A REPORT ON NANOMATERIALS & NANOMAGNETISM

Submitted By GAGANJOT SINGH University roll no. - 601202004 Under the esteemed guidance of Dr. POONAM UNIYAL (Assistant Professor, SPMS, Thapar University.)

School of Physics and Materials Science, Thapar University, Patiala [Pb.]

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Contents
1. Introduction to materials..........3 1.1 General.......3 1.2 Classification of materials .3 1.3 Selection of materials ....4 2. Nano Materials.....5 2.1 Introduction...............5 2.2 Improved properties of nano over bulk.6 2.3 Characterization of nano materials...7 2.3.1. Structural Characterization7 2.3.2. Chemical Characterization7 2.4 Properties of nano materials .....9 2.5 Applications of nano materials ......10 3. Nano Magnetism........11 3.1 Introduction.....11 3.2 Challenges in nano magnetism.......11 3.3 Dimensionality in nano magnetism ...........13 3.4 Magnetic Anisotropy .....15 3.5 Single Domain....16 3.6 Domain walls..........19 3.7 Applications....19 3.8 Future......21 3.9 Bismuth Ferrite.......21 3.10 Summary...........23 References.....24

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Chapter 1 Introduction to materials

1.1 General Material is anything made of matter, constituted of one or more substances. Wood, cement, hydrogen, air, water and any other matter are all examples of materials. Materials science and engineering plays a vital role in this modern age of science and technology. Various kinds of materials are used in industry, housing, agriculture, transportation, etc. to meet the plant and individual requirements. The rapid developments in the field of quantum theory of solids have opened vast opportunities for better understanding and utilization of various materials. The spectacular success in the field of space is primarily due to the rapid advances in high - temperature and high-strength materials. The selection of a specific material for a particular use is a very complex process. However, one can simplify the choice if the details about (i) operating parameters, (ii) manufacturing processes, (iii) functional requirements and (iv) cost considerations are known. 1.2. Classification of materials The factors which form the basis of various systems of classifications of materials in material science and engineering are: (i) the chemical composition of the material, (ii) the mode of the occurrence of the material in the nature, (iii) the refining and the manufacturing process to which the material is subjected prior it acquires the required properties, (iv) the atomic and crystalline structure of material and (v) the industrial and technical use of the material. Common engineering materials that fall within the scope of material science and engineering may be classified into one of the following six groups: 1) Metals (ferrous and non-ferrous) and alloys 2) Ceramics 3) Organic Polymers 4) Composites
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5) Semi-conductors 6) Biomaterials 7) Advanced Materials

Table 1: Different classes of materials

1.3. Selection of Materials One of the most challenging tasks of an engineer is the proper selection of the material for a particular job, e.g., a particular component of a machine or structure. An engineer must be in a position to choose the optimum combination of properties in a material at the lowest possible cost without compromising the quality. The properties and behavior of a material depends upon the several factors, e.g., composition, crystal structure, conditions during service and the interaction among them. The performance of materials may be found satisfactory within certain limitations or conditions. However, beyond these conditions, the performance of materials may not be found satisfactory.
Table 2: Factors affecting the material selection

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Chapter 2 Nano Materials

2.1. Introduction Nanomaterials is a term that includes all nano sized materials, including engineered nanoparticles, incidental nanoparticles and other nano-objects, like those that exist in nature. The European Commission adopted the definition of nano materials as given below. A natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or as an agglomerate and where, for 50% or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm 100 nm. In specific cases and where warranted by concerns for the environment, health, safety or competitiveness the number size distribution threshold of 50% may be replaced by a threshold between 1 and 50%. The European Commission adopted the above definition of a nano material. Nanomaterials are a field that takes materials science-based approach on nanotechnology. It studies materials with morphological features on the nanoscale, and especially those that have special properties stemming from their nanoscale dimensions. Nanoscale is usually defined as smaller than a one tenth of a micrometer in at least one dimension [1], though sometimes includes up to a micrometer. An important aspect of nanotechnology is the vastly increased ratio of surface area to volume present in many nanoscale materials, which makes possible new quantum mechanical effects. One example is the quantum size effect where the electronic properties of solids are altered with great reductions in particle size. Nanoparticles, for example, take advantage of their dramatically increased surface area to volume ratio. Their optical properties, e.g. fluorescence, become a function of the particle diameter. This effect does not come into play by going from macro to micro dimensions. However, it becomes pronounced when the nanometer size range is reached. A certain number of physical properties also alter with the change from macroscopic to nanoscopic system. Novel mechanical properties of nanomaterials are a subject of nano
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mechanics research. When brought into a bulk material, nanoparticles can strongly influence the mechanical properties of the material, like stiffness or elasticity. For example, traditional polymers can be reinforced by nanoparticles resulting in novel materials which can be used as lightweight replacements for metals. Such nano technologically enhanced materials may enable a weight reduction accompanied by an increase in stability and improved functionality. Catalytic activities also reveal new behavior in the interaction with biomaterials. 2.2. Improved Properties of Nanomaterials over Bulk Materials Nanomaterials offer better properties over their bulk counterparts. It has been observed that changes in particle properties can be observed when particle size is less than a particular level, called the critical size. Table presents the feature sizes for significant changes in properties in nanomaterials.
Table 3: Sizes for changes in properties in nano composites

