Introduction to Nanotechnology

The Ministry of Science and Higher Education of the Russian Federation Kazan National Research Technological University





Y. Timoshina, E. Voznesensky, I. Karimullin




                INTRODUCTION
                TO NANOTECHNOLOGY




Tutorial







Kazan
KNRTU Press

2021

         UDC 620.5(075)




Published by the decision of the Editorial Review Board of the Kazan National Research Technological University

Reviewers:
Ph.D. in Engineering M. Salyakhova
Executive Director, Ferry Watt LLC Y. Zhelonkin







         Timoshina Y.
         Introduction to Nanotechnology : tutorial / Y. Timoshina, E. Voznesensky, I. Karimullin; The Ministry of Education and Science of the Russian Federation, Kazan National Research Technological University. - Kazan : KNRTU Press, 2021. - 84 p.

         ISBN 978-5-7882-3078-8

      The basic concepts and definitions, the history of the development of nanotechnology, their potential and development prospects are considered. The classification of nanomaterials is presented, the structural features of nanomaterials, size effects, and properties of nano-objects are considered. The main approaches and technologies for producing nanomaterials, methods for studying nanoscale structures are presented, the diagnostic features and metrology problems in the field of nanotechnology are considered.
      Designed for bachelors and masters studying for degrees in "Nanoengineering" and "Materials Science and Materials Technology".
      Prepared at the Department of Plasma Chemistry and Nanotechnology of High Molecular Materials.

UDC 620.5(075)

ISBN 978-5-7882-3078-8    © Y. Timoshina, E. Voznesensky,
I. Karimullin, 2021
© Kazan National Research Technological University, 2021


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    INTRODUCTION



      Currently, one of the rapidly developing areas of high technology is nanotechnology, which has found its practical application in the field of information exchange and storage, healthcare, energy, various industries, materials science and other areas. The study of nano-objects, nanomaterials and nanostructures is based on a number of fundamental and applied sciences, where the merging of theoretical, methodological and experimental material accumulated in the fields of physics, chemistry, biology, mechanics and information technology.
      Using nanotechnology allows you to get a fundamentally new materials and devices with characteristics that exceed their current level, and nanomaterials may have internal properties or functions that are different from those inherent to individual atoms, molecules or bulk materials. These factors contribute to the concentration of special attention of the scientific and engineering community on the development of nanotechnology, which can lead to the creation of an updated technical and technological base of civilization.
      Additional development and implementation of nanotechnology was ensured by the development of regulatory documents as the main mechanism of technical regulation. However, as new opportunities for the development and application of nanotechnology appear, the boundaries of the nanoscale can be revised in accordance with modern scientific concepts, and the existing terms and definitions will evolve.
      Thus, nanotechnology can be considered as general-purpose technology, the task of which is to form a unified scientific and technical picture of the world and increase production efficiency based on the rapid development of high-tech industries.

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    1. NANOTECHNOLOGIES AS
    AN INTERDISCIPLINARY FIELD OF ACTIVITY




     1.1. Basic concepts and definitions




      The field of nanotechnology has its own specific system of terms, which continues to be formed and expanded with the development of research methods, as well as the discovery of new phenomena and materials.
      Nano (Russian designation: н; international: n) is one of the prefixes used in the International System of Units for the formation of units equal to one billionth of the original unit (1 nm = 10⁻⁹ m).
      In order to establish a uniform terminology in the field of nanotechnology at the interstate level, harmonized with international practice, from January 1, 2016, for the voluntary application in the Russian Federation, interstate standards for nanotechnology have been in force. The above definitions can, if necessary, be changed by introducing arbitrary features into them, revealing the meanings of the terms used in them, indicating objects related to a certain concept, but the changes should not violate the scope and content of concepts defined in these standards.
      Nanoscale - a range of linear sizes from approximately 1 to 100 nm. The upper limit of this range is considered approximate, because basically, the unique properties of nano-objects do not appear behind it. The lower limit value in this definition (approximately 1 nm) was introduced in order to exclude individual atoms or small groups of atoms from consideration as nanoobjects or elements of nanostructures.
      Nanoobject - a material object whose linear dimensions in one, two or three dimensions are in the nanoscale (this term applies to all discrete objects whose linear dimensions are in the nanoscale).
      The scientific basis of nanotechnology (nanoscience) - is a system of knowledge about the properties of matter in the nanoscale, in which the dimensional and structural dependences of properties and phenomena are manifested, different from those observed in individual atoms, molecules or bulk materials.
      Nanotechnology - a set of technological methods used for the study, design and production of materials, devices and systems, including targeted

