TWI535887B - Apparatus and method for the synthesis of high-quality of carbon film or inorganic material film - Google Patents
Apparatus and method for the synthesis of high-quality of carbon film or inorganic material film Download PDFInfo
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Description
本發明係為一種製備高品質碳薄膜或無機材料薄膜之設備與方法,特別關於一種連續式大面積合成高品質碳薄膜或無機材料薄膜之設備與方法。 The invention relates to an apparatus and a method for preparing a high-quality carbon film or an inorganic material film, in particular to a continuous large-area apparatus and method for synthesizing a high-quality carbon film or an inorganic material film.
石墨烯(graphene)是一種單原子層的石墨,具有二維結構和許多優異的性質,如高載子遷移率、高機械強度、高透明性及高導熱系數等。 Graphene is a monoatomic layer of graphite with a two-dimensional structure and many excellent properties such as high carrier mobility, high mechanical strength, high transparency and high thermal conductivity.
迄今已經有許多合成石墨烯的方法被提出,包括:(1)機械剝離石墨法,(2)磊晶成長法,(3)化學氣相沉積法(Chemical Vapor Deposition,CVD):於催化金屬上(例如:銅、鎳、鐵等)進行石墨烯的合成,(4)化學剝離法:利用氧化石墨以獲得氧化石墨烯(graphene oxide,GO)。 So far, many methods for synthesizing graphene have been proposed, including: (1) mechanically stripped graphite method, (2) epitaxial growth method, and (3) chemical vapor deposition (CVD): on catalytic metal. (for example: copper, nickel, iron, etc.) for the synthesis of graphene, (4) chemical stripping method: using graphite oxide to obtain graphene oxide (GO).
其中機械剝離法和磊晶成長法雖然可以得到高品質(低缺陷結構)的石墨烯,卻無法大面積合成。化學氣相沉積法使用過渡金屬作為催化劑來合成石墨烯,而就化學氣相沉積法合成石墨烯的技術來說,目前主要是以Ni和Cu的基板成長為主,尤其以Cu為基板的製程成為後續石墨烯大面積合成的主流。近期的研究工作使用化學氣相沉積法和例如鎳(Ni)與銅(Cu)等催化性具金屬的基材已經可以成長大面積且高品質的石墨烯層(Reina,A.et.al.,Nano Letters 2008,9,30-35;Li,X.et.al.,Science 2009,324,1312-1314;Sukang,B.,et.al.,Nature;Nanotechnology,2010,5,574-578)。 Among them, the mechanical exfoliation method and the epitaxial growth method can obtain high-quality (low-defect structure) graphene, but cannot be synthesized in a large area. The chemical vapor deposition method uses a transition metal as a catalyst to synthesize graphene, and the technique for synthesizing graphene by chemical vapor deposition is mainly based on the growth of substrates of Ni and Cu, especially the process of using Cu as a substrate. It becomes the mainstream of the subsequent large-area synthesis of graphene. Recent research has used chemical vapor deposition and catalytic metal-based substrates such as nickel (Ni) and copper (Cu) to grow large-area and high-quality graphene layers (Reina, A.et.al. , Nano Letters 2008, 9, 30-35; Li, X. et. al., Science 2009, 324, 1312-1314; Sukang, B., et. al., Nature; Nanotechnology, 2010, 5, 574-578).
然而Byun,S.J.et.al.使用鎳金屬基板並以化學氣相沉積法來合成石墨烯(Byun,S.J.et.al.,The Journal of Physical Chemistry Letters 2011,2,493-497),其碳源或無機材料源分子與鎳金屬在高溫時會發生固溶現象,並且,在降溫的過程中,碳原子會在鎳金屬表面析出並且重組成為石墨烯的結構,此方法無法精確地控制析出碳原子的量,故難以獲得精確控制的石墨烯層數。 However, Byun, SJet.al. uses a nickel metal substrate and chemical vapor deposition to synthesize graphene (Byun, SJet. al., The Journal of Physical Chemistry Letters 2011, 2, 493-497), its carbon source or inorganic The material source molecules and nickel metal will solid solution at high temperatures, and during the cooling process, carbon atoms will precipitate on the surface of the nickel metal and recombine into the structure of graphene. This method cannot accurately control the amount of carbon atoms precipitated. Therefore, it is difficult to obtain a precisely controlled number of graphene layers.
Cu為基板的合成法可以獲得大面積且幾乎為單層的高品質碳薄膜或無機材料薄膜(>90%覆蓋面積),因此在均勻性跟厚度上,具有較好的可控性。而就目前技術現況來說,以Cu為基板的化學氣相沉積法合成法,具有良好品質、大面積跟可控制性(Nano Letters,2009,9,4268.)。 The synthesis method of Cu as a substrate can obtain a large-area and almost single-layer high-quality carbon film or inorganic material film (>90% coverage area), and thus has good controllability in uniformity and thickness. As far as the current state of the art is concerned, the chemical vapor deposition method using Cu as a substrate has good quality, large area and controllability (Nano Letters, 2009, 9, 4268.).
然而,在化學氣相沉積法合成石墨烯,石墨烯會圍繞碳核生長,並在催化劑層表面隨機生長,當圍繞碳核生長的石墨烯遇到晶界時,因為晶粒的排列無方向性,導致石墨烯產生缺陷,而有大面積製造上的瓶頸,另外在水平爐管中做批次量的生成,所以雖然面積可以達A4大小,但並非連續性製程,估算其成本仍高於100美元/英吋,無法進入市場應用。 However, in the synthesis of graphene by chemical vapor deposition, graphene grows around the carbon core and randomly grows on the surface of the catalyst layer. When the graphene grown around the carbon core encounters grain boundaries, the orientation of the grains is non-directional. As a result, graphene is defective, and there is a bottleneck in large-area manufacturing. In addition, batch production is performed in the horizontal furnace tube. Therefore, although the area can reach A4 size, it is not a continuous process, and the estimated cost is still higher than 100. USD/GB, unable to enter the market application.
所以,目前業界極需發展出一種能生產大面積高品質碳薄膜或無機材料薄膜之製備裝置,並具有連續式大面積的製備能力,如此一來,利用此連續式大面積高品質碳薄膜或無機材料薄膜之製備裝置方能同時兼具成本與時效。 Therefore, it is extremely necessary in the industry to develop a preparation device capable of producing a large-area high-quality carbon film or an inorganic material film, and has a continuous large-area preparation capability, thereby utilizing the continuous large-area high-quality carbon film or The preparation device of the inorganic material film can simultaneously have both cost and time effect.
本發明提供一種連續式合成高品質碳薄膜或無機材料薄膜之設備,包括一外腔體、一基材傳送裝置、一具金屬的基材、一溫控裝置、一真空系統,以及一氣源控制其中,該外腔體可設有一進氣閘門以及一出氣閘門。該基材傳送裝置設置於該外腔體內,該基材傳送裝置包刮一捲出構件、複數個轉動滾筒以及一捲取構件,且該基材傳送裝置具有一移動路徑。該具金屬的基材 得沿著該移動路徑傳送,而該溫控裝置則相對應配置於該基材傳送裝置的上方或下方,當該具金屬的基材通過時,可對其加熱。而該真空系統與該外腔體連接,將一氣體由該進氣閘門抽入,及由該出氣閘門排出。該氣源控制器與該外腔體連接,用以控制一製程氣體的供給,其中該製程氣體具有一碳源或無機材料源。一加熱單元,靠近該具金屬的基材表面設置,和該具金屬的基材有一相對移動。 The invention provides an apparatus for continuously synthesizing a high quality carbon film or an inorganic material film, comprising an outer cavity, a substrate conveying device, a metal substrate, a temperature control device, a vacuum system, and a gas source In the control, the outer cavity may be provided with an intake gate and an air outlet gate. The substrate transfer device is disposed in the outer cavity, the substrate transfer device includes a take-up member, a plurality of rotating rollers, and a take-up member, and the substrate transfer device has a moving path. Metal substrate It is carried along the moving path, and the temperature control device is correspondingly disposed above or below the substrate conveying device, and when the metal substrate passes, it can be heated. The vacuum system is coupled to the outer chamber, and a gas is drawn in by the intake valve and discharged from the air outlet gate. The gas source controller is coupled to the outer chamber for controlling the supply of a process gas, wherein the process gas has a carbon source or a source of inorganic material. A heating unit is disposed adjacent to the surface of the metal substrate, and has a relative movement with the metal substrate.
本發明,該具金屬的基材包括銅、鐵、鈷、鎳、金、銀、鉑、銣或其混合物中的任一種構成。 In the present invention, the metal substrate comprises any one of copper, iron, cobalt, nickel, gold, silver, platinum, rhodium or a mixture thereof.
本發明,該外腔體內部至少容納一前處理腔體和一製程腔體,一第一緩衝區位於該前處理腔體和該製程腔體之間。 In the present invention, the outer cavity body houses at least one pre-processing cavity and one process cavity, and a first buffer zone is located between the pre-processing cavity and the process cavity.
本發明,更包括有一冷卻腔體,其中該前處理腔體、該製程腔體及該冷卻腔體依序沿著該具金屬的基材的移動路徑設置,一第二緩衝區位於該製程腔體及該冷卻腔體之間。 The present invention further includes a cooling chamber, wherein the pre-processing chamber, the processing chamber and the cooling chamber are sequentially disposed along a moving path of the metal substrate, and a second buffer is located in the processing chamber Between the body and the cooling cavity.
本發明,更包括有一冷卻滾輪,其中該前處理腔體、該製程腔體及該冷卻滾輪依序沿著該具金屬的基材的移動路徑設置,用於冷卻該形成高品質碳薄膜或無機材料薄膜之該具金屬的基材。 The invention further includes a cooling roller, wherein the pretreatment chamber, the processing chamber and the cooling roller are sequentially disposed along a moving path of the metal substrate for cooling the high quality carbon film or inorganic The metal substrate of the material film.
本發明,其中該加熱單元設置在冷卻腔體的前方或後方。 The invention is wherein the heating unit is disposed in front of or behind the cooling cavity.
本發明,其中該加熱單元設置在冷卻滾輪前方或後方。 The invention is wherein the heating unit is disposed in front of or behind the cooling roller.
本發明,其中該冷卻滾輪可以為水冷或氣冷。 The invention wherein the cooling roller can be water cooled or air cooled.
本發明,其中該其中第一緩衝區和第二緩衝區內的氣體流速約為0.05L/min-1000L/min。 The invention wherein the gas flow rate in the first buffer zone and the second buffer zone is between about 0.05 L/min and 1000 L/min.
本發明,其中該前處理腔體內具有一第一電漿產生單元和一第一過濾器,該製程腔體內具有一第二電漿產生單元和一第二過濾器。 In the present invention, the pretreatment chamber has a first plasma generating unit and a first filter, and the processing chamber has a second plasma generating unit and a second filter.
本發明,其中該第一電漿產生單元和該第二電漿產生單元為一面型電漿源。 In the present invention, the first plasma generating unit and the second plasma generating unit are one-sided plasma sources.
本發明,其中該加熱單元為一高溫鎢線。 The invention wherein the heating unit is a high temperature tungsten wire.
本發明,更包括一轉印裝置移除具金屬的基材。 The invention further includes a transfer device for removing a metal substrate.
本發明,其中該具金屬的基材為氧化矽基板、石英基板、藍寶石基板、氮化硼基板、玻璃基板、金屬基板、半導體基板或其組合。 In the present invention, the metal substrate is a ruthenium oxide substrate, a quartz substrate, a sapphire substrate, a boron nitride substrate, a glass substrate, a metal substrate, a semiconductor substrate, or a combination thereof.