Additionally, as dimensions reach the nanometer level, interactions at phase interfaces become largely improved, and this is important to enhance material properties. In this context, the surface area / volume ratio of reinforcement materials employed in the preparation of nanomaterials is crucial to understand their structure-property relationships. One of the major factors which alter the properties in nanomaterials is the increase in ratio of surface area to volume. The surface area of particle increases exponentially, creating more sites for bonding, catalysis or reaction with surrounding material, resulting in improved properties such as increased strength or chemical or heat resistance. Hence due to the high surface to volume ratio associated with nanometer sized particles, it is possible to control the fundamental properties of materials through surface/size effect.

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2.3. Characterization of nanomaterials Materials in the nanometer scale, such as colloidal dispersions and thin films, have been studied over many years and many physical properties related to the nanometer size, such as coloration of gold nanoparticles, have been known for centuries. One of the critical challenges faced currently by researchers in the nanotechnology and nano science fields is the inability and the lack of instruments to observe, measure and manipulate the materials at the nanometer. In the past, the studies have been focused mainly on the collective behaviors and properties of a large number of nano structured materials. A better fundamental understanding and various potential applications increasingly demand the ability and instrumentation to observe measure and manipulate the individual nanomaterials and nanostructures. Characterization and manipulation of individual nanostructures require not only extreme sensitivity and accuracy, but also atomic-level resolution. It therefore leads to various microcopies that will play a central role in characterization and measurements of nano structured materials and nanostructures. The development of novel tools and instruments is one of the greatest challenges in nanotechnology. In this chapter, various structural characterization methods that are most widely used in characterizing nanomaterials and nano structures are mentioned. These include: X-ray diffraction (XRD) [2] [3], various electron microscopy (EM) including scanning electron microscopy (SEM) and transmission microscopy (TEM) [4] [5] [6] [7], and scanning probe microscopy (SPM) [8]. 2.3.1. Structural Characterization Characterization of nanomaterials and nanostructures has been largely based on the surface analysis techniques and conventional characterization methods developed for bulk materials. For example, XRD has been widely used for the determination of crystallinity, crystal structures and lattice constants of nanoparticles, nano wires and thin films; SEM and TEM together with electron diffraction have been commonly used in characterization of nanoparticles; optical spectroscopy is used to determine the size of semiconductor quantum dots. SPM is a relatively new characterization technique and has found wide spread applications in nanotechnology. The two major members of the SPM family are scanning tunneling microscopy (STM) and atomic force microscopy (AFM).
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Although both STM and AFM are true surface image techniques that can produce topographic images of a surface with atomic resolution in all three dimensions, combining with appropriately designed attachments, the STM and AFM have found a much broadened range of applications, such as nano indentation, nanolithography (as discussed in the previous chapter), and patterned self-assembly. In the following, we mentioned characterization techniques in nanotechnology. 1. X-ray diffraction (XRD) 2. Scanning electron microscopy (SEM) 3. Transmission electron microscopy (TEM) 4. Scanning probe microscopy (SPM) 5. Gas adsorption 2.3.2. Chemical Characterization Chemical characterization is to determine the surface and interior atoms and compounds as well as their spatial distributions. As mentioned in the introduction section, many chemical analysis methods have been developed for the surface analysis or thin films, but are readily applicable to the characterization of nanostructures and nanomaterials. 2.3.2.1.Optical Spectroscopy 1. Absorption and transmission spectroscopy 2. Photoluminescence 3. Infrared spectroscopy 4. Raman spectroscopy 2.3.2.2. Electron spectroscopy 1. Energy dispersive X-ray spectroscopy 2. Auger electron spectroscopy 3. X-ray photo electron spectroscopy 2.3.2.3. Ionic spectroscopy 1. Rutherford back scattering spectroscopy 2. Secondary ion mass spectroscopy

