200821404 九、發明說明： 【發明所屬之技術領域】 本發明係關於-種奈米金屬粒子之製備方法及其奈米礙 官之製備方法與其發光元件之製備方法，特別係關於一種 利用電鐘製程還原金屬離子之奈米金屬粒子之製備方法及 其奈米碳管之製備方法與其發光元件之製備方法。 【先前技術】 研究人員根據不同的原理，目前已經發展出許多種奈米 金屬粒子列陣技術，例如電子束刻寫法、陽極氧化紹模板 法、微接觸印刷法及團聯式高分子模板法。 電子束刻寫法（參見：j. Mater Res，ν〇1 16，卩3246 ，2001)雖然可任意精準地佈植奈米金屬粒子，，然而其刻寫程 序相當耗時’不適於講求效率及大面積的量產製程。此外 ’電子束刻寫法亦必須使用複雜的曝先微影蝕刻製程，因 而其量產及大面積化之製造成本相當昂貴。 陽極氧化鋁模板法（參見：Appl phys Lett，ν〇ι乃， P367, 1999)係利用預先製作之模具在高純度的鋁基板上壓 印出小圓柱孔洞列陣，再將此表面圖案化之結基板浸入化 學電鍍液中當作陽極，進行氧化銘的單晶沈積。由於銘基 板表面具有圓孔洞，導致氧化鋁之磊晶速度不同，因而可 形成-圓柱孔_陣。然而，陽極氡化_板法僅可適用 於純鋁基板，且成長氧化鋁需要在一高溫的化學液中進行 〇 微接觸印刷法（參見·· Appl· Phys Lett·，76，2071，2000)係200821404 IX. Description of the invention: [Technical field of the invention] The present invention relates to a method for preparing a nano metal particle and a preparation method thereof and a method for preparing the same, and particularly to a method for using an electric clock A method for preparing a metal ion-reducing nano metal particle, a method for preparing the same, and a method for preparing the same. [Prior Art] According to different principles, researchers have developed a variety of nano metal particle array technologies, such as electron beam writing, anodizing template method, microcontact printing method and cluster-linked polymer template method. Electron beam writing (see: j. Mater Res, ν〇1 16, 卩 3246, 2001) Although the nano metal particles can be implanted with precision, the writing process is quite time consuming, 'not suitable for efficiency and large area. Mass production process. In addition, the electron beam writing method must also use a complicated exposure lithography process, so that the mass production and large-area manufacturing cost are quite expensive. The anodized aluminum stencil method (see: Appl phys Lett, ν〇ι, P367, 1999) uses a pre-made mold to emboss a small cylindrical array of holes on a high-purity aluminum substrate, and then pattern the surface. The junction substrate is immersed in an electroless plating solution as an anode to perform single crystal deposition of oxidized. Since the surface of the base plate has a circular hole, the epitaxial speed of the alumina is different, so that a cylindrical hole array can be formed. However, the anodic oxidation-plate method is only applicable to pure aluminum substrates, and the growth of alumina requires a micro-contact printing method in a high-temperature chemical liquid (see ··································································· system
114580.DOC 200821404 利用微光刻電鑄模造法（LIGA)製作出模具（作為e卩章>，並 使用含有金屬觸媒之溶液作為墨水，再利用蓋印章之原理 將金屬觸媒溶液印在基板表面上。然而，微接觸印㈣受 限於傳統LIGA製程的尺度’無法將金相媒作奈米級的列 陣（僅可作微米級列陣）。此外，微接觸印刷法亦易於產生局 部的金屬聚集。 團聯式高分子模板法（參見：日本專利公開案 JP2003342012-A及美國專利公開案us 2〇〇3〇185985_ai)係 利用團聯式高分子之自組裝而形成圖案於基板上，並利用 紫外光（UV)或反應性離子蝕刻（RIE)對團聯式高分子之其 中一個成份作選擇性姓刻，再將自組裝後的圖案轉印至下 一層材料。然而，為提高其圖案之深寬比，必需使用數層 不同材料作為轉印層並經過複數次之轉印程序，才能提昇 孔洞結構之深寬比到可應用的範圍。完成深寬比孔洞之後 ’再使用沈積技術將金屬媒觸沈積於高深寬比之孔洞内， 最後再洗去基板上之轉印層，而奈米金屬粒子則形成於基 板上之奈米孔洞中。團聯式高分子模板法類似於半體導曝 光微影蝕刻製程，其利用多層結構及蝕刻速率差異性因而 轉印製程過於繁複且生產成本相當高，故不具產業應用價 值。 【發明内容】 本發明提供一種利用電鍍製程還原金屬離子之奈米金屬 粒子之製備方法及其奈米碳管之製備方法與其發光元件之 製備方法。114580.DOC 200821404 Using a microlithography electroforming method (LIGA) to make a mold (as e-chapter), using a solution containing a metal catalyst as an ink, and then printing the metal catalyst solution using the principle of a stamp seal On the surface of the substrate. However, the micro-contact printing (4) is limited by the scale of the traditional LIGA process. 