Professional Documents
Culture Documents
Nanoelectronics and
Information Technology
Advanced Electronic Materials
and Novel Devices
Third, Completely Revised
and Enlarged Edition
Contents
General Introduction 13
1 Properties of Information 15
2 Mathematical Definition of Information 18
3 Processing of Information 20
4 Boolean Algebra and Switching Circuits 20
5 Switching Algebra and Switching Circuits 21
6 Multivalued Logic 21
7 Irreversible and Reversible Logic 22
8 Areas of Information Technology 24
I Fundamentals 27
1 Interdisciplinarity 29
2 Prerequisites 29
3 Material Properties and Material Classes 31
2
Contents
3
Contents
4
Contents
21 Molecular Electronics Functions and Features Arising from Tailor-Made Molecules 477
Marcel Mayor, Department of Chemistry and Institute for Nanotechnology,
University of Basel and Karlsruhe Institute of Technology (KIT), Switzerland and Germany
Michel Calame, Department of Physics and Swiss Nanoscience Institute, University of Basel, Switzerland
Rainer Waser, Peter Grnberg Institute, Research Center Jlich and
Institute of Electronic Materials, RWTH Aachen University, Germany
1 Introduction 479
2 Fundamentals of Molecular Electronic Building Blocks 481
3 Making Contact: Techniques of Single Molecule Junction Formation and Characterization 484
4 Electronic Functions: Rectification and Switching, Gating and Molecular Logic Gates 489
5 Fabrication and Integration Processes 494
6 Summary and Outlook 495
5
Contents
6
Contents
Cheol Seong Hwang, Department of Materials Science and Engineering & Inter-university Semiconductor Research Center,
Seoul National University, Korea
Ulrich Bttger, Faculty of Electrical Engineering and Information Technology & JARA-FIT, RWTH Aachen University, Germany
1 Introduction 637
2 Operation and Circuit Design 637
3 Dielectric and Ferroelectric Capacitors 641
4 Reliability Issues 646
5 Integration Technology 648
6 Physical Limits of Scaling 649
7 Concluding Comments 651
7
Contents
8
Contents
9
Contents
Abbreviations 1011
Symbols 1019
Authors 1025
Index 1031
11
Arbitrarily Selected Sample Pages
Please note
that the figure resolution
in this pdf file
is much less than in the original book.
I Fundamentals
direction of the emergent electrons is random directly after the boundary scattering event,
the magnetic field will bend their momenta towards the x-direction such that px is con-
served as in the case of a flat boundary. This means that in addition to the consideration
above, boundary scattering is diffusive only for roughnesses MF and at the same time
rc Ae. As B is increased from zero, the sample thus undergoes a transition from situation
(a) to (b) in Figure 8. In small but increasing magnetic fields, the electrons will be
increasingly deflected towards the y-direction, experience more diffusive boundary scat-
tering and Ae will decrease resulting in an increased resistance. However, once the cyclo-
tron radius gets smaller than the mean free path, the electrons move in the skipping orbits
along the edge and maintain their momentum in x-direction. Hence, in a sample with dif-
fusive scattering at the walls, the resistance will show a maximum as a function of B for
L x rc. This is in fact observed in semiconductor wires, see Figure 9, and represents a nice
illustration of the nontrivial interplay of different length scales. In metals, we have typi-
cally Fermi wavelengths of the order of 0.2 nm. Specular scattering in metals can be
expected only for atomically flat boundaries which is very hard to achieve. However, in
semiconductors, MF can easily get as large as 50 nm, such that smooth edges are within
reach of present-day fabrication technology.
100
Mesoscopic Electron Transport
3
mode with the lowest energy is occupied. The wire is diffusive if its length L is much
larger than the elastic mean free path Ae (Figure 11a). In this case, the electrons will suffer
many elastic scattering events during their trip along the wire. Note that the trajectories
indicated by an arrow are only meaningful for MF W, which means that the number of
occupied modes is sufficiently large, and a localized wave packet can be constructed.
This is not necessarily true in quantum wires. If only a few modes are occupied, the semi-
classical picture breaks down, and we should think of the electrons as plane waves inside
the quantum wire. In the opposite limit, L Ae, there is no elastic scattering in the wire,
except for boundary scattering at the walls (Figure 11b). Such ballistic wires are of inter-
est here. We note that in order to be ballistic, the wires often have to be very short and
form a point-like contact between the left and the right reservoir. In that case, they are
called quantum point contacts (QPC).
Elementary solid state physics tells us that Bloch electrons in a perfect crystal lattice
experience no resistance at all. We are therefore tempted to expect an infinite conduc-
tance. Surprisingly, however, we cannot avoid resistances as we transfer electrons across
ballistic wires. The measured conductance of such a wire is shown in Figure 12. Below
the surface of this sample, a quantum film of electrons resides that has been removed
underneath the bright lines, which are oxide lines in the GaAs surface. The whole area
shown here is free of scatterers at low temperatures. The structure can be thought of as a
three-terminal device. If a voltage is applied between the source and the drain termi-
nals, a current will pass through the narrow constriction defined by the two oxide lines
which represents the ballistic wire. Its width is of the order of the Fermi wavelength and
can be tuned by applying an additional voltage to the third terminal, labeled planar gate.
The conductance of this device as a function of the planar gate voltage is shown to the
right. At temperatures of a few kelvins, the conductance shows steps in units of 2e2h,
which vanish at more elevated temperatures. This is one of the most fundamental obser- Figure 12: Ballistic transport through a quantum
point contact. At the top, the surface topography of
vations [15], [16] in mesoscopic transport and will be explained below in more detail.
a GaAs microchip is shown. The picture has been
What is the resistance of such a ballistic quantum wire? As we have just seen, a taken with an atomic force microscope. The chip
two-terminal measurement gives quantized resistances. If, however, the resistance is hosts a quantum film about 30 nm below its
measured in a four-terminal geometry with the voltage probes inside the ballistic wire, it surface, which is removed underneath the bright
has been shown that the resistance is in fact zero [17]. We will now derive a picture for lines. A small and short wire of length 140 nm and
this phenomenon. width 80 nm connects source and drain. The
measurement below shows the conductance of the
Essentially, the explanation consists of two steps: wire as a function of the gate voltage. At low
1) There is no backscattering either inside the QPC or at its exit. temperatures, a conductance quantization in units
2) The occupation of the states in close proximity to the QPC is not described by a of 2e2h is visible, which vanishes around 20 K.
FermiDirac distribution.
To begin with, we look in more detail at the geometric shape of a QPC (Figure 13).
Clearly, the QPC is connected to source S and drain D via two transition regions, which
are quasi-one-dimensional. In a rather crude, but nevertheless very insightful, approxi-
mation, we replace the transition region by ballistic, strictly one-dimensional QWRs and
the QPC itself by a barrier with transmission probability T. We do so since we plan to
calculate the conductance of the QPC from a scattering approach, where incoming elec-
tronic plane waves are scattered into outgoing plane waves, which are eigenfunctions of
the one-dimensional wires. For simplicity, we assume an energy-independent transmis-
sion probability. The QPC is open for T 1.
We now calculate the conductance for our model QPC. For this purpose, recall that
the current density in its simplest form is given by j n2ev, where n2 is the two-dimen-
sional carrier density and v is the velocity of the electrons. The corresponding one-dimen-
sional expression is obtained by integrating over the cross section of the current; it reads
I n1ev. Here, I is the current and n1 is the one-dimensional electron density. This sim-
ple relation is generalized to our model system as follows. Suppose a voltage
V IS ID
e
drops between source and drain. The reservoirs fill the connected
Figure 13: A QPC attached to source and drain
states of the wire with k-vectors pointing away from the reservoir (outgoing states), up to (left) and its idealized model (right), where the
their respective electrochemical potentials. Now, I, n1 and v depend on energy. Further- transition regions are one-dimensional leads, and
more, the density of right-moving electrons at energy W is given by the density of states the constriction is a barrier with transmission
on the side i S, D of the barrier, multiplied by the corresponding Fermi function: probability T.
JG JJG
ni W
gi W
f W Ii
JJG HJJ
Here, g i W
( g i W
) is the density of states for right-moving (left-moving) electrons,
JG HJ
and the ni W
, ni W
denote the corresponding electron densities.
101
I Fundamentals
W
: H :dV (3)
: 2dV
Substitution of the LCAOs gives
ciZi H ciZi dV
i i
W (4)
2
c Z dV
i i
i
Rearranging for the sums yields
c j ck Z j H Zk dV
j k
W (5)
c j ck Z j Zk dV
j k
in which j, k 1 n.
Henceforth, we use the abbreviations
H jk Z j H Zk dV (6)
and
S jk Z j Zk dV (7)
in which Hjk Hkj and Sjk Skj for symmetry reasons. For j k, the integrals Hjk are
called Coulomb integrals and represent the effective energy of an electron in the field of
one nucleus and the other electrons in the system, i.e. it is the energy of an AO. The inte-
grals Hjk for j v k are known as resonance integrals and express the energy of an elec-
tron moving under the influence of two different nuclei. Hence, they are a measure of the
bonding energy. The Sjk are called overlap integrals because for j v k they describe the
overlap of the individual AOs. To make progress, we use the variation principle, which
states that if an arbitrary wave function is used to calculate the energy, then the value cal-
culated is never less than the true energy. Hence, we have to vary the coefficients ci and
seek for the energy minimum in order to obtain the best approximation for the true energy,
that is we set sWsci 0 for all i and have to solve the resulting set of simultaneous
equations. Rewriting Eq. (5)
W c j ck S jk c j ck H jk (8)
j k j k
136
Organic Molecules Structures and Electronic Properties
5
and differentiating with respect to ci gives a set of n equations:
W ck Sik W c j S ji ck H ik c j H ji (9)
k j k j
with i 1 n. Because Hjk Hkj and Sjk Skj, Eq. (9) can be written as
W ck S kj ck H kj (10)
k k
or
ck H kj WSkj
0 (11)
k
Equation (11) represents a set of linear homogeneous equations. The condition for
non-trivial solutions of this set is that the so-called secular determinant vanishes:
H11 WS11 H12 WS12 ! H1n WS1n
H 21 WS 21 H 22 WS22 ! H 2 n WS 2 n
0 (12)
# #
H n1 WSn1 H n 2 WSn 2 ! H nn WS nn
We will now apply the LCAO concept to the types of organic molecules introduced
in Sec. 2. To calculate the electronic properties, which are relevant for applications in
electronic devices, it is justifiable to consider only the Q-MOs because the binding
T-MOs are localized and have a much lower energy (Figure 15). For this reason, they do
not contribute in any charge transfer or optical excitation process. In the terminology of
solid-state physics, this means that we only deal with electronic states that are not too far
from the Fermi energy. Hence, in the following treatment we consider planar molecules
for which the framework of T-bonds is fixed. The LCAO approximation is used to calcu-
late the energies and electron density distributions of the Q-MOs from the 2pz-AOs of the
sp2-hybridized C atoms.
3.2 Hckel Approximations Figure 15: Sketch of the energy levels of the
T- and Q-bonds of ethane generated by binding
In the 1930s, Hckel [10] introduced a set of drastic approximations that considerably two sp2 hybridized C atoms. The energy
simplify the calculation of the secular determinants. The procedure is now called the values B and C refer to the LCAO theory
Hckel MO method (HMO method). We will use the HMO method because of its edu- explained in the text.
cational value and because it gives surprisingly reasonable physical results.
Assumption 1
The Coulomb integrals Hii that represent the energy of an electron in a 2pz-AO are treated
as identical for all sp2-hybridized C atoms and denoted B:
Hii B for all i
The value of B is given by the first ionisation energy of a C atom (approximately
10 eV).
Assumption 2
The resonance integrals Hjk depend on the length of the bond involved. The HMO
method neglects this dependence and sets
Hjk C for adjacent, T-bonded atoms, and
Hjk 0 for non-adjacent atoms.
