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Spectroscopic Methods for Nanomaterials Characterization

Spectroscopic Methods for Nanomaterials Characterization

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Spectroscopic Methods for Nanomaterials Characterization

794 pages
10 hours
May 19, 2017


Nanomaterials Characterization Techniques, Volume Two, part of an ongoing series, offers a detailed analysis of the different types of spectroscopic methods currently being used in nanocharacterization. These include, for example, the Raman spectroscopic method for the characterization of carbon nanotubes (CNTs).

This book outlines the different kinds of spectroscopic tools being used for the characterization of nanomaterials and discusses under what conditions each should be used. The book is intended to cover all the major spectroscopic techniques for nanocharacterization, making it an important resource for both the academic community at the research level and the industrial community involved in nanomanufacturing.

  • Explores how spectroscopy and X-ray-based nanocharacterization techniques are applied in modern industry
  • Analyzes all the major spectroscopy and X-ray-based nanocharacterization techniques, allowing the reader to choose the best for their situation
  • Presents a method-orientated approach that explains how to successfully use each technique
May 19, 2017

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Spectroscopic Methods for Nanomaterials Characterization - Elsevier Science

Spectroscopic Methods for Nanomaterials Characterization

Volume Two


Sabu Thomas

Raju Thomas

Ajesh K. Zachariah

Raghvendra Kumar Mishra

Table of Contents

Cover image

Title page


List of Contributors

Editor Biographies

Chapter 1. Atomic Force Microscopy as a Nanoanalytical Tool

1.1. Introduction

1.2. Specimen Preparation

1.3. Typical Examples of Nanomaterials Characterization by Atomic Force Microscopy

1.4. Concluding Remarks

Chapter 2. Electrochemical Characterization

2.1. Introduction

2.2. Electrochemical Cell

2.3. Electrochemical Characterization

2.4. Applications

2.5. Summary

Chapter 3. Ultraviolet Spectroscopy: A Facile Approach for the Characterization of Nanomaterials

3.1. Introduction

3.2. Spectrochemical Methods

3.3. Nanomaterials

3.4. Characterization of Nanoparticles

3.5. Advantages of UV Spectroscopy

3.6. Characterization of Nanoparticles Using UV Spectroscopy

3.7. Conclusions

Chapter 4. Fourier Transform Infrared Spectroscopy

4.1. Introduction

4.2. Working Principle

4.3. Sample Analysis Process

4.4. Analytical Information for Fourier Transform Infrared

4.5. Interpretation and Analysis of the Infrared Spectrum

4.6. Interpreting Some Functional Groups

4.7. Significance and Drawback of Fourier Transform Infrared

4.8. Applications of Fourier Transform Infrared

4.9. Conclusion

Chapter 5. Raman Spectroscopy

5.1. Introduction

5.2. Raman Scattering

5.3. Polarizability of the Bond

5.4. Difference Between Raman Scattering and Fluorescence

5.5. Stokes and Anti-Stokes Lines

5.6. Mutual Exclusion Principle

5.7. Rotational Raman Spectra

5.8. Vibrational Raman Spectra

5.9. Applications of Raman Spectroscopy

5.10. Advances in Raman Spectroscopy

5.11. Surface-Enhanced Raman Spectroscopy

5.12. Resonance Raman Spectroscopy

5.13. Stimulated Raman Spectroscopy

5.14. Coherent Anti-Stokes Raman Spectroscopy

5.15. Tip-Enhanced Raman Spectroscopy

5.16. Confocal Raman Microscopy

5.17. Current Status and Future Outlook

Chapter 6. High-Vacuum Tip-Enhanced Raman Spectroscopy

6.1. Introduction

6.2. Setup of High-Vacuum Tip-Enhanced Raman Spectroscopy

6.3. Conclusion and Prospects

Chapter 7. Confocal Raman Spectroscopy

7.1. Introduction

7.2. Image Formation

7.3. Experimental Setup for Confocal Raman Spectroscopy

7.4. Analysis by Using Confocal Raman Spectroscopy

7.5. Advantages Over Other Techniques and Limitations

7.6. Conclusions

Chapter 8. Inductively Coupled Plasma Mass Spectrometry

8.1. Introduction

8.2. Inductively Coupled Plasma

8.3. Plasma Discharge Devices

8.4. Sample Introduction

8.5. Interface

8.6. Ion-Focusing Lenses

8.7. Mass Analyzer

8.8. Detectors

8.9. Applications of Inductively Coupled Plasma Mass Spectrometry

8.10. Summary

Chapter 9. Electromagnetic Characterization of Materials by Vector Network Analyzer Experimental Setup

