201038470 六、發明說明： 【發明所屬之技術領域】 本發明係關於在基板表面生成自組裝且高度均勻之碳簇 分子陣列之方法。特定言之，本發明係關於可作為場發射 器光電元件及咼溫、高功率、抗高溫或高頻率電子元件 之碳鎮分子陣列嵌入式基板的新穎製備方法。 【先前技術】 在1985年之前’對於碳元素的認識只有兩種為人們所 知’分別是二維結構的石墨及三維結構的鑽石。直到 Kroto與SmaUy等人在一項研究星際塵埃之物性的實驗中， 利用強力聚焦雷射產生攝氏一萬度高溫打在石墨上將之汽 化，企圖得到只含碳的直鏈分子，用以模擬星際間純碳分 子的聚合物。實驗結果發現，在常溫下有種新化合物的產 量特別高’結構相當穩定，直徑大小約為7丨A的三十二面 體；其中二十面為六邊形’十二面為五邊形且彼此不會連 接在一起，符合孤立五邊形定則（Isolated PentagQns Rule ;簡稱IPR)，而其六十個頂點上分別被六十個碳原子 所佔據。於是在1985年時，Kroto與Smally藉由美國建築師 Buck-minster Fuller所設計出的圓頂建築物的概念提出了 碳六十分子的結構有如足球結構，故將此破六十分子球之 命名為「Buckminster-fullerene」，簡稱為巴克球 (Buckyballs)或碳簇分子（Fullerenes ;故又稱富勒缚）。 此後’類似碳六十的純碳分子，例如碳七十或碳八十四 或由更多碳原子組成之碳簇分子，相繼被發現，形狀則為 137042.doc 201038470 橢圓形或長型。各類碳鎮分子形狀小至碳二十，最大可至 碳奈米管（carbon nanotubes ;簡稱CNT)或是碳一千五百。 目称已發現形狀最小且結構最穩定的碳簇分子是碳三十： 由六個五邊形及五個六邊形所構成。其中在中間的一個五 邊形被五個六邊形所環繞|，另夕卜五個外圍的五邊形則連 接著六邊形，外圍的五個五邊形且彼此不會連接在一起， 符合孤立五邊形定則。碳三十擁有十個未鍵結完成的共價 鍵，分別位於五個外圍的五邊形。如圖1所示，在碳三十 的未鍵結完成共價鍵上增加數個碳原子所形成之六邊形， 即可形成較碳三十稍大的碳四十分子，利用同樣的方式在 未鍵結完成的共價鍵上增加六邊形的數目，即可形成更大 的发藏分子如碳五十甚至是碳奈米管。 碳簇分子之通式為Cn(n為大於Μ的偶數）。一般而言，η <40稱為低碳簇分子，11>4〇為高碳簇分子，η>4〇〇則為 巨碳簇分子，例如奈米碳管。奈米碳管之結構為捲成管狀 〇 的石墨外加兩顆做為封蓋的半球狀碳簇分子。1991年曰本 NEC公司的飯島澄男（S. Ijinma)於研究碳簇分子時偶然發 現多層奈米碳管（multiwaH carb〇n nan〇tubes ;簡稱 mwcnts)。隨後又發現單層奈米碳管（singie waU以此⑽ nanotubes ;簡稱SWCNTs)e單層奈米碳管已知有以下三種 結構：（1)扶手椅型（armchair) ; (2)鑛齒型（zigzag);及（3) 螺旋型（helix)。依據石墨層的寬度與捲曲方向的不同，奈 米碳管可以表現出金屬、半金屬、半導體等不同特性。 高碳簇分子或巨碳簇分子具有非常特別的性質，諸如低 137042.doc 201038470 :又：：強度、高動性、可撓曲、高表面積、表面曲度 间熱導度、導電性特異等等，所以吸引許多研究工作 者專注於開發其可能的應用方式，例如複合材料、微電子 兀件、平面顯示器、無線通訊、燃料電池以及鐘離子電池 等等。以奈米碳管為例，由於其具有極優異的導電性能， 且具有幾乎接近理論極限之尖端表面積（尖端曲率半^愈 小，其局部電場愈集中），因此，奈米碳管係已知最好的 料射材料，它具有極低場發射電Μ，可傳輸極大電流密 纟’且電流極穩定，非常適合做為場發射顯示器之電 發肘器^ 奈米碳管場發射顯示器(Carbon Ν咖tube Field Mission Di_y ’·簡稱CNT_FED)不僅保留了傳統陰極射線管顯示 器的影像品質，並具有省電及體積薄小之優點，同時結合 奈米碳管的低導通電場、高發射電流密度、高穩定性等特 性’成為兼具低驅動電壓、高發光效率、無視角問題、省 〇 電的大尺寸、低成本…等優點的全新平面顯示器。 目别業界中主要使用以下兩種方式製作奈米碳管場發射 器：第一，以塗佈:¾•式將含有奈来冑管的導電漿料或者有 機粘結劑在基板上印刷成圖形，通過後續處理使得奈米碳 管能夠從漿料之埋藏中露出頭來成為發射體；以及第二， 以催化成長方式直接在基板上生長奈米碳管圖形。 第一種方法的製程成本較低而且易於做到大尺寸，但很 難控制奈米碳管陣列十每一根碳管的方向。催化成長法則 通f採用化學氣相沈積法（CVD)在半導體基板上生長出奈 137042.doc 201038470 米碳管陣列作為發射體。此方法包括先將陰極板蝕刻為孔 徑大小固定之坑洞，利用（：¥1)法將金屬催化劑（一般為金 屬鐵、鈷、鎳）細粒填入細孔中，在高溫裂解c2h2，如此 可以沿著孔洞長出排列整齊的奈米碳管，再配合由pr〇f.201038470 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of generating a self-assembled and highly uniform array of carbon cluster molecules on a substrate surface. In particular, the present invention relates to novel methods of fabricating carbon-based molecular array embedded substrates that can be used as field emitter optoelectronic components and for temperature, high power, high temperature or high frequency electronic components. [Prior Art] Prior to 1985, there were only two known carbon elements, which were two-dimensional graphite and three-dimensional diamonds. Until Kroto and SmaUy et al. in an experiment to study the physical properties of interstellar dust, using a powerful focused laser to generate a high temperature of 10,000 degrees Celsius to vaporize on graphite, in an attempt to obtain a linear molecule containing only carbon, to simulate A polymer of interstellar pure carbon molecules. The experimental results show that the yield of a new compound at room temperature is particularly high. The structure is quite stable, and the trihedron with a diameter of about 7丨A; the twenty faces are hexagonal and the twelve faces are pentagons. They are not connected to each other and conform to the Isolated PentagQns Rule (IPR), and their sixty vertices are occupied by sixty carbon atoms. So in 1985, Kroto and Smally proposed the structure of a carbon hexapole, such as a football structure, by the concept of a dome designed by American architect Buck-minster Fuller. "Buckminster-fullerene", referred to as Buckyballs or carbon cluster molecules (Fullerenes; also known as Fuller). Thereafter, a carbon-like molecule similar to carbon sixty, such as carbon seventy or eighty-four carbon or a carbon cluster molecule composed of more carbon atoms, was successively found to have a shape of 137042.doc 201038470 elliptical or long. The molecular shape of various types of carbon towns is as small as carbon 20, and the largest is carbon nanotubes (CNT) or carbon 1,500. It has been found that the carbon cluster molecule with the smallest shape and the most stable structure is carbon thirty: it consists of six pentagons