'The metallographic medium cannot be used as a nano-scale array (only micron arrays can be used). In addition, micro-contact printing is also easy to produce. Localized metal aggregation. The group-linked polymer template method (see: Japanese Patent Publication No. JP2003342012-A and U.S. Patent Publication No. 2〇〇3〇185985_ai) is a pattern formed on a substrate by self-assembly of a cluster-linked polymer. Above, and using ultraviolet light (UV) or reactive ion etching (RIE) to selectively excel one of the components of the cluster-linked polymer, and then transfer the self-assembled pattern to the next layer of material. To increase the aspect ratio of the pattern, it is necessary to use several layers of different materials as the transfer layer and perform multiple transfer procedures to increase the aspect ratio of the hole structure to the applicable range. After the deposition technique, the metal medium is deposited in a hole of high aspect ratio, and finally the transfer layer on the substrate is washed away, and the nano metal particles are formed in the nano hole in the substrate. The molecular template method is similar to the half-body exposure lithography etching process, which utilizes the multi-layer structure and the etch rate difference, so that the transfer process is too complicated and the production cost is relatively high, so it has no industrial application value. [Invention] The present invention provides a utilization. Method for preparing nano metal particles for metal ion reduction by electroplating process, preparation method thereof for carbon nanotubes and preparation method of light-emitting element thereof.
114580.DOC 200821404 本發明之奈米金屬粒子之製備方法係將一導電基板浸泡 於一包含金屬離子之電鍍液中，再進行一電鍍製程以還原 該金屬離子而形成奈米金屬粒子於該導電基板之上。 本發明之奈米碳管之製備方法係將一導電基板浸泡於一 包含金屬離子之電鍍液中，再進行一電鍍製程以還原該金 屬離子而形成奈米金屬粒子於該導電基板之上。之後，利 用該奈米金屬粒子為催化劑，進行一化學氣相沈積製程以 形成奈米碳管於該導電基板上。 本發明之發光元件之製備方法係將一導電基板浸泡於一 包含金屬離子之電鍍液中，再進行一電鍍製程以還原該金 屬離子而形成奈米金屬粒子於該導電基板之上。其次，利 用該奈米金屬粒子為催化劑，進行一化學氣相沈積製程以 形成奈米碳管於該導電基板上。之後，形成一螢光物質於 該奈米碳管之上方。 習知奈米金屬粒子列陣技術都具有過程繁複且製作及時 間成本高的缺點。本發明提拱一種較直接、低成本且間距 尺寸調控裕度車父大之奈米金屬粒子之製備技術，其不需要 繁複的製作程序，僅需在導電基板上進行表面處理（例如利 用電漿轟擊導電基板表面）。申言之，表面處理後之導電基 板的表面粗糙度係隨位置變化在奈米尺度，本發明再將電 鍍製程施加之電位設計在該金屬離子之標準還原電位區間 附近猎以控制成核點。當成核生成後，即可以調整電鍍 製程之遁還圈數以控制後續奈米金屬粒子之成長尺寸，因 而可任意地在經過表面處理之導電基板上佈植尺寸可控制114580.DOC 200821404 The method for preparing nano metal particles of the present invention is to immerse a conductive substrate in a plating solution containing metal ions, and then perform an electroplating process to reduce the metal ions to form nano metal particles on the conductive substrate. Above. The carbon nanotube of the present invention is prepared by immersing a conductive substrate in a plating solution containing metal ions, and performing an electroplating process to reduce the metal ions to form nano metal particles on the conductive substrate. Thereafter, using the nano metal particles as a catalyst, a chemical vapor deposition process is performed to form a carbon nanotube on the conductive substrate. The light-emitting device of the present