Optical properties of graphene and Two dimensional transition metal dichalcogenides/Оптические свойства графена и двумерных дихалькогенидов переходных металлов тема диссертации и автореферата по ВАК РФ 00.00.00, кандидат наук Элсайед Марва Али Абделразик

• Элсайед Марва Али Абделразик
• кандидат наук
• 2022

Оглавление диссертации кандидат наук Элсайед Марва Али Абделразик

List of contents

Description of the dissertation work

Chapter 1. Two-dimensional layered van der Waals materials

1.1 Graphene: Forerunner of 2D systems

1.1.1 Atomic and crystalline structure

1.1.2 Spectacular optical behavior

1.1.3 Current applications and limitations

1.2 Transition metal dichalcogenides monolayers (ML TMDCs)

1.2.1 Geometric description and common polytypes

1.2.2 Band structure and main optical transitions

1.2.3 Exciton signature in monolayers

1.3 2D van der Waals heterostructures

1.4 Assessment of optical properties

Chapter 2. Experimental section

2.1 Materials

2.2 Research techniques and setups

2.2.1 Optical visualization

2.2.2 Raman and photoluminescence spectroscopies

2.2.3 Optical transmittance measurements

2.2.4 Atomic force microscopy

2.2.5 Scanning electron microscopy

2.2.6 X-ray diffraction

2.2.7 X-ray photoelectron spectroscopy

2.2.8 Dielectric response measurements

2.2.8.1 First- principle calculations

2.2.8.2 Imaging ellipsometry

2.2.8.3 Variable angle spectroscopic ellipsometry

2.2.8.4 Data analysis process

Chapter 3. Dielectric response of graphene for photonic applications

3.1 Introduction

3.2 Characterization of the graphene samples

3.3 Analysis of the dielectric response

3.4 Relevance of the study in nanophotonic applications

3.5 Conclusions

Chapter 4. Optical and structural characteristics of two-dimensional

epitaxial MoS2

4.1 Introduction

4.2 Surface and structural morphology study

4.3 Optical signatures of excitons in molybdenum disulfide monolayer

4.4 Applications of optical properties in nanophotonics

4.5 Conclusions

Chapter 5. New dielectric photonics by SnS2 and SnSe2 films

5.1 Introduction

5.2 Surface morphological and structural features

5.3 Crystal structure analysis and Raman characterization

5.4 Experimental investigations of optical properties

5.5 Theoretical investigations of dielectric functions

5.6 Prospects of SnS2 for dielectric nanophotonic applications

5.7 Conclusions

Thesis summary

Bibliography

Appendix A

Appendix B

Введение диссертации (часть автореферата) на тему «Optical properties of graphene and Two dimensional transition metal dichalcogenides/Оптические свойства графена и двумерных дихалькогенидов переходных металлов»

Description of the dissertation work

The thesis presents a thorough study of the optical properties of some prospective two-dimensional materials. Additionally, the microstructure and surface morphology of the studied samples were investigated by several advanced laboratory techniques. The following section provides the importance of the thesis work, identifies the main objectives and tasks, reflects the novelty of the study, theoretical and practical significance, propositions for the defense, and describes the structure of the thesis.

Relevance of the research topic

Research into two-dimensional (2D) materials began with the discovery of graphene, ushering in a new era of two-dimensional materials [1,2]. Beyond graphene, researchers have discovered other materials characterized by van der Waals (vdW) type bonds like multi-layered structures of 2D materials [3]. This discovery paved the way for a concerted effort aimed at revisiting research areas that appeared to have reached a point where everything was figured it out. Since then, research into atomically thin layers of semiconductors has become a critical topic in physics. The striking result is that material features can change substantially, approaching the limit of 2D nanotechnology, which marks a turning point in material science research. These materials are characterized by robust intra-layer covalent interactions and by weak vdW forces between the layers, thus leading to different properties that differ from those of 3D solids [4]. The materials obtained can be insulating, semiconductor or metallic, and have their own unique properties [5].

With the discovery of these new classes of materials - one-atom-thick materials, the demand for more efficient electrical, photonic devices, and the construction of novel architectures has become necessary. Interestingly, two-dimensional materials give rise to several unique phenomena. This involves quantum well systems with quantized energy levels, as well as two-dimensional electron gas systems capable of exhibiting the integer and fractional quantum Hall effects [6]. Two-dimensional materials have already proven totally distinct magnetic, optoelectronic, and optoelectronic properties, making them a perfect candidate for a variety of technological applications [7,8].

