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Microscopy Methods in Nanomaterials Characterization

Microscopy Methods in Nanomaterials Characterization

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Microscopy Methods in Nanomaterials Characterization

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778 pages
7 hours
Released:
May 17, 2017
ISBN:
9780323461474
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Book

Description

Microscopy Methods in Nanomaterials Characterization fills an important gap in the literature with a detailed look at microscopic and X-ray based characterization of nanomaterials. These microscopic techniques are used for the determination of surface morphology and the dispersion characteristics of nanomaterials.

This book deals with the detailed discussion of these aspects, and will provide the reader with a fundamental understanding of morphological tools, such as instrumentation, sample preparation and different kinds of analyses, etc. In addition, it covers the latest developments and trends morphological characterization using a variety of microscopes.

Materials scientists, materials engineers and scientists in related disciplines, including chemistry and physics, will find this to be a detailed, method-orientated guide to microscopy methods of nanocharacterization.

  • Takes a method-orientated approach that includes case studies that illustrate how to carry out each characterization technique
  • Discusses the advantages and disadvantages of each microscopy characterization technique, giving the reader greater understanding of conditions for different techniques
  • Presents an in-depth discussion of each technique, allowing the reader to gain a detailed understanding of each
Released:
May 17, 2017
ISBN:
9780323461474
Format:
Book

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Microscopy Methods in Nanomaterials Characterization - Elsevier Science

Microscopy Methods in Nanomaterials Characterization

Volume One

Editors

Sabu Thomas

Raju Thomas

Ajesh K. Zachariah

Raghvendra Kumar Mishra

Table of Contents

Cover image

Title page

Copyright

List of Contributors

Editor Biographies

Chapter 1. Scanning Electron Microscopy, ESEM, and X-ray Microanalysis

1.1. Introduction

1.2. Scanning Electron Microscopy

1.3. Energy Dispersive X-ray Microanalysis

1.4. Environmental Scanning Electron Microscopy

1.5. Cryo Scanning Electron Microscopy

1.6. Low-Voltage and High-Resolution Scanning Electron Microscopy

Chapter 2. Synthesis of Scanning Electron Microscopy Images of Nanostructures by High-Performance Monte Carlo Modeling

2.1. Introduction

2.2. Monte Carlo Modeling of Secondary-Electron Emission at Low Energies in Dielectrics

2.3. Efficient Simulation of Complex Three-Dimensional Geometries

2.4. Metrology of Nanostructures by Monte Carlo Modeling of SEM Images

2.5. Simulation of SEM Images in the Presence of Electric Fields

2.6. Conclusions

Chapter 3. Scanning Electron Microscopy Under Gaseous Environment

3.1. Introduction

3.2. Basics of Electron Optics and Vacuum Conditions

3.3. Electron–Specimen Interaction, Generated Signals and Detectors

3.4. Resolution at the Various Vacuum Modes

3.5. Imaging at Various Vacuum Modes and Corresponding Applications

3.6. Benefits and Limitations of Imaging in Gaseous/Liquid Environment

3.7. Summary

Chapter 4. Transmission Electron Microscopy of Nanostructures

4.1. Introduction: Specimen Preparation for Electron Transparency

4.2. Transmission Electron Microscope Instrumentation

4.3. Electron Microscopy Methods

4.4. Applications to Nanostructures

4.5. Tomography and the Projection Problem

4.6. Summary

Chapter 5. Plasmonic and Nonplasmonic Characterization of Nanomaterials

5.1. Introduction

5.2. Overview of Progress in Surface Plasmonics

5.3. Ideal Conditions for Generating Surface Plasmons

5.4. Practical Design Considerations for Structures Supporting Surface Plasmons

5.5. Instrumental Design of Plasmonic Imaging and Characterization Setups

5.6. Utilizing Evanescent Surface Waves to Create Superlenses and Hyperlenses

5.7. Limitations of Plasmonic Imaging and Characterization Setups

5.8. Nonplasmonic Techniques and Setups for Imaging and Characterization

5.9. Conclusion

Chapter 6. Characterization of Materials, Nanomaterials, and Thin Films by Nanoindentation

6.1. Introduction

6.2. Fundamentals of Nanoindentation

6.3. Nanoindentation of Materials

6.4. Nanoindentation of Composites

6.5. Nanoindentation of Nanostructured Materials and Thin Films

6.6. Summary

Glossary

Chapter 7. Superresolution Optical Microscopy

7.1. Introduction

7.2. Super-Resolution Microscopy Based on PSF Engineering

7.3. Superresolution Microscopy Based on Frequency Shift

7.4. Single-Molecule Localization Microscopy

7.5. Superresolution Optical Fluctuation Imaging

7.6. Summary

Chapter 8. X-ray Microanalysis and Electron Energy Loss Spectroscopy (EELS)

