A Report On Size Effects in Nanomaterial Properties by Akshat Tyagi

Under the guidance of

Dr. SrinivasA Rao Nelamarri Assistant professor Department of Physics

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MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY

(Deemed University, Jaipur, RajasthaN)
J.L.N. Road, Jaipur-302017

Acknowledgement
Many people have contributed to the success of this. Although a single sentence hardly suffices, I would like to thank Almighty God for blessing us with His grace. I extend my sincere and heartfelt thanks to Dr. Srinivasa Rao Nelamarri, Department of Physics, for providing us the right ambience for carrying out this work. I am profoundly indebted to my seminar guide, Dr.Srinivasa Rao Nelamarri for innumerable acts of timely advice, encouragement and I sincerely express my gratitude to him. Last but not the least, I thank all others, and especially my classmates who in one way or another helped me in the successful completion of this work.

Akshat Tyagi 2009uec382

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Abstract
The question we address in this report is the question how does size matter? We discuss as to how the properties of the nanomaterials are different from the conventional bulk materials and to co relate the fact that the properties of a material can be size dependent. Many properties such as physical, chemical, electrical, optical, mechanical and others are size dependent. In other words, properties of nanostructured materials can be tuned considerably simply by adjusting the size, shape or extent of agglomeration.

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Table of contents
Contents
Acknowledgement Abstract 1. Introduction 1.1 Introduction 1.2 Aim of Report 2. Melting points and lattice constants 3. Mechanical Properties 4. Optical Properties 5. Electrical Properties 6. Magnetic Properties 7. Chemical Properties 8. Bibliography

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1. Introduction
1.1 Introduction
Many properties of solids depend on the size range over which they are measured. Microscopic details become averaged when investigating bulk materials. At the macro- or large-scale range ordinarily studied in traditional fields of physics such as mechanics, electricity and magnetism, and optics, the sizes of the objects under study range from millimeters to kilometers. The properties that we associate with these materials are averaged properties, such as the density and elastic moduli in mechanics, the resistivity and magnetization in electricity and magnetism, and the dielectric constant in optics. When measurements are made in the micrometer or nanometer range, many properties of materials change, such as mechanical, ferroelectric, and ferromagnetic properties.

Some physical properties of nanomaterials are related to different origins: (i) large fraction of surface atoms (surface to volume ratio increases) (ii) large surface energy (iii) spatial confinement (iv) reduced imperfections
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(v) dominance of electromagnetic forces The following are just a few examples: (1) Nanomaterials 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 nanoparticle 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 nanomaterials could also be enhanced appreciably, due to the better ordering in microstructure, e.g. in polymeric fibrils. (5) Magnetic properties of nanostructured materials are distinctly different from that of bulk materials. Ferromagnetism of bulk materials disappears and transfers to superparamagnetism in the nanometer scale due to the huge surface energy. (6) Chemical properties : Since the electronic structure of nanoparticles depends on the size of the particle, the ability of the cluster to react with other species should depend on cluster size. This has important implications for the design of catalytic agents and effect on reactivity and reaction rates. Metallic nanoparticles can be used as very active

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catalysts. Chemical sensors from nanoparticles and nanowires enhanced the sensitivity and sensor selectivity.

1.2 Aim of Report

The aim of the report is to find the effect of size on the properties of nanomaterials.

2. Melting points and lattice constants

Nanoparticles of metals, inert gases, semiconductors and molecular crystals are all found to have lower melting temperatures as compared with their bulk forms, when the particle size decreases below 100 nm. The lowering of the melting points is in general explained by the fact that the surface energy increases with a decreasing size. The decrease in the phase transition temperature can be attributed to the changes in the ratio of surface energy to volume energy as a function of particle size.

It is possible to make an experimental determination of the size dependence of melting temperature of nanoparticles. Three different criteria have been explored for this determination: (i) the disappearance of the state of order in the solid (ii) the sharp variation of some physical properties, such as evaporation rate (iii) the sudden change in the particle shape.

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 = 2 To /Lr
= Deviation of melting point from the bulk value To = Bulk melting point = Surface tension coefficient for a liquid-solid interface = Particle density r = Particle radius L = Latent heat of fusion Lowering of the melting point is proportional to 1/r

Figure below shows that the lattice constants of nanoparticles decrease linearly with an increasing reciprocal particle radius. It is further noticed that the CdS nanoparticles with surface modification demonstrate less reduction in lattice constant than that of bare nanoparticles.

