NANOSCALE SYSTEMS LEARNING OBJECTIVES e Introduction, Length scales in physics, Nano-structural materials, Band structure of materials at nanoscale. Density of states of materials at nanoscale, Size-effects in nano systems 1.1. NANOSCIENCE (INTRODUCTION) The term nano refers to 10~® i.e, one billionth part of something. Nano can be ascribed to any unit of measurement. Thus one nanometer (nm) means one billionth of a meter i.e., 10-® m. One nanogram means 10~° gram, one nanosecond is 10° sec and similarly for other physical units. One nanometer is on the scale of atomic diameter. Four to five atoms placed side by side on a line make up one nanometer. Just to compare, DNA is about 3 nm in diameter which is also the diameter of most carbon nanotubes (CNTs), wavelength of visible light range from 400 nm to 780 nm, red blood cell (RBC) is about 6000 nm in size and human hair is about 100,000 nm thick. oanm \ 1 t +t + | 1 n 1 n 10-1 109 10! 102 108 108 108 108 nm 3nmDNA 10mm 100 jum diameter protein human hair diameter Visible light 400-780 nm 9 Nanoscience is the study of structures and materials on the scale of nanometers. For nanoscience to come into picture, at least one dimension of the material or structure should lie in the range 1 to 100 nm. We can also say that nanoscience is the study of phenomena and manipulation of materials at atomic, molecular and macromolecular scales. Nanomaterials are defined as those materials which have2 ‘Nanomaterials and Applications structured components with size less than 100 nm in at least one dimension. The smallest structures humans have made have dimensions of a few nm and the smallest structures we will ever make will have the dimensions of a few nm. This is because ultimately the structures are to be made from atoms or molecules. When structures are made small enough (i.e., in the nanometer range), they can take on interesting and useful properties. In nano-regime their properties are quite different as compared to their bulk counterparts. Some of the changes that may occur in the properties of materials for transformation from bulk to nano are as follows : Solids can become liquids at room temperature, e.g., gold. Insulators can become conductors, e.g., silicon. Inert materials can become catalyst, e.g., platinum. Stable materials can beome combustible, e.g., aluminium. vvvVvVVv Opaque substances can become transparent e.g., copper. When none of the dimensions of the structure or material is comparable with the de Broglie wavelength of electron or exciton Bohr radius for it, then the structure or material is treated as bulk. Peacock feathers and soap bubbles also get their iridescent coloration from light interacting with structures just tens of nanometers thick. Many such examples may be quoted here to show the change of properties when size is reduced and brought to nanometer regime. Nanostructures can be formed on solid surfaces such as metals, semiconductors (eg., Si) and carbon based materials (e.g., CNTs, graphene, diamond) as well as liquids. Specialized methods and techniques are needed to create nanostructures. In order to observe and study nanostructures, specialized equipments are needed. Nanoscience principles are now being used by scientists and engineers from several disciplines such as physics, chemistry, biology and material science for advanced applications in energy, medicine, computing, memories for information storage etc. Nanoscience is an emerging area of science and technology today and is a diverse field with very wide applications. Quantum mechanies is used for the description of nanoscale systems. The unusual electrical, optical, magnetic and mechanical properties shown by nanomaterials are explained on the basis of quantum physics. 1.2. NANOTECHNOLOGY Nanotechnology as defined by National Nanotechnology Initiative (NNT) of US, is the manipulation of matter with at least one dimension lying in the range 1 to 100 nanometers. In other words, nanotechnology is the design, characterization, production and application of structures, devices and systems on nanoscale. Nanotechnology may also be defined as the manipulation of matter on an atomic, molecular and supra molecular scale. It includes within its realm all types of research and technologies that deal with the special properties of matter which‘Nanomaterials and Applications 8 occur below the given critical size limit, Nanotechnology deals with both natural and artificial structures on the nanometer scale. This is a technology which is capable of manipulating even single atoms and molecules. Various fields of science such as surface science, organic chemistry, molecular biology, semiconductor physics, microfabrication, molecular engineering etc. come under the umbrella of nanotechnology or nanoscale technologies. Nanotechnology is basically the engineering of tiny machines with the projected ability to build things from the bottom up, using techniques and tools developed today to make complete, highly advanced products. It is promising answers to many types of problems in all fields of work. It is used or is expected to appear in products such as tennis rackets, self cleaning cars, paint, food, cosmetics and thermal underwear etc. It is supposed that, one day nanotechnology will provide a solution to all the human problems, whether it be hunger in developing countries or pollution in developed nations. Nanotechnology may be able to create many new materials and devices with a vast range of applications eg., in nanomedicine, nanoelectronics, biomaterials, energy production and cosmetics etc. Let's have a quote about