WO2020172863A1 - 以非极性晶面SiC为衬底的单层石墨烯及可控生长方法 - Google Patents

以非极性晶面SiC为衬底的单层石墨烯及可控生长方法 Download PDF

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WO2020172863A1
WO2020172863A1 PCT/CN2019/076541 CN2019076541W WO2020172863A1 WO 2020172863 A1 WO2020172863 A1 WO 2020172863A1 CN 2019076541 W CN2019076541 W CN 2019076541W WO 2020172863 A1 WO2020172863 A1 WO 2020172863A1
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polishing
crystal plane
sic
sic substrate
polar crystal
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马雷
∙ 亚历山大 德斯海尔∙沃尔特
纪佩璇
张凯敏
赵健
赵梅
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Tianjin University
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Definitions

  • the present disclosure relates to the technical field of semiconductor materials, in particular to a single-layer graphene with a non-polar crystal plane SiC as a substrate and a controllable growth method.
  • Graphene is a two-dimensional material composed of carbon atoms arranged in a hexagonal honeycomb shape. Because of its excellent properties in mechanics, electronics, optics, etc., it is considered to be a promising nanoelectronic device material. .
  • the use of single crystal SiC substrate to grow graphene epitaxially can effectively avoid the introduction of defects such as wrinkles, cracks, and impurity contamination during the preparation of electronic devices.
  • the substrate used for epitaxial graphene growth is a SiC wafer compatible with traditional semiconductor processes. In terms of current development trends, this seems to be the only basic material that can be used to prepare two-dimensional nanoelectronic devices.
  • the traditional SiC substrate epitaxial growth of graphene is mainly used for the two crystal planes of the hexagonal SiC substrate, the (0001) plane (that is, the Si plane) and the (000-1) plane (that is, the C plane).
  • the electrical properties of graphene still have a big difference.
  • the research group of Professor Walt de Heer in the United States discovered that the sidewall graphene nanoribbons grown on SiC substrates have unique and extremely excellent electrical transport properties.
  • the main purpose of the present disclosure is to provide a controllable growth method of single-layer graphene, in order to at least partially solve at least one of the above-mentioned technical problems.
  • a controllable growth method of single-layer graphene in which a single-layer graphene is epitaxially grown on a non-polar crystal plane at any angle of a non-polar crystal plane SiC substrate, and This uses the non-polar crystal surface to regulate the electrical transport properties of graphene.
  • a single-layer graphene prepared by using the above-mentioned controlled growth method, wherein the single-layer graphene is epitaxially grown on any non-polar SiC substrate. On the angled non-polar crystal plane, the electrical transport properties of the single-layer graphene are controlled by the non-polar crystal plane.
  • a method for preparing a non-polar crystal plane SiC substrate includes the following steps: according to the angle between a non-polar crystal plane and the (0001) plane or (000-1) plane To adjust the angle of the diamond wire relative to a SiC crystal column, use the diamond wire to cut the SiC crystal column to obtain a SiC wafer; perform grinding, mechanical polishing and chemical mechanical polishing on the SiC wafer to obtain an atomic level flatness After the non-polar crystal plane is verified to be correct, the SiC wafer is cut to obtain the non-polar crystal plane SiC substrate.
  • a non-polar crystal plane SiC substrate is provided, which is prepared by the above-mentioned preparation method.
  • the present disclosure solves the processing difficulties on the sidewall graphene nanoribbons, and at the same time realizes the large-scale growth of planarized single-layer graphene, especially, the large-area growth area with a non-polar surface at a specific angle
  • the ballistic transport properties of graphene ushered in an era for ballistic transport of graphene electronic devices.
  • FIG. 1 is the mutual position between two mutually perpendicular reference planes of a SiC substrate and a steel plate in Embodiment 1 of the disclosure;
  • FIG. 2 is a schematic diagram of the SiC (0001) plane parallel to the diamond wire in Embodiment 1 of the disclosure;
  • FIG. 3 is a schematic diagram of cutting a specific crystal plane of SiC in Embodiment 1 of the disclosure.
  • FIG. 7 is an SEM image of graphene grown in Example 3 of the disclosure.
  • LFM lateral force microscope
  • Example 10 is a low energy electron diffraction (LEED) image of graphene grown in Example 3 of the disclosure
  • Example 11 is a measurement result of the electrical transport properties of graphene with non-polar crystal planes in Example 3 of the disclosure.
  • FIG. 13 is a Raman diagram of graphene grown in Example 4 of the disclosure.
  • Figure 14 is an LFM diagram of graphene grown in Example 5 of the disclosure.
  • Example 15 is a Raman diagram of graphene grown in Example 5 of the disclosure.
  • Figure 17 is an LFM diagram of graphene grown in Comparative Example 1 of the present disclosure.
  • FIG. 18 is a Raman diagram of graphene grown in Comparative Example 1 of the disclosure.
  • FIG. 19 is the measurement result of the electrical transport properties of the grown graphene in Comparative Example 1 of the disclosure.
  • the present disclosure discloses a single-layer graphene with a non-polar crystal face SiC as a substrate and a controllable growth method.
  • the single-layer graphene is epitaxially grown on any non-polar crystal face SiC substrate, which is composed of different non-polar crystal faces.
  • the crystal plane regulates the properties of graphene, especially the electrical transport properties.
  • the "non-polar crystal plane SiC substrate” refers to a SiC substrate with at least one of the upper and lower surfaces being a non-polar crystal plane.