本發明,其中碳源或無機材料源可為氣相碳基前驅物、液相碳基前驅物、或固相碳基前驅物中任一種所裂解而成。 In the present invention, the carbon source or source of inorganic material may be formed by cracking any of a gas phase carbon-based precursor, a liquid phase carbon-based precursor, or a solid phase carbon-based precursor.
本發明,其中該碳基前驅物為甲烷、乙烯、乙炔、乙醇、苯、甲醇、碳基的高分子、奈米碳材料或其混合物中的任一種。 The present invention, wherein the carbon-based precursor is any one of methane, ethylene, acetylene, ethanol, benzene, methanol, a carbon-based polymer, a nanocarbon material, or a mixture thereof.
本發明,其中該碳源或無機材料源是經氮、硼或其混合物摻雜中的任一種。 The invention wherein the source of carbon or inorganic material is any one of nitrogen, boron or a mixture thereof.
本發明,其中該無機材料來源系氮化硼、二硫化鉬、硫化鋅、碲化鋅、硒化鋅、三硒化二鉍、碲化鉍或其混合物中的任一種。 In the present invention, the source of the inorganic material is any one of boron nitride, molybdenum disulfide, zinc sulfide, zinc telluride, zinc selenide, tantalum triazine, antimony telluride or a mixture thereof.
10‧‧‧連續式合成高品質碳薄膜或無機材料薄膜之設備 10‧‧‧Continuous equipment for the synthesis of high quality carbon or inorganic film
100‧‧‧連續式合成高品質碳薄膜或無機材料薄膜之設備 100‧‧‧Continuous equipment for the synthesis of high quality carbon film or inorganic film
105‧‧‧外腔體 105‧‧‧External cavity
110‧‧‧基材傳送裝置 110‧‧‧Substrate transfer device
110a‧‧‧捲出構件 110a‧‧‧Extracting components
110b‧‧‧捲取構件 110b‧‧‧Winding members
110c‧‧‧轉動滾筒 110c‧‧‧Rotating drum
110d‧‧‧具金屬的基材 110d‧‧‧Metal substrate
12‧‧‧外腔體 12‧‧‧External cavity
12a‧‧‧進氣閘門 12a‧‧‧Intake gate
12b‧‧‧出氣閘門 12b‧‧‧Exhaust gate
12c‧‧‧腔體出氣管 12c‧‧‧ cavity outlet tube
120‧‧‧前處理腔體 120‧‧‧Pretreatment chamber
120a‧‧‧入口 120a‧‧‧ entrance
120b‧‧‧出口 120b‧‧‧Export
120c‧‧‧第一電漿源 120c‧‧‧first plasma source
120d‧‧‧過濾器 120d‧‧‧Filter
120e‧‧‧溫控裝置 120e‧‧‧temperature control device
130‧‧‧製程腔體 130‧‧‧Processing cavity
130a‧‧‧入口 130a‧‧‧ entrance
130b‧‧‧出口 130b‧‧‧Export
130c‧‧‧第二電漿源 130c‧‧‧Second plasma source
130d‧‧‧過濾器 130d‧‧‧Filter
130e‧‧‧溫控裝置 130e‧‧‧temperature control device
14‧‧‧前處理腔體 14‧‧‧Pretreatment chamber
14a‧‧‧入口 14a‧‧‧ Entrance
14b‧‧‧出口 14b‧‧‧Export
14c‧‧‧第一電漿源 14c‧‧‧First plasma source
14d‧‧‧第一過濾器 14d‧‧‧first filter
16‧‧‧製程腔體 16‧‧‧Processing cavity
16a‧‧‧入口 16a‧‧‧ entrance
16b‧‧‧出口 16b‧‧‧Export
16c‧‧‧第二電漿源 16c‧‧‧Second plasma source
16d‧‧‧第二過濾器 16d‧‧‧Second filter
160a‧‧‧進氣閘門 160a‧‧‧intake gate
160b‧‧‧出氣閘門 160b‧‧‧Exhaust gate
160c‧‧‧腔體出氣管 160c‧‧‧ cavity outlet tube
165‧‧‧真空系統 165‧‧‧vacuum system
170‧‧‧溫控裝置 170‧‧‧temperature control device
18‧‧‧冷卻腔體 18‧‧‧ Cooling chamber
18a‧‧‧入口 18a‧‧‧ entrance
18b‧‧‧出口 18b‧‧‧Export
20‧‧‧第一緩衝區 20‧‧‧First buffer zone
200‧‧‧連續式合成高品質碳薄膜或無機材料薄膜之設備 200‧‧‧Continuous equipment for the synthesis of high quality carbon or inorganic film
210‧‧‧製程腔體 210‧‧‧Processing cavity
210a‧‧‧進氣閘門 210a‧‧‧Intake gate
210b‧‧‧出氣閘門 210b‧‧‧Exhaust gate
22‧‧‧第二緩衝區 22‧‧‧second buffer zone
222‧‧‧第一緩衝區 222‧‧‧ first buffer zone
223‧‧‧第二緩衝區 223‧‧‧second buffer zone
224‧‧‧第三緩衝區 224‧‧‧ third buffer zone
220‧‧‧電漿產生單元 220‧‧‧ Plasma generation unit
230‧‧‧過濾器 230‧‧‧Filter
235‧‧‧電漿 235‧‧‧ Plasma
24a、24b、24c‧‧‧溫控裝置 24a, 24b, 24c‧‧‧ temperature control device
240‧‧‧基材傳送裝置 240‧‧‧Substrate transfer device
240a‧‧‧捲出構件 240a‧‧‧Extracting components
240b‧‧‧捲入構件 240b‧‧‧ involved components
240c‧‧‧轉動滾筒 240c‧‧‧Rotating drum
240d‧‧‧冷卻滾輪 240d‧‧‧Cooling wheel
240e‧‧‧具金屬的基材 240e‧‧‧Metal substrate
250‧‧‧冷卻輪 250‧‧‧Cooling wheel
26‧‧‧真空系統 26‧‧‧ Vacuum system
260‧‧‧真空系統 260‧‧‧vacuum system
270‧‧‧箭頭 270‧‧‧ arrow
280‧‧‧箭頭 280‧‧‧ arrow
28‧‧‧基材傳送裝置 28‧‧‧Substrate transfer device
28a‧‧‧捲出構件 28a‧‧‧Extracting components
28b‧‧‧捲取構件 28b‧‧‧Winding members
28c‧‧‧轉動滾筒 28c‧‧‧Rotating roller
28d‧‧‧具金屬的基材 28d‧‧‧Metal substrate
30a‧‧‧氣源控制器 30a‧‧‧Air source controller
30b‧‧‧氣源控制器 30b‧‧‧Air source controller
30c‧‧‧氣源控制器 30c‧‧‧Air source controller
31a‧‧‧氣源控制器 31a‧‧‧Air source controller
31b‧‧‧氣源控制器 31b‧‧‧Air source controller
340‧‧‧溫控裝置 340‧‧‧temperature control device
340a‧‧‧加熱燈管 340a‧‧‧heating tube
4‧‧‧加熱單元 4‧‧‧heating unit
450‧‧‧冷卻輪 450‧‧‧Cooling wheel
圖1係繪示本發明各階段合成時間、氣體種類以及溫度示意圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the synthesis time, gas type and temperature of each stage of the present invention.
圖2係繪示本發明一實施例之連續式合成高品質碳薄膜或無機材料薄膜的設備示意圖。 2 is a schematic view showing the apparatus for continuously synthesizing a high quality carbon film or an inorganic material film according to an embodiment of the present invention.
圖3係繪示本發明另一實施例之連續式合成高品質碳薄膜或無機材料薄膜的設備示意圖。 3 is a schematic view showing the apparatus for continuously synthesizing a high quality carbon film or an inorganic material film according to another embodiment of the present invention.
圖4係繪示本發明又一實施例之連續式合成高品質碳薄膜或無機材料薄膜的設備示意圖。 4 is a schematic view showing an apparatus for continuously synthesizing a high quality carbon film or an inorganic material film according to still another embodiment of the present invention.
圖5係繪示本發明再一實施例之連續式合成高品質碳薄膜或無機材料薄膜的設備示意圖。 FIG. 5 is a schematic view showing the apparatus for continuously synthesizing a high quality carbon film or an inorganic material film according to still another embodiment of the present invention.
圖6係繪示本發明已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材未通過加熱單元示意圖。 FIG. 6 is a schematic view showing that a metal substrate having a high quality carbon film or an inorganic material film of the present invention does not pass through a heating unit.
圖7係繪示本發明已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材通過加熱單元後示意圖。 FIG. 7 is a schematic view showing the metal substrate of the present invention covered with a high quality carbon film or an inorganic material film after passing through a heating unit.
以下將透過實施例來解釋本發明內容,接下來的詳細說明及附圖,皆是為了能進一步說明本發明達到預定目的所採取的方式、手段及功效。然而,關於實施例中之說明僅為闡釋本發明之技術內容及其目的功效,而非用以直接限制本發明。 The present invention will be explained in the following examples, and the detailed description and the accompanying drawings are intended to further illustrate the manner, means and function of the present invention. However, the description of the embodiments is merely illustrative of the technical contents of the present invention and the effects thereof, and is not intended to limit the present invention.
本發明連續式合成高品質碳薄膜或無機材料薄膜的設備或方法可以應用在物理氣相沉積、化學氣相沉積、磊晶成長法、分子束磊晶法或單原子層沉積法等。本發明雖以化學氣相沉積法連續地在一具金屬的基材上合成高品質碳薄膜或無機材料薄膜做說明,其它方法只要能連續式合成高品質碳薄膜或無機材料薄膜都不脫離本發明精神。所謂的高品質碳薄膜或無機材料薄膜可以是如石墨烯之類的碳材料,而具金屬的基材可以為一種具金屬的基材或是在基材上具有一金屬薄膜。所謂的金屬可以是如鐵、鈷、鎳等過渡金屬材料。 The apparatus or method for continuously synthesizing a high-quality carbon film or an inorganic material film of the present invention can be applied to physical vapor deposition, chemical vapor deposition, epitaxial growth, molecular beam epitaxy or monoatomic layer deposition. Although the invention continuously synthesizes a high-quality carbon film or an inorganic material film on a metal substrate by chemical vapor deposition, other methods can continuously synthesize a high-quality carbon film or an inorganic material film without departing from the present invention. Inventive spirit. The so-called high-quality carbon film or inorganic material film may be a carbon material such as graphene, and the metal substrate may be a metal substrate or a metal film on the substrate. The so-called metal may be a transition metal material such as iron, cobalt or nickel.