and five hexagons. One of the pentagons in the middle is surrounded by five hexagons, and the other five pentagons are connected to the hexagons, and the five pentagons on the periphery are not connected to each other. Meet the rules of isolated pentagons. Carbon Thirty has ten co-bonds that are not keyed together and are located in five peripheral pentagons. As shown in Fig. 1, in the hexagonal form formed by adding a few carbon atoms to the unbonded covalent bond of carbon 30, a carbon tetraploid which is slightly larger than carbon 30 can be formed, in the same manner. By increasing the number of hexagons on the unbonded covalent bond, a larger generating molecule such as carbon fifty or even a carbon nanotube can be formed. The carbon cluster molecule has the general formula Cn (n is an even number greater than Μ). In general, η < 40 is referred to as a low carbon cluster molecule, 11 > 4 is a high carbon cluster molecule, and η > 4 is a macrocarbon cluster molecule such as a carbon nanotube. The structure of the carbon nanotubes is graphite rolled into a tubular shape plus two hemispherical carbon cluster molecules as caps. In 1991, S. Ijinma of NEC Corporation accidentally discovered multi-wafer carbon nanotubes (multiwH carb〇n nan〇tubes; mwcnts) when studying carbon cluster molecules. Subsequently, it was found that single-layer carbon nanotubes (singie waU) are known as the following three structures: (1) armchair (armchair); (2) ore-shaped type (zigzag); and (3) helix. Depending on the width of the graphite layer and the direction of the crimp, the carbon nanotubes can exhibit different properties such as metals, semi-metals, and semiconductors. High carbon cluster molecules or macrocarbon cluster molecules have very special properties, such as low 137042.doc 201038470: again: strength, high mobility, flexibility, high surface area, thermal conductivity between surface curvature, conductivity specific, etc. Etc., so many researchers are attracted to focus on developing possible applications, such as composites, microelectronics components, flat panel displays, wireless communications, fuel cells, and clock-ion batteries. Taking a carbon nanotube as an example, since it has excellent electrical conductivity and has a tip surface area close to the theoretical limit (the tip curvature is half and the local electric field is concentrated), the carbon nanotube system is known. The best material to be shot, it has a very low field emission, it can transmit a very large current, and the current is extremely stable. It is very suitable as an electric elbow for field emission display. ^ Nano carbon tube field emission display (Carbon Tube Field Mission Di_y '. CNT_FED for short, not only retains the image quality of the traditional cathode ray tube display, but also has the advantages of power saving and small volume, combined with the low conduction electric field and high emission current density of the carbon nanotubes. Features such as high stability have become new flat-panel displays that combine the advantages of low drive voltage, high luminous efficiency, no viewing angle, large size and low cost. In the industry, the following two methods are mainly used to make the carbon nanotube field emitter: First, the conductive paste or organic binder containing the Neil tube is printed on the substrate by coating: 3⁄4• By subsequent processing, the carbon nanotubes can be exposed from the burial of the slurry to become an emitter; and secondly, the carbon nanotube pattern can be directly grown on the substrate by catalytic growth. The first method has a low process cost and is easy to size, but it is difficult to control the orientation of each carbon tube of the carbon nanotube array. Catalytic growth rule The chemical vapor deposition (CVD) method was used to grow a naphthalene array on the semiconductor substrate as an emitter. The method comprises first etching the cathode plate into a pothole having a fixed pore size, and filling the fine particles of the metal catalyst (generally metal iron, cobalt, nickel) into the pores by the method of (:¥1), and c2h2 is cracked at a high temperature, It is possible to grow neatly arranged carbon nanotubes along the holes and cooperate with pr〇f.