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3. Mechanical properties
The mechanical properties of materials increase with a decreasing size. Two possible mechanisms have been proposed to explain the enhanced strength of nanowires or nanorods (in reality with diameters less than 10 microns). One is to ascribe the increase of strength to the high internal perfection of the nanowires or whiskers. The smaller the cross-section of a whisker or nanowires, the less is the probability of finding in it any imperfections such as dislocations, micro-twins, impurity precipitates, etc. Thermodynamically, imperfections in crystals are highly energetic and should be eliminated from the perfect crystal structures. Small size makes such elimination of imperfections possible. In addition, some imperfections in bulk materials, such as dislocations are often created to accommodate stresses generated in the synthesis and processing of bulk materials due to temperature gradient and other inhomogeneities. Such

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stresses are unlikely to exist in small structures, particularly in nanomaterials. Another mechanism is the perfection of the side faces of whiskers or nanowires. In general, smaller structures have less surface defects. It is particularly true when the materials are made through a bottom-up approach. Figure 8.18 shows a typical dependence of strength on the diameter of a sodium chloride whisker, and similar dependences are found in metals, semiconductors, and insulators.

Nanostructured materials may have different elastoplasticity from that of large-grained bulk materials. For example, near-perfect elastoelasticity was observed in pure nanocrystalline copper, prepared by means of powder metallurgy. The intrinsic elastic modulus of a nanostructured material is essentially the same as that of the bulk material having micrometer-sized grains until the grain size becomes very small, less than 5 nm. Youngs modulus is the factor relating stress and strain.
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It is the slope of the stress-strain curve in the linear region. The larger the value of Youngs modulus, the less elastic the material. Figure 6.8 is a plot of the ratio of Youngs modulus E in nanograined iron, to its value in conventional grain-sized iron Eo, as a function of grain size. The yield strength of a conventional grain-sized material is related to the grain size by the Hall-Petch equation

The reason for the increase in yield strength with smaller grain size is that materials having smaller grains have more grain boundaries, blocking dislocation movement.

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4. Optical properties

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Figure 4.20 shows the optical absorption spectra of a CdSe nanoparticle at two different sizes measured at 10 K. One can see that the lowest energy absorption region, referred to as the absorption edge, is shifted to higher energy as the particle size decreases. Since the absorption edge is due to the band gap, this means that the band gap increases as particle size decreases. Notice also that the intensity of the absorption increases as the particle size is reduced. The higher energy peaks are associated with the exciton, and they shift to
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higher energies with the decrease in particle size. These effects are a result of the confinement of the exciton. Essentially, as the particle size is reduced, the hole and the electron are forced closer together, and the separation between the energy levels changes

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5. EIectrical conductivity
The mechanisms responsible for change in electrical conductivity can be generally grouped into four categories: 1. Surface scattering 2. Quantized conduction including ballistic conduction 3. Coulomb charging and tunneling, and widening and discrete of band gap 4. Change of microstructures. In addition, increased perfection, such as reduced impurity, structural defects and dislocations, would affect the electrical conductivity of nanostructures and nanomaterials.

Effect of microstructure Electrical conductivity may change due to the formation of ordered microstructure, when the size is reduced to a nanometer scale. For example, polymer fibers demonstrated an enhanced electrical conductivity. The enhancement was explained by the ordered arrangement of the polymer chains. Within nanometer fibris, polymers are aligned parallel to the axis of the fibris, which results in increased contribution of intramolecular conduction and reduced contribution of intermolecular conduction. Since intermolecular conduction is far smaller than intramolecular conduction, ordered arrangement of polymers with polymer chains aligned parallel to the conduction direction would result in an increased electrical conduction. Figure 8.32 shows the electrical conductivity of polyheterocyclic fibris as a function of diameter.ls2 A drastic increase in electrical
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conductivity with a decreasing diameter was found at diameters less than 500 nm. Smaller the diameter, the better alignment of polymer is expected. A lower synthesis temperature also favors a better alignment and thus a higher electrical conductivity.

Quantum confinement causes the energy of the band gap to increase. Also at small dimensions when the energy gaps are quantized, the band overlap present in metals disappears and is actually transformed into a band gap.This explains why some metals become semiconductors as their size is decreased.

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6. Magnetic Properties
In a polycrystalline ferroelectric, the ferroelectric properties may disappear when the particles are smaller than a certain size. Such a relation could be understood considering the phase transition temperature reduces with the particle size. A reduction in particle size results in a high temperature crystal structure stable at low temperatures. Consequently, the Curie temperature, or the ferroelectric-paraelectric transition temperature decreases with a reduced particle size. When the Curie temperature drops below room temperature, ferroelectrics lose its ferroelectricity at room temperature. Dielectric constant or relative permittivity of ferroelectrics would increase with a decreasing grain size, and such a decrease becomes much more profound when the size is smaller than 1 micrometer.

Ferromagnetic particles become unstable when the particle size reduces below a certain size, since the surface energy provides a sufficient energy for domains to spontaneously switch polarization directions. As a result, ferromagnetics become paramagnetics. However, nanometer sized ferro18 | P a g e

magnetic turned to paramagnetic behaves differently from the conventional paramagnetic and is referred to as superparamagnetics.

