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ALD Applications
Atomic Layer Deposition (ALD) has the potential to optimize product design
across a wide array of applications -- from making silicon chips run faster,
to increasing the efficiency of solar panels, to improving the safety of
medical implants.
Thin films, strong adhesion characteristics, and reproducible results of ALD
make it ideal for many research labs and large batch manufacturing
environments.
The ability to produce thin films to exacting standards makes ALD a
compelling solution for depositing high-quality films to challenging
substrates, such as heterostructures, nanotubes, and organic
semiconductors.
Many technologists and researchers are replacing older deposition
techniques such as evaporation, sputtering, and chemical vapor deposition
with ALD to take advantage of its unique ability to produce conformal
coating in and around 3D objects in a highly consistent manner.
High-k dielectrics
Hydrophobic coating
Passivation layer
High aspect ratio diffusion barriers for Cu interconnects
Conformal coatings for micro fluidics applications
Fuel cells, e.g. single metal coating for catalyst layers
Features
Less than 1Å uniformity
13" anodized Al chamber
Minimal volume for fast cycle time and throughput
Up to 8" substrate
Heated chamber walls
Using the CVD method a wide variety of coatings may be formed, ranging
from soft, ductile coatings to those with hard, ceramic like properties.
Coating thicknesses can vary from a few micron to over 200 mm, with
hardnesses in the range 150–3000 HV (0.1Kg). Coatings formed by the
CVD being used to combat the severe attrition of components used in a
variety of industrial situations where corrosion, oxidation or wear is
experienced.
The methods commonly used to apply CVD coatings will be discussed and
their advantages and limitations examined. Several case studies will be
highlighted, where CVD coatings have been used to solve specific
industrial problems.method are currently
XPS can be used to analyze the surface chemistry of a material in its as-
received state, or after some treatment, for example: fracturing, cutting or
scraping in air or UHV to expose the bulk chemistry, ion beam etching to
clean off some or all of the surface contamination (with mild ion etching) or
to intentionally expose deeper layers of the sample (with more extensive
ion etching) in depth-profiling XPS, exposure to heat to study the changes
due to heating, exposure to reactive gases or solutions, exposure to ion
beam implant, exposure to ultraviolet light.
XPS is also known as ESCA (electron spectroscopy for chemical analysis),
an abbreviation introduced by Kai Siegbahn's research group to emphasize
the chemical (rather than merely elemental) information that the technique
provides.
Detection limits for most of the elements (on a modern instrument) are in
the parts per thousand range. Detection limits of parts per million (ppm) are
possible, but require special conditions: concentration at top surface or very
long collection time (overnight).
What elements and the quantity of those elements that are present within
the top 1-12 nm of the sample surface
The thickness of one or more thin layers (1–8 nm) of different materials
within the top 12 nm of the surface
Chemical state analysis of the surface of a silicon wafer readily reveals chemical
shifts due to the presence or absence of the chemical states of silicon in its
different formal oxidation states, such as: n-doped silicon and p-doped silicon
(metallic silicon in figure above), silicon suboxide (Si2O), silicon monoxide (SiO),
Si2O3, and silicon dioxide (SiO2). An example of this is seen in the figure above:
High-resolution spectrum of an oxidized silicon wafer in the energy range of the Si
2p signal.
Air was allowed to mix with acetylene gas from the gas cylinder in good
proportion to ignite the burner of the Spectrophotometer. Immediately after
ignition, the spectrophotometer was calibrated using blank (distilled water)
and standard solution (as supplied with the spectrophotometer). The
aerosol of the sample was then aspirated through the nebulizer into the
flame for analysis. Analysis was done for each element of interest at their
specific wavelength using the hollow cathode lamp of the element
under investigation. Finally, the result is displayed on the computer read-
out.
-spin state: Protons that align with the external magnetic field. They are in a lower
energy state. _-spin state: Protons that align against the external magnetic field.
