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4
Experimental Methodologies for the
Characterization of Nanoparticles
O U T L I N E
Engineered Nanoparticles
http://dx.doi.org/10.1016/B978-0-12-801406-6.00004-2 125 Copyright © 2016 Elsevier Inc. All rights reserved.
126 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
1. INTRODUCTION
Characterization is defined as the study of a
material’s features, such as chemical composition
and various physical, chemical, electrical, and
magnetic properties. Because the physicochem-
ical properties of nanoparticles vary exponen-
tially with variations in their size, the accurate
characterization of nanoparticles is critical to
their applications. The methods commonly
used for nanoparticle characterization are listed
in Figure 1. In general, nanoparticle properties
can be divided into the following groups: sur-
face, physicochemical, electronic, mechanical, FIGURE 1 A list of methods commonly used for charac-
magnetic, and thermodynamic properties. terization of different properties of nanoparticles. AAS,
atomic absorption spectroscopy; AES, auger electron spec-
The indices commonly measured for assess- troscopy; AFM, atomic force microscopy; APM, atomic probe
ing a nanoparticle’s chemical properties include microscope; APT, atomic probe tomography; BET, Brunauere
its atomic and molecular composition, element EmmetteTeller; CFM, chemical force microscopy; DSC, dif-
analysis, and determination of surface function- ferential scanning colorimeter; DTA, differential thermal
alization. Surface is characterized by determina- analysis; EDX, energy dispersion X-ray spectroscopy; EELS,
electron energy loss spectroscopy; EPMA, electron probe
tion of surface area, volume, purity, electronic microanalysis; ES-DMA, electrospray differential mobility
structure, functional groups, and the particle’s analysis; FS, fluorescence spectroscopy; ICP, inductivity
shape, texture, and roughness. Assessment of coupled plasma spectroscopy; LEED, low-energy electron
physical properties includes the determination diffraction; LSRP, localized surface plasmon resonance;
of dispersion and aggregation, size and distribu- MFM, magnetic force microscopy; NC, nanocalorimetry;
NMR, nuclear magnetic resonance; NRA, nuclear reaction
tion, and mechanical properties. Thermody- analysis; RBS, Rutherford back scattering; RS, Raman spec-
namic properties are assessed by measuring troscopy; SANS, small-angle neutron scattering; SAXS,
melting temperature, melting enthalpy, melting small-angle X-ray scattering; SEM, scanning electron micro-
entropy, evaporation temperature, Curie tem- scopy; STM, scanning tunneling microscope; STEM, scanning
perature, Debye temperature, and specific heat transmission electron microscopy; TEM, transmission elec-
tron microscopy; TGA, thermal gravimetric analysis; UPS,
capacity. Mechanical properties are assessed by ultraviolet photoemission; UV/Vis, ultraviolet/visible spec-
measuring magnetic susceptibility, magnetic trometry; XRD, X-ray diffraction; X/UV PS, X-ray or UV
moment, and hysteresis. photoelectron spectroscopy.
2. NANOPARTICLE ENUMERATION, SIZE, AND SHAPE 127
The physicochemical, optical, and electronic calibration, use of electrolyte as the medium
properties of nanoparticles are dependent on (limited to hydrophilic particles), and low-particle
their size and surface properties. A 2-nm particle concentration. In addition, errors may occur with
may have different electronic and surface proper- porous particles, particles below the minimum
ties than a 10-nm particle. Surface functionalized detectable size go unnoticed, and there is diffi-
nanoparticles may exhibit different properties culty with high-density materials.
than the corresponding bare particles. Therefore,
their size measurement is essential to ensure
2.2 Scanning Electron Microscopy
reproducible beneficial and/or toxic effects. In
this chapter, some of the important methods Scanning electron microscopy (SEM) with a
used for nanoparticle characterization are secondary electron detector can visualize crystal
described. shape, surface morphology, dispersed and
agglomerated nanoparticles, and surface func-
tionalizations (Lee et al., 1996; Montesinos
2. NANOPARTICLE et al., 1983). SEM can examine each particle,
ENUMERATION, SIZE, AND SHAPE including the aggregate particles, individually;
thus, the method is considered to be an absolute
2.1 Particle Counter measurement of particle size. It can be coupled
to image analysis computers for examination of
2.1.1 Conductivity Counters (Rosse and
each field for particle distribution. However,
Loizeau, 2003; Beyer, 1987)
the depth of focus is only 0.5 mm at 1000 and
Conductivity (Coulter) counters consist of the diffraction effects increase with small parti-
two chambers. Nanoparticles are suspended in cles, which causes blurring at the edges in the
an electrolyte solution and placed in the sample determination of particles.
chamber, while an electrolyte alone is placed in a Field emission scanning electron microscopy
reference chamber. Then, the nanoparticle solu- (FESEM) has narrower probing beams at low
tion passes through the electrolyte solution. As and high electron energy, so it provides improved
the nanoparticle solution passes through the spatial resolution while minimizing sample dam-
electrolyte solution, a change in conductivity age. The in-lens FESEM provides topographical
occurs and is measured. The difference in con- information at magnifications of 250-1,000,000
ductivity is a function of the particle size. with ion-free images. FESEM allows detection of
small-area contamination spots at electron-
2.1.2 Condensation Particle Counters
accelerating voltages, compatibility with energy-
In this method, nanoparticles are drawn in an dispersive X-ray spectroscopy, application of
aerosol sample continuously through a heated low kinetic energy electrons closer to the immedi-
saturator. Inside, alcohol or water is vaporized ate material surface, and elimination of con-
and the vapor diffuses into the sample stream. ducting coatings on insulating materials.
The aerosol sample saturated with the liquid
vapor becomes supersaturated and ready to
2.3 Laser Diffraction
condense. Nanoparticles serve as a condensation
area for the vapor; thus, they grow in size as their When a laser beam is passed through nanopar-
optical density is recorded. ticles, the photons are scattered (particle prop-
The advantages of counting methods include erties) or diffracted (wave properties), reflected,
measurement of true volume distribution and and/or transmitted. In this method, the diffracted
high resolution and a wide range of sample mea- light is detected over a range of angles in the
surements. The disadvantages include a need for forward direction (Lee and Groves, 1981).
128 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
The angles of diffraction are inversely related to flow similar to liquid chromatography, but
the particle size. The advantages of laser diffrac- without a stationary phase. The lower channel
tion include nonintrusive analysis, use of a low po- wall is made of a frit covered with an ultrafiltra-
wer laser beam, rapid assay time, precise and wide tion membrane, which is impermeable to the
working range, absolute measurement without sample (Giddings, 1993). Because of a force field
calibration, and versatility. However, it is expen- perpendicular to the channel flow, the particles
sive, all measurements are based on the volume concentrate according to their size in the direction
measurement assuming spherical particles, and of the lower accumulation wall. The particles
there must be a difference in the refractive indices closer to the accumulation wall are transported
of the particles and suspending medium. slower than those higher up in the channel,
causing smaller particles to elute first. The mean
2.4 Polarization Intensity Differential square radius can be calculated from first princi-
Scattering ples, if the Rayleigh-Debye-Gans approximation
holds (Wyatt, 1993). Sizes can be calculated
Polarization intensity differential scattering without any concentration information from light
(PIDS) is used in line with the conventional laser scattering alone. However, the size and the refrac-
diffraction sample cell. The polarized light of tive index increment can be used to calculate
three different wavelengths is scattered by the concentration (Wyatt Technology, 1998).
sample and recorded at six different angles.