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2.4. Properties of nano materials Between the dimensions on an atomic scale and the normal dimensions, which characterize bulk material is a size range where condensed matter exhibits some remarkable specific properties that may be significantly different from the physical properties of bulk materials. Some such peculiar properties are known, but there may be a lot more to be discovered. Some known physical properties of nanomaterials are related to different origins: for example, (i) large fraction of surface atoms, (ii) large surface energy, (iii) spatial confinement, and (iv) reduced imperfections. The following are just a few examples: (1) Nano materials may have a significantly lower melting point or phase transition temperature and appreciably reduced lattice constants, due to a huge fraction of surface atoms in the total amount of atoms. (2) Mechanical properties of nanomaterials may reach the theoretical strength, which are one or two orders of magnitude higher than that of single crystals in the bulk form. The enhancement in mechanical strength is simply due to the reduced probability of defects. (3) Optical properties of nanomaterials can be significantly different from bulk crystals. For example, the optical absorption peak of a semiconductor nano particle shifts to a short wavelength, due to an increased band gap. The color of metallic nanoparticles may change with their sizes due to surface Plasmon resonance. (4) Electrical conductivity decreases with a reduced dimension due to increased surface scattering. However, electrical conductivity of nano materials could also be enhanced appreciably, due to the better ordering in microstructure, e.g. in polymeric fibrils. (5) Magnetic properties of nano structured materials are distinctly different from that of bulk materials. Ferromagnetism of bulk materials disappears and transfers to super paramagnetism in the nanometer scale due to the huge surface energy. (6) Self-purification is an intrinsic thermodynamic property of nanostructures and nanomaterials. Any heat treatment increases the diffusion of impurities, intrinsic structural defects and dislocations, and one can easily push them to the nearby surface. Increased perfection would have appreciable impact on the chemical and physical properties. For example, chemical stability would be enhanced.
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2.5. Applications of Nanomaterials 1. Nano electronics 2. Nano medicines 3. Biological applications of nano particles 4. Catalysis by Gold particles 5. Band gap engineered quantum devices 6. Quantum well and quantum dot devices 7. Carbon nano tubes emitter 8. Photo-electro chemical cells

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Chapter 3 Nano Magnetism

3.1. Introduction Nanomagnetism describes the science and technology underlying the magnetic behavior of nano structured (1100 nm) systems. It focuses on the magnetic behavior of individual building blocks of nano structured systems as well as on combinations of individual building blocks that display collective magnetic phenomena. A fundamental understanding of nanomagnetism can be exploited to yield integrated systems with complex structures and architectures that possess new functionalities. A nanomagnet is a sub micro metric system that presents spontaneous magnetic order (magnetization) at zero applied magnetic fields (remanence). The small size of nano magnets prevents the formation of magnetic domains. The magnetization dynamics of sufficiently small nano magnets at low temperatures, typically single-molecule magnets, presents quantum phenomena, such as macroscopic spin tunneling. At larger temperatures, the magnetization undergoes random thermal fluctuations (super paramagnetism) which present a limit for the use of nano magnets for permanent information storage. Canonical examples of nano magnets are grains [9] (iron, cobalt, and nickel) and single-molecule magnets.
[10] [11]