As we shall see from the calculation of the ethene, C represents the binding energy
of an isolated Q-bond and is approximately 0.77 eV [6]. The assumption that C is the
same for all bonds implies that all bond lengths are equal.
Assumption 3
All overlap integrals are simplified to:
Sii 1 (all atomic orbitals are normalized) and
Sjk 0 for j y k.
This assumption looks quite severe; however, the effect on the MO energies and,
especially, on the relative position of the energy levels is rather small.
The application of these assumptions to ethene leads to a secular determinant
B W C
0 (13)
C B W
137
I Fundamentals
: 2dV 1 (18)
together with Eq. (1) and the Hckel assumptions, Eq. (18), that is
Figure 16: Result of the HMO
calculation for ethene: energy levels c j ck S jk ci2 1 (19)
and sketch of the wave functions of the j k
Q-MOs. The occupation of the energy
leads to c1 c2 1 2 (Figure 16).
levels is shown for the ground state.
For buta-1,3-diene, the HMO method leads to the secular determinant
x 1 0 0
1 x 1 0
0 (20)
0 1 x 1
0 0 1 x
The fourth-order polynomial derived from Eq. (20) gives four eigenvalues, namely
x o0.618 and o1.618. From these values, the coefficients ci can be calculated. They
are used to determine the phases and contributions of the four AOs to the four MOs
(Figure 17). The electrons fill the bonding Q-orbitals 1 and 2, and the antibonding Q-orbit-
als remain empty. The total energy of the Q-electrons is 4B 4.48C. If this value is com-
pared to the energy of two isolated Q-bonds, 4B 4C, we find that the energy due to
delocalization is 0.48C.
In Figure 17, the highest occupied orbital (HOMO) :2 and the lowest unoccupied
orbital (LUMO) :3 may be compared with the conduction band edge and the valence
band edge, respectively, of a semiconductor. The band gap of the semiconductor corre-
sponds to the HOMO-LUMO gap (HLG) in the MO picture of Q-conjugated organic
molecules. Accordingly, the energetically lowest optical absorption band is related to the
HLG energy. Figure 18 shows the result of HMO calculations for conjugated Q-systems
of linear hydrocarbons. For odd numbers of C atoms, an MO occurs at the energy B, i.e.
it is neither bonding nor antibonding. For neutral molecules, these nonbonding MOs are
occupied by a single electron, and the molecule is a radical.
For benzene, the most important aromatic hydrocarbon, the secular determinant is
given by
x 1 0 0 0 1
1 x 1 0 0 0
0 1 x 1 0 0 0 (21)
0 0 1 x 1 0
1 0 0 1 x 1
Figure 17: Result of the HMO calculation The MOs and their energies are illustrated in Figure 19. Note that :2 and :3 are
for buta-1,3-diene: energy levels and degenerate, as are :4 and :5. The total energy of the Q-electrons is 6B 8C, which
sketch of the wave functions of the Q-MOs. should be compared with the energy of the linear hexa-1,3,5-triene, 6B 6.98C. The dif-
The occupation of the energy levels is ference reveals that aromaticity yields an additional stabilization of approximately C
shown for the ground state. compared to the conjugated linear system of six C atoms due to lowering the kinetic
138
Organic Molecules Structures and Electronic Properties
5
energy of delocalized -electrons. Tables of the MO energies and orbital coefficients for
a large selection of hydrocarbons are collected in Ref. [11].
For increasing numbers of rings in polyaromatic compounds, the HLG decreases and d
finally vanishes for graphene, a two-dimensional infinite layer of fused benzene rings,s,
the building unit for graphite. As a consequence, graphite possesses metallic conductionn
in the in-plane directions.
Another example of a conjugated carbon system is the C60 buckminsterfullerene Figure 21: Electronic structure of C60. Left:
molecule, the most prominent representative of the soccer-ball shaped fullerenes [12]. energy levels as calculated by the HMO method
The C60 molecule has 12 regular pentagons and 20 hexagons (Figure 20). There are two [43]. The symmetries of the MOs are included.
types of bonds: one set is common to two hexagons and the other set is common to a Centre: energy levels as calculated with the density
hexagon and a pentagon. The lengths of these two kinds of bond, 139 pm and 145 pm, functional theory (DFT) [44][45] within the local
density framework. Right: the splitting of the
respectively, are intermediate between those for CC single bonds and CC double
degenerated HOMO and LUMO states into valence
bonds (see Sec. 2). The C atoms can be regarded as approximately sp2-hybridized. The and conductions bands in the Brillouin zone of the
T-bonds make up the mechanically very stable cage and the Q-electrons are almost com- fcc solid (fullerite) and the density of states D W
.
pletely delocalized over the molecule, with slightly enhanced amplitudes at hexagon The energy eigen values are broadened using
adjacencies. Before C60 had been discovered experimentally, an HMO calculation had 0.3 eV wide Gauss functions to give an impression
already identified the completely filled HOMO [13] and the energy eigenvalues [14]. of the spectral weight. The occupied states are
Figure 21 shows the energy states calculated by the HMO method and an ab initio density shown in grey.
functional theory approach. Further details are reported in Ref. [15].
139
I Fundamentals
As mentioned, today the HMO theory only serves educational purposes. In order to
obtain the accurate electronic structure and the MOs of complex molecules ab-initio first
principle calculations are employed using sophisticated programs (see, e.g., Ref. [16]).
As an example, Figure 22 shows the HOMO and LUMO of a coronene derivative [17].
Coronenes are disk-type polycyclic aromatic hydrocarbons which also can be regarded
as graphene chiplets.
140
Organic Molecules Structures and Electronic Properties
5
141
I Fundamentals
Figure 26: Sketch After having discussed the electronic structure of individual (small) molecules and
of the (simplified) individual polymer chains, we will now briefly describe the situation if many molecules
crystal structure or polymers are assembled to form bulk material. We will start from small Q-conjugated
of pentacene molecules which are stacked into an ideal crystal. Figure 26 shows a simplified example.
crystal.
Because all electrons of the molecule are engaged in covalent bonds, the van der Waals
interaction constitutes the only attractive intermolecular energy leading to (weak) bonds
between the molecules. The interaction is weak that is the MOs of the individual mole-
cules (Figure 27a) interact only slightly and, as a results, only narrow bands are formed
(Figure 27b). In agreement with the band theory, a weak coupling and the resulting small
bandwidth is related to a low electron mobility. In organic crystals electron mobilities
well below the maximal value about 10 cm2(Vs) are frequently encountered, compared
to values 1000 cm2(Vs) in Si crystals. Because of the weak intermolecular bonds,
highly ordered organic crystals are very difficult to fabricate. Typically, organic materials
show either a polycrystalline microstructure with considerable disorder between the crys-
tallites or they are completely amorphous. Disorder leads to a broadening of the energy
bands (Figure 27c). This broadening is, however, completely different to the broadening
by strong coupling. It is due to an energetic and spatial distribution of localized states, a
situation known also for inorganic amorphous semiconductors. Instead of sharp, well-
defined band edges, exponential tails of localized states extending into the band gap are
observed [19]. In the case of assemblies of organic molecules, the narrow bands of ideal
crystals often are broadened into bands which can be approximated by a Gaussian distri-
bution of localized states (Figure 27c). The same effects come into play when we turn
from an individual polymer chain to polymer bulk material. The difference is that the
energy bands formed for an individual chain are already relatively broad as described
above. The disorder introduced by forming the bulk material leads to an additional broad-
ening of the bands due to distributions of localized states.
142
Organic Molecules Structures and Electronic Properties
5
Covalent CC and the CH bonds are nonpolar, whereas the covalent bonding
between functional groups and the rest of the molecule usually exhibits a polar character
on account of the different electronegativities of the atoms involved. The electronegativ-
ity of an atom determines to what extent electrons are attracted within a covalent bond
and is determined by the electron affinity and the ionization energy of the atom [6].
Within a period of the periodic table the electronegativity increases with increasing order
number, for example along the series C, N, O, F. For example, the C-N bond in amines is
polarized so that the electron density is shifted towards the nitrogen, further enhancing
the dipole moment due to the electron lone pair (Figure 28). This effect is strongly
affected by the valence of the atoms involved and additional atoms within the functional
group. For example, N in a nitro group, NO2, behaves differently from an N in an amino
group, NH2.
Polarization effects that are caused by functional groups and act electrostatically
along T-bonds, are called inductive effects (I effects). If the functional group attracts
electrons (T-acceptor) and carries a negative partial charge, then the effect is called a
I effect; otherwise, it is denoted as a I effect (T-donor). For molecules with only one
functional group, the strength of the I effect can be inferred from the dipole moment
(Table 2). The relative strength of the I effect of various groups is shown in Figure 29. In
the case of unsaturated and aromatic molecules, functional groups may also affect the Table 2: Dipole moments of
selected molecules
electron density through another mechanism called the mesomeric effect (M effect, or
resonance effect) and involves the Q-electron system. The functional group may either
attract charge density (M effect, Q-acceptors) from the Q-system or donate partial
charges (M effect, Q-donor) into the Q-system from its own Q- or non-bonding elec-
trons (Figure 30). Because of the delocalization of Q-electrons in conjugated or aromatic
systems, the mesomeric effect is transferred to positions that may be quite distant from
the functional group. In addition, the effect shows a modulation in the sense that the par-
tial charge is especially pronounced at every second C atom within the conjugated sys-
tem. The mesomeric structures caused by a nitro group at a benzene system and the
resulting partial charges are illustrated in Figure 31.
Figure 28: Partial charges at the
amino methane molecule caused by
the electron attraction of the nitrogen
along the C-N T-bond. The arrow
indicates the dipole moment.
143
II Technology and Analysis
2 X-ray Techniques
2.1 Introduction
In this section, we will discuss the most relevant analysis techniques using monochro-
matic X-rays as incident probes and elastically scattered X-rays or X-ray fluorescence as
emitted responses from the sample. Conventional X-ray diffraction (XRD) is a very
important technique for characterizing the bulk structure of materials. It was introduced
by M. v. Laue, W. L. Bragg and W. H. Bragg at the beginning of the 20th century (Nobel
Prizes in 1914 and 1915). With the advent of very intense synchrotron-radiation-based
X-ray sources at the beginning of the 1980s, novel surface-sensitive X-ray diffraction
techniques were developed, dedicated to the characterization of surfaces, interfaces and
nanostructures. These will be discussed in the first part of this section.
In the second part of this section, chemically sensitive X-ray techniques will be pre-
sented based on element-specific X-ray absorption and emission lines. The strength of all
X-ray-based techniques is their intrinsic in-situ compatibility under very different condi-
tions such as elevated (gas) pressures, wide temperature range, strong electric or mag-
netic fields and any possible combination of these. In addition, they are non-destructive
Figure 1: Principle interaction processes when in many cases and do not require any special (destructive) sample preparation. Finally,
electrons or photons interact with atoms. they do not require any special property of the sample, as they may be applied to insulat-
Electronic excitation processes lead to the emission ing materials and solid, liquid or gaseous substances.
of fluorescence radiation, photoelectrons or Auger
electrons. In addition, (elastic) Thomson scattering
or (inelastic) Compton scattering may occur.
2.1.1 Basic Processes and Generation of X-rays
The generation of X-rays in laboratory sources is closely related to basic processes inside
an atom, when interacting with electrons or photons (see Figure 1) [1]. An incident elec-
tron or photon with a sufficiently high kinetic energy to overcome the binding energy of
inner shell electrons can remove an electron from the K shell of the target material. The
remaining hole is filled by an electron falling down from one of the next higher shells (L,
M, ) accompanied by the emission of an X-ray photon with characteristic fluorescence
energy (KB, KC, LB, LC, and so on). Due to spin-orbit splitting of the electronic L levels,
additional splitting into KB1 and KB2 lines is observed. A concurring process is Auger
electron emission, during which the energy of the descending electron is transferred to
another electron from the same energy level (e.g. KLL transition). Auger electron pro-
duction is more likely for lighter elements and is used for the chemical analysis of sur-
faces as discussed in 3.3.2, whereas fluorescence emission dominates for higher Z
elements. Note that in the case of an incident photon, the removal of an inner core shell
electron is known as photoemission, and forms the basis for X-ray photoelectron spec-
troscopy (see 3.3.1, Nobel Prize in Physics to M. Siegbahn in 1924).
