TWI504555B - A method for coating a nanosheet structure network on a substrate and the application thereof - Google Patents
A method for coating a nanosheet structure network on a substrate and the application thereof Download PDFInfo
- Publication number
- TWI504555B TWI504555B TW103124988A TW103124988A TWI504555B TW I504555 B TWI504555 B TW I504555B TW 103124988 A TW103124988 A TW 103124988A TW 103124988 A TW103124988 A TW 103124988A TW I504555 B TWI504555 B TW I504555B
- Authority
- TW
- Taiwan
- Prior art keywords
- substrate
- temperature furnace
- high temperature
- compound
- network
- Prior art date
Links
Description
本發明係關於一種形成一奈米片狀結構網絡在一基材上的製備方法，特別係關於一種藉由氣相沉積程序形成該奈米片狀結構網絡在該基材上的方法和一表面具有一奈米片狀結構網絡的基材的應用。該奈米片狀結構網絡和基材之間具有鍵結強度高的碳化物共價鍵結。其次，該奈米片狀結構網絡是一類石墨烯奈米片狀結構網絡，所以具有很好的抗腐蝕性、低摩擦係數、良好的熱導和電導性質以及光學性質。再者，該具有奈米片狀結構網絡之基材的性質可藉由改變氣相沉積程序所使用的氣相組成來調控，藉此而達到應用該基材在各種產業的目的。 The present invention relates to a method for preparing a nano-sheet structure network on a substrate, and more particularly to a method and a surface for forming the nano-sheet structure network on the substrate by a vapor deposition process Application of a substrate having a nano-sheet structure network. The nanosheet structure network and the substrate have a carbide bond with high bonding strength. Secondly, the nano-sheet structure network is a kind of graphene nano-sheet structure network, so it has good corrosion resistance, low friction coefficient, good thermal and electrical conductivity properties and optical properties. Furthermore, the properties of the substrate having a nano-sheet structure network can be controlled by changing the gas phase composition used in the vapor deposition process, thereby achieving the object of applying the substrate in various industries.
碳元素的同素異形體(allotropes)包括富勒烯、奈米碳管、石墨烯、石墨和鑽石，其中石墨烯因具有獨特的二維 結構而特別受到研究人員的重視。石墨烯是由碳原子所排列組成形狀為六角型且厚度為一個原子的奈米片狀結構，由於此獨特的二維結構導致石墨烯具有優秀的電導性(8 x 105S/m)、高導熱性質(about 5300W m-1 K-1)、優異的機械強度(tensile strength of 130GPa and Young’s modulus of 1 TPa)、低摩擦係數和良好的防蝕性質。 Allotropes of carbon include fullerenes, carbon nanotubes, graphene, graphite and diamonds, of which graphene is particularly valued by researchers because of its unique two-dimensional structure. Graphene is a nano-sheet structure composed of carbon atoms and having a hexagonal shape and a thickness of one atom. Due to this unique two-dimensional structure, graphene has excellent electrical conductivity (8 x 10 5 S/m). High thermal conductivity (about 5300W m -1 K -1 ), tensile strength of 130GPa and Young's modulus of 1 TPa, low coefficient of friction and good corrosion resistance.
一般以習知技術製備石墨烯是以石墨為原料，依序經過氧化插層，撥離和還原程序而得到石墨烯。在高分子材料中常常藉由添加石墨烯來進行高分子材料的改質。然而，對於陶瓷、玻璃、金屬和半導體材料而言，由於上述陶瓷等材料的操作溫度通常大於400℃，但是石墨烯在400℃以上的高溫時穩定性差，結構容易被破壞，因此在實際產業應用上，採用添加石墨烯的方式來進行陶瓷、玻璃、金屬和半導體材料等的改質並無法獲得預期的效果。 Graphene is generally prepared by a conventional technique using graphite as a raw material, followed by oxidation intercalation, dialing and reduction procedures to obtain graphene. In polymer materials, the modification of polymer materials is often carried out by adding graphene. However, for ceramics, glass, metals, and semiconductor materials, since the operating temperature of materials such as ceramics described above is usually greater than 400 ° C, graphene has poor stability at high temperatures above 400 ° C, and the structure is easily destroyed, so that it is practically applied in industry. In addition, the modification of ceramics, glass, metal, and semiconductor materials by means of adding graphene does not achieve the desired effect.
另一方面，雖可借由接著的方式將石墨烯塗佈固定在陶瓷、玻璃、金屬和半導體材料的表面，但是石墨烯表面是非常惰性的，所以石墨烯層很容易從上述陶瓷材料的表面剝離。且用於塗佈固定的接著劑通常不耐高溫。同時接著劑亦會降低改變石墨烯原有的優異性質。因此，此種方式並不適用於陶瓷、玻璃、金屬和半導體材料。 On the other hand, although graphene can be coated and fixed on the surface of ceramics, glass, metal and semiconductor materials by a subsequent method, the graphene surface is very inert, so the graphene layer is easily surfaced from the above ceramic material. Stripped. And the adhesive used for coating and fixing is generally not resistant to high temperatures. At the same time, the adhesive also reduces the original properties of the graphene. Therefore, this approach is not applicable to ceramic, glass, metal and semiconductor materials.
Yuegang Zhang等人在Nano Lett.2010,10,1542-1548揭露了一種將石墨烯沉積在介電材料上的方法；該方法是在介電材料的表面預先沉積一由銅元素所組成的薄膜，其次再借由氣相沉積法將石墨烯的結構形成於上述由銅元素所組成的薄膜之上，最後移除該薄膜而得到一表面具有石墨烯結構的介電材料。由此方法所得到的石墨烯結構和介電材料之間沒有共價鍵結的存在。因此，其高溫的穩定性差，且製造方法繁瑣，無法於材料表面上直接形成一石墨烯片狀結構。 Yuegang Zhang et al. , in Nano Lett. 2010, 10 , 1542-1548, discloses a method of depositing graphene on a dielectric material by pre-depositing a film of copper element on the surface of the dielectric material. Next, the structure of the graphene is formed on the film composed of the copper element by a vapor deposition method, and finally the film is removed to obtain a dielectric material having a graphene structure on the surface. There is no covalent bonding between the graphene structure and the dielectric material obtained by this method. Therefore, the stability at high temperature is poor, and the manufacturing method is cumbersome, and a graphene sheet-like structure cannot be directly formed on the surface of the material.
美國專利公開案US 20110070146 A1揭露了另一種製造石墨烯的方法；該方法包含，先形成一親水性氧化層在一基材上；其次，再形成一疏水性金屬觸媒層在該親水性氧化層上，然後於該疏水性金屬觸媒層上形成石墨烯結構；最後，分離該疏水性金屬觸媒層以得到一具有石墨烯結構的基材。在此方法中，製造步驟相當複雜，且需要以蝕刻程序移除金屬觸媒層，此蝕刻程序會產生大量酸性廢液，因此該製造方法對於環境保護並不友善，且該製造方法同樣無法直接於材料表面形成一石墨烯片狀結構。 Another method for producing graphene is disclosed in US Patent Publication No. US 20110070146 A1, which comprises first forming a hydrophilic oxide layer on a substrate, and secondly, forming a hydrophobic metal catalyst layer in the hydrophilic oxidation. On the layer, a graphene structure is then formed on the hydrophobic metal catalyst layer; finally, the hydrophobic metal catalyst layer is separated to obtain a substrate having a graphene structure. In this method, the manufacturing steps are quite complicated, and the metal catalyst layer needs to be removed by an etching process. This etching process generates a large amount of acidic waste liquid, so the manufacturing method is not friendly to environmental protection, and the manufacturing method is also not directly applicable. A graphene sheet structure is formed on the surface of the material.
