金屬催化非晶碳轉變石墨烯的晶化調控及生長機理研究
發(fā)布時間：2018-08-11 11:00
【摘要】：石墨烯因其高電子遷移率、室溫量子霍爾效應、高導熱率、高強韌等優(yōu)異性能,在傳感器、儲能、半導體材料等領域應用前景廣闊。然而,石墨烯的產(chǎn)業(yè)化受限于制備方法。金屬催化非晶碳轉變石墨烯作為一種新的石墨烯制備方法,具有高質量、大面積、層數(shù)精確可控的優(yōu)點,目前國內外相關研究剛剛起步,工藝尚不成熟,生長機理尚不明確。為了探索這種新制備方法,本文構筑基體(Si)/非晶碳(a-C)/催化金屬(Cu/Ni)三層結構,其中,采用磁過濾陰極真空電弧復合磁控濺射設備制備了a-C膜和Cu膜,電子束蒸鍍設備制備了Ni膜,經(jīng)快速熱處理方法在金屬催化劑表面制備石墨烯,結合Raman、XPS、TEM、SEM、XRD等檢測手段,重點研究了a-C種類及厚度、金屬催化劑種類及厚度、退火溫度、退火氣氛、退火時間對a-C轉變石墨烯過程的影響,并初步探討了其生長機理。本文前期通過Raman和SEM檢測結果,快速優(yōu)化出四面體非晶碳(ta-C)/Ni體系。研究結果表明,Si/ta-C/Ni體系在高溫(750°C~1000°C)退火時,退火氣氛顯著影響生成石墨烯的質量。Ar氣氛下Ni易發(fā)生熟化形成顆粒狀團簇,非晶碳出現(xiàn)石墨化,但未形成石墨烯。真空條件下,生成多層石墨烯,且缺陷多。改變溫度和ta-C/Ni厚度比,得出Si/ta-C10nm/Ni100nm退火900°C,保溫5min時,制備的石墨烯質量最佳。高溫生長過程遵循溶解-析出機理。低溫(200°C~600°C)退火時,退火氣氛及溫度顯著影響生成石墨烯的質量。不同氣氛下,Ni薄膜表面均連續(xù)完整,有助于石墨烯的大面積生長。Ar條件下,非晶碳出現(xiàn)石墨化,但未形成石墨烯。真空條件下,退火400°C時開始生成石墨烯,其中Si/taC40nm/Ni100nm退火500°C,保溫15min制備的石墨烯質量最佳,但層數(shù)約35層且缺陷多。究其原因,一方面由于金屬催化劑Ni的多晶性為石墨烯提供過多形核位點,促使沿Ni晶界和缺陷處擴散至表面的碳過多;另一方面由于ta-C/Ni復合結構中的碳膜厚度大,提供了富余的擴散碳量,導致石墨烯層數(shù)多且質量下降。低溫時C在Ni中的固溶度降低,碳的擴散行為占主導地位,因此生長機理由溶解-析出和金屬誘導協(xié)同作用決定。此研究為低溫、大面積、可控制備石墨烯提供了一種新思路。
[Abstract]:Because of its high electron mobility, room temperature quantum Hall effect, high thermal conductivity, high strength and toughness, graphene has a wide application prospect in sensor, energy storage, semiconductor materials and other fields. However, the industrialization of graphene is limited by the preparation method. As a new preparation method of graphene, metal-catalyzed amorphous carbon transition graphene has the advantages of high quality, large area and accurate control of layers. At present, the related research at home and abroad is just beginning, the technology is not mature, and the growth mechanism is not clear. In order to explore this new preparation method, a three-layer structure of (Si) / amorphous carbon (a-C) / catalytic metal (Cu/Ni) was constructed, in which a-C film and Cu film were prepared by magnetic filter cathode vacuum arc composite magnetron sputtering equipment, and Ni film was prepared by electron beam evaporation equipment. Graphene was prepared on the surface of the metal catalyst by rapid heat treatment. The type and thickness of a-C, the type and thickness of metal catalyst, the annealing temperature, the annealing atmosphere and so on were studied by means of Ramande XPSX TEMSEMU XRD and so on. The effect of annealing time on the process of a-C transition of graphene was investigated and the growth mechanism of a-C was discussed. The tetrahedral amorphous carbon (ta-C) / Ni system was rapidly optimized by Raman and SEM. The results show that the annealing temperature (750 擄C ~ 1 000 擄C) of Si-Si / ta-C- / Ni system has a significant effect on the formation of graphene in the atmosphere of Ni. Ar atmosphere, Ni is easy to mature to form granular clusters, amorphous carbon appears graphitization, but no graphene is formed. Under vacuum condition, multilayer graphene is formed, and there are many defects. By changing the ratio of temperature to thickness of ta-C/Ni, the best quality of graphene was obtained when Si/ta-C10nm/Ni100nm was annealed at 900 擄C and kept in 5min. The high temperature growth process follows the dissolution-precipitation mechanism. When annealed at low temperature (200 擄C) (600 擄C), the annealing atmosphere and temperature have a significant effect on the quality of graphene. The surface of Ni thin film is continuous and complete in different atmosphere, which is helpful to the graphitization of amorphous carbon under the condition of large area growth of graphene, but no graphene is formed. In vacuum condition, graphene was formed after annealing at 400 擄C, in which Si/taC40nm/Ni100nm annealed at 500 擄C, the quality of graphene prepared by 15min was the best, but the number of layers was about 35 layers and the defects were many. The reason is that, on the one hand, the polycrystalline nature of the metal catalyst Ni provides many nucleation sites for graphene, which promotes the diffusion of carbon to the surface along the grain boundaries and defects of Ni; on the other hand, the thickness of carbon film in the composite structure of ta-C/Ni is large. A surplus amount of diffused carbon is provided, which leads to a large number of graphene layers and a decrease in mass. At low temperature, the solubility of C in Ni decreases, and the diffusion behavior of carbon dominates. Therefore, the reason of solution-precipitation and metal-induced synergism is determined by the growth mechanism. This study provides a new idea for the preparation of graphene at low temperature, large area and controllable preparation.