invention is prepared by immersing a conductive substrate in a plating solution containing metal ions, and performing an electroplating process to reduce the metal ions to form nano metal particles on the conductive substrate. Next, using the nano metal particles as a catalyst, a chemical vapor deposition process is performed to form a carbon nanotube on the conductive substrate. Thereafter, a phosphor is formed above the carbon nanotubes. The conventional nano metal particle array technology has the disadvantages of complicated process and high cost in production time. The invention provides a preparation technology of a nanometer metal particle which is more direct, low-cost and has a small size adjustment margin. It does not require complicated fabrication procedures and only needs to be surface-treated on a conductive substrate (for example, using plasma Bombard the surface of the conductive substrate). It is claimed that the surface roughness of the surface-treated conductive substrate varies with position at the nanometer scale, and the present invention further designs the potential applied by the electroplating process to circulate near the standard reduction potential interval of the metal ion to control the nucleation point. When the nucleation is generated, the number of turns of the electroplating process can be adjusted to control the growth size of the subsequent nano metal particles, so that the size of the implanted conductive substrate can be arbitrarily controlled.
114580.DOC 200821404 之奈米金屬粒子。此外’若使用微影技術預先在導電基板 上氣作導電區域/非導電區域，本發明更可製作出較多元化 的奈米金屬粒子列陣佈局。 【實施方式】 圖1(a)及圖1(b)例示本發明之奈米金屬粒子16之製備方 法。本發明之製備方法係將一導電基板12浸泡於一包含金 屬離子22之電鍍液2〇中，再進行一電鍍製程（例如循環電位 電鍍製程）以還原該金屬離子22而形成奈米金屬粒子16於 該V電基板12之上。較佳地，該奈米金屬粒子16之尺寸係 介於1奈米至150奈米之間。該導電基板12可包含晶格尺寸 於5奈米至5〇〇奈米之氧化銦錫（IT〇)，該電鑛液2〇可包含 硝酸鎳、硫酸鎳或氯化鎳，而該奈米金屬粒子16可為鎳金 屬粒子。此外，該電鍍液2〇亦可為鐵離子或鈷離子等磁性 金屬離子，而該奈米金屬粒子16可為鐵金屬或鈷金屬等磁 性金屬粒子。 參考圖1(b)，該導電基板12可預先以微影技術形成複數 個導電區域14Α及非導電區域14Β，而該奈米金屬粒子16係 選擇性地成長於該導電區域14Α之上。該導電基板12之導電 區域14Α的表面粗糙度較佳地係介於奈米尺度（例如$奈米 至10微米之間）。另，若該導電基板12之表面粗糙度太小， 本發明可在進行該循環電位電鍍製程之前，另在該導電基 板12表面進行一表面粗化製程（例如拋光製程或電漿轟擊 製私）’使得該導電基板12之表面粗縫度介於奈米尺度。 圖2(a)至3(c)例示表面粗糙度對成核（nucleation)及成長114580.DOC 200821404 nano metal particles. In addition, if a conductive region/non-conductive region is previously made on the conductive substrate by using lithography, the present invention can produce a more diverse array of nano metal particle arrays. [Embodiment] Figs. 1(a) and 1(b) illustrate a method of preparing the nano metal particles 16 of the present invention. In the preparation method of the present invention, a conductive substrate 12 is immersed in a plating solution 2 containing metal ions 22, and then subjected to an electroplating process (for example, a cyclic potential plating process) to reduce the metal ions 22 to form nano metal particles 16 . Above the V electrical substrate 12. Preferably, the nano metal particles 16 have a size between 1 nm and 150 nm. The conductive substrate 12 may include indium tin oxide (IT〇) having a crystal lattice size of 5 nm to 5 nm, and the electric mineral liquid 2 may include nickel nitrate, nickel sulfate or nickel chloride, and the nano The metal particles 16 may be nickel metal particles. Further, the plating