綜上所述，在陶瓷、玻璃、金屬和半導體材料的基材表面上形成一石墨烯奈米片狀結構網絡的製程技術係目前產業界亟需研究發展和突破的課題。 In summary, the process technology for forming a graphene nano-sheet structure network on the surface of ceramic, glass, metal and semiconductor materials is in urgent need of research and development.
鑒於上述之發明背景，為了符合產業上的需求，本發明提供一種形成奈米片狀結構網絡在基材上的製備方法及一表面具有一奈米片狀結構網絡的基材以解決目前產業上所面臨的問題，同時提升陶瓷、金屬和半導體材料的表面改質之技術。 In view of the above-mentioned background of the invention, in order to meet the industrial requirements, the present invention provides a method for preparing a nanosheet-like structure network on a substrate and a substrate having a network of a nano-sheet structure to solve the current industry. The problems faced while improving the surface modification of ceramics, metals and semiconductor materials.
本發明之一目的在於提供一種形成奈米片狀結構網絡在基材上的製備方法，該方法包含下列步驟：提供一基材和一含矽化合物；在隔絕空氣和一溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中裂解該含矽化合物以形成一氣體組成；藉由氬氣傳送一碳氫化合物的蒸氣進入上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，該碳氫化合物的蒸氣和上述裂解之含矽化合物所形成的氣體組成混合形成一反應物；和在上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，藉由氣相沉積程序使該反應物形成一奈米片狀結構網絡在該基材之上，該奈米片狀結構網絡和該基材之間具有一共價鍵結。 An object of the present invention is to provide a method for preparing a nanosheet-like structure network on a substrate, the method comprising the steps of: providing a substrate and a ruthenium-containing compound; isolating air and at a temperature of 500 to 1500 ° C The high temperature furnace 100 or the quartz tube 110 of the high temperature furnace 100 cleaves the ruthenium containing compound to form a gas composition; the argon gas is used to transport a hydrocarbon vapor into the high temperature furnace at a temperature between 500 and 1500 ° C. In the quartz tube 110 of the 100 or high temperature furnace 100, the vapor of the hydrocarbon and the gas composition formed by the cracked ruthenium-containing compound are mixed to form a reactant; and the high temperature furnace 100 at a temperature between 500 and 1500 ° C. Or in the quartz tube 110 of the high temperature furnace 100, the reactant forms a network of nano-sheet structures on the substrate by a vapor deposition process, and the nano-sheet structure network and the substrate have a total Price bond.
本發明之另一目的在於提供另一種形成奈米片狀結構網絡在基材上的製備方法，該方法包含下列步驟：置入一 基材於一高溫爐100或高溫爐100的石英管110內中；執行一升溫程序使該高溫爐100或高溫爐100的石英管110的溫度達到500至1500℃之間；藉由氬氣傳送一蒸氣成份進入上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，該蒸氣成份係由一碳氫化合物和一矽化合物所組成；和在上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，藉由氣相沉積程序使該蒸氣成份形成一奈米片狀結構網絡在該基材之上，該奈米片狀結構網絡和該基材之間具有一共價鍵結。 Another object of the present invention is to provide a method for preparing a nanosheet-like structure network on a substrate, the method comprising the steps of: placing a The substrate is placed in a high temperature furnace 100 or a quartz tube 110 of the high temperature furnace 100; a temperature increasing process is performed to bring the temperature of the quartz tube 110 of the high temperature furnace 100 or the high temperature furnace 100 to between 500 and 1500 ° C; a vapor component is introduced into the high temperature furnace 100 having a temperature between 500 and 1500 ° C or a quartz tube 110 of the high temperature furnace 100, the vapor component being composed of a hydrocarbon and a ruthenium compound; and at the above temperature of 500 to In the high temperature furnace 100 between 1500 ° C or the quartz tube 110 of the high temperature furnace 100, the vapor component is formed into a network of nano-sheet structures on the substrate by a vapor deposition process, the nano-sheet network There is a covalent bond between the substrate and the substrate.
本發明之又一目的在於提供一表面具有一奈米結構網絡的基材，該奈米結構網絡係藉由一碳化物鍵結固定於該表面。上述之奈米結構網絡的拉曼光譜在1594±5cm-1處有一G寬帶及1338±5cm-1處有一D寬帶，由於該奈米結構網絡的拉曼光譜非常類似石墨烯奈米片狀結構的拉曼光譜，所以該奈米結構網絡是一類石墨烯奈米片狀結構網絡，具有石墨烯結構的相似性質，如優秀的電導性、高導熱性質、優異的機械強度、低摩擦係數和良好的防蝕性質；同時，該奈米結構網絡又以碳化物鍵結固定於基材表面上，上述之碳化物鍵結係選自下列群組之一及其組合：碳-氧-矽鍵結、碳-矽鍵結、碳-氧-金屬鍵結、碳-金屬鍵結、碳-氮鍵結和碳-氮-金屬鍵結。因此，具有上述奈米結構網絡的表面之基材的安定性優異，可廣泛運用在不同 產業領域。 It is yet another object of the present invention to provide a substrate having a network of nanostructures that is secured to the surface by a carbide bond. The Raman spectrum of the above-mentioned nanostructure network has a G broadband at 1594±5 cm -1 and a D broadband at 1338±5 cm -1 , because the Raman spectrum of the nanostructure network is very similar to the graphene nano sheet structure. Raman spectroscopy, so the nanostructure network is a type of graphene nanosheet structure network with similar properties of graphene structure, such as excellent electrical conductivity, high thermal conductivity, excellent mechanical strength, low friction coefficient and good At the same time, the nanostructure network is fixed to the surface of the substrate by carbide bonding, and the above carbide bond is selected from one of the following groups and a combination thereof: carbon-oxygen-oxime bond, Carbon-germanium bonding, carbon-oxygen-metal bonding, carbon-metal bonding, carbon-nitrogen bonding, and carbon-nitrogen-metal bonding. Therefore, the substrate having the surface of the above-described nanostructure network is excellent in stability and can be widely used in various industrial fields.