In X-ray tubes, electrons with a kinetic energy typically between 3060 keV are shot
onto a metallic target material (the anode) emitting characteristic X-ray fluorescence
radiation, as shown in Figure 2. In addition, continuous Bremsstrahlung is emitted up
to a photon energy corresponding to the electron acceleration voltage, because the elec-
trons may also be decelerated by the positively charged atomic nuclei and the electrons.
The sharp fluorescence emission lines are located for example at WhO 8.048 keV for
CuKB1-radiation or WhO 17.479 keV for MoKB1-radiation, corresponding to an X-ray
wavelength of M x 1.50.8 (via WhO 12398.53 eVM []). Low-energy photons
from 100 eV to about 5 keV are frequently called soft X-rays, high energy photons
(WhO 30 keV) hard X-rays.
If extremely high intensity, a polarized beam, and/or tunable photon energy is
required, an X-ray tube is an inadequate photon source. Instead, synchrotron radiation
Figure 2: facilities have to be used. The generation of synchrotron radiation is based on the princi-
(a) Principle of an X-ray tube. Accelerated ple that accelerated charged particles (electrons, positrons) with relativistic kinetic ener-
electrons hit the anode (most commonly made gies (99.999999 % of the speed of light) exhibit a strongly forward-focused emission
from Cr, Co, Cu, Mo, Ag or W). Due to cone of radiation [2]. Synchrotron radiation sources are today available all around the
secondary processes at the anode surface, X-ray world (for a complete list see [3]). Inside the storage ring, an electron (or positron) beam
radiation is emitted. is forced onto a closed orbit with specially designed magnetic devices (bending magnets,
(b) Emission spectrum of X-ray tube.
Characteristic X-ray fluorescence lines of the
wigglers, undulators) [4]. Typical values are electron energies of 28 GeV, a magnetic
anode material are superimposed on the field of 1 T and an electron current of 100300 mA. The radiation covers photon energies
bremsstrahlung spectrum (the KB1,2 fine from the visible light range (some eV) up to some 100 keV depending on the synchrotron.
structure is shown in the inset). The intensity of A sketch of how the X-rays are generated by a bending magnet is shown as an inset in
the characteristic lines is much higher than the Figure 3. The figure of merit for synchrotron radiation sources is their brilliance, defined
bremsstrahlung background and is used for as:
X-ray scattering experiments.
number of photons
Brilliance (1)
s mm 2 source area
mrad 2 0.1 % bandwidth
236
Structural and Chemical Characterization on the Nanoscale
10
Figure 3: Comparison of the brilliance
between a typical tube source and a
bending magnet. The 0.1 % bandwidth
depends on the selected energy. The
inset shows the principle of producing
X-ray photons at a synchrotron radiation
source. The electron beam is forced onto
a curved path by a magnet. This change
in the orientation of the electron velocity
vector (acceleration) gives rise to the
X-ray emission.
Bending magnets produce photons with an almost white, continuous emission spec-
trum down to a critical wavelength below which the intensity dramatically drops (see
Figure 3). The quasi-white beam is usually adapted to the experimentalists needs by
optical devices such as focusing mirrors, apertures and monochromators as pictured in
Figure 4. Afterwards, the primary beam has a well-defined collimation and energy band-
width.
The intensity of the synchrotron radiation can be increased significantly by installing
many bending magnets with flipping polarity one after the other. The electron beam wig-
gles through the device (which is therefore called a wiggler) and the resulting radiation
is the incoherent sum of the radiation produced at the sub-devices. In this way, the inten-
sity can be amplified by a factor of 50100 compared to a single bending magnet. By
choosing proper magnetic fields and distances between the single components, a
so-called undulator is obtained. Radiation of a particular wavelength adds up coherently
and the resulting brilliance is a function of N 2 where N is the number of sub-devices.
Therefore, the peak intensity can be 104 times larger than observed from a single bending
magnet [4]. The peak brilliance of pulsed X-ray sources (X-ray free electron lasers) is 20
orders of magnitude higher than that of a bending magnet.
We will discuss X-ray diffraction here for two limiting cases: in the first case, the
sample (surfaces, interfaces, thin films) is considered to consist of stratified interfaces
separating layers with homogeneous electron density, and respective refractive index n.
The X-rays are treated as electromagnetic waves, which have to fulfill the boundary con-
ditions at the interfaces according to the Maxwell equations. The X-ray reflectivity deter-
mined in this way represents an exact solution of the electromagnetic wave-field
boundary problem taking all reflected and transmitted wave fields into account [6]. In the
second case, the interaction of the X-ray beam with the sample is assumed to be so weak
Figure 6: Reflection and refraction of X-rays at an that multiple diffraction events can be excluded. This so-called kinematic approximation
interface between stratified media with refractive implies a straightforward calculation of the diffracted intensity from a periodic arrange-
indices n1,2. Total external reflection occurs when ment of entities like atoms or molecules in crystals.
BT 0. According to Snells law, the incident
angle for total external reflection is cos BT = n2n1.
2.2.1 X-ray Reflectivity
X-ray reflectivity (XRR) is a standard technique to characterize layered structures with
sub-nm resolution. In specular reflectivity experiments, the reflected intensity is recorded
as a function of the incident angle Bi with respect to the surface in a symmetric condition
(Bi B f , see Figure 6). X-rays undergo refraction at the interface of two media with
refraction indices n1,2. The refractive index n in the X-ray regime can be written as
(neglecting dispersion corrections):
2Qr0Se N 4Qr0Se
n 1 2
i with Bc (3)
ki 2ki ki2
Here r0 denotes the classical electron radius, Se the total electron density of the materials
and N the linear mass absorption coefficient. Note that in the X-ray regime, n 1 for mat-
ter. As a direct consequence, total external reflection may occur at the vacuum
(n1 1)/matter (n2 1) interface at the critical incident angle Bi Bc given by Eq. (3)
(BT 0). The reflected and transmitted amplitude ratios r and t through one interface can
be calculated using the Fresnel formulas known from optics in the limit of small angles:
Bi Bi 2 Bc 2 2Bi (4)
r and t
Bi Bi 2 Bc 2 Bi Bi 2 Bc 2
From Eq. (4), we can directly identify two limiting cases for the Fresnel reflectivity
RF rr*. For Bi l 0, we have RF 1 (total reflection) and for Bi Bc , it follows that
RF r Bi4, indicating that the reflectivity falls rapidly with an increasing incident angle.
The transmitted amplitude ratio is important for evanescent wave-based techniques as
discussed in 2.2.3.
In addition, imperfections of the interfaces (roughness) lead to a faster decrease
in reflectivity, which can be quantitatively taken into account. For a multilayer system, a
recursive (Parratt) formalism has to be applied including reflected and transmitted
amplitudes at each interface. As an example in Figure 7a, the X-ray reflectivity curve of
a 24.4-nm-thick chromium layer on top of a 20.3-nm-thick Nb buffer on Al2O3 is shown,
Figure 7: as obtained after growth under ultrahigh vacuum conditions. Upon oxidation, a
(a) X-ray reflectivity from a Cr layer on a 4.4-nm-thick oxide layer forms, giving rise to a beating in the reflected intensity. The data
Nb/Al2O3 buffer layer/substrate system before fit (solid line) allows us to reconstruct the average electron density profile as a function
(lower curve) and after oxidation (upper curve). of z perpendicular to the surface (Figure 7b). The typical roughness of the Cr layer is
The open circles represent the data points and 0.4 nm and of the Al2O3 substrate 0.12 nm. From reflectivity measurements, the layer
the solid lines are fits to the data according to thicknesses, densities and interfacial roughness can be determined independent of the
the Parratt formalism taking reflected and crystalline structure of the material. Neutron and soft X-ray reflectometry allow in addi-
transmitted amplitudes at each interface into
tion a determination of magnetization profiles in layered structures.
account. The intensity modulation with short
periods corresponds to the interference of
X-rays reflected from the Cr surface and the
Nb/Al2O3 interface. Note that the fit is not very 2.2.2 Bragg Scattering in Reduced Dimensions (Crystal Truncation Rod
sensitive to the individual Cr and Nb layer Scattering)
thicknesses because of their very similar Here, we consider the kinematical diffraction of X-rays (neglecting multiple scattering
electron density. Their individual layer
processes) from a periodic arrangement of atoms (epitaxial films or single crystals trun-
thickness needs to be determined by Bragg
scattering (see below). An additional beating
cated by a surface). In the simplest approximation, the incident wave is treated as a plane
occurs from the oxide layer. wave scattered from a charge distribution causing a spherical exit wave with the wave
(b) Electron density profile obtained by fitting the vector k. The scattered intensity is in the limit of the so-called Born approximation ([5],
reflectivity curves in (a). The total thickness of [6]) simply given by the square of the Fourier transform of the electron density distribu-
the Cr layer is reduced and at the same time a tion S r
:
4.4-nm-thick Cr oxide layer with different 2
I q
r (5)
electron density is formed.
S r
exp iq r
d3r
238
Structural and Chemical Characterization on the Nanoscale
10
A 3D crystal structure is made up by three lattice vectors a1,2,3 and three angles B, C,
H which are 90 for cubic structures. Using these lattice basis vectors, the electron density
of a crystal can be expressed as
N N1 , N 2 , N3
S r '
Scell r Rn
with Rn n1a1 n2a2 n3a3 (6)
n 0,0,0
in which Scell is the electron density of one unit cell and Nj runs over the whole crystal.
Using (5) Eq. (6) can be written as:
2
N
I q
r Scell r Rn
exp iq r
d 3r
n (7)
2
N
2
r F q
exp iq Rn
The function F is referred to as a structure factor and is the Fourier transformation of the
electron density of the unit cell, which varies slowly as a function of q. Using the geo-
metrical sum, Eq. (7) can be simplified to:
2
N1N 2 N 3
2
I q
r F q
exp iq < n1a1 n2a 2 n3a3 >
n1n2 n3
1 (8)
sin 2 N j q a j
2
3 2
r F q
1
j 1 sin 2 q a
j
2
Eq. (8) shows that the scattered intensity breaks up into the above mentioned struc-
ture factor and the product expression, which is known as the Laue function. The Laue
function exhibits pronounced maxima at the so-called Bragg condition:
Figure 8: Cr (110) Bragg reflection before
a2 q a3 a3 q a1 a1 q a2 (lower curve) and after oxidation (upper curve).
qBragg 2h 2k 2l
a1 a2 q a3
a1 a2 q a3
a1 a2 q a3
The scattered intensity (open circles) is plotted
(9) as a function of the momentum transfer
2Q perpendicular to the surface in units of the
2h a1* 2ka2* 2la3* Ghkl , Ghkl with h, k , l Z . magnitude of the reciprocal lattice vector
d hkl
2Q/d110, with d110 2.036 . d110 is the distance
The integer numbers h, k, and l are Miller indices and a1*3 reciprocal lattice basis vectors. of the (110) planes in body-centered cubic
(b.c.c.) chromium (see inset). The fit according
Each reciprocal lattice vector Ghkl points perpendicular to a set of real-space atomic (hkl) to Eq. 10 corresponds to the solid lines. The
planes with distance dhkl. For large crystals (and for very large numbers of N1, N2, and side oscillations arise from the finite number N3
N3), the Bragg peaks at qBragg become very intense and narrow delta-function-like peaks. of scattering Cr lattice planes, which is reduced
For thin films with a1,2 in the surface plane and a3 perpendicular to the surface, N1 upon oxidation (upper curve).
and N2 diverge and N3 has a finite value. Using Eq. (9), Eq. (8) takes on the following
form:
N Ql
sin 2 3
2 2
I q
r F q
E q|| G||
(10)
Ql
2
sin
2
Here q|| and G|| denote the component of the momentum transfer and the reciprocal lattice
vector in the surface plane, respectively. It is apparent that in the surface plane, the Bragg
condition has to be fulfilled, whereas the scattered intensity is spread out along the recip-
rocal lattice coordinate l perpendicular to the surface. As an example, an l scan through
the (110) reflection of an epitaxial Cr film is shown in Figure 8. The central Bragg peak
is accompanied by so-called Laue oscillations, which allow us to determine precisely the
number of atomic Cr layers N3. From the damping of the oscillations, the crystalline
roughness of the layers can additionally be determined.
