Optical Characterization methods

Rayleigh scattering Raman scattering

Technique Absorption spectrometry

Synopsis Scan in , measure intensity of transmission. Fixed in (laser), scan out Fix out , scan in (tunable laser or monochromator) Laser in, scan out very close to in

Solid State Physics Optical absorption, band gap, energy level spacing Optical recombination transitions. Sensitive to transitions that pump optical emissions. Stokes/antiStokes peaks provide information about phonon energies.

transmission excitation photons

photoluminescence

Photoluminescence (PL)

At a glance
Transmission: untouched photons Photoluminescence includes fluorescence (emission within 10-5 s) and phosphorescence (emission after 10-5 s). Emission wavelength usually longer than excitation wavelength (Stokes shift) Raman scattering: inelastic scattering, in semiconductors, it can be photon-phonon scattering Rayleigh scattering: elastic scattering, no change in wavelength

Photoluminescence Excitation (PLE)

Raman scattering

Energy levels in molecules and semiconductors

absorption emission

bulk semiconductor PL of bulk semiconductor usually have peak at band gap, while absorption and PLE is broad and can determine density of state.

Molecular energy level In molecules absorption and PLE peaks are couple of S1 and S2 with vibrational energy, while PL peaks are couple of S0 and vibrational energy.

Energy levels in quantum dots

CdSe quantum dot

PL and PLE peaks in CdSe quantum dots can be used to compute energy spacing and relaxation characteristics for electrons and holes

Left: The evolution of the UV-Vis and PL spectra of the core/shell nanocrystals upon the growth of the CdS shell in a typical reaction. Right: Asymmetric PL of core/shell nanocrystals with five monolayers of CdS shell.

Absorption Spectrometry
Measurement Principle
For single beam instrument, data is acquired twice, once with a reference cell, once with a sample cell in place. Signal ration is taken to give absorbance. A double-beam instrument adjust zero with the shutter closed; when the shutter opens the absorbance is read directly from the difference amplifier.

Application
Characterize optical absorption

(a) single-beam instrument, (b) double-beam instrument Setup

Both setups have a filter or monochromator for wavelength selection, a transducer and a readout device for data collection. Double-beam instrument splits the excitation source for faster acquisition and greater accuracy Our UV-VIS system is a single beam instrument with a monochromator

Advantage
Relatively simple instrument

Disadvantage
Limited sensitivity especially when the change in absorption is small compared to transmission.

Photoluminescence and PLE

PL&PLE spectra for quinine solution

PLE

PL

Diagram of a PL&PLE system

Setup A combined PL and PLE system has 2 monochromators for wavelength selection of excitation and emission. A single PL system can have a laser as an excitation source. A tunable laser can also be used instead of the excitation monochromator. A beam splitter and a reference detector is used to compensate for the variation in excitation intensity

Measurement Principle PL: excitation wavelength is fixed, emission intensity vs. wavelength is obtained by scanning a monochromator of spectrometer. PLE: emission is detected at a fixed wavelength while excitation wavelength is scan (by a monochromator or tunable laser) to obtain emission intensity vs. excitation wavelength. Application Provide both optical absorption and emission information Advantage PLE is similar to absorption in some sense, with much better sensitivity. Detection limits can be three orders of magnitude smaller than

Photoluminescence Setup: Princeton/ Acton

entrance slit, f/4 collimating mirror

fiber optics, f/2.5

xyz stage

focusing mirror

CCD
1024x256

f = 127 mm f/2.4 f = 63.5 mm f/1.2

SP-150 Spectrometer
f = 150 mm; f/4 dual grating turrets

cryostat Excitation laser