solution 2 may be a magnetic metal ion such as iron ion or cobalt ion, and the nano metal particle 16 may be a magnetic metal particle such as an iron metal or a cobalt metal. Referring to FIG. 1(b), the conductive substrate 12 may be formed in advance by a lithography technique to form a plurality of conductive regions 14 and non-conductive regions 14A, and the nano metal particles 16 are selectively grown on the conductive regions 14A. The surface roughness of the conductive region 14 of the conductive substrate 12 is preferably between the nanometer dimensions (e.g., between $ nanometers and 10 micrometers). In addition, if the surface roughness of the conductive substrate 12 is too small, the present invention may perform a surface roughening process on the surface of the conductive substrate 12 (for example, a polishing process or a plasma bombardment process) before performing the cyclic potential plating process. 'The surface roughness of the conductive substrate 12 is made to be on the nanometer scale. Figures 2(a) to 3(c) illustrate surface roughness versus nucleation and growth
114580.DOC 200821404 (growing)機制之影響。由於該導電基板12之表面粗糙度隨 位置變化係在奈米尺度，因此進行電鍍製程時金屬離子22 之還原反應會在奈米尺度之空間下選擇性地成長於特定表 面，例如導電基板12之ITO晶粒（grain)邊緣。本發明可藉由 没疋施加電位在金屬離子2 2之標準還原電位區間附近以控 制其成核點。當成核生成後，則可以遁還圈數來控制後續 結晶成長，以獲得具有較均勻尺寸之奈米金屬粒子丨6，如 圖2(a)及3(a)所示。如此，本發明即可任意在表面處理之導 電基板12上製備間距及尺寸可控制之奈米金屬粒子16。 相對地，若電鍍反應係在一相當平整之金屬表面進行， 例如錢鍍技術製備之高度平整銅表面，由於其表面粗糖度 相當小’因此在進行電鍍反應時，金屬離子22之還原反康 幾乎沒有”位置選擇性"地在銅金屬之平整表面進行，甚至 是以一層一層原子堆疊上去。如此，製備之奈米金屬粒子 16並無法以奈米間距佈植，如圖2(b)、3(b)及圖3(c)所示。 圖4(a)及圖4(b)例示電鍍模式對成核及成長機制之影響 。圖4(a)例示本發明利用循環電位電鍍製程製備奈米金屬粒 子16，其可使奈米金屬粒子16選擇性地成長於該導電基板 12之晶粒邊緣。相對地，若使用具有相同表面粗糙度分佈 之導電基板12，但採用不同之電鍍模式（例如使用直流電進 行電鑛反應）’則易於使成核點分佈不均，造成金屬局部聚 集（local aggregation)。由於電鍍反應之啟動需要電鍍系統 之電動勢（potential)或是電位（voltage)達到待鍍金屬之還原 電位值；然而，電鍍液20内含不同濃度之物種（specie)且物 200821404 種之"質傳效應（mass transfer)"亦影響電鍍反應之進行，因 此電鍍系統使用直流電並無法有效控制電鍍液20内發生之 電鍵反應（包含析鍍量及位置），因而易於使成核點分佈不均 ，造成金屬局部聚集（local aggregation)，如圖4(b)所示。 圖5(a)至圖6(b)例示導電基板12之表面結構對成核及成 長機制之影響。圖5(a)係在一晶圓上濺鍍銀（Ag)後之表面結 構，其表面結構相當平整，因此在進行鎳電鍍反應時，金 屬離子22之還原反應幾乎沒有”位置選擇性”地在銀金屬之 平整表面進行，如圖5(b)所示。特而言之，鎳金屬甚至是以 一層一層原子堆疊方式形成於銀金屬之平整表面，因此鎳 金屬無法以奈米間距佈植，如圖3(b)及圖3(c)所示。圖6(a) 係在一晶圓上濺鍍金（Au)後之表面結構，同樣可觀察到金 屬離子22之還原成長均勻性相當高，幾乎也是以一層一層 原子堆疊形成金屬層，因此亦無法形成以數十至數百奈米 間距分佈之奈米金屬粒子，如圖6(b)所示。 圖7例示本發明之表面處理後之專電基板12的電子影像 圖。該導電基板12之氧化銦錫（ITO)具有奈米尺度之表面粗 梭度。 圖8(a)至圖8(c)例示本發明利用循環電位電鍍法製備之 奈米金屬粒子16的電子影像圖，其倍率分別為150倍、 10,000倍及50,000倍。本發明在表面處理後之導電基板12 表面（具有導電區域14A/非導電區域14B)進行循環電位電 鍍法，其係以電位區間-0.6至-1.0伏特進行200圈循環進行 鎳金屬離子22之還原反應，可得到間距分佈在100至200奈 114580.DOC -11- 200821404 米之間且直徑约60奈米之鎳奈米金屬粒子16。 圖9(a)至圖9(c)例示本發明利用循環電位電鍍法製備之 奈米金屬粒子16的電子影像圖，其倍率分別為2,000倍、 10,000倍及50,000倍。本發明在表面處理後之導電基板12 表面（具有導電區域14A/非導電區域14B)進行循環電位電 鍍法，其係以電位區間-0.6至-0.75伏特進行500圈進行鎳金 屬離子22之還原反應，可得到間距分佈在500至1000奈米之 且直徑約120奈米之鎳奈米金屬粒子16。由圖8(a)至圖9(c) 所示之實施例可知，本發明使用表面處理之導電基板12配 合電鍍模式控制可得到間距分佈及直徑之調控裕度 (control window)在數十至數百奈米之奈米金屬粒子16。 圖10(a)至圖10(c)例示本發明製備之奈米碳管的電子影 像圖，其倍率分別為200倍、5,000倍及100,000倍。本發明 係使用圖7之導電基板12進行循環電位電鍍法形成奈米金 屬粒子16於該導電基板12之上。之後，以奈米金屬粒子16 φ 為催化劑，進行一電漿加強化學氣相沈積製程以製備平均 管徑約為30奈米、結構完整均勻且呈筆直形態排列之奈米 碳管。特而言之，電漿加強化學氣相沈積製程之反應氣體 可包含乙炔及氨，反應壓力約為1 -10陶爾（torr)。 圖11(a)及圖11(b)例示本發明製備之發光元件30，其係採 二極（diode)設計且可作為背光源（backing light)或顯示器。 本發明在該奈米碳管18上形成複數個間隔器24(spacer)，再 於該間隔器24上形成一螢光基板26(包含一透明導電基板 及一螢光物質）而完成該發光元件30。