100‧‧‧高溫爐 100‧‧‧High temperature furnace
110‧‧‧石英管 110‧‧‧Quartz tube
120‧‧‧真空法蘭 120‧‧‧vacuum flange
130‧‧‧溫度控制器 130‧‧‧temperature controller
200‧‧‧液體碳源傳送系統 200‧‧‧Liquid carbon source delivery system
210‧‧‧氬氣鋼瓶 210‧‧‧argon cylinder
220‧‧‧40ml/min流量計 220‧‧‧40ml/min flowmeter
230‧‧‧200ml/min流量計 230‧‧‧200ml/min flowmeter
240‧‧‧TMOS儲存容器 240‧‧‧TMOS storage container
250‧‧‧苯儲存容器 250‧‧‧Benzene storage container
260‧‧‧高溫爐真空系統 260‧‧‧High temperature furnace vacuum system
270‧‧‧液體真空系統 270‧‧‧Liquid vacuum system
300‧‧‧氣體碳源傳送系統 300‧‧‧Gas carbon source delivery system
310‧‧‧乙烯鋼瓶 310‧‧‧ vinyl cylinder
第一圖係為一具有石英管110、真空法蘭120和溫度控制器130高溫爐100。 The first figure is a high temperature furnace 100 having a quartz tube 110, a vacuum flange 120, and a temperature controller 130.
第二圖係為液體碳源傳送系統的示意圖。 The second figure is a schematic diagram of a liquid carbon source delivery system.
第三圖係為氣體碳源傳送系統的示意圖。 The third figure is a schematic diagram of a gas carbon source delivery system.
第四圖(a)係為石英板的相片(b)係以萘作為碳源並以化學氣相沉積法製備成表面具有類石墨烯奈米片狀結構網絡的石英板的相片。 The fourth photograph (a) is a photograph of a quartz plate (b) using a naphthalene as a carbon source and a photochemical vapor deposition method to prepare a quartz plate having a graphene-like nano-plate structure network.
第五圖係掃描式電子顯微鏡的類石墨烯奈米片狀結構網絡的比較圖。 The fifth figure is a comparison of the graphene-like nano-sheet structure network of the scanning electron microscope.
第六圖(a)係為石英的拉曼光譜，(b)係為商業化的石墨烯的拉曼光譜(c)係為石英表面具有類石墨烯奈米片狀結構網絡且該結構網絡具有碳化鍵的拉曼光譜(d)係為石英表面具有類石墨烯奈米片狀結構網絡但該結構網絡未具有碳化鍵的拉曼光譜。 Figure 6 (a) is a Raman spectrum of quartz, (b) is a commercialized graphene Raman spectrum (c) is a quartz surface having a graphene-like nano-like structure network and the structure network has The Raman spectrum (d) of the carbonized bond is a Raman spectrum having a graphene-like nano-plate structure network on the quartz surface but the structure network does not have carbonized bonds.
第七圖(a)係為矽晶圓的相片(b)係以萘作為碳源並以化學氣相沉積法製備成表面具有類石墨烯奈米片狀結構網絡的矽晶圓的相片。 The seventh photograph (a) is a photograph of a tantalum wafer (b) is a photograph of a tantalum wafer having a graphene-like nano-sheet-like structure network prepared by chemical vapor deposition using naphthalene as a carbon source.
第八圖係以苯作為碳源並以化學氣相沉積法製備成表面具有類石墨烯奈米片狀結構網絡的石英板的相片。 The eighth figure is a photograph of a quartz plate having a graphene-like nano-like sheet structure network prepared by chemical vapor deposition using benzene as a carbon source.
第九圖係以乙烯作為碳源並以化學氣相沉積法製備成表面具有類石墨烯奈米片狀結構網絡的石英板的相片。 The ninth picture is a photograph of a quartz plate having a graphene-like nano-like sheet structure network prepared by chemical vapor deposition using ethylene as a carbon source.
表一係為表面具有類石墨烯奈米片狀結構網絡之不同基材之性質比較。 Table 1 compares the properties of different substrates having a network of graphene-like nanostructures on the surface.
本發明在此所探討的是一種形成奈米片狀結構網絡在基材上的製備方法及一表面具有一奈米片狀結構網絡的基材。為了能徹底地瞭解本發明，將在下列的描述中提出詳盡的原料、步驟和應用。顯然地，本發明的施行並未限定於該領域之技藝者所熟習的特殊細節。另一方面，眾所周知的原料或步驟並未描述於細節中，以避免造成本發明不必要之限制。本發明的範例會詳細描述如下，然而除了這些詳細描述之外，本發明還可以廣泛地施行在其他的範例中，且本發明的範圍不受 限定，其以之後的專利範圍為準。 The present invention is directed to a method of forming a nanosheet-like network on a substrate and a substrate having a network of nanocrystalline sheets. In order to thoroughly understand the present invention, detailed materials, steps, and applications will be set forth in the following description. Obviously, the practice of the invention is not limited to the specific details that are apparent to those skilled in the art. On the other hand, well-known materials or steps are not described in detail to avoid unnecessarily limiting the invention. The examples of the present invention will be described in detail below, but the present invention can be widely practiced in other examples, and the scope of the present invention is not limited by the detailed description. Limited, which is subject to the scope of the patents that follow.
根據本發明的第一實施方式，本發明所提供一種形成奈米片狀結構網絡在基材上的製備方法，該方法包含下列步驟：提供一基材和一含矽化合物；在隔絕空氣和一溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中裂解該含矽化合物以形成一氣體組成；藉由氬氣傳送一碳氫化合物的蒸氣進入上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，該碳氫化合物的蒸氣和上述裂解之含矽化合物所形成的氣體組成混合形成一反應物；和在上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，藉由氣相沉積程序使該反應物形成一奈米片狀結構網絡在該基材之上，該奈米片狀結構網絡和該基材之間具有一共價鍵結。 According to a first embodiment of the present invention, there is provided a method of preparing a nanosheet-like structure network on a substrate, the method comprising the steps of: providing a substrate and a ruthenium-containing compound; The ruthenium-containing compound is cleaved in a high temperature furnace 100 having a temperature between 500 and 1500 ° C or a quartz tube 110 of the high temperature furnace 100 to form a gas composition; the vapor of a hydrocarbon is transported by argon gas to enter the above temperature at 500 to 1500 In the high temperature furnace 100 between °C or the quartz tube 110 of the high temperature furnace 100, the vapor of the hydrocarbon and the gas formed by the cracked cerium-containing compound are mixed to form a reactant; and at the above temperature of 500 to 1500 ° C In the high temperature furnace 100 or the quartz tube 110 of the high temperature furnace 100, the reactant forms a network of nanosheet structures on the substrate by a vapor deposition process, the nanosheet structure network and the There is a covalent bond between the substrates.
於一實施例，所述之基材係選自下列群組之一及其組合：陶瓷、石英、玻璃、矽晶圓和金屬。 In one embodiment, the substrate is selected from one of the group consisting of ceramics, quartz, glass, germanium wafers, and metals.
於另一實施例，所述之金屬係選自下列群組之一及其組合：碳鋼、銅、鈦及其合金。 In another embodiment, the metal is selected from one of the group consisting of carbon steel, copper, titanium, and alloys thereof.
為了使氣相沉積程序在金屬基材上達到較佳的效果，金屬基材的表面通常都會進行塗佈改質。 In order for the vapor deposition process to achieve a better effect on the metal substrate, the surface of the metal substrate is usually subjected to coating modification.