PIDS is claimed to be especially sensitive for
scattering caused by the smallest particles (Bott 3. CHEMICAL ANALYSIS
and Hart, 1991). OF NANOPARTICLES
FIGURE 2 Atomic probe field-ion microscopy (APFIM). (A) APFIM consists of a combination of a field-ion microscope
(FIM) and a detector (either time-of-flight mass spectrometer of a single-ion sensitivity and/or a phosphor screen). FIM con-
tains a specimen tip, an imaging gas such as Ne or He (1), a microchannel plate (2) with a pore-gap (3), the imaging gas ionizes
and desorbs the atoms (4) that passes through the pore-gap. The ions are detected through the time-of-flight detector (5). A
unique feature of the atom probe compared with the other analytical instrument is its extremely high spatial resolution and
the equal detection efficiency for light elements. (B) The phosphor image of individual particles with different configurations.
Each and every ionized particle is visible. Reprinted from Klapetek et al. (2011) with permission.
3. CHEMICAL ANALYSIS OF NANOPARTICLES 129
a time-of-flight mass spectrometer (TOF-MS),
and a power supply (Miller, 2000). When a high
electric field is applied on the surface of a probe’s
tip, imaging gas (such as He) atoms are ionized
and fluoresce the phosphor screen (Hono and
Murayama, 1997; http://nims.jp/apfim/apfim/
apfim.html). Higher electric fields also ionize FIGURE 3 Components of inductivity coupled plasma
the surface atoms that enter the time-of-flight (ICP) mass spectroscopy. Details are described in the text.
(TOF) chamber via an aperture of 0.5e5 nm.
The mass/charge ratio is measured by a mass can be applied to solutions, solids, and gases.
spectrometer. Because atoms always evaporate A typical configuration of an ICP-MS is shown
from the surface, the spatial resolution of the in Figure 3.
method is in the direction of a mono- Specimens (solutiondvaporized using a
atomic layer. The method provides extremely nebulizer, solidsdsampled using laser ablation
high spatial resolution and element characteriza- and gasesdsampled directly) are introduced
tion. Figure 2(B) shows the distribution of into an argon plasma consisting of electrons
nanoparticles scanned with no convolution. and positively charged argon ions. In the plasma,
the material splits into individual atoms that lose
3.2 Atomic Absorption Spectroscopy electrons and become positively charged ions
(anions are not detected by ICP-MS). The positive
Atomic absorption spectroscopy (AAS), in ion beam enters a quadrupole mass analyzer
both flame and electrothermal modes, is one of where the ions are separated according to their
the best methods for determination of the metal mass/charge (m/z) ratio. After passing the
concentrations in various specimens that dis- quadrupole, the ions hit a special mass detector
solved in acid (Kalbasi and Mosaddegh, 2012). that detects ions at the higher and lower range.
Separation, preconcentration, and dissolution ICP-MS, because of its excellent elemental sensi-
of samples are the vital steps in many proce- tivity and specificity, is an ideal detection tech-
dures, especially in the case of low-metal concen- nique for the characterization of metal-based
trations. AAS is relatively sensitive to Pd and Rh engineered nanoparticles. It allows simultaneous
(Scaccia and Goszczynska, 2004) and has been quantitative and confirmatory analysis of almost
used for the determination of metal levels in 100 metals in various matrices. In the single-
nanoparticles (Kalbasi and Mosaddegh, 2012; particle analysis mode, ICP-MS may decipher
Budiman et al., 2010). more information (dissolved nanoparticles, pres-
ence of impurities, decay with time, etc.) in a
relatively short time.
3.3 Inductively Coupled Plasma Mass
Selected references for detailed information
Spectrometry on the application of ICP-MS in characterizing
Inductively coupled plasma mass spectrom- metal nanoparticles include the following:
etry (ICP-MS; Figure 3) is a sensitive method Telgmann et al. (2014), Tadjiki et al. (2013),
for analysis and confirmation of metal ions Crayton (2012), Daniela et al. (2012), Mitrano
with a high linear dynamic range (Allabashi et al. (2012), Gschwind et al. (2011), Helfrich
et al., 2009). It is capable of analyzing and Bettmer (2011), Jimenez et al. (2010), and
almost all elements in the periodic table and Allabashi et al. (2009).
130 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
FIGURE 4 Components of matrix-assisted laser desorption (MALDI) time-of-flight (TOF) mass spectrometry (MS).
(A) Samples are mixed with a matrix and spotted onto a MALDI disc that is then placed into the MALDI chamber. A laser
beam desorbs and ionizes the specimen that enters into the TOF chamber. Ions get separated according to their m/z ratio
and detected by a mass analyzer. In TOF/TOF equipment, individual ions, after detection, enter into another TOF, in which
it is fragmented and the secondary ions are analyzed. M, matrix; S, sample; 1e5, primary ions in TOF1; ieiv, secondary ions
from TOF2. (B) Mass spectrum of polymeric nanoparticles. Each peak represents the individual ions. Reprinted from Bootza et al.
(2005) with permission.
3. CHEMICAL ANALYSIS OF NANOPARTICLES 131
FIGURE 5 Rutherford backscattering spectroscopy (RBS). (A) Principle of RBS. Nanoparticles are bombarded with high-
energy aHe beams that are either reflected by the surface atom or penetrate into inner layers and then are reflected by the inner
atoms. The reflected atoms are screened and the reflection angle is measured. The procedure provides atomic configuration at
different depths. (B) 1 MeV Heþ RBS spectra of (a) a planar Au layer with thickness d0 and (b) a tetragonal array of Au nano-
bricks with height d0 and width “a,” for different sample tilt angles (Zolnai, 2013). The solid lines are the simulation with best
RBS fit of the parameters d0 and “a,” respectively. The surface edge and depth scale for Au is indicated. At a 7 tilt angle, both
samples exhibited inverted parabolic curves. The RBC spectral characteristics are highly dependent on the nanoparticle shape.
Reprinted from Zolnai (2013) with permission.
FIGURE 10 Application of AFM in determining the surface properties of 20- and 100-nm polystyrene nanoparticles. (A)
The size distribution of nanoparticles. The 20- and 100-nm particles were used in this study. (B) AFM view of a mixture of 20-
and 100-nm nanoparticles. (C) A 3D reconstruction of the AFM data; the 20-nm particles are shown in the background.
Reprinted from Hoo et al. (2008) with permission.
4. SURFACE ANALYSIS 135
by a volumetric or continuous flow procedure
according to Eqn (1):
P 1 ðc 1ÞP
¼ þ (1)
VðP0 PÞ Vm c Vm cP0
In this equation, P is the partial vapor pres-
sure of adsorbate gas in equilibrium with the
surface at 77.4 K (b.p. of liquid nitrogen), P0 is
the saturated pressure of adsorbate gas, Va is FIGURE 11 Chemical force microscopy (CFM). CFM is
similar to the AFM, except that the tip is coupled to a reactive
the volume of gas adsorbed, Vm is the volume chemical group that repels or attracts the chemical moieties of
of gas adsorbed to produce an apparent mono- the surface. This allows formation of the chemical profile of a
layer on the sample surface, and C is a dimen- surface.
sionless constant related to the enthalpy of
adsorption of the adsorbate gas on the powder
sample. The P/V(P0 P) versus P/P0 plots 4.5 Low-Energy Electron Diffraction
give a straight line of slope (c 1)/VmC and an
intercept of 1/VmC. Therefore, Vm ¼ (1/slope þ Low-energy electron diffraction (LEED) is an
intercept). Vm represents the volume of gas excellent method to study surface reconstruction
adsorbed on the surface. Using Vm, the surface (defined as the atoms near the surface that may
area can be calculated using the following be disturbed from their equilibrium positions
equation: in the bulk). The surface reconstruction changes
the relative positions of the surface- and near-
PVm N0 sVm surface atoms. LEED involves bombardment of
A ¼ $N0 s ¼ (2)
RT 22400 the surface with low-energy electrons (approx.
