Figure 3-1: Energy level diagram of an organic molecule with π -electron structure, adapted from [1]. The fluorescence process occurs for transitions from the lowest vibrational first
excited state (S
10
) to the ground state, where energy is emitted as a photon of a
characteristic wavelength. This process forms the primary mechanism for
scintillation in organic plastic scintillators. Fluorescence occurs within a matter
of nanoseconds which gives plastic scintillators their fast re sponse capability.
Sometimes, transitions called inter-system crossing can occur whereby excited
singlet states are converted to triplet states. The lifetime of the T
10
triplet state is
longer than that of the S
10
state and so the de-excitation to the ground state from
the triplet state takes longer. As a result, a delayed light emission called
phosphorescence occurs. The wavelength of the light emitted in phosphorescence
is longer than that of light emitted by fluorescence.
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A final energy loss mechanism that may occur is the process of delayed
fluorescence. In this process, molecules in the triplet state may undergo thermal
excitation and excite back into the singlet state before undergoing fluorescence
to the ground state. [1] Phosphorescence and delayed fluorescence are considers
as quenchers of fluorescent light since these three radiative processes can
compete with each other.
The energy of fluorescent light is generally less than the energy required for
absorption because the fluorescence transition can occur to any of the ground
state’s vibrational levels and because absorption causes a change to the
equilibrium internuclear potential
[15]. However, a small amount of overlap may
occur between the absorption and emission wavelength ranges resulting in re -
absorption of scintillation light. Typical plastic scintillator bases have a very low
fluorescent yield and therefore aren’t very transparent to their own scintillation
light.
Primary fluor dopants are thus added in small concentrations (typically < 3% by
weight). Primary fluors are chosen such that their absorption spectra match the
emission spectra of the base and generally contain a high quantum yield of the
energy transfer transition. Light can be transferred between base and fluor via
either radiative re-absorption, or by a non-radiative coulombic interaction called
Forster resonance energy transfer. [15]
Forster energy transfer is limited by the distance between the interacting states
and is therefore more likely to occur with increasing fluor concentrations until a
saturation is reached. Light is then emitted by the fluors at higher wavelengths,
generally in the UV range of 340-360 nm.
Since this wavelength is still below the peak efficiency of common
photomultipliers, a secondary fluor is added at concentrations of < 0.1% by
weight. The secondary fluor acts as a wavelength shifter and prevents re-
absorption of scintillation light by the primary fluor. It also helps to increase the
bulk attenuation length of the emitted light. Energy transfer between the primary
and secondary fluors occurs via radiative exchange [15]. A schematic of the
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radiative transfer of energy from polymer base to the primary fluor and secondary
fluor is shown in Figure 3-2.