Free-standing Epitaxial Graphene on Silicon Carbide and Transport Barriers in Layered Materials


Book Description

This thesis is based on the topic of layered materials, in which different layers interact with each other via van der Waals forces. The majority of this thesis deals with epitaxial graphene (EG) obtained from silicon carbide (SiC). Free-standing epitaxial graphene (FSEG) structures are produced from EG using a photoelectrochemical (PEC) etching process developed for making suspended graphene structures on a large-scale. These structures are investigated for their mechanical and electrical properties. For doubly-clamped FSEG structures, a unique U-beam effect is observed which causes orders of magnitude increase in their mechanical resonance frequency compared to that expected using simple beam theory. Combined magnetotransport and Raman spectroscopy studies reveal that FSEG devices produced from nominally monolayer graphene on the Si-face of SiC exhibit properties of an inhomogeneously doped bilayer after becoming suspended. This suggests that the buffer layer which precedes graphene growth on the Si-face of SiC gets converted to a graphene layer after the PEC etching process. In the second theme of this thesis, transport barriers in layered materials are investigated. The EG-SiC interface is studied using a combination of electrical (I-V, C-V) and photocurrent spectroscopy techniques. It is shown that the interface may be described as having a Schottky barrier for electron transport with a Gaussian distribution of barrier heights. Another interface explored in this work is that between different layers of MoS2, a layered material belonging to the class of transition metal dichalcogenides. This interface maybe thought of as a one-dimensional junction. Fourpoint transport measurements indicate the presence of a barrier for electron transport at this interface. A simple model of the junction as a region with an increased threshold voltage and degraded mobility is suggested. The final chapter is a collection of works based on the topic of layered materials, which are not related to the main theme of the thesis. They include fabrication and characterization details of a dual-gated bilayer graphene device, an investigation of the graphene-Si interface and hexagonal boron nitride-based membranes. These are presented in the hope that they may be useful for further investigations along those directions.




Epitaxial Graphene on Silicon Carbide


Book Description

This is the first book dedicated exclusively to epitaxial graphene on silicon carbide (EG-SiC). It comprehensively addresses all fundamental aspects relevant for the study and technology development of EG materials and their applications, using quantum Hall effect studies and probe techniques such as scanning tunneling microscopy and atomic resolution imaging based on transmission electron microscopy. It presents the state of the art of the synthesis of EG-SiC and profusely explains it as a function of SiC substrate characteristics such as polytype, polarity, and wafer cut as well as the in situ and ex situ conditioning techniques, including H2 pre-deposition annealing and chemical mechanical polishing. It also describes growth studies, including the most popular characterization techniques, such as ultrahigh-vacuum, partial-pressure, or graphite-cap sublimation techniques, for high-quality controlled deposition. The book includes relevant examples on synthesis and characterization techniques as well as device fabrication processing and performance and complements them with theoretical modeling and simulation studies, which are helpful in the fundamental comprehension of EG-SiC substrates and their potential use in electronic applications. It addresses the fundamental aspects of EG-SiC using quantum Hall effect studies as well as probe techniques, such as scanning tunneling microscopy or atomic resolution imaging based on transmission electron microscopy. It comprises chapters that present reviews and vision on the current state of the art of experts in physics, electronic engineering, materials science, and nanotechnology from Europe and Asia.




Free charge carrier properties in group III nitrides and graphene studied by THz-to-MIR ellipsometry and optical Hall effect


