Comparison of the formation process and properties of epitaxial graphenes on Si- and C-face 6Hben SiC substrates

In this paper, the epitaxial graphene layers grown on Si- and C-face 6H-SiC substrates are investigated under a low pressure of 400 Pa at 1600 ℃. By using atomic force microscopy and Raman spectroscopy, we find that there are distinct differences in the formation and the properties between the epitaxial graphene layers grown on the Si-face and the C-face substrates, including the hydrogen etching process, the stacking type, and the number of layers. Hopefully, our results will be useful for improving the quality of the epitaxial graphene on SiC substrate.     

Comparison of the formation epitaxial graphenes on Si- and process and properties of C-face 6H-SiC substrates

In this paper,the epitaxial graphene layers grown on Si-and C-face 6H-SiC substrates are investigated under a low pressure of 400 Pa at 1600 C.By using atomic force microscopy and Raman spectroscopy,we find that there are distinct differences in the formation and the properties between the epitaxial graphene layers grown on the Si-face and the C-face substrates,including the hydrogen etching process,the stacking type,and the number of layers.Hopefully,our results will be useful for improving the quality of the epitaxial graphene on SiC substrate.     

The physics of epitaxial graphene on SiC(0001)

Various physical properties of epitaxial graphene grown on SiC(0001) are studied. First, the electronic transport in epitaxial bilayer graphene on SiC(0001) and quasi-free-standing bilayer graphene on SiC(0001) is investigated. The dependences of the resistance and the polarity of the Hall resistance at zero gate voltage on the top-gate voltage show that the carrier types are electron and hole, respectively. The mobility evaluated at various carrier densities indicates that the quasi-free-standing bilayer graphene shows higher mobility than the epitaxial bilayer graphene when they are compared at the same carrier density. The difference in mobility is thought to come from the domain size of the graphene sheet formed. To clarify a guiding principle for controlling graphene quality, the mechanism of epitaxial graphene growth is also studied theoretically. It is found that a new graphene sheet grows from the interface between the old graphene sheets and the SiC substrate. Further studies on the energetics reveal the importance of the role of the step on the SiC surface. A first-principles calculation unequivocally shows that the C prefers to release from the step edge and to aggregate as graphene nuclei along the step edge rather than be left on the terrace. It is also shown that the edges of the existing graphene more preferentially absorb the isolated C atoms. For some annealing conditions, experiments can also provide graphene islands on SiC(0001) surfaces. The atomic structures are studied theoretically together with their growth mechanism. The proposed embedded island structures actually act as a graphene island electronically, and those with zigzag edges have a magnetoelectric effect. Finally, the thermoelectric properties of graphene are theoretically examined. The results indicate that reducing the carrier scattering suppresses the thermoelectric power and enhances the thermoelectric figure of merit. The fine control of the Fermi energy position is thought to be key for the practical use of graphene as a thermoelectric material, which could be achieved with epitaxial graphene. All of these results reveal that epitaxial graphene is physically interesting.     

Transport characteristics of a single-layer graphene field-effect transistor grown on 4H-silicon carbide

We have investigated transport characteristics of epitaxial graphene grown on semi-insulating silicon-face 4H-silicon carbide (SiC) substrate by thermal decomposition method in relatively high N₂ pressure atmosphere. We have succeeded in forming 1–2 layers of graphene on SiC in controlled manner. The surface morphology of formed graphene was analyzed by atomic force microscopy (AFM), low-energy electron diffraction (LEED) and low-energy electron microscope (LEEM). We have confirmed single-layer graphene growth in average by this method. Top-gated, single-layer graphene field-effect transistors (FETs) were fabricated on epitaxial graphene grown on 4H-SiC. Increased on/off ratio of nearly 100 at low temperature and extremely small minimum conductance (0.018–0.3 in 4 e²/h) in gated Hall-bar samples suggest possible band-gap opening of single-layer epitaxial graphene grown on Si-face SiC.     