Here, N0 is Avogadro’s number and s is the 10e200 eV, the electron energy is gradually
area of the molecule. The method is described increased or decreased) and observation of dif-
in detail elsewhere (http://www.freestd.us/ fracted electrons as spots on a retarding-field
soft/258183.htm). analyzer to detect the electrons. The relative posi-
tion of the spots on the screen shows the surface
crystallographic structure. The diffracted spots
4.4 Chemical Force Microscopy will move as the energy of the incident electrons
Chemical force microscopy (CFM) is a modifi- changes; the intensity of the spots as a function
cation of AFM in which the tip is chemically of incident electron energy characterizes surface
modified (specific chemical groups are attached reconstructions (Figure 12). LEED has been used
to the tip so that they can interact with specific for surface characterization of nanoparticles
chemical groups of the nanoparticles) to make (Gulde et al., 2012; Kamimura and Dobash,
them sensitive to specific chemical interactions 2012; Gavaza et al., 2007; de la Figuera et al.,
(Figure 11; Frisbie et al., 1994; Noy et al., 1997). 2006; Bauer, 1994; van Hove and Tong, 1979).
By using chemically functionalized tips, CFM The retarding field analyzer consists of a
can quantify forces between different molecular series of concentric hemispherical grids. The first
groups, probe surface free energies on a nano- grid is usually grounded and the remaining
meter scale, determine pKa values of the surface grids have voltage applied to them. When a sam-
acid/base groups locally, and map the spatial ple is struck by a beam of electrons, some elec-
distribution of specific functional groups and trons are diffracted by the sample toward the
their ionization state. grids. An electron can pass through a grid or
136 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
FIGURE 14 Principle and application of low-energy ion scattering (LEIS). (A) When a positively charged ion strikes a
particle, it is scattered by the nucleus of the surface atom. The scattered ion has lower energy than the incident ion. The released
energy is either transferred to another atom or released as a photon (hn). In LEIS, the surface atom are not ejected from the
particle. (B) The ratio of the scattered particle energy (Es) to the incident particle energy (E0) is related to (i) mass of the incident
and the scattering atoms and (ii) the critical angle. (C) Mechanism of shadowing. When a flux of positively charged ion beams
approaches an atom, the nucleus repulses and bends the incident beams that interact with the nonscattered beams. Thus, an
inverse parabolic area (the shadowing area) without ions develops. (D) Blocking: If the ions penetrate and strike the inner-
layer’s electron, the scattered ions approach the shadowing area of the surface atoms. The secondary scattered ions will not
penetrate the shadowing area. The surface atom, therefore, blocks the ions scattered by the inner atom. (E) LEIS scan of
Cu(i), Cu(ii) and Sn-deposited Cu(iii). Cu{112} exhibited a signal block at regular intervals, indicating deeper penetration of
the incidence ions. Cu{011} exhibited poor blocking, suggesting poor penetration of the incident ions. Cu-Sn{011} completely
lacked blocking, suggesting that Sn deposition occurred onto the crystal surface. Reprinted from Walker et al. (2005) with
permission.
138 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
and incident ion energies and the angle through described by Bragg’s law for simple scattering:
which the ions are scattered (q) are used to char- nl ¼ 2d sin(q), in which “n” is an integer, l is
acterize the ions (Figure 14(B)). For details, the wavelength, d is the vector representing the
please review the following website: http:// displacement between reflection sites, and q is
xpssimplified.com/ion_scattering_spectroscopy. the angle between the reflected ray and the plane
php and the publications: Baer et al. (2012, 2013), formed by the material’s surface (Kirschbrown,
Bonatto et al. (2012), and Shoji et al. (1989). 2007; Glatter and Kratky, 1982; Lifshin, 1999;
Figure 14(C) shows that shadowing and block- Guinier et al., 1995). X-ray interacts with the sur-
ing are key aspects of IS. A beam of primary face particle’s electron clouds; thus, inhomoge-
positively charged ions, upon approaching the neity in the electron density will affect the
nucleus, are repulsed and create an inverse para- scattering pattern. In addition, scattering falls
bolic area, known as shadowing area, where no off with the incident beam angle. Therefore, at
ions will be found. small angles (<10 ), the inhomogeneity in the
If another atom, known as the blocking atom, electron clouds can be observed, which will pro-
is in the path of scattered beams, it will create vide information about the size and shape of
another inverse parabolic blocking area that macromolecules in the sample (Kirschbrown,
will reflect the secondary ions (Figure 14(D)). It 2007). Neutrons interact with the nucleus; there-
is important to remember that (1) the surface sig- fore, their scattering is independent of the inci-
nals do not show any blocking because of the dent angle. However, neutron scattering is
absence of a blocking atom, (2) the surface atoms different for each isotope. The composition of a
may block signals from inner atoms and (3) low-angle scattering apparatus is shown in
blocking will occur when the blocking atom is Figure 15(A), while the results of an experi-
in the path of the secondary ions. Figure 14(E) mental study are shown in Figure 15(B) (left:
shows the blocking curves for the surface of Cu SAXS, right: SANS).
(112 incidence) (top, (i)), Cu (011, incidence) In general, wide-angle X-ray scattering
(middle, (ii)), and Sn (011 incidence) bottom, (WAXS) is used to determine a crystal structure
(iii). The Cu (112) signal exhibits periodical on the atomic length scale, while SAXS or
blockings (sharp dip in scattering), Cu (011) SANS provide fast measurement of nanoparticle
exhibited minor blocking, while Sn (011) size distributions (Moglianetti et al., 2014;
exhibited no blocking. Walker et al. (2005) put Agbabiaka et al., 2012, 2013; Disch et al., 2012;
these and other data together and proposed the Prabhu and Reipa, 2012; Zheng et al., 2012; de
crystal structure for Cu (100). la Venta et al., 2009; Masona and Lin, 2007;
Pozzo and Walker, 2007; Nagao et al., 2004;
Chu and Liu, 2000).