Milne等學者發展的單一光罩與自對準技術，製作出高品 質的奈米碳管發射器。其缺陷是製程成本較高，且奈米碳 管末端通常發生彎曲、相互交織。為形成性能良好之發射 尖端，需對奈米碳管陣列進行後續處理，將奈米碳管陣列 之毛糙表面去除，形成整齊豎直之發射尖端，且採用該化 學氣相沈積方法在做成大面積高度均勻陰極發射體方面仍 存在一定困難。 因此，開發適合大尺寸面板、排列整齊而且成本低的碳 簇分子發射器製程仍是業界持續努力的方向。 【發明内容】 本發明之一目的為提供一種於基板表面生成自組裝且高 ❹度均勻之奴簇分子陣列的方法，其包括以下之步驟： (1) 提供一基板； (2) 在真空環境下將該基板加熱至約2〇〇t至約12〇〇 t ; (3) 提供一奴簇分子奈米粉末，並在該真空環境下藉 由物理氣相沈積法將該碳簇分子奈米粉末沈積在 該基板表面上’從而於該基板表面上形成自組裝 且高度均勻之碳簇分子陣列。 本發月之又一目的為提供一種由此製得之碳簇分子陣列 137042.doc 201038470 饮入式基板，其具有優異之場發射性能，可作為場發射器 用於任何場發射顯示器中。 本發明之再一目的為提供一種由此製得之碳簇分子陣列 嵌入式基板，其可替代習知碳化半導體材料，作為光電元 件及高溫、高功率、抗高溫或高頻率電子元件之用。 【實施方式】 本發明方法的步驟（1)在於提供一可供碳簇分子於其上 自组裝生成之基板。適合用於本發明之基板並無特殊限 制，包括，但不限於，鍺、矽、砷、鋁、硼、氮化矽、氧 化辞、氮化鎵、氮化硼、磷化鎵、砷化鎵、砷化銦、磷化 銦藍寶石、硫化鋅及硫化鑛。較佳係使用發（丨00)基板或 矽（111)基板。更佳係使用η型或p型矽（lu)基板。 本發明方法的步驟（2)在於在真空環境下將該基板加熱 至約200 C至約12〇〇乞，較佳約4〇〇。〇至約i〇〇〇°c之溫度， 更佳約700°c至約900°C之溫度。本文中「真空環境」乙詞 並無特殊定義，意指真空度約在1大氣壓以下，較佳lxl0-5Pa 、下更佳1 x 10 Pa以下之環境，此係此技術領域中具有 通常知識者所熟知。 本發明方法的步驟（3)包括在該真空環境下藉由物理氣 相沈^法使碳簇分子奈米粉末沈積在該基板表面上。不欲 又理順所限制，但咸信由於基板於真空環境下經預先加 :從而妷麩分子奈米粉末可藉此於基板表面自我組裝成 ,句勻之碳簇分子陣列。此處之「高度均勻碳蔡分子陣 列」，意指碳簇分子係高度均勻地分佈在基板上且大多數 137042.doc 201038470 垂直於基板表面緊密排列，再者，所形成之碳簇分子陣列 具有實質上一致之垂直高度。 ΟMilne and other scholars developed a single mask and self-alignment technology to produce high-quality carbon nanotube emitters. The drawback is that the process cost is high and the ends of the carbon nanotubes are usually bent and interwoven. In order to form a good performance emitter tip, the carbon nanotube array is subjected to subsequent treatment to remove the rough surface of the carbon nanotube array to form a neat vertical emission tip, and the chemical vapor deposition method is used to make the large There are still some difficulties in terms of a highly uniform cathode emitter. Therefore, the development of a carbon cluster molecular emitter process suitable for large-sized panels, neatly arranged, and low cost is still a continuing effort in the industry. SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for generating a self-assembled array of slave cluster molecules having a high degree of uniformity on a substrate surface, comprising the steps of: (1) providing a substrate; (2) in a vacuum environment The substrate is heated to about 2 〇〇t to about 12 〇〇t; (3) a slave cluster molecular nanopowder is provided, and the carbon cluster molecular nanometer is deposited by physical vapor deposition in the vacuum environment. A powder is deposited on the surface of the substrate to form a self-assembled and highly uniform array of carbon cluster molecules on the surface of the substrate. A further object of the present month is to provide an array of carbon cluster molecules thus produced. 137042.doc 201038470 Dish-in substrate, which has excellent field emission properties and can be used as a field emitter in any field emission display. It is still another object of the present invention to provide a carbon cluster molecular array embedded substrate thus produced which can be used as a photovoltaic element and as a high temperature, high power, high temperature resistant or high frequency electronic component in place of conventional carbonized semiconductor materials. [Embodiment] The step (1) of the method of the present invention consists in providing a substrate on which carbon cluster molecules can be self-assembled. The substrate suitable for use in the present invention is not particularly limited, and includes, but not limited to, ruthenium, osmium, arsenic, aluminum, boron, tantalum nitride, ruthenium oxide, gallium nitride, boron nitride, gallium phosphide, gallium arsenide. Indium arsenide, indium phosphite, sapphire, zinc sulfide and sulfide ore. Preferably, a hair (丨00) substrate or a ruthenium (111) substrate is used. More preferably, an n-type or p-type ruthenium (lu) substrate is used. Step (2) of the process of the invention consists in heating the substrate to a temperature of from about 200 C to about 12 Torr, preferably about 4 Torr, in a vacuum environment. The temperature is about i〇〇〇°c, more preferably about 700°C to about 900°C. The term "vacuum environment" is not specifically defined in this paper. It means that the vacuum is below 1 