of ferromagnetic metals

The vast majority of nano

magnets feature transition metal (titanium, vanadium, chromium, manganese, iron, cobalt or nickel) or rare earth (Gd, Eu, and Er) magnetic atoms. 3.2. Challenges in nano magnetism The grand challenges in nanomagnetism can be expressed in a number of ways depending on the audience. [12] At the most basic level the challenge is to create, explore and understand new materials that exhibit unexpected collective behavior, also known as emergent behavior. The creation of emergent matter energizes the synthesis community, and high-quality synthesis of new materials is critical to the future of all of condensed matter and materials physics. Nano science offers exciting new routes to create advanced materials and hierarchically assemble systems in a non-Edisonian manner. Utilizing the
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three basic tools of nano science - geometric confinement, physical proximity and selforganization - one can create materials by design. Confinement creates new properties from known materials via manipulation of dimensionality. Proximity effects allow multicomponent composites to behave as new materials that embrace properties that are often mutually exclusive and thus not found in single component systems. Self-organization utilizes rules of Nature to segregate and/or assemble systems on ultra small length scales that transcend the limits of present-day Litho graphic definition. Self-assembly shows promise of becoming a powerful approach to miniaturize structures in an affordable manner with very high uniformity. A challenge is to utilize self-organization, as is accomplished in biological systems, to create not just component materials, but fully functional, integrated systems. One can imagine pulling an entire computer processor out of a test tube in the future. Achieving such goals certainly encompasses non-equilibrium synthetic routes, and the creation of multifunctional materials. Competing interactions and the preponderance of low-lying energetic states and quantum fluctuations help create the complexity that gives rise to unanticipated phenomena in magnetic nano systems. We note that, during the exploration of magnetic surfaces, interfaces and multi layers undertaken a few decades ago, the discoveries of spin-valve read heads or magnetic random access memory was completely unanticipated. This realization underscores the fact that fundamental studies involving the creation of emergent matter is an important stimulant of advanced technologies. The second grand challenge in nanomagnetism, beyond the creation of emergent matter, is the exploration of its magnetic properties. This task requires all levels of characterization tools. Essential in this is the utilization of the advanced user facilities that are available to the research community. This underscores an important synergy between materials creation and exploration that requires national investments both in synthesis and in major user facilities. Additionally, understanding emergent behavior requires the talents of the theory community and the utilization of high-performance computing to simulate complex behavior. This challenge has many facets. It includes: (i) defining the rules that govern self-organization; (ii) understanding spin dynamics and equilibrium states at the spatial and temporal limits of interest; (iii) understanding spin transport phenomena, spin-torque effects, spin accumulation, spin diffusion, etc.; and (iv) relating such effects to the detailed structure of the material. This
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challenge also involves understanding how to create entangled spin systems, and how to control the process as well as read the states. A longer-term aspect of the challenge is to foster communication of information via spin currents and excitations without the flow of charge. This would be a novel approach to complement existing electronic circuitry that depends on charge flow. Why create, explore and understand nano magnetic emergent matter? An important reason is that the more detailed understanding which is the goal of basic science will enable the community to address the strategic needs of our society at large. It is vital to stimulate the economy and create new jobs by ushering in new technologies and innovations. New diagnostic tools and treatments for diseases will preserve health and wellbeing, as well as heal the ill and help the impaired. New sensors will help ensure homeland security, and advanced materials and approaches will provide for national defense needs. It is important to create materials and harness phenomena that will advance transportation requirements, and it is imperative to take leadership in meeting national goals of energy independence. Additionally, all of these initiatives must be advanced in a manner that is respectful of the environment. These are goals for the nanomagnetism community, for the nano science and nanotechnology communities, and for the larger materials research communities. The nanomagnetism community is in a particularly advantageous position to rise to these challenges because of the enormous potential derived from recent breakthroughs. Although magnetism is one of the oldest sciences known, it is a driving force in the new scientific era of nanotechnology. This statement is highlighted quite succinctly by examining the evolution of the Giant Magneto Resistance (GMR) effect, which made the transition from a laboratory curiosity to a technology driver within the short span of about ten years. From GMR, a host of new phenomena, materials, and potential technologies are blossoming. [13] 3.3. Dimensionality in nano magnetism Dimensionality is a general term which is used to describe the effect of size confinement on the physical properties of matter. It becomes very important, when the properties of matter are discussed on the nanometer scale. In general, one divides nanostructures into three different groups including: thin films (2D structures), nano wires (1D structure),