9.1. Introduction

9.2. Vector Network Analyzer

9.3. Measurement Techniques

9.4. Conclusion

9.5. List of Abbreviations

Chapter 10. Dielectric Spectroscopy

10.1. Introduction to Dielectric Spectroscopy

10.2. Dielectric Polarizations

10.3. Dielectric Relaxations

10.4. Dielectric Formalism

10.5. Nanotechnology and Nanomaterials

10.6. Dielectric Behavior of Nanomaterials

10.7. Conclusions

Chapter 11. Dielectric and Magnetic Loss Behavior of Nanooxides

11.1. Introduction

11.2. Applications

11.3. Summary

Chapter 12. Mössbauer Spectroscopy: Basic Principles and Practical Guide to Exotic Mössbauer Isotopes

12.1. Recoilless Emission and Absorption of γ Radiation

12.2. Hyperfine Interactions of Nuclei With the Atomic Electronic Shell

12.3. Mössbauer Spectroscopy of ¹⁵⁵Gd, ⁹⁹Ru, and ¹¹⁹Sn

12.4. Summary

Chapter 13. Nuclear Magnetic Resonance Spectroscopy

13.1. What Is Nuclear Magnetic Resonance?

13.2. Nuclear Spin and Nuclear Magnetic Resonance

13.3. Nuclear Magnetic Resonance Energies and Population Distribution

13.4. Nuclear Magnetic Resonance Instrumentation

13.5. Relaxation

13.6. Nuclear Magnetic Resonance Spectrum and Chemical Shift

13.7. Factors Affecting the Chemical Shift

13.8. Nuclear Magnetic Resonance Studies in Polymers Science and Nanotechnology

13.9. Concluding Remarks




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List of Contributors

Rameshwar Adhikari

Tribhuvan University, Kathmandu, Nepal

Nepal Polymer Institute (NPI), Kathmandu, Nepal

Basheer Ahamed,     B.S. Abdur Rahman University, Chennai, India

Gudimamilla Apparao,     Acharya Nagarjuna University, Guntur, India

Anjali Bishnoi,     Indian Institute of Technology HauzKhas, New Delhi, India

Jayesh Cherusseri,     Indian Institute of Technology Kanpur, Kanpur, India

Kuppanna Chidambaram,     VIT University, Vellore, India

Yogesh S. Choudhary,     Indian Institute of Space Science and Technology, Thiruvananthapuram, India

Andrea Delfini,     Sapienza University of Rome, Rome, Italy

Kalim Deshmukh,     B.S. Abdur Rahman University, Chennai, India

Aastha Dutta,     Maharashtra Institute of Technology, Aurangabad, India

Jianwu Fang,     Chang'an University, Xi'an, People's Republic of China

Gejo George,     HLL Lifecare Limited, Trivandrum, India

Sony George,     University of Kerala, Trivandrum, India

Gurram Giridhar,     Acharya Nagarjuna University, Guntur, India

Sven Henning,     Fraunhofer Institute for Microstructure of Materials and Systems (IMWS), Halle/Saale, Germany

Saravanakumar Jagannathan,     Universiti Teknologi Malaysia, Johor Bahru, Malaysia

Nebu John

University of Kerala, Trivandrum, India

Mar Thoma College, Tiruvalla, India

Lavanya Jothi,     Indian Institute of Space Science and Technology, Thiruvananthapuram, India

Jithin Joy,     Newman College, Thodupuzha, India

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

Mario Marchetti,     Sapienza University of Rome, Rome, Italy

Marta Marszalek,     Institute of Nuclear Physics Polish Academy of Sciences, Krakow, Poland

Davide Micheli,     Sapienza University of Rome, Rome, Italy

Goerg H. Michler,     Martin Luther University Halle-Wittenberg, Halle/Saale, Germany

Raghvendra Kumar Mishra,     Mahatma Gandhi University, Kottayam, India

Gomathi Nageswaran,     Indian Institute of Space Science and Technology, Thiruvananthapuram, India