  • the main physical mechanism is the influence of the physical properties of the specific crystal plane of SiC on the growth of graphene and the regulation of the interaction between the specific crystal plane and graphene, so that the specific crystal plane epitaxial graphene has the same common (0001) and (000-1) Very different physical properties on the surface.
  • the applicant has also overcome the following technical difficulties in the research process: At present, there is no complete and effective process for SiC cutting and polishing of non-polar surfaces at any angle, and large-area single-layer growth on SiC substrates with non-polar crystal surfaces at any angle Graphene also has no universally applicable method.
  • the present disclosure provides a controllable growth method of a single layer of graphene, which epitaxially grows a single layer of graphene on a non-polar crystal plane of a non-polar crystal plane of a non-polar crystal plane of a non-polar crystal plane at any angle , Thus using the non-polar crystal surface to regulate the electrical transport properties of graphene.
  • the non-polar crystal plane SiC substrate is a hexagonal crystal system, preferably a 4H-SiC substrate or a 6H-SiC substrate, and the non-polar crystal plane is preferably a (1-105) plane, which is 37.1 with a (0001) plane. °Included angle.
  • the non-polar crystal plane SiC substrate is prepared by the following steps:
  • the SiC wafer is cut to obtain the non-polar crystal plane SiC substrate.
  • the wire diameter of the diamond wire is 0.2 to 0.8 mm, preferably 0.6 mm, and the feed rate is 1.5 mm/min to 5 mm/min, preferably 3 mm/min.
  • the grinding conditions are: use diamond particles-containing grinding discs or sandpaper, diamond particles' particle size is 3-60 ⁇ m, polishing pressure is 20-250N, power head speed and grinding disc speed are 30-80r/min, 100-300r, respectively /min;
  • the grinding conditions are to grind the diamond particles with a diameter of 60 ⁇ m and 30 ⁇ m in sequence, and the polishing pressure is gradually increased from 100 to 200N during the grinding, and the power head speed and the grinding disk speed are 60r/min and 280r/min respectively. .
  • the mechanical polishing conditions are: diamond suspension is used, the diamond particle size is 0.05-9 ⁇ m, the polishing pressure is 20-80N, the polishing disc is synthetic silk cloth, the power head speed is 30-100r/min, and the grinding disc speed is 60 ⁇ 320r/min;
  • the conditions of mechanical polishing are to polish with diamond suspensions with diamond particle sizes of 3 ⁇ m and 1 ⁇ m, the polishing pressures are 80N and 60N respectively, and the power head speed and grinding wheel speed are 80r/min and 310r/min respectively. .
  • the conditions of chemical mechanical polishing are: use alkaline silica polishing liquid, pH is preferably 9-12, more preferably 11, polishing pressure is 20-80N, preferably 60N, polishing droplet acceleration is 5-50ml/ min, preferably 40 mL/min, the polishing pad has a fluff-like structure, the power head speed is 30-100 r/min, preferably 60 r/min, and the grinding disc rotation speed is 60-320 r/min, preferably 120 r/min.
  • the SiC wafer is cut into small wafers with a length of 3 to 8 mm and a width of 4 to 10 mm as a non-polar crystal plane SiC substrate.
  • graphene is grown by SiC pyrolysis method, which specifically includes the following steps:
  • the non-polar crystal face SiC substrate is heated to 1100-1350°C, preferably 1100°C under an inert atmosphere, heated for 20-100 minutes, preferably 80min, and then heated to 1500-1600°C, preferably 1500°C, heated for 20- 150min, preferably 120min;
  • the graphene growth ends after cooling to room temperature.
  • graphene can also be grown using organic matter coated on a non-polar crystal plane SiC substrate as a solid carbon source.
  • This method fills in some non-polar crystal planes that are difficult to directly grow graphene by pyrolysis.
  • the blanks include the following steps:
  • the non-polar crystal plane SiC substrate is heated to 1200-1400°C, preferably 1400°C under an inert atmosphere, heated for 20-100 minutes, preferably 81 minutes, and then heated to 1500-1700°C, preferably 1700°C, 20 ⁇ 150min, preferably 115min;
  • the graphene growth ends after cooling to room temperature.
  • the organic substance is, for example, photoresist, polystyrene, or polyacrylonitrile.
  • the present disclosure also provides a single-layer graphene prepared by the controllable growth method of single-layer graphene as described above, and the single-layer graphene is epitaxially grown on a non-polar crystal plane at any angle of the SiC substrate. On the non-polar crystal surface, the electrical transport properties of single-layer graphene are regulated by the non-polar crystal surface.
  • the present disclosure also provides a method for preparing a non-polar crystal plane SiC substrate, including the following steps:
  • Step A Adjust the angle of the diamond wire relative to a SiC crystal column according to the angle between a non-polar crystal plane and the (0001) plane or (000-1) plane, and use the diamond wire to cut the SiC crystal column to obtain SiC Chip
  • the SiC wafer is cut to obtain the non-polar crystal plane SiC substrate;
  • the present disclosure also provides a non-polar crystal plane SiC substrate, which is prepared by using the method for preparing a non-polar crystal plane SiC substrate as described above.
  • the included angle in other embodiments, is other non-polar crystal planes with different angles;
  • the SiC crystal column 2 has two mutually perpendicular reference surfaces 21 and 22.
  • a SiC crystal column 2 is vertically arranged on the clamp.
  • Steel plate 3 the clamp 1 can rotate 360° in the horizontal plane.
  • the SiC crystal column 2 is cut at a feed rate of 4.0 mm/min. Each time a SiC wafer is cut, the SiC crystal column 2 is controlled to advance a distance to the diamond wire 4, which is the sum of the thickness of the wafer and the wire diameter of the diamond wire 4.