高品質碳薄膜或無機材料薄膜的合成方法可以包括以下步驟:首先在一化學氣相沉積的反應器中通入氫氣氣體,其中,氫氣的壓力在標準狀態範圍10mTorr-760Torr,較佳的為760Torr,以固定流量範圍5-1000sccm(standard cubic centimeter per minute),較佳的為50sccm,通入時間為5sec-2hr,較佳時間為50分鐘。一具金屬的基材在溫度範圍150-1300℃,較佳溫度為1000℃下進行熱退火,退火時間5sec-2hr,較佳的為40分鐘,以從表面移除有機物質與氧化物。之後再將具碳源或無機材料源的混合氣體通入反應器,並在溫度範圍150-1300℃,較佳的為1000℃的溫度下成長高品質碳薄膜或無機材料薄膜,其中具 碳源或無機材料源的混合氣體流量範圍為5-1000sccm,較佳的為60sccm,而氫氣流量為15sccm。高品質碳薄膜或無機材料薄膜合成之後,再利用一再加熱單元將合成的高品質碳薄膜或無機材料薄膜做局部再加熱處理,以減少由晶界導致的缺陷,進一步優化高品質碳薄膜或無機材料薄膜在結晶時碳原子間鍵結不完全所產生的缺陷,此步驟能使高品質碳薄膜或無機材料薄膜覆蓋率及品質再次提升。 The method for synthesizing a high-quality carbon film or an inorganic material film may include the steps of first introducing a hydrogen gas into a chemical vapor deposition reactor, wherein the pressure of the hydrogen gas is in a standard state range of 10 mTorr to 760 Torr, preferably 760 Torr. The constant flow range is 5-1000 sccm (standard cubic centimeter per minute), preferably 50 sccm, and the access time is 5 sec - 2 hr, preferably 50 minutes. A metal substrate is thermally annealed at a temperature in the range of from 150 to 1300 ° C, preferably at 1000 ° C, for an annealing time of from 5 sec to 2 hr, preferably 40 minutes, to remove organic materials and oxides from the surface. Then, a mixed gas having a carbon source or an inorganic material source is introduced into the reactor, and a high-quality carbon film or an inorganic material film is grown at a temperature ranging from 150 to 1300 ° C, preferably 1000 ° C. The mixed gas flow rate of the carbon source or inorganic material source ranges from 5 to 1000 sccm, preferably 60 sccm, and the hydrogen flow rate is 15 sccm. After the high-quality carbon film or inorganic material film is synthesized, the synthesized high-quality carbon film or inorganic material film is locally reheated by a reheating unit to reduce defects caused by grain boundaries, and further optimize high-quality carbon film or inorganic The defect that the material film is incompletely bonded between carbon atoms during crystallization, this step can improve the coverage and quality of the high-quality carbon film or inorganic material film again.
本發明所使用的具碳源或無機材料源可為氣相碳基前驅物、液相碳基前驅物、或固相碳基前驅物中任一種所裂解而成,其中該碳基前驅物為甲烷、乙烯、乙炔、乙醇、苯、甲醇、碳基的高分子、奈米碳材料或其混合物中的任一種。其中該碳源或無機材料源是經氮、硼或其混合物摻雜中的任一種。其中該無機材料來源系氮化硼、二硫化鉬、硫化鋅、碲化鋅、硒化鋅、三硒化二鉍、碲化鉍或其混合物中的任一種。具金屬的基材,所述的金屬可以為銅、鐵、鈷、鎳、金、銀或其混合物的任一種,所述的基材可為氧化矽基板、石英基板、藍寶石基板、氮化硼基板、玻璃基板、金屬基板、半導體基板或其組合中的任一種。 The carbon source or inorganic material source used in the present invention may be formed by cracking any one of a gas phase carbon-based precursor, a liquid phase carbon-based precursor, or a solid phase carbon-based precursor, wherein the carbon-based precursor is Any of methane, ethylene, acetylene, ethanol, benzene, methanol, a carbon-based polymer, a nanocarbon material, or a mixture thereof. Wherein the source of carbon or inorganic material is any one of doped with nitrogen, boron or a mixture thereof. Wherein the inorganic material source is any one of boron nitride, molybdenum disulfide, zinc sulfide, zinc telluride, zinc selenide, tantalum triazine, antimony telluride or a mixture thereof. The metal substrate may be any one of copper, iron, cobalt, nickel, gold, silver or a mixture thereof, and the substrate may be a ruthenium oxide substrate, a quartz substrate, a sapphire substrate, or a boron nitride. Any one of a substrate, a glass substrate, a metal substrate, a semiconductor substrate, or a combination thereof.
請先參閱圖1,本發明連續式合成高品質碳薄膜或無機材料薄膜之方法可主要分成三個處理階段來完成製程。其中第一階段為氫氣前處理,通入含氫之混合氣體,例如氫氣和氬氣的混合氣體,請詳見圖1中所示羅馬數字I以及II的部份,將具金屬的基材表面做預還原;接著進入第二階段,請參照圖1中羅馬數字III的部份,成長階段通入反應氣體(甲烷、氫氣、氬氣),其中碳源或無機材料源反應氣體除了甲烷之外,亦可以選用乙炔或乙烯等,藉此階段成長高品質碳薄膜或無機材料薄膜;第三階段是冷卻階段,請參照圖1中羅馬數字IV的部份,通入通入含氫之混合氣體,例如氫氣和氬氣的混合氣體,或通入惰氣,例如氮氣或氬氣降溫穩定高品質碳薄膜或無機材料薄膜。第一階段先在 一個氫氣的環境中對金屬基板進行40分鐘的升溫處理,使金屬基板所處環境溫度由室溫升至1025℃,接著,在1025℃的恆溫狀態下在氫氣環境下對金屬基板進行20分鐘的前處理;然後,進行第二階段,在1025℃的恆溫狀態下通入反應氣體20分鐘,以在具金屬的基材上成長高品質碳薄膜或無機材料薄膜;最後,進入第三階段,通入氬氣並對金屬基板進行40分鐘的進行降溫處理,逐步由1025℃降至室溫25℃以下。 Referring first to FIG. 1, the method for continuously synthesizing a high quality carbon film or an inorganic material film of the present invention can be mainly divided into three processing stages to complete the process. The first stage is hydrogen pretreatment, and a mixed gas containing hydrogen, such as a mixed gas of hydrogen and argon, please refer to the part of Roman numerals I and II shown in Fig. 1, which will be the surface of the metal substrate. Pre-reduction; then enter the second stage, please refer to the part of Roman numeral III in Figure 1, the reaction phase is introduced into the reaction gas (methane, hydrogen, argon), wherein the carbon source or inorganic material source reaction gas in addition to methane It is also possible to use acetylene or ethylene to grow high-quality carbon film or inorganic material film in this stage; the third stage is the cooling stage, please refer to the part of Roman numeral IV in Figure 1, and pass the hydrogen-containing mixed gas. For example, a mixed gas of hydrogen and argon, or an inert gas such as nitrogen or argon, is used to stabilize a high-quality carbon film or a film of an inorganic material. The first stage is first In a hydrogen atmosphere, the metal substrate is heated for 40 minutes, the ambient temperature of the metal substrate is raised from room temperature to 1025 ° C, and then the metal substrate is subjected to a hydrogen atmosphere at a constant temperature of 1025 ° C for 20 minutes. Pre-treatment; then, in the second stage, the reaction gas is introduced at a constant temperature of 1025 ° C for 20 minutes to grow a high-quality carbon film or inorganic material film on a metal substrate; finally, enter the third stage, Argon gas was introduced and the metal substrate was subjected to a temperature reduction treatment for 40 minutes, and gradually decreased from 1025 ° C to room temperature below 25 ° C.
本發明所述的連續式合成高品質碳薄膜或無機材料薄膜之設備與方法,係為一種捲對捲(Roll-to-Roll)裝置,採用以滾輪傳輸為架構進行軟性基材收放、輸送及輔助加工等相關製程。捲對捲裝置使用滾輪來控制軟性基材的移動,並維持穩定的傳輸速度,透過對各項參數控制,以進行精密加工作業。所述之具金屬的基材可以為一種可撓曲的軟性基材,長度為數十公尺長,在製程前可以捲曲成為一筒狀,在合成高品質碳薄膜或無機材料薄膜的製程中,可以連續的展開,在反應器中的碳源或無機材料源氣體可以沉積在連續通過的具金屬的基材的表面,形成高品質碳薄膜或無機材料薄膜,經冷卻到溫度範圍25-300℃,較佳的為25℃後再捲曲成為一筒狀,為一種捲對捲連續式合成高品質碳薄膜或無機材料薄膜方式。 The apparatus and method for continuously synthesizing high-quality carbon film or inorganic material film according to the present invention is a roll-to-roll device, which adopts roller transmission as a structure for flexible substrate retracting and conveying. And related processes such as auxiliary processing. The roll-to-roll device uses a roller to control the movement of the soft substrate and maintains a stable transfer speed, and controls various parameters for precision machining. The metal substrate may be a flexible flexible substrate having a length of several tens of meters and being crimped into a cylindrical shape before the process, in the process of synthesizing a high quality carbon film or an inorganic material film. Can be continuously deployed, the carbon source or inorganic material source gas in the reactor can be deposited on the surface of the continuously passing metal substrate to form a high quality carbon film or inorganic material film, which is cooled to a temperature range of 25-300 °C, preferably 25 ° C, is then crimped into a cylindrical shape, which is a roll-to-roll continuous synthesis of high-quality carbon film or inorganic material film.
捲對捲連續式合成高品質碳薄膜或無機材料薄膜方式有大面積、高量產、低成本等特性,是商業化產品朝向連續生產之主要技術方法之一。然而,在採用此捲對捲(Roll-to-Roll)裝置的同時,必須設置相對應的腔體,以對應連續式合成高品質碳薄膜或無機材料薄膜的製程方式,並且必須設置對應數量的真空泵來控制不同腔體中之化學氣相沉積氣氛,而且,在不同腔體之間還需設置緩衝區,以阻隔不同腔體的化學氣相沉積氣體。 The roll-to-roll continuous synthesis of high-quality carbon film or inorganic material film has the characteristics of large area, high volume production, low cost, etc. It is one of the main technical methods for commercial products to be continuously produced. However, in the case of using this roll-to-roll device, the corresponding cavity must be provided to correspond to the process of continuously synthesizing a high-quality carbon film or an inorganic material film, and a corresponding number must be set. A vacuum pump is used to control the chemical vapor deposition atmosphere in different chambers, and a buffer zone is also required between the different chambers to block the chemical vapor deposition gases of different chambers.
因此,在上述的捲對捲連續化學氣相沉積設備中,由於需使用多個腔體、多個真空泵以及緩衝區,必須將多個腔體中所通入氣體的化學氣相沉 積氣氛進行適當控制。有關本發明之前述及其他技術內容、特點及功效,以下配合四個實施例詳細說明本發明之連續式合成高品質碳薄膜或無機材料薄膜的設備與方法。 Therefore, in the above-described roll-to-roll continuous chemical vapor deposition apparatus, since a plurality of cavities, a plurality of vacuum pumps, and a buffer zone are required, it is necessary to chemically vaporize a gas in a plurality of cavities. The atmosphere is properly controlled. With respect to the foregoing and other technical contents, features and effects of the present invention, the apparatus and method for continuously synthesizing a high quality carbon film or inorganic material film of the present invention will be described in detail below with reference to four embodiments.
在本發明的第一較佳實施例中,係採用含有捲對捲裝置以及三個製程腔體的設備,藉以連續式大面積合成高品質碳薄膜或無機材料薄膜。請參閱圖2所示,為本發明第一個較佳實施例中連續式合成高品質碳薄膜或無機材料薄膜之設備10的示意圖,此處需事先說明的是,雖然在圖2中僅繪示出用以說明本發明之連續式合成高品質碳薄膜或無機材料薄膜之設備10的主要構件,然而,本領域具有通常知識的技術人員應可依其具有的相關知識,輕易的推知本發明之連續式合成高品質碳薄膜或無機材料薄膜之設備10所應具有的所有構件。而且,須注意圖中所示者為本發明選用之實施例結構,此僅供說明之用,並不受此種結構的限制。 In the first preferred embodiment of the present invention, a device including a roll-to-roll device and three process chambers is used to continuously synthesize a high-quality carbon film or an inorganic material film over a large area. Please refer to FIG. 2, which is a schematic diagram of a device 10 for continuously synthesizing a high-quality carbon film or an inorganic material film according to a first preferred embodiment of the present invention, which needs to be described in advance, although only in FIG. The main components of the apparatus 10 for describing the continuous synthesis of a high quality carbon film or an inorganic material film of the present invention are shown. However, those skilled in the art should readily infer the present invention based on the relevant knowledge. All components of the apparatus 10 for continuous synthesis of high quality carbon film or inorganic material film. Moreover, it should be noted that those illustrated in the drawings are illustrative of the embodiment of the invention, which is for illustrative purposes only and is not limited by the structure.