Khadheer S.K. Pasha,     VIT University, Vellore, India

Roberto Pastore,     Sapienza University of Rome, Rome, Italy

Deepalekshmi Ponnamma,     Qatar University, Doha, Qatar

Shaohua Qu,     Northwestern Polytechnical University, Xi'an, People's Republic of China

P.S. Rama Sreekanth,     National Institute of Science and Technology, Odisha, India

Kishor K. Sadasivuni,     Qatar University, Doha, Qatar

Sowmya Sankaran,     B.S. Abdur Rahman University, Chennai, India

Fabio Santoni,     Sapienza University of Rome, Rome, Italy

Mengtao Sun

University of Science and Technology Beijing, Beijing, People's Republic of China

Chinese Academy of Sciences, Beijing, People's Republic of China

Sabu Thomas,     Mahatma Gandhi University, Kottayam, India

Antonio Vricella,     Sapienza University of Rome, Rome, Italy

Liuding Wang,     Northwestern Polytechnical University, Xi'an, People's Republic of China

Runcy Wilson,     HLL Lifecare Limited, Trivandrum, India

Guanglei Wu,     Qingdao University, Qingdao, People's Republic of China

Hongjing Wu,     Northwestern Polytechnical University, Xi'an, People's Republic of China

Hui Xing,     Northwestern Polytechnical University, Xi'an, People's Republic of China

Duyang Zang,     Northwestern Polytechnical University, Xi'an, People's Republic of China

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

Atomic Force Microscopy as a Nanoanalytical Tool

Rameshwar Adhikari¹,², Sven Henning³, and Goerg H. Michler⁴     ¹Tribhuvan University, Kathmandu, Nepal     ²Nepal Polymer Institute (NPI), Kathmandu, Nepal     ³Fraunhofer Institute for Microstructure of Materials and Systems (IMWS), Halle/Saale, Germany     ⁴Martin Luther University Halle-Wittenberg, Halle/Saale, Germany


Atomic force microscopy (AFM), also commonly known as scanning force microscopy, has evolved as an extremely useful tool for the study of the structure and properties of nanostructured systems including nanoparticles (NPs), composites, and soft matters such as polymers and biological tissues. In particular, AFM serves as an excellent complement to electron microscopic techniques, on one hand, and represents a unique tool to study the physical and functional properties of heterogeneous systems on the nanoscale on the other. The aim of this chapter is to elucidate the contribution of AFM to the structural characterization of nanomaterials with an introduction to the principles of the basic AFM techniques and sample preparation methods. A comparison with electron microscopy will also be presented, selecting some illustrative examples of imaging of NPs, soft matter, and composites. We demonstrate that AFM can conveniently be used not only to image the morphology of the materials with nanometer resolution but also to gain insight into the manipulation of the NPs in a controlled manner.


Atomic force microscopy; Electron microscopy; Morphology; Nanocomposite; Nanoparticles; Tapping mode

Chapter Outline

1.1 Introduction

1.2 Specimen Preparation

1.2.1 Thin Films

1.2.2 Physical and Chemical Etching, Ion Etching

1.2.3 Ultramicrotomy

1.3 Typical Examples of Nanomaterials Characterization by Atomic Force Microscopy

1.3.1 Nanoparticles Imaging and Manipulation

1.3.2 Biobased Nanomaterials and Nanoencapsulation

1.3.3 Comparison With Electron Microscopy

1.4 Concluding Remarks



1.1. Introduction

As the development of new materials has played a considerable role in the advancement of human civilization, microscopic techniques have offered probably the most important contribution toward the development of the new materials themselves. The microscope delivers the most direct information on the structure and properties of materials on different length scales, not only allowing the experimentalist to interpret the correlation between very internal structures of the materials and their properties but also permitting the innovator to design new structures relevant for targeted specific applications. In this regard, the electron microscope, and more recently the scanning probe microscope (SPM), have been developed as reliable tools for the characterization of nanomaterials. It should be noted that different scattering techniques, in particular the X-ray methods, have made significant contributions to the understanding of the structure–property correlations of the materials, although the information is averaged over a large volume. An SPM not only can access the structure of materials in the macroscopic to nanoscale range but also studies various phenomena such as adhesion, friction, electrical, magnetic, mechanical, and thermal properties of the materials on a very local level.