Book Description

Development of silicon based electronics have revolutionized our every day life during the last five decades. Nowadays silicon based devices operate close to their theoretical limits that is becoming a bottleneck for further progress. In particular, for the growing field of high frequency and high power electronics, silicon cannot offer the required properties. Development of materials capable of providing high current densities, carrier mobilities and high breakdown fields is crucial for further progress in state of the art electronics. Epitaxial graphene grown on semi-insulating silicon carbide substrates has a high potential to be integrated in current planar device technologies. High electron mobilities and sheet carrier densities make graphene extremely attractive for high frequency analog applications. One of the remaining challenges is the interaction of epitaxial graphene with the substrate. Typically, much lower free charge carrier mobilities, compared to free standing graphene, and doping, due to charge transfer from the substrate, is reported. Thus, a good understanding of the intrinsic free charge carriers properties and the factors affecting them is very important for further development of epitaxial graphene. Group III-nitrides have been extensively studied and already have proven their high efficiency as light emitting diodes for short wavelengths. High carrier mobilities and breakdown electric fields were demonstrated for group III-nitrides, making them attractive for high frequency and high power applications. Currently, In-rich InGaN alloys and AlGaN/GaN high electron mobility structures are of high interest for the research community due to open fundamental questions such as free charge carrier properties at high temperatures and wavefunction hybridization in AlGaN/GaN heterostructures. Electrical characterization techniques, commonly used for the determination of free charge carrier properties, require good ohmic and Schottky contacts, which in certain cases can be difficult to achieve. Access to electrical properties of buried conductive channels in multilayered structures requires modification of samples and good knowledge of the electrical properties of all electrical junctions within the structure. Moreover, the use of contacts to electrically characterize two-dimensional electronic materials, such as graphene, can alter their intrinsic properties. Furthermore, the determination of effective mass parameters commonly employs cyclotron resonance and Shubnikov-de Haas oscillations measurements, which require long scattering times of free charge carriers, high magnetic fields and low temperatures. The optical Hall effect is an external magnetic-field induced birefringence of conductive layers due to the free charge carriers interaction with long-wavelength electromagnetic waves under the influence of the Lorentz force. The optical Hall effect can be measured by generalized ellipsometry and provides a powerful method for the determination of free charge carrier properties in a non-destructive and contactless manner. The optical Hall effect measurements can provide quantitative information about free charge carrier type, concentration, mobility and effective mass parameters at temperatures ranging from few kelvins to room temperature and above. It further allows to differentiate the free charge carrier properties of individual layers in multilayer samples. The employment of a backside cavity for transparent samples can enhance the optical Hall effect and allows to access free charge carrier properties at relatively low magnetic fields using permanent magnet. The optical Hall effect measurements at mid-infrared spectral range can be used to probe quantum mechanical phenomena such as Landau levels in graphene. The magnetic field dependence of the inter-Landau level transition energies and optical polarization selection rules provide information about coupling properties between graphene layers and the electronic band structure. Measurement of the optical Hall effect by generalized ellipsometry is an indirect technique requiring subsequent data analysis. Parameterized optical models are fitted to match experimentally measured ellipsometric spectra by varying physically significant model parameters. Analysis of the generalized ellipsometry data at long wavelengths for samples containing free charge carriers by optical models based on the classical Drude formulation, augmented with an external magnetic field contribution, allows to extract carrier concentration, mobility and effective mass parameters. The development of the integrated FIR and THz frequency-domain ellipsometer at the Terahertz Materials Analysis Center in Linköping University was part of the graduate studies presented in this dissertation. The THz ellipsometer capabilities are demonstrated by determination of Si and sapphire optical constants, and free charge carrier properties of two-dimensional electron gas in GaN-based high electron mobility transistor structures. The THz ellipsometry is further shown to be capable of determining free charge carrier properties and following their changes upon variation of ambient conditions in atomically thin layers with an example of epitaxial graphene. A potential of the THz OHE with the cavity enhancement (THz-CE-OHE) for determination of the free charge carrier properties in atomically thin layers were demonstrated by the measurements of the carrier properties in monolayer and multilayer epitaxial graphene on Si-face 4H-SiC. The data analysis revealed p-type doping for monolayer graphene with a carrier density in the low 1012 cm-2 range and a carrier mobility of 1550 cm2V-1s-1. For the multilayer graphene, n-type doping with a carrier density in the low 1013 cm-2 range, a mobility of 470 cm2V-1s-1 and an effective mass of (0.14 ± 0.03)m0 were extracted. Different type of doping among monolayer and multilayer graphene is explained as a result of different hydrophobicity among samples. Further, we have employed THz-CE-OHE to determine for the first time anisotropic mobility parameter in quasi-free-standing bilayer epitaxial graphene induced by step-like surface morphology of 4H-SiC. Correlation of atomic force microscopy, Raman scattering spectroscopy, scanning probe Kelvin probe microscopy, low energy electron microscopy and diffraction analysis allows us to investigate the possible scattering mechanisms and suggests that anisotropic mobility is induced by varying local mobility parameter due to interaction between graphene and underlaying substrate. The origin of the layers decoupling in multilayer graphene on C-face 4H-SiC was studied by MIR-OHE, transmission electron microscopy and electron energy loss spectroscopy. The results revealed the decoupling of the layers induced by the increased interlayer spacing which is attributed to the Si atoms trapped between graphene layers. MIR ellipsometry and MIR-OHE measurements were employed to determine the electron effective mass in a wurtzite In0.33Ga0.67N epitaxial layer. The data analysis revealed the effective mass parameters parallel and perpendicular to the c-axis which can be considered as equal within sensitivity of our measurements. The determined effective mass is consistent with linear dependence on the In content. Analysis of the free charge carrier properties in AlGaN/GaN high electron mobility structures with modified interfaces showed that AlGaN/GaN interface structure has a significant effect on the mobility parameter. A sample with a sharp interface layers exhibits a record mobility of 2332 ± 73 cm2V-1s-1. The determined effective mass parameters showed an increase compared to the bulk GaN value, which is attributed to the penetration of the electron wavefunction into the AlGaN barrier layer. Temperature dependence of free charge carrier properties in GaN-based high electron mobility transistor structures with AlGaN and InAlN barrier layers were measured by terahertz optical Hall effect technique in a temperature range from 7.2 K to 398 K. The results revealed strong changes in the effective mass and mobility parameters. At temperatures below 57 K very high carrier mobility parameters above 20000 cm2V-1s-1 for AlGaN-barrier sample and much lower mobilities of ~ 5000 cm2V-1s-1 for InAlN-barrier sample were obtained. At low temperatures the effective mass parameters for both samples are very similar to bulk GaN value, while at temperatures above 131 K effective mass shows a strong increase with temperature. The effective masses of 0.344 m0 (@370 K) and 0.439 m0 (@398 K) were obtained for AlGaN- and InAlN-barrier samples, respectively. We discussed the possible origins of effective mass enhancement in high electron mobility transistor structures.