For a half-infinite crystal terminated by a well-defined surface, the scattered inten-
sity can be calculated starting from Eq. (8):
2 1
I q
r F q
E q|| G||
Ql (11)
4sin 2
2
239
II Technology and Analysis
The Bragg reflections at integer l values are interconnected by rods of diffracted intensity
(crystal truncation rods, CTR), as schematically presented in Figure 9a. In Figure 9b, the
characteristic intensity distribution along such a CTR is shown: there is finite intensity in
between the Bragg reflections which can be analyzed to obtain crystallographic informa-
tion on the surface structure. During the experiment, sample and detector are oriented
with respect to the incident beam to fulfill the Bragg condition q Ghkl with l as a con-
tinuous variable, as depicted in Figure 10. This is controlled on modern X-ray diffracto-
meters by a computer. The technique is commonly called surface X-ray diffraction
(SXRD) [7].
As an example, the CTR signal of an ultrathin epitaxial Ga oxide layer on a
CoGa(100) substrate is shown in Figure 11a [9]. From a fit of the complete data set, the
structural model in Figure 11b can be obtained. The oxide layer gives rise to characteris-
tic intensity modulations along the CTRs. The following information can be obtained
from SXRD experiments:
atomic positions, surface/interface structure up to pm resolution
surface composition using Z contrast
thickness of epitaxial overlayers
overlayer relative position (registry) to the substrate
surface/interface roughness
thermal vibration amplitudes of surface atoms
In general, all additional experimental and theoretical information available is used as an
input for the fit, because in surface crystallography, only a smaller number of structure
factors can be obtained from the experiment, compared to a bulk crystal structure analysis
for a comparable number of atoms in the unit cell.
Figure 9:
(a) Reciprocal lattice of a half-infinite system; the
L axis is perpendicular to the surface, the H axis 2.2.3 Grazing Incidence X-ray Diffraction
is in the surface plane. At integer (H, L) values
E-function-like Bragg reflections from the bulk For small incident angles Bi and/or exit angle Bf (in the order of the critical angle Bc for
are indicated (blue circles). They are total external reflection) and finite in-plane momentum transfer q|| (see Figure 10), the
interlinked by rods of scattered intensity (green incident and the exit beam undergo strong refraction effects and the diffracted intensity
lines) running perpendicular to the surface. In can no longer be treated in kinematical approximation. The distorted wave Born approx-
the case of a doubling of the surface-structure imation has to be used instead, which includes refraction effects of the incident and the
real-space periodicity, half-order surface rods exit beam fully dynamically and the diffraction process itself in kinematic approximation.
arise, which contain information on the The following general expression can be derived for the scattered intensity [10]
reconstructed near-surface region only (dashed
lines). I q'
r T Bi
2 S q '
2 T Bf
2 (12)
(b) Magnitude of the structure factor F along a
crystal truncation rod (CTR). The surface Here T Bi,Bf
tt* (see Eq. (4)) denotes the optical transmission function of the incident
contribution is shown as red line, the structure and exit beam, respectively, which is plotted in Figure 12a as a function of the incident
factor of the bulk-terminated surface as a blue
or exit angle. Note, that Eq. (12) is symmetric in Bi and Bf because of the reciprocity of
line and the coherent sum of both as a green
line. The structure factor is much weaker in the X-ray light path. Below the angle of total external reflection, the wave field only prop-
between the Bragg reflections than the bulk agates parallel to the surface with a penetration depth - which depends on Bi and Bf as
Bragg peaks, which necessitates the use of plotted in Figure 12b.
synchrotron radiation for the measurements. S q'
denotes the kinematic structure amplitude of any diffraction process, such as
Note that for a 3D infinite system, the signal in Bragg scattering from near-surface lattice planes, small angle scattering, or interstitial
between the Bragg peaks would be fully diffuse scattering. Most importantly for grazing incidence X-ray diffraction (GIXRD),
cancelled out by destructive interference.
the diffraction signal S q'
can be obtained with a depth resolution from nm to Nm,
depending on the choice of Bi and Bf as shown in Figure 12b. It can be used to study sur-
face-induced disorder phenomena as presented for the surface premelting of aluminum
(110) in Figure 13. A similar scheme can be employed for grazing-incidence neutron dif-
fraction [10].
240
Structural and Chemical Characterization on the Nanoscale
10
Figure 12:
(a) Fresnel reflectivity R (left y-axis) and
transmission function T (right y-axis)
according to Eq. 4 as a function of the
incident angle Bc or the exit angle Bf.
T exhibits an enhancement up to a
factor of four at the critical angle Bc
for total external reflection. The
X-ray reflectivity decays rapidly
above Bc.
(b) Information depth -as a function of
the incident angle for varying exit
angles. In the limit Bi 0 -
a
materials property is limited to a few
nm. For exit angles smaller than Bc,
the information depth can be limited
to a specific value.
Figure 14:
(a) Grazing incidence small-angle scattering corresponding GISAXS scan (Figure 10c) shows characteristic Bragg satellites from the
(GISAXS) pattern from rhodium nanoparticles regular stripe structure. In general, a quantitative analysis of GISAXS data is possible,
on MgO(100). The pattern is characteristic for but it is hampered by the sometimes difficult deconvolution of the distance and the size
a truncated octahedral shape, as indicated in the information of the nanostructures. Neutron small-angle scattering provides additional
inset.
information on the lateral magnetic order of nanostructures.
(b) Atomic force microscopy (AFM) image of a
germanium surface after nanopatterning by a
xenon ion beam (2 keV kinetic energy). The
ripples form perpendicular to the ion beam
incident direction (white arrow).
2.3 Chemically Sensitive Techniques
(c) GISAXS diffraction signal with an incident In principle, the techniques discussed above can be applied in a chemically sensitive way
beam parallel to the ripples (open circles). The by tuning the photon energy to one of the absorption edges of the constituting elements,
solid line is a simulation based on an average which reduces the scattering contribution of the corresponding atoms. This allows the
distance of the ripples of 56 nm. The dashed scattering contrast between different elements to be varied in a compound material. In
line corresponds to an incoherent background neutron diffraction experiments, the scattering contrast can be varied by the use of differ-
signal from disordered parts of the surface. ent isotopes. A direct method to analyze the chemical composition of a material is the
(Adopted from [14]).
detection of fluorescence radiation. This technique is routinely applied to characterize
metallic contaminations on the surface of silicon wafers used in the semiconductor indus-
try. Finally, the element-specific absorption properties of materials can also be exploited
to investigate the local structure of each constituent by analyzing the extended X-ray
absorption fine structure.
242
Structural and Chemical Characterization on the Nanoscale
10
2.3.2 Extended X-ray Absorption Fine Structure
The Extended X-ray Absorption Fine Structure (EXAFS) analysis allows the determina-
tion of the local structure of poorly ordered materials, such as small nanoparticles
(diameter 3 nm) or glasses [17]. The attenuation of X-rays by a material with linear
mass absorption coefficient N &
and thickness d is described by Lambert-Beers law [6]:
I I 0 eN E
d (13)
The linear mass absorption coefficient N depends strongly on the incident photon
energy E: when E is high enough to emit an electron from an atomic shell via photoemis-
sion, as discussed in 2.1.1, N undergoes an abrupt increase, as pictured in Figure 16a
(so-called K, L, M, edges). For solids or liquids, the outgoing photoelectron wave is dif-
fracted by the surrounding atoms, giving rise to constructive or destructive interference
depending on the photoelectron energy and the distance of the emitting atom from its
nearest neighbors. This interference in turn modulates the absorption probability above
the edge, as can be seen in Figure 16a. The quantitative analysis of the EXAFS oscilla-
tions gives detailed information on the nearest neighbor distances, coordination shells
and vibrational amplitudes, as shown in Figure 16b. Conventional EXAFS measure-
ments are performed in transmission, but in principle, the probability of secondary pro-
cesses, such as Auger electron or fluorescence emission, also contains the EXAFS signal,
which therefore makes the technique suitable for investigating well-defined nanostruc-
tures or surfaces.
243
II Technology and Analysis
the islands is 4.51010 cm2 and the lateral island size is 17.5 o 0.5 nm. The challenges in
the growth of these semiconductor islands are to grow islands of desired size and density
and with a high size uniformity. As in the case of the 2D islands a higher growth temper-
ature generally leads to the formation of larger islands, a higher growth rate leads to the
formation of smaller islands. The size of the islands increases with coverage. Often the
density of the islands saturates in an early stage of the growth. These are general trends;
details may depend on the material system and the particular deposition technique. In
some cases (self-limiting growth) the size of the islands saturates and the density
increases with coverage. This kind of growth mode leads to a high size uniformity of the
islands. The size uniformity achieved in self-organized growth of semiconductor islands
can be as small as a few percent. The confinement of charge carriers in nanoscale islands
in all three directions gives rise to atomic like energy levels. Quantum dot lasers operating
at room temperature have now been realized [11]. The islands grown on a flat substrate
are usually not ordered laterally due to the random nature of the nucleation process. In
the following it will be shown how nucleation at specific sites can be achieved.
Figure 16:
(a) STM image of two-dimensional Ge/Si
nanowires grown by step-flow at a pre-existing
step edge on a Si 111
substrate. Si wires
(yellow) and Ge wires (red) can be
distinguished by different apparent heights.
(b) The cross section across the nanowires.
(c) Atomic structure of a Ge wire on the Si
substrate capped by Bi. The cross section of the
Ge wire contains only _20 Ge atoms [13], [14].
312
Bottom-Up Approaches by Self-Organization Techniques
13
4 Molecular Self-Assembly
4.1 General Aspects of Molecular Self-Assembly
Molecular self-assembly uses the spontaneous assembly capabilities of molecular build-
ing blocks to build up regular arrangements, that is, the capability to rearrange continu-
ously until a complete ordered monolayer of molecules is formed. The term
self-assembled monolayer (SAM) describes originally according to Whitesides [15] a
two-dimensional film with the thickness of one molecule that is attached to a
well-defined solid surface through covalent bonds. However, also physisorbed monolay-
ers can be considered as a class of SAMs since they meet the criteria of a self-assembly
process. The non-covalent bonds formed in this case between molecules and the surface
can be based on van der Waals forces, charge transfer or dipole-dipole interactions. Over-
all physisorbed monolayers are more dynamic than chemisorbed SAMs due to the con-
siderably weaker interaction between molecules and substrate. Molecular self-assembly
is controlled as well by kinetic effects, as thermodynamic conditions, as also by the prop-
erties of the molecular building-blocks. However, the experimentalists aim to exclude
kinetic effects by choosing low deposition rates to achieve thermodynamically stable
structures.
Bare surfaces of metals and metal oxides tend to adsorb organic materials because
these adsorbates lower the free energy of the interface between the respective material
and the ambient environment. The character of the chemical bond between the adsorbed
molecules and the metal surface determines the self-assembly process, the interfacial
electronic contact and the strength of the geometrical fixation. Covalent bonds are estab-
lished, if there is a significant overlap of the electron densities of the molecules and the
metal resulting in a strong electronic and structural coupling. The spontaneous formation
of SAMs on substrates through covalent bonds requires organic molecules with a chem-
ical functionality or headgroup and a specific affinity for a selected substrate. There are
a number of headgroups, which bind to specific substrates forming directed covalent
links. One frequently used covalent link is the bond between a thiol group on the molec-
ular side and a noble metal substrate. Gold is favorable due to its proper nonoxidizing sur-
face, but thiol or selenol bonds are also possible for Ag, Pt, Cu, Hg, Ge, Ni and even
semiconductor surfaces. The reason for the great success of the S-Au bond is its good sta-
bility at ambient temperature and the ease of reorganization to form an ordered array.