Owing to their ability to offer nanoscale resolution and versatile applicability, SPM techniques have emerged as an indispensable nanomaterials characterization tool. The invention of the first atomic force microscope by Binnig and its introduction by Binnig et al. [1,2] in 1986 opened up the possibility of obtaining surface images with atomic resolution on conductors and insulators by utilizing very small tip–sample interaction forces. Thus, among the SPM techniques, the AFM is a highly versatile and popular nanoanalytical tool. Thus, it has been common practice in past decades to supplement electron microscopy with the AFM.

A brief survey of the fundamentals and relevant applications of this technique in nanomaterials research is presented in this chapter. For a detailed account of the fundamentals and application of AFM techniques applied to different materials, the readers may consult more concise reviews [3–7].

In atomic force microscopy, the solid surfaces are scanned in a raster pattern by an extremely sharp mechanical probe attached to a cantilever. Highly localized tip–sample interaction forces are measured as a function of the specimen's local position. In its basic function, AFM provides high-resolution imaging of the surface relief of the specimen between lateral scales of a few nanometers to about a hundred micrometers as demonstrated by some examples presented in Fig. 1.1.

Fig. 1.1 presents tapping-mode AFM images of different magnifications of thin isotactic polypropylene (iPP) film sandwiched between polystyrene (PS) layers prepared by the microlayer coextrusion technique [8–10]. The most popular AFM mode of operation is the so-called tapping mode or intermittent-contact mode, in which the sample is scanned with an oscillating probe. The contrast mechanism in the AFM operation is based on the local mechanical properties of the specimen [11–14].

Figure 1.1  Tapping-mode atomic force microscopy images of different magnifications of isotactic polypropylene illustrating the surface topography (A and C) and phase morphology (B and D), showing the ability of the technique to image structural details at different length scales.

The images on the top in Fig. 1.1 show the so-called spherulitic texture of the iPP with a sphere diameter of a few micrometers, which is not fully grown due to quenching of the samples during processing. The height images are particularly helpful to illustrate the spherulitic texture and surface topography of the sample. A portion of Fig. 1.1A and B is magnified in Fig. 1.1C and D, respectively. The height image (Fig. 1.1C) still preserves information on the surface topography of the specimen, whereas the nanostructured surface morphology of the specimen with cross-hatched crystalline lamellae is visible in the phase image (Fig. 1.1D). By using image processing software, which is usually made available by the atomic force microscope manufacturer, or by using common image processing tools, the morphological details of the specimens can be easily evaluated. In the given case, the thickness of bright-appearing crystalline lamellae in the iPP sample can be measured as being about 10  nm, whereas the interlamellar distance is about 15  nm.

Thus, by using the single probe, the morphological details including microscopic structure as well as nanoscale phase information and materials heterogeneity can be accessed and quantified using the AFM. Simultaneously, information about the sample topography can be quite precisely evaluated. AFM is the only nondestructive microscopic technique that simultaneously provides thus the nanoscale structural information of the material based on different physicomechanical properties as well as topography and roughness.

By applying special investigation modes AFM can additionally be used to measure normal and lateral forces, adhesion, friction, elastic/plastic mechanical properties (such as indentation hardness and modulus of elasticity), and electrical and magnetic properties in dependence on the local position on the sample surface. AFM not only allows the direct and straightforward analysis of morphology but also enables the easy assessment of morphology development under annealing conditions and upon loading [15–25]. The most important advantage of the AFM is that the materials can be imaged without any chemical modifications, thus allowing direct and straightforward evaluation of the nanostructure.

There are various kinds of atomic force microscopes available on the market, one of the first manufacturers being Digital Instruments, Inc. (Santa Barbara, CA, USA), which commercialized the trade names Multimode and Dimension 3000 for the atomic force microscopes. These are quite widely used and we illustrate the functioning of the atomic force microscope on the basis of Dimension 3000 (D3000) instrumentation. Fig. 1.2A depicts the main part of the D3000 atomic force microscope, a microscope particularly designed for large specimens, while the sketch in Fig. 1.2B illustrates the AFM operation principle.

The sample is generally mounted on a motorized xy stage and the force sensor (a sharp tip) is mounted on the cantilever holder and fixed at the piezo-driven xyz scanner. The sample is held in fixed position while the tube-shaped piezo-scanner attached with a sharp probe scans the surface below along the x,y directions in a raster pattern. The scanner is designed in such a way that its motion along the z direction controls the tip–sample surface distance precisely. A feedback loop linked to the sensed interaction force drives the vertical scanner motion along the z direction.