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monitoring and control of the structure, chemical composition and interaction of their individual elements of the nanoscale.
      Nanomaterial - a solid or liquid material, fully or partially consisting of structural elements whose size in at least one dimension is in the nanoscale. Nanomaterial is a general term for such concepts as "a combination of nano-objects" and "nanostructured material".
      Nanostructure - a composition of interconnected components of various substances, one or more of which have linear dimensions in the nanoscale. The boundary between the constituent parts is determined by the boundary termination of the properties.
      Nanostructured material - a material having an internal or surface nanostructure.
      Engineered nanomaterial - a nanomaterial manufactured for a specific purpose or for the implementation of a specific function.
      Manufactured nanomaterial - a nanomaterial with certain properties or a specific composition, intentionally manufactured for commercial purposes.
      Incidental nanomaterial - a nanomaterial that is inadvertently formed during a process (technological, biotechnological, etc.).
      Nanotechnological manufacturing (nanomanufacturing) - the intentional synthesis, manufacture or control of nanomaterials, as well as individual stages of the manufacturing process in the nanoscale for commercial purposes.
      Nanotechnology manufacturing process (nanomanufacturing process) - a set of measures aimed at the intentional synthesis, manufacture or control of nanomaterials, as well as individual stages of the manufacturing process in the nanoscale for commercial purposes.
      Nanoscale phenomenon - an effect inherent in nano-objects or a site with dimensions in the nanoscale.
      Nanoscale property - a characteristic of a nano-object or area with dimensions in the nanoscale.
      In modern standards, many definitions of terms are formulated so that in the future with their help it was possible to develop the optimal structure of terminological systems in the field of nanotechnology with hierarchically interrelated terms. An example of a hierarchical relationship between the definitions of the terms "nanomaterial", "nanoobject" and "nanostructured material" is presented in Fig. 1.1.

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  Fig. 1.1. An example of a hierarchical relationship between the definitions of the terms "nanomaterial", "nanoobject" and "nanostructured material"

      Nanostructured materials have an internal or surface nanostructure. Nanoobjects (material objects whose linear dimensions are in the nanoscale in one, two or three dimensions) can be nanostructured.
      The material should not be classified as nanostructured materials, based only on its crystalline structure (the presence of a three-dimensional arrangement of atoms or molecules that form the crystal lattice; short-range atomic order in amorphous or quasi-amorphous phases; grain boundaries; fragment boundaries within grains, dislocations, etc.). A material is classified as a nanostructured material if, when determining its granulometric composition, a significant predominance of grains (nanocrystals), voids or pores with sizes in the nanoscale is revealed, as well as if the material is obtained in the process of deposition of nanoobjects into a solid matrix. In addition, almost all materials have surfaces with morphological and chemical inhomogeneity in the nanoscale. However, only those materials whose surfaces are deliberately modified or textured in order to obtain morphological or chemical heterogeneity in the nanoscale should be classified as nanostructured.
      Substances that contain nano-objects or nano-structured materials are not necessarily nano-structured materials themselves.
      Nanoobjects (or their aggregates or agglomerates) in nanopowders and in liquid nanodispersed systems are not arranged randomly, but form a shortrange order (structure). In many cases, the interaction of liquid molecules (especially polar liquids) and nanoobjects (or their aggregates or agglomerates) occurs on their surface in a thin boundary layer. Thus, a "nanostructure" is formed in the liquid and the uniformity of the properties of the liquid changes. This can be revealed through physical and chemical measurements.