These putative opposed effects are in line with the idea, that a thiolate forms a stable bond
to an Au-atom and both build together a new entity, which is able to diffuse on the gold
surface easily. Thus the ability, of for example alkanethiols, to rearrange is based on the
mobility of substrate atoms.
Besides the prominent thiolates other functional molecules, like alcohols (ROH) or
acids, have been demonstrated to form organized monolayers on metals or metal oxide
surfaces, like Al2O3, TiO2, ZrO2, or HfO2. SAMs of alkylchlorosilanes (RSiCl3) and
other silane derivatives require hydroxylated surfaces as substrates for their formation.
The driving force for this self-assembly is the in situ formation of polysiloxane, which is
connected to surface silanol groups (-SiOH) via robust Si-O-Si bridges [16]. These
monolayers have successfully been prepared on substrates like silicon oxide, aluminium
oxide, quartz, glass, and mica. Notable advances also have been made by coupling alk-
enes and alkines on Si and Si-H surfaces. Covalent coupling of vinyl compounds on H-ter-
minated silicon yields very stable Si-C covalent bonds [17]. A method for the direct
assembly of arylgroups on silicon and gallium arsenide has been developed by using aryl
diazonium salts. There is a spontaneous ejection of N2 and direct carbon-silicon forma-
tion [18]. But the C-Si bonds are so strong that a facile rearrangement in order to form a
highly ordered SAM is implausible.
Planar molecules with extended Q-systems have been found to physisorb on sur-
faces, that is highly oriented pyrolytic graphite (HOPG), Au 111
, Cu 110
etc., in a
flat-lying geometry. This allows functional groups at the molecular periphery to approach
each other easily and to build up intermolecular interactions, predominantly like hydro-
gen bonds and metal-ligand interactions. If the molecules are mobile enough to diffuse
on the surface the intermolecular interactions will guide the adsorbed molecules into
two-dimensional supramolecular systems (supramolecular chemistry the chemistry of
the intermolecular non-covalent bond [19]). By adjusting the molecular backbone size
and the position or number of the functional recognition groups complex supramolec-
ular nanostructures can be designed [20].
313
II Technology and Analysis
Figure 20:
(a) Schematic of benzoate bonded with two
oxygen atoms (red) to the outermost surface
row of Cu 110
(brown),
(b) high resolution STM image of benzoate
assembled on Cu 110
forming molecular rows
in <001>-direction; the c 8q2
supercell is 4.5 One Dimensional Molecular Structure
indicated,
(c) schematic showing the arrangement of Carboxylic acids are known to link, after deprotonation, with the carboxylate moiety to
benzoate (light grey) on the Cu 110
surface, copper or nickel surfaces forming ordered self-assembled monolayers. Both oxygen
the c 8q2
supercell is indicated [23]. atoms in the carboxylate group are equidistant to the surface and build up a rigid, upright
adsorption geometry, like observed for formic, acetic and thiophene carboxylic acid.
Combining this molecular property with a patterned substrate surface, like Cu 110
, adds
up in one-dimensional molecular rows. In Figure 20 the close-packed c 8q2
surface
structure of benzoate molecules binding on top of two copper atoms on the outermost sur-
face layer rows is depicted [23]. In this self-assembly process the inorganic nanostruc-
tured template takes over the role to direct the carboxylates to predefined adsorption sites.
316
Bottom-Up Approaches by Self-Organization Techniques
13
Figure 22:
(a) Chemical formula of
hexa-peri-hexabenzocoronene (HBC)
decorated with six anthraquinone (AQ)
functions.
(b) STM current image of HBC-AQ6
molecules with coadsorbed charge
transfer complexes.
(c) I-Vs through HBC-cores in domains
where charge transfer complexes are
adsorbed or no charge transfer
complexes were present.
(d) Schematic of a prototypical
single-molecule CFET [28].
or not charge transfer complexes are coadsorbed next to HBC. This set-up can be
regarded as a single-molecule chemical field-effect transistor, since the change in the
I-Vs results from the chemical formation/solution of a charge-transfer complex ( gate)
which alters the electron transmittance through the covalently attached HBC ( channel)
(Figure 22). Despite the fact, that the gates cannot be addressed selectively and the device
structure changes simultaneously with the electron transmission properties, this approach
is a major step towards monomolecular electronics with a whole transistor integrated in
one molecule.
317
III Logic Devices
K N0 M S2 (6)
d NW Q
A 2A
The rotation of the magnetization vector in the Nel wall creates magnetic volume
charges. Consequently, the expression for the domain wall width contains a term describ-
ing the dipolar energy. The wall is stable, however, because the volume charges have a
smaller stray field than surface charges. Comparing the expressions Eq. (5) and Eq. (6) it
becomes clear that for the same material parameters, Nel walls are narrower than Bloch
walls.
With respect to applications in magnetic memory and logics domain walls in mag-
netic nanowires have received considerable interest. These nanowires are artificially pat-
terned entities of about 10 nm thickness, 50100 nm width and several 10 m length. The
shape anisotropy of these wires creates a magnetic easy axis in the wire long axis direc-
tion that defines the stable orientations of magnetization. This yields the desired uniaxial
magnetic system that we need to define logical 1 and 0. In these nanowires there are
domains of opposite magnetization directions which are separated by a transition region
through which the magnetization must rotate by 180n (Figure 7). Several theoretical and
experimental investigations have shown that in such nanowires two distinct types of
domain walls can exist: the transverse wall and the vortex wall [10], [11]. The transverse
wall forms the basis for the domain wall logics discussed in Sect. 4.
437
III Logic Devices
energy, the magnetization vector in the center of the disk turns out of the film plane form-
ing the vortex core. For symmetry reasons the magnetization vector in this vortex core
can point either up or down, that is it has two stable states. The vortex core itself, of
course, causes a magnetic stray field. In order to confine this stray field, away from the
vortex core the magnetization turns continuously into the plane. As a consequence of
these competing interactions the vortex core measures only a few nanometers in width.
Experiments have proven that the vortex core is a very stable magnetic entity and rel-
atively high magnetic fields of a few 100 mT are needed to switch it quasistatically
between the two stable positions. It is important to note that the magnetization in the vor-
tex core does not depend on the in-plane rotation of the magnetization in the rest of the
disc. Due to these particular properties vortex cores have been proposed for applications
in magnetic memory and logics. As discussed above, however, the magnetic element con-
taining the vortex and vortex core cannot be made arbitrarily small, otherwise a transition
into a single-domain state will occur [3]. From a current perspective this puts some limits
to the packing density of vortex-core based devices.
438
Spin-Based Logics Principles and Concepts
19
The maximum TMR values obtained with amorphous or polycrystalline Al2O3 tun-
neling barriers reach a saturation around 70 % [15], [16]. A variety of other oxides was
tested over the years, but the breakthrough was initiated in 2001 by a theoretical prediction
of TMR values exceeding 1000 % for a single-crystalline MgO(100) barrier with Fe(100)
electrodes [17], [18]. The microscopic mechanism for this spin-dependent tunneling pro-
cess involves spin transport through selected symmetry-matched electronic states in the
metallic electrode and the insulating barrier. The experimental confirmation of TMR val-
ues in excess of 100 % at room temperature followed in 2004 [19], [20], [21]. This coher-
ent tunneling mechanism, which can be seen as a state symmetry-related half-metallicity,
has presently enabled TMR values exceeding 600 % in MgO/CoFeB-based magnetic
tunnel junctions [22].
In terms of their magnetic and electrical performance, the present generation of mag-
netic tunneling junctions is already well suited for applications in magnetic logics.
439
III Logic Devices
Being a rather simple device at first glance, a realization of the spin FET poses some
major challenges, which we are only starting to meet now. Its operation may be broken
down into three sequential steps: the injection of spin-polarized charge carriers from the
source into the semiconductor, the transfer of the spin-polarized electron ensemble
through the semiconductor, and the detection of the spin polarization by means of the
drain electrode. As it turns out the major obstacle for an efficient spin injection is the con-
ductivity mismatch between ferromagnetic metal and semiconductor, which strongly
reduces the effective spin polarization in the semiconductor in diffusive transport [26].
This problem can be overcome by a careful electronic design of the metal-semiconductor
interface or by inserting insulators as tunneling barriers [27], [28], [29]. Successful spin
injection at room temperature into silicon has been already demonstrated [30].
In a similar way as a MTJ a spin-FET may be employed to define a simple logical
bit by the parallel and antiparallel state of the source and drain magnetization directions,
at the same time providing an integrated read-out mechanism. The gate control of the cur-
rent spin polarization, however, may open a possibility for enhanced functionalities, that
is in multivalued logics.
440
Spin-Based Logics Principles and Concepts
19
4 Magnetic Cellular Automata
The simplest structural approach to magnetic logics makes use of a two-dimensional geo-
metrical arrangement of magnetic clusters or nanodots and follows the principles of cel-
lular automata, hence they are called magnetic cellular automata MCA or sometimes also
magnetic (quantum) cellular automata MQCA. The size and shape of each entity is cho-
sen such as to provide a uniformly magnetized state with bistable magnetic switching
behaviour and sufficient thermal stability at room temperature. For circular Permalloy
(Ni80Fe20) nanodots, experimental investigations have shown that a uniform magnetiza-
tion state in thin film elements is indeed obtained if the size approaches the 100 nm length
scale [39]. In addition, a strong uniaxial anisotropy introduced by the elements shape
may improve the definition of the bistability. These conditions are fulfilled with thin
elliptical Permalloy elements on the 100 nm length scale.
The nanodots must be arranged into information conduits and logical gates in order
to set up functions for information processing. Such an information conduit may consist
of a linear chain of nanodots which are connected to each other by a well-defined mag-
netic interaction. Pioneering work by the Cowburn group has shown that circular mag-
netic platelets of 60 mm diameter can be efficiently coupled to each other by dipolar
fields, when the distance of the dots becomes of the order of or smaller than their lateral
extension [40].
The fundamental transfer of information on such a chain takes place in the following Figure 12: Linear chain of magnetic
manner. In the ground state all dots are magnetized in the same direction, for example, nanodots acting as an information conduit.
along the chain direction (Figure 12). This configuration may define the state 0. In order (a) Fully aligned dot magnetization;
to write the state 1 onto the chain, first the magnetization direction in a dedicated writing (b) reversal of the magnetization in an
injection pad at the end of the chain;
pad is reversed. The writing pad is coupled to the end of the chain by dipolar interactions
(c) by reversing the magnetization of the
(stray field). Due to the coupling, also the magnetization in the end dot of the chain is neighboring nanodot, a soliton (dotted
reversed, thereby propagating the information 1 into the chain. The information is thus line) is injected onto the chain;
effectively encoded in a magnetic soliton, which takes the form of a virtual domain wall (d) by applying an external field the
between the neighbouring dots. In order to propagate the information further along the soliton is driven along the conduit.
conduit, the soliton must be driven from one end of the chain to the other. This is achieved
by applying an appropriate field along the axis of the chain. In this way the entire chain
may be set to a state 1 by the soliton propagation [41]. If the chain is ending in a logical
gate structure, we can control the input of the gate by the state of the last dot in the chain.
In order for this principle to work, the magnetic switching fields and coupling
parameters in the dot system need to be carefully designed. An example for the case of
dipolar coupling between the elements is shown in Figure 15. The stable magnetization
direction is aligned with the long axis of the element. The bistable states are 1 w MR
(magnetization pointing to the right) and 0 w MR (magnetization pointing to the left).