於一實施例，金屬的表面具有二氧化矽的塗佈層。 In one embodiment, the surface of the metal has a coating layer of hafnium oxide.
為了達成奈米片狀結構網絡和基材之間具有共價鍵結的目的，含矽化合物或是含氮化合物係為本發明所提供之製備方法中所必要的原料。 In order to achieve the purpose of covalent bonding between the nano-sheet structure network and the substrate, the ruthenium-containing compound or the nitrogen-containing compound is a raw material necessary for the preparation method provided by the present invention.
在一實施例，含矽化合物係選自下列群組之一及其組合：矽膠、聚二甲基矽烷、有機矽、矽烷接枝高分子、含矽茂金屬高分子和甲基三氯矽烷。 In one embodiment, the ruthenium containing compound is selected from the group consisting of tannin extract, polydimethyl decane, organic ruthenium, decane graft polymer, ruthenium containing metallocene polymer, and methyl trichloromethane.
在另一實施例，含矽化合物更添加一化合物，該化合物係選自下列群組之一及其組合：黃金、鹵化銅和茂金屬化合物。 In another embodiment, the ruthenium containing compound is further added to a compound selected from one of the group consisting of gold, copper halide, and metallocene compounds.
在一實施例，含氮化合物係選自下列群組之一及其組合：聚丙烯晴(polyacrylonitrile)、氰基高分子、含氮雜環類高分子。 In one embodiment, the nitrogen-containing compound is selected from one of the group consisting of polyacrylonitrile, a cyano polymer, and a nitrogen-containing heterocyclic polymer.
在所述之製備方法步驟為：隔絕空氣和一溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中裂解該含矽化合物以形成一氣體組成。 The preparation method is carried out by isolating the air and a quartz tube 110 of a high temperature furnace 100 or a high temperature furnace 100 having a temperature between 500 and 1500 ° C to cleave the ruthenium containing compound to form a gas composition.
在一較佳實施例，上述之溫度在750至950℃之間。 In a preferred embodiment, the above temperature is between 750 and 950 °C.
在一實施例，係藉由持續通入氬氣創造隔絕空氣的環境。 In one embodiment, an environment that isolates air is created by continuously introducing argon.
在所述之製備方法步驟為：藉由氬氣傳送一碳氫化合物的蒸氣進入上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，該碳氫化合物的蒸氣和上述裂解之含矽化合物所形成的氣體組成混合形成一反應物；和在上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，藉由氣相沉積程序使該反應物形成一奈米片狀結構網絡在該基材之上，該奈米片狀結構網絡和該基材之間具有一共價鍵結。 In the preparation method, the step of: introducing a hydrocarbon vapor by argon into the high temperature furnace 100 or the quartz tube 110 of the high temperature furnace 100 having a temperature between 500 and 1500 ° C, the vapor of the hydrocarbon Mixing with a gas composition formed by the above-mentioned cracked ruthenium-containing compound to form a reactant; and in a quartz tube 110 of a high-temperature furnace 100 or a high-temperature furnace 100 having a temperature between 500 and 1500 ° C, by a vapor deposition process The reactant forms a network of nanosheet structures over the substrate, the nanosheet network having a covalent bond between the substrate and the substrate.
在一實施例，作為氣相沉積程序所需碳源的碳氫化合物係選自下列群組之一及其組合：酮類、醛類、酯類、烷類、烯類和炔類。 In one embodiment, the hydrocarbon that is the carbon source required for the vapor deposition process is selected from one of the group consisting of ketones, aldehydes, esters, alkanes, alkenes, and alkynes.
在另一實施例，上述之烯類係選自下列群組之一及其組合：萘、苯、甲苯、二甲苯和乙烯。 In another embodiment, the above-described olefins are selected from one of the group consisting of naphthalene, benzene, toluene, xylene, and ethylene.
為了達到奈米片狀結構網絡和基材之間具有共價 鍵結的目的，製備方法的操作溫度需要控制在500至1500℃之間。 In order to achieve a covalent relationship between the nanosheet structure network and the substrate For the purpose of bonding, the operating temperature of the preparation method needs to be controlled between 500 and 1500 °C.
在一較佳實施例，上述之溫度在750至950℃之間。 In a preferred embodiment, the above temperature is between 750 and 950 °C.
根據本發明所提供的製備方法所形成的奈米片狀結構網絡是一類石墨烯奈米片狀結構網絡。 The nanosheet structure network formed by the preparation method provided by the present invention is a type of graphene nanosheet structure network.
上述奈米片狀結構網絡和基材之間具有之共價鍵結係為碳化物共價鍵結。 The covalent bond between the above-mentioned nanosheet structure network and the substrate is a carbide covalent bond.
在一實施例，所述之碳化物共價鍵結係選自下列群組之一及其組合：碳-氧-矽鍵結、碳-矽鍵結、碳-氧-金屬鍵結、碳-金屬鍵結、碳-氮鍵結和碳-氮-金屬鍵結。 In one embodiment, the carbide covalent bonding is selected from one of the following groups and combinations thereof: carbon-oxygen-oxime linkage, carbon-ruthenium linkage, carbon-oxygen-metal linkage, carbon- Metal bonding, carbon-nitrogen bonding, and carbon-nitrogen-metal bonding.
根據本發明的第二實施方式，本發明所提供另一種形成奈米片狀結構網絡在基材上的製備方法，該方法包含下列步驟：置入一基材於一高溫爐100或高溫爐100的石英管110內中；執行一升溫程序使該高溫爐100或高溫爐100的石英管110的溫度達到500至1500℃之間；藉由氬氣傳送一蒸氣成份進入上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，該蒸氣成份係由一碳氫化合物和一矽化合物 所組成；和在上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，藉由氣相沉積程序使該蒸氣成份形成一奈米片狀結構網絡在該基材之上，該奈米片狀結構網絡和該基材之間具有一共價鍵結。 According to a second embodiment of the present invention, the present invention provides another method for preparing a nanosheet structure network on a substrate, the method comprising the steps of: placing a substrate in a high temperature furnace 100 or a high temperature furnace 100 The temperature of the quartz tube 110 of the high temperature furnace 100 or the high temperature furnace 100 is between 500 and 1500 ° C; the vapor component is transferred by argon gas into the above temperature at 500 to 1500 ° C. In the high temperature furnace 100 or the quartz tube 110 of the high temperature furnace 100, the vapor component is composed of a hydrocarbon and a ruthenium compound. And in the quartz tube 110 of the high temperature furnace 100 or the high temperature furnace 100 having the above temperature between 500 and 1500 ° C, the vapor component is formed into a nano-sheet structure network by a vapor deposition process on the substrate Above, there is a covalent bond between the network of nanosheet structures and the substrate.
在一實施例，所述之基材係選自下列群組之一及其組合：陶瓷、石英、玻璃、矽晶圓和金屬。 In one embodiment, the substrate is selected from one of the group consisting of ceramics, quartz, glass, germanium wafers, and metals.
在另一實施例，所述之金屬係選自下列群組之一及其任意組合：碳鋼、銅、鈦及其合金。 In another embodiment, the metal is selected from one of the group consisting of carbon steel, copper, titanium, and alloys thereof.