所述之連續式合成高品質碳薄膜或無機材料薄膜之設備10主要具有一外腔體12、一基材傳送裝置28、一真空系統26、一氣源控制器30a、30b、30c、一前處理腔體14、一製程腔體16、一冷卻腔體18、第一緩衝區20、一第二緩衝區22、以及一溫控裝置24a、24b、24c。 The apparatus 10 for continuously synthesizing a high quality carbon film or an inorganic material film mainly has an outer cavity 12, a substrate transfer device 28, a vacuum system 26, a gas source controller 30a, 30b, 30c, a front The processing chamber 14, a process chamber 16, a cooling chamber 18, a first buffer 20, a second buffer 22, and a temperature control device 24a, 24b, 24c.
如圖2所示,基材傳送裝置28用以使具金屬的基材28d沿著一個移動路徑進行傳送,移動路徑如箭頭方向。基材傳送裝置28由一捲出構件28a、捲取構件28b、轉動滾筒28c構成。藉由轉動滾筒28c將具金屬的基材28d由一捲出構件28a捲出,並且透過轉動滾筒28c在外腔體12內沿著移動路徑移動(如箭頭方向),最後再透過捲取構件28b卷成筒狀。其中,捲出構件28a與捲取構件28b是分別裝設在連續式合成高品質碳薄膜或無機材料薄膜之設備10的上游處與下游處。其中,捲出構件28a與捲取構件28b皆適用於捲繞具金屬的基材28d,而具金屬的基材28d是以兩端分別固定在捲出構件28a與捲取構件28b上,藉由捲取構 件28b的轉動,具金屬的基材28d將會連續的由捲出構件28a移動至捲取構件28b。上述捲出構件28a與捲取構件28b例如是由軸承與轉輪(未圖示)所構成,其中軸承樞設於連續式合成高品質碳薄膜或無機材料薄膜之設備10上,轉輪裝設於軸承上,至於具金屬的基材28d則捲繞於轉輪上。捲取構件28b的轉動可藉由將捲取構件28b連接至驅動構件(未圖示)以達成,其例如是可將捲取構件28b的軸承經由適當的齒輪配置而連接至馬達,以藉由馬達的轉動而帶動捲取構件28b的轉動。 As shown in Fig. 2, the substrate transfer device 28 is used to transport the metal substrate 28d along a moving path, such as the direction of the arrow. The substrate transfer device 28 is composed of a take-up member 28a, a take-up member 28b, and a rotary drum 28c. The metal substrate 28d is unwound from a take-up member 28a by rotating the drum 28c, and is moved along the moving path (such as the direction of the arrow) in the outer chamber 12 through the rotating drum 28c, and finally passed through the take-up member 28b. In a tube shape. Among them, the unwinding member 28a and the take-up member 28b are respectively installed upstream and downstream of the apparatus 10 for continuously synthesizing a high-quality carbon film or an inorganic material film. Wherein, the take-up member 28a and the take-up member 28b are both suitable for winding the metal substrate 28d, and the metal substrate 28d is fixed at both ends to the take-up member 28a and the take-up member 28b, respectively. Volume structure The rotation of the piece 28b, the metal substrate 28d will be continuously moved by the take-up member 28a to the take-up member 28b. The unwinding member 28a and the take-up member 28b are, for example, composed of a bearing and a runner (not shown), wherein the bearing is pivotally mounted on the apparatus 10 for continuously synthesizing a high-quality carbon film or an inorganic material film, and the runner is mounted. On the bearing, the metal substrate 28d is wound around the runner. Rotation of the take-up member 28b can be achieved by attaching the take-up member 28b to a drive member (not shown), for example, by connecting the bearing of the take-up member 28b to the motor via a suitable gear arrangement, The rotation of the motor drives the rotation of the take-up member 28b.
所述之外腔體12具有一進氣閘門12a、一出氣閘門12b,且內部設置有一前處理腔體14、一製程腔體16及一冷卻腔體18。所述的前處理腔體14、製程腔體16和一冷卻腔體18可以沿著具金屬的基材28d移動路徑設置,其中具金屬的基材28d可以依移動路徑依序通過前處理腔體14、製程腔體16及冷卻腔體18。一溫控裝置24a、24b、24c可對具金屬的基材28d進行加熱作業。 The outer cavity 12 has an air intake gate 12a and an air outlet gate 12b, and is internally provided with a front processing chamber 14, a processing chamber 16, and a cooling chamber 18. The pre-processing chamber 14, the process chamber 16 and a cooling chamber 18 may be disposed along a moving path of the metal substrate 28d, wherein the metal substrate 28d may sequentially pass through the pre-processing chamber according to the moving path. 14. Process chamber 16 and cooling chamber 18. A temperature control device 24a, 24b, 24c can heat the metal substrate 28d.
所述的前處理腔體14和製程腔體16之間具有一第一緩衝區20;製程腔體16和冷卻腔體18之間具有一第二緩衝區22。其中第一緩衝區20係隔絶前處理腔體14和製程腔體16的氣體相互流通,第二緩衝區22係隔絶製程腔體16和冷卻腔體18的氣體相互流通。在第一緩衝區20的氣體係由遠離前處理腔體14的出口14b和製程腔體16的入口16a的方向流動;在第二緩衝區22內的氣體係由遠離製程腔體16出口16b和冷卻腔體18入口18a的方向流動,以避免從前處理腔體14、製程腔體16和冷卻腔體18流出的氣體互相污染,其中第一緩衝區20第二緩衝區22內的氣體流速約為0.05L/min-1000L/min。 A first buffer zone 20 is defined between the pre-treatment chamber 14 and the process chamber 16; a second buffer zone 22 is defined between the process chamber 16 and the cooling chamber 18. The first buffer zone 20 is configured to insulate the gas of the pre-treatment chamber 14 and the process chamber 16 from each other, and the second buffer zone 22 isolates the gases of the process chamber 16 and the cooling chamber 18 from flowing into each other. The gas system in the first buffer zone 20 flows in a direction away from the outlet 14b of the pretreatment chamber 14 and the inlet 16a of the process chamber 16; the gas system in the second buffer zone 22 is remote from the process chamber 16 outlet 16b and The flow of the cooling chamber 18 in the direction of the inlet 18a prevents the gas flowing out of the pre-processing chamber 14, the process chamber 16 and the cooling chamber 18 from contaminating each other, wherein the gas flow rate in the second buffer zone 22 of the first buffer zone 20 is approximately 0.05 L / min - 1000 L / min.
前處理腔體14、製程腔體16和一冷卻腔體18沿著具金屬的基材28d移動路徑設置,使具金屬的基材28d可以依移動路徑依序通過前處理腔體14、製程腔體16及冷卻腔體18。具金屬的基材28d藉由捲出構件28a與捲取構件28b的驅動,將會連續的經過前處理腔體14、製程腔體16和一冷卻腔體18。具金屬的基材28d從前處理腔體14的入口14a進入,前處理腔體14完成抽氣降低壓 力,進行40分鐘的升溫處理,使具金屬的基材28d所處環境溫度由室溫升至1025℃,接著,在1025℃的恆溫狀態下對具金屬的基材28d進行20分鐘的前處理,以從表面移除有機物質與氧化物。氫氣藉由氣源控制器30a導入前處理腔體14中,氫氣以固定流量通入50分鐘,流量為50sccm(standard cubic centimeter per minute),亦即在標準狀態(壓力760Toor)下流量為每分鐘50立方公分,前處理腔體14可以對具金屬的基材28d進行第一階段的前處理製程;第一階段的前處理製程結束後,具金屬的基材28d從前處理腔體14的出口14b離開,並經由入口16a進入製程腔體16,當具金屬的基材28d移動到製程腔體16時,進行具金屬的基材28d的化學氣相沉積製程,即進行高品質碳薄膜或無機材料薄膜合成製程,具金屬的基材28d在進入製程腔體16之前會先經過位於前處理腔體14與製程腔體16之間的第一緩衝區20,第一緩衝區20為一抽氣緩衝區,藉由一抽氣作動造成此區域對出口14b及入口16a形成相對負壓,可以避免前處理腔體14與製程腔體16兩腔體不同氣氛之交叉污染,其中圖2之虛線箭頭係表示抽氣作動時的氣流方向。另外,要說明的是前處理腔體14內的溫度係由溫控裝置24a調整,具金屬的基材28d進入具有製程設定參數之製程腔體16中,例如製程腔體16在1025℃的恆溫狀態下由通入反應氣體(甲烷、氫氣)20分鐘,以在具金屬的基材28d上成長高品質碳薄膜或無機材料薄膜,其中,乃藉由氣源控制器30b將反應氣體(甲烷、氫氣)導入製程腔體16,在適當條件下沉積大面積的高品質碳薄膜或無機材料薄膜於具金屬的基材28d上,其中甲烷流量為60sccm而氫氣流量為15sccm;第二階段的高品質碳薄膜或無機材料薄膜合成製程結束後,具有高品質碳薄膜或無機材料薄膜的具金屬的基材28d從製程腔體16的出口16b離開,並經由入口18a進入冷卻腔體18,高品質碳薄膜或無機材料薄膜當具金屬的基材28d移動到冷卻腔體18,通入氬氣並對具金屬的基材28d進行40分鐘的進行降溫處理,逐步由1025℃降至室溫以下,具金屬的基材28d在進入冷卻腔體18之前會先經過位於 製程腔體16與冷卻腔體18之間的第二緩衝區22,第二緩衝區22為亦為一抽氣緩衝區,藉由一抽氣作動造成此區域先對出口16b及入口18a形成相對負壓,可以避免製程腔體16與冷卻腔體18兩製程腔體不同氣氛之交叉污染,其中圖2之虛線箭頭係表示抽氣作動時的氣流方向,之後,具金屬的基材28d進入冷卻腔體18中,藉由氣源控制器30c將大量氬氣通入冷卻腔體18中,以對金屬基板進行40分鐘的進行降溫處理,逐步由1025℃降至室溫,最後,具有高品質碳薄膜或無機材料薄膜具金屬的基材28d由捲取構件28b收納成捲。 The pre-processing chamber 14, the processing chamber 16 and a cooling chamber 18 are disposed along the moving path of the metal substrate 28d, so that the metal substrate 28d can sequentially pass through the pre-processing chamber 14 and the processing chamber according to the moving path. Body 16 and cooling chamber 18. The metal substrate 28d, through the driving of the take-up member 28a and the take-up member 28b, will continuously pass through the pre-treatment chamber 14, the process chamber 16, and a cooling chamber 18. The metal substrate 28d enters from the inlet 14a of the pretreatment chamber 14, and the pretreatment chamber 14 completes the pumping down pressure. The temperature was raised for 40 minutes, and the ambient temperature of the metal substrate 28d was raised from room temperature to 1025 ° C. Then, the metal substrate 28 d was pretreated for 20 minutes at a constant temperature of 1025 ° C. To remove organic matter and oxides from the surface. The hydrogen gas is introduced into the pretreatment chamber 14 by the gas source controller 30a, and the hydrogen gas is introduced at a fixed flow rate for 50 minutes at a flow rate of 50 sccm (standard cubic centimeter per minute), that is, the flow rate per minute is under standard conditions (pressure 760 Toor). 50 cubic centimeters, the pretreatment chamber 14 can perform the first stage pretreatment process on the metal substrate 28d; after the first stage pretreatment process, the metal substrate 28d exits the outlet 14b of the pretreatment chamber 14. Leaving and entering the process chamber 16 via the inlet 16a, when the metal substrate 28d is moved to the process chamber 16, a chemical vapor deposition process of the metal substrate 28d is performed, that is, a high quality carbon film or inorganic material is performed. The thin film synthesis process, the metal substrate 28d first passes through the first buffer 20 between the pre-processing chamber 14 and the process chamber 16 before entering the process chamber 16, and the first buffer 20 is a pumping buffer. The region, by a pumping action, causes the region to form a relative negative pressure on the outlet 14b and the inlet 16a, thereby avoiding cross-contamination of the different atmospheres of the pre-processing chamber 14 and the processing chamber 16 in different atmospheres, wherein the dotted arrow of FIG. table Shows the direction of the airflow when the pumping is actuated. In addition, it is to be noted that the temperature in the pretreatment chamber 14 is adjusted by the temperature control device 24a, and the metal substrate 28d enters the process chamber 16 having process setting parameters, for example, the process chamber 16 is at a constant temperature of 1025 ° C. In the state, a reaction gas (methane, hydrogen) is introduced for 20 minutes to grow a high-quality carbon film or a film of an inorganic material on the metal substrate 28d, wherein the reaction gas (methane, by the gas source controller 30b) Hydrogen is introduced into the process chamber 16, and a large-area high-quality carbon film or inorganic material film is deposited on the metal substrate 28d under appropriate conditions, wherein the methane flow rate is 60 sccm and the hydrogen flow rate is 15 sccm; the second stage is of high quality. After the carbon film or inorganic material film synthesis process is finished, the metal substrate 28d having a high quality carbon film or inorganic material film exits from the outlet 16b of the process chamber 16 and enters the cooling chamber 18 via the inlet 18a, high quality carbon. The film or inorganic material film moves to the cooling cavity 18 when the metal substrate 28d is passed, argon gas is introduced, and the metal substrate 28d is cooled for 40 minutes, and gradually reduced from 1025 ° C to the chamber. Hereinafter, the substrate 28d with the metal 18 will go through before entering the cooling chamber is located The second buffer zone 22 between the process chamber 16 and the cooling chamber 18, the second buffer zone 22 is also a pumping buffer, and the area is firstly opposed to the outlet 16b and the inlet 18a by a pumping action. Negative pressure can avoid cross-contamination of different atmospheres of the process chamber 16 and the cooling chamber 18, wherein the dotted arrow in FIG. 2 indicates the direction of the air flow during the pumping operation, and then the metal substrate 28d enters the cooling. In the cavity 18, a large amount of argon gas is introduced into the cooling cavity 18 by the gas source controller 30c to cool the metal substrate for 40 minutes, gradually decreasing from 1025 ° C to room temperature, and finally, having high quality. The metal substrate 28d having a carbon film or an inorganic material film is accommodated in a roll by the take-up member 28b.
