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Phosphorescence

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Phosphorescent, europium-doped strontium silicate-


aluminate oxide powder under visible light, long-wave
UV light, and in total darkness

Phosphorescence is a type of
photoluminescence related to
fluorescence. Unlike fluorescence,
phosphorescent material does not
immediately re-emit the radiation it
absorbs. The slower time scales of the re-
emission are associated with "forbidden"
energy state transitions in quantum
mechanics. As these transitions occur
very slowly in certain materials, absorbed
radiation is re-emitted at a lower intensity
for up to several hours after the original
excitation.

Everyday examples of phosphorescent


materials are the glow-in-the-dark toys,
stickers, paint, and clock dials that glow
after being charged with a bright light such
as in any normal reading or room light.
Typically, the glow slowly fades out,
sometimes within a few minutes or up to a
few hours in a dark room.[1]

The study of phosphorescent materials led


to the discovery of radioactivity in 1896.

Explanations
Simple

Jablonski diagram of an energy scheme used to


l i th diff b t fl d
explain the difference between fluorescence and
phosphorescence. The excitation of molecule A to its
singlet excited state (1A*)is followed by intersystem
crossing to the triplet state (3A) that relaxes to the
ground state by phosphorescence.

In simple terms, phosphorescence is a


process in which energy absorbed by a
substance is released relatively slowly in
the form of light. This is in some cases the
mechanism used for "glow-in-the-dark"
materials which are "charged" by exposure
to light. Unlike the relatively swift reactions
in fluorescence, such as those seen in a
common fluorescent tube,
phosphorescent materials "store"
absorbed energy for a longer time, as the
processes required to re-emit energy occur
less often.

Quantum mechanical

After an electron absorbs a photon of high energy, it


may undergo vibrational relaxations and intersystem
crossing to another spin state. Again the system
relaxes vibrationally in the new spin state and
eventually emits light by phosphorescence.

Most photoluminescent events, in which a


chemical substrate absorbs and then re-
emits a photon of light, are fast, in the
order of 10 nanoseconds. Light is
absorbed and emitted at these fast time
scales in cases where the energy of the
photons involved matches the available
energy states and allowed transitions of
the substrate. In the special case of
phosphorescence, the electron which
absorbed the photon (energy) undergoes
an unusual intersystem crossing into an
energy state of higher spin multiplicity (see
term symbol), usually a triplet state. As a
result, the excited electron can become
trapped in the triplet state with only
"forbidden" transitions available to return
to the lower energy singlet state. These
transitions, although "forbidden", will still
occur in quantum mechanics but are
kinetically unfavored and thus progress at
significantly slower time scales. Most
phosphorescent compounds are still
relatively fast emitters, with triplet
lifetimes on the order of milliseconds.
However, some compounds have triplet
lifetimes up to minutes or even hours,
allowing these substances to effectively
store light energy in the form of very
slowly degrading excited electron states. If
the phosphorescent quantum yield is high,
these substances will release significant
amounts of light over long time scales,
creating so-called "glow-in-the-dark"
materials.
Equation

where S is a singlet and T a triplet whose


subscripts denote states (0 is the ground
state, and 1 the excited state). Transitions
can also occur to higher energy levels, but
the first excited state is denoted for
simplicity.

Chemiluminescence
Some examples of glow-in-the-dark
materials do not glow by
phosphorescence. For example, glow
sticks glow due to a chemiluminescent
process which is commonly mistaken for
phosphorescence. In chemiluminescence,
an excited state is created via a chemical
reaction. The light emission tracks the
kinetic progress of the underlying
chemical reaction. The excited state will
then transfer to a dye molecule, also
known as a sensitizer or fluorophor, and
subsequently fluoresce back to the ground
state.

Materials
Common pigments used in
phosphorescent materials include zinc
sulfide and strontium aluminate. Use of
zinc sulfide for safety related products
dates back to the 1930s. However, the
development of strontium aluminate, with
a luminance approximately 10 times
greater than zinc sulfide, has relegated
most zinc sulfide based products to the
novelty category. Strontium aluminate
based pigments are now used in exit
signs, pathway marking, and other safety
related signage.[2]

An extremely intense pulse of UV light in a flashtube


produced this blue phosphorescence in the fused silica
envelope.
Phosphorescence of the quartz ignition tube of an air-
gap flash

Phosphorescen
t pigments –
zinc sulfide vs.
strontium
aluminate
left: Zinc sulfide
right: Strontium
aluminate

Pigments in the
dark
Pigments in the
dark after 4 min

Phosphorescent
Phosphorescent pigment
red (calcium sulfide)

Phosphorescent pigment
red in the dark
Phosphorescent pigment
blue (alkaline earth metal
silicate )

Phosphorescent pigment
blue in the dark
See also

Phosphorescent bird figure

Luminous paint
Microsphere
Persistent luminescence
Phosphor
Phosphoroscope
Tritium
References
1. Karl A. Franz, Wolfgang G. Kehr, Alfred
Siggel, Jürgen Wieczoreck, and Waldemar
Adam "Luminescent Materials" in Ullmann's
Encyclopedia of Industrial Chemistry 2002,
Wiley-VCH, Weinheim.
doi:10.1002/14356007.a15_519
2. Zitoun, D.; Bernaud, L.; Manteghetti, A.
Microwave Synthesis of a Long-Lasting
Phosphor. J. Chem. Educ. 2009, 86, 72-
75.doi:10.1021/ed086p72

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