atmosphere, preferably lxl0-5Pa, and better below 1 x 10 Pa. This is a common knowledge in this technical field. Well known. The step (3) of the method of the present invention comprises depositing carbon cluster molecular nanopowder on the surface of the substrate by physical gas phase precipitation in the vacuum environment. If you do not want to straighten out the limitations, but because the substrate is pre-applied in a vacuum environment: the bran molecular nano-nano powder can be self-assembled on the surface of the substrate to form an array of carbon cluster molecules. Here, the "highly uniform carbon-clay molecular array" means that the carbon cluster molecules are highly uniformly distributed on the substrate and most of the 137042.doc 201038470 is closely arranged perpendicular to the substrate surface, and further, the formed carbon cluster molecular array has A substantially uniform vertical height. Ο
適合用於本發明之物理氣相沈積法包括，但不限於，蒸 鍍法、分子束磊晶法及濺鍍法。根據本發明之一實施態 樣’碳鎮分子奈米粉末係藉由蒸鍍方式在真空環境下加熱 蒸發為氣體從而沈積在該基板表面上。蒸鍍操作溫度介於 約200°C至約1200。(：之間，其與碳簇分子的種類有關。原 則上碳原子數目越高蒸鍍操作溫度也隨之增高。以碳八十 四為例，蒸鍍操作溫度介於約55〇1至約75(rc之間。若使 用奴一百二十作為碳簇分子來源，蒸鍍操作溫度則介於約 6〇〇°C至約90(TC之間。若使用碳三百作為碳簇分子來源， 蒸鍍操作溫度則介於約70(rc至約u〇〇t之間。根據本發 明之另一實施態樣，碳簇分子奈米粉末亦可藉由分子束磊 晶法方式在真空環境下沈積在基板表面上。此外，亦可將 碳鎮分子奈米粉末壓縮成靶材，再以濺鍍法在真空環境下 使碳簇分子沈積在基板表面上。 、根據本發明之一實施態樣，在㈣⑴與㈣⑺之間可 視情況包含一預清潔基板之步驟。該預清潔步驟包含以溶 劑清洗基板表面，隨後在真空環境下加熱該基板以去除其 板表面氧化層及雜質。適合用於預清潔㈣之溶劑種類二 此技術領域中具有通常技藝者所熟知者，包括，但不限 於，去離子水、酮類、醇類、酸類、鹼類及其組合。 用於本發明之碳簇分子奈米粉末係商業上可講得者。各 種此技術領域中具有通常知識者所熟知之碳蔟分子皆可用 137042.doc 201038470 7發明方法中’⑼而於基板上形成自組裝且高度均句之 15歹/適之碳竊分子包括，但不限於，冑二十、碳二十 四、碳三十六、碳四十、碳四十二、碳四十八'碳五十、 碳五十五、碳六十、碳六十二、碳六十四、碳六十八、碳 七十、碳七十二、碳七十六、碳七十八、碳八十、碳八十 :、碳八十四、碳九十、碳九十四、碳九十六、碳—百、Physical vapor deposition methods suitable for use in the present invention include, but are not limited to, evaporation, molecular beam epitaxy, and sputtering. According to one embodiment of the present invention, the carbon-carbon molecular nano-powder is deposited on the surface of the substrate by evaporation in a vacuum atmosphere by evaporation to a gas. The evaporation operating temperature is between about 200 ° C and about 1200. (: Between, it is related to the type of carbon cluster molecules. In principle, the higher the number of carbon atoms, the higher the vapor deposition operation temperature. Taking carbon eighty-four as an example, the evaporation operation temperature is between about 55 〇 1 and about 75 (between rc. If slaves are used as a source of carbon cluster molecules, the evaporation operation temperature is between about 6 ° C and about 90 (TC). If carbon is used as a carbon cluster molecular source The evaporation operation temperature is between about 70 (rc and about u〇〇t. According to another embodiment of the present invention, the carbon cluster molecular nano powder can also be in a vacuum environment by molecular beam epitaxy. Deposited on the surface of the substrate. Further, the carbon-based molecular nano-powder powder may be compressed into a target, and the carbon cluster molecules are deposited on the surface of the substrate in a vacuum environment by sputtering. According to an embodiment of the present invention For example, a step of pre-cleaning the substrate may be included between (4) (1) and (4) (7). The pre-cleaning step comprises washing the surface of the substrate with a solvent, and then heating the substrate in a vacuum environment to remove oxides and impurities on the surface of the plate. Pre-cleaning (4) solvent type II Those skilled in the art are familiar with, including, but not limited to, deionized water, ketones, alcohols, acids, bases, and combinations thereof. The carbon cluster molecular nanopowders used in the present invention are commercially available. Any of the carbon 蔟 molecules well known to those of ordinary skill in the art can be used in the method of 137042.doc 201038470 7 '(9) and form a self-assembled and highly uniform sentence on the substrate. , but not limited to, 胄20, carbon twenty-four, carbon thirty-six, carbon forty, carbon forty-two, carbon forty eight 'carbon fifty, carbon fifty five, carbon sixty, carbon sixty two, carbon Sixty-four, carbon sixty eight, carbon seventy, carbon seventy two, carbon seventy six, carbon seventy eight, carbon eighty, carbon eighty: carbon eighty, carbon ninety, carbon ninety four , carbon ninety-six, carbon-hundred,