為了使氣相沉積程序在金屬基材上達到較佳的效果，金屬基材的表面通常都會進行塗佈改質。 In order for the vapor deposition process to achieve a better effect on the metal substrate, the surface of the metal substrate is usually subjected to coating modification.
在一實施例，金屬的表面具有二氧化矽的塗佈層。 In one embodiment, the surface of the metal has a coating layer of hafnium oxide.
在所述之製備方法步驟為：執行一升溫程序使該高溫爐100或高溫爐100的石英管110的溫度達到500至1500℃之間；藉由氬氣傳送一蒸氣成份進入上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，該蒸氣成份係由一碳氫化合物和一矽化合物所組成；和在上述溫度在500至1500℃之間的高溫爐100或高溫爐100的石英管110中，藉由氣相沉積程序使該蒸氣成份形成一奈米片狀結構網絡在 該基材之上，該奈米片狀結構和該基材之間具有一共價鍵結。 The preparation method comprises the steps of: performing a temperature increasing process to bring the temperature of the quartz tube 110 of the high temperature furnace 100 or the high temperature furnace 100 to between 500 and 1500 ° C; and transferring a vapor component by argon gas into the above temperature at 500 to In the high temperature furnace 100 between 1500 ° C or the quartz tube 110 of the high temperature furnace 100, the vapor component is composed of a hydrocarbon and a ruthenium compound; and the high temperature furnace 100 at a temperature between 500 and 1500 ° C or In the quartz tube 110 of the high temperature furnace 100, the vapor component is formed into a network of nano-sheet structures by a vapor deposition process. Above the substrate, there is a covalent bond between the nanosheet structure and the substrate.
為了達到奈米片狀結構網絡和基材之間具有共價鍵結的目的，製備方法的操作溫度需要控制在500至1500℃之間。 In order to achieve covalent bonding between the nanosheet structure network and the substrate, the operating temperature of the preparation method needs to be controlled between 500 and 1500 °C.
在一較佳實施例，上述之操作溫度在750至950℃之間。 In a preferred embodiment, the above operating temperature is between 750 and 950 °C.
在一實施例，係藉由持續通入氬氣創造隔絕空氣的環境。 In one embodiment, an environment that isolates air is created by continuously introducing argon.
在一實施例，作為氣相沉積程序所需碳源的碳氫化合物係選自下列群組之一及其組合：苯、甲苯和二甲苯。 In one embodiment, the hydrocarbon source that is the carbon source required for the vapor deposition process is selected from one of the following groups and combinations thereof: benzene, toluene, and xylene.
在另一實施例，為了達成奈米片狀結構和基材之間具有共價鍵結的目的，含矽化合物是四烷基矽化合物。 In another embodiment, the ruthenium containing compound is a tetraalkyl ruthenium compound for the purpose of achieving covalent bonding between the nanosheet structure and the substrate.
在一較佳實施例，含矽化合物是四乙基矽化合物。 In a preferred embodiment, the ruthenium containing compound is a tetraethyl ruthenium compound.
在另一實施例，含矽化合物更添加一化合物，該化合物係選自下列群組之一及其組合：、黃金、鹵化銅和茂金屬化合物。 In another embodiment, the ruthenium containing compound is further added to a compound selected from one of the group consisting of gold, copper halide, and metallocene compounds.
根據本發明所提供的製備方法所形成的奈米片狀結構網絡是一類石墨烯奈米片狀結構網絡。 The nanosheet structure network formed by the preparation method provided by the present invention is a type of graphene nanosheet structure network.
上述奈米片狀結構網絡和基材之間具有之共價鍵結係為碳化物共價鍵結。 The covalent bond between the above-mentioned nanosheet structure network and the substrate is a carbide covalent bond.
在一實施例，所述之碳化物共價鍵結係選自下列群組之一及其組合：碳-氧-矽鍵結、碳-矽鍵結。 In one embodiment, the carbide covalent linkage is selected from one of the group consisting of: a carbon-oxygen-oxime linkage, a carbon-ruthenium linkage.
本發明的第三實施方式係藉由上述第一或第二實施方式所提供的形成奈米片狀結構網絡在基材上的製備方法進一步提供一表面具有一奈米結構網絡的基材，該奈米結構網絡係藉由一碳化物鍵結(carbide bond)固定於該基材表面。其中上述之奈米結構網絡的拉曼光譜在1594±5cm-1處有一G寬帶及1338±5cm-1處有一D寬帶。 The third embodiment of the present invention further provides a substrate having a nano-structure network on the surface by the method for preparing a nano-sheet structure network provided on the substrate provided by the first or second embodiment. The nanostructure network is fixed to the surface of the substrate by a carbide bond. The Raman spectrum of the above-mentioned nanostructure network has a G broadband at 1594±5 cm -1 and a D broadband at 1338±5 cm -1 .
在一實施例，上述之碳化物鍵結(carbide bond)係選自下列群組之一及其組合：碳-氧-矽鍵結、碳-矽鍵結、碳-氧-金屬鍵結、碳-金屬鍵結、碳-氮鍵結和碳-氮-金屬鍵結。 In one embodiment, the above carbide bond is selected from one of the following groups and combinations thereof: carbon-oxygen-oxime linkage, carbon-ruthenium linkage, carbon-oxygen-metal linkage, carbon - metal bond, carbon-nitrogen bond and carbon-nitrogen-metal bond.
由於上述之奈米結構網絡的拉曼光譜非常類似於石墨烯奈米片狀結構的拉曼光譜，所以該奈米結構網絡是一類石墨烯奈米片狀結構網絡，具有相似於石墨烯奈米片狀結構網 絡的性質，如優秀的電導性、高導熱性質、優異的機械強度、低摩擦係數和良好的防蝕性質；同時，該奈米結構網絡又以碳化物鍵結(carbide bond)固定於基材表面上，因此，具有上述奈米結構網絡的表面之基材的安定性優異，可廣泛運用在不同產業。 Since the Raman spectrum of the nanostructure network described above is very similar to the Raman spectrum of the graphene nanosheet structure, the nanostructure network is a type of graphene nanosheet structure network having a similarity to graphene nanoparticles. Sheet structure network The properties of the network, such as excellent electrical conductivity, high thermal conductivity, excellent mechanical strength, low coefficient of friction and good corrosion resistance; at the same time, the nanostructure network is fixed to the surface of the substrate by carbide bond Therefore, the substrate having the surface of the above-described nanostructure network is excellent in stability and can be widely used in various industries.
在一實施例，上述表面具有一奈米結構網絡的基材用做太陽能電池的元件組成。 In one embodiment, the substrate having a nanostructure network on the surface is used as an element of a solar cell.
在一實施例，上述表面具有一奈米結構網絡的基材用做半導體的元件組成。 In one embodiment, the substrate having a nanostructure network on the surface is composed of an element of a semiconductor.
在一實施例，上述表面具有一奈米結構網絡的基材用做光學模組的元件組成。 In one embodiment, the substrate having a nanostructure network on the surface is used as an element of an optical module.