Figure 1.2  (A) A portion of the D3000 atomic force microscope (AFM) showing the scanner head; and (B) a sketch showing the operational principle of the AFM. PZT , piezoelectric tube. Adapted from H. Schönherr, G.J. Vancso, Scanning Force Microscopy of Polymers, Springer Laboratory, Springer-Verlag Berlin Heidelberg, Germany, 1986.

The small-sample atomic force microscopes, such as multimode atomic force microscopes, which are meant for more precise high-resolution imaging of specimens, have slightly different construction of the specimen and sensor holders. The specimen is placed on the top of the piezoelectric tube xyz scanner and the force sensor is attached to the fixed cantilever. The tip remains stationary while the xyz piezo-tube moves so than the sample surface is scanned by the stationary probe. The distance-dependent tip–sample interaction forces provide the physical basis for AFM, whose nature is in fact very complicated. A detailed account of these forces can be found in Refs. [26–28].

Briefly, there is an interplay of superimposed short- and long-range forces that lies in the range of several tens of piconewtons [9]. With decreasing tip–surface distance, the net force becomes first attractive and then repulsive. Consequently, when the tip is brought in close proximity to the surface, at first it senses an increasing attractive force, which reaches a maximum value and then decreases. This attraction finally changes to a repulsion that again rapidly increases with decreasing tip–surface distance. Thus, atomic resolution with an AFM is possible only with a sharp tip positioned on a flexible cantilever at a net repulsive force of 100  pN or lower.

When the tip attached to the piezoelectric scanner scans the surface, the forces are measured through deflections of the cantilever, this being monitored by the change in photodiode differential signal using a focused laser beam. To achieve more controlled imaging conditions a feedback loop is used, which monitors the tip–sample force and adjusts the scanner z position. In the so-called constant force mode, the feedback circuit is used to modulate the voltage applied to the scanner and adjusts the height of the piezo-element holding the cantilever vertical deflection (in other words, the force between the tip and the sample) constant. Thus, the AFM records the piezo-displacement along the z direction, which is a direct measure of the sample roughness (sample topography). The data are presented in the form of a height image. However, if the feedback gains are low, the piezo-tube remains practically at a fixed position (i.e., at constant height), and the atomic force microscope collects the cantilever vertical deflection data. This operation mode is referred to as constant-height mode and the data are presented in the form of a deflection image.

Depending on whether the probe is subjected to an additional oscillation or not, the AFM techniques can be discriminated between the dynamic and the static operation modes. The so-called contact mode, and lateral force microscopy (or friction mode), belong to the static AFM operations, whereas noncontact AFM, force-modulation, and tapping-mode techniques are categorized under the dynamic operation modes.

The commercially available tips usually consist of silicon (Si) or silicon nitride (Si3N4) cantilevers microfabricated via photolithographic techniques. The commercially available cantilevers have different shapes (triangular or rectangular) and have variable lengths (100–500  μm) and thicknesses (1–4  μm). The spring constant of the cantilevers varies from 0.01 to 50  N/m. The cantilevers should be flexible enough to be deflected by small forces, but also stiff enough to be withdrawn from the sample surface especially in the tapping-mode operations. The radius of curvature of the tip lies typically in the range of a few nanometers. An extensive laboratory manual of AFM operation, in particular with reference to the quantitative and qualitative analysis of nanomaterials, can be found in the literature [26–29].

1.2. Specimen Preparation

In most of the literature related to AFM of nanomaterials it is claimed that there is no necessity of sample preparation for AFM. It is true that chemical modification of the specimen is not required for AFM investigations; i.e., the specimen can be imaged in its native state. Additionally, unlike during electron microscopy, there is no risk of sample damage (and imaging of thus obtained artifacts) due to exposure to the electron beam. However, there are other sources of artifacts that may arise in the AFM imaging. A careful survey of AFM images published in the literature reveals, unfortunately, that many of them recorded in a wide variety of samples under different conditions look similar in many respects, which are clearly imaging artifacts [29]. A successful AFM imaging requires that the samples are properly prepared with flat, clean, and artifact-free surfaces. Equally important are the choice of imaging modes, selection of the probes, and other experimental parameters. Some common methods of sample preparation for AFM studies of nanomaterials are briefly discussed next.