As a next step a gate structure based on the nanodots has to be realized. A simple
type of gate is characterized by two input channels and one output channel. Nakatani
et al. have shown that a T-shape arrangement of four elliptical dots can be regarded as
a magnetic logic gate [42], [43]. Three of the dots serve as inputs (A, C, Z), whereas the
center fourth one (B) acts as the output. The resulting magnetic stray field generated by
the three input dots determines the magnetization direction and thus the logical state of
the output dot. The magnetic interplay of the four dots may be seen in Figure 13 which
reproduces the result of micromagnetic simulations. These simulations take into account
the realistic magnetization distribution in the dots which differs somewhat from a uni-
form magnetization. The dots were set to 40 nm q 80 nm in size, with 20 nm separation
in both the vertical and horizontal direction.
This gate has eight distinct magnetic configurations depending on the state of the
three input lines (Figure 13). In order to see the operation of the gate it is instructive to
consult the truth table (Table 1). We can see that the inputs A, C and the output B can be
used to represent either a NOR or a NAND operation, depending on the input on the line Table 1: Truth table for the
Z. In other words, the function of the gate can be toggled by the third input. device in Figure 13.
441
First, we introduce definitions to describe the geometry scaling shown in Figure 15
vs. the minimum feature size F. The die size, ADS, is the total area of a memory chip
which has grown in the past, but is expected to grow only slightly during the coming
memory generations for economic reasons. Large DRAMs and processors in the year
2010 had die sizes in the range from 100 to 250 mm2. The fraction of the storage matrix
area on the chip is given by XMatrix . For the 1 Gb DRAM generation, the storage matrix
area is approx. 60 % of the total die area, i.e. XMatrix 0.6. During the next RAM gener-
ations, this value is likely to stay almost constant or to increase very slightly (Figure 15).
The area of an individual storage cell at a node of the matrix is denoted ACA, which is
given by the square of the feature size, F2, times the cell area factor, XCA, which describes
how many F 2 are needed to realize the cell:
ACA X CA F 2 (8)
For example, on a typical 1 Gb DRAM chip a cell area factor XCA 6 is required to
realize a cell. According to the ITRS, it is expected that it will be possible to reduce XCA
to 4 in the long run (Figure 15). From these considerations one can calculate the total stor-
age capacity of a chip, i.e. the RAM capacity (bitschip) by
X Matrix ADS
RAM capacity (9)
X CA F 2
Figure 15 indicates, that a feature size in the range of 5 to 8 nm is needed in order to
manufacture an 1 Terabit (Tb) memory within 1 cm2. This is true of all types of
matrix-based memories which are able to follow the extrapolations for XMatrix and XCA
sketched in the diagram. The storage density in bitscm2 shows the progress in technol-
ogy more clearly than the total RAM capacity.
X Matrix
RAM density (10)
X CA F 2
In fact, the functional density of existing RAM technologies is scaled aggressively
up to the technological and physical limits. Also 3-D integration techniques (see
Chapter 34), i.e. vertical cells or multilayer stacks, as well as multilevel concepts, i.e.
several bits per cell (see, e.g., Chapter 26) are relevant which highly increase the RAM
density per projected area. For a better comparison, Figure 15 does not take 3-D concepts
and multilevel concepts into account.
In addition to the geometrical aspects, there are general trends for the electrical spec-
ifications which are independent of the specific type of memory. Since the overall perfor-
mance of a memory (energy per read or write operation, access times, etc.) are influenced
by the performance of both, the memory node (memory element plus selector) and the bit
and word lines of the array, we will briefly consider an empty array of just bit and word
lines first [21]. Assuming both the width of the interconnect lines and the separation
between neighbour lines have the same value F (Figure 16), one can easily obtain the fol-
3.1 Classifications
One of the most relevant classifications for the user of MSD systems concerns the write
procedure:
pre-written media are modulated during the fabrication process (such as standard
CDs, DVDs, BDs made by music and movie companies).
write-once media may be once written by the user. They are often called WORM
media (write once read many). A typical example is the BD-R (BluRay Recordable).
read/write (short: R/W media) can be re-written multiple times by the user. Magnetic
tapes and discs as well as magneto-optical and phase-change discs are common R/W
media.
A variety of physical access principles have been developed. The table in Figure 18 lists
some examples of MSD systems based on access by mechanical forces, by optical means,
by magnetic fields, and by electrical fields. Some of the systems will be described in
more detail below.
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V Memory Devices and Storage Systems
Another classification concerns the exchange of media. In some cases, such as mag-
netic hard discs, the access heads and the media are manufactured as an integrated unit.
In the case of hard discs, this is required because head and media need to be mutually cal-
ibrated with extreme precision. In operation, the head is flying approximately ten nano-
meters above the disc surface. In addition, the disc has to be isolated from dust particles
by a perfectly sealed case. If dust is of lower concern and the operating distance between
the access head and medium is significantly larger, exchangeable media systems such as
floppy disc systems or CD/DVD/BD systems are built [23], [36].
3.2 Dimensionalities
The speed of access to an arbitrary position in a MSD depends on the dimensionality of
mutual motion of the access unit and the medium:
1-D access All tape-based media (magnetic tapes, punch tape) are lead in an 1-D
motion along the access head. Accessing a new position means winding the tape until
the position is reached.
2-D access Any modem disc (magnetic hard discs, optical discs) is rotated and, in
addition, the head is positioned in an radial direction. This represents a full 2-D access.
3-D access Information stored in a volume medium can be accessed optically, for
example by the depth of focus or the viewing angle. This approach is exploited in the
holographic systems described in Chapter 32.
This classification can only be regarded as a first approximation. In many cases, a kind
of fractioned dimensionality is realized. For example, the magnetic recording in the Dig-
ital Audio Type (DAT) and in video tape systems utilizes the width of the tape to expand
the area for information storage by inclined recording. Similarly, the high-density DVDs
and BDs have several layers which are accessed by different depths of focus.
Figure 19: The Jacquard loom using punched
cards to control the weaving of pattern into fabrics.
(a) drawing showing the loom with the Jacquard
system on top. 3.3 Early Mechanical Recording Media
(b) a more detailed view of the Jacquard system The first data storage media in history for direct process control were the punched cards
and the chain of punched cards [23], [24]. developed by Joseph-Marie Jacquard in 1805. The Jacquard system enabled looms to
produce fabrics with individual woven patterns (Figure 19). These patterns were encoded
on the exchangeable punched cards using designated perforation positions. Later in the
19th century, Charles Babbage developed a (never realized) plan for an Analytical
Engine, the forerunner of the modern digital computer, and he envisioned punched cards
for the input of instructions and data.
The electrical reading and sorting of punched cards was introduced by Herman Hollerith
in machines for automating the tabulation work of the census in the United States in 1890.
Hollerith founded the Tabulating Business Machine Company, to manufacture these
machines. This company later merged with other firms to become IBM in 1924. Punched
cards were used as a storage media for computers until the 1970s (Figure 20) [26]. They have
Figure 20: Picture of a punched card for feeding been complemented by punched (or perforated) paper tapes since the 1950s (Figure 21).
computer systems [25]. The total width of the card For many decades of the 20th century, record players were the most popular systems
is 185 mm. for sound reproduction. Record players consist of motor-driven turntables for carrying
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Introduction to Part V
V
the record disc and the pick-up hold by a tone-arm. The analog sound information is
encoded in a groove impressed into the disc. It is read by moving the needle of the
pick-up as it is moving along the groove. The mechanical motions of the needle are elec-
tromagnetically or piezoelectrically converted into electric signals in the pick-up head
and passed on to the amplifier.
The scanning probe based concept (Chapter 31) can be regarded as a possible suc-
cessor of these early systems. It uses a digital coding similar to the punched cards and
tapes now on a nm-scale instead of a mm-scale, in order to obtain a very high density
data storage.
(a) (b)
While most of the systems are based on analog recording, i.e. the magnitude of the
magnetization of the tape represents the amplitude of the signal, there is also a range of
digitally coded tape systems, such as the Digital Audio Tape (DAT) and digital video for-
mats. These systems were also used in data storage applications. Many TB of data are
stored in magnetic cartridge archives which can be accessed automatically through
robot systems (Figure 23).
Magnetic disc systems have been introduced for data storage in the 1950s. The
media are metal or polymer discs coated on one or both sides with magnetic material.
R/W heads fly over the disc surface at close distance. In hermetically sealed hard disc
drives (HDD) up to 20 discs are mounted on the spindle of a drive unit (Figure 24). In the
1970s, the floppy disc was introduced. The medium is a flexible disc and represents a
typical exchangeable medium. Because of the geometrical tolerances required by the
exchangeability and the lower protection against dust, the storage capacity is much less
than in hard discs. A HDD is mainly composed of [31]:
1) The slider carrying the magnetic read/write heads. Data are written onto the disk with Figure 23: At the Fermilab, access to huge
the inductive write element and can be read back with the MR or GMR read element. amounts of data is provided by robotic systems
The slider is mounted onto the end of a stainless steel gimbal-suspension, forming a retrieving magnetic tape cartridges [34].
so called head-gimbal assembly. The slider has a profiled surface facing the medium
that forms an air-bearing surface allowing the head to fly at a close distance above
the medium. In modern HDDs, the fly height is less than 10 nm.
2) The magnetic disks (up to 10). Todays disks are between 1 inch and 5.25 inches in
diameter. The disk substrates are made of aluminum or glass. Both surfaces are cov-
ered with thin sputtered magnetic layers. The disk typically rotates at 5,40015,000
RPM giving a relative velocity of the slider of more than 100 kmh.
3) Electronics for data detection and write circuit. A channel converts the digital data to
be stored into write currents and supplies them to the head coil and on the other hand
receives signals from the read-element and translates them to digital data.
4) Mechanical servo and control system including the spindle, actuator and voice coil
motor. It provides a means of moving the head/slider to the desired track and also fine Figure 24: Schematic drawing of a hard
adjustments to retain the head in the center of the track. disc drive (HDD) and its parts [31].
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V Memory Devices and Storage Systems
Figure 25: Schematic illustration of the Figure 26: Geometrical format of the Compact Disc (CD).
perpendicular recording principle [31].
In modern HDD systems, perpendicular recording is used, i.e. the magnetic domain are ori-
ented perpendicular to the surface of the magnetic layer allowing for a very high bit density.
As illustrated in Figure 25 a narrow write gap is formed between P2 and a soft magnetic
under-layers which is serving as a flux return path towards the much wider P1 pole piece.
616
Introduction to Part V
V
between the byte data. 24 of these 17-bit units together with three bytes for error detection
Figure 27: Track distances and pits sizes for
and correction plus some overhead are called a frame. Since the audio signal on a stan- the CD, the DVD, and the BluRay disc (BD).
dard CD is resolved by 16 bit, a frame contains six audio values per channel:
1 frame: 24 byte 6 audio values per channel
1 sector 98 frames: 6 98 588 values per section
1 second 75 sectors: 588 75 44100 values
This reveals the standard sampling rate of 44.1 kHz used for audio CD systems. In the
case of the CD-ROM, some of the data bytes per sector are used for an addition error-cor-
rection, in order to increase the data security.
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V Memory Devices and Storage Systems
In the initial high resistance state (OFF-state) of the cell, no electrodeposit of the
metal M is present on the inert CE (Figure 12A). Hence, in the OFF-state the cell has to
be considered as an electrochemical half cell comprising of the AE and the adjacent elec-
trolyte layer, a serial resistance representing the electrolyte film, and a serial capacitor
comprising of the CE and the adjacent electrolyte layer (Figure 13). Because of second-
ary reactions, this may turn into a complete cell which shows a dedicated open cell volt-
age (emf voltage). For more comprehensive reviews on ECM, the reader is referred to
Ref. [41][44].
Figure 13: Equivalent circuit diagram of an ECM During the SET operation (Figure 12B and -C), a positive voltage is applied at the
cell in the OFF-state [9]. ZF denotes the Faraday active electrode (here: the Ag electrode) and Ag is oxidized to Ag ions which drift
impedance of the active electrode, Ci,Ag and Ci,Pt are towards the CE because of the electric field. At the CE acting as a cathode, an electro-
the interface capacitances of the electrochemically chemical reduction and an electro-crystallization of Ag on the surface of the inert elec-
active and inert electrode, respectively. Re and Ce
trode takes place. This process results in the formation of a Ag filament, which grows
represent the resistance and capacitance of the
electrolyte. Rp denotes a parallel resistance based on
towards the active electrode until an electrical contact is established which defines the
the electronic leakage current through the cell due ON-state (Figure 12D) and where further filament growth is limited by a compliance cur-
to, for example, thermoionic emission and hopping rent Icc . To RESET the cell a voltage with the opposite polarity is applied which leads to
conduction, or tunnelling in case of very thin the dissolution of the filament (OFF-state, Figure 12A).
electrolytes.