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      If the liquid medium is only a background, and there are no special relationships between the nano-objects contained in it, then such nanosuspensions, which are an accumulation of many nano-objects, are not nanostructured materials. Therefore, the term "nanosuspension" denotes an intermediate zone between the concepts of "nanostructured material" and "material consisting of nanoobjects".
      Nanostructured powder - a powder containing nanostructured agglomerates, nanostructured aggregates or other particles of nanostructured material.
      Nanostructured aggregate - an aggregate formed from nano-objects.
      Nanostructured agglomerate - an agglomerate of nano-objects or nanostructured aggregates agglomerate.
      Nanostructuredparticle "core-shell" - a particle consisting of a core diameter of 1 to 100 nm and a shell (or shells) with a thickness of 1 to 100 nm.
      Nanostructured capsule - a capsule with a shell with a thickness of 1 to 100 nm, designed to place, hold, transfer or release a substance into it.
      Nanocomposite material (nanocomposite) - a solid substance composed of two or more separated phases, of which one or more are nanophase.
      The nanocomposite does not contain gas nanophase. The gas nanophase contains a nanoporous material. The material, the nanophase of which was obtained only by the deposition method, is not nanocomposite.
      A nanocomposite material with a polymer matrix, a nanocomposite with a polymer matrix (polymer matrix nanocomposite) - a nanocomposite material containing one or more basic polymer phases.
      Clay-reinforced nanocomposite material with polymer matrix; nanocomposite matrix resin reinforced with clay (polymer clay nanocomposite) -nanocomposite material with a polymeric matrix containing clay nanostructured phase.
      Nanocomposite material with a metal matrix; nanocomposite with a metal matrix (metal matrix nanocomposite) - a nanocomposite material containing one or more basic metal phases.
      Nanocomposite material with ceramic matrix; nanocomposite with a ceramic matrix (ceramic matrix nanocomposite) - a nanocomposite material containing one or more basic ceramic phases.
      Solid nanofoam - a solid matrix material filled with gas phase.
      Nanofoam has a low density. Nanofoam contains a nanostructured matrix, consisting, for example, of cavities and walls with dimensions in the nanoscale, or / and a gas nanophase of nanoscale bubbles (closed nanofoam).
      Nanoporous material - a solid material with nanopores.

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      The nanoporous material can have an amorphous, crystalline or amorphous-crystalline structure.
      The fluid nanodisperse system (fluid nanodispersion) - heterogeneous material comprising nano-objects or nanophase dispersed in a continuous liquid phase.
      Nanosuspension - a fluid nanodispersed system containing a dispersed solid phase.
      Nanoemulsion - microdispersible fluid system comprising one or more liquid nanophase.
      Lliquid nanofoam - nanodisperse system fluid filled gas nanophase.
      Nano-aerosol - microdispersible fluid system with a gaseous matrix, comprising one or more liquid or solid nanophase including nano-objects.
      Such a hierarchical relationship does not exclude the presence of an internal or surface structure in the nanoscale of the nanoobject, and the established terms are arranged in a systematic manner, reflecting the system of basic concepts in the field of nanotechnology.






    1.2. History of the development of nanotechnology



      The background to the development of modern nanotechnology is associated with the activities of scientists from many countries of the world, who throughout the development of science have addressed the issue of the potential importance of the study of small particles. As early as 1661, the Irish physicist and chemist R. Boyle in his work "Skeptic Chemist" suggested that all material objects consist of ultra-small corpuscles, which are quite stable and form various substances and objects in various combinations.
      An example of the first practical application of nanotechnology can be considered the invention of roll film in 1883 by the founder of the famous company Kodak D. Eastman. The film he developed was an emulsion of silver halide deposited on a transparent elastic base of cellulose acetate, which decomposes under the influence of light to form pure silver nanoparticles, which were the pixels of the resulting image.