Study of novel electronic materials by mid-infrared and terahertz optical Hall effect


Book Description

Development of silicon based electronics have revolutionized our every day life during the last three decades. Nowadays Si based devices operate close to their theoretical limits that is becoming a bottleneck for further progress. In particular, for the growing field of high frequency and high power electronics, Si cannot offer the required properties. Development of materials capable of providing high current densities, carrier mobilities and high breakdown fields is crucial for a progress in state of the art electronics. Epitaxial graphene grown on semi-insulating silicon carbide substrates has a high potential to be integrated in the current planar device technologies. High electron mobilities and sheet carrier densities make graphene extremely attractive for high frequency analog applications. One of the remaining challenges is the interaction of epitaxial graphene with the substrate. Typically, much lower free charge carrier mobilities, compared to free standing graphene, and doping, due to charge transfer from the substrate, is reported. Thus, a good understanding of the intrinsic free charge carriers properties and the factors affecting them is very important for further development of epitaxial graphene. III-group nitrides have been extensively studied and already have proven their high efficiency as light sources for short wavelengths. High carrier mobilities and breakdown electric fields were demonstrated for III-group nitrides, making them attractive for high frequency and high power applications. Currently, In-rich InGaN alloys and AlGaN/GaN high electron mobility structures are of high interest for the research community due to open fundamental questions. Electrical characterization techniques, commonly used for the determination of free charge carrier properties, require good ohmic and Schottky contacts, which in certain cases can be difficult to achieve. Access to electrical properties of buried conductive channels in multilayered structures requires modification of samples and good knowledge of the electrical properties of all electrical contact within the structure. Moreover, the use of electrical contacts to electrically characterize two-dimensional electronic materials, such as graphene, can alter their intrinsic properties. Furthermore, the determination of effective mass parameters commonly employs cyclotron resonance and Shubnikov-de Haas oscillations measurements, which require long scattering times of free charge carriers, high magnetic fields and low temperatures. The optical Hall effect is an external magnetic field induced optical anisotropy in conductive layers due to the motion of the free charge carriers under the influence of the Lorentz force, and is equivalent to the electrical Hall effect at optical frequencies. The optical Hall effect can be measured by generalized ellipsometry and provides a powerful method for the determination of free charge carrier properties in a non-destructive and contactless manner. In principle, a single optical Hall effect measurement can provide quantitative information about free charge carrier types, concentrations, mobilities and effective mass parameters at temperatures ranging from few kelvins to room temperature and above. Further, it was demonstrated that for transparent samples, a backside cavity can be employed to enhance the optical Hall effect. Measurement of the optical Hall effect by generalized ellipsometry is an indirect technique requiring subsequent data analysis. Parameterized optical models are fitted to match experimentally measured ellipsometric data by varying physically significant parameters. Analysis of the optical response of samples, containing free charge carriers, employing optical models based on the classical Drude model, which is augmented with an external magnetic field contribution, provide access to the free charge carrier properties. The main research results of the graduate studies presented in this licentiate thesis are summarized in the five scientific papers. Paper I. Description of the custom-built terahertz frequency-domain spectroscopic ellipsometer at Linköping University. The terahertz ellipsometer capabilities are demonstrated by an accurate determination of the isotropic and anisotropic refractive indices of silicon and m-plane sapphire, respectively. Further, terahertz optical Hall effect measurements of an AlGaN/GaN high electron mobility structures were employed to extract the two-dimensional electron gas sheet density, mobility and effective mass parameters. Last, in-situ optical Hall effect measurement on epitaxial graphene in a gas cell with controllable environment, were used to study the effects of environmental doping on the mobility and carrier concentration. Paper II. Presents terahertz cavity-enhanced optical Hall measurements of the monolayer and multilayer epitaxial graphene on semi-insulating 4H-SiC (0001) substrates. The data analysis revealed p-type doping for monolayer graphene with a carrier density in the low 1012 cm?2 range and a carrier mobility of 1550 cm2/V·s. For the multilayer epitaxial graphene, n-type doping with a carrier density in the low 1013 cm?2 range, a mobility of 470 cm2/V·s and an effective mass of (0.14 ± 0.03) m0 were extracted. The measurements demonstrate that cavity-enhanced optical Hall effect measurements can be applied to study electronic properties of two-dimensional materials. Paper III. Terahertz cavity-enhanced optical Hall effect measurements are employed to study anisotropic transport in as-grown monolayer, quasi free-standing monolayer and quasi free-standing bilayer epitaxial graphene on semi-insulating 4H-SiC (0001) substrates. The data analysis revealed a strong anisotropy in the carrier mobilities of the quasi freestanding bilayer graphene. The anisotropy is demonstrated to be induced by carriers scattering at the step edges of the SiC, by showing that the mobility is higher along the step than across them. The scattering mechanism is discussed based on the results of the optical Hall effect, low-energy electron microscopy, low-energy electron diffraction and Raman measurements. Paper IV. Mid-infrared spectroscopic ellipsometry and mid-infrared optical Hall effect measurements are employed to determine the electron effective mass in an In0.33Ga0.67N epitaxial layer. The data analysis reveals slightly anisotropic effective mass and carrier mobility parameters together with the optical phonon frequencies and broadenings. Paper V. Terahertz cavity-enhanced optical Hall measurements are employed to study the free charge carrier properties in a set of AlGaN/GaN high electron mobility structures with modified interfaces. The results show that the interface structure has a significant effect on the free charge carrier mobility and that the sample with a sharp interface between an AlGaN barrier and a GaN buffer layers exhibits a record mobility of 2332±73 cm2/V·s. The determined effective mass parameters showed an increase compared to the GaN value, that is attributed the the penetration of the electron wavefunction into the AlGaN barrier layer.