在前處理腔體14的入口14a及冷卻腔體18的出口18b處,亦為一個抽氣緩衝區(圖未示),藉由一抽氣作動分別造成此區域對入口14a及出口18b形成相對負壓,可以避免前處理腔體14與冷卻腔體18內的氣體和外腔體12內的氣體交叉污染。 At the inlet 14a of the pre-treatment chamber 14 and the outlet 18b of the cooling chamber 18, it is also a pumping buffer (not shown), which is caused by the pumping action to respectively form the area to the inlet 14a and the outlet 18b. Negative pressure can prevent cross-contamination of the pre-treatment chamber 14 with the gas within the cooling chamber 18 and the gas within the outer chamber 12.
在其它實施例中,除了甲烷之外,亦可以選用乙炔或乙烯等作為碳源或無機材料源反應氣體,以成長高品質碳薄膜或無機材料薄膜。另外,要說明的是製程腔體16和冷卻腔體18內的溫度也可以由溫控裝置24b、24c調整。真空系統26藉由外腔體12之進氣閘門12a與出氣閘門12b,將氣體抽入及排出以維持真空狀態。真空系統26亦可分別直接與前處理腔體14、製程腔體16、冷卻腔體18連接,而在必要時分別將前處理腔體14、製程腔體16、冷卻腔體18的製程氣體抽出以維持真空狀態。其中,真空系統26可採用一般常見的機械泵與擴散泵的組合。 In other embodiments, in addition to methane, acetylene or ethylene may be used as a carbon source or an inorganic material source reaction gas to grow a high quality carbon film or an inorganic material film. Additionally, it is to be noted that the temperature within the process chamber 16 and the cooling chamber 18 can also be adjusted by the temperature control devices 24b, 24c. The vacuum system 26 draws in and exhausts gas through the intake valve 12a and the outlet valve 12b of the outer chamber 12 to maintain a vacuum state. The vacuum system 26 can also be directly connected to the pre-processing chamber 14, the processing chamber 16, and the cooling chamber 18, respectively, and if necessary, extract the process gases of the pre-processing chamber 14, the processing chamber 16, and the cooling chamber 18. To maintain a vacuum. Among them, the vacuum system 26 can be a combination of a common mechanical pump and a diffusion pump.
如圖2所示,氣源控制器30a、30b、30c提供前處理腔體14、製程腔體16、冷卻腔體18的氣源控制。氣源控制器30a、30b、30c設置在外腔體12內,用以提供連續式合成高品質碳薄膜或無機材料薄膜所需要的氣體。而其中特別值得注意的是,本發明在進行連續式合成高品質碳薄膜或無機材料薄膜時,氣源控制器30a、30b、30c操作參數彼此並不相同,其中操作參數例如 是30a為含氫氣之混氣,流量範圍為0.5sccm-500sccm,較佳的為20sccm;30b為含有碳源的混合氣體CH4/H2/Ar,其中碳源為0.5sccm-800sccm,較佳的為20sccm,氫氣0.5sccm-1000sccm,較佳的為20sccm,氬氣0.5sccm-1000sccm,較佳的為900sccm;30c為氬氣或氮氣0.5sccm-1000sccm,較佳的為氬氣500sccm。氣源控制器30a、30b、30c用以控制化學沉積時供給至少一個氣源的操作參數,其中控制構件將化學沉積時供給至少一個氣源的操作參數控制為彼此不同,在進行化學氣相沉積時能夠依照實際化學氣相沉積製程上的需要,對所使用的化學氣相沉積氣氛的種類以及混合比例進行適當的選擇與設定。 As shown in FIG. 2, the air source controllers 30a, 30b, 30c provide air source control of the pre-processing chamber 14, the process chamber 16, and the cooling chamber 18. The gas source controllers 30a, 30b, 30c are disposed in the outer chamber 12 for providing a gas required for continuous synthesis of a high quality carbon film or an inorganic material film. It is particularly noteworthy that the operating parameters of the gas source controllers 30a, 30b, 30c are not identical to each other when the continuous synthesis of the high quality carbon film or the inorganic material film is performed, wherein the operating parameters are, for example, 30a is a mixed gas containing hydrogen, a flow rate ranging from 0.5 sccm to 500 sccm, preferably 20 sccm; and 30 b is a mixed gas CH4/H2/Ar containing a carbon source, wherein the carbon source is from 0.5 sccm to 800 sccm, preferably 20 sccm, hydrogen 0.5 sccm-1000 sccm, preferably 20 sccm, argon gas 0.5 sccm-1000 sccm, preferably 900 sccm; 30c is argon or nitrogen 0.5 sccm-1000 sccm, preferably argon 500 sccm. The gas source controllers 30a, 30b, 30c are configured to control operating parameters for supplying at least one gas source during chemical deposition, wherein the control member controls the operating parameters supplied to the at least one gas source during chemical deposition to be different from each other, for performing chemical vapor deposition The type and mixing ratio of the chemical vapor deposition atmosphere to be used can be appropriately selected and set according to the requirements of the actual chemical vapor deposition process.
如圖3所示,為本發明第二較佳實施例,和第一較佳實施例不同處在於本實施例係利用電漿輔助化學氣相沉積法(Plasma Assisted Chemical Vapor Deposition,CVD)連續地在一具金屬的基材28d上合成高品質碳薄膜或無機材料薄膜,在電漿輔助化學氣相沉積法中,其主要利用微波電漿的輔助系統,搭配連續式捲對捲裝置來達到低溫、連續式成長高品質碳薄膜或無機材料薄膜於具金屬的基材28d上,電漿可以幫助裂解所需碳源或無機材料源,輔助於低溫合成。 As shown in FIG. 3, which is a second preferred embodiment of the present invention, the difference from the first preferred embodiment is that the present embodiment continuously uses Plasma Assisted Chemical Vapor Deposition (CVD). A high-quality carbon film or an inorganic material film is synthesized on a metal substrate 28d. In the plasma-assisted chemical vapor deposition method, the microwave plasma auxiliary system is mainly used, and the continuous roll-to-roll device is used to achieve low temperature. Continuously growing high-quality carbon film or inorganic material film on the metal substrate 28d, the plasma can help crack the desired carbon source or inorganic material source, and assist in low temperature synthesis.
本實施例中,在前處理腔體14更可以包含有一第一電漿源14c以及一第一過濾器14d,製程腔體16包含有一第二電漿源16c以及一第二過濾器16d。在本實施例中藉由電漿源提供一氣體游離環境,透過電漿的形成來降低連續式合成高品質碳薄膜或無機材料薄膜的製程溫度。本實施例電漿輔助化學氣相沉積法連續式合成高品質碳薄膜或無機材料薄膜,藉由電場讓氣體解離產生電子與離子,當這些電子受射頻或微波等電磁場加速後,碰撞氣體就會產生更多離子與電子而產生電漿。過濾器設置在電漿源和具金屬的基材28d之間,可以減少離子轟擊與紫外光子(UV photon)對高品質碳薄膜或無機材料薄膜的破壞與損傷。就本實施例而言,先在前處理腔體14施行具金屬的基材28d的前處理,前處理腔體14完成抽氣降低壓力,進行40分鐘的升溫處理,使具金屬的基材28d所處 環境溫度由室溫升至1025℃,接著,在1025℃的恆溫狀態下利用氫氣電漿對具金屬的基材28d進行20分鐘的前處理,以從表面移除有機物質與氧化物,亦即利用電漿輔助裂解氫氣,除了幫助降低製程溫度,可同時形成氫之活性離子團,進行具金屬的基材28d面之還原;接著,在製程腔體16施行具金屬的基材28d的沉積製程階段,亦即在製程腔體16通入反應氣體(甲烷、氫氣、氬氣),其中碳源或無機材料源反應氣體可以是甲烷、乙炔、乙烯等,藉此沉積製程階段於具金屬的基材28d上合成高品質碳薄膜或無機材料薄膜,在製程腔體16中係使用電漿輔助化學氣相沉積法(Plasma assisted Chemical Vapor Deposition,PACVD)連續地在一具金屬的基材28d上合成高品質碳薄膜或無機材料薄膜,也就是說,在使用電漿輔助化學氣相沉積的製程腔體16中通入甲烷與氫氣的混合氣體作為碳源或無機材料源氣體,並在1000℃的溫度下成長高品質碳薄膜或無機材料薄膜薄膜,其中甲烷流量為60sccm而氫氣流量為15sccm,並施加2.45GHz的微波使其產生電漿,電漿提供裂解碳源或無機材料源氣體的能量,被裂解碳源或無機材料源氣體沉積在具金屬的基材28d的表面上,具金屬的基材28d的表面就可合成高品質碳薄膜或無機材料薄膜;最後,在冷卻腔體18施行高品質碳薄膜或無機材料薄膜的冷卻處理,降溫以穩定高品質碳薄膜或無機材料薄膜。 In this embodiment, the pre-processing chamber 14 further includes a first plasma source 14c and a first filter 14d. The processing chamber 16 includes a second plasma source 16c and a second filter 16d. In this embodiment, a gas free environment is provided by the plasma source to reduce the process temperature of the continuous synthesis of the high quality carbon film or the inorganic material film by the formation of the plasma. In the present embodiment, the plasma-assisted chemical vapor deposition method continuously synthesizes a high-quality carbon film or an inorganic material film, and the gas is dissociated by an electric field to generate electrons and ions. When these electrons are accelerated by an electromagnetic field such as radio frequency or microwave, the collision gas will be collided. Produce more ions and electrons to produce plasma. The filter is disposed between the plasma source and the metal substrate 28d to reduce damage and damage of high quality carbon film or inorganic material film by ion bombardment and UV photon. For the present embodiment, the pretreatment chamber 14 is first subjected to a pretreatment of the metal substrate 28d, and the pretreatment chamber 14 is subjected to pumping to reduce the pressure, and a temperature rising treatment is performed for 40 minutes to form a metal substrate 28d. Where you are The ambient temperature is raised from room temperature to 1025 ° C, and then the metal substrate 28 d is pretreated with hydrogen plasma at a constant temperature of 1025 ° C for 20 minutes to remove organic substances and oxides from the surface, that is, The use of plasma to assist in the cracking of hydrogen, in addition to helping to reduce the process temperature, can simultaneously form a reactive ion cluster of hydrogen to carry out the reduction of the 28d surface of the metal substrate; and then, a deposition process of the substrate 28d having the metal in the process chamber 16 is performed. In the stage, that is, the reaction gas (methane, hydrogen, argon) is introduced into the process chamber 16, wherein the carbon source or the inorganic material source reaction gas may be methane, acetylene, ethylene, etc., thereby depositing a process stage in the metal-based group. A high-quality carbon film or an inorganic material film is synthesized on the material 28d, and is continuously synthesized on a metal substrate 28d by plasma assisted chemical vapor deposition (PACVD) in the process chamber 16. High-quality carbon film or inorganic material film, that is, a mixed gas of methane and hydrogen is used as a carbon source or inorganic in a process chamber 16 using plasma-assisted chemical vapor deposition. The source gas is grown at a temperature of 1000 ° C to produce a high-quality carbon film or a thin film of an inorganic material film having a methane flow rate of 60 sccm and a hydrogen flow rate of 15 sccm, and applying a microwave of 2.45 GHz to generate a plasma, and the plasma provides cracked carbon. The energy of the source or inorganic material source gas is deposited on the surface of the metal substrate 28d by the cracked carbon source or the inorganic material source gas, and the surface of the metal substrate 28d can be synthesized into a high quality carbon film or an inorganic material film; Finally, a cooling treatment of a high-quality carbon film or an inorganic material film is performed on the cooling chamber 18 to lower the temperature to stabilize the high-quality carbon film or the inorganic material film.