Ο =百零-、碳-百二十、碳一百四十、碳三百、單壁夺 求碳管、雙壁奈米碳管及多壁奈米碳管。 ’、 :月方法不僅製程簡單、成本低，且由於碳竊分子陣 列复兩度均句分佈，由此製得之結構發射效率高且起始電 1非$適合用於場發射顯示器中作為場發射器。再 者：由於碳簇分子於基板上緊密排列，所形成之結構也不 易受到氫、氧及氮（包含彼等元素之原子態、離子態或分 子態及其化合物）的侵敍。 另方面，當使用半導體材料作為基板時，根據本發明 方法所形成之錢分子陣職人式基板也非常適合作為習 知碳化半導體材料之替代物。 碳化半導體材料是新_代最重要的半導體材料之一，其 擁有許多優異的物理及化學性質，例如寬能帶、高功率、 抗高溫及高頻率等性質。以碳化矽為例，由於其擁有許多 優異的物理及化學性質，在各種領域上都有.著絕佳的應 用。在力學性質方面，由於其硬度極高（摩氏硬度9.0)，僅 次於鑽石(1〇.〇)，遠大於矽(7.〇)及砷化鎵(〜5.0-5.5)，故可 應用於複σ材料之強化材料、研磨材料、切削卫具、幫浦 137042.doc 201038470 内襯及纖維補強材料等。在熱學性質方面，由於碳化矽具 有在室溫下其具有高熱導率（3〜5 W/cm.K)，高於矽（1.5 W/cm.K)及砷化鎵（0.5 W/cm.K)，且其高熔點（2830°C)的特 性，遠高於矽（1420°C)及砷化鎵（1240°C)，可承受較高的 操作溫度，耐熱震（thermal shock resistance)、抗高溫氧 化，因此可應用於飛機及汽車引擎感測器、喷射引擎點火 裝置及渦輪引擎葉片等。 碳化矽在電學性質方面，其具有寬能帶（1.8-3.0 eV)的特 〇 性，大於矽（1.12 eV)及砷化鎵（1.42 eV)，可阻抗電子穿 透，適合作為光激發二極體（Light Emitting Diode，LED) 的發光材料[3]。此外，其高飽和電子漂移率（high saturation drift velocity)之特性也促使碳化石夕激發出短波 長的光，適合用作藍光光激發二極體（blue LED)、近太陽 盲光紫外光探測器（nearly solar blind UV photodetectors)、 高頻電源供應器及相控陣列雷達系統（phased array radar system)。碳化石夕具有高崩潰電場（2.2~4 x 106V/cm)，遠高 ❹Ο = 100--, carbon-120, carbon one hundred and forty, carbon three hundred, single-walled carbon tube, double-walled carbon nanotube and multi-walled carbon tube. ', : The monthly method is not only simple in process, low in cost, but also due to the multiple distribution of carbon-splitting molecular arrays, the resulting structure has high emission efficiency and the initial electricity is not suitable for use in field emission displays as a field. launcher. Furthermore, since the carbon cluster molecules are closely arranged on the substrate, the formed structure is not susceptible to the intrusion of hydrogen, oxygen and nitrogen (including atomic, ionic or molecular states of their elements and their compounds). On the other hand, when a semiconductor material is used as the substrate, the molecular matrix substrate formed by the method of the present invention is also very suitable as a substitute for the conventional carbonized semiconductor material. Carbonized semiconductor materials are one of the most important semiconductor materials in the new generation. They have many excellent physical and chemical properties, such as wide band, high power, high temperature resistance and high frequency. Taking strontium carbide as an example, it has excellent applications in various fields due to its many excellent physical and chemical properties. In terms of mechanical properties, due to its extremely high hardness (Mohs hardness 9.0), it is second only to diamond (1〇.〇), much larger than 矽(7.〇) and gallium arsenide (~5.0-5.5), so it can be applied. Reinforcement materials, abrasive materials, cutting aids, and spurs 137042.doc 201038470 linings and fiber reinforcement materials. In terms of thermal properties, tantalum carbide has a high thermal conductivity (3~5 W/cm.K) at room temperature, higher than 矽 (1.5 W/cm.K) and gallium arsenide (0.5 W/cm. K), and its high melting point (2830 ° C) characteristics, much higher than 矽 (1420 ° C) and gallium arsenide (1240 ° C), can withstand higher operating temperatures, thermal shock resistance, High temperature oxidation resistance, so it can be applied to aircraft and car engine sensors, jet engine ignition devices and turbine engine blades. In terms of electrical properties, niobium carbide has a characteristic of wide band (1.8-3.0 eV), larger than 矽 (1.12 eV) and gallium arsenide (1.42 eV), and can be impedance electron penetration, suitable as a photoexcited dipole. Light Emitting Diode (LED) luminescent material [3]. In addition, its high saturation drift velocity characteristics also promote the carbonization of short-wavelength light, suitable for use as a blue light-emitting diode (blue LED), near-sun blind ultraviolet detector (nearly solar blind UV photodetectors), high frequency power supply and phased array radar system. Carbonized fossils have a high collapse electric field (2.2~4 x 106V/cm), which is much higher.