Epitaxial Graphene on SiIicon Carbide


Book Description

The discovery of free-standing graphene in 2004 has attracted wide attention in both scientific community and industry because of its unusual electronic structure and properties. Due to the possible applications of graphene, many attempts to produce high-quality wafer-scale graphene films have been actively tried in the materials science and other scientific communities. Thermal decomposition of silicon carbide (SiC) is currently considered as one of the most promising routes toward the synthesis of well-controlled and characterized graphene films for electronic applications. This thesis focuses on the synthesis, structure and properties of epitaxial graphene on SiC. In the first chapter, I will investigate the structural properties of EG layers grown on the C-face of 4H-SiC in vacuum or Ar environments using synchrotron-based X-ray diffraction. The qualities and characteristics of layers will be also correlated with carrier mobilities obtained from Hall measurements. Since the Ar atmosphere produced higher quality graphene films on SiC than in vacuum, the inert-gas mediated thermal decomposition of SiC is regarded so far as the most effective method for the controlled EG growth. However, most studies have been done on the Si-face of SiC because of its slower reaction kinetics, which results in relatively uniform film thickness compared to the C-face. Nevertheless, there is significant interest in the C-face of SiC due to the superior electrical properties of EG grown on C-face SiC as compared to that grown on the Si-face. We find that Ar background pressure produces uniform graphene films on the C-face and the electronic properties (i.e. carrier mobility) of the films surpass that of vacuum-grown films due to larger crystalline domains formed in EG when the Ar pressure is above a certain threshold. In the second chapter, I will propose an alternative low-temperature, spatially controlled and scalable epitaxial graphene synthesis technique based on laser-induced surface decomposition of SiC. The high temperatures required in the conventional method are not compatible with large-scale device integration where different materials must be deposited and patterned prior to the formation of the semiconductor layer and limit the synthesis to single-crystal SiC substrates. Our technique is compatible with large-scale device integration. Furthermore, laser synthesis of graphene offers the advantage of combining synthesis and patterning in one step as the process can be designed to form graphene devices in predetermined locations on the substrate. In the last chapter, I will compare the structural properties of laser-synthesized EG on the Si-face and on the C-face of SiC. EG films on the C-face of 4H-SiC were successfully synthesized without the formation of carbon nanotubes by our laser technique, which are usually observed on the C-face upon vacuum high temperature anneals. The structural properties of these films were investigated by grazing incidence X-ray diffraction (GIXD) using synchrotron radiation and transmission electron microscopy. Since the graphene formation by UV laser irradiation is partially a photophysical process, I will illustrate the structural implications of the differences between the two formation processes.