They are in a higher energy state
The _E is the energy difference between the _ and _ spin states. This depends on
the applied magnetic field. As shown by the graph above, the greater the strength
of the applied magnetic field, the larger the energy difference between the two
spin states. When radiation, that has the same energy as the _E, is placed upon
the sample, the spin flips from _ to _ spin states. Then, the nuclei undergoes
relaxation. Relaxation is when the nuclei return to their original state. In this
process, they emit electromagnetic signals whose frequencies depend on _E as
well. The HNMR spectrometer reads these signals and plots them on a graph of
signal frequency versus intensity. Resonance is when the nuclei flip back and forth
between _ and _ spin states due to the radiation that is placed on them. To
summarize, an NMR signal is observed when the radiation supplied matches the
_E. And, the energy required to cause spin flip is dependent on the magnetic
environment experienced by the nucleus
GC-MS schematic
These two components, used together, allow a much finer degree of
substance identification than either unit used separately. It is not possible
to make an accurate identification of a particular molecule by gas
chromatography or mass spectrometry alone. The mass spectrometry
process normally requires a very pure sample while gas chromatography
using a traditional detector (e.g. Flame ionization detector) cannot
differentiate between multiple molecules that happen to take the same
amount of time to travel through the column (i.e. have the same retention
time), which results in two or more molecules that co-elute. Sometimes two
different molecules can also have a similar pattern of ionized fragments in a
mass spectrometer (mass spectrum). Combining the two processes
reduces the possibility of error, as it is extremely unlikely that two different
molecules will behave in the same way in both a gas chromatograph and a
mass spectrometer. Therefore, when an identifying mass spectrum
appears at a characteristic retention time in a GC-MS analysis, it typically
increases certainty that the analyte of interest is in the sample.
Description
The Gas Chromatography/Mass Spectrometry (GC/MS) instrument
separates chemical mixtures (the GC component) and identifies the
components at a molecular level (the MS component). It is one of the
most accurate tools for analyzing environmental samples. The GC works
on the principle that a mixture will separate into individual substances
when heated. The heated gases are carried through a column with an
inert gas (such as helium). As the separated substances emerge from the
column opening, they flow into the MS. Mass spectrometry identifies
compounds by the mass of the analyte molecule. A ÒlibraryÓ of known
mass spectra, covering several thousand compounds, is stored on a
computer. Mass spectrometry is considered the only definitive analytical
detector.
High-performance liquid chromatography
applications
High-performance liquid chromatography (HPLC; formerly referred to
as high-pressure liquid chromatography) is a technique in analytical
chemistry used to separate, identify, and quantify each component in a
mixture. It relies on pumps to pass a pressurized liquid solvent containing
the sample mixture through a column filled with a solid adsorbent material.
Each component in the sample interacts slightly differently with the
adsorbent material, causing different flow rates for the different
components and leading to the separation of the components as they flow
out of the column.
HPLC has been used for manufacturing (e.g., during the production
process of pharmaceutical and biological products), legal (e.g., detecting
performance enhancement drugs in urine), research (e.g., separating the
components of a complex biological sample, or of similar synthetic
chemicals from each other), and medical (e.g., detecting vitamin D levels in
blood serum) purposes.[1]
Chromatography can be described as a mass transfer process
involving adsorption. HPLC relies on pumps to pass a pressurized liquid
and a sample mixture through a column filled with adsorbent, leading to the
separation of the sample components. The active component of the
column, the adsorbent, is typically a granular material made of solid
particles (e.g., silica, polymers, etc.), 2–50 μm in size. The components of
the sample mixture are separated from each other due to their different
degrees of interaction with the adsorbent particles. The pressurized liquid is
typically a mixture of solvents (e.g., water, acetonitrile and/or methanol)
and is referred to as a "mobile phase". Its composition
and temperature play a major role in the separation process by influencing
the interactions taking place between sample components and adsorbent.