8.1. X-ray Microanalysis

8.2. Electron Energy-Loss Spectroscopy

Chapter 9. Wide-Angle X-ray Diffraction (WXRD): Technique for Characterization of Nanomaterials and Polymer Nanocomposites

9.1. Introduction

9.2. Fundamentals of X-Ray Diffraction

9.3. Principles of X-Ray Diffraction

9.4. Working of X-Ray Diffraction

9.5. Applications of X-Ray Diffraction

9.6. Experimental Details

9.7. X-ray Diffraction for Nanomaterials and Polymer Nanocomposites

9.8. Summary

Chapter 10. Small-Angle Neutron Scattering (SANS)

10.1. Introduction

10.2. Basic Theory of Small-Angle Neutron Scattering

10.3. Experiment Preparation

10.4. Supporting Methods

10.5. Model Data Calculation and Optimization

10.6. Small-Angle Neutron Scattering Model Functions in Solutions and Gels

10.7. Applications in Complex Nanostructured Aqueous Media

10.8. Concluding Remarks

Chapter 11. Auger Electron Spectroscopy

11.1. Introduction

11.2. What Is Auger Electron Spectroscopy?

11.3. Why Is AES So Suitable for Surface Analysis?

11.4. Applications of Auger Electron Spectroscopy

11.5. Auger Electron Spectroscopy and Nanotechnology

11.6. Instrumentation

11.7. The Important Characteristics of Auger Spectrometers

11.8. Conclusion

Chapter 12. Energy-Dispersive X-ray Spectroscopy Techniques for Nanomaterial

12.1. Introduction

12.2. Energy-Dispersive X-ray Spectroscopy Analysis

12.3. Basic Principle of EDX

12.4. Conjugation of EDX With WDX and Electron Microscope

12.5. Advanced Technology

12.6. Sample Preparation and Analysis

12.7. Recent EDX Technology for Lithium and Low-Energy X-rays Detection

12.8. EDX Analysis for Intermetallic Compound

12.9. Conclusion

Index

Copyright

Elsevier

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Notices

Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

Practitioners and researchers may always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

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ISBN: 978-0-323-46141-2

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List of Contributors

Rameshwar Adhikari,     Tribhuvan University, Kathmandu, Nepal

Gudimalla AppaRao,     Acharya Nagarjuna University, Guntur, India

Zahava Barkay,     Tel-Aviv University, Tel-Aviv, Israel

Anjali Bishnoi

Shroff S. R. Rotary Institute of Chemical Technology, Gujarat, India

Indian Institute of Technology, New Delhi, India

Mauro Ciappa,     ETH Zurich, Zurich, Switzerland

Darshan B. Desai,     Texas Tech University, Lubbock, TX, United States

Yue Fang,     Zhejiang University, Hangzhou, People's Republic of China

Gurram Giridhar,     Acharya Nagarjuna University, Guntur, India

Sven Henning,     Fraunhofer IMWS, Halle (Saale), Germany

Zhong Hu,     South Dakota State University, Brookings, SD, United States

Yujia Huang,     Zhejiang University, Hangzhou, People's Republic of China

Arkady M. Ilyin,     Al-Farabi Kazakh National University, Almaty, Republic of Kazakhstan

Nirav Joshi,     University of São Paulo, São Paulo, Brazil

Cuifang Kuang,     Zhejiang University, Hangzhou, People's Republic of China

Sunil Kumar

Shroff S. R. Rotary Institute of Chemical Technology, Gujarat, India

Indian Institute of Technology, New Delhi, India

Shaocong Liu,     Zhejiang University, Hangzhou, People's Republic of China

Xu Liu,     Zhejiang University, Hangzhou, People's Republic of China

R.K.N.R. Manepalli,     Hindu College, Machilipatnam, India

Raghvendra Kumar Mishra,     Mahatma Gandhi University, Kottayam, Kerala, India

Aristeidis Papagiannopoulos,     National Hellenic Research Foundation, Athens, Greece

