200408092 、發明說明（1) 發明領域+ 本發明是關於一種太伞曾 a闕机一括” … 不未導電凸塊及其製造方法，特別 n l不只奴官作為電性連接之導電凸塊及其製造 万法。 【發明背景】 #尺ΐ ::導體凡件的結構，對增加元件密度以及減少元 产侔赭戈:? ί求不斷提高，因在匕，封裝以及接合技術的 = 。近年來’ |晶接合技 覆晶直接晶片接合（f i彳^ · ί . DCA、姑 τ ρ弓 上 hip direct chip attachment, DCA)技術開始被運用於 . 覆晶接合技術主要係；：：；二；i (packaglng)。 (b卿）’此凸塊係長個一個的凸塊 性輸入/輸出之卢^ c輸/輪出）的表面，以作為電 取代習知封裝技中所凸塊主要是由錫鉛焊錫所構成，以 印刷電路板的技i =用的導線架（：Lead frame)接合於 距離，且適用於：π:低晶片與基板間的電子訊號傳輸 、用於同連几件的封裝。 由覆晶接合技術所製作 y 因此，需限f(1 θ y μ A 、 A /、形狀多為球形， m_lng)做為晶連二：線 1 / 〇間的距籬的炎0 A , A . % 1土堤接的方式，其 种干极氩日 〜〇 〇微米之間；然而，甚以萝曰、 做為晶片與基板間 苴右以復日日接合技 到150微米以上， 連接；;/〇間的距離則需增加 的。 確保母個1/0之電性連通是沒有問題200408092, Description of the invention (1) Field of invention + The present invention relates to a type of umbrella which is not conductive, and its manufacturing method, and in particular, it is not only slaves that are electrically connected conductive bumps and its manufacturing Wan Fa. [Background of the Invention] # ΐΐ :: The structure of conductors, which increases the density of components and reduces the yield of elementary production :? 求 Continue to improve, because of the dagger, packaging and bonding technology =. In recent years' | Chip bonding technology Chip direct chip bonding (fi 彳 ^ · ί. DCA, Gu τ ρ bow direct chip attachment, DCA) technology began to be used. The main system of chip bonding technology;:; two; i ( (packaglng). (bqing) 'This bump is a long bumpy input / output (^ c input / output) surface in order to replace the bumps in the conventional packaging technology mainly by tin-lead It is composed of solder and is connected to the distance by the lead frame (: Lead frame) of the printed circuit board. It is suitable for: π: electronic signal transmission between the low chip and the substrate, and used for packaging of several pieces connected together. Produced by flip-chip bonding technology (1 θ y μ A, A /, most of the shape is spherical, m_lng) as the crystal connection two: the line between the 1 / 〇 Yan 0 A, A.% 1 earth bank connection method, its kind of dry pole Between argon day and 〇00 micron; however, even Luo Yue, as the wafer and the substrate 苴 right to the day and day bonding technology to more than 150 microns, connected;; distance between / 〇 need to be increased. 1/0 electrical connectivity is no problem
第4頁 200408092 五、發明說明（2) " 隨著科技的進步，晶片也朝著多功能的方向發展，然 而，晶片上的功能越強大，則代表著晶片上j/0的數目也 會跟著增加。然而，在晶片上的面積有限、1/0數目越多 的狀況下，必須縮小每個I/O間的距離，才能夠容納更多 的 I/O。 由於利用覆晶接合技術進行封裝，其電性導通的表現 較佳，因此，我們將繼續採用原本的覆晶接合技術，但又 希望能夠縮小每個I/O間的距離，以容納更多的1/〇，因 此’希望透過改善凸塊材料的方式，以縮小丨/〇間的距 離。 近年來，奈米奴官因其兼具有半導體及導體的雙重性 質，因此有人開始以奈米碳管作為封裝中晶片與基板之間 電性連接的導線，以取代現有覆晶封裝中的導線。 目前以奈米碳管作為電性連接的方式，多是以化學氣 相沉積（Chemical Vapor DeP〇siti〇n; CVD)並配合電娱己丨 導的方式’使奈米碳管從I/O上朝著某一方向水平或是垂 直的成長，以接合二種元件，然而，此方法最低的操作溫 度約為70(TC左右，可能會造成晶片的損毀，因此，並不 適用於封裝製程。 另一種利用金屬和石炭 (metal-carbide)之間的反應，使碳管與矽、鉬、鈦及鷂 等金屬反應，使二者間產生鍵結而結合，此方法同樣需利 用高溫製程，因此，不適用於封裝製程。 