The filamentary nature of the ON-state has been first reported for lateral As2S3 cells
(Figure 15) [46]. Typically only one filament will provide the contact for the ON-state,
although there may be several nuclei, because the voltage will drop immediately, when
the first filament made the contact and Icc is reached. In lateral cells, the filamentary
growth occurs always at the surface, since there the filament formation is energetically
favored compared to the mechanical stress energy required by the formation of a new
phase in a solid. In thin film MIM cells to be used as ReRAM devices, the filament must
grow through the I-layer during the electroforming and the SET operation. Here,
extended defects such as nanopores or grain boundaries are considered to facilitate the
filament formation by limiting the local mechanical stress and may be regarded as pre-
requisites for a proper ECM operation. The diameter of the filament and the strength of
the electrical contact between the filament and the AE are controlled by the level of the
compliance current Icc which is set for the operation.
As explained in Sec. 4.4, the RON value of ReRAM cells is controlled by Icc . The
range for ECM cells is particularly large [28]. From an application point of view, this
reflects excellent multilevel programming capabilities of ECM cells, since RON can be
established over several orders of magnitude. RON will be determined by the physical
nature of the filament and the contact at the AE. For low RON values, relative thick fila-
ments and a galvanic contact at the AE must be assumed. For high RON values, filaments
may have a thickness of few nanometers only and a tunnel gap may be present between
the filament tip and the AE.
We will now discuss the kinetics of the electroforming and the SET process and we
will try to identify the possible rate-limiting processes. As shown by the example given in
Figure 16a, at constant voltage sweep rate, the voltage VSET,form during the initial electro-
forming cycle is significantly higher than the SET voltage VSET for the subsequent switch-
ing cycles. Furthermore, VSET,form increases linearly with the thickness of the SiO2-film,
whereas the SET voltage for all subsequent switching events, VSET , is almost thickness
Figure 16: Currentvoltage characteristic of a
independent (Figure 16b). This behavior reveals that during the electroforming cycle, the Cu/SiO2 ECM cell showing the first
rate of the forming process (i.e. the 1st SET process) presumably is determined by an elec- (electroforming) and subsequent cycles.
tric field driven migration of Cu cations in the SiO2-film, i.e. step 2 might be the rate-lim- (a) Forming and subsequent switching cycles
iting step during this process. After the formation of the first Cu filament and its measured at a sweep rate 1 Vs on a Cu/SiO2/Pt
dissolution during the first RESET, the remaining structural template of the dissolved fil- cell with a 15 nm thick oxide layer.
ament in the film may act as a fast transport and growth path. In any case, the much lower (b) Oxide film thickness dependence of the SET
SET voltage VSET and its thickness independence observed during the subsequent switch- voltage for the electroforming, VSET,form , and
ing cycles can be explained by a path for fast ion transport and preferential filament growth subsequent switching cycles, VSET [14].
that is formed in the amorphous SiO2 film during the first electroforming cycle.
The kinetics of the SET process in the ECM cells is illustrated in Figure 17 which
shows a tSET vs. VSET plot of experimental data obtained from pulse experiments in the
ECM memory system Ag/GexSy/W. A clear exponential relationship between the switch-
ing time and the switching voltage is observed for VSET 2 0.4 V while for long switching
times a critical SET voltage seems to be approached. The pronounced exponential rela-
tionship and, in particular, a critical threshold voltage for the SET process explain, how
the voltagetime dilemma is overcome for the SET process in ECM cells. If we apply the
discussion in Section 4.3, then steps 1 to 3 may, in principle, be responsible for the non-
linear kinetics if they were the rate-limiting step. However, a detailed analysis renders
step 2 less likely to be rate-limiting [14]. This conclusion is further supported by the fact
that the SET voltage, VSET , is almost not thickness dependent as discussed above. In
step 3, the cathodic electron transfer reaction controlled by the Butler-Volmer
Equation (11) and the nucleation probability both show an exponential dependence on
the voltage and, thus, may represent the highly nonlinear rate-limiting step. Alternatively, Figure 17: Switching time versus SET voltage
this role may also be resumed by the electron transfer of the anodic oxidation step 1. It on a Ag/GexSy/W cell [47]. An exponential
should be noted that as soon as an electrical contact is made by the filament and a signif- relation is clearly observed at high voltages. For
icant current (I 2 3 A) flows, the further growth of the filament may be temperature long switching times the SET voltage seems to
assisted by Joule heating. saturate.
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V Memory Devices and Storage Systems
The growth (and dissolution) rate r of the metallic filament according to step 4 can
be derived using Faradays law [48], [49] as:
MM
r J M z (15)
ze &ASm,M
Here, J M z is the ionic current density, MM the atomic mass and Sm,M the mass den-
sity of the deposited metal. According to Eq. (15), the switching speed of the ECM cells
could also be determined by the growth rate of the filament. An estimation shows that a
Faradaic current of 1 A and an assumed (constant) filament diameter of 3 nm would
bridge an I-layer of 10 nm within 1 ns. For determining the resistance of very thin fil-
aments, mesoscopic effects have to be taken into account (Chapters 3 and 33).
5.4 Variants
Numerous variants of ECM-type resistive switching systems have been reported since the
mid 1970s, some of which have only much later been identified to belong to this type.
Here we report upon the two most relevant variants.
One variant can be described as a mixed ionic-electronic conducting (MIEC) supply
system (see Figure 19). The electrochemically active electrode metal M is in intimate elec-
trochemically reversible contact with a MIEC phase where the ionic conduction is due to
Mz. The interface of this MIEC phase to the I-layer represents the active electrode in the
Figure 19: Illustration of a MIEC supply sense discussed above. Obvious the MIEC layer fulfils the purpose of a metal electrode act
ECM system. Here a Cu-based cell is shown. as a supply and reservoir for Mz ions and to provide an electronic contact. In addition, it
A mixed-ionic electronic conduction (MIEC) helps to preserve the morphology much better than a pure metal electrode, because it con-
layer is present between the electrochemically sists of additional components which are not consumed or re-precipitated while they sup-
active electrode (AE) and the resistive I-layer
port the MIEC activity. It is important to note that the electronic partial conductivity in the
of a standard ECM cell. The MIEC layer
contains the active CuE ions (compensated by MIEC system is high and any electric field will drop mainly across the I-layer while there
electrons) which are required to form the is almost no field in the MIEC layer. Ions in this layer are transported by diffusion.
metal filament during SET. Examples for A typical example of an organometallic MIEC supply ECM system is the Cu doped
MIEC layers are Cu:TCNQ, CuTex, and Cu2S. tetracyanoquinodimethane (Cu-TCNQ) MIEC layer, typically in a Cu/Cu:TCNQ device
698
Redox-based Resistive Switching Memories
30
structure with an Al counter electrode. The system has been known since the late 1970s
and it was originally believed that the resistive switching stems from an internal redox
reaction when Cu:TCNQ is formed. Later it was shown that due to the processing, an
inherent Al2O3 layer is formed on the Al electrode which is the true I-layer supporting
the switching operation [52], [53]. An inorganic variant of the MIEC supply system is
given by CuTex deposited on a doped Si electrode covered by a very thin Al2O3 I-layer
[54]. Also the traditional ECM systems based on the (mixed-conducting) Ag- or
Cu-doped GeSx and GeSex phases can be turned into a supply system by introducing a
thin GeO2 or SiO2 layer, which is much less electronically conducting and acts as an
I-layer. This measure has been used to reduce the SET/RESET currents considerably
while still obtaining stable switching.
Another important variant is called the gap-type atomic switch, which obtained its
name because of its ultimate scalabilty (Sec. 5.5). This variant also relies on a MIEC
layer forming an electrochemically reversible electrode, for example Ag/Ag2S, and an
inert counter electrode such as Pt. The original gap-type atomic switch was published by
the Aono group in 2005 [55]. It has been built from cross points of wires. During the ini-
tial processing and electroforming, a controlled vacuum nano-gap (_ 1 nm) between the
MIEC surface and the Pt is created. In a subsequent SET operation, a negative potential
is applied to the Pt electrode, which leads to electron tunnelling towards the Ag2S surface.
Ag ions in the surface are reduced and a Ag nucleus is formed, which grows towards the
Pt electrode until a metallic contact is achieved (Figure 20c). By reversing the polarity,
the device can be RESET. This type of switching can also be achieved using an STM tip
as top electrode, which is placed within tunnelling distance to a Cu2S thin film [56].
Please note that in contrast to the description of the standard ECM cell, the metallic fila-
ment grows in opposite direction, i.e. towards the inert electrode due to the presence of
the vacuum gap. The growth direction in all variants of ECM cells, in general, is predom-
inantly determined by the path which leads to the least mechanical stress when the new
metal phase is formed, in order to minimize the overall free energy of the system.
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VI Data Transmission and Interfaces
824
RF and Microwave Communication Systems, Circuits and Devices
36
In Eq. (16) A represents the area of the microbridge, g0 the equilibrium position at
zero voltage, and F0 8.85 1012 AsVm. The spring constant k depends on the bridge
dimensions and the Young modulus of the bridge material. Accordingly, the total force on
the spring (electrostatic force minus spring repelling force) has a minimum at g 2g03.
Consequently, the pull-down voltage Vp at which the bridge collapses is given by:
8kg 03
Vp (17)
27F0 A
As an example, for g0 2.5 mm, A 100 mm2 and k 10 Nm the pull-down volt-
age comes out to be 23 V. Such values are typical for electrostatic microwave MEMS
switches. Since the electrostatic force increases upon decreasing the gap, the voltage to
keep the switch in the down state is lower than the switching voltage.
The fundamental mechanical resonance frequency of a double-clamped flexural
beam of length l and thickness d in direction of motion is given by the expression
1 k E d
fr 1.03 (18)
2Q m S l2
with E representing Youngs modulus and S the density of the beam material
(Au: E x 80 GPa, S 19280 kgm3). For typical dimensions of MEMS switches
(l 300 mm, d 2 mm) this value is in the order of 50 kHz. Typically, the resonance is
damped from typical Q-values in vacuum of about 501000 to values of only
0.3 b Q b 5 by operating the switch at atmospheric pressure (damping by removing the
air underneath the bridge). Due to the risk of contamination, pakkaging of the MEMS
switches has to be performed under clean room conditions. With such a design, switching
times in the order of 250 ms and several billions of switching cycles can be achieved.
Possible application areas of RF-MEMS are switched filter banks for wireless com-
munications systems (both for base stations and portable units), phase shifters for radar
systems switching networks, for example for communication satellites. Although MEMS
technology has reached a high level of maturity, reliability is still an issue. Current R&D
are addressing issues of packaging and how to avoid the sticking of the cantilever in the
down-position as a results of electrostatic charging [13].
FBARs (Film Bulk Acoustic Resonators) and NEMS resonators: Today, acoustic res- Figure 12: Picture of a capacitive MEMS
onators based on bulk single crystals of quartz are all-present as time defining (i.e. fre- switch (a), cross section view (b) and
quency stabilizing) element in almost any commercial electronic device. For the equivalent circuit (c) with Cu and Cd
microwave frequency range, surface rather than bulk acoustic resonators are most com- representing the value of the capacitance
monly used, that is as filters in mobile phones (SAW = surface acoustic wave devices) in the up and down state (from [15]).
Due to the possibilities associated with micromachining bulk acoustic resonators for
the microwave regime have become feasible, representing ultimate performance with
respect to their miniaturisation and on-chip integration potential. As an example, for sil-
icon a double-clamped flexural beam of l 10 mm and d 1 mm would resonate at
about 50100 MHz according to Eq. (18) (E 160 GPa and S 2330 kgm3 for silicon.