然而所述之第一電漿源14c、第一過濾器14d、第二電漿源16c以及第二過濾器14d僅為本發明之輔助條件,並不限制本發明必須使用電漿才能達成。 However, the first plasma source 14c, the first filter 14d, the second plasma source 16c, and the second filter 14d are merely auxiliary conditions of the present invention, and do not limit the invention to be achieved by using plasma.
此處值得注意的是,上述圖2及圖3所揭露者為一種捲對捲式的連續式沉積設備,但是本發明並不限定於此,本發明的基材傳送裝置28可為本領域所經常使用的輸送帶式傳送系統。而且,具金屬的基材28d也不限定為連續的帶狀,具金屬的基材28d例如是具有特定尺寸的片狀物,利用載盤進行承載,然後將載盤設置於輸送帶式傳送系統上以進行基材的傳送,並使本發明的製程腔 體設置於輸送帶式傳送系統的基材傳送/移動路徑上。由上述可知,只要將本發明的製程腔體設置在各種已知的連續式基材傳送裝置上,就可能建構出能夠達成本發明目的的連續式製程腔體設備。 It should be noted here that the above-mentioned FIG. 2 and FIG. 3 are a roll-to-roll continuous deposition apparatus, but the present invention is not limited thereto, and the substrate transfer device 28 of the present invention can be used in the art. A conveyor belt conveyor system that is often used. Further, the metal substrate 28d is not limited to a continuous strip shape, and the metal substrate 28d is, for example, a sheet having a specific size, carried by a carrier, and then the carrier is placed on a conveyor belt conveying system. Transfer the substrate and make the process chamber of the present invention The body is disposed on the substrate transport/moving path of the conveyor belt conveyor system. From the above, it will be appreciated that as long as the process chamber of the present invention is disposed on various known continuous substrate transfer devices, it is possible to construct a continuous process chamber apparatus that achieves the objectives of the present invention.
如圖2及圖3中所示,前處理腔體14、製程腔體16、冷卻腔體18可透過腔體出氣管12c與真空系統26連接,而抽氣的開閉則可在腔體出氣管12c上的任意處設置閥門,依據使用者需求調整使用。 As shown in FIG. 2 and FIG. 3, the pre-processing chamber 14, the processing chamber 16, and the cooling chamber 18 can be connected to the vacuum system 26 through the chamber outlet tube 12c, and the pumping opening and closing can be performed in the chamber outlet tube. Set the valve anywhere on the 12c and adjust it according to the user's needs.
在說明圖2及圖3之三個腔體的實施例後,本發明第三較佳實施例,請請參考圖4之兩個腔體的連續式合成高品質碳薄膜或無機材料薄膜之設備實施例說明。如圖4所示,為本發明連續式合成高品質碳薄膜或無機材料薄膜之設備100示意圖,此處需事先說明的是,雖然在本案的圖4中僅繪示出用以說明本發明之連續式合成高品質碳薄膜或無機材料薄膜之設備100的主要構件,然而,本領域具有通常知識的技術人員應可依其具有的相關知識,輕易的推知本實施例之連續式合成高品質碳薄膜或無機材料薄膜之設備100所應具有的所有構件。而且,須注意圖中所示者為本實施例選用之結構,此僅供說明之用,本發明並不受此種結構的限制。 After explaining the embodiment of the three cavities of FIG. 2 and FIG. 3, in the third preferred embodiment of the present invention, please refer to the apparatus for continuously synthesizing high quality carbon film or inorganic material film of the two cavities of FIG. Example description. As shown in FIG. 4, it is a schematic diagram of an apparatus 100 for continuously synthesizing a high quality carbon film or an inorganic material film according to the present invention. It should be noted in advance that although only the present invention is illustrated in FIG. 4 of the present invention. The main components of the apparatus 100 for continuously synthesizing a high quality carbon film or an inorganic material film, however, those skilled in the art should be able to easily infer the continuous synthesis of high quality carbon of the present embodiment based on the relevant knowledge. All components of the apparatus 100 for film or inorganic material film. Moreover, it should be noted that the structures shown in the drawings are selected for the purposes of this embodiment, and are for illustrative purposes only, and the present invention is not limited by such structures.
圖4為本發明之第三較佳實施例,本發明之連續式合成高品質碳薄膜或無機材料薄膜之設備100為一種捲對捲連續式合成高品質碳薄膜或無機材料薄膜裝置。連續式合成高品質碳薄膜或無機材料薄膜之設備100主要具有一外腔體105具有一進氣閘門160a、一出氣閘門160b;外腔體105內部至少容納一前處理腔體120和一製程腔體130;一基材傳送裝置110由一捲出構件110a、捲取構件110b、轉動滾筒110c構成;一真空系統165、一氣源控制器31a及31b;一第一緩衝區222;一第二緩衝區223;以及一溫控裝置14;一冷卻輪250,連續式合成高品質碳薄膜或無機材料薄膜之設備100乃採用兩個腔體完成高品質碳薄膜或無機材料薄膜製備。 4 is a third preferred embodiment of the present invention. The apparatus 100 for continuously synthesizing a high quality carbon film or inorganic material film of the present invention is a roll-to-roll continuous synthetic high quality carbon film or inorganic material film device. The device 100 for continuously synthesizing a high-quality carbon film or an inorganic material film mainly has an outer cavity 105 having an intake gate 160a and an air outlet gate 160b; the outer cavity 105 has at least one pre-processing cavity 120 and a process cavity therein. The body 130 is composed of a take-up member 110a, a take-up member 110b, and a rotating drum 110c; a vacuum system 165, a gas source controller 31a and 31b; a first buffer 222; a second The buffer zone 223; and a temperature control device 14; a cooling wheel 250, the device 100 for continuously synthesizing a high quality carbon film or an inorganic material film is prepared by using two cavities to complete a high quality carbon film or an inorganic material film.
如圖4所示,本第三較佳實施例和第一及第二實施例相同之處不再贅述,僅描述不同之處。溫控裝置14設置於前處理腔體120和製程腔體130之間,且前處理腔體120和製程腔體130設置於一具金屬的基材110d的移動路徑上,亦即是,具金屬的基材110d藉由前述之捲出構件110a與捲取構件110b的驅動,將會連續的經過前處理腔體120的入口120a、出口120b、製程腔體130的出入口130a、出口130b,而當具金屬的基材110d在製程腔體130中移動時,即進行具金屬的基材110d的高品質碳薄膜或無機材料薄膜沉積。 As shown in FIG. 4, the third preferred embodiment is the same as the first and second embodiments, and the differences are only described. The temperature control device 14 is disposed between the pre-processing chamber 120 and the processing chamber 130, and the pre-processing chamber 120 and the processing chamber 130 are disposed on a moving path of a metal substrate 110d, that is, with a metal By driving the unwinding member 110a and the take-up member 110b, the substrate 110d will continuously pass through the inlet 120a of the pre-treatment chamber 120, the outlet 120b, the inlet and outlet 130a of the processing chamber 130, and the outlet 130b. When the metal substrate 110d moves in the process chamber 130, a high quality carbon film or an inorganic material film of the metal substrate 110d is deposited.
本實施例之第一緩衝區222、第二緩衝區223、第三緩衝區224功能相似於圖2和圖3之第一緩衝區20與第一緩衝區22的功能,在此不再贅述。 The function of the first buffer area 222, the second buffer area 223, and the third buffer area 224 of the present embodiment is similar to that of the first buffer area 20 and the first buffer area 22 of FIG. 2 and FIG. 3, and details are not described herein again.
在圖4之第三較佳實施例中,係先在前處理腔體120內對具金屬的基材110d進行第一電漿源120c處理,第一電漿源120c可以為一具氫電漿源,亦即於溫度600℃將氫氣與氬氣之混合氣體注入前處理腔體120,其中電漿功率最大150W。之後,經第一電漿源120c以及過濾器120d前處理之具金屬的基材110d陸續離開前處理腔體120並進入製程腔體130,同理,在製程腔體130中亦經過第二電漿源130c以及過濾器130d處理,過程中不破真空。請注意,本實施例之具金屬的基材110d在製程腔體130成長高品質碳薄膜或無機材料薄膜,係於溫度1000℃、壓力200mTorr-10Torr下進行,且反應氣體以長條型氣簾(shower)注入,其中反應氣體為甲烷、氫氣、氬氣的混合氣體。具金屬的基材110d的厚度為25μm,寬度最大為21cm,薄膜成長之工作面積為70cm x 30cm,捲動速度最小為5mm/s而最大為100mm/s。另外,本實施例之第一電漿源120c、第二電漿源130c與具金屬的基材110d的高度可調整。請特別注意,本實施例之製程腔體130與捲取構件110b之間係設置一冷卻輪250,以氣冷或水冷方式將成長了高品質碳薄膜或無機材料薄膜之具金屬的基材110d冷卻至200度以下,才由捲取構件110b收料。 In the third preferred embodiment of FIG. 4, the metal substrate 110d is first treated in the pretreatment chamber 120 by the first plasma source 120c. The first plasma source 120c may be a hydrogen plasma. The source, that is, a mixed gas of hydrogen and argon is injected into the pretreatment chamber 120 at a temperature of 600 ° C, wherein the plasma power is at most 150 W. Thereafter, the metal substrate 110d pretreated by the first plasma source 120c and the filter 120d successively leaves the pretreatment chamber 120 and enters the process chamber 130. Similarly, the second chamber is also passed through the processing chamber 130. The slurry source 130c and the filter 130d are processed without breaking the vacuum during the process. Please note that the metal substrate 110d of the present embodiment grows a high-quality carbon film or an inorganic material film in the process chamber 130 at a temperature of 1000 ° C and a pressure of 200 mTorr to 10 Torr, and the reaction gas is a long air curtain ( Shower) wherein the reaction gas is a mixed gas of methane, hydrogen, and argon. The metal substrate 110d has a thickness of 25 μm, a width of at most 21 cm, a film growth working area of 70 cm x 30 cm, and a scrolling speed of at least 5 mm/s and a maximum of 100 mm/s. In addition, the heights of the first plasma source 120c and the second plasma source 130c of the present embodiment and the metal substrate 110d can be adjusted. In particular, a cooling wheel 250 is disposed between the process chamber 130 and the take-up member 110b of the present embodiment, and the metal substrate 110d having a high-quality carbon film or an inorganic material film is grown in an air-cooled or water-cooled manner. It is cooled to 200 degrees or less before being taken up by the take-up member 110b.