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and nano dots or nanoparticles (0D structures). The magnetization of these different groups is significantly influenced by confinement. 3.3.1. Thin magnetic films The electronic structure at the surface of a given material differs considerably from the bulk. Early studies of nickel mono layers on copper substrates show significant changes in the density of states as a function of surface energy. The different coordination number of atoms and the number of incomplete bonds at the surface modifies the local density of states. The d orbital is more localized and interacts more strongly with spin magnetic moments giving a higher net magnetization at the surface. This is an example of size effect in one dimension. The magnetization reversal in thin ferromagnetic films is affected by such size confinement. The nucleation and propagation of magnetic domains which involve Bloch walls in the bulk is more likely to involve Nel walls when the thickness decreases. Thickness confirms the tendency of the formation of Nel walls in the thinner film. In thin films with uniaxial in-plane anisotropy, magnetic domains form stripes and are separated by Nel walls for thicknesses below 50 nm. In thin films with perpendicular anisotropy, circular magnetic domains form which are highly mobile. These magnetic bubbles hold potential for magnetic storage technology. [14] 3.3.2. Nano wires or one dimensional magnets Fundamental interest in arrays of ferromagnetic nano wires lies in the emergence of novel magnetic and transport properties as the dimension approaches the length scale of a few nano meters to a few tens of Nano meters. Current interest in research on ferromagnetic nano wires is stimulated by the potential application to future ultra-high-density magnetic recording media.[15]The controlled production of magnetic nano wire arrays with outstanding characteristics is important to control the magnetization process. Free standing nanowires can be fabricated by different methods such as lithography and template electrodeposition [16] [17] [18] [19] [20]. The smaller diameter wires have high out-ofplane remanence while larger diameter wires have low remanence. This is consistent with the predictions of a micro magnetic model, which indicates a change from a flower (or single domain) to a vortex remanent state with increasing diameter. The flowervortex transition occurs at a diameter of 3.5 times of exchange length for cylinders without any magneto crystalline anisotropy
[21]

. However, it is important to note that the remanence

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only decreases slowly as the vortex develops, and high aspect ratio vortex state particles can still have significant remanence. 3.3.3. Nanodots and superparamagnetism Competition between exchange and anisotropy constants
[22]

induces a critical size of

nanodots. The state of lowest free energy of a ferromagnetic particle is one of uniform magnetization below a certain critical size. For larger particles, the magnetization is nonuniform. These two modes are known to correspond to single domain and vortex states which have been studied extensively over last decade
[23] [24]

. Arrays of magnetic

nanodots have been fabricated, the magnetization curves obtained for the arrays of circular dots exhibiting the two reversal modes. The effect of diameter and thickness is quite important. As the size approaches the critical radius, the single domain mode is predominant
[25]

. Nanodots smaller than the critical radius, tend to give up ferromagnetic

alignment, becoming superparamagnetic.

Figure: 1 M vs. H curve for superparamagnetism This behavior takes place when the fluctuations of magnetic moments caused by the thermal energy distort the intrinsic alignment of the ferromagnet. Considering a single domain particle with two distinct magnetic states, when the thermal energy becomes comparable with the energy barrier between the two states, superparamagnetism is established.

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3.4. Magnetic anisotropy The term magnetic anisotropy is used to describe the dependence of the internal energy on the direction of the spontaneous magnetization, creating easy and hard directions of magnetization. The total magnetization of a system will prefer to lie along the easy axis. The energetic difference between the easy and hard axis results from two microscopic interactions: the spin-orbit interaction and the long-range dipolar coupling of magnetic moments. The anisotropy energy arises from the spin-orbit interaction and the partial quenching of the angular momentum. The spin-orbit coupling is responsible for the intrinsic (magneto crystalline) anisotropy, surface anisotropy, and magneto striction, while the shape anisotropy is a dipolar contribution and is calculated e.g. by assuming a uniform distribution of magnetic poles on plane surfaces. Anisotropy energies are usually in the range 102-107 Jm-3. This corresponds to energy per atom in the range 10-8-10-3 eV. The anisotropy energy is larger in lattices (of magnetic ions) of low symmetry and smaller in lattices of high symmetry. In bulk materials, magneto crystalline and magneto static energies are the main source of anisotropy whereas in fine particles, thin films and nano structures, other kinds of anisotropies such as shape and surface anisotropy are relevant in addition to these usual anisotropies. In the following we will discuss four different contributions to magnetic anisotropy: magneto crystalline anisotropy, shape anisotropy, strain anisotropy and surface anisotropy. 3.4.1. Magneto crystalline anisotropy Magnetic anisotropy is meant as the dependence of the internal energy on the direction of spontaneous magnetization. An energy term of this kind is called as magnetic anisotropy energy. Generally the magnetic anisotropy energy term possesses the crystal symmetry of the material, and known as crystal magnetic anisotropy or magneto crystalline anisotropy
[26]