  • a grinding and polishing method that can achieve atomic level flatness of non-polar crystal planes at any angle of SiC, the specific steps are as follows:
  • the polishing disk is a diamond particle grinding disk.
  • the diamond particle diameters of 60 ⁇ m and 30 ⁇ m are used to apply the diamond particle diameter to the SiC wafer.
  • the polishing pressure is gradually increased from 100 to 200N during the polishing process.
  • the power head speed and the grinding wheel speed are respectively 60r/min and 280r/min.
  • the water flow is kept flushing to reduce the friction during the polishing process.
  • the SiC wafer is mechanically polished on a polishing machine. Two diamond suspensions are used successively.
  • the diamond particle size is 3 ⁇ m and 1 ⁇ m
  • the polishing pressure is 80N and 60N
  • the polishing disc is synthetic silk cloth with medium hardness.
  • the head speed and grinding disc speed are 80r/min and 310r/min respectively;
  • the speed of the power head and the speed of the grinding disc are 60r/min and 120r/min respectively;
  • Example 2 The SiC wafer obtained by grinding and polishing in Example 2 was adhered to the ceramic with paraffin, and then cut into a 3.5 ⁇ 4.5mm non-polar crystal SiC substrate, which was pretreated to remove paraffin and thoroughly cleaned;
  • the temperature is quickly cooled to room temperature to complete the graphene growth.
  • the graphene test result is that, as shown in Figure 7, it can be observed that all areas in the figure are almost the same, and graphene covers all; as shown in Figure 8, the brightly colored areas in the figure are SiC areas, and the darker colors are graphene. It can be observed that the graphene is almost completely covered; as shown in Figure 9, the half-height width of the 2D peak in the figure is 28.8, indicating that the obtained graphene is a single-layer graphene.
  • Embodiment 3 The difference between this embodiment and Embodiment 3 is that the crucible used is the crucible used for the second time. Specific steps are as follows:
  • the temperature is quickly lowered to room temperature to complete the graphene growth.
  • the graphene test result is as shown in Figure 12, the darker area in the figure is graphene, and it can be seen that the graphene grows in steps; as shown in Figure 13, the half-height width of the 2D peak in the figure is 39.8, which means The graphene obtained is a single-layer graphene. Because the more the crucible is used, the more silicon is attached to the inner wall of the crucible, and the silicon atoms are not easy to evaporate, so the less graphene grows. From the G peak position (1600cm -1 ) and the 2D peak position (2749 cm -1 ) blue-shifted. It can be seen that the graphene and SiC substrate have a strong bonding force.