4.7 Small-Angle X-ray Scattering and
Small-Angle Neutron Scattering
4.8 Ultraviolet-Visible Light
The principles of small-angle X-ray scattering
(SAXS) and small-angle neutron scattering
Absorption Spectroscopy
(SANS) are that a collision between an incoming As discussed in Chapter 3, electrons, depend-
wave (X-ray for SAXS and neutrons for SANS) ing upon their orbital energy, exhibit natural
and a surface particle results in scattering of vibrational frequency. When electrons encounter
the waves in all directions. As the reflected a light wave of a frequency matching their vibra-
waves interfere with one another, there will be tional frequencies, those electrons will absorb the
constructive interference along certain angles, energy of the light wave and acquire a vibra-
causing peaks to appear. This process is tional motion. The vibrating electron interacts
4. SURFACE ANALYSIS 139
FIGURE 15 Principle and application of small-angle X-ray scattering (SAXS) or neutron scattering (SANS). (A) X-ray
photon rays or neutron rays, upon encountering a specimen, penetrate them and then get scattered. In SAXS or SANS, photons
or neutrons exhibiting less than 3 scattering are detected. (B) Two dimensional-detector images of a SAXS (left side) and a
SANS (right side) patterns of tripalmitin nanodispersions. The first interference peaks due to the particle stacking are marked
by black arrows. The reflections are marked by white arrows. In the X-ray image, the broad shadow of the beam stop for the
primary beam is visible. Reprinted from Bunjes and Unruh (2007) with permission.
with the neighboring electrons and converts the example, an aqueous solution of bulk gold and
vibration into heat energy. Absorption spectros- bulk silver exhibited maximum absorption at
copy, therefore, refers to the measurement of the 580 and 430 nm, respectively. However, 20-nm
light absorption by a material as a function of the gold and silver nanoparticles exhibited
wavelength. The visible region of the spectrum is maximum absorption at 540 nm (another strong
in the wavelength range of 380 nm (violet) to absorbance occurs at 450 nm) and 390 nm,
740 nm (red), and the near-ultraviolet (UV) re- respectively. Gold nanoparticles absorb near
gion extends to wavelengths of about 200 nm. the wavelengths of 520 and 450 nm, which ap-
The UV-visible spectrophotometer analyzes pears to be due to the s-p (conduction band)
over the wavelength range of 200e900 nm. Ab- and d-s (interband) transitions of electrons,
sorption increases as the matter’s electrons respectively. As the size of gold nanoparticles
encounter light of a wavelength matching the increased from 10 to 100 nm, their absorption
electrons’ vibrational frequency. maxima increased from 400 to >560 nm with
Because the electronic energy states vary from broadening of the peak. Because the wavelength
one atom or molecule to another, the radiation of a light wave is inversely related to its energy,
absorbed by one substance will usually differ an increase in the nanoparticle size absorbs radi-
from that absorbed by another substance. For ation of lower energy. This unique optical
140 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
4.10 Energy-Dispersive
X-ray Spectroscopy
SEM uses a focused beam of high-energy elec-
trons to generate a variety of signals at the surface
of solid specimens, including nanoparticles. The
incoming electrons also eject electrons from the
specimen, resulting in the formation of a posi-
tively charged “electron hole” in the occupied
bands. The “holes” attract electrons from higher
states. The movement of electrons from a higher
state to the “hole” results in the emission of
X-rays. The energy characteristic of X-rays is
unique to the atoms in nanoparticles. Energy-
dispersive X-ray spectroscopy (EDX) detects
FIGURE 17 Components of scanning electron micro- X-rays emitted from the sample to characterize
scopy (SEM). SEM consists of an electron source that fires a the elemental composition of the analyzed
beam of electrons at the object under examination. The volume (Epicier et al., 2010; von Bohlen et al.,
beam goes through a couple of lenses made of magnets
capable of bending the path of electrons. By doing so, the
2010; Patri et al., 2009; Herzing et al., 2008).
lenses focus and control the electron beam, ensuring that
the electrons focus onto the specimen. The sample chamber
is sturdy and insulated from vibration. The sample chambers 5. PHYSIOCHEMICAL PROPERTIES
also manipulate the specimen, placing it at different angles
and moving it in all directions. SEM contains various types
of detectors capable of (1) producing the most detailed im- 5.1 Atom Probe Tomography
ages of an object’s surface and (2) revealing the composition
of a substance. The key point is that SEMs require a vacuum
Atom probe tomography (APT) offers both 3D
to operate. Without a vacuum, the scattered electron beam imaging and chemical composition measurements
would distort the surface of the specimen. at the atomic scale (around 0.1e0.3 nm resolution
142 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
in depth and 0.3e0.5 nm laterally). In this which limits its sensitivity (Chung et al., 2008;
technique, the sample is adsorbed onto a http://probelab.geo.umn.edu/electron_micro
sharp tip that is applied with high DC probe.html).
voltage (5e20 kV), which induces a very
high electrostatic field at the tip surface (Devaraj
et al., 2014; http://www.cameca.com/instru 5.3 Electrospray Differential
ments-for-research/atom-probe.aspx). Under Mobility Analysis
laser, a few atoms are evaporated from Electrospray differential mobility analysis
the surface and projected onto a position- (ES-DMA) analyzes the effective particle size of
sensitive detector (PSD) with high detection aerosolized nanoparticles by measuring their
efficiency (Figure 18). APT has been extensively electrical mobility under ambient conditions.
used for characterization of nanometer-sized par- The method is based on the principle that the
ticles (selected references: Chen et al., 2013; mobility velocity (V) of a charged particle is pro-
Dawahre et al., 2013; De Luca et al., 2013; Diercks portional to the electric field (E) according to the
et al., 2013; Du et al., 2013a,b). equation V ¼ ZE where Z is the proportionality
constant (Guha et al., 2012; Flagan, 2008). Z can
5.2 Electron Probe Microanalysis be defined as CcDm/Dm, where Dm is the
mobility equivalent spherical diameter of a parti-
A beam of accelerated electrons is focused on
cle and Cc is the Cunningham slip factor (Kim
the surface of a specimen, resulting in generation
et al., 2005), which corrects for the nonslip
of X-rays characteristic of the specimen. The rays
boundary condition. For particles <50 nm Cc is
are detected at particular wavelengths and their
inversely proportional to their diameter, while
intensities are measured to determine concentra-
for larger particles, Cc increases linearly with
tions. All elements (except H, He, and Li) can be
increasing particle diameter (Dm). Thus, for
detected because each element emits a specific
very small particles (<50 nm), the differential
set of X-rays. This analytical technique has a
mobility analysis separates particles based on
high spatial resolution and sensitivity, and indi-
differences in the particle area, whereas for
vidual analysis time is reasonably short,
larger particles (>100 nm) separation is based
requiring only a minute or two in most cases.
on differences in diameter (Figure 20).
As shown in Figure 19, multiple detectors can
The benefits of ES-DMA include the following:
be assembled on the platform for multiple ana-
lyses. Additionally, the electron microprobe 1. ES-DMA provides a simple means to
can function like SEM and obtain highly magni- determine the nanoparticle size, and it has
fied secondary- and backscattered-electron im- shown excellent agreement with more
ages of a sample. The energy dispersive conventional imaging techniques such as
spectroscopy (EDS) system allows quantitative transmission electron microscopy (TEM) and
analysis by simply counting the X-rays received SEM (Grassian, 2008; Wacaser et al., 2007;
in the channels that correspond to a peak of in- Pease et al., 2007, 2008). ES-DMA does not
terest. It is also used for analysis of the chemical have any issues with bubbles in the colloid,
composition of metals, alloys, ceramics, and shows excellent accuracy (<10%) in the
glasses. The composition of individual particles particle size distribution, and resolves peaks
or grains and chemical changes on a small scale less than 1 nm apart (Allmaier et al., 2008;
can be assessed. A key disadvantage of EDS is Kinney and Pui, 1991). Dynamic light
that corrections must be made for overlapping scattering (DLS) and other indirect methods
peaks and the background noise is much higher, can have difficulty with nanoparticle size
5. PHYSIOCHEMICAL PROPERTIES 143
FIGURE 18 Atomic probe tomography (APT) in conjunction with scanning tunneling electron microscopy (STM) of Au
nanoparticles deposited over MgO. (A) STM images of a sample before and after APT analysis. (B) Ionic view of the APT
reconstruction where cyan points correspond to O, magenta to Mg, and yellow to Au. (C) Visualization of Au-rich regions.
