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182 C HA PT E R 6

Nanomaterials: Classes and Fundamentals

Nanocrystalline multilayers

t ≤ 100 nm

Microcrystalline multilayers

Since we now have several working models for the categorization of 2-D nanomaterials, let’s move on to 3-D nanomaterials. Following our previous definition, bulk nanomaterials are materials that do not have any dimension at the nanoscale. However, bulk nanomaterials still exhibit features at the nanoscale. As previously discussed, bulk nanomaterials with dimensions larger than the nanoscale can be composed of crystallites or grains at the nanoscale, as shown in Figure 6.11. These materials are then called nanocrystalline materials. Figure 6.12 summarizes 2-D and 3-D crystalline structures. Another group of 3-D nanomaterials are the so-called nanocomposites. These materials are formed of two or more materials with very distinctive properties that act synergistically to create properties that cannot be achieved by each single material alone. The matrix of the nanocomposite, which can be polymeric, metallic, or ceramic, has dimensions larger than the nanoscale, whereas the reinforcing phase is commonly at the nanoscale. Examples of this type of 3-D nanomaterial are shown in Figures 6.13 and 6.14, where various nanocomposites are shown. Distinctions are based on the types of reinforcing nanomaterials added, such as nanoparticles, nanowires, nanotubes, or nanolayers. Within the nanocomposite classification, we should also consider materials with multinanolayers composed of various materials or sandwiches of nanolayers bonded to a matrix core. Many applications, especially in nanoelectronics, require the use of various kinds of physical features, such as channels, grooves, and raised lines, that are at the nanoscale (see Figure 6.15). A typical copper interconnect is shown in Figure 6.16. Nanofilms, nanocoatings, and multilayer 2-D nanomaterials can be patterned with various features at various scales. In the case of multilayered nanomaterials, the patterns can be made on any layer. These patterns can have different geometries and dimensions at the nanoscale or at larger scales. Most electronic materials fall into the category of patterned 2-D nanomaterials. Figure 6.17 broadly summarizes types of nanomaterials in relation to their dimensionalities.

t ≤ 100 nm

FIGURE 6.10 Two-dimensional nanocrystalline and microcrystalline multilayered nanomaterials.

Nanoscale

d

Bulk

FIGURE 6.11 Three-dimensional nanocrystalline nanomaterial in bulk form.

6.2

SIZE EFFECTS

Surface-to-Volume Ratio Versus Shape
One of the most fundamental differences between nanomaterials and larger-scale materials is that nanoscale materials have an extraordinary ratio of surface area to volume. Though the properties of traditional large-scale materials are often determined entirely by

Matrix reinforced with nanoparticles Matrix reinforced with nanowires/nanotubes Laminates Sandwiches Matrix-reinforced nanocomposites Layered nanocomposites FIGURE 6.12 Summary of 2-D and 3-D crystalline structures.13 Matrix-reinforced and layered nanocomposites.Large-Scale Forms One layer Nanocrystalline Substrate Lx Ly tn ≤ 100 nm Microcrystalline Multiple layers tn ≤ 100 nm Substrate tn ≤ 100 nm Microcrystalline layers Crystalline structures Nanocrystalline structures Substrate Microcrystalline structure Substrate Microcrystalline and crystalline structures Crystalline structure (any dimension) FIGURE 6. .

For these reasons.1) . for nanomaterials this surface-to-volume ratio is inverted. a nanomaterial’s shape is of great interest because various shapes will produce distinct surface-to-volume ratios and therefore different properties. whether 0-D. the properties of their bulk. as we will see shortly. We start with a sphere of radius r. or 2-D nanomaterials are used to make film and bulk nanocomposites. 1-D.2) (6. the surface area is given by A = 4πr 2 whereas the volume of a sphere is given by V= 4πr 3 3 (6. In this case. As a result. The expressions that follow can be used to calculate the surface-to-volume ratios in nanomaterials with different shapes and to illustrate the effects of their diversity. The filler materials.184 C HA PT E R 6 Nanomaterials: Classes and Fundamentals Basic Geometry Large Scale Forms (dimensions at micro or macroscale) Point 0-D d 100 nm Nanocomposite thick film Bulk nanocomposites Line 1-D Nanocomposite thick film Wires Rods Tubes d 100 nm Bulk nanocomposites Surface 2-D Thin film on substrate Bulk nanocomposites d 100 nm FIGURE 6. This inverted ratio and its effects on nanomaterials properties is a key feature of nanoscience and nanotechnology. This is typically the shape of nanoparticles used in many applications. due to the relatively small contribution of a small surface area. the larger surface area of nanomaterials (compared to their volume) plays a larger role in dictating these materials’ important properties.14 Basic types of large-scale nanomaterials bulk forms.

