and can be used for teaching‐calibrating purposes. The spectrophotometer used enables to change the BW in the range 0.1–5 nm. Furthermore, it has SS in the range 10–1000 nm min−1 and RT in the interval 0.03–240 s. After an explorative spectrum, the band of the holmium filter centered at about 360 nm has been selected. The SS has been fixed to 20 nm min−1 and the RT to 0.25 s. The first experiment consists in changing the BW.
As reported in Figure 1.8, the different BWs give rise to spectral distortion evidencing that an inaccurate choice compromises the interpretation of the experimental result. In particular, larger BW widens the spectral shape. As reported in the inset of the figure, the effect of distortion can be quantitatively determined by measuring the FWHM. A linear dependence of the FWHM is found on the BW for large values of the latter, whereas for small BW the true width of the band is measured. In particular, the condition BW = 0.4 FWHM somehow guarantees a good estimation of the true width of the band.
Figure 1.8 Top: Absorption spectra of holmium glass filter at various bandwidths of the spectrophotometer from 0.1 to 5 nm. The inset reports the dependence of the full width at half maximum on the various employed bandwidths. Bottom: Absorption spectra of holmium glass filter at various scan speeds of the spectrophotometer from 10 to 1000 nm min−1. The inset reports the dependence of the full width at half maximum on the various employed scan speeds.
In the second experiment, the SS has been changed, fixing the BW = 0.5 nm and the RT = 1 s. As reported in Figure 1.8, the fast scanning of the spectrum induces a strong distortion because of the delay in the response of the detector with respect to the change in the wavelength. These examples show that the instrumental parameters should be opportunely set in order to avoid distortion and at the same time guarantee a good signal‐to‐noise ratio to enable a good analysis of the results.
As a further case, the absorption spectrum of a high‐purity fused quartz glass of commercial origin (Infrasil 301, by Hereaus [28]) is shown in Figure 1.9 with the optimized instrumental parameters BW = 2 nm, RT = 4 s, and SS = 10 nm min−1. The spectrum is reported as a function of energy to clarify those physical features not correctly described by the wavelength, like the spectral shape. Furthermore, the absorption coefficient is reported taking into account the thickness of the experimental sample. It is possible to observe that the used glass features an absorption band peaked at about 5.14 eV superimposed to a larger absorption at higher energy. The lower energy peak is associated to an electronic transition and it is of interest for the determination of the radiative relaxation linked to the photoluminescence presented in Section 1.4.2.1.
Figure 1.9 Absorption spectrum of a commercial fused quartz glass featuring an absorption band in the UV range.
1.4.1.2 CCD Fiber Optic Device
Many setups for absorption measurements are nowadays using fiber optics technology. These systems use compact light sources and CCD detectors coupled to gratings to obtain fiber optics spectrometers. The light from the source is driven by an optical fiber to the sample holder directing the light collimated by a lens perpendicular to the sample surface. The light exiting from the sample is collected by a second lens and is directed to another optical fiber that drives the light to the grating that disperses it and then is detected by a CCD. These systems are typically of small dimension and are portable, with many advantages for coupling them in various kinds of experiments like in situ measurements. The opportune choice of source, fibers, and detector enables to use these systems for UV‐Vis‐IR spectroscopy.
A fiber optic instrument equipped with two light sources: a deuterium lamp and a tungsten lamp, and a spectral resolution of 1.7 nm has been used to detect the absorption of quantum dots of CdSe/ZnS. In particular, commercial core–shell nanoparticles with nominal 4 nm core of CdSe and ZnS shell have been dispersed in solution of toluene to detect the absorption as a function of nanoparticles’ concentration [29, 30]. A quartz cuvette of 1 cm has been used for the measurements. Due to quantum confinement effect, the nanoparticles feature an absorption band related to the size of the semiconducting core [29]. As reported in Figure 1.10, a prominent band at 585 nm can be observed for all the concentrations used ranging from 10−3 up to 10−1 mg ml−1. This spectral position is compatible with literature data for this nanoparticles size. The inset of the figure reports the amplitude of absorbance for the maximum of the band as a function of the concentration. A linear trend is found in accordance with the Lambert–Beer law Eq. (1.6).
1.4.2 Photoluminescence
In a photoluminescence experiment, a sample is illuminated by a source to induce the absorption process and the excitation of the electron from the ground state to an excited state. Returning backto the ground state, the electron could emit light. This emission is spectroscopically studied. In a typical photoluminescence setup, as reported in the block scheme of Figure 1.7, two monochromators are used to select the excitation wavelength and the emission wavelength. In the following, the two kinds of measurements that can be done are illustrated.
Figure 1.10 Absorption spectra of CdSe/ZnS core–shell nanoparticles at different concentrations in toluene solution. The inset shows the peak absorbance amplitude at 585 nm as a function of concentration; the straight line is a guide for the eye.
1.4.2.1 Emission and Excitation Spectra: Energy Levels Reconstruction
As discussed above, the photoluminescence experiment consists in illuminating the sample with an opportune wavelength selected by the excitation monochromator. This wavelength is fixed inside the range of an absorption band recorded in a preliminary absorption experiment, as those illustrated in the previous paragraphs. The light emitted by the sample is recorded by a detector after passing through a second monochromator. The scan of the latter gives rise to the spectrum, usually called emission spectrum. As an example, the emission spectrum of the sample of high‐purity fused quartz glass of commercial origin (Infrasil 301, by Hereaus [28]), reported in Section