  • Embodiment 3 The difference between this embodiment and Embodiment 3 is that organic matter is used as a solid carbon source for graphene growth, so that different substrates can control the physical properties of graphene. Specific steps are as follows:
  • the first stage is carried out in vacuum, the vacuum degree reaches about 5 ⁇ 10 -6 mbar, and the temperature is maintained at 800°C for 40 minutes;
  • the graphene test result is: as shown in Figure 14, the graphene is almost completely covered. As shown in Figure 15, the half-height width of the 2D peak is 42 indicating that the obtained graphene is a single-layer graphene.
  • the graphene test results are: as shown in Figures 16 and 17, the graphene is almost completely covered. As shown in Figure 18, the half-height width of the 2D peak is 43, indicating that the obtained graphene is a single-layer graphene.
  • Figure 19 is a graph of electrical transport properties measured on the Si surface.

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Abstract

一种以非极性晶面SiC为衬底的单层石墨烯及可控生长方法，所述可控生长方法是在非极性晶面SiC衬底的任意角度的非极性晶面上外延生长单层石墨烯，由此利用所述非极性晶面对石墨烯的电输运性质进行调控；通过所述可控生长方法能够在所述非极性晶面SiC衬底的其中一非极性晶面上得到弹道输运性质的单层石墨烯。

Description

以非极性晶面SiC为衬底的单层石墨烯及可控生长方法 技术领域
本公开涉及半导体材料技术领域，尤其涉及一种以非极性晶面SiC为衬底的单层石墨烯及可控生长方法。
背景技术
随着现代微电子技术的快速发展，传统硅基半导体电子器件已经无法满足人们的需求，寻找一种新的电子学器件基础材料迫在眉睫。石墨烯是由碳原子按照六角蜂窝状排列而成的二维材料，由于其在力学、电子学、光学等方面表现出的各种优异性能，被大家认为是极具应用前景的纳米电子器件材料。与机械剥离法和化学沉积法相比，使用单晶SiC衬底外延生长石墨烯可以有效的避免在电子器件制备过程中引入缺陷，如褶皱、裂缝、杂质污染等不利因素。最重要的是，外延石墨烯生长所采用的衬底是与传统半导体工艺兼容的SiC晶片，就目前的发展趋势而言，这似乎也是唯一可用于制备二维纳米电子器件的基础材料。
传统的SiC衬底外延法生长石墨烯主要用于六方晶系SiC衬底的两个晶面，(0001)面(即Si面)以及(000-1)面(即C面)，得到的外延石墨烯性能与机械剥离的石墨烯相比，其电学性能依旧存在较大差异。2014年由美国Walt de Heer教授研究组发现的在SiC衬底上生长的侧壁石墨烯纳米带具有独特且极其优异的电输运性质。但是该方法同现代平面化电子加工工艺难以契合，主要是由于该结构必须在侧壁上，即首先要对SiC衬底进行纵向纳米级的微纳加工和后续热处理以期获得侧壁石墨烯生长和调控所必须的特定晶面指数的非极性面。而在现代半导体加工没有完全适用于SiC三维纳米机构加工的成熟工艺，同时由于所有的侧壁石墨烯均生长在三维的侧壁上对后续的半导体器件的制造增加了不小的难度。
公开内容
有鉴于此，本公开的主要目的在于提供一种单层石墨烯的可控生长 方法，以期至少部分地解决上述提及的技术问题中的至少之一。
为实现上述目的，本公开技术方案如下：
作为本公开的一个方面，提供了一种单层石墨烯的可控生长方法，其中，在非极性晶面SiC衬底的任意角度的非极性晶面上外延生长单层石墨烯，由此利用所述非极性晶面对石墨烯的电输运性质进行调控。
作为本公开的另一个方面，提供了一种利用如上所述的可控生长方法制得的单层石墨烯，其中，所述单层石墨烯外延生长于非极性晶面SiC衬底的任意角度的非极性晶面上，所述单层石墨烯的电输运性质由所述非极性晶面进行调控。
作为本公开的再一个方面，提供了一种非极性晶面SiC衬底的制备方法，包括以下步骤：根据一非极性晶面与(0001)面或(000-1)面的夹角，来调整金刚石线相对于一SiC晶柱的角度，利用金刚石线对所述SiC晶柱进行切割得到SiC晶片；对所述SiC晶片进行研磨、机械抛光和化学机械抛光，得到具有原子级平整度的非极性晶面；在所述非极性晶面被验证无误后，对所述SiC晶片进行切割，得到所述非极性晶面SiC衬底。