Sabu Thomas,     Mahatma Gandhi University, Kottayam, Kerala, India

Thomas Walther,     University of Sheffield, Sheffield, England, United Kingdom

Ajesh K. Zachariah,     Mar Thoma College, Tiruvalla, Kerala, India

Editor Biographies

Professor (Dr.) Sabu Thomas is the Director of International and Interuniversity Center for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India. He is also a full professor of Polymer Science and Engineering and School of Chemical Science of the same University. He is a fellow of many professional bodies. Professor Thomas has co-authored many papers in international peer-reviewed journals in the area of polymer processing. He has organized several international conferences. Professor Thomas's research group is in specialized areas of polymers, which includes polymer blends, fiber-filled polymer composites, particulate-filled polymer composites and their morphological characterization, aging, and degradation, pervaporation phenomena, sorption, and diffusion, interpenetrating polymer systems, recyclability and reuse of waste plastics and rubbers, elastomeric cross-linking, and dual porous nanocomposite scaffolds for tissue engineering. Professor Thomas's research group has extensive exchange programs with different industries, research, and academic institutions all over the world and is performing world-class collaborative research in various fields. The Professor's Center is equipped with various sophisticated instruments and has established state-of-the-art experimental facilities which cater to the needs of researchers within the country and abroad. He has more than 700 publications, 50 books, H Index-78 and 3 patents to his credit. He is a reviewer to many international journals. Professor Thomas has attained 5th Position in the list of Most Productive Researchers in India in 2008–16.

Professor (Dr.) Raju Thomas is currently Vice Chancellor of Middle East University FZE, Al Hamra, Ras Al Khaimah, United Arab Emirates. Dr. Thomas started his Professorship from the Research and Postgraduate Department of Chemistry, Mar Thoma College, Thiruvalla-3, Kerala, India. Dr. Thomas procured his PhD under the supervision of Professor (Dr.) Sabu Thomas, Director of International and Interuniversity Center for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India. He has extensive research experience in Nanoscience and Nanotechnology. He has 12  years of research experience in the Organic Chemistry and Polymer Chemistry laboratories of the School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India. He has also worked in the laboratory of Applied Rheology and Polymer processing of Katholieke University, Leuven, Belgium, and in the laboratory at Leibniz Institute of Polymer Research, Dresden, Germany. He has widely studied the kinetics of curing, morphology development, and structural characteristics of in situ-cured nanocomposites based on epoxy resin and reactive rubbers. His research is reflected in his six published research articles in international journals, and additional articles which are currently under review. In addition, many articles have been published in popular journals. He has co-authored many chapters and is co-editor of a book entitled Micro and Nanostructured Epoxy/Rubber Blends which was recently published by Wiley and Sons. He has attended many national and international seminars/conferences and presented many research papers. He is an approved research guide in Chemistry at Mahatma Gandhi University, Kottayam, India and has availed projects from University Grants Commission (UGC), Department of Science and Technology–Science and Engineering Research Board (DST–SERB) and Kerala Science Council for Science, Technology, and Environment (KSCSTE).

Dr. Ajesh K. Zachariah is working as Assistant Professor in the Department of Chemistry, Mar Thoma College, Kerala, India. He has many publications in the field of materials chemistry, and polymer nanocomposites and has one national patent. He is an expert in sophisticated techniques such as Atomic Force Microscopy (AFM), X-ray diffraction Technique (XRD), Gas Permeability Tester, and Dynamic Mechanical Analyzer (DMA). He has many years' experience in the field of nanoscience and nanotechnology.

Raghvendra Kumar Mishra is currently working as Senior Research Fellow at the International and Interuniversity Center for Nanoscience and Nanotechnology, Mahatma Gandhi University, India. He has received India's most prestigious Visvesvaraya Research Fellowship, and he is currently serving as Visvesvaraya Fellow. He has widely studied the processing of blends, in situ generation micro- and nanofibrillar composites, electromagnetic shielding effect of nanocomposites, decorating and alignment of carbon nanotubes, and thermal, dynamic mechanical, and structural relationships in polymer blends and nanocomposites. He has won several awards from different organizations and technology events. He is serving as reviewer in many international journals, for example, Environmental Chemistry Letters (Springer). He has research experience in Mechanical Engineering, Materials Science and Technology, and Nanoscience and Nanotechnology. His areas of research are multidisciplinary, which include thermodynamics, heat transfer, refrigeration and air-conditioning, fluid mechanics, machine design, solid mechanics, machine theory, power plant engineering, metal and ceramic processing. In addition, he specializes in polymers, which include polymer recycling, polymer blends, fiber-filled polymer composites, particulate-filled polymer composites and their morphological characterization, aging and degradation, nanomaterials e.g., metallic, metallic oxide, carbon nanotubes, graphene, conducting polymer blends, composites and nanocomposites, biodegradable polymer blends and composites. He has expertise in sophisticated characterization techniques such as dynamic mechanical analyzer, differential scanning calorimetry, thermogravimetric analysis, spectroscopy, vector network analyzer, scanning electron microcopy, and atomic force microscopy (AFM).