當施加一預定電壓（ 114580.DOC -12- 200821404 例如350伏特）於該導電基板12與該螢光基板26之間，該導 電基板12上之奈米碳管18將因尖端放電效應而射出電子， 其轟擊該蝥光基板26之螢光物質而產生光束，如圖11 (b)所 示〇 圖12例示本發明製備之發光元件40，其係採三極（tri〇de) 設計。本發明可在該導電基板12與該間隔器24之間形成一 介電區塊32以及一導電區塊34，因而具有三個導電端（即導 電區域34、螢光基板26及導電基板12)，如圖12所示。 習知奈米金屬粒子列陣技術都具有過程繁複且製作及時 間成本高的缺點。本發明提拱一種較直接、低成本且間距 尺寸調控裕度較大之奈米金屬粒子16的製備技術，其不需 要繁複的製作程序，僅需在導電基板12上進行表面處理（例 如利用電漿轟擊導電基板表面）。申言之，表面處理後之導 電基板12的表面粗糙度係隨位置變化在奈米尺度，本發明 再將電鍍製程施加之電位值設計在該金屬離子22之標準還 原電位區間附近，藉以控制成核點。當成核生成後，即可 以調整電鍍製程之遁還圈數以控制後續奈米金屬粒子16之 成長尺寸，因而可任意地在經過表面處理之導電基板12上 佈植尺寸可控制之奈米金屬粒子16。此外，若使用微影技 術預先在導電基板12上製作導電區域14A/非導電區域14b ，本發明更可製作出較多元化的奈米金屬粒子列陣佈局。 此外’為避免發生場發射之屏蔽效應，奈米碳管需要以 一預定之間距（依碳管長度而有所不同，文獻提出管長與間 距的比例約為1:1或是1:2)予以分隔。一般而言，高分子自114580.DOC 200821404 (growing) The impact of the mechanism. Since the surface roughness of the conductive substrate 12 is on the nanometer scale as the position changes, the reduction reaction of the metal ions 22 during the electroplating process selectively grows on a specific surface in a space of a nanometer scale, for example, the conductive substrate 12 ITO grain edge. The present invention can control its nucleation sites by applying a potential near the standard reduction potential interval of the metal ion 2 2 . When nucleation is generated, the number of turns can be used to control subsequent crystal growth to obtain nano metal particles 丨6 having a relatively uniform size, as shown in Figs. 2(a) and 3(a). Thus, in the present invention, the nano metal particles 16 of which the pitch and size can be controlled can be prepared arbitrarily on the surface-treated conductive substrate 12. In contrast, if the electroplating reaction is carried out on a fairly flat metal surface, such as a highly flat copper surface prepared by a carbon plating technique, the surface roughness is relatively small, so that the metal ion 22 is reduced in the electroplating reaction. No "position selectivity" is carried out on the flat surface of copper metal, even stacked one by one. Thus, the prepared nano metal particles 16 cannot be implanted at a nanometer pitch, as shown in Fig. 2(b). 3(b) and Fig. 3(c). Figures 4(a) and 4(b) illustrate the effect of plating mode on nucleation and growth mechanism. Figure 4(a) illustrates the preparation of the present invention using a cyclic potential plating process. The nano metal particles 16 can selectively grow the nano metal particles 16 on the grain edges of the conductive substrate 12. In contrast, if the conductive substrate 12 having the same surface roughness distribution is used, different plating modes are used. (for example, using direct current for electromineral reaction) 'is easy to distribute the nucleation point unevenly, resulting in local aggregation of the metal. The electromotive force of the electroplating system is required due to the initiation of the electroplating reaction (potent) Ial) or the voltage reaches the reduction potential of the metal to be plated; however, the plating solution 20 contains different concentrations of species and the 200821404 species "mass transfer" also affects plating. Since the reaction proceeds, the electroplating system uses direct current and cannot effectively control the electric bond reaction (including the amount of deposition