除此之外’還有以添加焊錫（例如：錫/錯、金/錫）等 物負與奈米碳管結合的方式，但是，由於必須在碳管的尖Page 4 200408092 V. Description of the invention (2) " With the advancement of technology, the chip is also developing in the direction of multi-function. However, the more powerful the function on the chip, the more the number of j / 0 on the chip will be. Follow up. However, in a situation where the area on the wafer is limited and the number of I / Os is larger, the distance between each I / O must be reduced to be able to accommodate more I / Os. Because the flip-chip bonding technology is used for packaging, its electrical conduction performance is better. Therefore, we will continue to use the original flip-chip bonding technology, but hope to reduce the distance between each I / O to accommodate more 1 / 〇, so 'I hope to reduce the distance between 丨 / 〇 by improving the way of the bump material. In recent years, due to the dual nature of semiconductors and conductors, nanometer officials have begun to use nanometer carbon tubes as wires for the electrical connection between chips and substrates in packages to replace the wires in existing flip-chip packages. . Currently, carbon nanotubes are used as electrical connections, and chemical vapor deposition (Chemical Vapor DepositiOn; CVD) is often used to make the nanocarbon tubes from I / O. It grows horizontally or vertically in a certain direction to join two components. However, the lowest operating temperature of this method is about 70 ° C, which may cause chip damage, so it is not suitable for packaging processes. Another method uses the reaction between metal and metal-carbide to make the carbon tube react with metals such as silicon, molybdenum, titanium, and hafnium to cause bonding between the two. This method also requires high-temperature processes, so In addition, it is not suitable for the packaging process. In addition, there is a way to add solder (such as: tin / wrong, gold / tin) and the nano carbon tube, but because it must be at the tip of the carbon tube
第5頁 200408092 五、發明說明（3) 另外塗覆上一層金屬，以增加石炭管與焊锡間的接合力， 因此，造成製作上的困難。在美國專利第6 3 4 0 8 2 2號所揭 露的三種方法：物理氣相沉積（非等向性）、電鍍及無電鍍 〆儿積(electroless&electro lytic deposition)及 4匕學氣 相沉積（等向性），同樣也面臨到實際製作上的困難，例 如：在物理氣相沉積方法中，如何只將金屬塗覆於奈米碳 =的一侧？在電鍍及無電鍍沉積方法中，如何讓催化劑或 是種子層只長在奈米碳管的頂端？在化學氣相沉積方法 I、’，如何控制在奈米碳管的表面只長一層金原子？這些長 ^米複管的方法都有實際製作上的困難。 【發明之目的及概述】 種白鑒於以上習知技術的問題，本發明之目的在於提供一 目級裝奈米導電凸塊及其製造方法，利用太二 電性遠拉a、首^ 〜用不木石反官作為 連接之導電凸塊，且以化學自組裝的 v電凸塊之製作。 、I7】凡成此 C;目的，本發明在數個奈米碳管之二端加入數 1，接著藉由此官能基與基板上特定金屬 上1大錯合鍵結能力，使奈米碳管自組裝於金屬塾之蜀 d:的官能基可搭配不同的金屬，以使金屬和夺/平 人吕間產生強大的結合力。 蜀不不木 筠強了 =此利用上述方式做出來的凸塊其鍵結的強度仍不 度。q此，可引進烊錫來增㊣奈米石炭管與基板的鍵結強 此 首先，在奈米碳管之二端加入數個官能基，再藉由 第6頁 200408092Page 5 200408092 V. Description of the invention (3) In addition, a layer of metal is coated to increase the bonding force between the charcoal tube and the solder, thus causing manufacturing difficulties. Three methods disclosed in U.S. Patent No. 6 3 0 8 2 2: physical vapor deposition (non-isotropic), electroplating and electroless deposition, and 4D vapor deposition (Isotropic), but also face difficulties in practical production, for example: in the physical vapor deposition method, how to coat the metal only on the side of nano-carbon =? In electroplating and electroless deposition methods, how to make the catalyst or seed layer grow only on the top of the carbon nanotube? In chemical vapor deposition methods I, ’, how to control only one layer of gold atoms on the surface of the carbon nanotube? These methods of double tube length have practical difficulties in production. [Objective