【學位授予單位】：沈陽工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ127.11
本文編號：2176804
[Abstract]:Because of its high electron mobility, room temperature quantum Hall effect, high thermal conductivity, high strength and toughness, graphene has a wide application prospect in sensor, energy storage, semiconductor materials and other fields. However, the industrialization of graphene is limited by the preparation method. As a new preparation method of graphene, metal-catalyzed amorphous carbon transition graphene has the advantages of high quality, large area and accurate control of layers. At present, the related research at home and abroad is just beginning, the technology is not mature, and the growth mechanism is not clear. In order to explore this new preparation method, a three-layer structure of (Si) / amorphous carbon (a-C) / catalytic metal (Cu/Ni) was constructed, in which a-C film and Cu film were prepared by magnetic filter cathode vacuum arc composite magnetron sputtering equipment, and Ni film was prepared by electron beam evaporation equipment. Graphene was prepared on the surface of the metal catalyst by rapid heat treatment. The type and thickness of a-C, the type and thickness of metal catalyst, the annealing temperature, the annealing atmosphere and so on were studied by means of Ramande XPSX TEMSEMU XRD and so on. The effect of annealing time on the process of a-C transition of graphene was investigated and the growth mechanism of a-C was discussed. The tetrahedral amorphous carbon (ta-C) / Ni system was rapidly optimized by Raman and SEM. The results show that the annealing temperature (750 擄C ~ 1 000 擄C) of Si-Si / ta-C- / Ni system has a significant effect on the formation of graphene in the atmosphere of Ni. Ar atmosphere, Ni is easy to mature to form granular clusters, amorphous carbon appears graphitization, but no graphene is formed. Under vacuum condition, multilayer graphene is formed, and there are many defects. By changing the ratio of temperature to thickness of ta-C/Ni, the best quality of graphene was obtained when Si/ta-C10nm/Ni100nm was annealed at 900 擄C and kept in 5min. The high temperature growth process follows the dissolution-precipitation mechanism. When annealed at low temperature (200 擄C) (600 擄C), the annealing atmosphere and temperature have a significant effect on the quality of graphene. The surface of Ni thin film is continuous and complete in different atmosphere, which is helpful to the graphitization of amorphous carbon under the condition of large area growth of graphene, but no graphene is formed. In vacuum condition, graphene was formed after annealing at 400 擄C, in which Si/taC40nm/Ni100nm annealed at 500 擄C, the quality of graphene prepared by 15min was the best, but the number of layers was about 35 layers and the defects were many. The reason is that, on the one hand, the polycrystalline nature of the metal catalyst Ni provides many nucleation sites for graphene, which promotes the diffusion of carbon to the surface along the grain boundaries and defects of Ni; on the other hand, the thickness of carbon film in the composite structure of ta-C/Ni is large. A surplus amount of diffused carbon is provided, which leads to a large number of graphene layers and a decrease in mass. At low temperature, the solubility of C in Ni decreases, and the diffusion behavior of carbon dominates. Therefore, the reason of solution-precipitation and metal-induced synergism is determined by the growth mechanism. This study provides a new idea for the preparation of graphene at low temperature, large area and controllable preparation.
【學位授予單位】：沈陽工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ127.11
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