The most intriguing categories of 2D materials are graphene and TMDCs semiconductors. The optoelectronic properties of these materials are quite fascinating. Semi-metallic graphene, for example, has a high photoactivity governed by hot carriers

[9], whereas the photo-response of 2D-TMDCs is dominated by strong excitonic effects

[10]. However, the spectrum of applications is determined by the characteristics exploited. For instance, the semi-metallic nature of graphene allows it to act as transparent electrodes for PN junctions in solar cells, and its high mobility allows its use in high-frequency integrated circuits [11]. However, its restricted zero-band structure limits its application in the field of semiconductors, primarily for field-effect transistors.

Transition metal dichalcogenides monolayers (2D TMDCs), on the other hand, surpass the restrictions of graphene. The band gap is therefore not only non-zero, but also direct and controllable. The bandgap values of TMDCs compounds range from 0.1 to 3 eV, allowing them to be tailored to the appropriate wavelength range for a variety of devices [5].

However, the wide frameworks and various functionalities of these materials, the effective implementation of them and of their heterostructures in scientific and technological devices is incredibly dependent on an understanding of their optical properties. Careful consideration of the optical properties and complex dielectric functions of the two-dimensional materials used, ensures optimal performance and effectively contributes to the upgrading and development of these devices [12-14], which will be clarified in the thesis work. Hence, a lack of knowledge of their optical characteristics, on the other hand, could seriously limit their applicability. Therefore, the study of optical response of such materials is a very critical and important topic. A thorough understanding of the linear optical properties of 2D materials is essential for the rapid development of high-performance photonic, plasmonic, and optoelectronics, as well as paving the way for researchers and developers to construct sophisticated devices.

The Objectives of the thesis

The specific objectives of the thesis work address the following challenges: 1. Developing a reliable methodology based on ellipsometry for determining the dielectric response of some 2D materials over a broadband of spectra.

2. Understanding the influence of the predominant exciton of 2D materials on their optical response.

3. Studying the influence of dielectric including surroundings manufacturing, thee type of the underlying substrate, and layer thickness, the optical response of 2D materials.

4. Determination the impact of the optical properties of 2D materials on the output characteristics of optical devices through using examples of surface plasmon resonance-based biosensors with 2D vdW materials.

The study targeted one of the most promising materials; graphene and transition metal dichalcogenides semiconductors (Monolayers, as well as atomically thin films). The presented results can be used in photonics and optoelectronics, thus contributing to the development and design of high-performance devices based on 2D-materials and their heterostructures.

Research objects: The raw materials for the thesis investigations are graphene monolayers (thickness less than 0.35 nm) synthesized by chemical vapor deposition technique (CVD), transition metal semiconductor monolayers (TMDCs) represented by Molecular epitaxy MoS2, and atomically thin films of CVD- SnS2 and SnSe2. Scientific novelty of the dissertation work

❖ The optical properties of chemical vapor deposited (CVD) monolayer graphene on three different substrates were thoroughly investigated for the ultraviolet, visible, and near-infrared spectral ranges (from 240 to 1000 nm). A perfect ellipsometric model consisting of substrate layers and a single layer of graphene was used to achieve high convergence. Without any extra assumptions, such as the existence of water or any other media on or under the graphene, ellipsometry data were analyzed and modeled with high accuracy. The accuracy of our ellipsometric analysis was explained using a technique that combines measurements of X-ray photoelectron spectroscopy (XPS), atomic force (AFM) and scanning electron (SEM) microscopy, Raman spectroscopy, optical transmission spectroscopy measurements, and theoretical calculations. The optical constants of graphene showed less than 5% variation with substrate change and are remarkably like those of graphite, implying that obtained optical constants can also be applied to multilayer graphene structures. Additionally, the operation of several

SPR sensors has been shown to exhibit considerable variations in predicted signal intensity and is highly dependent on the graphene optical response sources employed.