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      The first scientist to use measurements in nanometers is considered to be the famous physicist A. Einstein, who in 1905 theoretically proved that the size of a sugar molecule is equal to one nanometer.
      In 1931, the German physicists M. Knoll and E. Ruska created an transmission electron microscope (TEM), which became the prototype of a new generation of devices that made it possible to look into the world of nano-objects, for which in 1986 they received the Nobel Prize. In 1938, Siemens released the first industrial electron microscope with a resolution of about 10 nm.
      The fundamental importance of small-sized objects was emphasized by the American physicist and Nobel laureate F. Feynman in 1959, when his lecture "There's Plenty of Room at the Bottom" was presented to the audience at the California Institute of Technology. Feynman expressed ideas for controlling the structure of matter and emphasized that by learning to regulate and control structures at the atomic level, we will get materials with completely unexpected properties and discover completely unusual effects. This presentation can be considered a launching pad for the field of nanoresearch. R. Feynman put forward ideas about manipulating individual atoms to create new small structures, engraving lines with a width of several atoms using an electron beam, creating electric chains of nanometer scales, the use of nanostructures in biological systems, etc.
      The term "nanotechnology" was first proposed by the Japanese physicist N. Taniguchi in 1974 in his report "On the Basic Concept of 'NanoTechnology'".
      This term was used to describe the ultrafine processing of materials with nanometer accuracy, and the term “nanotechnology” was proposed to call mechanisms smaller than one micrometer in size.
      In 1981, IBM employees G. Binnig and H. Rohrer created a scanning tunneling microscope, awarded the Nobel Prize in 1986. This device allowed not only to obtain a three-dimensional image of the structure from an electrically conductive material with a resolution of the order of the sizes of individual atoms, but also to effect on matter at the atomic level, i. e. manipulate atoms. And in 1986, G. Binnig, C. F. Quate, and Ch. Gerber created a scanning atomic force microscope, which made it possible, in contrast to a scanning tunneling microscope, to study the atomic structure of not only conductive, but also any materials, including organic molecules, biological objects, etc.
      The appearance of the first scanning tunneling and atomic force microscopes served as an impetus for the further development of nanotechnology and the study of materials at the atomic level. Nanotechnology gained

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popularity, and scientists began to predict the active development and practical application of nanotechnology, based on the achievements of its predecessors.
      In Russia, work on obtaining nanomaterials was started in the 50s of the twentieth century. It should be noted that in the USSR these materials were initially called ultrafine materials or ultrafine systems. The scientific and technical direction for the development and study of the properties of ultrafine materials was developed at the enterprises of the nuclear industry, where ultrafine powders with a particle size of about 100 nm were obtained. These powders were successfully used for the manufacture of highly porous membranes for the diffusion method of separation of uranium isotopes.
      The first state programs for the development of nanotechnology can be considered the project on the development of atomic and molecular manipulation techniques "Atomic Technology" (Japan, 1991) and the creation of a Nanotechnology Laboratory (USA, 1993). And in 1996, a group of US government agencies led by the National Science Foundation organized a study of the current world state of nanoscience. The result of the group’s activities was detailed recommendations for the development of this field of knowledge, and a long-term state program called "National Nanotechnological Discipline" was formed. Studies carried out in the framework of this program, allowed to draw two conclusions. The first is that nanostructured materials can obtain new properties and unusual characteristics, which is based on the fact that a characteristic or critical length is associated with each property of a substance. The basic physical and chemical properties change when the dimensions of solids become comparable to characteristic lengths, most of which lie in the nanometer range. The second conclusion concerns the fact that nanotechnologies belong to many different branches of knowledge, such as chemistry, physics, ecology, electrotechnics, mechanics, chemical technology, etc. Due to the interdisciplinarity of this field of research, understanding and use of the results obtained in different branches of nanoscience is complicated. In 2000, the United States launched a large-scale nanotechnology research program called the National Nanotechnology Initiative (NNI). Similar programs have been adopted by the European Union, Japan, China, Brazil and several other countries.
      In the 21st century, the rapid development of applied nanotechnology began, the first commercial nanomaterials appeared - nanopowders, nanocoatings, bulk nanomaterials, nanochemical and nanobiological preparations; the first electronic devices, nanosensors for various purposes were created; Numerous methods for producing nanomaterials have been developed.

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