Atomic force microscope

The atomic force microscope (AFM) or scanning force microscope (SFM) is a very high-resolution

type of scanning probe microscopy, with demonstrated resolution of fractions of ananometer, more than
1000 times better than the optical diffraction limit.

Basic principles
The AFM consists of a cantilever with a sharp tip (probe) at its end that is used to scan the specimen
surface. The cantilever is typically silicon or silicon nitride with a tip radius of curvatureon the order of
nanometers. When the tip is brought into proximity of a sample surface, forces between the tip and the
sample lead to a deflection of the cantilever according to Hooke's law. Depending on the situation, forces
that are measured in AFM include mechanical contact force, van der Waals forces,capillary
forces, chemical bonding, electrostatic forces, magnetic forces (see magnetic force microscope,
MFM), Casimir forces, solvation forces, etc. As well as force, additional quantities may simultaneously be
measured through the use of specialised types of probe (see scanning thermal microscopy, photothermal
microspectroscopy, etc.). Typically, the deflection is measured using a laser spot reflected from the top
surface of the cantilever into an array of photodiodes. Other methods that are used include optical
interferometry, capacitive sensing or piezoresistive AFM cantilevers. These cantilevers are fabricated with
piezoresistive elements that act as a strain gauge. Using a Wheatstone bridge, strain in the AFM
cantilever due to deflection can be measured, but this method is not as sensitive as laser deflection or
interferometry.

If the tip was scanned at a constant height, a risk would exist that the tip collides with the surface, causing
damage. Hence, in most cases a feedback mechanism is employed to adjust the tip-to-sample distance to
maintain a constant force between the tip and the sample. Traditionally, the sample is mounted on
a piezoelectric tube, that can move the sample in the z direction for maintaining a constant force, and
the x and y directions for scanning the sample. Alternatively a 'tripod' configuration of three piezo crystals
may be employed, with each responsible for scanning in the x,y and z directions. This eliminates some of
the distortion effects seen with a tube scanner. In newer designs, the tip is mounted on a vertical piezo
scanner while the sample is being scanned in X and Y using another piezo block. The resulting map of
the area s = f(x,y) represents the topography of the sample.

The AFM can be operated in a number of modes, depending on the application. In general, possible
imaging modes are divided into static (also called contact) modes and a variety of dynamic (or non-
contact) modes where the cantilever is vibrated.
Advantages and disadvantages
The AFM has several advantages over the scanning electron microscope (SEM). Unlike the electron
microscope which provides a two-dimensional projection or a two-dimensional image of a sample, the
AFM provides a true three-dimensional surface profile. Additionally, samples viewed by AFM do not
require any special treatments (such as metal/carbon coatings) that would irreversibly change or damage
the sample. While an electron microscope needs an expensive vacuum environment for proper operation,
most AFM modes can work perfectly well in ambient air or even a liquid environment. This makes it
possible to study biological macromolecules and even living organisms. In principle, AFM can provide
higher resolution than SEM. It has been shown to give true atomic resolution in ultra-high vacuum (UHV)
and, more recently, in liquid environments. High resolution AFM is comparable in resolution to scanning
tunneling microscopy andtransmission electron microscopy.

A disadvantage of AFM compared with the scanning electron microscope (SEM) is the image size. The
SEM can image an area on the order of millimetres by millimetres with a depth of field on the order of
millimetres. The AFM can only image a maximum height on the order of 10-20 micrometres and a
maximum scanning area of around 150 by 150 micrometres.

Another inconvenience is that an incorrect choice of tip for the required resolution can lead to image
artifacts. Traditionally the AFM could not scan images as fast as an SEM, requiring several minutes for a
typical scan, while a SEM is capable of scanning at near real-time (although at relatively low quality) after
the chamber is evacuated. The relatively slow rate of scanning during AFM imaging often leads to thermal
drift in the image[9][10] making the AFM microscope less suited for measuring accurate distances between
topographical features on the image. However, several fast-acting designs [11][12] were suggested to
increase microscope scanning productivity including what is being termed videoAFM (reasonable quality
images are being obtained with videoAFM at video rate — faster than the average SEM). To eliminate
image distortions induced by thermodrift, several methods [9][10] were also proposed.

AFM images can also be affected by hysteresis of the piezoelectric material[13] and cross-talk between the
x, y, z axes that may require software enhancement and filtering. Such filtering could "flatten" out real
topographical features. However, newer AFMs closed-loop scanners which practically eliminate these
problems. Some AFMs also use separated orthogonal scanners (as opposed to a single tube) which also
serve to eliminate part of the cross-talk problems.

Due to the nature of AFM probes, they cannot normally measure steep walls or overhangs. Specially
made cantilevers and AFMs can be used to modulate the probe sideways as well as up and down (as
with dynamic contact and non-contact modes) to measure sidewalls, at the cost of more expensive
cantilevers, lower lateral resolution and additional artifacts.
Raman spectroscopy
Raman spectroscopy (named after C. V. Raman, pronounced /ˈrɑːmən/) is aspectroscopic technique
used to study vibrational, rotational, and other low-frequency modes in a system. [1] It relies on inelastic
scattering, or Raman scattering, of monochromatic light, usually from a laser in the visible, near infrared,
or near ultraviolet range. The laser light interacts with phonons or other excitations in the system,
resulting in the energy of the laser photons being shifted up or down. The shift in energy gives information
about the phonon modes in the system. Infrared spectroscopy yields similar, but complementary,
information.