於矽（2.5 X 105V/cm)及砷化鎵（3x 105V/cm)，可應用在高組 裝密度（high device packing density)的積體電路上。此 外，碳化矽並具有高功率、高介電常數等特性，可提高轉 換功率並降低能量耗損，可應用於蕭基特二極體（Schottky diodes)、金氧半場效電晶體（Metal-Oxide-Semiconductor Field-Effect Transistor，MOSFET)、高頻MESFET元件、接 面場效電晶體（Junction Field Effect Transistor，JFET)、雙 載子接面電晶體（Bipolar Junction Transistor, BJT)、PiN 137042.doc 201038470 dl〇deS、絕緣栅雙極電晶體（Insulated Gate Bipolar Transistor，IGBT)、高功率及高壓整流器及太陽能電池之 /專膜’在光電元件及高溫電子元件的應用上極具發展潛 力。 然而，習知碳化半導體材料不僅製備過程繁複，且基材 表面上的缺陷（defect)過多導致電阻過大且熱導性不佳， 以致於製造出的元件（device)效能不佳。 根據本發明方法所形成之碳箱分子陣列嵌人式基板不僅 具有習知碳化半導體材料之優點（例如，高能帶隙 (bandgap)及高崩潰電場（breakd〇wn v〇itage))，且同時可避 免習知碳化半導體生成物之孔洞效應，非常適合作為習知 碳化半導體材料之替代物，作為光電元件及高溫、高功 率、抗高溫或高頻率電子元件之用。 以下實施例係用於對本發明作進_步說明，唯非用以限 制本發明之範圍。任何此技術技藝中具有通常知識者可輕 ^ ㈣成之修飾及改變均包括於本案說明㈣示内容及所附 申諳專利範圍之範圍内。 實施例 (1) 提供一 η型矽（111)基板。 (2) 將該石夕基板依序置於去離子水、丙嗣及甲醇溶液 中以超音波震洗。 (3) 在超高真空腔體（〜lxl0-8pa)内將該矽基板緩慢加教 至约_。(：，並在此溫度停留6〜12小時。隨後將該石夕基板 緩慢加熱至約⑵代’㈣Π)秒〜5分鐘後再降溫至室溫， 137042.doc 201038470 整個過程都在超高 以去除表面的氧化層及不乾淨的物質 真空腔體中進行。 ()在超鬲真工腔體内將該石夕基板緩慢加熱至約7〇〇。匸 至約900 C，並使基板維持在此溫度。 ⑴在超高真空腔體内將純度98%的市售碳八十四夺米 粉末⑷dHch Chem· c〇 )，利用熱蒸鑛搶（vac^d Miniature LCell)加熱至約55〇。(：至約75(Γ(：。隨後，在距 Ο Ο 離該矽基板4〜10公分處，於1〜4〇分鐘内將碳八十四奈米粉 末f直地熱蒸鍍在該⑪基板表面上，使礙人十四在該石夕基 板表面上自我組裝，形成高度均勻之陣列，如圖2所示。 測試方法及結果 (1) 分佈均勻性評估 使用掃描穿隧顯微鏡（STM)對上述實例中製得之碳八 十四陣列進行三維分析，結果如圖2至5所示。stm 照片顯示碳八十四係高度均勻地分佈在矽基板上。 再者’剖面分析圖亦顯示大多數碳八十四係垂直於 石夕基板表面緊密排列，且所形成之碳八十四陣列具 有實質上一致之垂直高度。 此外’由於碳八十四於矽基板上緊密排列，所形成 之碳化矽基板也不易受到氫、氧及氮（包含彼等元素 之原子態、離子態或分子態及其化合物）的侵蝕。 (2) 發射特性評估 起始電壓 使用STM針對上述實例中製得之碳八十四陣列量測工_ 137042.doc 10· 201038470 _所示曲線係針對白色 起始電壓僅約I.36V左 V曲線，結果如圓6所示，圖 X點之量測值。由圈6可知， 右。 場發射效率Yu Yu (2.5 X 105V/cm) and gallium arsenide (3x 105V/cm) can be applied to integrated circuits with high device packing density. In addition, tantalum carbide has high power, high dielectric constant and other characteristics, which can improve conversion power and reduce energy consumption. It can be applied to Schottky diodes and metal oxide half field effect transistors (Metal-Oxide- Semiconductor Field-Effect Transistor (MOSFET), high frequency MESFET component, Junction Field Effect Transistor (JFET), Bipolar Junction Transistor (BJT), PiN 137042.doc 201038470 dl 〇deS, Insulated Gate Bipolar Transistor (IGBT), high power and high voltage rectifiers and solar cell/special film have great potential for the application of optoelectronic components and high temperature electronic components. However, conventional carbonized semiconductor materials are not only complicated in the preparation process, but also have too many defects on the surface of the substrate to cause excessive resistance and poor thermal conductivity, so that the manufactured device is not effective. The carbon nanotube molecular array embedded substrate formed by the method of the present invention not only has the advantages of the conventional carbonized semiconductor material (for example, a high energy bandgap and a high breakdown electric field), and at the same time Avoiding the hole effect of conventional carbonized semiconductor products, it is very suitable as a substitute for conventional carbonized semiconductor materials, as a photovoltaic element and high temperature, high power, high temperature resistant or high frequency electronic components. The following examples are intended to be illustrative of the invention and are not intended to limit the scope of the invention. Modifications and alterations of any skill in the art may be included in the scope of the description (4) of the present invention and the scope of the appended claims. Embodiment (1) An n-type germanium (111) substrate is provided. (2) The Shishi substrate was sequentially placed in deionized water, propionate and methanol solution for ultrasonic washing. (3) Slowly teach the crucible substrate to approximately _ in the ultra-high vacuum chamber (~lxl0-8pa). (:, and stay at this temperature for 6 to 12 hours. Then slowly heat the Shishi substrate to about (2) generation '(four) Π) seconds to 5 minutes and then cool to room temperature, 137042.doc 201038470 The whole process is super high Removal of the surface oxide layer and the dirty material in the vacuum chamber. () Slowly heat the Shishi substrate to about 7 在 in a super-real working chamber.