These interactions are physical in nature, such as hydrophobic (dispersive),
dipole–dipole and ionic, most often a combination.
HPLC is distinguished from traditional ("low pressure") liquid
chromatography because operational pressures are significantly higher
(50–350 bar), while ordinary liquid chromatography typically relies on the
force of gravity to pass the mobile phase through the column. Due to the
small sample amount separated in analytical HPLC, typical column
dimensions are 2.1–4.6 mm diameter, and 30–250 mm length. Also HPLC
columns are made with smaller adsorbent particles (2–50 μm in average
particle size). This gives HPLC superior resolving power (the ability to
distinguish between compounds) when separating mixtures, which makes it
a popular chromatographic technique.
The schematic of a HPLC instrument typically includes a degasser,
sampler, pumps, and a detector. The sampler brings the sample mixture
into the mobile phase stream which carries it into the column. The pumps
deliver the desired flow and composition of the mobile phase through the
column. The detector generates a signal proportional to the amount of
sample component emerging from the column, hence allowing
for quantitative analysis of the sample components. A
digital microprocessor and user software control the HPLC instrument and
provide data analysis. Some models of mechanical pumps in a HPLC
instrument can mix multiple solvents together in ratios changing in time,
generating a composition gradient in the mobile phase. Various detectors
are in common use, such as UV/Vis, photodiode array (PDA) or based
on mass spectrometry. Most HPLC instruments also have a column oven
that allows for adjusting the temperature at which the separation is
performed.
Theoretical
Operation
The sample mixture to be separated and analyzed is introduced, in a
discrete small volume (typically microliters), into the stream of mobile
phase percolating through the column. The components of the sample
move through the column at different velocities, which are a function of
specific physical interactions with the adsorbent (also called stationary
phase). The velocity of each component depends on its chemical nature,
on the nature of the stationary phase (column) and on the composition of
the mobile phase. The time at which a specific analyte elutes (emerges
from the column) is called its retention time. The retention time measured
under particular conditions is an identifying characteristic of a given
analyte.
Many different types of columns are available, filled with adsorbents
varying in particle size, and in the nature of their surface ("surface
chemistry"). The use of smaller particle size packing materials requires the
use of higher operational pressure ("backpressure") and typically improves
chromatographic resolution (i.e., the degree of separation between
consecutive analytes emerging from the column). Sorbent particles may be
hydrophobic or polar in nature.
Common mobile phases used include any miscible combination
of water with various organic solvents (the most common
are acetonitrile and methanol). Some HPLC techniques use water-free
mobile phases (see Normal-phase chromatography below). The aqueous
component of the mobile phase may contain acids (such as formic,
phosphoric or trifluoroacetic acid) or salts to assist in the separation of the
sample components. The composition of the mobile phase may be kept
constant ("isocratic elution mode") or varied ("gradient elution mode")
during the chromatographic analysis. Isocratic elution is typically effective
in the separation of sample components that are very different in their
affinity for the stationary phase. In gradient elution the composition of the
mobile phase is varied typically from low to high eluting strength. The
eluting strength of the mobile phase is reflected by analyte retention times
with high eluting strength producing fast elution (=short retention times). A
typical gradient profile in reversed phase chromatography might start at 5%
acetonitrile (in water or aqueous buffer) and progress linearly to 95%
acetonitrile over 5–25 minutes. Periods of constant mobile phase
composition may be part of any gradient profile. For example, the mobile
phase composition may be kept constant at 5% acetonitrile for 1–3 min,
followed by a linear change up to 95% acetonitrile.
A rotary fraction collector collecting HPLC output. The system is being used
to isolate a fraction containing Complex I from E. coli plasma membranes.