(D) Proximity histogram plotted across the Au nanoparticles. (E) The distribution of Au (yellow (light gray in the printed ver-
sions)) and MgO (blue (gray in the printed versions)) ions. This suggests that APT provides three-dimensional characterization
of materials providing spatially resolved mass spectra at subnanometer spatial resolution and part-per-million level mass sen-
sitivities. Reprinted from Daveraj et al. (2014) with permission.
144 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
FIGURE 20 Electrospray differential mobility analysis (ES-DMA). The analyte dissolved in a volatile buffer solution is
injected into a fused silica capillary under pressure and then electrosprayed to produce multiply charged droplets containing
the analyte. The droplets are then mixed with air and the nebulized to achieve charged ions. A negative bias is applied to get
positive ions (if needed, negative ions can be collected by applying a positive bias). The ions are reduced and then detected as
described previously (Guha et al., 2012). Size distribution can be obtained using condensation particle counter or an
electrometer.
5. PHYSIOCHEMICAL PROPERTIES 145
5.4 Nuclear Magnetic Resonance while the nucleus aligns against the direction of
the applied field. As the strength of the negative
Nuclear magnetic resonance (NMR) spectros- field around the nucleus increases, a relatively
copy is a highly versatile methodology used to great strength of the magnetic field is required
study the structure of and interaction between for magnetization of nucleus. The hypothetical
molecules, the kinetics or dynamics of molecules, compound B (Figure 21(B)) has a less dense elec-
and the composition of biological and/or tron cloud (relatively unshielded) than com-
synthetic composites. The principle of NMR pound C (Figure 21(C)), which is highly
spectroscopy is based on nuclear magnetism. shielded. Thus, the nuclear spin of compound B
Because the nucleus is a positively charged par- flips (from þ1/2 to 1/2 state) at a relatively
ticle in a magnetic field, it acts as a tiny magnet weak applied field than compound A. The shield-
and tends to align as shown in Figure 21(A). ing effect generates a structure-specific response
As an example, a proton (1H), when placed un- in magnetic resonance imaging (MRI).
der a magnetic field, exhibits two possible align- The typical MRI equipment consists of a sam-
ments: either with the field direction (low-energy ple chamber sandwiched between two magnets
spin, þ1/2) or opposed to it (high-energy and connected to a radio wave (Figure 22). The
spin, 1/2). Energy is required to change the sample is placed into the chamber and the radio
more stable alignment (þ1/2) to the less stable wave is turned on. The magnetic field is
(1/2) alignment. increased gradually. At a critical magnetic field,
In magnetic nanoparticles, magnetization of the specimen’s nuclear spin flips, resulting in
protons depends upon the electron cloud around generation of the electrical current that is traced.
it. The negatively charged electrons, in a magnetic A spectrum is achieved that is detailed enough
field, spin in the direction of the applied field, to serve as a useful “fingerprint” for a chemical.
FIGURE 21 The principle of NMR spectroscopy. In the presence of a magnetic field, the nucleus acts as a tiny magnets and
tends to be aligned as shown in (A). When a proton (1H) is placed under a magnetic field, it exhibits two possible alignments:
low-energy spin (þ1/2) or high-energy spin (1/2). The electron cloud also responds to the magnetic field and aligns against
the field and protects the nucleus from the effects of the external field (B). Therefore, the density of electron cloud around the
nucleus is inversely related to a nucleus’s magnetization in a magnetic field. A relatively high field is needed to invert nuclear
spin from þ1/2 to 1/2 (C).
146 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
For chemicals that lack hydrogen atoms, the 5.6 Raman Spectroscopy
photon MRI will not generate a signal. A 13C
Raman spectroscopy, widely used for study-
NMR can be useful for such chemicals. NMR
ing the structure and properties of nanoparticles,
has been extensively used to characterize nano-
is based on the inelastic light scattering by mole-
particles (Cheng et al., 2012; Shao et al., 2010,
cules (Raman (1928) and Raman and Krishnan
2012; Issa et al., 2011; Mayer, 2005).
(1928), winner of the Nobel Prize in Physics in
1930). The incoming photons interact transiently
5.5 Nuclear Reaction Analysis with atoms and then scatter into the surround-
ings in all directions (detected by an RBS detec-
Nuclear reaction analysis (NRA) provides a
tor). During the brief interaction with
sensitive means to measure low-Z elements (e.g.,
molecules, photons lose energy to the interacting
carbon, nitrogen, oxygen, and boron) in nanopar-
atoms that emit g- and X-rays, imaged by the
ticles. In NRA, a specimen is bombarded with a
respective detectors. Because the laser beam
beam of heavy ions that induces a nuclear reac-
can be considered an oscillating electromagnetic
tion with nuclei in the nanoparticle atoms (EAG,
wave with frequency v0, its interaction with the
2007). The products of the nuclear reaction are
specimen induces an electric dipole moment
measured. NRA provides a simple way of
characterized by the equation P ¼ aE, where E
measuring the depth profiles by measuring the
is an electric field and a is the induced molecular
nuclear reaction yields as a function of the beam
polarity. The Raman effect causes a transient and
kinetic energy (Figure 23(A)). Because NRA
periodical deformity in the molecules; thus, mol-
is based on nuclear reactions, it is element
ecules start vibrating with the characteristic fre-
specific. The most commonly used beam in
quency “ym,” which is a measurable index. The
NRA is 3He. The method is nondestructive and
amplitude of vibration is called a nuclear
provides elemental composition and/or structur-
displacement. The laser excites molecules and
ednamely, the depth profiles from the surface re-
transforms them into oscillating dipoles
gion. Figure 23(B) shows back scattering (detected
(Figure 24(A)).
by an RBS detector) and penetration of the inci-
The oscillating dipoles emit light at three
dent ion in the specimen (DX region). When par-
different frequencies (Figure 24(A)): Raman-1,
ticles strike the specimen surface, they transfer
-2, and -3:
energy to the specimen atom and initiate a nu-
clear reaction, resulting in the release of g- and Raman-1: A molecule absorbs a photon with
X-rays that can be captured by particle-induced frequency “y0.” The excited molecule returns
5. PHYSIOCHEMICAL PROPERTIES 147
FIGURE 23 Principle of the nuclear reaction assay (NRA). (A) When low Z atoms are bombarded with 3He, it is converted
into 2H, 1H, and 4H. In addition, some energy is released as X- and or g-rays. 3He is detected by an NRA detector, while
backscattering can be detected by the RBS detector. (B) Release of X- and g-rays during nuclear reaction. The 3He reaction
(n þ 3He / 3H þ 1H) generates 0.764 MeV of energy that is released as g- and X-rays. As 3He (energy E0) strikes the nanopar-
ticle surface, it is reflected from the surface (E1) or reflected after penetration (E2 and E3). The deeper the 3He penetrates, the
more energy it loses; thus, the exiting particle will have lower energy. Reflection, g- and X-rays can be measured using
RBS, PIXE, and PIGE detectors, respectively.
back to the same vibrational state and emits frequency. In Stokes scattering, v0 is higher
light with the same frequency (v0) as the than vs.
excitation source. This type of interaction is Raman-3: A photon with frequency y0 is
called an elastic Rayleigh scattering absorbed by a Raman-active molecule already
(Figure 24(B)). in the excited vibrational state. The excessive
Raman-2: A photon (with frequency y0) is energy of the excited Raman active mode is
absorbed by a molecule at the basal released, the molecule returns to the basic
vibrational state. Part of the photon’s energy vibrational state, and the resulting frequency
is transferred to the Raman-active mode with of scattered light goes up to v0 þ vm. This
frequency ym, and the resulting frequency of Raman frequency is called the anti-stokes
the scattered light is reduced to y0 ym. This frequency. In anti-stokes scattering, v0 is lower
Raman frequency is called the Stokes than vs.