作为本公开的又一个方面，提供了一种非极性晶面SiC衬底，其为利用如上所述的制备方法制得。
基于上述技术方案，本公开的有益效果在于：
(1)我们基于侧壁石墨烯特点、生长条件和物理机理的分析，提出在任意非极性晶面上生长石墨烯，利用任意非极性晶面本身的物理性质对于其上生长石墨烯的调控以及利用任意非极性晶面同石墨烯的相互作用大规模调控石墨烯性质的方法。
(2)进一步提出对SiC晶体直接进行任意角度切割而实现任意非极性晶面，根据不同晶面SiC的硬度不一样，在切割过程中采用最佳的切割进给速度来实现所需厚度任意晶面SiC的切割。同时在目前对SiC零角度抛光现有技术的基础上，公开了对任意晶面SiC实现原子级平整度的抛光技术。
(3)本公开解决了在侧壁石墨烯纳米带上的加工难题，同时实现 了大规模生长平面化的单层石墨烯，尤其是，在一特定角度非极性面上生长出大面积具有弹道输运性质的石墨烯，为弹道输运石墨烯电子器件开创了纪元。
附图说明
图1为本公开实施例1中SiC衬底两相互垂直的参考面与钢板相互垂直之间的相互位置；
图2为本公开实施例1中SiC(0001)面与金刚石线平行示意图；
图3为本公开实施例1中切割SiC特定晶面的示意图；
图4为本公开实施例2中经过研磨后SiC的扫描电镜(SEM)图；
图5为本公开实施例2中经过机械抛光后SiC的原子力显微镜(AFM)图；
图6为本公开实施例2中经过化学机械抛光后SiC的AFM图；
图7为本公开实施例3中生长石墨烯的SEM图；
图8为本公开实施例3中生长石墨烯的横向力显微镜(LFM)图；
图9为本公开实施例3中生长石墨烯的拉曼图；
图10为本公开实施例3中生长石墨烯的低能量电子衍射(LEED)图；
图11为本公开实施例3中非极性晶面石墨烯的电输运性质测量结果；
图12为本公开实施例4中生长石墨烯的SEM图；
图13为本公开实施例4中生长石墨烯的拉曼图；
图14为本公开实施例5中生长石墨烯的LFM图；
图15为本公开实施例5中生长石墨烯的拉曼图；
图16为本公开对比例1中生长石墨烯的SEM图；
图17为本公开对比例1中生长石墨烯的LFM图；
图18为本公开对比例1中生长石墨烯的拉曼图；
图19为本公开对比例1中生长石墨烯的电输运性质测量结果。
上述附图中，附图标记含义如下：
1：夹具；
2：SiC晶柱；
21、22：参考面；
3：钢板；
4：金刚石线。
具体实施方式
为使本公开的目的、技术方案和优点更加清楚明白，以下结合具体实施例，并参照附图，对本公开作进一步的详细说明。
本公开公开了一种以非极性晶面SiC为衬底的单层石墨烯及可控生长方法，在任意非极性晶面SiC衬底上外延生长单层石墨烯，由不同非极性晶面对石墨烯性质，尤其是电输运性质进行调控。此处“非极性晶面SiC衬底”即为上、下表面中至少有一面为非极性晶面的SiC衬底。其主要物理机制是通过SiC特定晶面的物理性质对石墨烯生长的影响以及该特定晶面同石墨烯之间的相互作用的调控，使得特定晶面外延石墨烯具有了同普通(0001)和(000-1)面上非常不同的物理性质。申请人在研究过程中还克服了以下技术难点：目前对任意角度非极性面SiC切割和磨抛还没有完整有效的工艺，对任意角度非极性晶面SiC衬底上大面积生长单层石墨烯也没有普遍适用的方法。
具体地，本公开提供了一种单层石墨烯的可控生长方法，在非极性晶面的非极性晶面SiC衬底的任意角度的非极性晶面上外延生长单层石墨烯，由此利用非极性晶面对石墨烯的电输运性质进行调控。
其中，非极性晶面SiC衬底为六方晶系，优选为4H-SiC衬底或6H-SiC衬底，非极性晶面优选为(1-105)面，与(0001)面成37.1°夹角。
其中，非极性晶面SiC衬底通过以下步骤制备：
根据一非极性晶面与(0001)面或(000-1)面的夹角，来调整金刚石线相对于一SiC晶柱的角度，利用金刚石线对SiC晶柱进行切割得到SiC晶片；
对SiC晶片进行研磨、机械抛光和化学机械抛光，得到具有原子级平整度的非极性晶面；
在非极性晶面被验证无误后，对SiC晶片进行切割，得到非极性晶面SiC衬底。
其中，金刚石线的线径在0.2～0.8mm，优选为0.6mm，进给速度为1.5mm/min～5mm/min，优选为3mm/min。
其中，研磨的条件为：采用含金刚石颗粒的磨盘或砂纸，金刚石颗粒的粒径为3～60μm，抛光压力为20～250N，动力头速度和磨盘转速分别为30～80r/min、100～300r/min；
作为优选，研磨的条件为依次以金刚石颗粒粒径为60μm和30μm的磨盘进行研磨，并且在研磨时抛光压力从100～200N逐渐增加，动力头速度和磨盘转速分别为60r/min、280r/min。
其中，机械抛光的条件为：采用金刚石悬浮液，金刚石颗粒粒径为0.05～9μm，抛光压力为20～80N，抛光盘为合成丝绸布，动力头速度为30～100r/min，磨盘转速为60～320r/min；
作为优选，机械抛光的条件为依次以金刚石颗粒粒径为3μm和1μm的金刚石悬浮液进行抛光，抛光压力依次分别为80N和60N，动力头速度和磨盘转速分别为80r/min和为310r/min。
其中化学机械抛光的条件为：使用碱性的二氧化硅抛光液，pH优选为9～12，更优选为11，抛光压力为20～80N，优选为60N，抛光液滴加速度为5～50ml/min，优选为40mL/min，抛光垫为绒毛类结构，动力头速度为30～100r/min，优选为60r/min，磨盘转速为60～320r/min，优选为120r/min。
其中，SiC晶片被切割为长度为3～8mm，宽度为4～10mm的小晶片作为非极性晶面SiC衬底。
其中，石墨烯通过SiC热解法进行生长，具体包括以下步骤：
对非极性晶面SiC衬底进行预处理；
将经预处理后的非极性晶面SiC衬底在真空环境中，500～900℃下加热20～60min，优选为500℃下加热60min；