Chapter 1

Scanning Electron Microscopy, ESEM, and X-ray Microanalysis

Sven Henning¹, and Rameshwar Adhikari²     ¹Fraunhofer IMWS, Halle (Saale), Germany     ²Tribhuvan University, Kathmandu, Nepal

Abstract

The chapter gives a brief summary of the principles, advantages, and applications of scanning electron microscopy (SEM) and electron probe-based X-ray microanalysis (EDX). The focus is put on practical aspects, as there are issues of sample preparation and mechanisms of signal detection and contrast generation that should enable users to define the problems and interpret the results adequately. Further on, the advantages of environmental (or variable pressure) SEM are discussed. The general part is completed with a number of examples from different groups of materials. Finally, an overview of recent developments toward ultrahigh-resolution SEM and new mechanisms of contrast enhancement is given, covering interactions and specific advantages obtained by low-voltage techniques in combination with a new generation of signal detectors, especially the so-called inlens detectors.

Keywords

Advantages; Applications; Carbon nanotubes; ESEM; Glass fibers; Inlens detectors; Nanomaterials; Polymeric materials; Principles; Scanning electron microscopy; Signal detectors; X-ray microanalysis

Chapter Outline

1.1 Introduction

1.2 Scanning Electron Microscopy

1.2.1 Principle

1.2.2 Vacuum System

1.2.3 Electron Beam Generation and Electron Optics

1.2.3.1 Electron Beam Generation

1.2.4 Signals, Detectors, and Image Formation

1.2.5 Sample Preparation

1.2.5.1 Mounting

1.2.5.2 Fracture Surfaces

1.2.5.3 Microtomed Sections and Cross Sections

1.2.5.4 Target Preparation

1.2.5.5 Focused Ion Beam

1.2.5.6 Drying

1.2.5.7 Conductive Coating

1.2.6 Examples

1.3 Energy Dispersive X-ray Microanalysis

1.3.1 Signal Generation and Detection

1.3.2 Examples

1.4 Environmental Scanning Electron Microscopy

1.4.1 Principle and Advantages

1.4.2 Instrumentation

1.4.3 Examples

1.5 Cryo Scanning Electron Microscopy

1.5.1 Instrumentation

1.5.2 Examples

1.6 Low-Voltage and High-Resolution Scanning Electron Microscopy

1.6.1 Low-Voltage Scanning Electron Microscopy and Inlens Detectors

1.6.2 Helium Ion Microscopy

References

1.1. Introduction

Scanning electron microscopy (SEM) is probably one of the most versatile tools for the analysis of micro- and nanostructures with a wide range of applications. SEM techniques provide information on the topography and composition of surfaces by the collection and processing of signals that are generated by a sharp electron probe within a certain interaction volume. The main advantages can be summarized as follows: First, SEM provides the imposing visualization of structures (image to imagination). This is due to the capability to produce pictures with high plasticity and almost stereoscopic appearance, and, depending on imaging conditions, a large depth of focus even for samples with bold relief. Second, there is the huge range of adjustable magnifications from reading-glass magnification (approximately 10 times), e.g., for overview mapping of large sample areas or to identify regions of interest, and the possibility to zoom into the range of some nanometers, depending on the instrument (standard vs. high resolution) and sample properties. Third, there is the analytical power to achieve information on the material composition by the selection of signals originating from specific interactions, as there are, for instance, characteristic X-ray quanta or backscattered electrons.

The chapter is based on a lecture series addressed to students as well as to SEM users from academia and industry. The aim of the lecture is to demonstrate the opportunities and limitations of SEM applications. It should enable the potential user (or customer of SEM service facilities) to formulate the aim of the investigation more precisely, identify proper sample preparation techniques, and perform a qualified image interpretation based on the knowledge of general principles of the image formation and basic mechanisms of contrast generation.

1.2. Scanning Electron Microscopy

1.2.1. Principle

Comparable to reflected-light optical microscopy, SEM is a method to image surfaces of a sample. In the years 1937–38, the German physicist and inventor Manfred von Ardenne constructed an instrument that allowed the generation of magnified images of a sample by scanning the surface using an electron beam (the electron probe) in a line-by-line manner. The signals that are evoked by the interaction of the electron probe with a certain interaction volume close to the sample surface can be amplified and are translated to bright spots of lower or higher intensity, depending on the signal intensity, in a simultaneous line-by-line manner on a cathode ray tube (CRT) (Fig. 1.1). The magnification of the so-called Raster-Elektronenmikroskop is defined by the ratio of the frame size of the scanned sample area and the size of the CRT monitor. The development of the instrument was prepared, on one hand, by the invention of the transmission electron microscope by Knoll and Ruska a few years earlier (1931, Nobel Prize 1986). On the other hand, von Ardenne was already known for his a pioneering in electronic television, presenting the first television system using a CRT in 1931.

Today, SEM has evolved into a powerful, versatile tool used in many fields of nanotechnology. The range of SEM magnification is shown in Fig. 1.2: The maximum resolution that can be achieved is around 1  nm, depending on the setup and quality of the instrument, operating parameters, and properties of the sample material itself.