nanotechnology from “Small Wonders, Endless Frontiers” which is as follows : “With potential applications in virtually every existing industry and new applications yet to be discovered, nanoscale science and technology will no doubt emerge as one of the major drivers of economic growth in the first part of the new millennium”. Nanotechnology owes its existence to the astonishing development in the field of microelectronics. It has developed at a fast pace due to the invention of many, observational and characterizing tools, particularly scanning tunneling microscope (STM) and atomic force microscope (AFM). There are two basic approaches used in nanotechnology-top down and bottom up. Conventional microtechnology is a top-down technology in which microstructures are fabricated by manipulating a large piece of materials typically a single crystal of silicon, using processes such as lithography, etching, and metallization etc. Top-down methods of making nanostructures require large installations and are quite expensive. They need huge amount of capital to be invested. The invention of advanced instruments such as STM or AFM for observation and manipulation of individual atoms and molecules have led to a new approach to technology called bottom-up approach. In this method, instead of making small structures out of large structures, the small structures are made directly by assembling of molecules and atoms. This bottom-up approach of synthesis of nanostructures is supposed to work within all living systems since the very beginning of life on earth. Bottom up approach does not require large installations to be put up and hence is a cost effective method. As any other new technology, nanotechnology also raises some serious concerns about social, economic, environmental, and military implications. Nanotechnology isi Nanomaterials and Applications supposed to release some toxic wastes into the environment which may have some potential effects on global economics and may affect badly the human health. It is supposed that environmental concerns about nanotechnology may be of the same magnitude as that of asbestos. Asbestos fibers were widely used for years before anyone could realize that they were health hazard. Thus we can say that nanotechnology is the technology of designing and making functional objects at the nanoscale and the science underlying nanotechnology is called nanoscience. 1.4. SIZE DEPENDENCE OF PROPERTIES : NANOMATERIALS Nanoscale materials lie in a physical size regime between bulk macroscopic materials and molecular compounds. Solids may be classified as : Solids Amorphous (or glass like) Polycrystalline Crystalline ‘No long range order (Multiple domains) Long range order and exists Short range order exists periodicity exists Much of the Nanoscience and Nanotechnology focusses on nanometer sized crystalline solids. With reduction in size of the material, statistical mechanical effects and quantum mechanical effects play an important role. When material goes into nanoregime (size between 1 to 100 nm at least along one dimension) “quantum size effect” leads to change in electronic properties of solids. Mechanical, electrical and optical properties also get altered upon reaching into quantum realm (or nano regime). The most notable one is the increase in surface area to volume ratio (ie., $/V ratio) for nanomaterials over bulk. ‘This increase in S/V ratio gives rise to change in mechanical, thermal and catalytic properties of materials. The increase in S/V ratio for nanometerials occurs because in nanometer sized systems upto 50% of the atoms lie at the surface of a nanostructure. The surface is therefore potentially important in dictating a material's optical and electrical properties when nanometer sized. The increase in surface area is important in applications where S/V ratio plays a critical role such as in catalysis as well as in photovoltaics. The catalytic activity of nanomaterials also opens potential risks in their interaction with biomaterials. Bulk materials generally exhibit continuous absorption and electronic spectra whereas nanoscale materials show discrete optical and electronic spectra. Some of the changes in properties of materials upon going from bulk to nanosize are : opaque materials can become transparent (e.g., copper); stable materials, can turn into combustible (e.g., aluminium); insoluble substances may become soluble (e.g., gold); chemicallly inert substances may become a catalyst (¢.g., gold) etc. Other notable changes in the properties that occur due to size reduction of particles are : increase in surface energy, decrease in melting point, increase in chemical reactivities, change in optical band gap etc. Thus much of the nanotechnology involves these quantum and surface phenomena that matter manifests at the nanoscale.‘Nanomaterials and Applications 5 1.5. NANOTECHNOLOGY IN VARIOUS FIELDS Nanotechnology is the ensemble of technologies which are concerned with manipulation of matter on atomic and molecular level. At such a small level, materials show drastically changed properties which are not shown by them at the micro- or macro level. Devices that have emerged out of nanotechnology show the existence of new functionalities in them and have a promise to improve things in almost every field related to human life. Some of the major areas of human life which are expected to be greatly affected by nanotechnology are — electronics and communication, medical field, health and environment, food, energy, sensors, water etc. Nanotechnology may lead to new and improved health treatments; cleaner, faster and safer manufacturing; reduced use of some harmful or scarce resources; smaller and faster devices etc. Let us discuss briefly about the influence of nanotechnology on these fields. 