在一實施例，上述表面具有一奈米結構網絡的基材用做防蝕材料的元件組成。 In one embodiment, the substrate having a nanostructure network on the surface is composed of an element of an anti-corrosion material.
在一實施例，上述表面具有一奈米結構網絡的基材用做不沾鍋的組成。 In one embodiment, the substrate having a nanostructure network on the surface is used as a non-stick pan.
在一實施例，上述表面具有一奈米結構網絡的基材用做散熱模組的元件組成。 In one embodiment, the substrate having a nanostructure network on the surface is composed of components used as a heat dissipation module.
以下利用範例更進一步說明本發明，此處僅是舉例說明本發明的實施態樣，熟習本技術者可依據這些實施例及範例，進行各種等效改變或修飾，但本發明的範圍係以後述的請求範圍為基準，不限於這些實施例及範例。 The invention is further illustrated by the following examples, which are merely illustrative of the embodiments of the present invention, and those skilled in the art can make various equivalent changes or modifications according to the embodiments and examples, but the scope of the present invention will be described later. The scope of the request is based on the reference and is not limited to these embodiments and examples.
範例一.以化學氣相沉積法製備一種表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的石英板。 Example 1. A quartz plate with a graphene nanosheet structure network with covalently bonded ruthenium carbide (ruthenium oxyhydroxide) on the surface was prepared by chemical vapor deposition.
使用固體萘(純度99%，購至Aldrich)作為化學氣相沉積法形成類石墨烯結構在基材上的碳源。首先，將兩片厚度為1/16”大小為1”x 1”的石英板和含矽化合物(1克)放入高溫爐的石英管中，通入氬氣10分鐘後，加熱高溫爐的石英管至溫度750℃。以氬氣傳送萘的蒸氣進入溫度在750℃的石英管，進行化學氣相沉積程序50分鐘後，冷卻石英管回到室溫後取出石英板。第四圖(b)係為以萘作為碳源並以化學氣相沉積法製備成表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的石英板。 Solid naphthalene (purity 99%, purchased from Aldrich) was used as a carbon source for forming a graphene-like structure on a substrate by chemical vapor deposition. First, two quartz plates with a thickness of 1" x 1" and a bismuth-containing compound (1 gram) were placed in a quartz tube of a high-temperature furnace, and argon gas was introduced for 10 minutes, and then the furnace was heated. The quartz tube was heated to a temperature of 750 ° C. The vapor of naphthalene was transferred to a quartz tube at a temperature of 750 ° C for argon gas, and after a chemical vapor deposition process for 50 minutes, the quartz tube was cooled and returned to room temperature, and then the quartz plate was taken out. It is a quartz plate in which a graphene nanosheet-like structure network having a covalent bond of niobium carbide (ruthenium oxycarbide) is prepared by chemical vapor deposition using naphthalene as a carbon source.
當石英管溫度達到500℃以上時，含矽化合物會發生熱裂解而產生包括Si(CH3)-OH,H2Si(CH3)2,CH4,CO，和O2的氣體，上述的氣體可以和類石墨烯奈米片狀結構網絡邊 緣的碳原子反應形成碳化矽共價鍵結和碳氧化矽共價鍵結。因為石英板主要係由矽、碳、氧和氮等元素所組成，所以當石英板在750℃或以上時，此溫度條件能使石英板和類石墨烯奈米片狀結構網絡之間產生碳化矽共價鍵結和碳氧化矽共價鍵結。 When the temperature of the quartz tube reaches 500 ° C or higher, the cerium-containing compound undergoes thermal cracking to generate a gas including Si(CH 3 )-OH, H 2 Si(CH 3 ) 2 , CH 4 , CO, and O 2 , as described above. The gas can react with the carbon atoms at the edge of the graphene-like nanosheet-like network to form a covalently bonded ruthenium carbide and covalently bonded to the ruthenium oxyhydroxide. Because the quartz plate is mainly composed of elements such as bismuth, carbon, oxygen and nitrogen, when the quartz plate is at 750 ° C or above, this temperature condition can cause carbonization between the quartz plate and the graphene-like nano-sheet structure network. The covalent bond and the ruthenium oxyhydroxide are covalently bonded.
第五圖係為掃描式電子顯微鏡的類石墨烯奈米片狀結構網絡圖，其類石墨烯奈米片狀結構網絡的厚度約為3um。 The fifth figure is a graphene-like nano-sheet structure network diagram of a scanning electron microscope, and the graphene-like nano-sheet structure network has a thickness of about 3 um.
上述範例一所製備表面具有碳化矽共價鍵結的類石墨烯奈米片狀結構網絡的石英板，該石英板之電阻約在12-24KΩ；此外，該石英板表面的類石墨烯結構網絡層無法以強酸或是其他物理力量移除，且在溫度在450℃時該石英板表面的類石墨烯奈米片狀結構網絡層仍具有很好的熱穩定性。進一步以AFM分析其Young’s modulus為170GPa，而Hertzian hardness為22.5GPa。 In the above example, a quartz plate having a graphene-like nano-sheet network having covalently bonded ruthenium carbide is prepared, and the resistance of the quartz plate is about 12-24 K?; in addition, a graphene-like structure network on the surface of the quartz plate The layer cannot be removed by strong acid or other physical forces, and the graphene-like nanosheet-like network layer on the surface of the quartz plate still has good thermal stability at a temperature of 450 °C. Further, the Young's modulus was analyzed by AFM to be 170 GPa, and the Hertzian hardness was 22.5 GPa.
由於拉曼光譜對於碳元素材料的電子結構變化非常靈敏，因此以拉曼光譜分析石墨烯和相關碳元素材料可得到非常有用的資訊；本實驗分析所使用的拉曼光譜分析儀為Renishaw 1000 microspectrometer，使用的波長為514.5nm。 第六圖(a)所示係為石英的拉曼光譜，作為實驗對照組；第六圖(b)係為商業化生產的石墨烯的拉曼光譜，該石墨烯係由氧化石墨烯還原而製成，其拉曼光譜顯示在1586cm-1有一G寬帶(Gband)和1348cm-1有一D寬帶(D band)，而在2703cm-1有一2D寬帶，此外在2934cm-1有D+G的結合寬帶。第六圖(c)係為石英表面具有類石墨烯奈米片狀結構網絡且該結構網絡具有碳化鍵的拉曼光譜。第六圖(d)係為石英表面具有類石墨烯奈米片狀結構網絡但該結構網絡未具有碳化鍵的拉曼光譜，由第六圖(c)和(d)可清楚觀察到G寬帶(G band)和D寬帶(D band)的存在，且同時亦具有一寬廣的D+G的結合寬帶，此拉曼光譜證明該石英表面確實具有類石墨烯奈米片狀結構網絡。 Since Raman spectroscopy is very sensitive to the electronic structure change of carbon materials, it is very useful to analyze graphene and related carbon materials by Raman spectroscopy. The Raman spectrum analyzer used in this experiment is Renishaw 1000 microspectrometer. The wavelength used was 514.5 nm. The sixth figure (a) shows the Raman spectrum of quartz as the experimental control group; the sixth figure (b) shows the Raman spectrum of the commercially produced graphene, which is reduced by graphene oxide. made, which showed a Raman spectrum G broadband (Gband) at 1586cm -1 and 1348cm -1 D has a broadband (Band D), and 2703cm -1 in a broadband 2D, in addition there are incorporated in the D + G 2934cm -1 Broadband. The sixth figure (c) is a Raman spectrum in which the quartz surface has a graphene-like nano-plate structure network and the structure network has carbonized bonds. The sixth figure (d) is a Raman spectrum with a graphene-like nano-plate structure network on the quartz surface but the structure network does not have carbonized bonds. G-bandwidth can be clearly observed from the sixth figure (c) and (d). The presence of (G band) and D-band (D band), and at the same time, has a broad D+G combined broadband. This Raman spectroscopy proves that the quartz surface does have a graphene-like nano-like structure network.