❖ A molecular beam epitaxy (MBE)-grown monolayer of MoS2 on a sapphire substrate was thoroughly investigated for its optical and structural characteristics. Using the Accurion Ep4 imaging ellipsometer, which can capture the signal from a small micrometer-scaled area, the dielectric response of MBE MoS2 was measured in a broad spectral range from 250 to 1700 nm and compared them with the available data of CVD-grown and exfoliated monolayer MoS2. A combination of optical microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoemission spectroscopy (XPS), Raman spectroscopy, and photoluminescence imaging was used to evaluate the structural features of MoS2 samples. It was found that molecular beam epitaxy technique produces a polycrystalline monolayer film with high crystallinity and a higher quantum yield of luminescence than CVD monolayers of MoS2, closer to superior properties of exfoliated MoS2, but at a large scale. The accuracy of the optical properties was further validated by measuring the optical transmittance spectrum, which agrees perfectly with calculations based on the optical constants obtained through ellipsometry. Furthermore, we compared the features of SPR sensors calculated using different constants to show the significance of our accurate measurements for practical applications. It was found that when alternative sources of optical properties are employed, even systems with only a few atomic layers of MoS2 show radical changes in sensitivity and expected signal intensity.

❖ The linear optical characteristics of thin films of SnS2 and SnSe2 produced by chemical vapor deposition (CVD) were investigated through experimental and theoretical investigation. Using a variety of laboratory techniques, including optical microscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray diffraction (XRD), the surface morphology, roughness, homogeneity, thickness, and phase structures of the research samples were all examined. Utilizing spectroscopic ellipsometry and first-principles calculations from ultraviolet to mid-infrared wavelengths (300 - 3300 nm), the entire broadband dielectric tensors of SnS2 and SnSe2 were derived. To further verify, the optical

transmittance spectra of the films were measured and compared with the transfer matrix calculations based on the observed optical constants. In addition to the traditional high-refractive-index materials Si, GaP, and TiO2, SnS2 revealed a novel high-refractive-index material. The thin films of SnS2 and SnSe2 have been proven to be promising for nanophotonics demanding high refractive index and low absorption, as well as next-generation SnS2 and SnSe2-based devices. Theoretical and experimental significance of the thesis results

As a result of the work, the optical, structural, and factors influencing the optical properties of some two-dimensional materials at monolayer and low dimension thickness were thoroughly investigated, along with theoretical substantiation of the obtained results.

Over a wide energy spectrum, a method for accurately measuring the optical constants of thin films and monolayers of TMDCs has been developed, considering the sample fabrication technique, grown substrate, and internal structures. Personal contribution of the author

All the major findings of the dissertation were either acquired by the author or with her direct participation. The author took an active part in all stages of the work from the formulation of the problem to the writing of articles.

Basic research methods

Spectroscopic ellipsometry, atomic force and scanning electron microscopy, X-ray diffractometry, scanning near-field optical microscopy, and SPR spectroscopy were all employed in the research. Furthermore, the method of transfer matrices and first-principles computations were applied in this research work.

Scientific provisions submitted for defense:

1. A method for determining the optical constants of two-dimensional materials that considers the predominantly exciton nature of the optical response and returns the dielectric function that satisfies the Kramers-Kronig relations.

2. Optical constants of graphene obtained by the method of chemical vapor deposition in the spectral range of 240 - 1000 nm.

3. Optical constants of two-dimensional molybdenum disulfide obtained by molecular beam epitaxy in the spectral range of 250 - 1700 nm.

4. Linear properties of tin sulfide and selenide obtained by chemical vapor deposition in the spectral range of 300 - 3300 nm.

Reliability of experimental results:

The reliability of all experimental results of the study is ensured using approved calibrated modern measuring instruments, and test measurements of standard samples. The reliability of the experimental results obtained is confirmed by theoretical calculations and comparison with theoretical models. The conclusions formulated in the dissertation received qualified approbation at international and Russian conferences, their reliability is confirmed publication of research results in international scientific journals on research topics. Approbation of work

The key findings of the dissertation were presented and discussed at seminars held by the Laboratory of Nano-optics and Plasmonics, center for photonics and 2D materials, MIPT, as well as oral and poster presentations at Russian and international conferences.

• The annual MIPT conferences within the sections "Nanoscale Optoelectronics" and "Photonics and Two-Dimensional Materials" (2019, 2020 and 2021).

• International Congress on Graphene, 2D Materials and Applications, 30th September -04th October 2019, Sochi, Russia.

• VIII International Youth Scientific Conference at Physics and technologies // May 1721, 2021, Ekaterinburg, Russia.

• The International conference on photonics and information optics, January 27-29, 2021, Moscow.

List of thesis publications

Based on the dissertation materials, five publications have been published (four of them are included in the WoS and Scopus citation databases.