148 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
FIGURE 24 Principle and application of Raman spectrometry. (A) When a molecule absorbs high-intensity laser photons,
an oscillating polarization in the molecules is formed at the virtual energy state or VES. The oscillating molecule emits photons
of different wavelengths (Raman scattering) that can be measured by a detector. (B) Description of Rayleigh, Stokes, and anti-
Stokes scattering (details are described in the text). Abbreviations: VES, virtual energy state that is a transitional energy state,
1st Vib; S, 1st vibrational energy state; V0, vibrational energy of the incident laser photons; Vs, vibrational energy of scattered
photons; Fluo., Fluorescence; Phot., Photons. (C) Principle of surface enhanced Raman spectroscopy (top). In traditional Raman
spectroscopy, the inelastic scattered photons (Rw) are in low abundance compared to the Rayleigh scattered photons (Sc).
However, when the specimen is placed on plasmonic metal nanoparticles (Sp) (middle) or placed within a gap-plasmon
(Gp) (bottom), the Raman vibrational energy couples with the metal’s plasmon, resulting in amplification of the Raman scat-
tering. (D) Comparison of the Raman spectra of purified SWNTs acquired with 2.54 and 1.96 eV excitations for (1) G band (tan-
genital vibration related to the graphene), (2) D band (related to the disorder-induced vibrations or defects) and (3) radial
breathing mode (RBM) band modes ((a) for 1 and 2, and (b) for 3). The G/D ratio deciphers the purity of the carbon nanotubes
(>0.5 G/G ration indicated presence of large defects). Reprinted from Dillon et al. (2004) with permission.
A key disadvantage of traditional Raman et al. (1974) improved the method’s sensitivity
spectroscopy is its low sensitivity, which has 106 folds. The single-atom SERS (Nie and Emory,
prevented its application in chemical biological 1997; Kneipp et al., 1995, 1997, 1998) has allowed
systems. Developments of surface enhanced measurement of the signal in a single atom
Raman spectroscopy (SERS) by Fleischmann (Figure 24(D)). These improvements have
5. PHYSIOCHEMICAL PROPERTIES 149
allowed widespread application of Raman spec- • Detection of various biomolecules (McGeehan
troscopy, as follows. et al., 2011; Carey, 1983; Lord and Yu, 1970)
• Applications in multiplexed Raman imaging,
• Characterization of optical and electronic
which is capable of detecting multiple targets
properties of nanoparticles (Aleksandra et al.,
simultaneously (Li et al., 2014; Zavaleta et al.,
2014; Ferrari and Basko, 2013; Maher, 2012;
2014)
Soler and Qu, 2012; Alvarado et al., 2009)
• Tissue engineering (Perlaki et al., 2014)
• Identification of defects in carbon nanotubes
• Photothermal effect of metal nanoparticles
and fullerenes (Tachibana, 2013; Dresselhaus
(Bialkowski, 1996)
et al., 2010; Costa et al., 2008; Hennrich
et al., 2005)
• Scanning of nanoparticles in biological, 5.7 Scanning Tunneling Microscopy
food, and environmental samples (Zheng
Scanning tunneling microscopy (STM, for
and He, 2014; Giovannozzi et al., 2014;
which Gerd Binnig and Heinrich Rohrer
Nima et al., 2014; Mustafa, 2013;
received the Nobel Prize in 1986 for developing)
Hargreaves et al., 2008)
does not use a conventional microscope because
• Identification of normal and cancerous cells
it does not magnify the sample image. It consists
(Gonz alez-Solís et al., 2009, 2011, 2013;
Shangyuan et al., 2011; Rodriguez-L opez, of a fine electrically conductive tip (one atom at
the end of the tip) that traverses just above the
2009; Pichardo-Molina et al., 2006;
surface of an electrically conductive nanoparticle
Shafer-Peltier et al., 2002)
(Figure 25(A); Binnig and Rohrer, 1986; Bonnell
• As a minimally invasive screening tool
and Huey, 2001; Hu et al., 2009). When a voltage
for acute renal transplantation rejection
is applied to the tip, electrons from the nanopar-
(Chung et al., 2008, 2009; Tu and
ticles jump (called a “tunnel”) across the space
Chang, 2012; Han et al., 2009; Brown
between the tip and sample. The flow of
et al., 2009a,b)
FIGURE 25 Scanning tunneling microscope (STM). (A) The STM consists of a probe that can move up/down and side-
ways, a sample chamber, an electrical circuit to apply potential to the tip and an ampere meter to measure the current devel-
oped by the tunneling electrons. The probe tip consists of one or two atom(s). When the tip is placed within a picometer
(1012 m) on the surface of a nanoparticle and a small positive potential is applied to the tip, the electron can tunnel or
jump to the tip. Tunneling of the electron generates a current that is measured using an ammeter. (B) Repeatedly sliding
the tip sideways a small distance, then raising or lowering the tip to maintain a constant current, builds up a one-
dimensional profile of the surface height. Repeating the shifts and scans, over and over again, allows the creation of a two-
dimensional profile of the surface.
150 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
electrons generates a current that can be detected materials’ atomic number (Z-) and chemical
(Swartzentruber, 1996). As the tip moves along composition. The X-rays generated by the
the surface, its position is adjusted to make samples can be collected using an electron-
sure the tip’s distance from the surface remains disruptive X-ray spectroscopy detector. Elec-
constant. This keeps the current constant. The trons’ energy loss is detected using a Gatan image
movement of the tip is traced and recorded. filter to map the compositional and electronic
The detailed features are graphically displayed properties of materials.
on a computer screen.
The sensitivity of STM approaches that of
atoms and molecules. The method has been
5.9 Surface Plasmon Resonance
applied in determining the electronic properties Surface plasmon resonance (SPR)din addi-
of semiconductors (Figure 25(B)) and the nano- tion to becoming an important tool in bio-
particle’s surface characteristics (Moglianetti sensing technology, biochemistry, biology, and
et al., 2014; Datar et al., 2012; Shi et al., 2011; Xu medical sciencesdalso enhances the surface
and Chen, 2009; Chaing, 1997; Avouris, 1996; sensitivity of several spectroscopic measure-
Martel et al., 1996; Dai et al., 1996; Crommie ments, including fluorescence and Raman scat-
et al., 1993, 1995; Shen et al., 1995). tering. SPR has also found some applications
in the detection of molecular adsorption and
analysis of DNA, proteins, and metabolites.
5.8 Scanning Transmission
The aim of this section is to describe the princi-
Electron Microscopy ples and applications of SPR.