Typically, a sample is illuminated with a laser beam. Light from the illuminated spot is collected with
a lens and sent through a monochromator. Wavelengths close to the laser line, due to elastic Rayleigh
scattering, are filtered out while the rest of the collected light is dispersed onto a detector.

Spontaneous Raman scattering is typically very weak, and as a result the main difficulty of Raman
spectroscopy is separating the weak inelastically scattered light from the intense Rayleigh scattered laser
light. Historically, Raman spectrometers used holographic gratings and multiple dispersion stages to
achieve a high degree of laser rejection. In the past, photomultiplierswere the detectors of choice for
dispersive Raman setups, which resulted in long acquisition times. However, modern instrumentation
almost universally employs notch or edge filters for laser rejection and spectrographs (either axial
transmissive (AT), Czerny-Turner (CT) monochromator) or FT (Fourier transform
spectroscopy based), and CCD detectors.

There are a number of advanced types of Raman spectroscopy, including surface-enhanced

Raman, tip-enhanced Raman, polarised Raman, stimulated Raman (analogous to stimulated
emission), transmission Raman, spatially-offset Raman, and hyper Raman.

[edit]Basic theory
The Raman effect occurs when light impinges upon a molecule and interacts with the electron cloud and
the bonds of that molecule. For the spontaneous Raman effect, a photon excites the molecule from
the ground state to a virtual energy state. When the molecule relaxes it emits a photon and it returns to a
different rotational or vibrational state. The difference in energy between the original state and this new
state leads to a shift in the emitted photon's frequency away from the excitation wavelength.

If the final state of the molecule is more energetic than the initial state, then the emitted photon will be
shifted to a lower frequency in order for the total energy of the system to remain balanced. This shift in
frequency is designated as a Stokes shift. If the final state is less energetic than the initial state, then the
emitted photon will be shifted to a higher frequency, and this is designated as an Anti-Stokes shift. Raman
scattering is an example of inelastic scattering because of the energy transfer between the photons and
the molecules during their interaction.

A change in the molecular polarization potential — or amount of deformation of the electron cloud — with
respect to the vibrational coordinate is required for a molecule to exhibit a Raman effect. The amount of
the polarizability change will determine the Raman scattering intensity. The pattern of shifted frequencies
is determined by the rotational and vibrational states of the sample.

Applications
Raman spectroscopy is commonly used in chemistry, since vibrational information is specific to
the chemical bonds and symmetry of molecules. It therefore provides a fingerprint by which the molecule
can be identified. For instance, the vibrational frequencies of SiO, Si 2O2, and Si3O3 were identified and
assigned on the basis of normal coordinate analyses using infrared and Raman spectra. [3] The fingerprint
region of organic molecules is in the (wavenumber) range 500-2000 cm−1. Another way that the technique
is used is to study changes in chemical bonding, e.g., when a substrate is added to an enzyme.

Raman gas analyzers have many practical applications. For instance, they are used in medicine for real-
time monitoring of anaesthetic and respiratory gas mixtures during surgery.

In solid state physics, spontaneous Raman spectroscopy is used to, among other things, characterize
materials, measure temperature, and find the crystallographic orientation of a sample. As with single
molecules, a given solid material has characteristic phonon modes that can help an experimenter identify
it. In addition, Raman spectroscopy can be used to observe other low frequency excitations of the solid,
such asplasmons, magnons, and superconducting gap excitations. The spontaneous Raman signal gives
information on the population of a given phonon mode in the ratio between the Stokes (downshifted)
intensity and anti-Stokes (upshifted) intensity.

Raman scattering by an anisotropic crystal gives information on the crystal orientation. The polarization of

the Raman scattered light with respect to the crystal and the polarization of the laser light can be used to
find the orientation of the crystal, if the crystal structure (specifically, its point group) is known.

Raman active fibers, such as aramid and carbon, have vibrational modes that show a shift in Raman
frequency with applied stress. Polypropylene fibers also exhibit similar shifts. The radial breathing mode is
a commonly used technique to evaluate the diameter of carbon nanotubes. In nanotechnology, a Raman
microscope can be used to analyze nanowires to better understand the composition of the structures.

Spatially-offset Raman spectroscopy (SORS), which is less sensitive to surface layers than conventional
Raman, can be used to discovercounterfeit drugs without opening their internal packaging, and for non-
invasive monitoring of biological tissue.[4] Raman spectroscopy can be used to investigate the chemical
composition of historical documents such as the Book of Kells and contribute to knowledge of the social
and economic conditions at the time the documents were produced. [5] This is especially helpful because
Raman spectroscopy offers a non-invasive way to determine the best course
of preservation or conservation treatment for such materials.

Raman spectroscopy is being investigated as a means to detect explosives for airport security.[6]