Basic Principles of Raman Spectroscopy and Its Applications For Semiconductor Characterization
Basic Principles of Raman Spectroscopy and Its Applications For Semiconductor Characterization
Basic Principles of Raman Spectroscopy and Its Applications For Semiconductor Characterization
Kiril Kirilov
Faculty of Physics, Sofia University, 5. blvd. J.Bourchier, 1164 Sofia,Bulgaria
predicted by Adolf Smekal in 1923 named after one of its discoverers in 1928, the Indian scientist Sir Chandrasekhara Venkata Raman
Raman scattering is the inelastic scattering of a photon change in photon energy By nature weak effect (approximately 1 in 107 photons)
Sir C. V. Raman
Light intensity
Rayleigh line elastic scattering Raman Stokes line scattered photon give up energy Raman Anti-stokes line scattered photon gain energy
Schematic diagram of the Raman scattering process The vertical direction represents energy
Classical Theory
The electric field Ei of the light wave acts on the charges in the material Interaction of light with a single molecule considered Induced dipole moment Pi of a molecule (vector)
(1)
Pi pi ij E j ijk E j Ek ...
Raman effect Hyper Raman effect
induced permanent dipole moment ij polarizability (tensor) i, j, k, l subscripts running over directions x, y, z pi
Classical Theory
Both pi and ij may change if the molecule vibrates Then pi and ij may be expanded as Taylor series
Assuming small atomic displacements qn, we can approximate the time dependence
(3)
(2)
n ,L frequency of displacement and electric field These expressions can be substituted into a linear version of (1)
Classical Theory
IR absorption
Rayleigh scattering
Sample Geometry
Brewster Setup
Back Scattering
Forward Scattering
Right-angle Scattering
non-transparent sample
transparent sample
Porto notation
Convention of representing experimental scattering geometries Example: x(zx)y
excitation light incident on the sample along x axis, polarized along z direction scattered light was detected along y axis, polarized along x direction
Useful notation if the axes are defined with respect to the crystal axes of symmetry, then xz relate to Raman tensor components
Crystal tension
Commonly employed for the analysis of the pressure dependence of phonon modes is quadratic relationship
0 ' P " P
0, , fitting parameters
Crystal temperature
Non-invasively temperature monitoring (T=10-1275K) during growth, processing, high power electronic devices It is used simple empirical relation to describe temperature dependence of the phonon frequencies Simple but accurate Unfortunately the parameters from fitting cant be related to properties of the material More complex theoretical modeling provides this connection (Cui [96])
(T ) 0
A exp( Bhc0 / k BT ) 1
Carriers concentration
Crystal direction
Micro-Raman, LabRam HR spectrometer , 20 mW polarized vertically HeNe laser, spot size of about 1 m Two switcheable gratings
Scanning range: 1800gr range:0-950 nm ,600gr range:02850 nm Accuracy: In the range between 450 nm and 850 nm, the wavenumber accuracy is 1 cm-1 with 1800 l/mm grating
L+ L- .
Confocal microscopy
very high spatial resolution: the lateral and depth resolutions were 250 nm and 1.7 m, respectively, using a confocal Raman microspectrometer with the 632.8 nm line from a He-Ne laser with a pinhole of 100 m diameter much higher resulting photon flux than achieved in conventional Raman setups. benefit of enhanced fluorescence quenching. high photon flux can also cause sample degradation, and for this reason some setups require a thermally conducting substrate. Water does not generally interfere with Raman spectral analysis.
a surface sensitive technique that results in the enhancement of Raman scattering by molecules adsorbed on rough metal surfaces. The enhancement factor can be as much as 1014-1015, which allows the technique to be sensitive enough to detect single molecules.[1](Wikipedia)
The excitation wavelength is matched to an electronic transition of the molecule or crystal, so that vibrational modes associated with the excited electronic state are greatly enhanced. This is useful for studying large molecules such as polypeptides, which might show hundreds of bands in "conventional" Raman spectra. It is also useful for associating normal modes with their observed frequency shifts.[10]
Hyper Raman - A non-linear effect in which the vibrational modes interact with the second harmonic of the excitation beam. This requires very high power, but allows the observation of vibrational modes which are normally "silent". It frequently relies on SERS-type enhancement to boost the sensitivity.[11] Spontaneous Raman Spectroscopy - Used to study the temperature dependence of the Raman spectra of molecules. Optical Tweezers Raman Spectroscopy (OTRS) - Used to study individual particles, and even biochemical processes in single cells trapped by optical tweezers. Spatially Offset Raman Spectroscopy (SORS) - The Raman scatter is collected from regions laterally offset away from the excitation laser spot, leading to significantly lower contributions from the surface layer than with traditional Raman spectroscopy.[12] This technique allows highly accurate chemical analysis of objects beneath obscuring surfaces, such as tissue, coatings and bottles. Examples of uses include analysis of: bone beneath skin,[2] tablets inside plastic bottles,[3] explosives inside containers[4] and counterfeit tablets inside blister packs. Tip-Enhanced Raman Spectroscopy (TERS) - Uses a silver or gold tip to enhance the Raman signals of molecules situated in its vicinity. The spatial resolution is approximately the size of the tip apex (20-30 nm). TERS has been shown to have sensitivity down to the single molecule level.
Important relations