Si面4H-SiC衬底上外延石墨烯近平衡态制备

SiC热解法是制备大面积、高质量石墨烯的理想选择之一.外延石墨烯的晶体质量仍是制约其应用的关键因素之一.本文通过SiC热解法在4H-SiC(0001)衬底上制备单层外延石墨烯.通过引入氩气惰性气氛和硅蒸气,使SiC衬底表面的Si原子升华与返回概率接近平衡,外延石墨烯生长速率大大减慢,单层石墨烯的生长时间从15 min延长至75 min.测试分析表明,生长速率减慢,外延石墨烯中缺陷减少,晶体质量提高,使得外延石墨烯的电性能都得到改善,单层外延石墨烯的最高载流子迁移率达到1200 cm2/V·s,方阻604?/.以上结果表明,控制生长气氛,减慢生长速率是实现高质量外延石墨烯的可行途径之一.     

Raman analysis of epitaxial graphene grown on 4Hben SiC (0001) substrate under low pressure condition

In this paper, we report a feasible route of growing epitaxial graphene on 4H-SiC (0001) substrate in a low pressure of 4 mbar (1 bar=10⁵ Pa) with an argon flux of 2 standard liters per minute at 1200, 1300, 1400, and 1500 ℃ in a commercial chemical vapour deposition SiC reactor. Using Raman spectroscopy and scanning electron microscopy, we confirm that epitaxial graphene evidently forms on SiC surface above 1300 ℃ with a size of several microns. By fitting the 2D band of Raman data with two-Lorentzian function, and comparing with the published reports, we conclude that epitaxial graphene grown at 1300 ℃ is four-layer graphene.     

Ultrafast relaxation of hot optical phonons in monolayer and multilayer graphene on different substrates

Hot carrier cooling in few-layer and multilayer epitaxial graphene on SiC, and chemical vapor deposition (CVD) grown graphene transferred onto a glass substrate was investigated by transient absorption spectroscopy and imaging. Coupling to the substrate was found to play a critical role in charge carrier cooling. For both multilayer epitaxial graphene and monolayer CVD graphene, charge carriers transfer heat predominantly to intrinsic in-plane optical phonons of graphene. At high pump intensity, a significant number of optical phonons are accumulated, and the optical phonon lifetime presents a bottleneck for charge carrier cooling. This hot phonon effect did not occur in few-layer epitaxial graphene because of strong coupling to the substrate, which provided additional cooling channels. The limiting charge carrier lifetimes at high excitation densities were 1.8 ± 0.1 ps and 1.4 ± 0.1 ps for multilayer epitaxial graphene and monolayer CVD graphene, respectively. These values represent lower limits on the optical phonon lifetime for the graphene samples.     

Significant photoelectrical response of epitaxial graphene grown on Si-terminated 6H-SiC

Photoelectrical response characteristics of epitaxial graphene (EG) films on Si- and C-terminated 6H-SiC, and transferred chemical vapor deposition (CVD) graphene films on Si-terminated 6H-SiC have been investigated. The results show that upon illumination by a xenon lamp, the photocurrent of EG grown on Si-terminated SiC significantly increases by 147.6%, while the photocurrents of EG grown on C-terminated SiC, and transferred CVD graphene on Si-terminated SiC slightly decrease by 0.5% and 2.7%, respectively. The interfacial buffer layer between EG and Si-terminated 6H-SiC is responsible for the significant photoelectrical response of EG. Its strong photoelectrical response makes it promising for optoelectronic applications.     

Effect of surface morphology on the electron mobility of epitaxial graphene grown on 0° and 8° Si-terminated 4H-SiC substrates

Graphene with different surface morphologies were fabricated on 8° -off-axis and on-axis 4H-SiC(0001) substrates by high-temperature thermal decompositions. Graphene grown on Si-terminated 8° -off-axis 4H-SiC(0001) shows lower Hall mobility than the counterpart of on-axis SiC substrates. The terrace width is not responsible for the different electron mobility of graphene grown on different substrates, as the terrace width is much larger than the mean free path of the electrons. The electron mobility of graphene remains unchanged with an increasing terrace width on Siterminated on-axis SiC. Interface scattering and short-range scattering are the main factors affecting the mobility of epitaxial graphene. After the optimization of the growth process, the Hall mobility of the graphene reaches 1770 cm 2 /V·s at a carrier density of 9.8.×10 12 cm 2 . Wafer-size graphene was successfully achieved with an excellent double-layer thickness uniformity of 89.7% on a 3-inch SiC substrate.     