1.2.2. Vacuum System

Because SEM works with electrons that have to be generated, accelerated, focused, and guided toward the sample, the whole SEM column is set under vacuum. An (ultra) high vacuum is indispensable for SEMs to avoid scattering of the electrons along their path by residual gas atoms (free path length), high voltage discharge, and contamination of the electron gun and other electron optical components. The quality of the required vacuum, i.e., the pressure in the microscope column, is an important cost factor. It depends, for instance, on the type of the electron gun that is used. Usually, more than one type of vacuum pump is employed to attain the required vacuum. Commonly, a cascade consisting of a mechanical pump and a diffusion pump is utilized to pump down from atmospheric pressure to a basic vacuum level. Different types and arrangements of pumps are summarized as follows [4]:

Figure 1.1  Historic photograph of Manfred von Ardenne's first Raster-Elektronenmikroskop hoher Auflösung [1] and schematic drawing of the SEM function [2] .

Figure 1.2  Range of resolution of scanning electron microscopy compared to other microscopic techniques [2] .

Mechanical pumps consist of a motor-driven rotor that compresses a large volume of gas into a small volume and thereby increases the gas pressure. If pressure of the compressed gas is great enough, it can be expelled to the atmosphere by a unidirectional valve. As the pressure of the chamber increases, the efficiency of the vacuum pump decreases rapidly, although it can achieve a vacuum better than 5  ×  10−⁵  torr (Torricelli). In diffusion pumps, vaporized oil circulates from the top part of the pump to the bottom part. The gas at the top of the pump is transported along with the vaporized oil to the bottom where it is discharged by the mechanical pump. A heater component is utilized to vaporize the oil, and coolants cool down the oil so that it can be used circularly. The diffusion pump can achieve 5  ×  10−⁵  torr rapidly. Diffusion pumps start to work at a pressure of approximately 1  ×  10−²  torr. For that reason, a mechanical pump is used to pump down the chamber to the pressure at which the diffusion pump can begin to operate. Such a setup is normally used in SEMs that are operated with a thermionic tungsten cathode. In turbo pumps, gas molecules are pushed in a particular direction by the action of rotating blades. The rotor blades transport molecules from the microscope chamber side to the subsequent pump in the pumping cascade. Ion pumps can achieve higher vacuum levels that are necessary for the operation of thermionic lanthanum hexaboride (LaB6) guns (10−⁶ to 10−⁷  torr) or field emission guns (10−⁹ to 10−¹⁰ torr).

1.2.3. Electron Beam Generation and Electron Optics

Electrons are generated and accelerated down the column by a so-called electron gun, and they pass through a set of electromagnetic lenses and apertures. The electron beam forms a fine probe that impinges the surface of the specimen in the microscope chamber. The beam itself is scanned in a rectangular line-by-line manner (raster) across the surface of the sample by means of scan coils that are situated above the objective lens. The system includes an electromagnetic device (stigmator) to correct astigmatism as one of the optical aberrations that occur in electron optical systems.

1.2.3.1. Electron Beam Generation

In Thermionic emission guns, free electrons are produced by heating up a thermal emitter, namely a tungsten hairpin filament or a pyramidal-shaped LaB6 crystal. If the temperature is high enough, electrons have sufficient thermal energy to surmount the work function of the material–vacuum interface and leave the tungsten cathode. A thermionic electron gun is a triode system consisting of the cathode (C) connected to a highly negative potential, the (grounded) anode aperture (A), and the Wehnelt electrode (W) in between, which has a potential that is hundreds of volts more negative than the cathode potential (Fig. 1.3D). Therefore, electrons emitted from the point of the electrically heated cathode are accelerated toward the anode, and they are strongly influenced by the function of the Wehnelt electrode. The negatively biased Wehnelt electrode restricts the electron emission and allows focusing the electrons to a so-called crossover as they are accelerated to the anode [2]. LaB6 crystals, having a sharp tip as depicted in Fig. 1.3B, exhibit a much lower work function, give a better signal-to-noise ratio, and allow smaller beam diameters and, therefore, a better resolution than tungsten filament cathodes. The lifetime is significantly higher. Nevertheless, LaB6 is a very reactive material; the gun vacuum has to be 10–100 times better than that for tungsten cathodes. LaB6 cathodes are susceptible to thermal shock, so it is important to take care when heating and cooling.

Figure 1.3  Scanning electron spectroscopy images of various electron sources: tungsten filament (A), LaB 6 emitter (B), tungsten field-emitting tip (C), and schematic diagrams of a thermionic gun (D) and a field-emission gun (E). From G.H. Michler, Electron Microscopy of Polymers, Springer-Verlag, Heidelberg Berlin, 2008.

