and can effectively achieve excellent cell compatibility. The surface of the coating thermally induces the precipitation of the silver-based wire of the gold alloy layer.
2.本發明之含固相反應之富金層銀基導線製造方法係藉由水熱法將鈣、鈦或鋯金屬離子以氧化方式吸附於金粉之奈米核殼複合金粒子上，可有效解決使用塗佈技術而不易將相關金屬層鍍上金金屬層與厚度 不均勻之缺點，不僅解決鍍層剝離的問題，亦可達到製備銀金鈣、銀金鈦或銀金鋯等精細線之目標。 2. The method for manufacturing a gold-rich wire containing a solid phase reaction containing a solid phase reaction is characterized in that a calcium, titanium or zirconium metal ion is adsorbed on a gold powder nano-shell composite gold particle by a hydrothermal method, which is effective Solve the use of coating technology and not easily plate the relevant metal layer with gold metal layer and thickness The disadvantage of unevenness not only solves the problem of peeling of the plating layer, but also achieves the goal of preparing fine lines such as silver gold calcium, silver gold titanium or silver gold zirconium.
3.本發明之含固相反應之富金層銀基導線製造方法係藉由人工體液模擬人體血漿之體溫37℃浸置96小時的試驗，可有效與血漿反應而不生成絕緣體之鈣鹽層，有效達到以本發明之含固相反應之富金層銀基導線做為人體內之生醫級晶片傳導時，防止鈣鹽層造成短路而無法有效傳遞訊號的缺點。 3. The method for manufacturing a gold-rich wire containing a solid phase reaction containing a solid phase reaction is an artificial body fluid simulating a body temperature of 37 ° C for 96 hours, which can effectively react with plasma without generating an insulator calcium salt layer. It is effective to achieve the disadvantage that the calcium salt layer is short-circuited and cannot effectively transmit signals when the gold-rich wire containing the solid phase reaction-containing gold-rich wire of the present invention is used as a medical-grade wafer in the human body.
綜上所述，本發明之含固相反應之富金層銀基導線製造方法，的確能藉由上述所揭露之實施例，達到所預期之使用功效，且本發明亦未曾公開於申請前，誠已完全符合專利法之規定與要求。爰依法提出發明專利之申請，懇請惠予審查，並賜准專利，則實感德便。 In summary, the method for manufacturing a gold-rich wire containing a solid phase reaction of the solid phase reaction of the present invention can achieve the intended use efficiency by the above disclosed embodiments, and the present invention has not been disclosed before the application. Cheng has fully complied with the requirements and requirements of the Patent Law.爰Issuing an application for a patent for invention in accordance with the law, and asking for a review, and granting a patent, is truly sensible.
惟，上述所揭之圖示及說明，僅為本發明之較佳實施例，非為限定本發明之保護範圍；大凡熟悉該項技藝之人士，其所依本發明之特徵範疇，所作之其它等效變化或修飾，皆應視為不脫離本發明之設計範疇。 The illustrations and descriptions of the present invention are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; those skilled in the art, which are characterized by the scope of the present invention, Equivalent variations or modifications are considered to be within the scope of the design of the invention.
(S1)‧‧‧步驟一 (S1)‧‧‧Step one
(S2)‧‧‧步驟二 (S2)‧‧‧Step 2
(S3)‧‧‧步驟三 (S3) ‧ ‧ Step 3
(S4)‧‧‧步驟四 (S4)‧‧‧Step four
(S5)‧‧‧步驟五 (S5) ‧ ‧ step five
(S6)‧‧‧步驟六 (S6) ‧‧‧Step six
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| TW201001652A (en) * | 2008-06-27 | 2010-01-01 | Mk Electron Co Ltd | Ag-based alloy wire for semiconductor package |
| TW201034970A (en) * | 2008-12-31 | 2010-10-01 | Ind Tech Res Inst | Nano metal solution, nanometal complex grains and manufacturing method of metal film |
| US20120031656A1 (en) * | 2009-04-24 | 2012-02-09 | Yoshio Oka | Substrate for printed wiring board, printed wiring board, and methods for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201546918A (en) | 2015-12-16 |
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