範例二、以化學氣相沉積法製備一種表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的矽晶圓。 Example 2: A germanium wafer with a graphene nanosheet-like structure network with covalently bonded ruthenium carbide (ruthenium oxyhydroxide) on the surface was prepared by chemical vapor deposition.
製備方法如範例一所述，基材由石英板改為矽晶圓，最後得到表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的矽晶圓，成品如第七圖所示。 The preparation method is as described in the first example, the substrate is changed from a quartz plate to a tantalum wafer, and finally a tantalum wafer having a graphene nanosheet structure network such as tantalum carbide (cobalt ruthenium oxide) covalently bonded is obtained, and the finished product is obtained. As shown in the seventh figure.
範例三、以化學氣相沉積法製備一種表面具有碳 化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的石英板。 Example 3: Preparing a surface with carbon by chemical vapor deposition A quartz plate of a graphene nanosheet structure network such as covalently bonded bismuth (carbonium oxide).
使用苯(純度99.9%，購至Aldrich)作為化學氣相沉積法形成類石墨烯結構在基材上的碳源。首先，將兩片厚度為1/16”大小為1”x 3”的石英板放入高溫爐的石英管中，通入氬氣10分鐘後，加熱高溫爐的石英管至溫度950℃。以氬氣傳送苯和四甲基矽化合物(Tetramethylorthosilicate)的蒸氣進入溫度在950℃的石英管，進行化學氣相沉積程序60分鐘後，冷卻石英管回到室溫後取出石英板。即得到以苯作為碳源並以化學氣相沉積法製備成表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的石英板，成品如第八圖所示。 A carbon source of a graphene-like structure on a substrate was formed using benzene (purity 99.9%, purchased from Aldrich) as a chemical vapor deposition method. First, two quartz plates with a thickness of 1/16" and a size of 1" x 3" were placed in a quartz tube of a high-temperature furnace. After argon gas was passed for 10 minutes, the quartz tube of the high-temperature furnace was heated to a temperature of 950 ° C. The vapor of benzene and Tetramethylorthosilicate was transferred to a quartz tube at a temperature of 950 ° C for argon gas. After 60 minutes of chemical vapor deposition, the quartz tube was cooled and returned to room temperature, and then the quartz plate was taken out. As a carbon source and a chemical vapor deposition method, a quartz plate having a graphene nanosheet structure network having a covalent bond of niobium carbide (ruthenium oxycarbide) is prepared, and the finished product is as shown in the eighth drawing.
範例四、以化學氣相沉積法製備一種表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的石英板。 Example 4: A quartz plate with a graphene nanosheet structure network with covalently bonded ruthenium carbide (ruthenium oxyhydroxide) on the surface was prepared by chemical vapor deposition.
使用乙烯(純度99.5%)作為化學氣相沉積法形成類石墨烯結構在基材上的碳源。首先，將兩片厚度為1/8”大小為1”x 1”的石英板和含矽化合物(1克)放入高溫爐的石英管中，通入氬氣10分鐘後，加熱高溫爐的石英管至溫度 950℃。以氬氣傳送乙烯氣體一同進入溫度在950℃的石英管，進行化學氣相沉積程序50分鐘後，冷卻石英管回到室溫後取出石英板。即可得到以乙烯作為碳源並以化學氣相沉積法製備成表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的石英板。成品如第九圖所示。 Ethylene (purity 99.5%) was used as a carbon source for forming a graphene-like structure on a substrate by chemical vapor deposition. First, two quartz plates with a thickness of 1" x 1" and a bismuth-containing compound (1 gram) were placed in a quartz tube of a high-temperature furnace, and argon gas was introduced for 10 minutes, and then the furnace was heated. Quartz tube to temperature 950 ° C. The ethylene gas was supplied with argon gas and entered into a quartz tube at a temperature of 950 ° C. After a chemical vapor deposition process for 50 minutes, the quartz tube was cooled and returned to room temperature, and then the quartz plate was taken out. A quartz plate having a graphene nanosheet structure network having a surface of a covalently bonded ruthenium carbide (ruthenium oxyhydroxide) surface prepared by chemical vapor deposition using ethylene as a carbon source can be obtained. The finished product is shown in the ninth figure.
範例五、以化學氣相沉積法製備一種表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的鋼板。 Example 5. A steel sheet having a graphene nanosheet structure network having a covalent bond of niobium carbide (ruthenium oxycarbide) on the surface was prepared by chemical vapor deposition.
製備方法如範例一所述，基材由石英板改為經二氧化矽塗佈處理過的鋼板，最後得到表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的鋼板。 The preparation method is as described in the first example, the substrate is changed from a quartz plate to a steel plate coated with cerium oxide, and finally a graphene nano-sheet structure having a covalent bond of lanthanum carbide (cerium oxyhydroxide) on the surface is obtained. Network steel plate.
範例六、以化學氣相沉積法製備一種表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的鋼板。 Example 6. A steel sheet having a graphene nanosheet structure network having a covalent bond of niobium carbide (ruthenium oxycarbide) on the surface is prepared by chemical vapor deposition.
使用甲苯(純度99.8%，購至Aldrich)作為化學氣相沉積法形成類石墨烯結構在基材上的碳源。首先，將兩片經二氧化矽塗佈處理過的鋼板放入高溫爐的石英管中，通入氬氣10分鐘後，加熱高溫爐的石英管至溫度850℃。以氬氣傳送甲苯和四乙基矽化合物(Tetraethylorthosilicate)的蒸氣進入溫度 在850℃的石英管，進行化學氣相沉積程序60分鐘後，冷卻石英管回到室溫後取出石英板。即得到以甲苯作為碳源並以化學氣相沉積法製備成表面具有碳化矽(碳氧化矽)共價鍵結之類石墨烯奈米片狀結構網絡的鋼板。 Toluene (purity of 99.8%, purchased from Aldrich) was used as a carbon source for forming a graphene-like structure on a substrate by chemical vapor deposition. First, two sheets of the steel sheet coated with cerium oxide were placed in a quartz tube of a high-temperature furnace, and argon gas was introduced for 10 minutes, and then the quartz tube of the high-temperature furnace was heated to a temperature of 850 °C. Transfer of vapor of toluene and tetraethyl fluorene compound (Tetraethylorthosilicate) into the temperature with argon After performing a chemical vapor deposition process on a quartz tube at 850 ° C for 60 minutes, the quartz tube was cooled and returned to room temperature, and then the quartz plate was taken out. That is, a steel sheet having a graphene nanosheet-like structure network having a covalent bond of niobium carbide (ruthenium oxycarbide) on the surface thereof was prepared by a chemical vapor deposition method using toluene as a carbon source.