SiN and AlN are promising materials for microbridge resonators with Qs in the range of
several 10,000 [14]. Carbon nano tubes and, and in particular, single layers of graphite
( graphene), represent an extremely promising approach due to an extremely high
Young modulus of the order of 1 TPa, low density and high elasticity [5]. In order to
achieve frequencies in the GHz range submicron lithography is required. For such dimen-
sions the issues of resonance excitation, precise control of resonance frequency and small
values of resonant energy need to be addressed in order build devices for practical use in
telecommunication.
As an alternative, free-standing bridges of piezoelectric materials of 100 mm length
can be used to build bulk acoustic resonators for the GHz range [4]. Figure 13 shows the
schematic of an FBAR (Film Bulk Acoustic Resonator) structure consisting of ZnO (or
AlN) membrane with thin-film metallic electrodes (deposited on a silicon wafer with sub-
sequent underetching). The fundamental resonance occurs when the film thickness is half
the wavelength. For the fundamental mode being at f 2 GHz, the corresponding thick-
ness is 2.6 m (sound velocity of AlN: 10,400 ms).
FBAR filter devices for mobile phones are in use in mobile phones and have already
surpassed the performance of state-of-the art SAW devices. Similar to MEMS switches, Figure 13: Free standing bimetal bridge with a
the issue of packaging is rather crucial, since high Qs above 1000 can only be achieved combined thermal/electrostatic actuation scheme,
at reduced atmospheric pressure therefore, packaging is an important issue. fabricated by a sacrificial layer technology from a
Au/Nb bilayer (from [6]).
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VI Data Transmission and Interfaces
5.2 Compression
Since the gain B1 3 4
B3v 2 for the sinusoidal component depends on the input ampli-
tude, the gain and the output amplitude will decrease at higher input power levels as
shown in Figure 16. Due to the RF measurement capabilities it is quite convenient to
characterize the power in dBm and the gain in dB. The circuits nonlinearity has to be
Figure 15: Output spectrum of the nonlinearity described is a figure of merit, which can be measured easily. The 1 dB compression point
due to a sinusoidal excitation. The color of the is one of these figures. Figure 16 illustrates the determination of the 1 dB input compres-
components indicated the order of the generating sion point, where either the output power or the gain is measured versus the input power.
nonlinearity. The 1 dB compression point is the input power level where the output power or the gain
diverts by 1 dB from the ideal linear behavior. The 1 dB compression point can be related
to ratio B1B3 of the nonlinearities Taylor series expansion
2 B 0.0725 B1
P1dB
3Rin
1101/20
1
B3 Rin B3
(22)
The above relation gives an easy way to model the compression behavior of an arbi-
trary nonlinearity for a system simulator or Hardware-Description-Language-based ver-
ification models.
826
RF and Microwave Communication Systems, Circuits and Devices
36
The 1 dB compression point basically gives the upper bound for the linear behavior
of a circuit or subsystem. If the received signal contains any type of amplitude modula-
tion, the signal level has to be kept below the compression point with some margin. For
signal with frequency- or phase-modulation only the single level can exceed the compres-
sion point without any degradation of the RX quality.
Intermodulation
Mostly a receiver has to cope with multiple signals present at the input. An example is
given in Figure 17, where a small wanted signal is accompanied by two large signals on
adjacent frequencies. If the frequencies are equally spaced, than a frequency component
generated by a third order nonlinearity will fall into the bandwidth of the wanted signal
and degrade the RX quality severely.
The origin of this phenomenon will be studied by applying two sinusoidal
vin v1 cos X1t v2 cos X2t to the input of the nonlinearity, which yields to
2 B v3
vout B0 B1vin B2vin 3 in
B0 B1v1 cos X1t B1v2 cos X2t Figure 17: Degradation mechanism
due to third order intermodulation. Toe
B2 v12 cos 2 X1t 2v1v2 cos X1t cos X2t v22 cos 2 X2t
(23) interfering signal at X1 and X2 are
generating an intermodulation product
v3 cos3 X1t 3v 2v2 cos 2 X1t cos X2t
at the frequency 2X2-X1, which may be
B3 1 1
3v1v22 cos X1t cos 2 X2t v23 cos3 X2t the frequency of the wanted RF signal.
Figure 18:
Spectrum due to
two tone
excitation.
The frequency components generated by the different order nonlinearities are visu-
alized in Figure 18. The high frequency components located around 2 X1 X2
2 and
3 X1 X2
2 can be filtered easily. The components located around the fundamental
X1 X2
2 cannot be filtered out and therefore are potentially degrading the RX quality.
They are generated by direct amplification of the two sinusoidal input signals and by third
order intermodulation. Last but not least the second order nonlinearity generates a DC
component consisting of two contributions due to the two input tones.
Under typical operating conditions of a wireless receiver intermodulation sets the lim-
its of the receivers capability to cope with interfering signals, which will yet be discussed.
Figure 20:
Geometrical
calculation of the 3rd
order intercept point.
The 3rd order intercept
point is given by the
interception of the
extrapolated
fundamental and 3rd
order component.
The value of the 3rd order input intercept point (IIP3) can be derived from the geo-
metric interpretation of Figure 20, which leads to
dB PX1
dB P2X1X2
IIP3 dB Pin,X1
(24)
2
For a receiver chain it is required to calculate the overall intercept point in a similar
fashion as Frijs equation is needed to calculate the total noise. In [16] a more detailed
derivation of following equation can be found
n1
1 1 G G G
GP,i
P,1 P,2 P,1 y i1 (25)
PIP3 PIP3,1 PIP3,2 PIP3,3 PIP3,n
Following the concepts presented a 2nd order intercept point is defined as well. The
measurement is slightly more complicated due to the fact that the output components gen-
Figure 21: Remodulation in a homodyne erated by the 2nd order are located at DC or at twice the input frequency. Therefore they
transmitter due to parasitic feedback of the might be attenuated heavily by the circuitry and all power levels have to be referred to
transmitted signal. The frequency of the the input. A detailed derivation of the IIP2 can be found in [17].
output signal and the oscillator differ due
to modulation. Therefore the parasitic
feedback of the output signal can cause a
Linearity Requirements of Devices and Circuits
degradation of the signal quality.
It is difficult to give a general recommendation concerning the linearity of a circuit,
because a lot of short comings of the device might be compensated by the creativity and
inspiration of the circuit and system designers. Nevertheless for a RF frontend there will
always be a LNA and mixer, which are going to set the upper edge of the dynamic range
by their linearity. A good compromise between noise, gain and linearity has to found for
the devices used in the RF frontend.
A good integrated LNA requires a high gain, a low noise factor and an input imped-
ance, which can easily be matched to the preceding filter. Whereas the linearity of the
LNA is not as import, because the LNA is the first active component in the receive chain
and there is no gain in front of the LNA. According to Eq. (25) the intercept point will be
reduced by the gain of the preceding stages. Typically the mixer is the last broad band
stage in front of the channel select filter resulting in the highest IP3 requirements.
828
RF and Microwave Communication Systems, Circuits and Devices
36
tendency to lock to an external disturbance has been a major implementation burden for
quite a long time. Integration has solved this problem by shifting the VCO frequency
away from the output frequency once again, but this time the VCO has been moved to an
even multiple of the output frequency typically two or four. In the case of a GSM trans-
mitter the VCO operates at 3.6 GHz, which is twice the frequency of GSM 1800 and four
times GSM 900. The local oscillator requires a coil in order to reduce the unwanted emis-
sion caused by VCOs phase noise. At 3.6 GHz the coil is quite small and the quality fac-
tor can be optimized to meet the requirements. Moreover the small coil area reduces any
potential magnetic coupling as well. Finally the 90 phase shift for the quadrature upcon-
version is generated by a divide by two circuits as shown in Figure 22. This quadrature
Figure 23: Unwanted emission in a homodyne
generation assumes a 50 % duty cycle of the oscillators output signal, where the positive transmitter. All spurious tones as well as the
and negatives edges are used to trigger the divide-by-two-circuit. The good accuracy of broadband noise in the adjacent channels will be
the 90 phase shift generated by the frequency divider is another advantage of the high transmitted as there is no subsequent narrowband
integration level. filter.
The homodyne or direct upconversion transmitter has some inherent issues as well,
which cannot be solved by the integration level. In a heterodyne transmitter the modu-
lated IF signal can be filter by narrowband channel filter before the final upconversion to
the desired carrier frequency. Due to the direct conversion no additional filtering after the
quadrature modulator can be applied. Therefore spurious tones generated by the fre-
quency synthesizer stabilizing the VCO as well as the VCOs noise are present in the out-
put signal as shown in Figure 23. These components present in the output spectrum are
unwanted emissions in adjacent channels. From a system point of view they will result in
a reduction of the overall capacity because the frequency of the adjacent channel cannot
be reused in neighboring cells without degrading the SNR.
Figure 23 shows another fundamental limitation of quadrature modulators, which is
caused by the local oscillator feed trough. The modulator is typically based on two double
balanced multipliers implemented using Gilbert cells as shown in Figure 24. For an ideal Figure 24: Feed through of the local oscillator
fully differential operation the DC bias of the input voltages is eliminated signal in a Gilbert cell multiplier used as mixer.
Even neighboring transistors in a differential pair
vTX t
vTX+ t
vTX t
k vLO+ t
vLO t
vBB+ t
vBB t
829
VI Data Transmission and Interfaces
7.1 Selectivity
The performance of A/D-converters has been improved quite a lot since 2000. CMOS
scaling has provided some gain with respect to the maximum available resolution. Never-
theless the major improvements are due to architectural choices or the use of new con-
Figure 26: Simplified block diagram cepts. Changing the architecture of an over-sampling 4%-A/D-converter from discrete
of a homodyne receiver suited for time processing to continuous time processing allows much higher sampling rates. The
integration. Integration allows a precise continuous time loop filter of the 4%-modulator eliminates the need of a dedicated
generation of the 90 required for the anti-aliasing filter and provides additional interference rejection for the adjacent channels.
down conversion. Moreover the
The channel selection as well as the 4%-modulators loop filter are implemented as RC-fil-
amplitude can be matched in the two
orthogonal baseband signal paths. ters sharing the same calibration circuitry. The increased A/D-resolution covers today the
fully dynamic range requirement of a GSM receiver, which can be built therefore without
any high gain amplification at baseband. Thus the influence of DC offsets in the front end
reduced and the remaining influence can be compensated in the digital domain easily.
Despite all the advantages provided by the increasing integration level there are still
fundamental mechanism which can only be handled by the pure analog performance of
the devices and circuits. One example is the spectral purity of the local oscillator signal
used for the down conversion of the received signal. A VCO or more general a complete
synthesizer does not generate a pure sinusoidal. The output signal will always exhibit
spurious tones, 1f-noise as well as broadband noise, which lead to a limitation of the
receivers selectivity. Figure 27 illustrates this selectivity limitation considering only the
influence of LO spurs for the time being. The mixer convolutes the spectrum of the RF
input signals with the LO signal spectrum. Large interferes present at the input may be
converted to the same output frequency as the wanted signal. At this intermediate fre-
quency IF, which is zero for a homodyne receiver, the channel select filter will remove
the interfering components in adjacent channels. As the LO spurs may convert an inter-
ferer into the passband of the channel filter this component cannot be removed and will
therefore act as a co-channel signal limiting the receivers selectivity. The 1f-noise and
the broadband noise present in the LO spectrum will generate a noise contribution within
the channel filters passband. The mechanism describes the purity requirements for the
LO signal, which might be quite demanding if large interferes are present. Two mobiles
operating in close proximity at the edge of a cell should not limit the sensitivity of each
other. Thus GSM calls for 162 dBcHz phase noise in 20 MHz offset, which is the fre-
quency separation between the lowest RC channel and the highest TX channel of this half
duplex FDD system.
830
RF and Microwave Communication Systems, Circuits and Devices
36
831
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