. The simplest forms of crystal anisotropies are the uniaxial anisotropy in the case of a

hexagonal and the cubic anisotropy in the case of a cubic crystal. For example, hexagonal cobalt exhibits uniaxial anisotropy, which makes the stable direction of internal magnetization (or easy direction) parallel to the c axis of the crystal at room temperature. 3.5. Single domain In magnetism, it refers to the state of a ferromagnet
[27]

in which the magnetization does

not vary across the magnet. A magnetic particle that stays in a single domain state for all
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magnetic fields is called a single domain particle

[28]

. They are very important in a lot of

applications because they have a high coercivity. They are the main source of hardness in hard magnets, the carriers of magnetic memory in tape drives, and the best recorders of the ancient Earth's magnetic field. 3.5.1. History & Definitions of a single-domain particle Early theories of magnetization in ferromagnets assumed that ferromagnets are divided into magnetic domains and that the magnetization changed by the movement of domain walls. However, as early as 1930, Frenkel and Dorfman predicted that sufficiently small particles could only hold one domain, although they greatly overestimated the upper size limit for such particles
[29]

. The possibility of single domain particles received little

attention until two developments in the late 1940s: (1) Improved calculations of the upper size limit by Kittel and Nel, and (2) A calculation of the magnetization curves for systems of single-domain particles by Stoner and Wohlfarth [30] [31]. Early investigators pointed out that a single-domain particle could be defined in more than one way [32]. Perhaps most commonly, it is implicitly defined as a particle that is in a single-domain state throughout the hysteresis cycle, including during the transition between two such states. However, it might be in a single-domain state except during reversal. Often particles are considered single-domain if their saturation remanence is consistent with the single-domain state. More recently, it was realized that a particle's state could be single-domain for some range of magnetic fields and then change continuously into a non-uniform state
[33]

. Another common definition of single-domain

particle is one in which the single-domain state has the lowest energy of all possible states. 3.5.2. Limits on the single-domain size Experimentally, it is observed that though the magnitude of the magnetization is uniform throughout a homogeneous specimen at uniform temperature, the direction of the magnetization is in general not uniform, but varies from one region to another, on a scale corresponding to visual observations with a microscope. Uniformity of direction is attained only by applying a field, or by choosing as a specimen, a body which is itself of microscopic dimensions (a fine particle). The size range for which a ferromagnet become
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single-domain is generally quite narrow and first quantitative results in this direction are due to William Fuller Brown, Jr. who, in his fundamental paper [34] rigorously proved (in the framework of Micro magnetic. This paper states the existence of a critical radius such that the state of lowest free energy is one of uniform magnetization if the existence of a critical size under which spherical ferromagnetic particles stay uniformly magnetized in zero applied field. Although pure single-domain particles (mathematically) exist for some special geometry only, for most ferromagnets a state of quasi-uniformity of magnetization is achieved when the diameter of the particle is in between about atomic meters and nanometers. The size range is bounded below by the transition to super paramagnetism and above by the formation of multiple magnetic domains. 1) Lower limit: super paramagnetism Thermal fluctuations cause the magnetization to dance around in a random manner. In the single domain state, the moment rarely strays far from the local stable state. Energy barriers prevent the magnetization from jumping from one state to another. However, if the energy barrier gets small enough, the moment can jump from state to state frequently enough to make the particle super paramagnetic. The frequency of jumps has a strong exponential dependence on the energy barrier, and the energy barrier is proportional to the volume, so there is a critical volume at which the transition occurs. This volume can be thought of as the volume at which the blocking temperature is at room temperature. 2) Upper limit: transition to multiple domains As size of a ferromagnet increases, the single-domain state incurs an increasing energy cost because of the demagnetizing field. This field tends to rotate the magnetization in a way that reduces the total moment of the magnet, and in larger magnets the magnetization is organized in magnetic domains. The demagnetizing energy is balanced by the energy of the exchange interaction, which tends to keep spins aligned. There is a critical size at which the balance tips in favor of the demagnetizing field and the multi domain state is favored. Most calculations of the upper size limit for the single-domain state identify it with this critical size [35] [36] [37].