In scanning transmission electron microscopy Plasmon resonance is an interfacial phenome-
(STEM), a highly focused electron probe non in which light passing through a prism con-
is scanned across the material and various types taining a media of higher refractive index (n1) to
of scattering are collected as a function of posi- a media of lower refractive index (n2) is partly
tion. The transmitted electrons at a high scattering reflected and, depending upon the incidence
angle form high-resolution images, revealing the angle, partly refracted (Figure 26(A)). Above a
FIGURE 26 Principle and application of surface plasmon resonance. The details are described in the text.
5. PHYSIOCHEMICAL PROPERTIES 151
certain critical angle (qc) of incidence, the inci- Metal nanoparticles, especially gold and sil-
dent light is completely reflected and does not ver nanoparticles, have great potential for chem-
cross into another medium. This stage is total ical and biological sensor applications, due to
internal reflection (TIR). However, when the their plasmonic properties, unique spectral
incident light angle is below the critical angle, response to the local environment of the nano-
then part of the light wave is refracted into particle surface, and ease of monitoring the light
the medium with a lower refractive index signal due to their strong scattering or absorp-
(Figure 26(B)). However, the refracted beam re- tion (Kumar, 2012; Lee and El-Sayed, 2006; Hut-
mains at the surface in the form of an electro- ter and Fendler, 2004; Haes et al., 2004a,b; Haes
magnetic field, penetrating a short distance into and Van Duyne, 2002a,b, 2003a,b). An excitation
the medium of a lower refractive index, creating of the surface by polarized monochromatic light
an exponentially attenuating evanescent wave. If results in a strong scattering of light and appear-
another prism is placed close to (picometer dis- ance of surface plasmon, the frequency and in-
tance) the n1-prism, light refracts and passes tensity of which are characteristic of the type of
through the second prism (Figure 26(C)). The material (Hutter and Fendler, 2004).
wave function of the evanescent wave (kevan) For more information regarding SPR, please
can be explained by the equation shown in review the following manuscripts:
Figure 26(G).
When a layer of gold nanoparticles is placed be- • SPR and surface properties: Haynes et al. (2003),
tween the two media n1 and n2 Figure 26(E), and Haynes and Van Duyne (2003a), Schatz and
the incident light is monochromatic/p-polarized, Van Duyne (2002), Kahl et al. (1998), and
the intensity of the reflected light is reduced at a Freeman et al. (1995).
specific incident angle, producing a sharp drop • Optical filters: Haynes and Van Duyne (2003b),
in reflectance (Figure 26(F), broken line). This pro- and Dirix et al. (1999).
cess is called surface plasmon resonance, possibly • Plasmonic devices: Maier et al. (2001, 2003),
due to the resonance energy transfer between Andersen and Rowlen (2002), and Shelby
evanescent wave and surface plasmon. The et al. (2001).
resonance conditions are influenced by the speci- • Sensors: Shashkov et al. (2010), Amanda et al.
mens adsorbed onto the gold nanoparticles (2004), Haes et al. (2004a,b), Aizpurua et al.
(Figure 26(H)); therefore, in the presence of a (2003), Hirsch et al. (2003), Bailey et al. (2003),
specimen, the minimal reflectance may occur at Hase and Van Duyne (2002a,b, 2003a,b),
a different angle (Figure 26(I), solid black line). Riboh et al. (2003), Fritzsche and Taton (2003),
If another particle binds to the specimen (line Obare et al. (2002), Nath and Chilkoti (2002),
receptor-protein binding), there is a further and Mucic et al. (1998). Aslan et al. (2004) has
change in the angle at which minimal absorbance developed a nanogold-plasmon-resonance-
occurs (Figure 26(I), solid red (gray in print ver- based glucose sensor based on the
sions) line). A linear relationship exists between aggregation and disassociation of 20-nm gold
resonance energy and mass concentration of mol- particles. The plasmon absorption was shifted
ecules such as proteins, sugars, and DNA. The due to interaction of nanoparticle and glucose.
SPR, expressed in resonance units, is therefore a Hu et al. (2004) described a dielectric film
measure of mass concentration at the sensor chip (SiO2)-based novel ultrahigh-resolution
surface. This means that the analyte and ligand as- surface plasmon resonance biosensor having
sociation and dissociation can be observed, and 0.1 pg/mm2 sensitivity. This sensor can detect
ultimately rate constants as well as equilibrium the interaction of small molecules in low
constants can be calculated using SPR. concentrations. Chau et al. (2006) developed a
152 4. EXPERIMENTAL METHODOLOGIES FOR THE CHARACTERIZATION OF NANOPARTICLES
fiber-optic based localized surface plasmon et al., 2011; Tonti and Zanoni, 2009; Turner
resonance (LSPR) for sensing Ni2þ ion and and Al Jobory, 1962). Ultrahigh vacuum
label-free detection of streptavidin and facilitates sample cleanliness. A high-
staphylococcal enterotoxin B at the picomolar resolution electron energy analyzer
level using self-assembled gold nanoparticles. minimizes the spread of photoelectrons,
SPR has also been used for detection of allowing accurate determination of energies
explosives, such as trinitrotoluene (TNT) at and enhanced peak separation for accurate
the parts per trillion (ppt) level (Kawaguchi chemical identifications (Kumiko, 2009;
et al., 2007, 2008). Sensitivity was improved to Jablonski, 2000; Millard and Bartholomew,
ppt levels by LSPR using gold nanoparticles 1977; Kobayashi, 1976; Carlson, 1975).
and further signal amplification. • Electron binding energy and elemental
• Other applications of LSPR sensors are detection characterization of the surface: As described
of volatile organic compounds (Chen and Lu, earlier, electrons remain bound to a positively
2009; Cheng et al., 2007), hydrogen peroxide charged “hole” in occupied orbitals. The
(Filippo et al., 2009), and pathogens such as electronehole binding energy increases as the
Salmonella (Fua et al., 2009). distance from the nucleus decreases; thus,
electrons in the K-shell possess the highest
binding energy, while the valence electrons
5.10 X-ray or Ultraviolet
possess the lowest binding energy.
Photoelectron Spectroscopy
Photoelectrons are emitted when a molecule
In photoelectron spectroscopy, a specimen’s (M) is ionized by a beam of photons, in which
surface is bombarded with either X-rays (XPS; the molecule loses an electron:
for expulsion of K electrons) or UV photons M þ hn / Mþ(Eint) þ e, a reaction also
(UPS; for valance electron). If electrons absorb known as photoionization reaction. This
sufficient energy, they are expelled from atoms reaction occurs in three steps.
in the near-surface region (photoelectrons) of • The molecule absorbs photons and
the sample. The photoelectrons emitted by pho- activates valence or K-shell electrons.
tons are unique because they are ejected from • For absorption, the photon’s energy must
the valence or the inner orbits (such as K orbit) match the electron’s binding energy. The
and they have energies characteristic of the excited electron may dissociate from the
atom they came from. Thus, XPS may allow “hole,” leave the orbit, and travel to the
elemental and chemical determinations of the surface of the molecule. If the excited
nanoparticles. Compared to X-rays, UV pho- electrons collide with another particle, they
tons have lower energies and probe the elec- will lose energy.
trons in the outermost valence levels of the • The excited electron that escapes the
surface atoms. Thus, UPS yields information surface of the molecule into the vacuum
regarding the surface electronic structure. will be detected using appropriate
Many excellent reviews articles have described detectors.