匸 to about 900 C and maintain the substrate at this temperature. (1) Commercially available carbon eighty-four ounces of rice powder (4) dHch Chem·c〇) having a purity of 98% in an ultra-high vacuum chamber, and heated to about 55 Torr by a hot steam blast (vac^d Miniature LCell). (: to about 75 (Γ.: Then, at a distance of 4 to 10 cm from the substrate of the crucible, the carbon eighty-nano-nano powder f is directly vapor-deposited on the 11 substrate in 1 to 4 minutes. On the surface, the fourteen people are self-assembled on the surface of the stone substrate to form a highly uniform array, as shown in Fig. 2. Test methods and results (1) Distribution uniformity evaluation using scanning tunneling microscope (STM) The eighty-fourth carbon array prepared in the above example was analyzed in three dimensions, and the results are shown in Figures 2 to 5. The stm photo shows that the carbon eighty-four series is highly evenly distributed on the ruthenium substrate. Most of the carbon eighty-four series are closely arranged perpendicular to the surface of the stone substrate, and the formed eighty-four carbon arrays have substantially uniform vertical heights. Further, the carbonization is formed because the carbon eighty-four is closely arranged on the substrate. The tantalum substrate is also less susceptible to attack by hydrogen, oxygen and nitrogen (including atomic, ionic or molecular states of their elements and their compounds). (2) Emission characteristics evaluation starting voltage using STM for the carbon produced in the above examples Eighty-four array measurement _ 137042.doc 10· 201038470 _ The curve shown is for the white starting voltage only about I.36V left V curve, the result is shown as circle 6, the measured value of the point X. It can be seen from circle 6, right. Field emission efficiency
根據場發射量子理論，埋1 I 卞_仵知在未外加電場的情形According to the field emission quantum theory, the buried 1 I 卞 _ knows that there is no applied electric field
下’導體内的電子必須具備足夠的能量，才有機會 越過位能障到達另—端的真空側，但是當此能量障 礙所延伸的空間範圍很窄時，若加上-微小電場使 :寻能障的形狀改變，那麼便可驅使部分電子穿越過 月障而出現在能量障礙的另一端。由於電場的強弱 直接影響場發射的電流大小，當增加元件的操作電 壓會造成電場增加，此時電子所需穿透的位能障會 減少，故所得到的電流則會增強，但這不符合業界 所希望的低壓操作。故若能製作一物體呈尖端狀， 則在尖端處有較高的電場，則可獲得較低的啟動電 場（E〇n)與較高的啟動電流密度（Jon)。根據Fowler- N〇rdheim理論將電場與電流密度做ln(J/E2)對1/E之 圖（即為F-N plot) ’若是場發射電流其應是成直線關 係’此可作為判斷是否為場發射電子的依據，此外 藉由计算場增強因子泠（Field Enhancement factor)可 付知其場發射效率之優劣。 由圖7至12之電流密度對電場的特性圖及場發射的F_ N特性圖可知，本發明實施例所製得之碳八十四陣列 具有相當優異的場發射效率。 137042.doc •11 · 201038470 (3) 能帶隙評估 將所測量的測電流與電壓牲 电铿特性圖轉換成圖13所示之 dl/dV特性圖，可測量复能 里/、此帶隙約為3.09eV。由此可 知本發明實施例所製得 衣仔之奴八十四陣列確實具有相 當優異的寬能帶隙特性。 (4) 崩潰電場評估 Ο 〇 在真空下場發射將所測量的測電流與電壓㈣圖轉 換成圖/所示之F_N特性圖，可測量其崩潰電場約為 4.1X106 V/cm。由此可知本發明實施例所製得之碳八 十四陣列確實具有相當優異的高崩潰電場特性。 衣表明方法不僅製程簡單、成本低，且經由實驗數據證 明’所製得之碳鎮分子陣列呈高度均勻分佈，具有良好的 發射特性及小的起始電塵、能帶隙（bandgap)高、崩潰電場 (breakdown v〇hage)高、又可避免碳化半導體生成物之孔 ㈣應常適合用於場發射顯示器中作為場發射器之用 或作為省知碳化半導體材料之替代物。相信本發明方法對 於場發射顯示器及碳化半導體材料應用領域必能有重大 改良與突破。 、 雖然本發明已以較佳實施例揭露如上，然其並非用以限 j本發明，任何熟習此技藝者，在不脫離本發明之精神與 範圍内，當可作些許之更動與潤飾，因此本發明之保護範 圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1為碳簇分子增長示意圖。 137042.doc • 12- 201038470 圖2及3為本發明實施例所製得之碳八十四陣列的掃描穿 隧顚微鏡（STM)所攝得之照片（40x4W)及其剖面分析圖。 圖4為本發明實施例所製得之碳八十四陣列的㈣照片 (20x20nm2)及其剖面分析圖。 圖5為本發明實施例所製得之碳八十四陣列的π%照片 (12.5xl2.5nm2)及其剖面分析圖。 圖6為在真空下以STM測量本發明實施例所製得之碳八 十四陣列所獲得之電流對電壓的特性圖。 圖7為在真空下以STM測量本發明實施例所製得之碳八 十四陣列其場發射的電流密度對電場的特性圖。其啟動電 抓密度與啟動電場分別為丨〇〇 gA/cm2&丨422 。 圖8為在真空下以STM測量本發明實施例所製得之碳八 十四陣列其場發射的F_N特性圖，其場增強因子β約為 51.9，崩潰電場約為41xl〇6v/cm。 圓9為在一大氣壓下以原子力顯微鏡（AFM)測量本發明 實施例所製得之碳八十四陣列其場發射的電流密度對電場 的待性圖。其啟動電流密度與啟動電場分別為⑽μΑΑ^2 及 8035ν/μηι » 圖10為在一大氣壓下以量本發明實施例所製得之 碳八十四陣列其場發射的F_N特性圖。其場增強因子β約為 4.4。 圖11在一大氣壓下測量本發明實施例所製得之碳八十四 陣列其場發射的電流密度對電場的特性圖。其啟動電流密 度與啟動電場分別為1 μΑ/cm2及1 · 12V/μιη » 137042.doc 201038470 圖為在一大氣壓下測量本發明實施例所製得之碳八十 四陣列其場發射的F_N特性圖。其場增強因子p約為 4.3xl〇3。 十四陣列所择；^ > dTHV Μ &例所製得之碳八 汁獲侍之dldV的特性圖 3.09eV。 里其忐帶隙約為 〇The electrons in the lower conductor must have enough energy to have the opportunity to cross the potential barrier to reach the vacuum side of the other end, but when the energy barrier extends a narrow range of space, if a small electric field is added: The shape of the barrier changes, so that some electrons can be driven through the moon barrier and appear at the other end of the energy barrier. Since the strength of the electric field directly affects the current of the field emission, when the operating voltage of the component is increased, the electric field is increased. At this time, the potential energy barrier required for the electron is reduced, so the current obtained is increased, but this does not match. Low pressure operation desired by the industry. Therefore, if an object can be made to have a tip shape, a higher electric field at the tip end can obtain a lower starting electric field (E〇n) and a higher starting current density (Jon). According to Fowler-N〇rdheim theory, the electric field and current density are plotted as ln(J/E2) versus 1/E (that is, FN plot) 'If the field emission current should be in a straight line relationship', this can be used as a judgement The basis for the emission of electrons, in addition to the field enhancement factor (Field Enhancement factor) can be known for its field emission efficiency. From the characteristics of the current density versus electric field of Figs. 7 to 12 and the F_N characteristic map of the field emission, it is known that the eighty-four array of carbon produced by the embodiment of the present invention has quite excellent field emission efficiency. 