Integration of 2D Materials for Electronics Applications


Book Description

This book is a printed edition of the Special Issue "Integration of 2D Materials for Electronics Applications" that was published in Crystals




Growing Graphene on Semiconductors


Book Description

Graphene, the wonder material of the 21st century, is expected to play an important role in future nanoelectronic applications, but the only way to achieve this goal is to grow graphene directly on a semiconductor, integrating it in the chain for the production of electronic circuits and devices. This book summarizes the latest achievements in this field, with particular attention to the graphitization of SiC. Through high-temperature annealing in a controlled environment, it is possible to decompose the topmost SiC layers, obtaining quasi-ideal graphene by Si sublimation with record electronic mobilities, while selective growth on patterned structures makes possible the opening of a gap by quantum confinement. The book starts with a review chapter on the significance and challenges of graphene growth on semiconductors, followed by three chapters dedicated to an up-to-date analysis of the synthesis of graphene in ultrahigh vacuum, and concludes with two chapters discussing possible ways of tailoring the electronic band structure of epitaxial graphene by atomic intercalation and of creating a gap by the growth of templated graphene nanostructures.




2-D Electronic Materials


Book Description

Graphene holds great promise as a material for high-speed electronics, especially as Si technology approaches its performance limits. Growth of epitaxial graphene by thermal decomposition of SiC is considered to be one of the most promising production routes since it has the potential to produce homogenous, wafer-size films directly on a semi-insulating or semiconducting substrate. Furthermore, graphene's planar 2-D structure enables devices and circuit designs with standard top-down lithography and processing techniques. However, the growth mechanism of graphene on SiC is not very well understood and much work remains to be done to improve the morphology, domain size and epitaxial quality of the grown graphene in order to take advantage of the unique properties of the material. This research work was aimed at using a modified CVD chamber in the Cornell University Wide-Bandgap-Semiconductor Laboratory to optimize the growth of epitaxial graphene by controlled decomposition of 6H-SiC(0001) in an argon mediated gas flow at near atmospheric pressure. Grown films were characterized using Raman spectroscopy, atomic force microscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and electrical measurements. Uniform large-area monolayer and few-layer epitaxial graphene were successfully grown on SiC terraces of up to 8 [MICRO SIGN]m wide, and with Hall mobilities of up to 840 cm2/V.s. The as-grown graphene was found to be intrinsically electron doped with sheet carrier density in the range of 3 - 9 x 1012 cm-2. However, certain growth features that tended to disrupt growth by uniform step flow decomposition were observed. These included deep rounded pits at higher temperatures, shallow triangular pits, arrow-like incursions across terraces, finger growths, residual SiC islands on terraces, nucleation of graphene at multiple defect points on terraces, and extra graphene layers at step edges. Further research is required to determine the mechanisms of formation of these features and to determine how they can be eliminated or reduced. For the first time SiC grown epitaxial graphene films, transferred from the substrate by a special process, was imaged in plan-view by TEM. The TEM images, along with selected-area electron diffraction, showed that a bilayer film had the AB Bernal stacking.!




Properties of Synthetic Two-Dimensional Materials and Heterostructures


Book Description

This book represents a significant advance in our understanding of the synthesis and properties of two-dimensional (2D) materials. The author’s work breaks new ground in the understanding of a number of 2D crystals, including atomically thin transition metal dichalcogenides, graphene, and their heterostructures, that are technologically important to next-generation electronics. In addition to critical new results on the direct growth of 2D heterostructures, it also details growth mechanisms, surface science, and device applications of “epi-grade” 2D semiconductors, which are essential to low-power electronics, as well as for extending Moore’s law. Most importantly, it provides an effective alternative to mechanically exfoliate 2D layers for practical applications.