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3.5.3. Domain formation Next is to focus on how domain formation occurs in an initially saturated specimen. In general this process constitutes a very considerable resistance to the process of demagnetization in many specimens. Saturation is expected in a magnetic specimen when the demagnetizing fields can be overcome in certain magnetic fields. However, the real demagnetizing fields are non-uniform over the volume of the specimen. Usually the end regions are much more difficult to saturate than the bulk of the crystal, and residual domains persist near the ends until external magnetic fields can completely make saturation [38]. The demagnetizing effect of the end surfaces can be eliminated assuming a ring-shaped specimen; however residual domains are still expected to be stabilized by pores, inclusions and grain boundaries. Considerable demagnetizing fields can arise from grain boundaries and this requires higher fields which are considerably higher than bulk saturation. A critical field designated as Hn (nucleation fields) may be needed some time to start nucleation of domains. However it is quite possible that critical fields may represent the initiation of wall motion rather than the nucleation of the walls, and in this case they may be designated as starting fields (Hs). 3.6. Domain walls Domain walls are interfaces between regions in which the spontaneous magnetization has different directions. At or within the wall the magnetization must change direction. A simplistic picture of a domain wall which makes an abrupt change between two domains. For this ferromagnetic specimen the easy axis is y and a row of atoms is shown parallel to x-axis, with the 180 domain wall lying in the y-z plane. In this case the domain wall will have a large exchange energy associated with it because the spins adjacent to the wall are anti-parallel and the exchange energy in a ferromagnet is a minimum only when adjacent spins are parallel. 3.7. Applications 3.7.1. Applications in R&D Magnetic nano-particle applications are being investigated in multiple disciplines from biomedical sensors, drug delivery, magnetic resonance imaging, data storage, nanoelectronics, etc. Two applications, which are being heavily investigated by several

research groups, are: detoxification of contaminated personnel for the military and drug
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delivery and treatment. Current techniques in both of these fields are very limited and minimally robust and nano-technology has the potential to enhance the capabilities in both fields immensely. 3.7.2. Detoxification of Contaminated Personnel Military Biochemical warfare is steadily becoming a greater threat worldwide. In the case of a conflict where a soldier is exposed to toxins there are very few options for survival. Current medical detoxification treatment methods available are dialysis and blood purification, both of which have low rates of success and take extensive periods of time to undergo. Magnetic nano-particles are being investigated for their capability to bind with toxins within the body. The various synthesis techniques including the thermal decomposition of metal-carbonyl complexes have shown that magnetic nano-particles are stabilized by an organic surfactant which acts as a capping layer. If a chemically active capping layer, which will functionally bind to the toxins within the body, can be utilized, then magnetic nano-particles can be sent into the bloodstream of a contaminated person. Then, by utilizing a magnetic field gradient, toxins can be extracted from the body. In research this methodology has been labeled tag and drag and is depicted in Figure.

Figure 2: Tag and Drag Detoxification of Contaminated Personnel via Magnetic Nano-particles.

Current research has shown success in this tag and drag approach using gold coated iron, nickel, and cobalt ferromagnetic nano-particles. The next phase of research is identifying pre-dominant toxins, functional organic capping layers, and bio-compatibility. 3.7.3. Drug Delivery and Efficacy Drug delivery and effective application of drugs within the body is another heavily investigated application for magnetic nano-particles. Researchers are particularly
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investigating ferromagnetic nano-particles with respect to treatment of various cancers. The goal is to have medicines functionally bind to magnetic nano-particles and utilize a magnetic gradient to guide the nano-particle to the affected region. Once at the affected region, the hysteretic behavior of ferromagnetic particles is utilized to provide thermal activation. Hysteresis occurs in ferromagnets because when an external field is applied and removed, a portion of the field is absorbed by the ferromagnet, called the remnant magnetization. When a reverse field is applied, this remnant magnetization has to be overcome. This effectively yields an energy loss in the form of heat which is