将非极性晶面SiC衬底在惰性气氛下升温至1100～1350℃，优选为1100℃，加热20～100min，优选为80min，然后升温至1500～1600℃，优 选为1500℃，加热20～150min，优选为120min；
待降温至室温后石墨烯生长结束。
其中，石墨烯还可以以涂覆于非极性晶面SiC衬底上的有机物为固态碳源进行生长，该方法填补了某些非极性晶面上难以直接通过热解法外延生长石墨烯的空白，具体包括以下步骤：
对所述非极性晶面SiC衬底进行预处理；
将经预处理后的所述非极性晶面SiC衬底旋涂10～100nm厚的有机物；
将所述非极性晶面SiC衬底在真空环境中，在500～1000℃下加热20～60min，优选为800℃下加热40min；
将所述非极性晶面SiC衬底在惰性气氛下升温至1200～1400℃，优选为1400℃，加热20～100min，优选为81min，然后升温至1500～1700℃，优选为1700℃，加热20～150min，优选为115min；
待降温至室温后石墨烯生长结束。
其中，有机物例如为光刻胶、聚苯乙烯或聚丙烯腈等。
此外，本公开还提供了一种利用如上所述的单层石墨烯的可控生长方法制得的单层石墨烯，该单层石墨烯外延生长于非极性晶面SiC衬底的任意角度的非极性晶面上，单层石墨烯的电输运性质由非极性晶面进行调控。
基于上述，本公开还提供了一种非极性晶面SiC衬底的制备方法，包括以下步骤：
步骤A：根据一非极性晶面与(0001)面或(000-1)面的夹角，来调整金刚石线相对于一SiC晶柱的角度，利用金刚石线对SiC晶柱进行切割得到SiC晶片；
对SiC晶片进行研磨、机械抛光和化学机械抛光，得到具有原子级平整度的非极性晶面；
在非极性晶面被验证无误后，对SiC晶片进行切割，得到非极性晶面SiC衬底；
其中，上述步骤的具体操作与前文所述相同。
进一步地，本公开还提供了一种非极性晶面SiC衬底，其为利用如上所述的非极性晶面SiC衬底的制备方法制得。
下面列举多个实施例配合附图对本公开的技术方案做进一步的详细说明。需要说明的是，下文中的具体实施例仅用于示例，并不用于限制本公开。
实施例1非极性晶面的切割
一种精确切割成任意角度非极性晶面SiC的方法，具体步骤如下：
(1)需要先确定所需非极性晶面与(0001)面之间的夹角，本实施例中该非极性晶面为(1-105)，与(0001)面成θ＝37.1°夹角，在其他实施例中为其他不同角度的非极性晶面；
(2)利用夹具1对一SiC晶柱2进行固定，如图1所示，该SiC晶柱2具有两个相互垂直的参考面21、22，如图2所示，该夹具上垂直设置有一钢板3，该夹具1可在水平面内旋转360°，在固定SiC晶柱前需确保夹具平面高度水平，进而此时钢板处于竖直状态；
在对SiC晶柱2进行固定时，需要将SiC晶柱2两个相互垂直的参考面21、22分别与钢板3两个相互垂直面对齐，从而SiC的两个参考面21、22分别为水平面和竖直面；
(3)将SiC晶柱2按上述要求固定好之后，通过在水平面内旋转夹具1使得SiC(0001)晶面平行于金刚石线4；
(4)切割SiC晶柱2的所需非极性晶面是指如图3所示，以竖直轴为旋转轴将夹具1及SiC晶柱2旋转θ＝37.1°，将金刚石线4以4.0mm/min的进给速度对SiC晶柱2进行切割，每切完一SiC晶片，控制SiC晶柱2向金刚石线4前进一距离，该距离为晶片厚度与金刚石线4线径之和。
实施例2非极性晶面的磨抛
一种可实现SiC任意角度非极性晶面达到原子级平整度的磨抛方法，具体步骤如下：
(1)将实施例1切割后的SiC晶片用石蜡粘贴在动力头盘上，然 后在抛光机上进行研磨，抛光盘为金刚石颗粒磨盘，先后采用金刚石颗粒粒径为60μm和30μm的磨盘对SiC晶片进行研磨，抛光压力在抛光过程中从100～200N逐渐增加，动力头速度和磨盘转速分别为60r/min、280r/min，在抛光过程中保持水流一直在冲洗，以降低在研磨过程中由于摩擦产生的热；
(2)将SiC晶片在抛光机上进行机械抛光，先后使用两种金刚石悬浮液，金刚石颗粒粒径分别为3μm和1μm，抛光压力分别为80N和60N，抛光盘为中等硬度的合成丝绸布，动力头速度和磨盘转速分别为80r/min、310r/min；
(3)将SiC晶片在抛光机上进行化学机械抛光，使用碱性的二氧化硅悬浮液(pH＝11)，溶液滴加速率为40ml/min，抛光压力为60N，抛光垫为绒毛类结构，动力头速度和磨盘转速分别为60r/min、120r/min；
(4)将抛光后的SiC晶片放在加热到50℃的超声清洗机中清洗，先后选择丙酮、乙醇和水进行超声，各20分钟；
(5)使用X定向仪验证非极性晶面，可查表或者计算得到所需晶面的衍射角，若无消光现象，可直接检测。反之，可逆向旋转θ＝37.1°，得出结果为(0001)晶面的衍射角即可证明所得晶面为所需非极性晶面。
如图4～6所示，经过研磨后SiC表面有明显较深的划痕(如图4)，而经过机械抛光后表面划痕达到2～3nm(如图5)，最终通过化学机械抛光表面没有划痕，表面起伏为pm量级(如图6)。
实施例3以非极性晶面SiC为衬底的大面积单层石墨烯生长
基于衬底天然周期性原位生长调控石墨烯性质的概念，提出了一种在任意角度非极性晶面非极性晶面SiC衬底上生长大面积单层石墨烯的方法，具体步骤如下：
(1)将实施例2经过磨抛所得的SiC晶片利用石蜡粘在陶瓷上，进而切割成3.5×4.5mm非极性晶面SiC衬底，对其进行预处理以去除石蜡和彻底清洗；
(2)将经预处理的3.5×4.5mm的非极性晶面SiC衬底放在新制备 的石墨坩锅内，再将石墨坩锅放在感应加热炉铜圈加热位置；
(3)第一阶段，在真空环境下，升温到500℃保持60min；
(4)第二阶段，通入高纯氩气，氩气流量为500sccm，将温度升高至1100℃保持80min；
(5)第三阶段，将温度升高到1500℃保持120min；
(6)第四阶段，快速降温到室温，完成石墨烯生长。
