X-RAY PHOTOELECTRON SPECTROSCOPY (X PS)

Chapter 3 of the book: Techniques for analysis and characterization of materials

Present by:

Kevin Fabia Abril Romero

Present to:

Pedro Nel Martinez Henao (Engineer)

Militar University of New Granada faculty of engineering

Engineering the materials

Cajicá 2022

IND C
ESPECTROSCOPIA RAMAN

The experiment

Back in Calcutta, he focused his research on the study of light scattered by solids and liquids.

The analysis of scattered light was at first carried out visually rather than by determining the

changes in the wavelengths of the radiation. As a source of radiation, the Sun was used, whose

white light is actually a mixture of many colors. Logically, if the light source had all colors, it

was difficult to measure a change in the wavelength of the scattered radiation.

Therefore, a violet filter was used so that only the violet radiation reached the sample. Virtually

all of the light leaving the sample is equal to the violet entering.
FUNDAMENTALS OF THE TECHNIQUE

The interaction between the incident radiation and the molecule under study results in an

excitation of the molecule. The excited molecule relaxes, but it can relax in two ways. It either

returns to the energetic state in which it was or ends up in a different energetic state. If it returns

to the energy state it was in, energy equal to that absorbed is released.

However, one out of every million or ten million times the molecule does not return to its initial

state. Normally, the molecule ends up at a higher energy level, so that the energy released is less

than that absorbed, thus increasing the wavelength and decreasing the frequency of the radiation.
Transitions between energy levels correspond to transitions between vibrational states. It should

be remembered that infrared spectroscopy studies transitions between vibrational states. The

vibrational states in which the molecules are found depend on temperature.

Excited population / ground state population = e-E/kT

For this reason, Stokes-type transitions are more likely than anti-Stokes transitions at moderate

temperatures. The ratio of intensities between the Stokes and anti-Stokes bands corresponds to

the temperature of the sample, so that in reality a Raman device could be used as an extremely

expensive and complex thermometer. Therefore, the Raman spectrum of any species, which

usually has more than one band, has an equivalent reflection in the anti-Stokes region.

EXCITATION LINES
The Raman phenomenon produces the same bands regardless of the excitation line. excitation

line. However, there are other differences associated with the use of different excitation lines.

These are essentially of two types: Raman signal intensity and fluorescence problems.

The intensity of the Raman signal is directly proportional to the fourth power of the excitation

frequency.

of the excitation frequency. The frequency of the radiation, v (expressed in c m 1,

measures its energy and is an inverse value of the wavelength, X (expressed in nm). Some

representative lines in Raman excitation are 250 nm (ultraviolet), 514 nm

(visible green), 633 nm (visible red), 780 nm (near infrared) and 1064 nm (infrared). If we

consider that a given sample gives a Raman signal of intensity as 1 in the infrared (1,064 nm), as

we move to the ultraviolet the intensity of the Raman signal increases in the proportion

illustrated in the graph in Figure 5.5.

Figure 5.5. This is an extraordinary increase, more than two orders of magnitude increase since

excitation in the ultraviolet.

increase from excitation in the IR.

Sometimes the sample under study fluoresces. Raman, so that the presence of fluorescence in the

measurement window "drowns" the Raman signal and can damage the detector. The higher the

energy of the radiation reaching the sample, the stronger the fluorescence emission tends to be.

Thus, for samples with fluorescence, it is extremely difficult to work with green light.

When we move to red light, the fluorescence decreases, but it is still important. In the near

infrared and infrared the fluorescence is minimal.

SELECTION RULES

Although IR and Raman look at transitions between vibrational states, not all vibrations are

active in Raman and not all vibrations are active in IR. Vibrations that involve a modification of

the polarizability of the bonds are active in Raman. The prediction of the vibrational modes that

will be active in IR or Raman is easy for simple molecules. In general, for certain functional
groups it can be established that stretching vibrations of covalent bonds, such as C=C, P=S, S-S

or C-S, will be intense in Raman and weak absorbers in IR.