and position) occurring in the plating solution 20, so that it is easy to make the nucleation point unevenly distributed, resulting in local aggregation of the metal, such as Fig. 4(b) shows Fig. 5(a) to Fig. 6(b) illustrate the effect of the surface structure of the conductive substrate 12 on the nucleation and growth mechanism. Fig. 5(a) is a silver plating on a wafer ( The surface structure after Ag) has a fairly flat surface structure. Therefore, when the nickel plating reaction is performed, the reduction reaction of the metal ions 22 is hardly "position-selective" on the flat surface of the silver metal, as shown in Fig. 5(b). In particular, nickel metal is formed on the flat surface of silver metal even by layer-by-layer atomic stacking, so nickel metal cannot be implanted at nanometer spacing, as shown in Figure 3(b) and Figure 3(c). Figure 6(a) is splashed on a wafer The surface structure after gold (Au) can also be observed that the reduction uniformity of metal ions 22 is quite high, and the metal layer is almost formed by layer-by-layer atomic stacking, so that it cannot be formed at a distance of tens to hundreds of nanometers. The nano metal particles are shown in Fig. 6(b). Fig. 7 is an electron image diagram of the surface-treated dielectric substrate 12 of the present invention. The indium tin oxide (ITO) of the conductive substrate 12 has a surface roughness of a nanometer scale. Fig. 8(a) to Fig. 8(c) illustrate an electron image of the nano metal particles 16 prepared by the cyclic potential plating method of the present invention, the magnifications being 150 times, 10,000 times and 50,000 times, respectively. The present invention performs a cyclic potential plating method on the surface of the surface of the conductive substrate 12 (having a conductive region 14A/non-conductive region 14B), which is performed by performing a cycle of -0.6 to -1.0 volts for 200 cycles of nickel metal ion 22 reduction. By reaction, nickel nano metal particles 16 having a pitch distribution between 100 and 200 nm 114580.DOC -11 - 200821404 m and having a diameter of about 60 nm can be obtained. Fig. 9 (a) to Fig. 9 (c) illustrate an electron image of the nano metal particles 16 prepared by the cyclic potential plating method of the present invention, the magnifications thereof being 2,000 times, 10,000 times and 50,000 times, respectively. The present invention performs a cyclic potential plating method on the surface of the surface of the conductive substrate 12 (having the conductive region 14A/non-conductive region 14B), and performs a reduction reaction of the nickel metal ions 22 by performing a 500-turn period with a potential interval of -0.6 to -0.75 volts. Nickel nano metal particles 16 having a pitch of 500 to 1000 nm and a diameter of about 120 nm can be obtained. 