and Summary of the Invention] In view of the problems of the above-mentioned conventional technologies, the purpose of the present invention is to provide a nanometer-scale nanometer conductive bump and a manufacturing method thereof. Mu Shi anti-offices are used as connected conductive bumps, and are made of chemically self-assembled v-electric bumps. I7] Where this is achieved C. Purpose, the present invention adds the number 1 to the two ends of several carbon nanotubes, and then uses this functional group to make a large misalignment bond with a specific metal on the substrate to make the carbon nanotubes The functional groups that are self-assembled on the metal can be combined with different metals to produce a strong binding force between the metal and the duo / pingren lu. Shu is not stubborn = the bond strength of the bumps made by the above method is still not good. q Herein, tin tin can be introduced to increase the bonding strength between the nano carbon tube and the substrate. First, add several functional groups to the two ends of the nano carbon tube, and then use page 6 200408092
官能基舆模板上之金屬墊間的鍵結力，使奈米碳管之一山 利用化學自組裝的方法，選擇性自組裝於金屬墊:上。^ 八。接著’將上述奈米碳管另一端之官能基抓取數個奈米 金屬球，並形成奈米金屬層，此奈米金屬層即為焊接ϋ 潤/然層，再將此奈米金屬層與基板之焊墊焊接，最後，'去 除上述之模板’即形成奈米導電凸塊。 為使對本發明的目的、構造特徵及其功能有進一步的 了解，茲配合圖示詳細說明如下： 【實施例詳細說明】 根據本發明所揭露之自組裝奈米導電凸塊及其製造方 法：，其製作過程說明如下： 首先，如「第1圖」所示，在奈米石炭管10的末端以化 千方法加入如破醇（thiol)、醯胺（amide)、醇（hydroxy) 及幾酸（carbonyl acid)等官能基11 ^加入硫醇可在奈米 雙管1 0的二端長出硫原子；而加入醯胺則可於奈米碳管1 〇 的二端長出氮原子；加入醇或是羰酸則可在奈米碳管1 〇的 〜立而長出氧原子。 接著，請參考「第2圖」所示，再藉由這些官能基11 轉基板2 0上特定金屬塾2 1的強大錯合鍵結能力，而使奈米 石炭管1 0選擇性自組裝於特定金屬墊2 1上。例如：硫原子與 金原子有彳艮強的吸引力、氮原子與銅原子或是銀原子之間 會產生彳艮強的吸引力，而氧原子則是與銅原子或是顧原子 有很強的吸引力。因此，不同的官能基可搭配不同的金 屬，以使金屬和奈米碳管1 0間產生強大的結合力。 200408092 五、發明說明（5) " _~ --- 接著，請參考「第3A〜3D圖」所示，為本 塊；作流程圖，此實施例係採用：入硫醇的 工；示乂石反吕1 〇的二端長出硫原子，硫原子再與金屬 結合，並藉由奈米碳管1〇之間的凡德瓦作 用 而使，、付以相互吸引，而直立於金屬墊2丨上以來成 線束狀的凸塊。此方法在室溫溶液中即可進行，不= 像=知技術中利用化學氣相沉積法生長奈米碳管1 〇，=在 高溫狀況下才能進行，因此可避免破壞晶片上的元件Γ 然而，利用上述方式做出來的凸塊其鍵結的強度仍 夠強，因此，為增強奈米碳管1〇與基板2〇的鍵結 ，病 們可引進焊錫來作為連結。首先，如「第3Α圖」所示， 在一個可移除的模板“㈣“以㈠”上’利用上， 將奈米碳管10在模板3〇上長成線束狀的凸塊。缺 ^夾 見「㈣圖」所示，加入奈米金球40，則奈米碳管1〇;: 端裸露的硫醇官能基u會因為硫原子和金原子的錯合鍵社 能力，而使硫原子來抓取奈米金球4〇，將奈米金球4 = 於奈米碳管10的頂端，當使用的奈米碳管1〇密度夠密，太 米金球40尺寸夠小的狀況下，此單層的奈米金球40 ;成； 焊接時=潤濕層，以幫助奈米碳管丨〇附著於基板2 〇之上: 接著，如「第3 c圖」所示，使用金屬墊2工（此金 21即為焊墊）材料為金21a與錫21b( Au/Sn)的雙層結 板20，將上述已抓取奈米金球40之奈米碟管板2〇 = 之金屬墊2 1接觸，再經由加熱的過程，會使得金2 1 & 2 1 b反應形成金锡化合物，且同時將奈米碳管1 〇焊接於美The bonding force between the metal pads on the functional group template enables one of the carbon nanotubes to be selectively self-assembled on the metal pad using a chemical self-assembly method. ^ Eight. Next, 'grab the functional groups on the other end of the nano carbon tube to grab several nano metal balls and form a nano metal layer. This nano metal layer is a soldering wet / natural layer, and then this nano metal layer and the substrate The solder pads are soldered. Finally, the nano-conductive bumps are formed by 'removing the above template'. In order to further understand the purpose, structural features, and functions of the present invention, the following detailed description is given in conjunction with the drawings: [Detailed description of the embodiment] The self-assembled nano-conductive