石墨烯测试结果为，如图7所示，可观察到图中所有区域几乎一致，石墨烯全部覆盖；如图8所示，图中颜色亮的区域为SiC区域，颜色较深为石墨烯，可观察到石墨烯几乎全部覆盖；如图9所示，图中2D峰的半高峰宽为28.8，表示得到的石墨烯为单层石墨烯，从图中的G峰位置(1580cm -1)和2D峰位置(2695cm -1)没有发生蓝移，可以看出石墨烯和SiC衬底相互作用力弱；如图10所示，光斑位置表明了石墨烯的对称性；如图11所示，反应了非极性晶面外延石墨烯独特的量子霍尔效应，具有弹道输运性质，可以实现无功耗或极低功耗的电输运。
实施例4以非极性晶面SiC为衬底的大面积单层石墨烯生长
本实施例与实施例3的区别在于：使用的坩埚为第二次使用的坩埚。具体步骤如下：
(1)将与实施例3相同的3.5×4.5mm的非极性晶面SiC衬底放在石墨坩锅内(生长面朝下)，再将石墨坩锅放在感应加热炉铜圈加热位置；
(2)第一阶段，在真空环境下，升温到500℃保持60min；
(3)第二阶段，通入高纯氩气，氩气流量为500sccm，将温度升高至1100℃保持80min；
(4)第三阶段，将温度升高到1500℃保持120min；
(5)第四阶段，快速降温到室温，完成石墨烯生长。
石墨烯测试结果为，如图12所示，图中颜色较深区域为石墨烯，可看出石墨烯生长为台阶状；如图13所示，图中2D峰的半高峰宽为39.8，表示得到的石墨烯为单层石墨烯，由于坩埚的使用次数越多，坩 埚内壁硅的附着量越多，硅原子不易于蒸发出来，从而生长的石墨烯越少，从图中G峰位置(1600cm -1)和2D峰位置(2749cm -1)发生蓝移，可以看出石墨烯和SiC衬底结合力强。
实施例5以非极性晶面SiC为衬底的大面积单层石墨烯生长
本实施例与实施例3区别在于：利用有机物作为固态碳源进行石墨烯生长，实现不同衬底对石墨烯物性的调控。具体步骤如下：
(1)对3.5×4.5mm的非极性晶面SiC衬底进行预处理以去除石蜡和彻底清洗；具体为：利用热水浴去除石蜡，丙酮、酒精、去离子水各超声30min进行清洗；
(2)将清洗后的片子用N2吹干，旋涂60nm左右的AZ光刻胶；
(3)将非极性晶面SiC衬底放入石墨坩埚中，再将石墨坩埚放入感应加热炉中；
(4)第一阶段在真空中进行，真空度达到5×10 -6mbar左右，800℃维持40min；
(5)第二阶段在100sccm流动氩气下，1400℃维持81min；
(6)第三阶段在100sccm流动氩气下，1700℃维持115min；
(7)第四阶段炉冷，石墨烯生长结束。
石墨烯测试结果为：如图14所示，石墨烯几乎全部覆盖，如图15所示，2D峰的半高峰宽为42表示得到的石墨烯为单双层石墨烯。
对比例1以(0001)面SiC为衬底的大面积石墨烯生长
具体步骤如下：
(1)对3.5×4.5mm的(0001)SiC衬底进行预处理，以去除石蜡和彻底清洗；具体为：利用热水浴去除石蜡，丙酮、酒精、去离子水各超声30min进行清洗；
(2)将SiC衬底放入石墨坩埚中，再将石墨坩埚放入感应加热炉中；
(3)整个生长过程均在真空中进行，真空度在5×10 -6mbar以下；
(4)第一阶段在800℃维持30min；
(5)第二阶段在1200℃维持30min；
(6)第三阶段在1520℃维持40min；
(7)第四阶段炉冷，石墨烯生长结束。
石墨烯测试结果为：如图16和17所示，石墨烯几乎全部覆盖，如图18所示，2D峰的半高峰宽为43，表示得到的石墨烯为单双层石墨烯。图19为在Si面测得的电输运性质图。
以上所述的具体实施例，对本公开的目的、技术方案和有益效果进行了进一步详细说明，应理解的是，以上所述仅为本公开的具体实施例而已，并不用于限制本公开，凡在本公开的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。

Claims (30)

  1. 一种单层石墨烯的可控生长方法，其特征在于，在非极性晶面SiC衬底的任意角度的非极性晶面上外延生长单层石墨烯，由此利用所述非极性晶面对石墨烯的电输运性质进行调控。
  2. 根据权利要求1所述的可控生长方法，其特征在于，所述非极性晶面SiC衬底为六方晶系，所述非极性晶面为(1-105)面，与(0001)面成37.1°夹角。
  3. 根据权利要求2所述的可控生长方法，其特征在于，所述非极性晶面SiC衬底为4H-SiC衬底或6H-SiC衬底。
  4. 根据权利要求1所述的可控生长方法，其特征在于，所述非极性晶面SiC衬底通过以下步骤制备：
    根据一非极性晶面与(0001)面或(000-1)面的夹角，来调整金刚石线相对于一SiC晶柱的角度，利用金刚石线对所述SiC晶柱进行切割得到SiC晶片；
    对所述SiC晶片进行研磨、机械抛光和化学机械抛光，得到具有原子级平整度的非极性晶面；
    对所述SiC晶片进行切割，得到所述非极性晶面SiC衬底。
  5. 根据权利要求4所述的可控生长方法，其特征在于，所述金刚石线的线径在0.2～0.8mm，进给速度为1.5～5mm/min。
  6. 根据权利要求5所述的可控生长方法，其特征在于，所述金刚石线的线径为0.6mm，进给速度为3mm/min。
  7. 根据权利要求4所述的可控生长方法，其特征在于，所述研磨的条件为：采用含金刚石颗粒的磨盘或砂纸，金刚石颗粒的粒径为3～60μm，抛光压力为20～250N，动力头速度和磨盘转速分别为30～80r/min、100～300r/min。
  8. 根据权利要求7所述的可控生长方法，其特征在于，所述研磨的条件为：依次以金刚石颗粒粒径为60μm和30μm的磨盘进行研磨，并且在研磨时抛光压力从100～200N逐渐增加，动力头速度和磨盘转速 分别为60r/min和280r/min。
  9. 根据权利要求4所述的可控生长方法，其特征在于，所述机械抛光的条件为：采用金刚石悬浮液，金刚石颗粒粒径为0.05～9μm，抛光压力为20～80N，抛光盘为合成丝绸布，动力头速度为30～100r/min，磨盘转速为60～320r/min。