8(a) to 9(c), the present invention uses the surface-treated conductive substrate 12 in combination with the plating mode control to obtain a pitch distribution and a diameter control window in the tens to Hundreds of nanometers of nano metal particles 16. Fig. 10 (a) to Fig. 10 (c) illustrate electronic images of carbon nanotubes prepared by the present invention, the magnifications being 200 times, 5,000 times and 100,000 times, respectively. In the present invention, the nano-particles 16 are formed on the conductive substrate 12 by cyclic potential plating using the conductive substrate 12 of FIG. Thereafter, a plasma enhanced chemical vapor deposition process was carried out using the nano metal particles 16 φ as a catalyst to prepare a carbon nanotube having an average diameter of about 30 nm, a uniform structure, and a straight shape. In particular, the reactive gas of the plasma enhanced chemical vapor deposition process may comprise acetylene and ammonia at a reaction pressure of about 1 to 10 torr. Figures 11(a) and 11(b) illustrate a light-emitting element 30 prepared in accordance with the present invention which is designed as a diode and can be used as a backlight or display. In the present invention, a plurality of spacers 24 are formed on the carbon nanotubes 18, and a fluorescent substrate 26 (including a transparent conductive substrate and a fluorescent substance) is formed on the spacers 24 to complete the light-emitting elements. 30. When a predetermined voltage (114580.DOC -12-200821404, for example, 350 volts) is applied between the conductive substrate 12 and the fluorescent substrate 26, the carbon nanotubes 18 on the conductive substrate 12 will emit electrons due to the tip discharge effect. The light-emitting material of the phosphor substrate 26 is bombarded to generate a light beam. As shown in FIG. 11(b), FIG. 12 illustrates the light-emitting element 40 prepared by the present invention, which adopts a tri-polar design. The present invention can form a dielectric block 32 and a conductive block 34 between the conductive substrate 12 and the spacer 24, thereby having three conductive ends (ie, the conductive region 34, the fluorescent substrate 26, and the conductive substrate 12). , as shown in Figure 12. The conventional nano metal particle array technology has the disadvantages of complicated process and high cost in production time. The invention provides a preparation technology of a nano metal particle 16 which is relatively straightforward, low-cost and has a large margin of size adjustment. It does not require complicated fabrication procedures and only needs to be surface-treated on the conductive substrate 12 (for example, using electricity). The slurry bombards the surface of the conductive substrate). It is claimed that the surface roughness of the surface-treated conductive substrate 12 varies with position on the nanometer scale, and the present invention further designs the potential value applied by the electroplating process near the standard reduction potential interval of the metal ion 22, thereby controlling the formation. Nuclear point. After the nucleation is generated, the number of turns of the electroplating process can be adjusted to control the growth size of the subsequent nano metal particles 16, so that the size-controlled nano metal particles can be arbitrarily disposed on the surface-treated conductive substrate 12. 16. In addition, if the conductive region 14A/non-conductive region 14b is previously formed on the conductive substrate 12 by using lithography, the present invention can produce a more diverse array of nano metal particle arrays. In addition, in order to avoid the shielding effect of field emission, the carbon nanotubes need to be separated by a predetermined distance (depending on the length of the carbon tube, the ratio of tube length to spacing is about 1:1 or 1:2 in the literature). Separate. In general, the polymer itself