with layer thickness often greater FIGURE 6. (Courtesy of Jin An and P. University of Texas at Austin. The copper lines were produced by electrodeposition of copper on previously patterned channels existent in the dielectric material. holes). .Size Effects 185 Nanoscale Structures Large-Scale Forms Copper Dielectric Features t ≤ 100 nm One layer t ≤ 100 nm Substrate t ≤ 100 nm Microscale Multilayers t ≤ 100 nm Substrate Nanoscale Features t ≤ 100 nm Feature dimensions at nanoscale..15 Two-dimensional nanomaterials containing patterns of features (e.16 Nanocopper interconnects used in electronic devices. Ferreira.) Microsccale structure Substrate Microscale and macroscale features t >100 nm FIGURE 6. channels. J.g.

foils (gilding foil) Nano surface layers Multilayer structures FIGURE 6. Clearly. the surface-to-volume ratio of a sphere is given by 4πr 2 A 4πr 3 3 = = 3 r V (6.3.18 Surface-to-volume ratios for a sphere. Next.186 C HA PT E R 6 Nanomaterials: Classes and Fundamentals Classes Class 1 Discrete nanoobjects 0-D All 3 dimensions on nano scale Class 2 Surface nanofeatured materials Class 3 Bulk nanostructured materials Nanoparticles (smoke.4) FIGURE 6. the volume and surface area of the cube are given by V = L3 and A = 6L2.18. as the radius is decreased below a certain value. The ratios of surface-to-volume as a function of critical dimension for the cylinder case are shown in Figure 6. cube. Nanoscale materials have extremely high surface-to-area ratios as compared to larger-scale materials. Let’s now turn to a cube of side L. although the severe increase in surface-to-volume ratio occurs at larger critical dimensions. the results for various radii are shown in Figure 6.3) On the basis of Equation 6. the surface-to-volume ratio is given by A πr 2 H 2 = = V 2πrH r (6. whereas the surface area A = 2πrH. the volume V = πr2H. diesel fumes) Nanocrystalline films Nanocrystalline materials Nanoparticle composites Dimensionality 1-D 2 dimensions on nano scale Nanorods and tubes (carbon nano tubes) Nano interconnects Nanotube-reinforced composites 2-D 1 dimension on nano scale Nanofilms. Thus. Therefore the surface-tovolume ratio of a cube is given by A 6L2 6 = 3 = V L L (6. there is a dramatic increase in surface-to-volume ratio. and cylinder as a function of critical dimensions. consider a cylinder of radius r and height H—for example.5) . respectively.18. a nanowire. In this case. The trend is similar to the sphere case. In this case. Thus.17 General characteristics of nanomaterial classes and their dimensionality.