bumps disclosed in the present invention and the manufacturing method thereof: The production process is described as follows: First, as shown in "Figure 1", add the thiol, amide, hydroxy, and citric acid to the end of the nano-carbon pipe 10 by the chemical method. (Carbonyl acid) and other functional groups 11 ^ adding thiols can grow sulfur atoms at the two ends of the nano double tube 10; and adding amidine can grow nitrogen atoms at the two ends of the nano carbon tube 10; adding Alcohols or carbonyl acids can grow oxygen atoms in the carbon nanotubes. Next, please refer to the "Figure 2", and then use these functional groups 11 to transfer the strong miscibility of specific metal 塾 2 1 on the substrate 20 to make the nano-carbon tube 10 selectively self-assemble to a specific Metal pad 2 on 1. For example: the sulfur atom and gold atom have strong attraction, the nitrogen atom and copper or silver atom have strong attraction, and the oxygen atom has strong attraction with copper or Gu atom. Appeal. Therefore, different functional groups can be combined with different metals to produce a strong binding force between the metal and the carbon nanotube 10. 200408092 V. Description of the invention (5) " _ ~ --- Then, please refer to the "Figures 3A ~ 3D" as this block; as a flowchart, this embodiment uses: the process of entering thiols; The vermiculite anti-luo 10 grows sulfur atoms at the two ends, and the sulfur atoms are then combined with the metal, and they are attracted to each other by the van der Waals action between the nano carbon tubes 10, standing upright on the metal pad. 2 丨 Simple bumps. This method can be performed in a solution at room temperature, not = image = known technology using chemical vapor deposition to grow nano carbon tubes 10, = can only be performed at high temperatures, so it can avoid damaging the components on the wafer Γ However The bonding strength of the bumps made by the above method is still strong enough. Therefore, in order to strengthen the bonding between the nano carbon tube 10 and the substrate 20, patients can introduce solder as a connection. First, as shown in "Fig. 3A", on a removable template "㈣" "〇", the carbon nanotubes 10 are grown on the template 30 to form wire-like bumps. ^ As shown in the "㈣ diagram", if nano-gold ball 40 is added, the nano-carbon tube 10 ;: The exposed thiol functional group u will cause the sulfur atom due to the misbonding ability of the sulfur atom and the gold atom. Let's grab the nano gold ball 40, place the nano gold ball 4 = on the top of the nano carbon tube 10, when the used nano carbon tube 10 is dense enough, and the nano gold ball 40 is small enough. This single-layer nano-gold ball 40; into; when welding = wetting layer to help the nano-carbon tube adhere to the substrate 2 〇: Then, as shown in "Figure 3c", use metal The pad 2 (the gold 21 is the solder pad) is made of the double-layered junction board 20 of gold 21a and tin 21b (Au / Sn). The metal pad 21 is in contact, and then through the heating process, gold 2 1 & 2 1 b reacts to form a gold tin compound, and at the same time, the nano carbon tube 10 is welded to the United States.