Ionic bond stretching vibrations will be weak in Raman and absorb intensely in the IR. If the

molecule under study is centro-symmetric, there is mutual exclusion so that bands active in

Raman are not active in IR and vice versa. When the molecules have other geometries, the

intense Raman bands are weak in IR and vice versa.

INSTRUMENTATION

Raman spectroscopy equipment is made up of several elements:

a) Excitation source

b) Illumination of the sample and collection of the scattered signal.

c) Sample holder or treatment cells

d) Elastic scattering removal

e) Spectrometer, gratings, or FT-Raman systems

f) Detectors
Excitation sources

Due to the need for high intensity monochromatic radiation, the source of excitation for Raman

equipment are lasers.

source of excitation of Raman equipment are lasers.

Illumination of the sample and collection of the scattered signal

The main challenge is to efficiently collect the scattered radiation and direct it to the

spectrometer.

the scattered radiation and directing it to the spectrometer.

Elastic scattering elimination

Once the scattered radiation enters the spectrometer, it is necessary to separate the elastic

(Rayleigh) scattering from the inelastic (Raman) scattering.

the elastic (Rayleigh) scattering from the inelastic (Raman) scattering, since the former is a

million times more intense than the latter.

million times more intense than the inelastic (Raman) scattering.

Double monochromator systems

In this way, there are systems with two monochromators, where the first one eliminates the

elastic scattering, preventing it from reaching the second monochromator, which scatters the

radiation towards the detector.

the second monochromator, which scatters the radiation towards the detector.

Triple monochromator systems

In this configuration the strengths and weaknesses of the double monochromator system are

increased.

the spectral resolution increases notably but the signal decays very strongly.

very strongly.

Detectors

The Raman signal is very weak, so signal registration is a serious problem.

problem.

Photomultipliers

Photomultipliers are photocathodes that emit electrons when a photon hits them.

hits them.

CALIBRATION OF THE EQUIPMENT

As with all spectroscopic equipment, frequency and intensity readings should not be taken for

granted, since it is necessary to calibrate the equipment prior to the performance of spectra.

Frequency calibration

When a precision close to 1 cm-1 is required, internal references, such as solvent bands, solutes

that do not affect such as solvent bands, solutes that do not affect the sample for solvents or

solids added to solid samples.

solutes, solutes that do not affect the sample for dissolution or solutes added to solid state

samples.

Intensity calibration

Raman intensity depends on many factors. Unlike IR spectroscopy, where the amount of

absorbed radiation depends linearly on three factors, in Raman spectroscopy a scattered radiation

is measured, and this greatly complicates the number of factors that determine the intensity.

the number of factors that determine the intensity.

DEALING WITH THE SAMPLE

Unlike IR, in Raman the treatment of samples is highly variable and extremely versatile.

extremely versatile. In fact, there are almost as many manipulations as there are needs. On the

other hand, Raman studies have great advantages over IR. The

samples can be studied in solid, liquid or gas state.

• Gases

Gases are usually confined in a 1-2 cm long glass tube with thin walls (ca. 1 mm).

not too thick (ca. 1 mm).

• Liquids

Liquid samples can be sealed in tubes or bulbs. Even if you are working with very

even very small quantities, capillary tubes of a little more than one tenth of a mm in

diameter can be used. Care must be taken with the heating of the samples due to the

incidence of the by the incidence of the laser.

• Solids

Powder samples can be packed in capillary tubes or compacted as tablets, similar to

the way KBr tablets are prepared in IR. tablets, similar to how KBr tablets are

prepared in IR.

COMMERCIAL EQUIPMENT

The Raman market is one of the fastest growing markets in recent years, and one that is expected

to make spectacular
expected to advance dramatically, far ahead of any other technique.

The models, even the manufacturers, are constantly changing and new models and new brands

are emerging

new models and new brands are appearing, covering a wide spectrum of features, performance,

applications and prices,

performance, applications and prices.