In field-emission guns (FEGs), free electrons are generated by extraction from the material, e.g., tungsten, by quantum tunneling. Under ultrahigh vacuum, a material subjected to a sufficiently strong electric field will emit electrons in the region of maximum field strength. Such a process even works at room temperature (cold FEG). In Fig. 1.3C, a typical tungsten cathode with a sharply pointed tip of a radius of 100  nm is depicted. The function of a field emission gun is shown in Fig. 1.3E: A first anode is positively biased [several kilovolts (kV)] to the cathode. The extraction voltage (V1) generates the field strength at the cathode tip to extract electrons. The second anode accelerates the electrons to the final energy determined by voltage V2 between the cathode tip and the grounded second anode [2]. The main advantage of FEGs is the generation of a very narrow primary electron beam, i.e., a very fine electron probe. Another important advantage is the absence of thermal energy spread; the beam is highly monochromatic. On the other hand, the beam current is relatively low.

In a thermal FEG, the emitter is heated to a certain temperature. Due to the reduction of the work function by the strong electric field, the Schottky effect is responsible for electron emission (Schottky FEG). The work function of the emitter can be further reduced by covering the tungsten tip with a thin ZrO layer. This results in a decrease of emission noise and provides a stable emission current, which is not influenced by contamination layers. Thus, the Schottky FEG combines high electron yield, stable beam parameters, and a narrow electron beam. Thus, such a setup is the choice for instruments that combine high-resolution imaging with analytical methods.

A comparison of the most important features of electron guns is given in Table 1.1. It has to be considered that FEG sources require better vacuum, and they are more expensive than tungsten or LaB6 cathodes. On the other hand, they provide electron probes of much higher brightness, much lower energy spread, and a much lower spot size allowing higher resolutions.

Table 1.1

Comparison of Features of Different Types of Electron Guns

Data for an accelerating voltage of 20  kV. TE, thermionic emission gun; FE, field-emission electron gun; SE, Schottky emission electron gun.

From Scanning electron microscope A to Z: basic knowledge for using the SEM, JEOL USA http://www.jeolusa.com/RESOURCES/Electron-Optics/Documents-Downloads.

1.2.4. Signals, Detectors, and Image Formation

Signal generation in SEM is a result of the interaction between the incident electron beam and a thin surface layer of the sample, which depends on the beam energy. The primary electrons (PEs) are charged particles and so they interact strongly with the electrically charged particles of the atoms in the sample, i.e., both with negatively charged electron clouds and positively charged nuclei. The interaction is said to be inelastic if some of the energy of the PE is lost during the interaction. If no energy is lost, the interaction is said to be elastic. Because of the interaction of the electron beam with the specimen, a variety of signals can be collected by appropriate detectors (Fig. 1.5).

Secondary electrons (SEs) are a result of inelastic scattering of PEs with weakly bonded electrons of the outer shells of atoms in the whole interaction volume. They possess a low energy of 3–50  electron volts (eV). Thus, only SEs from a volume close to the surface escape from the material and can be collected and amplified by means of appropriate detectors. It has to be mentioned that SEs can be categorized into SE types I to IV, representing SEs of different origins. For SE imaging, SE type I originating from the surface of the interaction area itself is considered. SEs are usually exploited to image the surface topography of a sample. The contrast, in this case, is largely a function of the tilting angle of the sample surface with respect to the incident primary electron beam. Moreover, there are so-called edge effects and shadowing effects, making SE topography images appear in a very plastic manner.

SEs are usually collected and amplified by means of an Everhart–Thornley detector (Fig. 1.4). The detector is a combination of a scintillator and a photomultiplier. Low-energy SEs are attracted and collected by a grid electrode that is positively biased with a voltage of about 200  V. The electrons are accelerated toward the scintillator that is at a voltage of about +10  kV. Detected by the scintillating layer, they are transformed into light and transferred to the photomultiplier (PMT). Here, light causes emission of photoelectrons that are amplified by electron multiplication. The result is an electronic signal that is proportional to the amount of collected SEs.

Backscattered electrons (BSEs) are generated by elastic scattering of PEs when they interact with sample atoms. Due a much higher energy than SE (60%–80% of the energy of the PEs), they are able to escape from deeper regions of the interaction volume. The signal that is usually detected by a semiconductor device is strongly dependent on the average atomic number of the interacting atoms.

Figure 1.4  Schematic drawing of the function of an Everhart Thornley detector. Redrawn from G.H. Michler, Electron Microscopy of Polymers, Springer-Verlag, Heidelberg Berlin, 2008; Scanning electron microscope A to Z: basic knowledge for using the SEM, JEOL USA http://www.jeolusa.com/RESOURCES/Electron-Optics/Documents-Downloads.

Semiconductor BSE detectors consist of two or four semiconductor diodes which are symmetrically arranged around the opening of the pole piece of the objective lens. BSEs generate electron–hole pairs, and their quantity depends on the energy and the number of the electrons. The output signal is proportional to the BSEs reaching the detector. Depending on the processing of the signal outputs from the different diodes, it is possible to generate both topography-sensitive and material-specific signals [2].