114580.DOC -13- 200821404 組裝製作之間距難以超過100奈米，因而限縮其應用範圍。 相對地，本發明可將導電區域14A/非導電區域14β之間距設 计而調控奈米碳管之佈植間距在100奈米以下至數百奈米 之間’不會受限於場發射之屏蔽效應。 本發明之技術内容及技術特點已揭示如上，然而熟悉本 項技術之人士仍可能基於本發明之教示及揭示而作種種不 背離本發明精神之替換及修飾。因此，本發明之保護範圍 應不限於實施例所揭示者，而應包括各種不背離本發明之 替換及修飾，並為以下之申請專利範圍所涵蓋。 【圖式簡要說明】 圖1 (a)及圖1 (b)例示本發明之奈米金屬粒子之製備方法； 圖2(a)至3(c)例示表面粗糙度對成核及成長機制之影響； 圖4(a)及圖4(b)例示電鍍模式對成核及成長機制之影響； 圖5(a)至圖6(b)例示導電基板之表面結構對成核及成長 機制之影響； 圖7例示本發明之表面處理後之導電基板的表面電子影 像圖； 圖8(a)至圖8(c)例示本發明利用循環電位電鍍法製備之 奈米金屬粒子的電子影像圖； 圖9(a)至圖9(c)例示本發明利用循環電位電鍍法製備之 奈米金屬粒子的電子影像圖； 圖10(a)至圖l〇(c)例示本發明製備之奈米碳管的電子影 像圖； 圖11(a)及圖11(b)例示本發明製備之二極發光元件；以及 114580.DOC •14- 200821404 圖12例示本發明製備之三極發光元件。 【主要元件符號說明】 12 導電基板 14A 導電區域 14B 非導電區域 16 奈米金屬粒子 18 奈米碳管 20 電鍍液 22 金屬離子 24 間隔器 26 螢光基板 30 發光元件 40 發光元件 114580.DOC - 15 -114580.DOC -13- 200821404 The distance between assembly and production is difficult to exceed 100 nm, thus limiting its application range. In contrast, the present invention can design the conductive region 14A / non-conductive region 14β between the distance and regulate the spacing of the carbon nanotubes between 100 nanometers and hundreds of nanometers 'not limited by field emission Shielding effect. The technical contents and technical features of the present invention have been disclosed as above, and those skilled in the art can still make various substitutions and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be construed as being limited by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1(a) and FIG. 1(b) illustrate a method of preparing a nano metal particle of the present invention; FIGS. 2(a) to 3(c) illustrate surface roughness versus nucleation and growth mechanism. Figure 4 (a) and Figure 4 (b) illustrate the effect of plating mode on nucleation and growth mechanism; Figure 5 (a) to Figure 6 (b) illustrate the effect of surface structure of the conductive substrate on nucleation and growth mechanism Figure 7 is a view showing a surface electron image of the surface-treated conductive substrate of the present invention; Figures 8(a) to 8(c) are diagrams showing an electron image of the nano metal particles prepared by the cyclic potential plating method of the present invention; 9(a) to 9(c) illustrate an electron image of the nano metal particles prepared by the cyclic potential plating method of the present invention; FIGS. 10(a) to 10(c) illustrate the carbon nanotubes prepared by the present invention. FIG. 11(a) and FIG. 11(b) illustrate a bipolar light-emitting element prepared by the present invention; and 114580.DOC • 14-200821404 FIG. 12 illustrates a three-pole light-emitting element prepared by the present invention. [Main component symbol description] 12 Conductive substrate 14A Conductive region 14B Non-conductive region 16 Nano metal particles 18 Carbon nanotubes 20 Plating solution 22 Metal ions 24 Spacer 26 Fluorescent substrate 30 Light-emitting element 40 Light-emitting element 114580.DOC - 15 -