137042.doc •11 · 201038470 (3) Bandgap evaluation converts the measured current and voltage characteristics into the dl/dV characteristic diagram shown in Figure 13, which can measure the complex energy and/or the band gap. It is about 3.09 eV. Thus, it can be seen that the eighty-four array of slaves made in the embodiment of the present invention does have a relatively excellent wide band gap characteristic. (4) Crash electric field evaluation Ο 〇 In the vacuum field emission, the measured current and voltage (4) map is converted into the F_N characteristic diagram shown in Fig. / The measured collapse electric field is about 4.1X106 V/cm. From this, it is understood that the carbon eighty-four arrays obtained in the examples of the present invention do have quite excellent high breakdown electric field characteristics. The coating shows that the method is not only simple in process, low in cost, but also proves through experiments that 'the carbon array of the obtained carbon is highly uniformly distributed, has good emission characteristics, and has small initial dust and high bandgap. Holes with high breakdown electric field (HW) and avoidance of carbonized semiconductor products (4) should be suitable for use as field emitters in field emission displays or as a substitute for known carbonized semiconductor materials. It is believed that the method of the present invention is capable of significant improvements and breakthroughs in the field of application of field emission displays and carbonized semiconductor materials. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. [Simple description of the diagram] Figure 1 is a schematic diagram of the molecular growth of carbon clusters. 137042.doc • 12- 201038470 FIGS. 2 and 3 are photographs (40×4 W) taken from a scanning tunneling micromirror (STM) of an eighty-four array of carbon obtained in an embodiment of the present invention, and a cross-sectional analysis diagram thereof. 4 is a (four) photograph (20×20 nm 2 ) of a carbon eight-four array prepared according to an embodiment of the present invention and a cross-sectional analysis diagram thereof. Fig. 5 is a π% photograph (12.5xl2.5nm2) of a carbon eighty-four array prepared according to an embodiment of the present invention and a cross-sectional analysis diagram thereof. Fig. 6 is a graph showing the current versus voltage obtained by measuring the carbon eighty-four arrays obtained in the examples of the present invention by STM under vacuum. Fig. 7 is a graph showing the characteristics of the current density versus electric field of the field emission of the carbon eighty-four array obtained by the embodiment of the present invention under vacuum under STM. The starting electric catching density and the starting electric field are 丨〇〇 gA/cm2 & 422, respectively. Fig. 8 is a F_N characteristic diagram of the field emission of the carbon eighty-four array obtained by the embodiment of the present invention under vacuum, with a field enhancement factor β of about 51.9 and a collapse electric field of about 41 x 1 〇 6 v/cm. Circle 9 is a graph of the current density versus electric field of the field emission of the eighty-four array of carbons produced by the atomic force microscope (AFM) at atmospheric pressure in an embodiment of the present invention. The starting current density and the starting electric field are (10) μΑΑ^2 and 8035ν/μηι, respectively. Fig. 10 is a F_N characteristic diagram of the field emission of the carbon eighty-four array obtained by the embodiment of the present invention under atmospheric pressure. Its field enhancement factor β is about 4.4. Fig. 11 is a graph showing the measurement of the current density versus electric field of the field emission of the eighty-four array of carbon obtained in the embodiment of the present invention under atmospheric pressure. The starting current density and the starting electric field are 1 μΑ/cm 2 and 1 · 12 V/μηη respectively. 137042.doc 201038470 The figure shows the F_N characteristics of the field emission of the eighty-four array of carbon obtained by the embodiment of the present invention under atmospheric pressure. Figure. Its field enhancement factor p is approximately 4.3xl〇3. The fourteen arrays are selected; ^ > dTHV Μ & example of the carbon octopus obtained dldV characteristic map 3.09eV. The gap between the Liqi and the 约为 is about 〇
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