以上雖以特定實施例說明本發明，但並不因此限定本發明之範圍，只要不脫離本發明之要旨，熟悉本技藝者瞭解在不脫離本發明的意圖及範圍下可進行各種變形或變更。另外本發明的任一實施例或申請專利範圍不須達成本發明所揭露之全部目的或優點或特點。此外，摘要部分和標題僅是用來輔助專利文件搜尋之用，並非用來限制本發明之權利範圍。 The present invention has been described in detail with reference to the preferred embodiments of the present invention, and the scope of the invention is not limited thereto, and it is understood that various modifications and changes can be made without departing from the spirit and scope of the invention. In addition, any of the objects or advantages or features of the present invention are not required to be achieved by any embodiment or application of the invention. In addition, the abstract sections and headings are only used to assist in the search of patent documents and are not intended to limit the scope of the invention.
Claims (5)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW103124988A TWI504555B (en) | 2014-07-21 | 2014-07-21 | A method for coating a nanosheet structure network on a substrate and the application thereof |
| CN201410498442.3A CN105274489B (en) | 2014-07-21 | 2014-09-25 | Preparation method for forming nano sheet structure network on substrate and substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW103124988A TWI504555B (en) | 2014-07-21 | 2014-07-21 | A method for coating a nanosheet structure network on a substrate and the application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TWI504555B true TWI504555B (en) | 2015-10-21 |
| TW201604124A TW201604124A (en) | 2016-02-01 |
Family
ID=54851779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW103124988A TWI504555B (en) | 2014-07-21 | 2014-07-21 | A method for coating a nanosheet structure network on a substrate and the application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105274489B (en) |
| TW (1) | TWI504555B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039279A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院化学研究所 | Graphene-like material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966987A (en) * | 2010-10-13 | 2011-02-09 | 重庆启越涌阳微电子科技发展有限公司 | Fractal graphene material with negative electron affinity as well as preparation method and application thereof |
| TW201211302A (en) * | 2010-06-10 | 2012-03-16 | Applied Materials Inc | Graphene deposition |
| US20120282527A1 (en) * | 2011-05-04 | 2012-11-08 | Khalil Amine | Composite materials for battery applications |
| WO2013066474A2 (en) * | 2011-08-15 | 2013-05-10 | Purdue Research Foundation | Methods and apparatus for the fabrication and use of graphene petal nanosheet structures |
| WO2013093358A1 (en) * | 2011-12-22 | 2013-06-27 | Arkema France | Method for producing an assembly of carbon nanotubes and graphene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6444326B1 (en) * | 1999-03-05 | 2002-09-03 | Restek Corporation | Surface modification of solid supports through the thermal decomposition and functionalization of silanes |
| US7172792B2 (en) * | 2002-12-20 | 2007-02-06 | Applied Materials, Inc. | Method for forming a high quality low temperature silicon nitride film |
| CN102268653A (en) * | 2011-06-24 | 2011-12-07 | 北京科技大学 | Preparation method of hard alloy tool diamond interlayer |
-
2014
- 2014-07-21 TW TW103124988A patent/TWI504555B/en not_active IP Right Cessation
- 2014-09-25 CN CN201410498442.3A patent/CN105274489B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201211302A (en) * | 2010-06-10 | 2012-03-16 | Applied Materials Inc | Graphene deposition |
| CN101966987A (en) * | 2010-10-13 | 2011-02-09 | 重庆启越涌阳微电子科技发展有限公司 | Fractal graphene material with negative electron affinity as well as preparation method and application thereof |
| US20120282527A1 (en) * | 2011-05-04 | 2012-11-08 | Khalil Amine | Composite materials for battery applications |
| WO2013066474A2 (en) * | 2011-08-15 | 2013-05-10 | Purdue Research Foundation | Methods and apparatus for the fabrication and use of graphene petal nanosheet structures |
| WO2013093358A1 (en) * | 2011-12-22 | 2013-06-27 | Arkema France | Method for producing an assembly of carbon nanotubes and graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105274489B (en) | 2018-06-19 |
| CN105274489A (en) | 2016-01-27 |
| TW201604124A (en) | 2016-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Synthesis of graphene films on copper foils by chemical vapor deposition | |
| Li et al. | Rational kinetics control toward universal growth of 2D vertically stacked heterostructures | |
| Hong et al. | Chemical vapor deposition of layered two-dimensional MoSi2N4 materials | |
| Chang et al. | Growth of large single-crystalline monolayer hexagonal boron nitride by oxide-assisted chemical vapor deposition | |
| Wang et al. | Recent progress in synthesis of two-dimensional hexagonal boron nitride | |
| Yin et al. | Boron nitride nanostructures: fabrication, functionalization and applications | |
| Gong et al. | Synthesis of millimeter‐scale transition metal dichalcogenides single crystals | |
| JP6488350B2 (en) | Direct and continuous formation of boron nitride and graphene on substrates | |
| Pakdel et al. | Nano boron nitride flatland | |
| Shi et al. | Synthesis of few-layer hexagonal boron nitride thin film by chemical vapor deposition | |
| Hu et al. | Synthesis and characterization of SiC nanowires through a reduction− carburization route | |
| Tay et al. | Direct growth of nanocrystalline hexagonal boron nitride films on dielectric substrates | |
| Khan et al. | Synthesis of large and few atomic layers of hexagonal boron nitride on melted copper | |
| JP5224554B2 (en) | Method for producing graphene / SiC composite material and graphene / SiC composite material obtained thereby | |
| Sun et al. | Direct chemical vapor deposition growth of graphene on insulating substrates | |
| McNerny et al. | Direct fabrication of graphene on SiO2 enabled by thin film stress engineering | |
| Jana et al. | Progress in CVD synthesis of layered hexagonal boron nitride with tunable properties and their applications | |
| Lin et al. | Atomic-scale structural and chemical characterization of hexagonal boron nitride layers synthesized at the wafer-scale with monolayer thickness control | |
| Wang et al. | Elastic properties of 2D ultrathin tungsten nitride crystals grown by chemical vapor deposition | |
| Shi et al. | Substrate developments for the chemical vapor deposition synthesis of graphene | |
| Zhang et al. | Clean transfer of 2D transition metal dichalcogenides using cellulose acetate for atomic resolution characterizations | |
| Kim et al. | A new horizon for hexagonal boron nitride film | |
| Saha et al. | Comprehensive characterization and analysis of hexagonal boron nitride on sapphire | |
| Wen et al. | Ultraclean and large-area monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition | |
| Song et al. | Graphene/h‐BN heterostructures: recent advances in controllable preparation and functional applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |