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

the Raman effect

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

A Typical Setup (simplified)

Schematic Raman spectrum

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 process

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)

qn generalized coordinates of normal modes

Classical Theory

IR absorption

Rayleigh scattering

Raman scattering (Stokes & anti-Stokes)

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

In solid state physics

spontaneous Raman spectroscopy is used to among other things, characterize materials: measure temperature. find the crystallographic orientation of a sample. Determine Crystal stress: through E2h mode Determine carrier concentration: through A1(LO) mode and LPP can be used to observe other low frequency excitations of the solid, such as plasmons, magnons, and superconducting gap excitations. Obtain information on the population of a given phonon mode in the ratio between the Stokes intensity and anti-Stokes intensity. In nanotechnology, a Raman microscope can be used to analyze nanowires to better understand the composition of the structures.

Determine Crystal stress: through E2h mode

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

0, A, B fitting parameters Diamond, GaN[Liu], AlN E2(high) for AlGaN

Carriers concentration

Crystal direction

Raman setups at our faculty

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

Objectives x10, x20, x50, x100 Peltier cooled CCD1024x256 (T=-70oC)

Doping and Plasmon-phonon coupled modes

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.

Surface enhanced Raman spectroscopy (SERS)

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)

Resonance Raman spectroscopy

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]

Other Raman techniques

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

107 [cm ] [nm]

1

[cm 1 ] 8067,77 * E[eV ]