第8頁 200408092 五、發明說明（6) " ----^ , 板20之上，最後，如「第3D圖」所示，將模板3〇移除 形成奈米導電凸塊。 j 、 【達成之功效】 利用本發明所揭露之自組裝奈米導電凸塊及其製造方 法’可降低目前覆晶封裝技術中丨/〇間的距離，且此程 在室溫下即可製作，可避免習知之以化學氣相沉積法& $ 奈米碳管所需的高溫製程。 、 x食 且本發明係利用化學自組裝的方式，使奈米碳管選 性的沉積於基板的金屬墊之上，相較於其他製作方法，、 如：物理氣相沉積法（非等向性沉積）、電鍍及無電鍍沉積例Page 8 200408092 V. Description of the invention (6) " ---- ^, on the plate 20, and finally, as shown in the "3D drawing", the template 30 is removed to form a nano-conductive bump. j. [Achieved effect] Using the self-assembled nano-conductive bumps and the manufacturing method thereof disclosed in the present invention can reduce the distance between 丨 / 〇 in the current flip chip packaging technology, and this process can be made at room temperature , Which can avoid the high-temperature process required by the chemical vapor deposition & carbon nanotubes. The invention uses chemical self-assembly to selectively deposit carbon nanotubes on the metal pad of the substrate, compared to other manufacturing methods, such as: physical vapor deposition (non-isotropic) Deposition), electroplating and electroless deposition
(electroless&electrolytic deposition)，或是化學々 I 相沉積法（等向性沉積），需精準地控制金屬只沉積於^奈^ 碳管的一側面，或是一頂端，在實際製作上簡單許多:二； 以上所述者，僅為本發明其中的較佳實施例而已，。 非用來限定本發明的實施範圍；即凡依本發明申請專利f 圍所作的均等變化與修飾，皆為本發明專利範圍所涵執·(electroless & electrolytic deposition), or chemical 々I phase deposition (isotropic deposition), it is necessary to precisely control the metal to be deposited on only one side or top of the carbon tube, which is much simpler in actual production : Two; The above are merely preferred embodiments of the present invention. It is not used to limit the scope of implementation of the present invention; that is, all equivalent changes and modifications made in accordance with the patent application f of the present invention are covered by the scope of the invention patent.
第9頁 200408092 圖式簡單說明 第1圖為奈米碳管末端以化學方法加入官能基之示意圖 第2圖為奈米碳管自組裝於金屬墊之示意圖；及 第3 A〜3D圖為本發明之自組裝奈米導電凸塊製作流程圖 【圖式符號說明】Page 9 20040809 Brief description of the diagram. Figure 1 is a schematic diagram of adding functional groups chemically at the end of the carbon nanotube. Figure 2 is a schematic diagram of the self-assembly of the carbon nanotube on a metal pad. Flow chart for making self-assembled nano-conductive bumps of the invention [illustrated symbol]
第10頁 10 奈米碳管 11 官能基 ο η 乙U 基板 21 金屬墊 21a 金 21b 錫 30 模板 40 奈米金球Page 10 10 Nano carbon tube 11 Functional group ο η B U substrate 21 Metal pad 21a Gold 21b Tin 30 Template 40 Nano gold ball