14 × 108 nm2. However. so far we can conclude that one single particle with 10 microns can generate 1 billion nanosized particles with a diameter of 10 nm. This means an increase in surface area by a factor of 1000. let’s put this information into context.23 × 1011 = = 1 × 109 particles V (10 nm) 523 (6.6) Hence. we get V (10 nm) = 523 nm3. first we calculate the volume of a sphere with 10 microns. since we have 1 billion 10 nm particles. We then calculate the volume of a sphere with 10 nm. the surface area of all these particles amounts to 3.18. After stressing the importance of the increase in surface area in nanomaterials relative to traditional larger-scale materials.2. Therefore the fraction of surface atoms increases as the particle size goes down. the surface-to-volume ratio increases. to calculate the number of nanosized particles generated by the 10 micron particle. Again. Magic Numbers As discussed. for the case of the 10 nm particle A (10 nm) = 314 nm2. On the other hand. with the help of Equation 6. we can relate the number of surface and bulk atoms according to the expressions V= 4π 3 rA n 3 (6. for a decrease in particle radius.7) . Following Equation 6. the total volume remains the same. Following Equation 6. from a spherical particle of 10 µm to be reduced to a group of particles with 10 nanometers. With the help of a few simple calculations.Size Effects 187 As shown in Figure 6.1 gives A (10 µm) = 3. the overall trend remains for the case of the cube. Because the mass of the 10 micron particle is converted to a group of nanosized particles. To do this. We are thus left with the task of finding the increase in surface area in going from one particle to 1 billion particles. we can determine how much of an increase in surface area will result—for example. we simply need to divide V (10 µm) by V (10 nm)in the form: N= V (10 µm) 5. This can be done by first calculating the surface area of the 10 micron particle. Therefore. but the significant variation in surface-to-volume ratio is observed at larger critical dimensions compared with the sphere and cylinder cases. In general.14 × 1011 nm2.2 gives V (10 µm) = 5. whereas the total volume remains the same. for a sphere. assuming that the volume remains constant.23 × 1011 nm3.

For illustration purposes. from a thermodynamic point of view. we have to take into consideration the crystal structure. silver (Ag). the 14 atoms are all surface atoms. and n is the number of atoms. where γi is the surface energy per unit area Ai of exposed surfaces. In this case. Among the possible shapes.19 Face-centered cubic (FCC) structure.10 and 6. For ideal FCC metals.11) Thus. the fraction of atoms FA on the surface of a spherical nanoparticle can be given by FA = 3 rA n1 3 (6. aluminum (Al). the total number of bulk (interior) atoms can be given by B N Total = 4n3 − 6n2 + 3n − 1 (6. the surface energy of atomic planes with high symmetry should follow the order γ{111}Pt < γ{100}Pt < γ{110}Pt due to surface atomic density. the equilibrium crystal shape can be created. so-called structural magic numbers. we assume a nanoparticle with a face-centered cubic (FCC) structure. for n layers of atoms added.1. If another layer of atoms is added so that the crystal structure is maintained. . We start with the FCC crystal structure shown in Figure 6. In general. This crystal structure is of practical importance because nanoparticles of gold (Au). Clearly. The assumption so far has been that a nanoparticle would exhibit a cube-type shape. These numbers. On the basis of calculated surface energies. the equilibrium shape of nanocrystalline particles is determined by ∑ A i γ i = minimum (6. On this basis. in addition to the shape of the particle. copper (Cu) and platinum (Pt) exhibit such a structure. which is a 14-sided polyhedron (see Figure 6.188 C HA PT E R 6 Nanomaterials: Classes and Fundamentals 2 23 A = 4π rA n (6. are shown in Table 6. All 14 atoms are on the surface.. Others are surface atoms.20 The smallest FCC nanoparticle that can exist: a cubo-octahedron.9) a b FIGURE 6. a specific number of atoms must be introduced. nickel (Ni).19. A bulk atom is at the center.8) c where V is the volume of the nanoparticle.20). A is the surface area of the nanoparticle. We now consider a crystalline nanoparticle.12) FIGURE 6. However.11 relate the number of surface and bulk atoms as a function of the number of layers. the total number of surface atoms can be given by S N Total = 12n2 + 2 (6. if edge and curvature effects are negligible.10) On the other hand. rA is the atomic radius. the smallest FCC nanoparticle that can exist is a cubo-octahedron. Equations 6.

If additional layers of atoms are added to the cubo-octahedral nanoparticle such that the shape and crystal structure of the particle are maintained.83 0.1 2.3 25.Size Effects 189 Table 6. the total number of surface atoms can be given by S N Total = 10n2 − 20n + 12 (6.8 22.9 53. representing special electronic configuration may . In this case.314 0. sometimes the dominant factor in determining the minimum in energy of nanoparticles is the interaction of the valence electrons of the atoms with an averaged molecular potential.299 Surface/Bulk Ratio — 3. In particular.4 34.13) whereas the total number of bulk (interior) atoms can be given by B N Total = 1 (10n3 − 15n2 + 11n − 3) 3 (6.14) Table 6.350 0.3 63.9 This nanoparticle has 12 surface atoms and one bulk atom.002 Bulk Atoms 0 13 62 171 364 665 1098 1687 2456 3429 4630 6083 3. However.455 0.78 1.395 0.13 0. a series of structural magic numbers can be found. electronic magic numbers.284 0.9 23.655 0.2 shows the number of surface and bulk atoms for each value of n as well as the ratio of surface-to-volume atoms.1 Structural Magic Numbers for a Cube-Type FCC Nanoparticle n 1 2 3 4 5 6 7 8 9 10 11 12 100 Surface Atoms 14 50 110 194 302 434 590 770 974 1202 1454 1730 120. for n layers of atoms added.0304 Surface Atoms (%) 100 79.3 39.9 31.3 28. These structural magic numbers do not take into account the electronic structure of the atoms in the nanoparticle.535 0.1 45.940.85 1.

8 3.3 76.9 39.2 1. the surface atoms are not bonded in the direction normal to the surface plane.31 0.280. This is because potassium has the 4s orbital (outermost shell) occupied and thus clusters for which the total number of valence electrons fill an electronic shell are especially stable. surface atoms will have more freedom to move and thus higher entropy. the atomic arrangement at the surface is different from that within the bulk.6 52. As a result.8 0.2 28. 58.6 0.4 0.000 Bulk Atoms 1 13 55 147 309 561 923 1415 2057 2869 3871 3.6 1. 40.3 25. In addition.2 Structural Magic Numbers for a Cubo-Octahedral FCC Nanoparticle n 2 3 4 5 6 7 8 9 10 11 12 100 Surface Atoms 12 42 92 162 252 362 492 642 812 1002 1212 98. For example.9 23.8 31. These two conditions are the origin of the surface free energy of materials.0 occur for certain cluster sizes. ε/2 Surface Curvature All solid materials have finite sizes. For a pure material.34 0. 20. . the surface free energy γ can be expressed as FIGURE 6.4 62. Hence if the energy of each bond is ε/2 (the energy is divided by 2 because each bond is shared by two atoms). then for each surface atom not bonded there is an excess internal energy of ε/2 over that of the atoms in the bulk. Thus.21.029 Surface Atoms (%) 92.39 0.4 44. and 92 atoms occur frequently. potassium clusters produced in a supersonic jet beam and composed of 8.21 For each surface atom there is an excess internal energy of ε/2 due to the absence of bonds.2 34.190 C HA PT E R 6 Nanomaterials: Classes and Fundamentals Table 6.1 0. electronic magic numbers correspond to main electronic shell closings.000 Surface/Bulk Ratio 12 3.5 0. As shown in Figure 6. in general.

These effects are normally called capillarity effects due to the fact that the initial studies were done in fine glass tubes called capillaries.16) FIGURE 6.15) C r where ES is the internal energy. the local curvature may vary along the curve. Equally important is the fact that the geometry of the surface. will cause a change in the system’s pressure. By convention. at the nanoscale. In general. whereas the reciprocal of the radius k =1 r (6.23 Concave and convex surface curvatures. In addition. Ωγ excess .Size Effects 191 γ = E S − TSS (6. Therefore. The radius r is called the radius of curvature at C. consider the 2-D curve shown in Figure 6.23). variations in surface curvature will result in changes in the Gibbs free energy given by ∆G = ∆PV = 2γ V r (6. Another important property that is significantly altered by the curvature effect is the equilibrium number of vacancies (see the section on crystalline defects in Chapter 4). that is.22. specifically its local curvature.18) bulk where ∆Gv is the equilibrium Gibbs free energy change for the excess is the excess Gibbs formation of vacancies in the bulk and ∆Gv free energy change for vacancy formation due to curvature effects. because the sign for the local curvature depends on whether the surface is convex or concave.22. where Ω is the atomic Assuming no surface stress. the local curvature is defined as positive if the surface is convex and negative if concave (see Figure 6.17. and SS is the surface thermal entropy. On the basis of Equation 6. A circle of radius r just touches the curve at point C.17) FIGURE 6.17. described in Equation 6. this effect is very significant. if a nanoparticle is under atmospheric pressure. the pressure inside the particle can be higher or lower than outside. the total Gibbs free energy change for the formation of vacancies in a nanoparticle can be expressed by Total bulk excess ∆Gv = ∆Gv + ∆Gv (6. it will be subject to an extra pressure ∆P due to the positive curvature of the nanoparticle’s surface. For example.22 Surface curvature in two dimensions. As the total energy (Gibbs free energy) of a system is affected by changes in pressure. ∆Gv = r . the magnitude of the pressure difference increases as the particle size decreases. To introduce the concept of surface curvature. as the local curvature increases. T is the temperature. Convex Concave is called the local curvature of the curve at C. As shown in Figure 6.

0 0 5 10 Size (nm) Convex surface Silver Gold Platinum Concave surface Ωγ   Total Xv = X vBulk 1 −   rkB T  (6. and thus Equation 6. the local curvature is defined as positive if the surface is convex and negative if concave.24 Diffusivity at 900° in silver. Therefore.0 0. and electrical resistance. diffusion.23 becomes Ωγ   Total Xv = X vBulk 1 +   rkB T  15 20 (6.192 C HA PT E R 6 Nanomaterials: Classes and Fundamentals volume.20) where kB is the Boltzmann constant and T the temperature. Figure 6.24) On the other hand. γ the surface energy. the concentration of vacancies can be written as  Ωγ  Total bulk Xv = Xv exp  −  rkB T   (6.21) For the bulk case. Equation 6.25) FIGURE 6. and platinum nanoparticles of different sizes normalized with respect to bulk diffusivities. by convention. where curvature effects can be neglected.22) However for a nanoparticle. catalytic activity. and r the radius of curvature.24 shows the .5 0. the concentration of vacancies can be expressed as bulk  ∆Gv  bulk Xv = exp  −  kB T   (6. can be rewritten as 900°C 2. gold. This means that the vacancy concentration under a concave surface is greater than under a flat surface.23. for concave surfaces. playing a significant role in a variety of properties such as heat capacity.20 yields bulk  ∆Gv   Ωγ  Total Xv = exp  − exp  −   rkB T    kB T  (6. the total equilibrium vacancy concentration in a nanoparticle can be given by Total bulk ∆Gv = ∆Gv + Total  ∆Gv  Total Xv = exp  −   kB T  (6.19 into Equation 6.19) r Therefore.0 Normalized diffusivity 1.5 1. thereby controlling several processing methods such as alloying and sintering. the mean curvature is given by −1/r. Equation 6. for a convex surface.23) As discussed. which in turn is greater than under a convex surface. Inserting Equation 6. This result has important implications for nanoparticles due to their small radius of curvature.18 can be rewritten as: Ωγ (6.

25 and 6. leading to the coalescence of nanoparticles and elimination of the neck region. One other important physical property of a material is its lattice parameter. it has significant impact on a variety of properties. when two nanoparticles are in contact with each other (see Figures 6. the effect is quite significant. due to the curvature effect. R is the radius of the convex surface and r is the radius of the concave surface.25 Aberration-corrected STEM image of two nanoparticles sintering at room temperature.Size Effects 193 effect of curvature on the diffusivity of nanoparticles of silver.26).) where ∆P is the difference in pressure between the interior of a liquid droplet and its outside environment. If the droplet is now solid and crystalline with a cubic structure and lattice parameter a (the droplet is now a nanoparticle).27) r R which measures the volume change of the material as the pressure applied increases. atoms readily migrate from convex surfaces with positive curvature (high positive energy) to concave surfaces with negative curvature (high negative energy). Allard. Equation 6. giving FIGURE 6. γ is the surface energy. we consider the Gauss-Laplace formula given by ∆P = 4γ d (6. Clearly. In this case. and P.28 reveals that the . This behavior has profound consequences on the sintering of nanoparticles.26 can then be inserted in Equation 6. γ 3K ∆a = d 4 a (6. As a consequence. It is normalized with respect to Vo to represent the fractional change in volume with increasing pressure. nanoparticles exhibit a high tendency to sintering. we can write for the compressibility of the nanoparticle: K= 1 VO  ∂V   T  ∂P  (6. even at room temperature. and d is the diameter of the droplet. for a constant temperature. because the radius of curvature decreases. To understand the effects of scale on the lattice parameter.28) Since the surface energy increases as the particle decreases. for nanoparticle sizes below 10 nm. University of Texas at Austin.26 Schematic showing the sintering process of two nanoparticles. Because this parameter represents the dimensions of the simplest unit of a crystal that is propagated in 3-D. J. Equation 6.26) FIGURE 6. (Courtesy of Michael Asoro. In fact. the neck region between the nanoparticles has a concave surface. Ferreira. Larry F. gold. In other words. Oak Ridge National Laboratory. University of Texas at Austin. and platinum. which results in reduced pressure. Vo = a3.27.

27 Lattice parameter of Al (aluminum) as a function of particle size.194 C HA PT E R 6 Nanomaterials: Classes and Fundamentals Lattice parameter (nm) lattice parameter is reduced for a decrease in particle size (Figure (6. Woltersdorf. If the crystal size is reduced to the nanometer scale. and E. thereby controlling the behavior of materials when subjected to a stress above the yield stress. Nepijko. The direct consequence of this behavior is that nanoparticles below a critical size are self-healing as defects generated by any particular process are unstable and ejected. the strain energy of a perfect edge dislocation loop contained in a nanoparticle of size R is given by WS ≅ µb 2 4π R − rd   ln  R    { } (6.28). the assumption associated with an infinite crystal size becomes increasingly invalid.) µb 2 r ln 4π c {} (6. In addition. A comparison of Equations 6. In other words.29 and 6. In the case of an infinite crystal. might or might not be separated from an . in the nanoscale regime. 1981. Surface Science.27)). The valence band. Strain Confinement Planar defects. Quantum Effects In bulk crystalline materials.S.29) where µ is the shear modulus. Pippel. Therefore. dislocations play a crucial role in plastic deformation. it is vital to take into account the effect posed by the nearby free surfaces. b is the Burgers vector.30) where rd is the distance between the dislocation line and the surface of the particle and the other symbols have the same meaning as before. (Adapted from J. pp. the atomic energy levels spread out into energy bands (see Figure 6. A. there are image forces acting on the dislocation half-loop. and c is the core cutoff parameter. the dislocation will be increasingly affected by the presence of nearby surfaces. causing dislocation ejection toward the nanoparticle’s surface. the presence of the nearby surfaces will impose a force on the dislocations.30 reveals that for small particle sizes. As a consequence. As a consequence. the strain energy of a perfect edge dislocation loop is given by WS ≅ Particle diameter (nm) FIGURE 6. 106. As discussed in Chapter 4. 64–69. r is the radius of the dislocation stress field. such as dislocations are also affected when present in a nanoparticle. the stress field of the dislocations is reduced. which is filled with electrons.

Size Effects 195 Conduction band Vacant state Conduction band Vacant state Conduction band Vacant state Energy Energy Valence band Occupied state Energy Gap Valence band Valence band Occupied state Occupied state Occupied state Occupied state Conductor Occupied state Semiconductor Insulator FIGURE 6. In the case of 2-D nanomaterials. very little energy is required to bring electrons from the valence band to the conduction band. empty conduction band by an energy gap. The effect of confinement on the resulting energy states can be calculated by quantum mechanics. as the “particle in the box” problem. insulators. for 3-D nanomaterials the electrons are fully delocalized. This overall behavior of bulk crystalline materials changes when the dimensions are reduced to the nanoscale. no electron delocalization (freedom to move) occurs. For 1-D nanomaterials. .28b). For conductor materials such as metals. the band gap is not as wide. for 0-D nanomaterials the electrons are fully confined. In the case of semiconductor materials such as silicon. Therefore. where all the dimensions are at the nanoscale. an electron is confined in 3-D space. Therefore. electron confinement occurs in 2-D.28 Energy bands in bulk conductors. the conduction electrons will be confined across the thickness but delocalized in the plane of the sheet. from which it cannot escape and is confined by the dimensions of the nanostructure. and semiconductors.28a). For insulator materials such as ceramics. Under these conditions of confinement. In 1-D and 2-D nanomaterials. 1-D. the conduction band suffers profound alterations. electron confinement and delocalization coexist. In 0-D. and thus it is possible to excite the electrons from the valence band to the conduction band with some amount of energy. Therefore. the energy band gap is quite significant (Figure 6. an electron is considered to exist inside of an infinitely deep potential well (region of negative energies). there is typically no band gap (Figure 6. and thus transferring electrons from the valence band to the conduction band is difficult. For 0-D nanomaterials. whereas delocalization takes place along the long axis of the nanowire/rod/tube. In this treatment. On the other hand. where electrons are free to flow.