applications of XPS and UPS in characterization
There is a linear relationship between the
of nanoparticles. Selected manuscripts include
photoelectron count and the electron binding
the following:
energy (photoelectron spectrum) coupled to the
• Chemical properties: Studies have evaluated the respective orbital energy (Figure 27). The energy
bonding environments of surface layers via spectrum of a photoelectron is unique for each
XPS and valence states via UPS (Techane atom. Therefore, XPS or UPS can characterize
5. PHYSIOCHEMICAL PROPERTIES 153
FIGURE 28 Principle and application of X-ray diffraction. (A) The scattering of X-rays by crystals. The intensity of the
scattered rays differs due to interference effects. (B) Bragg’s law. A crystal (each circle represents individual atom) is defined
as a set of discrete parallel planes separated by a constant parameter “d.” The incident X-ray photons would be reflected. If the
phase shift is a multiple of 2p (nl ¼ 2d sin qn) where n is an integer, l is the wavelength of incident-ray photons, d is the
spacing between the planes in the atomic lattice, and q is the angle between the incident ray and the scattering planes, the inter-
ference among the scattered rays would be constructive and Bragg’s peak will be generated. (C and D) Collection of data in
reflection and transmission modes, respectively.
moment exist. Paired and unpaired electrons paramagnetic contribution to the magnetic sus-
both revolve around the nucleus, exhibiting ceptibility (cA) using Eqns (3e5) shown below.
angular momentum and a net magnetic mo-
mentum. The electrons of each orbital exhibit a CLðDR DR0 Þ
cg ¼ (3)
spin quantum number denoted as ms, which is m 109
constituted by either upward (ms ¼ þ1/2) or cM ¼ M cg (4)
downward (ms ¼ 1/2) arrows. Thus, 2pz or- X
bitals contain þ1/2 and 1/2 electrons. The par- cA ¼ cM ca ðsince ca is negative;
(5)
ticles containing all paired electrons are called for paramagnetic particles cA > cM Þ
diamagnetic particles, and they do not exhibit
net magnetic moment (see Chapter 2). However, In this equation, cM is molar magnetic suscep-
when a particle, in addition to “paired electrons” tibility, cg is mass magnetic susceptibility, M is
also contains unpaired electrons (þ1/2 in the molecular weight, L is the sample length in cen-
absence of a field), the paired electrons cause timeters, m is the sample mass in grams, and C is
diamagnetic effects, while the unpaired electrons the balance calibration constant (different for
exhibit high anisotropy and cause paramagnetic each balance; printed on the back of the instru-
effects (S > 0). ment). DR is the difference in mass (or force) of
Diamagnetic particles, when placed between samples collected with and without magnetic
the poles of a strong magnet, exert a repulsion field. DR0 is the difference in mass (or force) of
on the applied field (tending to reduce strength blank glass tubes collected with and without
of the applied force). Because of repulsion, the magnetic field. The effective magnetic moment
diamagnetic particles experience weight loss (in (mEff) is calculated using the equation below (T
the Gouy balance; Saunderson, 1968) or repel is the temperature in K):
the magnetic poles (in Evans balance; Evans, pffiffiffiffiffiffiffiffiffi
1974). Their mass magnetic susceptibility (cg) mðEff Þ ¼ 2:828 cA T (6)
will be sum of the diamagnetic susceptibility The NMR method for the determination of
(ca). Because ca represents repulsive forces, it magnetic susceptibility and moment was first
has a negative value; thus, the diamagnetic sus- described by Evans in 1959 and then improved
ceptibility has a negative value. Unlike diamag- by Loliger and Scheffold (1972), Grant (1995),
netic particles, when a paramagnetic particle is and Piguet (1997). Evans (1959) devised
placed between the poles of a strong magnet, it Eqns (7) and (8) for calculation of mass magnetic
will experience an attraction for the field and susceptibility (cg) and molar magnetic suscepti-
weigh more with a Gouy balance or show greater bility (cM), respectively,
attraction of the magnetic poles with the Evans
balance. The cM value of a paramagnetic particle dV ðd0 ds Þ
cg ¼ þ c0 þ c0 (7)
is S (contribution of unpaired electrons or n0 Sf m m
paramagnetic effect or cA that has positive
values) þ (contribution of the paired electrons or p
dn M p d 0 d 0
s
p
ca that has negative values). Because cM ¼ cM ¼ þ c 0 Mp þ c 0 Mp
n0 Sf m Mp
cA þ (ca), cA > cM for paramagnetic particles.
Calculations: Mass (Gouy method) or force cdia
m ðfor bulk particlesÞ (8)
(Evans method) values are used to calculate
mass magnetic susceptibility (cg), which is con- However, later studies Grant (1995) and
verted in molar magnetic susceptibility (cM) and Piguet (1997) have proposed that, in smaller
6. MAGNETIC PROPERTIES 157
dilute solutions, ðd0 d0s Þ=Mp can be neglected (remnant flux force) and the specimen still remains
and mEff can be calculated using Eqn (9): partially magnetized. Then, the current must be
sffiffiffiffiffiffiffiffiffiffiffi reversed so that H increases in the opposite direc-
TMp dnp p
Sf mp dia tion to demagnetize the specimen. The amount of
mEff ¼ 2:828 þ S f m c0 c
Sf mp n0 Mp M field required to demagnetize the specimen is
called the coercive force (Figure 30).
ðfor bulk particlesÞ
If the reversed current increases further, the
(9) particle saturates in the opposite direction
Grant (1995) has shown that Eqn (9) is suit- (point 4). Then, if the current is reversed and
able only for bulk particles. He simplified increased, B increases, taking the path of 5, 6,
Eqns (8) and (9) into Eqns (10) and (11), respec- and 1. This magnetization journey from 0 to 1,
tively, which are more suitable for magnetic 2, 3, 4, 5, 6 and back to 1 is called the hysteresis
nanoparticles: loop. The hysteric loop is commonly studied us-
ing a “loop tracer,” as shown in the block dia-
p dnp Mp gram (Figure 31). The tracers consist of four
cM ¼ cdia
m ðfor nanoparticlesÞ (10)
n0 S f m basic parts (Kulik et al., 1993):
rffiffiffiffiffi!1=2 • Specimen coil: nanoparticles or bulk particles.
dn • Excitation system: High current power
mEff ¼ 0:138 ðfor nanoparticlesÞ
c amplifier, Helmholtz coil pair, control of
(11) current strength and direction.
p
In these equations, cM is the paramagnetic
contribution toward cM, dv is the shift in NMR
frequency from the value found in pure solvent
(>0 for paramagnetism and <0 for diamagne-
tism), m is the concentration of the solute, Sf is
the shape factor for the magnet (Field et al.,
1988), c0 is the susceptibility of pure solvent,
d0 and ds are densities of pure solvent and solu-
p
tion, respectively, cdia
M and cM are diamagnetic
and paramagnetic susceptibility, respectively,
Mp is the molar mass of dissolved paramagnetic
p
compound, and ds and ddia s are the density of so-
FIGURE 30 Description of hysteresis loop for ferromag-
lution containing paramagnetic and diamagnetic nets. The point 0 represents lack of external magnetic force.
As force field (H) is increases, magnetic flux (B) also in-
compounds, respectively. creases nonlinearly from point 0 to point 1, the saturation
point. Then, the field is reduced to 0. The flux, instead of
6.2 Magnetic Hysteresis returning to 0, goes to point 2 (the remnant flux force)
and the specimen still remains partially magnetized. To
One of the key properties of ferromagnetic demagnetize the specimen, the current must be reversed
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