  10. 根据权利要求9所述的可控生长方法，其特征在于，所述机械抛光的条件为：依次以金刚石颗粒粒径为3μm和1μm的金刚石悬浮液进行抛光，抛光压力依次分别为80N和60N，动力头速度和磨盘转速分别为80r/min和为310r/min。
  11. 根据权利要求4所述的可控生长方法，其特征在于，所述化学机械抛光的条件为：使用碱性的二氧化硅抛光液，抛光压力为20～80N，抛光液滴加速度为5～50ml/min，抛光垫为绒毛类结构，动力头速度为30～100r/min，磨盘转速为60～320r/min。
  12. 根据权利要求11所述的可控生长方法，其特征在于，所述化学机械抛光的条件为：所述碱性的二氧化硅抛光液的pH值为9～12，抛光压力为60N，抛光液滴加速度为40mL/min，动力头速度为60r/min，磨盘转速为120r/min。
  13. 根据权利要求4所述的可控生长方法，其特征在于，所述SiC晶片被切割成长度为3～8mm、宽度为4～10mm的小晶片，作为非极性晶面SiC衬底。
  14. 根据权利要求1所述的可控生长方法，其特征在于，所述石墨烯通过SiC热解法进行生长，具体包括以下步骤：
    对所述非极性晶面SiC衬底进行预处理；
    将经预处理后的所述非极性晶面SiC衬底在真空环境中，500～900℃下加热20～60min；
    将所述非极性晶面SiC衬底在惰性气氛下升温至1100～1350℃，加热20～100min，然后升温至1500～1600℃，加热20～150min；
    待降温至室温后石墨烯生长结束。
  15. 根据权利要求14所述的可控生长方法，其特征在于，将经预 处理后的所述非极性晶面SiC衬底在真空环境中、500℃下加热60min；
    将所述非极性晶面SiC衬底在惰性气氛下升温至1100℃，加热80min，然后升温至1500℃，加热120min。
  16. 根据权利要求1所述的可控生长方法，其特征在于，所述石墨烯以涂覆于非极性晶面SiC衬底上的有机物为固态碳源进行生长，具体包括以下步骤：
    对所述非极性晶面SiC衬底进行预处理；
    将经预处理后的所述非极性晶面SiC衬底旋涂10～100nm厚的有机物；
    将所述非极性晶面SiC衬底在真空环境中，在500～1000℃下加热20～60min；
    将所述非极性晶面SiC衬底在惰性气氛下升温至1200～1400℃，加热20～100min，然后升温至1500～1700℃，加热20～150min；
    待降温至室温后石墨烯生长结束。
  17. 根据权利要求16所述的可控生长方法，其特征在于，将所述非极性晶面SiC衬底在真空环境中，在800℃下加热40min；
    将所述非极性晶面SiC衬底在惰性气氛下升温至1400℃，加热81min，然后升温至1700℃，加热115min。
  18. 根据权利要求16所述的可控生长方法，其特征在于：
    所述有机物为光刻胶、聚苯乙烯或聚丙烯腈。
  19. 一种利用如权利要求1至18任意一项所述的单层石墨烯的可控生长方法制得的单层石墨烯。
  20. 一种非极性晶面SiC衬底的制备方法，其特征在于，包括以下步骤：
    根据一非极性晶面与(0001)面或(000-1)面的夹角，来调整金刚石线相对于一SiC晶柱的角度，利用金刚石线对所述SiC晶柱进行切割得到SiC晶片；
    对所述SiC晶片进行研磨、机械抛光和化学机械抛光，得到具有原子级平整度的非极性晶面；
    对所述SiC晶片进行切割，得到所述非极性晶面SiC衬底。
  21. 根据权利要求20所述的制备方法，其特征在于，所述金刚石线的线径在0.2～0.8mm，进给速度为1.5～5mm/min。
  22. 根据权利要求21所述的制备方法，其特征在于，所述金刚石线的线径为0.6mm，进给速度为3mm/min。
  23. 根据权利要求20所述的制备方法，其特征在于，所述研磨的条件为：采用含金刚石颗粒的磨盘或砂纸，金刚石颗粒的粒径为3～60μm，抛光压力为20～250N，动力头速度和磨盘转速分别为30～80r/min、100～300r/min。
  24. 根据权利要求23所述的制备方法，其特征在于，所述研磨的条件为：依次以金刚石颗粒粒径为60μm和30μm的磨盘进行研磨，并且在研磨时抛光压力从100～200N逐渐增加，动力头速度和磨盘转速分别为60r/min、280r/min。
  25. 根据权利要求4所述的制备方法，其特征在于，所述机械抛光的条件为：采用金刚石悬浮液，金刚石颗粒粒径为0.05～9μm，抛光压力为20～80N，抛光盘为合成丝绸布，动力头速度为30～100r/min，磨盘转速为60～320r/min。
  26. 根据权利要求25所述的制备方法，其特征在于，所述机械抛光的条件为：依次以金刚石颗粒粒径为3μm和1μm的金刚石悬浮液进行抛光，抛光压力依次分别为80N和60N，动力头速度和磨盘转速分别为80r/min和为310r/min。
  27. 根据权利要求20所述的制备方法，其特征在于，所述化学机械抛光的条件为：使用碱性的二氧化硅抛光液，抛光压力为20～80N，抛光液滴加速度为5～50ml/min，抛光垫为绒毛类结构，动力头速度为30～100r/min，磨盘转速为60～320r/min。
  28. 根据权利要求27所述的制备方法，其特征在于，所述化学机械抛光的条件为：所述碱性的二氧化硅抛光液的pH值为9～12，抛光压力为60N，抛光液滴加速度为40mL/min，动力头速度为60r/min，磨盘转速为120r/min。
  29. 根据权利要求20所述的制备方法，其特征在于，所述SiC晶片被切割成长度为3～8mm、宽度为4～10mm的小晶片，作为非极性晶面SiC衬底。
  30. 一种利用如权利要求20至29任意一项所述的非极性晶面SiC衬底的制备方法制得的非极性晶面SiC衬底。
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