1. M.A. El-Sayed, A.V. Arsenin, A.A. Vyshnevyy, A.A. Voronov, V.S. Volkov, Comparative analysis of optical properties of CVD graphene and graphite via

spectroscopic ellipsometry // AIP Conference Proceedings 2359, 020020 (2021). https://doi.org/10.1063/5.0055462

2. M.A. El-Sayed, G.A. Ermolaev, K.V. Voronin, R.I. Romanov, G.I. Tselikov, D.I. Yakubovsky, N.V. Doroshina, A.B. Nemtsov, V.R. Solovey, A.A. Voronov, S.M. Novikov, A.A. Vyshnevyy, A.M. Markeev, A.V. Arsenin, V.S. Volkov, Optical constants of chemical vapor deposited graphene for photonic applications // Nanomaterials 11(5), 1230 (2021). https://doi.org/10.3390/nano11051230

3. G.A. Ermolaev, M.A. El-Sayed, D.I. Yakubovsky, K.V. Voronin, R.I. Romanov, M.K. Tatmyshevskiy, N.V. Doroshina, A.B. Nemtsov, A.A.Voronov, S.M. Novikov, A.M. Markeev, G.I. Tselikov, A.A. Vyshnevyy, A.V. Arsenin, V.S. Volkov, Optical Constants and Structural Properties of Epitaxial MoS2 Monolayers // Nanomaterials 11(6), 1411 (2021). https://doi.org/10.3390/nano11061411

4. G.A. Ermolaev, D.I. Yakubovsky, M.A. El-Sayed, M.K. Tatmyshevskiy, A.B. Mazitov, A.A. Popkova, I.M. Antropov, V.O. Bessonov, A.S. Slavich, G.I. Tselikov, I.A. Kruglov, S.M. Novikov, A.A. Vyshnevyy, A.A. Fedyanin, A.V. Arsenin, V.S. Volkov, Broadband optical constants and nonlinear properties of SnS2 and SnSe2 // Nanomaterials 12 (1), 141 (2022). Indexed by Scopus and Web of Science. https://doi.org/10.3390/nano12010141

5. Сюй А.В., Целиков Г.И., Дорошина Н.В. Элсайед М.А, Антонычева Е.А., Сюй М.В. Лазерный синтез наночастиц ZnS // Вып. № 26 / под редакцией В.И. Иванова. - Хабаровск: Изд-во ДВГУПС, 2021. - № 26. - с. 10-17. https://www.elibrary.ru/item.asp?id=47330927

List of conferences on the dissertation topic

1. М.А. Элсайед, Сравнительный анализ оптических свойств графена и графита // 62-я научная конференция МФТИ, 18-23 ноября 2019 г., г. Долгопрудный, Россия.

2. М.А. Элсайед, Н. В. Дорошина, Д. И. Якубовский, П. Мишра, Г.И. Целиков, Г. А. Ермолаев, В. Соловей, А.А. Вишневый, С.М. Новиков, А.В. Арсенин, В.С. Волков, Оптические свойства графена, синтезированного химическим

осаждением из газовой фазы // 63-я научная конференция МФТИ, 23-29 ноября 2020 г., г. Долгопрудный, Россия.

3. Marwa A. El-Sayed, Natalia V. Doroshina, Dmitry I. Yakubovsky, Layer thinning and etching of Quasi-ID TiS3 Nanoribbons using Raman spectroscopy // VIII International Youth Scientific Conference at Physics and technologies, May 17-21, 2021, Ekaterinburg, Russia.

4. М.А. Элсайед, Г. А. Ермолаев, И. Якубовский, М.К. Татмышевский, А.С. Славич, С. М. Новиков, Г.И. Целиков, А.А. Вишневый, А. В. Арсенин, В. С. Волков, Исследование оптических констант диселенида и дисульфида олова методом спектроскопической эллипсометрии // 64-я научная конференция МФТИ, 29 ноября - 03 декабря 2021 г., г. Долгопрудный, Россия.

5. M.A. El-Sayed, N.V. Doroshina, S.M. Novikov, A.A. Cherry, A.V. Arsenin, V.S. Volkov, Analysis of the Raman spectra of van der Waals heterostructures of molybdenum disulfide // International conference on photonics and information optics, January 27-29, 2021, Moscow, Russia.

The structure of the thesis

The thesis consists of an introduction, five chapters, a conclusion summarizes the main results of the dissertation work, and two appendices.