1.2.1. Thin Films

The ideal samples for AFM operations are thin films prepared by casting and spraying or sputtering procedures [30–33]. Freshly prepared thin films (ranging from a few tens of nanometers to a few micrometers in thickness) cast from their solutions or suspensions can be most conveniently imaged by the AFM. If the film surface is not sufficiently flat, one can study the substrate side of the film. The experimentalist should be, however, aware that the structures of the thin film in the presence of free air can be completely different from those of the bulk material.

1.2.2. Physical and Chemical Etching, Ion Etching

This method is particularly interesting for polymer samples and their nanocomposites. The specimens can be prepared by means of chemical and physical etching procedures or by ion etching [34–36]. The chemical etching method is especially suitable for removing the matrix from the surface so that the NPs can be exposed and measured [26].

1.2.3. Ultramicrotomy

Ultramicrotomy (and more frequently cryo-ultramicrotomy in the case of soft materials) is the method of choice if the experimentalist is concerned with the bulk morphology of and its correlation with the properties of the sample [37]. The bulk surface left after the cryo-ultramicrotomy for transmission electron microscopy (TEM) can be directly imaged by the AFM. However, proper care should be taken to minimize the sectioning-induced mechanical deformation of the sample, which might be a reason for erroneous interpretation of AFM data.

1.3. Typical Examples of Nanomaterials Characterization by Atomic Force Microscopy

Nanoparticulate materials having various dimensionalities can be prepared in different ways including the solvent-assisted methods such as spraying and dip and spin coating, even using different kinds of media and reducing agents [23,38–47]. Different AFM imaging modes can be employed to investigate the shape and size of nanoparticles (NPs) [27]. For soft materials, the tapping mode or intermittent-contact mode is the method of choice, whereas magnetic force microscopy is of particular interest for investigation of the materials comprising magnetic NPs [38–41]. In this section, we will introduce the typical applications of AFM in the characterization of the structure and properties of nanomaterials.

1.3.1. Nanoparticles Imaging and Manipulation

One of the popular methods of dispersing the NPs is the ultracentrifugation method, in which the size of the NP agglomerates can be adjusted via concentration of the colloidal solution as well as the agitation speed during processing. Fig. 1.3 shows the National Institute of Standards and Technology (NIST) standard of citrate-stabilized gold NPs (AuNPs) dispersed by the ultracentrifugation method [48]. It can be seen that the NPs collected on the freshly cleaved mica surface can be imaged successfully by the AFM. The NPs have diameters of approximately 10  nm (Fig. 1.3A) and 30  nm (Fig. 1.3B), the same range as reported by the NIST standard.

Figure 1.3  Typical atomic force microscopy micrographs of citrate-stabilized Au nanoparticles of different diameters prepared by the ultracentrifugation method and deposited on a mica surface [48] .

Imaging is a way to illustrate the structure of nanomaterials and correlate that structural information with the material properties targeted to different applications. The AFM offers, in addition, the possibility of manipulation of the NPs, the process being extremely important for designing devices.

With an objective of investigation of the size-dependent mechanical properties of the NPs including substrate adhesion, interactions, and frictional forces involved, several research works were conducted (for example, Refs. [11–14,38,49,50]). One of the phenomena thus observed was a variation in frictional forces involved in the manipulation in the NPs [38]. An example of NP imaging with manipulation of PS NPs deposited on a silicon surface is presented in Fig. 1.4. The NPs can be pushed or dragged aside by the AFM tip in a controlled way using a very small force. The AFM height image of the NPs is shown in Fig. 1.4A, showing a particle at the center to be manipulated by the AFM tip. Fig. 1.4B shows the same specimen position after the displacement of the NP toward the right of the image plane [38].

Figure 1.4  Atomic force microscopy images of nanoparticles on the mica substrate (A) before and (B) after the manipulation [38] .

The ability of the AFM in the imaging of the NPs is not limited to spherical particles but can be extended to any kind of NP. One basic requirement of AFM imaging is, however, that the substrate should be absolutely flat and free of any impurities on the surface. The AFM technique offers the most straightforward way to image NPs but is limited to structural information extraction from the surface of the NPs, the access to internal morphological details being impossible. TEM provides the very useful complement to this technique [38].

1.3.2. Biobased Nanomaterials and Nanoencapsulation

Biobased polymeric materials, such as transparent nanocrystalline cellulose, are becoming increasingly popular in applications such as optoelectronic devices. Nanocellulose paper was successfully incorporated with conductive fillers such as carbon nanotubes (CNTs), silver (Ag) nanowires, tin-doped indium oxide, etc. [51]. It has been demonstrated that such papers may be useful in optoelectronics such as displays, touch screens, and interactive paper.