About 50 litres of bacteria were needed to isolate this amount.[2]
The chosen composition of the mobile phase (also called eluent) depends
on the intensity of interactions between various sample components
("analytes") and stationary phase (e.g., hydrophobic interactions in
reversed-phase HPLC). Depending on their affinity for the stationary and
mobile phases analytes partition between the two during the separation
process taking place in the column. This partitioning process is similar to
that which occurs during a liquid–liquid extraction but is continuous, not
step-wise. In this example, using a water/acetonitrile gradient, more
hydrophobic components will elute (come off the column) late, once the
mobile phase gets more concentrated in acetonitrile (i.e., in a mobile phase
of higher eluting strength).
The choice of mobile phase components, additives (such as salts or acids)
and gradient conditions depends on the nature of the column and sample
components. Often a series of trial runs is performed with the sample in
order to find the HPLC method which gives adequate separation.
Applications
Surface structures
Samples for SEM need typically to be dry and conductive. Therefore, biological
specimens are fixated, dehydrated and coated with thin layer of metal. Small
specimens are dehydrated chemically, via ascending concentration series of
alcohol and hexamethyldisilazane (HDMS), but larger specimens can be dried
using a critical point drying (CPD) instrument. In either case, water within the
specimen is substituted with a solvent with lower surface tension that helps
keeping the specimen structure intact. Our new SEM (Zeiss Sigma HD|VP) has
maximum reolution of about 1 nm.
However, also non-conductive specimens can be imaged with appropriate
instrumentation and detection (so-called variable pressure mode). Utilizing an
environmetal mode in our old SEM (Philips XL30 ESEM-TMP) even moist
samples can be analyzed.
Surface 3D
Elemental analysis
Similarly to TEM, elemental composition can be analyzed at the same time with
SEM imaging. However, SEM is especially useful to analyze elemental
distribution (i.e. elemental mapping) in the sample. Keep in mind that typically the
elemental information is collected from about 1 micron deep layer.
Scanning-transmission mode
TEM grids can be inserted and analyzed with SEM, too! If low magnification is
sufficient and you are more familiar to SEM than to TEM, you may use SEM for
transmission imaging.
topography
morphology
composition
Different types of electrons are emitted from samples upon interacting with the
electron beam. A BackScattered Electron (BSE) detector is placed above the
sample to help detect backscattered electrons. Images show contrast information
between areas with different chemical compositions as heavier elements (high
atomic number) will appear brighter. A Secondary Electron (SE) detector is placed
at the side of the electron chamber, at an angle, in order to increase the efficiency
of detecting secondary electrons which can provide more detailed surface
information.
Scanning electron microscope (SEM) Uses
Applications of FESEM
The GeminiSEM imaging facilities are the ideal choice for maximum
sample flexibility for high performance, high resolution imaging and
excellent compositional materials analysis. This advance facility can be
used in a wide range of options, application-specific modules and
workflows and give satisfaction for various applications for top surface
imaging and elemental analysis of nanopowders, nanofilm and
nanofiber. These cover various fields such as mineralogy, ceramics,
polymer, metallurgy, electronic devices, chemistry, physics and life
sciences. In nanoscience researches, the GeminiSEM 500 Nano-twin lens
can be used to get image for materials that beam-sensitive and detailed
nanoscale structures at low beam energy. The efficient detection
allowing operating at low currents for minimum beam damage and
excellent materials contrasts can be obtained. This equipment has
successfully used to characterize the carbon nanostructures, engineered
and self organized nanosystems, and nanocomposite materials [6]. In
metallurgy studies, the Gemini complete detection system can be used
to characterize inclusions at ultra-high resolution and discriminate
between different phases with unparalleled contrast. Whereas in
electronic devices and semiconductors, GeminiSEM 500 enables rapid,
reliable and damage-free characterization of nanoscale defects and
sensitive resist structures at low beam energies. For life sciences
applications, GeminiSEM 500 can give images of subcellular structure
and tissue mapping. In polymeric materials, the image of nano fiber such
as kenaf and high density polyethylene can be obtained at high
resolution. In MTEC, BTI we tried to use FESEM to characterize the
minerals; monazite and xenotime to support the thorium flagship
research. We used EDS elemental mapping to get the distribution of
elements present. Furthermore we use WDS mapping to get the
distribution of low concentration elements in the materials and
quantitative analysis to accurately measure the content of the elements
that cannot be detected by EDS.