Signals may also be created by processes in which electrons are knocked out of (inner) electron shells of an atom due to the impact of PEs. Atoms enter an excited energy state. The empty electron orbitals have to be filled by an electron from outer shells. The energy can be released through the emission of a photon. Alternatively, in X-ray emission, energy is released through the emission of an Auger electron (AE). As AEs possess relatively low energies, similarly to SEs, they can only escape from a depth of a few nanometers. If the above mentioned vacant electron state is an outer state (outer electron shells), the energy difference is smaller, and the emitted photon will be in the visible wavelength range. The cathodoluminescence (CL) phenomenon can be exploited as a signal for image formation (Fig. 1.5).

Because the incident electrons are able to penetrate into the sample volume, interactions between the PEs and atoms of the material take place within a certain interaction volume (Fig. 1.6). The penetration depth and, hence, the size of the bulblike interaction volume strongly depend on the energy of the PEs that is defined by the accelerating voltage as well as on the material properties (composition, average atomic number). The complex character of the interaction, the energies and escape depths of the detectable signals, and the consequences concerning the resolution of SEM imaging are described in detail in a book by Reimer [6].

Figure 1.5  Schematic drawing of the interactions between primary electrons (PEs) of the incident electron probe and an atom. From G.H. Michler, Electron Microscopy of Polymers, Springer-Verlag, Heidelberg Berlin, 2008.

There are different types of contrast mechanisms that are exploited in SEM. Of course, the intensity of signals strongly depends on the average atomic number of the elements that are at hand inside the interaction volume, causing a material contrast. Similarly, signals can strongly depend on the orientation of crystalline structures (grain structure, texture of the crystalline material). Moreover, the signal intensity strongly depends on topographic features of the sample surface. The important mechanisms of topographic contrast formation are the following:

Topographic contrast is obtained because the intensity of SE emission is a function of the tilt angle between the incident electron beam and the sample surface area under investigation. The smaller the angle, the bigger is the streaking path for the interaction of PEs and the surface layer from which SEs and BSEs are able to escape, and the bigger is the cross-sectional area of the interaction volume. Thus, the signal intensity increases with smaller incident angles (Fig. 1.7A).

Figure 1.6  Schematic of the interaction volume with the representation of the origin of the different signals. Redrawn from RÖDER, lecture script Martin Luther University Halle–Wittenberg.

If the detector is placed laterally with respect to the sample, contrast can be obtained by a shadowing effect. Electrons that are escaping from areas that are facing toward the detector are more easily detected than electrons that emerge from surfaces that are far from the detector or that are facing to the opposite direction. Thus, object areas that are turned away from the detector appear darker than areas faced toward the detector. For that reason, it is essential to know the position of the detector with respect to the direction of observation!

Figure 1.7  Visualization of two effects of topographic contrast generation: (A) tilt effect, (B) edge effect. From L. Reimer, Scanning Electron Microscopy: Physics of Image Formation and Microanalysis, Springer Science & Business Media, 1998.

Edge effect is similar to the abovementioned tilt effect. It is more pronounced in samples consisting of lighter elements. Here, sharp edges that stand out of smooth areas or between tilted areas appear exceptionally bright. This effect is caused by the steep shoulders of an extreme tilt angle. On the other hand, pits and reentrant edges (notches) appear dark (Fig. 1.7B).

Roughness-induced contrast is a consequence of the edge effect: A surface having (microscopic) roughness will appear brighter than a (microscopically) smooth surface of the same material due to the multitude of small edges with high signal intensity.

1.2.5. Sample Preparation

SEM sample preparation requires, first, a clean desk, if possible in a dust-protected environment, and appropriate tools. One should always use clean blades, tweezers, etc., that can be defatted, e.g., using acetone. Contamination by humidity, dust, fingerprints, rinsing, or etching agents must be avoided. To protect the sample and with respect to the high vacuum in the SEM gloves are recommended. Delicate samples should be stored in a desiccator or under vacuum.

Sample preparation can be quite simple and straightforward (powders, freestanding surfaces, fracture surfaces). Very often, preparation means manipulating the sample to expose the region of interest (defects, internal structures, morphology, or texture of a heterogeneous material). Very often, it is necessary to produce cross sections of a bulk sample in a defined spatial direction. Biological and biomedical samples require special treatments for the conservation of structures [8]. More complex samples, such as hybrid packages or microelectronic devices, require the application of a sequence of sophisticated multistep procedures including the localization of a defect inside packed units (e.g., using lock-in thermography [9]), chemical removal of encapsulations, and/or mechanical manipulation using milling machines followed by laser and/or ion beam milling procedures of increasing precision and conservation of original structures. A collection of basic steps follows.