本實施例所述之第一電漿源120c、第一過濾器120d、第二電漿源130c以及第二過濾器130d僅為本發明之輔助條件,並不限制本發明必須使用電漿才能達成。在另一實施態樣中,前處理腔體120包含一溫控裝置120e,製程腔體130包含一溫控裝置130e,溫控裝置120和溫控裝置130e的功能和第一及第二較佳實施例之溫控裝置24a、24b、24c功能相同,在此不再贅述。 The first plasma source 120c, the first filter 120d, the second plasma source 130c, and the second filter 130d described in this embodiment are only auxiliary conditions of the present invention, and do not limit the invention to use plasma to achieve . In another embodiment, the pre-processing chamber 120 includes a temperature control device 120e, and the processing chamber 130 includes a temperature control device 130e, functions of the temperature control device 120 and the temperature control device 130e, and first and second preferred The temperature control devices 24a, 24b, and 24c of the embodiment have the same functions, and are not described herein again.
在此要特別說明的是,在圖4之第三較實施例中,真空系統165藉由外腔體105之進氣閘門160a與出氣閘門160b,將製程氣體抽入及排出以維持真空狀態。在其它實施例中,真空系統165亦具有獨立連接各製程腔體之管線,如圖4所示,腔體出氣管160c分別直接與前處理腔體120、製程腔體130連接,而在必要時分別將前處理腔體120、製程腔體130的製程氣體抽出以維持真空狀態,該腔體出氣管160c亦可設有氣閥,方便技術人員調整使用。 It should be particularly noted that in the third comparative embodiment of FIG. 4, the vacuum system 165 draws in and discharges the process gas by the intake valve 160a and the outlet valve 160b of the outer chamber 105 to maintain the vacuum state. In other embodiments, the vacuum system 165 also has a pipeline for independently connecting the process chambers. As shown in FIG. 4, the chamber outlet tubes 160c are directly connected to the pretreatment chamber 120 and the process chamber 130, respectively, when necessary. The process gas of the pre-processing chamber 120 and the processing chamber 130 is respectively extracted to maintain a vacuum state, and the cavity outlet pipe 160c may also be provided with a gas valve, which is convenient for the technician to adjust and use.
在另一實施態樣中,前處理腔體120和製程腔體130亦可以具有一共同的溫控裝置170。溫控裝置170可以為一遠紅外線(Infra-red,IR)加熱器,利用電磁輻射熱傳原理,以直接方式傳熱而達到前處理腔體120及製程腔體130。在本實施例中,前處理腔體120、和製程腔體130和溫控裝置170的位置配置僅為一例示,只要能夠連續式大面積合成高品質碳薄膜或無機材料薄膜之配置即為本發明之精神,在說明圖4之兩個腔體的實施例後,以下請參考圖5之一個製程腔體的設備實施例說明。本發明第四較佳實施例,請參閱圖5所示,為本發明連續式合成高品質碳薄膜或無機材料薄膜之設備200示意圖,此處需事先說明的是,雖然在本案的圖5中僅繪示出用以說明本發明之連續式合成高品質碳薄膜或無機材料薄膜之設備200的主要構件,然而,本領域具有通常知識的技術人員應可依其具有的相關知識,輕易的推知本實施例之連續式合成高品質碳薄膜或無機材料薄膜之設備200所應具有的所有構件。而且,須注意圖中所示者為本發明選用 之實施例結構,此僅供說明之用,並不受此種結構的限制。 In another embodiment, the pre-treatment chamber 120 and the process chamber 130 may also have a common temperature control device 170. The temperature control device 170 can be an Infra-red (IR) heater that utilizes the principle of electromagnetic radiation heat transfer to directly transfer heat to the pre-treatment chamber 120 and the process chamber 130. In the present embodiment, the positional arrangement of the pretreatment chamber 120, the process chamber 130, and the temperature control device 170 is merely an example, as long as the configuration of the continuous large-area synthesis of a high-quality carbon film or an inorganic material film is In the spirit of the invention, after explaining the embodiment of the two cavities of FIG. 4, reference is now made to the apparatus embodiment of one of the process chambers of FIG. A fourth preferred embodiment of the present invention, as shown in FIG. 5, is a schematic diagram of a device 200 for continuously synthesizing a high-quality carbon film or an inorganic material film according to the present invention. It should be noted in advance that although in FIG. 5 of the present case, Only the main components of the apparatus 200 for describing the continuous synthesis of high quality carbon film or inorganic material film of the present invention are shown. However, those skilled in the art should be able to easily infer according to the relevant knowledge. All of the members of the apparatus 200 for continuously synthesizing a high quality carbon film or an inorganic material film of this embodiment. Moreover, it should be noted that the one shown in the figure is selected for the present invention. The structure of the embodiment is for illustrative purposes only and is not limited by such structure.
在圖5之實施例中,本發明之連續式合成高品質碳薄膜或無機材料薄膜之設備200為一種捲對捲連續式合成高品質碳薄膜或無機材料薄膜裝置。連續式合成高品質碳薄膜或無機材料薄膜之設備200主要具有一製程腔體210、一氣源控制器(圖未顯示)、以及一具有過濾器230之電漿產生單元220。請注意,連續式合成高品質碳薄膜或無機材料薄膜之設備200乃採用一個腔體完成高品質碳薄膜或無機材料薄膜製備。 In the embodiment of Fig. 5, the apparatus 200 for continuously synthesizing a high quality carbon film or inorganic material film of the present invention is a roll-to-roll continuous synthetic high quality carbon film or inorganic material film device. The apparatus 200 for continuously synthesizing a high quality carbon film or an inorganic material film mainly has a process chamber 210, a gas source controller (not shown), and a plasma generating unit 220 having a filter 230. Please note that the continuous synthesis of high quality carbon film or inorganic material film device 200 uses a cavity to complete the preparation of a high quality carbon film or inorganic material film.
如圖5所示,製程腔體210具有一進氣閘門21021、一出氣閘門210b,製程腔體210上方連接上述具有過濾器230之電漿產生單元220。製程腔體210內部至少容納一基材傳送裝置240、一真空系統260、一冷卻輪450、以及一溫控裝置340。其中,過濾器230之電漿產生單元220在製程腔體210內形成一電漿235。本實施例之基材傳送裝置包括捲出構件240a、捲入構件240b、轉動滾筒240c以及一冷卻輪450,用於傳送具金屬的基材240e。其中,製程氣體可依箭頭270與箭頭280的方向,經由進氣閘門210a、出氣閘門210b進入與離開製程腔體210。其中,溫控裝置340包含加熱燈管340a,用於加熱具金屬的基材240e。其中,冷卻輪450用於傳送同時冷卻成長了高品質碳薄膜或無機材料薄膜的具金屬的基材240e。 As shown in FIG. 5, the process chamber 210 has an intake valve 21021 and an air outlet gate 210b. The plasma generating unit 220 having the filter 230 is connected to the processing chamber 210. The process chamber 210 houses at least one substrate transfer device 240, a vacuum system 260, a cooling wheel 450, and a temperature control device 340. The plasma generating unit 220 of the filter 230 forms a plasma 235 in the processing chamber 210. The substrate transfer device of this embodiment includes a take-up member 240a, a take-up member 240b, a rotating drum 240c, and a cooling wheel 450 for transferring a metal-containing substrate 240e. The process gas can enter and exit the process chamber 210 via the intake gate 210a and the outlet valve 210b in the direction of arrow 270 and arrow 280. The temperature control device 340 includes a heating lamp tube 340a for heating the metal substrate 240e. Among them, the cooling wheel 450 is for conveying a metal substrate 240e which simultaneously cools a high quality carbon film or an inorganic material film.
在圖5之實施例中,具金屬的基材240e在製程腔體210成長高品質碳薄膜或無機材料薄膜,係於溫度600~1000℃、壓力200mTorr-10Torr下進行,且反應氣體以長條型氣簾(shower)注入,其中反應氣體為甲烷、氫氣、氬氣的混合氣體。具金屬的基材240e的厚度為25μm,寬度最大為21cm,薄膜成長之工作面積為70cm x 30cm,捲動速度最小為5mm/s而最大為100mm/s。另外,本實施例之電漿235與金屬的基材240e的高度可調整。請特別注意,本實施例之冷卻輪450以氣冷或水冷方式將成長了高品質碳薄膜或無機材料薄膜之金屬的基 材240e冷卻至200度以下,才由捲取構件240b收料。 In the embodiment of FIG. 5, the metal substrate 240e is grown in the process chamber 210 to form a high-quality carbon film or an inorganic material film at a temperature of 600 to 1000 ° C and a pressure of 200 mTorr to 10 Torr, and the reaction gas is elongated. A type of shower is injected, wherein the reaction gas is a mixed gas of methane, hydrogen, and argon. The metal substrate 240e has a thickness of 25 μm, a width of at most 21 cm, a film growth working area of 70 cm x 30 cm, and a scrolling speed of at least 5 mm/s and a maximum of 100 mm/s. In addition, the height of the plasma 235 and the metal substrate 240e of the present embodiment can be adjusted. Please pay special attention to the fact that the cooling wheel 450 of the present embodiment is a gas-cooled or water-cooled method for growing a metal of a high-quality carbon film or an inorganic material film. The material 240e is cooled to 200 degrees or less before being taken up by the take-up member 240b.
就圖5之實施例而言,可將金屬的基材240e替換為預先披覆一層碳薄膜結構(例如可為非晶型碳:如濺鍍碳層、可高溫碳化之高分子(PMMA)等)的銅箔或鎳箔等具金屬的基材。然後,在製程腔體210內於800~1000℃下,通入氫氣與氬氣的混合氣體(或稱為含氫氣的氣體)作為反應氣體,使銅箔上之碳層轉化為高品質碳薄膜或無機材料薄膜結構,搭配連續式捲對捲系統,獲得一連續合成大面積高品質碳薄膜或無機材料薄膜之目的。 In the embodiment of FIG. 5, the metal substrate 240e may be replaced with a carbon film structure (for example, amorphous carbon: such as a sputtered carbon layer, a high-temperature carbonized polymer (PMMA), etc.). A metal substrate such as copper foil or nickel foil. Then, a mixed gas of hydrogen and argon (or a gas containing hydrogen) is introduced into the process chamber 210 at 800 to 1000 ° C as a reaction gas to convert the carbon layer on the copper foil into a high-quality carbon film. Or an inorganic material film structure, combined with a continuous roll-to-roll system, to obtain a continuous synthesis of large-area high-quality carbon film or inorganic material film.