1. Electronics : Electronics is being used in computers, in communication devices (e.g., mobile phones) and in consumer products such as TV, air conditioners, refrigerators etc. Nanoscale electronic devices (any dimension between 1 to 100 nm) have potential to show unique properties and new functionalities. Nanotechnology can provide us electronic devices with reduced weight and less power consumption. Low energy consumption flat panel displays or computer monitors using carbon nanotubes and/or silicon nanowires are possible to manufacture due to nanotechnology. Nanowires or small molecules may be used in computers. Spintronics (i.e., spin based electronics), a branch of nanotechnology, is expected to greatly improve the storage capacity of memory devices such as hard disks, RAM etc. Magnetic random access memory (MRAM) has already been commercialised with great storage capacities. Giant Magneto Resistance (GMR) and Tunnel Magneto Reistance (TMR) effects can be used to create non-volatile main memory of computers. Quantum computers based on “Qubits” and using fast quantum algorithms are expected to do.billions of computations in parallel making them many times faster and powerful than present day fastest super computers. Spin based devices such as spin FET, spin LED, encoders, decoders etc. to be used in computers are being developed. Thus nanotechnology has potential to provide faster, cheaper, compact and more efficient electronic devices as compared to the conventional electronic devices. 2, Nanotechnology in Medical Field : Nanotechnology is being used in targeted drug delivery system (using nanoparticles) in which right amounts of drugs, heat, light etc. are delivered to diseased cells (e.g., cancerous cells) of the patients body. This will reduce the possibility of damaging healthy cells in the patient's body due to treatments such as chemotherapy etc. Nanorobots are being used to make repairs at the cellular level.“j ‘Nanomaterials and Applications Biomolecules to be used as medical diagnostic tools are an important area of nanotechnology research. 3. Optics and Optoelectronics : Nanotechnology has entered into the field of optics through the use of nanowire materials for the construction of electroluminescent devices such as light emitting diodes (LEDs) which are more effecient in producing light and have a greater life cycle. Quantum dot materials are being used for constructing multicolour lasers which are cheaper and give a higher beam quality. This development is a fine example of use of nanotechnology in optoelectronics. 4, Energy : Nanotechnology has already made a dent into the field of energy production. Nanowire materials based cheaper and more efficient solar cells for efficient energy production are being developed and commercialized due to nanotechnology research. Quantum dot materials due to their tunable, size dependent absorption and emission spectra are being used in fabricating efficient solar cells which can operate even under cloudy conditions and rainy days when conventional solar cells are unable to operate. These solar cells are cheaper due to involvement of low temperature process. So in future, due to nanotechnology, energy needs of the world may be fulfilled easily in a cost effective manner. 5. Sensors : Nanowire materials may be used as efficient sensors for detecting minute amounts of toxic wastes, chemical weapons and explosives ete. The presence of small number of gas molecules make a significant change in the electrical properties of the sensing elements. Some of the detecting or sensing elements used as sensors are — carbon nanotubes (CNTs), ZnO nanowires, Palladium nanoparticles etc. Thus, nanotechnology based sensors are more sensitive and more effective in doing their job. 6. Fuel Cells : Nanotechnology based fuel cells are expected to be more efficient in their working as well as cheaper due to the reduced cost of catalysts used in them. 7. Food : Nanotechnology is being used in the development of new materials to change the taste of food, and also used for food safety and health benefits given by food. 8. Batteries : Nanotechnology has resulted into the development of rechargeable lithium ion batteries to be used in mobile phones and laptops. These batteries are more powerful than the conventional lithium ion batteries. 9. Water and Environment : Nanotechnology is, and can, provide us cleaner drinking water through removal of industrial wastes from water. This is accomplished by a chemical reaction converting contaminants into less harmful (or harmless) substances in a cost effective manner. Nanotechnology have a great promise for sensing and detection of pollutants, treatment and remediation of contaminants, and prevention of pollution, Dendrimer materials are particularly attractive as functional materials for treatment of water.‘Nanomaterials and Applications 7 Nanotechnology may result into improved characterization of environmental problems, significantly reduced environmental impacts due to use of cleaner manufacturing practices, and reduced material and energy use. Besides above mentioned areas of impact of nanotechnology, there are many other fields which might benefit from this great revolution (j.e., nanotechnology) of 21st century which may have impacts in human life as large as industrial revolution or invention of steam engine or invention of electric bulb and electricity in the past centuries,