Заключение диссертации по теме «Другие cпециальности», Элсайед Марва Али Абделразик

5.7 Conclusions

In conclusion, theoretical calculations, and experimental investigations of the anisotropic optical constants of SnS2 and SnSe2 across a wide spectral range (300 - 3300 nm) have been performed. Such findings demonstrate the high dielectric response, broad range, and lack of absorption of SnS2 and SnSe2. More notably, SnS2 fits into this range, providing it a novel high-refractive-index substance that works together with Si, GaP, and TiO2 as well as other high-refractive-index substances. From a broader perspective, this research offers a foundation for advanced optical engineering using SnS2 and SnSe2 films.

Thesis summary

The activity of this thesis focused on experimental studies of the optical properties of some promising 2D vdW materials (monolayers and atomically thin films) over a broadband of spectra. In additions, the characterization of their structural, thickness, chemical composition, microstructure, surface morphology and roughness by means of various laboratory techniques. The main results of the thesis can be summarized as follows.

❖ It allowed for the development of a trustworthy method based on spectroscopic ellipsometry for figuring out the dielectric response of single layer graphene and other 2D systems, over a broad range of spectra.

❖ It was possible to reconstruct images with high spatial resolution through dark and bright field optical microscopy of the 2D materials under study.

❖ Raman spectroscopy and photoluminescence (PL) allowed the study of both the vibrational and electronic properties of each sample.

❖ From the study of the spatial distribution of the Raman spectrum and PL peaks it was possible to recognize the monolayer signature, the number of layers with defects in the surface structure. The various microspectroscopy techniques (XPS, XRD, AFM) have also made it possible to confirm the effectiveness of the optical response method analysis for the recognition of the complete picture of the macro- and microstructures.

❖ In the UV-visible-near-IR (240-1000 nm) range, the optical properties of a single sheet of graphene synthesized by chemical vapor deposition and deposited on glass, quartz, and SiO2/Si substrates were addressed. A good convergence has been achieved without the auxiliary layers that are typically added to account for residual water and PMMA. Transmittance experiments, which show impressive agreement with estimates based on the obtained optical constants, were used to further confirm the accuracy of the reported optical response. Notably, the derived optical constants are applicable to multilayer graphene structures since they are very similar to those of graphite and only fluctuate by less than 5% when the substrate changes. This research provides exact and typical graphene optical responses for the design of photonic devices.

❖ For the first time, a thorough analysis of the structural and optical characteristics of monolayer MoS2 produced via MBE was conducted. Through Raman and AFM tests, we proved that the sample does indeed include a single-atomic layer of MoS2, and XPS studies validated its great purity. Dark-field microscopy, SEM, and AFM imaging confirmed the material to be highly crystalline, with a typical crystallite size of 0.65 nm. The superior quantum yield of MBE MoS2 as illustrated by PL measurements demonstrated its advantages for active photonic applications. MBE MoS2 optical constants were found to be intermediate between CVD and exfoliated MoS2. For example, the refractive indexes of CVD, MBE, and exfoliated MoS2 at X = 750 nm are 3.2, 4.0, and 5.2, respectively. Furthermore, the importance of our precise measurements for practical applications was demonstrated by comparing the characteristics of SPR sensors calculated with different constants. When alternative sources of optical characteristics are employed, even devices with just a few atomic layers of MoS2 show considerable changes in sensitivity and expected signal strength. These results provide a solid foundation for the utilization of transition metal dichalcogenides for photonic applications.

❖ For the first time, The Linear optical constants, and anisotropic features of SnS2 and SnSe2 over a broad spectral range (300-3300 nm) were experimentally and theoretically determined. SnS2 and SnSe2 have been demonstrated to have a robust dielectric response and transparency over a broad spectral range. Using first-principles calculations, it was possible to identify the optical anisotropy, which is more pronounced for SnS2 having a birefringence of 5n = nab - nc = 0.3 and is almost undetectable for SnSe2. SnS2 has been demonstrated to be a one-of-a-kind high-refractive-index material that complements the traditional high-refractive-index materials TiO2, GaP, and Si2. This research paves the way for advanced optical engineering with SnS2 and SnSe2.

Finally, the results presented in this thesis are consistent with those that have been reported in the literature. The thesis provided reliable data on the dielectric response of different promising 2D materials. The results are applicable to the development of novel devices for basic research as well as applications in optoelectronics and photonics.

Список литературы диссертационного исследования кандидат наук Элсайед Марва Али Абделразик, 2022 год

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