A suspension of nanocellulose was prepared by solution casting of the thin film onto a mica substrate. Fig. 1.5A shows the tapping-mode AFM height image of a nanocellulose suspension dried on a freshly cleaved mica sheet. The crystalline texture of the nanocellulose can be easily identified in the height profile imaged by the tapping-mode AFM. Fig. 1.5B shows a photograph of the transparent nanocellulose film after incorporation of tin-doped indium oxide. The film was found to be highly conductive and had a total transmittance of 65% at 550  nm. The nanocrystals of the cellulose were further demonstrated as being made up of beaded structures [52].

Figure 1.5  (A) Atomic force microscopy height image of a nanocellulose film prepared by solution casting on a mica sheet. (B) Transparent and conductive nanopaper based on tin-doped indium oxide with a performance of 12   U 12   Ω/sq. and 65% total transmittance at 550   nm [52] .

Similarly highly transparent materials obtained by incorporation of amorphous calcium carbonate NPs were prepared with nanocellulose and studied by AFM complemented by electron microscopic techniques [53]. Later nanocomposites were prepared by surface functionalization of the single-walled CNTs (SWCNTs) [48]. Controlled defibrillation of cellulose leading to the formation of a nanostructured material was achieved and the morphology of the material was studied using AFM.

It is needless to state that nanotechnological advancements have contributed significantly to solving several problems in health sciences through the development of many effective drug delivery systems and carriers including nanobubbles and vesicles [46,54–56].

These developments have been triggered in many instances by the recent progress in functional polymers and surfactants that can be used as coating and stabilizers as well as additives in combination with nanomaterials. Highly magnetic NPs with controlled shapes and size have wide application in magnetic resonance imaging techniques, drug delivery, and various therapeutic substances. Fig. 1.6 presents an example of tapping-mode AFM height and phase imaging of polymethyl methacrylate–grafted magnetite NPs that were prepared by a reversible addition/fragmentation chain transfer polymerization–assisted coating of polymer. The polymer-coated Fe3O4/SiO2 hybrid NPs were well dispersed also in aqueous solution and coated onto a flat surface. Fig. 1.6 shows that the size of the individual NPs was around 40–50  nm, which was also confirmed by the TEM analysis [55].

Figure 1.6  Tapping-mode atomic force microscopy height (A) and phase (B) image of polymethyl methacrylate–grafted Fe 3 O 4 /SiO 2 magnetic nanoparticles [55] .

A closer look at the micrographs reveals that the particles in the height image (Fig. 1.6A) appear quite different from in the phase image (Fig. 1.6B). The fact that the surface of the particles is smooth in the phase image implies the compositional homogeneity of the sphere coating. The roughness of the particles in the height image can be attributed to the shrinkage of the particles during the processing onto the substrate, which might be partly contributed by the interaction of the NPs with the substrate than with the polymer. Such information, which is otherwise not straightforward to obtain by electron microscopic methods, can be easily derived by the use of the AFM technique.

1.3.3. Comparison With Electron Microscopy

In the previous section, some typical examples of AFM imaging of NPs were presented. We have noted that different microscopic techniques may be complementary for the comprehensive characterization of nanomaterials. In this section, we shed more light on the comparative analysis of morphological features of heterogeneous material emphasizing the need for selection of a suitable technique depending on the solution of the problem at hand.

In an attempt at preparing soluble SWCNTs, the nanotubes were chemically functionalized and further treated with surfactant [56] and coated onto a mica surface followed by AFM imaging in tapping mode. The result is shown in Fig. 1.7A. The nanotubes could be well dispersed in the given solvent and were successfully imaged. The hollow tube-like structure of the nanocarbons could not, however, be ascertained by the AFM. We prepared a composite of multiwalled CNTs (MWCNTs) with a rubbery styrene–butadiene copolymer [57] and imaged the cryo-fractured surface with a scanning electron microscope (SEM) equipped with a field emission gun. The well-dispersed MWCNTs could be wonderfully imaged in the composite by the SEM. The same is true also for the sample prepared by a casting procedure. The structures imaged by the SEM are indeed more distinct than those imaged by the AFM (compare also with Fig. 1.7C).

The same sample was

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