- Ahura Scientific, Inc. - Wilmington, MA, Estados Unidos

- Avantes Inc. - Broomfield, CO, Estados Unidos

- Bruker Optics Inc. - Billerica, MA, Estados Unidos

- ChemImage Corp. - Pittsburgh, PA, Estados Unidos

- Cobolt AB - Solna, Suecia

- Craic Technologies - San Dimas, CA, Estados Unidos

- DeltaNu, Inc. - Laramie, WY, Estados Unidos

- HORIBA Jobin Yvon SAS, HORIBA Scientific - Longjumeau, Francia

- Innovative Photonic Solutions - Monmouth Junction, N j, Estados Unidos

- InPhotonics, Inc. - Norwood, MA, Estados Unidos

- JASCO Inc. - Easton, MD, Estados Unidos

- Kaiser Optical Systems, Inc. - Ann Arbor, MI, Estados Unidos

- Kimmon Electric US, LP - Centennial, CO, Estados Unidos

- Lahat Technologies Ltd. - Misgav, Israel

- LaserPath Technologies, LLC - Oviedo, FL, Estados Unidos

- LaVision GmbH - Goettingen, Alemania

- LaVision Inc. - Ypsilanti, MI, Estados Unidos

- Ocean Optics EMEA - Duiven, Holanda

- Ondax, Inc. - Monrovia, CA, Estados Unidos

- Perkin-Elmer, Reino Unido

- Photon Technology International, Inc. - Birmingham, NJ, Estados Unidos

194 Tecnicas de analisis y caracterizacion de materiales

- Real-Time Analyzers, Inc. - Middletown, CT, Estados Unidos

- Renishaw, Inc. - Hoffman Estates, IL, Estados Unidos

- Renishaw plc, Spectroscopy Products Div. - Wotton-under-Edge, Reino Unido

- RSP Systems - Odense M, Dinamarca

- Senspex Inc. - Albuquerque, NM, Estados Unidos

- Serstech AB - Lund, Suecia

- Symphotic TII Corp. - Camarillo, CA, Estados Unidos

- Taboada Research Instruments, Inc. - San Antonio, TX, Estados Unidos

- Tautec LLC - Columbia, MD, Estados Unidos

- Thermo Fisher Scientific Inc., Molecular Spectroscopy - Madison, WI, Estados Unidos

- Warsash Scientific Pty. Ltd. - Strawberry Hills, Australia

- WITec GmbH - Ulm, Alemania

APLICACIONES DE LA ESPECTROSCOPIA RAMAN

La espectroscopia Raman encuentra aplicacion en un elevado numero de campos como son la

ciencia de materiales, bioquimica/biologia/medicina, quimica estructural, quimica de

catalizadores, quimica combinatoria, ciencias de la tierra y otras aplicaciones.

Structural chemistry

The symmetry of the molecules determines the Raman bands possible and the frequencies of the

bond vibrations are affected by changes in bond distance. These can sometimes be followed by

Raman spectroscopy. The diatomic approach developed by Hardcastle and Wachs allows the

determination of bond orders and their bond distance. Hardcastle and Wachs worked with

crystallographic data and determined the equation that establishes the bond distance between two

ions of a vibrating bond.

In this way a correlation can be established between bond length and Raman shift, as well as

between bond order and Raman shift. Changes in the bond distances, whether due to additives,

pressure, temperature or other parameters, will therefore be reflected in the Raman spectra.
Earth Sciences

Raman spectroscopy is of great versatility in the study of gems and minerals, which can be

identified in extremely short times.

minerals, which can be identified in extremely short times.

A striking aspect is that Raman not only looks at the Earth, but also at other worlds.

worlds. At NASA, Raman spectrometers have been acquired to study samples collected from

outside the

samples collected from outside, and work is underway on a small vehicle incorporating a small

Raman spectrometer with which to study the composition of Martian soil.

Combinatorial chemistry

Since 1996, it is a rapidly growing technology that started to be used in the pharmaceutical

industry for the discovery of new bioactive molecules, medicines, etc. Combinatorial chemistry

has been extended in many directions, including the preparation of new inorganic materials.

Raman microscopy, Raman mapping and global imaging make it a very attractive technology for

combinatorial methods.