Field emission scanning electron microscope Theory
The first true scanning electron microscope (SEM) was described and developed in 1942 by
Zworykin, who showed that secondary electrons (SE) provided topographic contrast by
biasing the collector positively relative to the specimen. He reached the resolution of 50 nm
when using an electron multiplier tube as a pre-amplifier of the SE emission current [1].
Since then, many improvements had been made until the first commercial SEM was made in
1965 by Cambridge Scientific Instruments Mark I called ‘Stereoscan’ [2]. This instrument
showed great SE detection using Everhart-Thornley detector (ETD)
which was found by Everhart and Thronley in 1960. ETD is a detector to
collect electrons with a positively biased grid comprising a scintillator to
convert the electrons and a light-pipe to transfer the light directly to a
photomultiplier tube (PMT) [1]. The SEMs that we are using today are
not very different from this one. The early SEM used heated tungsten
hairpin or filament cathode as the electron source, which known as
thermionic emitter (Fig. 1a). The development of lanthanum hexaboride
(LaB6) cathodes in 1975 which replacing tungsten became the major
improvement in instrument performance [3] and still can be found on
many instruments today. Thermionic emitter emits high current with
beam size of 4-8 nm. It is although inexpensive and reliable, the beam
currents produced are definitely low brightness and resulting
evaporation of filament so-called thermal drift, which limits the optical
performance especially at high-resolution. This classic SEM also
accustomed users to operating at high beam voltage i.e 15-30 kV either
necessary or not. This has led to many assumptions that SEM is
incapable of producing high-resolution images for many heat intolerant
samples such as biological and polymer materials. Figure 1: Field emitter
gun; the electron source in field emission scanning electron microscope.
The only electron source designed for high-resolution imaging and
suitable for various kinds of materials is field emission, which uses field
emitter gun (FEG) to emit electrons. The SEM that uses FEG as the
emitter type is called field emission scanning electron microscope
(FESEM); whereby the emitter type is used as a part of its name to
distinguish it from the classic SEM. FEG is made up of tungsten wire that
has diameter about 100 nm (Fig. 1b), preferably a single crystal type,
designed in such that the 310 plane is perpendicular to the electron
optical axis. The gun tip is placed near an anode which held at +2-6 kV,
the sharpness of the point produces fields of ˜1010 V/m near its surface
(Fig. 1c). This will result electrons to tunnel through the barrier into the
vacuum at a much focused beam (˜2 nm). The current emitted is seldom
reaching more than 5-10 μA, however it has brightness far higher than
thermionic emitter [4]. The first reliable FESEM was developed in 1968
by Prof. Crewe at Argonne National Laboratory [5]. FESEM is developed
based on a technology for high-resolution imaging and different
contrasting methods aiming for a comprehensive characterization of
specimens. FESEM can be used in wide range of applications including
imaging surface sensitive and non-conductive samples without the need
for pre-treatment. FESEM also comes with various attachments for
elemental analysis. This
Components[
The electron source of the TEM is at the top, where the lensing system (4,7
and 8) focuses the beam on the specimen and then projects it onto the
viewing screen (10). The beam control is on the right (13 and 14)
A TEM is composed of several components, which include a vacuum
system in which the electrons travel, an electron emission source for
generation of the electron stream, a series of electromagnetic lenses, as
well as electrostatic plates. The latter two allow the operator to guide and
manipulate the beam as required. Also required is a device to allow the
insertion into, motion within, and removal of specimens from the beam
path. Imaging devices are subsequently used to create an image from the
electrons that exit the system