proportional to the area within the hysteresis loop. Researchers are utilizing this thermal energy for localized heating within the body. Once the medicine has been guided via a magnetic gradient to a desired location, the magnetic field is varied to create hysteresis. This in effect causes localized heating that helps in the activation and completion of a chemical reaction between the applied medicine and the adversely affected area. Current research is attempting to develop magnetic nano-particles with large magnetic moments and resistance to physical breakdown within the body. 3.7.4. Information storage Research is going into the use of using MNPs for magnetic recording media. The most promising candidates for high-density storage are the face-centered tetragonal phase Fe Pt alloy. Grain sizes can be as small as 3 nanometers. If it is possible to modify the MNPs at this small scale, the information density that can be achieved with this media could easily surpass 1 Terabyte per square inch. 3.8. Future Research and Development For magnetic nano-particles, current and future research is geared towards size distribution control. For most applications it is critical to have a specific size as well as very tight distribution. Current research is pushing to synthesize super-lattices of For the

magnetic nano-particles which show size distribution of less than 5%.

applications discussed in this paper, future research is being geared towards discovering biocompatible capping layers. particles in vivo. This is essential in order to utilize magnetic nano-

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3.9. Bismuth ferrite 3.9.1. Introduction toBiFeO3 BiFeO3 (BFO) is an inorganic chemical compound with a perovskite structure. It is one of the most promising lead-free piezoelectric materials by exhibiting multi ferroic properties at room temperature. Multiferroic materials exhibit ferroelectric or anti ferroelectric properties in combination with ferromagnetic (or antiferromagnetic) properties in the same phase. BiFeO3 is the only prototype among all other multi ferroic oxides which shows both ferromagnetism and ferro electricity in a single crystal above room temperature. It has ferroelectric Curie temperature Tc = 1143K and antiferromagnetic Nel temperature TN= 643K. The ions responsible for the production of ferro electricity and magnetism are Bi3+ and Fe+3 ions. Ferro electricity is produced due to Bi3+ and anti ferromagnetism is due to Fe+3 ions [39]. 3.9.2. Crystal structure of BiFeO3 It is having rhombohedrally distorted perovskite structure with R3c space group at room temperature.

Figure 3: BiFeO3 in Perovskite structure

Bi3+ ion occupy the corner position, Fe3+ in the body centered position, and O2- in all face centered position. The lattice parameters are a = 5.587 , b = 5.587 and c = 13.867 with = = 900 and =1200. The hexagonal unit cell contains 6 formulas.

Generally ferroelectricity is produced by vacant d0 orbital and ferromagnetism is observed due to partially filled dn orbital. In BiFeO3, ferroelectricity is produced due to stereo chemical activity of Bi3+ ion and ferromagnetism is due to Fe+3ions [39].
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Production of ferroelectricity in bismuth ferrite Bi3+ and Fe3+cations displaced along the [1 1 1] threefold polar axis and off centered with respect to the body centre of the oxygen octahedron, which in turn gives rise to ferroelectricity. Production of ferromagnetism in bismuth ferrite It is produced due to rotations of adjacent oxygen FeO6 octahedral around the [1 1 1] pseudo cubic direction (figure 3). 3.9.3. Applications of BiFeO3 1. Due to multiferroic nature of BiFeO3 it has broader applications in the field of transducers, magnetic field sensors and information storage industry. 2. Due to its magneto electric coupling it has the advantage that data can be written electrically and read magnetically. It exploits the best aspects of ferroelectric random access memory (Fe - RAM) and magnetic data storage. Multiferroism leads to fast, low-power consumption, multifunctional memory devices exploiting the best attributes of conventional ferroelectric and magnetic random-access memories. 3. Recently, ferroelectric random access memories (Fe RAMs) have achieved fast access speeds (5 ns), high densities (64 Mb) [39]. 3.10. Summary

Ongoing research has shown that synthesis of magnetic nano-particles is achievable. The applications for magnetic nano-particles are very diverse. In order to make use of the potential of magnetic nano-particles, work in synthesis refinement is necessary, to control geometric and magnetic properties. From an application aspect, research is being geared to find functional surfactants which serve to meet application requirements. Biocompatibility in the case of drug deliver and detoxification applications and conductivity in the case of electronic applications are examples of such. As research evolves and solutions to current limitations are resolved, the integration of magnetic nano-particles into everyday use becomes a clearer reality.

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