31a–c).. the use of nanostructures provides the possibility for tuning these properties. see Figure 6. the effects of confinement on the energy state can be written respectively as (0-D) 3-D bulk E  π 2 ℏ2  2 2 2 En =  n + ny + nz ) 2 ( x 2 mL    π 2 ℏ2  2 2 En =  n + ny ) 2 ( x  2mL   π 2 ℏ2  2 En =  n 2 ( x )  2mL  (6. is also strongly dependent on the dimensionality of the structure.e. i. ny. photoemission spectroscopy. quantum wire (confinement in two dimensions and delocalization in one dimension). leading to a spectrum of discreet energies. biological tagging. quantum well (confinement in one dimension and delocalization in one dimension). As shown in Equations 6. and a quantum dot (0-D nanomaterial). This also means that the number of electrons dN within a narrow energy range dE. N (En). the band gap of a material can be shifted toward higher energies by spatially confining the electronic carriers. the ability to control the density of states is crucial for applications such as infrared detectors. so is the number of conduction electrons. the thermopower effect. and bulk material (delocalization in threedimensions. . L is the width (confinement) of the infinitely deep potential well. that exist in a particular state. single-photon sources. a quantum wire (1-D nanomaterial). Overall. lasers. a quantum well (2-D nanomaterial). the wider is the separation between the energy levels.196 C HA PT E R 6 Nanomaterials: Classes and Fundamentals D(E) and 2-D. Because the density of states determines various properties. D(E) = dN/dE. and nx. As En is dependent on the dimensionality of the system (Equations 6. D(E) 1-D quantum wire E D(E) E 1-D quantum dot FIGURE 6. For example.31b) (6.31c) (1-D) (2-D) D(E) E 2-D quantum well where h ¯ ≡ h/2π. and nz are the principal quantum numbers in the three dimensions x. specific heat. Therefore the density of states as a function of the energy E for conduction electrons will be very different for a quantum dot (confinement in three dimensions). m is the mass of the electron. and photonic structures. y. optical memories. the smaller the dimensions of the nanostructure (smaller L). Another important feature of an energy state En is the number of conduction electrons. and z.31a) (6. In this fashion.29 Density of states in a bulk material. which represent the density of states D(E). and the superconducting energy gap are all influenced by the density of states. superconductors. excitons in semiconductors.31a–c. h is Planck’s constant.29).

Jr. ISBN 0-75030578-9. S. Ferreira. 1986. 106. Albe. S. Concentration of thermal vacancies in metallic nanoparticles. and P. 2003. 3237–3244. ISBN 0-07-016313-8 M. and E. J. and I. 1996. Rabenberg. pp. McGraw-Hill. and F. pp. Inc. De Hoff. J. 1995. S. C. T. L. Institute of Physics. P. 88. Pippel. 51. properties. Muller. C. and R. On the nucleation of partial dislocations in nanoparticles. Woltersdorf. 2008. E. C. Wetjen. 2007. Thermodynamics in materials science. Lamber. Carlton. Jaeger. Surface Science. 55.. Introduction to solid-state physics. J. Size dependence of the lattice parameter of small particles. pp. Kittel. and K. Cammarata (eds. Introduction to nanotechnology. Owens. Physical Review B. Philosophical Magazine Letters.). pp. ISBN 0-471-07935-9. WileyInterscience. 1993. and applications. . Edelstein. A. 6th ed. R. John Wiley & Sons. 64–69. 1981. Nepijko. 10968–10971. R. 715–724. Poole. Dependence of lattice parameters of small particles on the size of nuclei. A. Acta Materialia. Nano materials: Synthesis.Further Reading 197 FURTHER READING C.