1.2.5.1. Mounting

Samples are mounted on SEM stubs of a size and material specified by the instrument supplier. Note that the sample must not exceed the size given by the chamber size or lock (door) size. The height of the sample is crucial: It defines the possible range of working distance that can be achieved. The sample itself can be clamped mechanically, or it can be glued by a special (conductive, vacuum compatible) glue or by means of double-sided adhesive SEM pads. The samples should be fixed well to avoid any movement under electron beam irradiation due to heating or charging. Smaller bulk samples and powders can be mounted and observed directly. Small amounts of a powder, for example, can be pressed slightly on double-sided adhesive pad, and residual powder can be removed carefully, e.g., by compressed air. The material should be fixed in a manner that a contamination of the microscope column is avoided. Special care should be taken with magnetic items/particles.

1.2.5.2. Fracture Surfaces

Fracture surfaces are found because of a catastrophic failure of a material or a part or after mechanical testing of an engineering sample. In this case, the damage or fracture analyses in the SEM are performed directly. Very often, artificial fracture surfaces are produced to gain insight into a bulk material or to produce a representative cross section of a sample. The technique depends on the sample properties: A brittle material can be broken, for instance, by means of a hammer. More ductile or elastic materials like many polymers and rubbers must be hardened; the most common way is to freeze the samples well below their glass transition temperature by means of liquid nitrogen. Thus, brittle fracture can be achieved.

1.2.5.3. Microtomed Sections and Cross Sections

A more elegant way to produce cross sections of a sample is to produce thin slices (sections) of a thickness of several hundred nanometers to some tens of microns using (ultra) microtomes or cryo-ultramicrotomes (for soft materials). The procedures are similar to those applied for light optical microscopy or transmission electron microscopy (TEM). Sections can be placed, for instance, on standard SEM stubs for SEM observation. Alternatively, sections can be fixed on perforated TEM copper grids. In this case, the observation of thin sections of optimum thickness in the SEM can improve the resolution especially for BSE imaging, because signals from very deep regions of the interaction volume (and, therefore, relatively broad escape areas) are excluded. Such a technique is applied to operate an SEM as a kind of scanning transmission microscope. Nevertheless, it is more common to use the microtomed block face for SEM investigations.

1.2.5.4. Target Preparation

As mentioned earlier, it might become necessary to prepare SEM samples from a defined region of a complex part or component. Moreover, such samples might require a quite delicate handling because the sample is unique and not easy to reproduce. In such a case, the following techniques (or combinations) can be applied.

A relatively rough preparation can be done by sawing and mechanical milling. For the latter, instruments are available that allow mechanical manipulation under light optical control so that the preparation can be very exact within some tens of micrometers. Very smooth surfaces can be achieved by mechanical polishing. Such surfaces are suitable for higher-resolution images of samples showing material contrast or for analytical SEM. Ion milling is applied to manufacture extremely smooth surfaces or to thin down samples to electron transparency.

1.2.5.5. Focused Ion Beam

This method is probably one of the most elegant ways to produce smooth and ultrathin samples for electron microscopic observation [10]. SEM and TEM samples can be prepared with excellent conservation of structures, especially interfaces between different classes of materials. The method is especially suitable for the preparation of microscopic regions of interest (e.g., a single transistor in a semiconductor chip): The field of operation is observed using an SEM that is incorporated into the focused ion beam (FIB) instrument. The design of an FIB instrument is similar to that of the SEM. In the case of the FIB, a beam of gallium ions is emitted from a liquid-metal ion source and is focused by electrostatic lenses. The spot size is in the range of a few nanometers. The impinging ion beam is removing atoms from the sample surface (sputter process). Because the sputter process acts very locally, very fine trenches can be prepared. An example is given in Fig. 1.8A: On two opposite sides of a region of interest, trenches are cut by a line-by-line removal of the sample material. By that process, a so-called lamella is thinned down to the desired thickness (usually to electron transparency, which is some tens to some hundreds of nanometers, depending on the material). Subsequently, the ligaments of the lamella are cut, and the sample is transferred to a TEM or high-resolution SEM (Fig. 1.8B).

Whereas FIB technique is the gold standard for many materials and systems all across the areas of electronics, metallurgy, petrology, ceramics, and so on, beam-sensitive materials such as many polymers and biological tissues still are delicate to handle by FIB. In this case, ultramicrotomy might be an alternative.

Figure 1.8  Example for the preparation of samples using FIB technology. (A) Sample surface showing the trenches dug at each side of the lamellae; and (B) silica nanoparticles embedded in a polymer matrix become visible within the thin and smooth lamellae.

1.2.5.6. Drying

For all investigations using a standard SEM setup (i.e., high

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