Influence of defects in SiC （0001） on epitaxial graphene

Defects in silicon carbide(SiC) substrate are crucial to the properties of the epitaxial graphene(EG) grown on it. Here we report the effect of defects in SiC on the crystalline quality of EGs through comparative studies of the characteristics of the EGs grown on SiC(0001) substrates with different defect densities. It is found that EGs on high quality SiC possess regular steps on the surface of the SiC and there is no discernible D peak in its Raman spectrum. Conversely, the EG on the SiC with a high density of defects has a strong D peak, irregular stepped morphology and poor uniformity in graphene layer numbers. It is the defects in the SiC that are responsible for the irregular stepped morphology and lead to the small domain size in the EG.     

Ultrafast relaxation of excited Dirac fermions in epitaxial graphene using optical differential transmission spectroscopy

We investigate the ultrafast relaxation dynamics of hot Dirac fermionic quasiparticles in multilayer epitaxial graphene using ultrafast optical differential transmission spectroscopy. We observe differential transmission spectra which are well described by interband transitions with no electron-hole interaction. Following the initial thermalization and emission of high-energy phonons, the electron cooling is determined by electron-acoustic phonon scattering, found to occur on the time scale of 1 ps for highly doped layers, and 4-11 ps in undoped layers. The spectra also provide strong evidence for the multilayer structure and doping profile of thermally grown epitaxial graphene on SiC.     

Quasi‐Freestanding Graphene on SiC(0001) by Ar‐Mediated Intercalation of Antimony: A Route Toward Intercalation of High‐Vapor‐Pressure Elements

A novel strategy for the intercalation of antimony (Sb) under the $\text{(6}\sqrt{\mathrm{3}}\times \mathrm{6}\sqrt{\mathrm{3}})R\text{30}$° reconstruction, also known as buffer layer, on SiC(0001) is reported. Using X‐ray photoelectron spectroscopy, low‐energy electron diffraction, and angle‐resolved photoelectron spectroscopy, it is demonstrated that, while the intercalation of the volatile Sb is not possible by annealing the Sb‐coated buffer layer in ultrahigh vacuum, it can be achieved by annealing the sample in an atmosphere of Ar, which suppresses Sb desorption. The intercalation leads to a decoupling of the buffer layer from the SiC(0001) surface and the formation of quasi‐freestanding graphene. The intercalation process paves the way for future studies of the formation of quasi‐freestanding graphene by intercalation of high‐vapor‐pressure elements, which are not accessible by previously known intercalation techniques, and thus provides new avenues for the manipulation of epitaxial graphene on SiC.     

Why multilayer graphene on 4H-SiC(0001[over ]) behaves like a single sheet of graphene

We show experimentally that multilayer graphene grown on the carbon terminated SiC(0001[over ]) surface contains rotational stacking faults related to the epitaxial condition at the graphene-SiC interface. Via first-principles calculation, we demonstrate that such faults produce an electronic structure indistinguishable from an isolated single graphene sheet in the vicinity of the Dirac point. This explains prior experimental results that showed single-layer electronic properties, even for epitaxial graphene films tens of layers thick.     

介电层表面直接生长石墨烯的研究进展

作为21世纪备受瞩目的材料,石墨烯兼具优异的电、热、光与力学性质,具有十分广阔的研究价值与应用价值.目前主要通过在金属基底上生长获得石墨烯,并将其转移至目标介电层基底上以构筑电子器件.转移过程不可避免地引入了褶皱、裂纹、破损以及聚合物/金属残留,严重损害了石墨烯的性能.因而直接在介电基底上制备高质量的石墨烯薄膜具有重要意义.本文总结了近年来在介电衬底上直接生长石墨烯的研究进展:阐述了金属辅助法、等离子体增强法以及热力学或动力学调控法等多种生长手段;介绍了多种介电/绝缘基底包括SiO_2/Si,Al_2O_3,SrTiO_3,h-BN,SiC,Si_3N_4以及玻璃表面生长石墨烯的特点与性能,分析了其可能的生长机理.根据拉曼谱图、薄层电阻、透光率、载流子迁移率等评估指标,将多种方法得到的石墨烯质量进行了总结与比较,并提出了直接在介电衬底上生成石墨烯的研究难点与趋势.     