加熱單元本發明上述各實施例之連續式合成高品質碳薄膜或無機材料薄膜的設備10、100、200皆可包括一加熱單元4(如圖5所示),加熱單元4在圖2至圖4為潔簡目的並未繪示,僅以圖5做說明,但各實施例皆可以具有柤同之構件單元,具有相的發明目的。該加熱單元4可以為耐高溫之鎢材料或是具有電組絲的石英棒所構成,以作為第二溫控裝置,可以設置在靠近已覆蓋高品質碳薄膜或無機材料薄膜的銅箔上下表面,使加熱單元4能對之加熱,目的為使已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e溫度上升到可以使高品質碳薄膜或無機材料薄膜結晶的溫度。本發明之加熱單元4,只要是具備能提供高溫熱源即為本構件單元發明之目的,不超出本發明所欲保護之範圍 Heating Unit The apparatus 10, 100, 200 for continuously synthesizing a high quality carbon film or an inorganic material film according to each of the above embodiments of the present invention may include a heating unit 4 (shown in FIG. 5), and the heating unit 4 is shown in FIG. 4 is not shown for simplicity and is only illustrated in FIG. 5, but each of the embodiments may have different component units and have the purpose of the invention. The heating unit 4 may be made of a high temperature resistant tungsten material or a quartz rod having an electric group wire as a second temperature control device, which may be disposed on the upper and lower surfaces of the copper foil which is covered with a high quality carbon film or an inorganic material film. The heating unit 4 can be heated to increase the temperature of the metal-containing substrate 240e which has been covered with the high-quality carbon film or the inorganic material film to a temperature at which the high-quality carbon film or the inorganic material film can be crystallized. The heating unit 4 of the present invention is not limited to the scope of the present invention as long as it has the purpose of providing a high-temperature heat source, that is, the invention of the component unit.
加熱單元4可以設置在冷卻滾輪240d前方或後方,在圖5中,加熱單元4可以設置在冷卻滾輪240d之前(在圖2及圖3中,可以設置在入口18a之前或在出口18b之後;在圖4中,可以設置在冷卻輪250之前或之後),加熱單元4在已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e上做一微區加熱。加熱單元4可以於已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e上做掃描,以促進上述具金屬的基材240e表面石墨化。在本發明各實施例中,不論是加熱單元4相對於已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e上做移動或是已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e相對於加熱 單元4移動,都不影響本發明之精神。在本發明各實施例中,移動的方式不論是從上到下、下到上、由內而外、由外而內、或是以其畫圖方式移動,只要能將已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e,加熱到結晶溫度都屬於本發明之保護範圍。 The heating unit 4 may be disposed in front of or behind the cooling roller 240d. In FIG. 5, the heating unit 4 may be disposed before the cooling roller 240d (in FIGS. 2 and 3, it may be disposed before the inlet 18a or after the outlet 18b; In Fig. 4, it may be provided before or after the cooling wheel 250), and the heating unit 4 performs a micro-zone heating on the metal-coated substrate 240e which has been covered with a high-quality carbon film or an inorganic material film. The heating unit 4 can be scanned on a metal substrate 240e that has been covered with a high quality carbon film or an inorganic material film to promote surface graphitization of the metal substrate 240e. In various embodiments of the present invention, whether the heating unit 4 is moved relative to a metal substrate 240e that has been covered with a high quality carbon film or inorganic material film or has been covered with a high quality carbon film or inorganic material film. Substrate 240e relative to heating The movement of unit 4 does not affect the spirit of the invention. In various embodiments of the present invention, the manner of movement is from top to bottom, bottom to top, from inside to outside, from outside to inside, or in a drawing manner, as long as it can cover a high quality carbon film or The metal substrate 240e of the inorganic material film, heated to the crystallization temperature, is within the scope of the present invention.
如圖6所示,加熱單元4的為一線形加熱棒,加熱單元4固定在一位置,已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e連續的往同一方向移動(箭頭方向),當加熱單元4侷部加熱例如1000℃,會使得適量的碳再度溶解在金屬,透過不同的加熱溫度及控制加熱單元4和已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e的相對速度,可以控制碳薄膜或無機材料薄膜的品質。如圖6所示,未通過加熱單元4的碳薄膜或無機材料薄膜在許多晶界上有有缺陷,當通過加熱單元4再加熱後,如圖7所示,碳薄膜或無機材料薄膜晶界上的缺陷數量會減少,可以合成具有均勻且較大面積的碳薄膜或無機材料薄膜。 As shown in FIG. 6, the heating unit 4 is a linear heating rod, and the heating unit 4 is fixed at a position, and the metal substrate 240e which has covered the high-quality carbon film or the inorganic material film continuously moves in the same direction (arrow direction) When the heating unit 4 is locally heated, for example, 1000 ° C, an appropriate amount of carbon is dissolved in the metal again, and the heating unit 4 is controlled and the metal substrate having the high quality carbon film or the inorganic material film is covered. The relative speed of 240e can control the quality of carbon film or inorganic material film. As shown in FIG. 6, the carbon film or the inorganic material film that has not passed through the heating unit 4 is defective in many grain boundaries. When reheated by the heating unit 4, as shown in FIG. 7, the carbon film or the inorganic material film grain boundary The number of defects on the surface is reduced, and a carbon film or an inorganic material film having a uniform and large area can be synthesized.
在習知化學汽相沉積法中,碳薄膜或無機材料薄膜全部加熱,碳薄膜或無機材料薄膜以多晶形式生長。根據本發明,使用加熱單元4可以使碳適量再溶解在金屬中,因此,根據本發明通過加熱單元4可以改善晶界的缺陷,進而能夠實現對大面積的合成。 In the conventional chemical vapor deposition method, a carbon thin film or an inorganic material thin film is entirely heated, and a carbon thin film or an inorganic material thin film is grown in a polycrystalline form. According to the present invention, the amount of carbon can be redissolved in the metal by using the heating unit 4, and therefore, the defect of the grain boundary can be improved by the heating unit 4 according to the present invention, and the synthesis of a large area can be realized.
根據本發明,加熱單元4和已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e的相對移動具有預定的方向性,所以碳薄膜或無機材料薄膜晶粒各自排列具有預定的方向性。即晶粒具有與加熱單元4的移動一致的方向性,並且因此減少由晶界導致的缺陷。 According to the present invention, the relative movement of the heating unit 4 and the metal-containing substrate 240e which has been covered with the high-quality carbon film or the inorganic material film has a predetermined directivity, so that the carbon film or the inorganic material film grains are each arranged with a predetermined directivity. . That is, the crystal grains have a directivity consistent with the movement of the heating unit 4, and thus the defects caused by the grain boundaries are reduced.
在本實施例中,連續熱處理在相對加熱單元4移動同時進行,但根據一定目的不僅可以使用加熱單元4而且也可以使用各種材料。此外,加熱單元4的形狀不限於線形。 In the present embodiment, the continuous heat treatment is performed while moving relative to the heating unit 4, but not only the heating unit 4 but also various materials may be used depending on the purpose. Further, the shape of the heating unit 4 is not limited to a line shape.
進一步來說,利用高溫鎢線在已覆蓋高品質碳薄膜或無機材料薄膜的具金屬的基材240e上做一微區加熱,更進一步優化高品質碳薄膜或無機材料薄膜結晶時碳原子間鍵結不完全所產生的缺陷,此步驟能使高品質碳薄膜或無機材料薄膜覆蓋率及修復缺陷而使品質再次提升並且增加高品質碳薄膜或無機材料薄膜晶粒大小,以局部加熱方式升溫,所遭遇均勻性與覆蓋率不易控制的問題。在高品質碳薄膜或無機材料薄膜的合成過程中,具金屬的基材240e是催化劑的角色,局部加熱亦可以使適量的碳溶解在催化劑中,溶解在催化劑中的碳量可以透過局部加熱的溫度及時間來控制,增加碳溶解量可以增加高品質碳薄膜或無機材料薄膜的厚度,以獲得高品質的。此外,本系統設計的加熱單元,可以協助製作可調控溫度範圍在500~900℃的均勻加熱區段。 Further, a micro-zone heating is performed on the metal-based substrate 240e which has been covered with a high-quality carbon film or an inorganic material film by using a high-temperature tungsten wire, and the carbon atom bond between the high-quality carbon film or the inorganic material film is further optimized. Defects caused by incomplete junctions, this step enables high-quality carbon film or inorganic material film coverage and repair defects to improve the quality and increase the grain size of high-quality carbon film or inorganic material film, and heat up by local heating. The problem of uniformity and coverage that is difficult to control. In the synthesis process of a high-quality carbon film or an inorganic material film, the metal substrate 240e is a catalyst, and local heating can also dissolve an appropriate amount of carbon in the catalyst, and the amount of carbon dissolved in the catalyst can be locally heated. Temperature and time to control, increase the amount of carbon dissolved can increase the thickness of high-quality carbon film or inorganic material film to obtain high quality. In addition, the heating unit designed in this system can assist in the production of a uniform heating section with a temperature range of 500~900 °C.
此外,藉由上述實施例之連續式合成薄膜的設備搭配一高均勻性面形電漿與特製過濾器,可以解決過去以電漿系統成長高品質碳薄膜或無機材料薄膜時,因離子轟擊與紫外光等高能光子(UV photon)對高品質碳薄膜或無機材料薄膜的破壞與損傷造成大量缺陷結構,導致成長之高品質碳薄膜或無機材料薄膜導電特性不佳之問題。 In addition, the apparatus for continuously synthesizing a film according to the above embodiment can be combined with a highly uniform surface-shaped plasma and a special filter to solve the problem of ion bombardment and high-quality carbon film or inorganic material film in the past. The destruction and damage of high-quality carbon film or inorganic material film by ultraviolet photon (UV photon) causes a large number of defect structures, resulting in a problem of poor conductivity of high-quality carbon film or inorganic material film.
另外,本發明實施例之連續式合成高品質碳薄膜或無機材料薄膜的設備更可包括一轉印裝置,用以轉印高品質碳薄膜或無機材料薄膜。 In addition, the apparatus for continuously synthesizing a high-quality carbon film or an inorganic material film according to an embodiment of the present invention may further include a transfer device for transferring a high-quality carbon film or an inorganic material film.
200‧‧‧連續式合成高品質碳薄膜或無機材料薄膜之設備 200‧‧‧Continuous equipment for the synthesis of high quality carbon or inorganic film
210‧‧‧製程腔體 210‧‧‧Processing cavity
210a‧‧‧進氣閘門 210a‧‧‧Intake gate
210b‧‧‧出氣閘門 210b‧‧‧Exhaust gate
220‧‧‧電漿產生單元 220‧‧‧ Plasma generation unit
230‧‧‧過濾器 230‧‧‧Filter
235‧‧‧電漿 235‧‧‧ Plasma
240‧‧‧基材傳送裝置 240‧‧‧Substrate transfer device
240a‧‧‧捲出構件 240a‧‧‧Extracting components
240b‧‧‧捲入構件 240b‧‧‧ involved components
240c‧‧‧轉動滾筒 240c‧‧‧Rotating drum
240d‧‧‧冷卻滾輪 240d‧‧‧Cooling wheel
240e‧‧‧具金屬的基材 240e‧‧‧Metal substrate
260‧‧‧真空系統 260‧‧‧vacuum system
340‧‧‧溫控裝置 340‧‧‧temperature control device
340a‧‧‧加熱燈管 340a‧‧‧heating tube
270‧‧‧箭頭 270‧‧‧ arrow
280‧‧‧箭頭 280‧‧‧ arrow
4‧‧‧加熱單元 4‧‧‧heating unit
450‧‧‧冷卻輪 450‧‧‧Cooling wheel
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TWI613366B (en) * | 2016-11-16 | 2018-02-01 | 財團法人紡織產業綜合研究所 | Air flow generating device |
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TWI613366B (en) * | 2016-11-16 | 2018-02-01 | 財團法人紡織產業綜合研究所 | Air flow generating device |
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