Bulk gold and Pt are non-magnetic, but at the nano size they are magnetic. Surface atoms are not only different to bulk atoms, but they can also be modified by interaction with other chemical species, that is, by capping the nanoparticles. This phenomenon opens the possibility to modify the physical properties of the nanoparticles by capping them with appropriate molecules. Actually, it should be possible that non-ferromagnetic bulk materials exhibit ferromagnetic-like behavior when prepared in nano range. One can obtain magnetic nanoparticles of Pd, Pt and the surprising case of Au (that is diamagnetic in bulk) from non-magnetic bulk materials. In the case of Pt and Pd, the ferromagnetism arises from the structural changes associated with size effects.

However, gold nanoparticles become ferromagnetic when they are capped with appropriate molecules: the charge localized at the particle surface gives rise to ferromagnetic-like behavior.

Surface and the core of Au nanoparticles with 2 nm in diameter show ferromagnetic and paramagnetic character, respectively. The large spin-orbit coupling of these noble metals can yield to a large anisotropy and therefore exhibit high ordering temperatures. More surprisingly, permanent magnetism was observed up to room temperature for thiol-capped Au nanoparticles. For nanoparticles with sizes below 2 nm the localized carriers are in the 5d band. Bulk Au has an extremely low density of states and becomes diamagnetic, as is also the case for bare Au nanoparticles. This observation suggested that modification of the d band structure by chemical bonding can induce ferromagnetic like character in metallic clusters.
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The diverse applications of magnets require the magnetization curve to have different properties. Magnets used in transformers and rotating electrical machinery are subjected to rapidly alternating AC magnetic fields, so they repeat their magnetization curve many times a second, causing a loss of efficiency and a rise in the temperature of the magnet. Such magnets are called soft magnetic materials. On the other hand, in the case of permanent magnets used as a part of high-field systems, large coercive fields are required, and the widest possible hysteresis loop is desirable. Such magnets are called hard magnets. High-saturation magnetizations are also needed in permanent magnets. Nanostructuring of bulk magnetic materials can be used to design the magnetization curve. A magnetic material with grain-sized single domain magnetic moments, which has no hysteresis at any temperature, is said to be super-paramagnetic.

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 The size of magnetic nanoparticles has also been shown to influence the value M, at which the magnetization saturates. the magnetization increases significantly below a grain size of 20 nm. Thus, decreasing the particle size of a granular magnetic material can considerably improve the quality of magnets fabricated from it.

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7. Chemical Properties
There is experimental evidence for the effect of size on the reactivity of nanoparticles. Figure 4.13 shows the results of studies of the reaction of oxygen with aluminum particles. The top figure is the mass spectrum of the aluminum particles before the oxygen is introduced. The bottom figure shows the spectrum after oxygen enters the chamber. The results show that two peaks have increased substantially and certain peaks (12, 14, 19, and 20) have disappeared. The Al13 and Al23, peaks have increased substantially, and peaks from Al15 to Al22 have decreased.

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These data provide clear evidence for the dependence of the reactivity of aluminum clusters on the number of atoms in the cluster. Similar size dependences have been observed for the reactivity of other metals. Figure 4.14 plots the reaction rate of iron with hydrogen as a function of the size of the iron nanoparticles. The data show that particles of certain sizes such as the one with 10 atoms and sizes greater than 18 atoms are more reactive with hydrogen than others.

Nanomaterials in catalysis Surface chemistry is important in catalysis. Nanostructured materials have some advantages: - Huge surface area, high proportion of atoms on the surface - Enhanced intrinsic chemical activity as size gets smaller which is likely due to changes in crystal shape - Ex: When the shape changes from cubic to polyhedral, the number of edges and corner sites goes up significantly - As crystal size gets smaller, anion/cation vacancies can increase, thus affecting surface energy; also surface atoms can be distorted in their bonding patterns - Enhanced solubility, sintering at lower T, more adsorptive capacity.
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Bibliography
1. Harsha, K.S.S, "Principles of Physical Vapor Deposition of Thin Films", Elsevier, Great Britain (2006), p.400. 2. George, J., "Preparation of thin films", Marcel Dekker, Inc., New York (1992), p.13-9. 3. Madou, M.J., "Fundamentals of Microfabrication: The science of Miniaturization" 2nd Ed., CRC Press (2002), p.135-6. 4. Kesapragada, S. V., et al. "Nanospring pressure sensors grown by glancing angle deposition." Nano letters 6.4 (2006): 854-857. 5. Robbie, K., and M. J. Brett. "Sculptured thin films and glancing angle deposition: Growth mechanics and applications." Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 15.3 (1997): 1460-1465. 6. Driskell, Jeremy D., et al. "The use of aligned silver nanorod arrays prepared by oblique angle deposition as surface enhanced Raman scattering substrates." The Journal of Physical Chemistry C 112.4 (2008): 895-901.

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