Graphene films grown on sapphire substrates via solid source molecular beam epitaxy

A method for growing graphene on a sapphire substrate by depositing an SiC buffer layer and then annealing at high temperature in solid source molecular beam epitaxy (SSMBE) equipment was presented. The structural and electronic properties of the samples were characterized by reflection high energy diffraction (RHEED), X-ray diffraction Φ scans, Raman spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results of the RHEED and Φ scan, as well as the Raman spectra, showed that an epitaxial hexagonal α-SiC layer was grown on the sapphire substrate. The results of the Raman and NEXAFS spectra revealed that the graphene films with the AB Bernal stacking structure were formed on the sapphire substrate after annealing. The layer number of the graphene was between four and five, and the thickness of the unreacted SiC layer was about 1--1.5 nm.     

Nucleation of epitaxial graphene on SiC substrate by thermal annealing and chemical vapor deposition

Growth of epitaxial graphene (EG) on silicon carbide (SiC) is regarded as one of the most effective routes to high-quality graphene towards practical applicability. We try to build up a model to illuminate the nucleation process of EG on SiC by thermal decomposition. The model is derived from some experimental results and discloses that surface diffusion plays an important role in the nucleation. For the chemical vapor deposition process used, the organic gas as carbon precursor enables carbon deposition quickly for supporting the growth of high-quality graphene via vapor transformation, so that the nucleated and final graphene becomes almost stress-free and mimics the free-standing graphene. Our findings have a potential in preparing high-quality graphene by controlling the nucleation conditions.     

化学气相沉积法制备的石墨烯晶畴的氢气刻蚀

利用化学气相沉积法在抛光铜衬底上制备出六角形石墨烯晶畴, 并且在高温条件下对石墨烯晶畴进行氢气刻蚀, 利用光学显微镜和扫描电子显微镜对石墨烯晶畴进行观测, 发现高温条件下石墨烯晶畴表面能够被氢气刻蚀出网络状和线状结构的刻蚀条纹. 通过电子背散射衍射测试证明了刻蚀条纹的形态、密度与铜衬底的晶向有密切关系. 通过对比实验证明了石墨烯表面上的刻蚀条纹是由于石墨烯和铜衬底的热膨胀系数不同, 在降温过程中, 石墨烯表面形成了褶皱, 褶皱在高温氢气气氛下发生氢化反应形成的. 对转移到二氧化硅衬底的石墨烯晶畴进行原子力显微镜测试, 测试结果表明刻蚀条纹的形貌、密度与石墨烯表面褶皱的形貌、密度十分相似. 进一步证明了刻蚀条纹是由于褶皱结构被氢气刻蚀引起的. 实验结果表明, 即使在六角形石墨烯晶畴表面也存在褶皱和点缺陷. 本文提供了一种便捷的方法来观察铜衬底上石墨烯褶皱的分布与形态; 同时, 为进一步提高化学气相沉积法制备石墨烯的质量提供了更多参考.     

Cobalt-assisted large-area epitaxial graphene growth in thermal cracker enhanced gas source molecular beam epitaxy

Large-area epitaxial graphene films were grown on cobalt by thermal cracker enhanced gas source molecular beam epitaxy. Growth conditions including growth temperature and growth time play important roles in the resulting morphology of as-grown films. High-quality graphene films can be achieved in a small growth window. Fast cooling rate was not required in this process due to direct growth mechanism under atomic carbon growth condition. Large-area graphene films with high single-layer and bi-layer coverage of 93% were confirmed by Raman spectroscopy and transmission electron microscopy.     

Formation of graphene on amorphous SiC film by surface-confined heating with electron beam irradiation

It is demonstrated experimentally that graphene can form on the surface of an amorphous SiC film by irradiating electron beam (e-beam) at low acceleration voltage. As the electron irradiation fluency increases, the crystallinity and uniformity of graphene improve, which is confirmed by the changes of the measured Raman spectra and secondary electron microscopy images. Due to the shallow penetration depth of e-beam with low acceleration voltage, only the region near the surface of SiC film will be heated by the thermalization of irradiated electrons with multiple scattering processes. The thermalized electrons are expected to weaken the bond strength between Si and C atoms so that the thermal agitation required for triggering the sublimation of Si atoms decreases. With these assistances of irradiated electrons, it is considered that graphene can grow on the surface of SiC film at temperature reduced substantially in comparison with the conventional vacuum annealing process.