Phosphor
   HOME

TheInfoList



OR:

A phosphor is a substance that exhibits the
phenomenon A phenomenon ( : phenomena) is an observable event. The term came into its modern philosophical usage through Immanuel Kant, who contrasted it with the noumenon, which ''cannot'' be directly observed. Kant was heavily influenced by Gottfrie ...
of
luminescence Luminescence is spontaneous emission of light by a substance not resulting from heat; or "cold light". It is thus a form of cold-body radiation. It can be caused by chemical reactions, electrical energy, subatomic motions or stress on a crys ...
; it emits light when exposed to some type of
radiant energy Radiant may refer to: Computers, software, and video games * Radiant (software), a content management system * GtkRadiant, a level editor created by id Software for their games * Radiant AI, a technology developed by Bethesda Softworks for ''Th ...
. The term is used both for
fluorescent Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, ...
or phosphorescent substances which glow on exposure to
ultraviolet Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation ...
or visible light, and cathodoluminescent substances which glow when struck by an electron beam ( cathode rays) in a cathode-ray tube. When a phosphor is exposed to radiation, the orbital
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have n ...
s in its
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and b ...
s are excited to a higher energy level; when they return to their former level they emit the energy as light of a certain color. Phosphors can be classified into two categories:
fluorescent Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, ...
substances which emit the energy immediately and stop glowing when the exciting radiation is turned off, and phosphorescent substances which emit the energy after a delay, so they keep glowing after the radiation is turned off, decaying in brightness over a period of milliseconds to days. Fluorescent materials are used in applications in which the phosphor is excited continuously: cathode-ray tubes (CRT) and plasma video display screens, fluoroscope screens, fluorescent lights, scintillation sensors, and white LEDs, and
luminous paint Luminous paint or luminescent paint is paint that exhibits luminescence. In other words, it gives off visible light through fluorescence, phosphorescence, or radioluminescence. There are three types of luminous paints: fluorescent paint, ph ...
s for
black light A blacklight, also called a UV-A light, Wood's lamp, or ultraviolet light, is a lamp that emits long-wave (UV-A) ultraviolet light and very little visible light. One type of lamp has a violet filter material, either on the bulb or in a sepa ...
art. Phosphorescent materials are used where a persistent light is needed, such as glow-in-the-dark watch faces and aircraft instruments, and in radar screens to allow the target 'blips' to remain visible as the radar beam rotates. CRT phosphors were standardized beginning around
World War II World War II or the Second World War, often abbreviated as WWII or WW2, was a world war that lasted from 1939 to 1945. It involved the World War II by country, vast majority of the world's countries—including all of the great power ...
and designated by the letter "P" followed by a number.
Phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ea ...
, the light-emitting chemical element for which phosphors are named, emits light due to
chemiluminescence Chemiluminescence (also chemoluminescence) is the emission of light (luminescence) as the result of a chemical reaction. There may also be limited emission of heat. Given reactants A and B, with an excited intermediate ◊, : + -> lozenge - ...
, not phosphorescence.


Light-emission process

The scintillation process in inorganic materials is due to the
electronic band structure In solid-state physics, the electronic band structure (or simply band structure) of a solid describes the range of energy levels that electrons may have within it, as well as the ranges of energy that they may not have (called '' band gaps'' or ...
found in the
crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macro ...
s. An incoming particle can excite an electron from the valence band to either the
conduction band In solid-state physics, the valence band and conduction band are the bands closest to the Fermi level, and thus determine the electrical conductivity of the solid. In nonmetals, the valence band is the highest range of electron energies in ...
or the
exciton An exciton is a bound state of an electron and an electron hole which are attracted to each other by the electrostatic Coulomb force. It is an electrically neutral quasiparticle that exists in insulators, semiconductors and some liquids. ...
band (located just below the conduction band and separated from the valence band by an energy gap). This leaves an associated hole behind, in the valence band. Impurities create electronic levels in the
forbidden gap In solid-state physics, a band gap, also called an energy gap, is an energy range in a solid where no electronic states can exist. In graphs of the electronic band structure of solids, the band gap generally refers to the energy difference (in ...
. The excitons are loosely bound electron–hole pairs that wander through the
crystal lattice In geometry and crystallography, a Bravais lattice, named after , is an infinite array of discrete points generated by a set of discrete translation operations described in three dimensional space by : \mathbf = n_1 \mathbf_1 + n_2 \mathbf_2 + n ...
until they are captured as a whole by impurity centers. The latter then rapidly de-excite by emitting scintillation light (fast component). In the case of inorganic
scintillator A scintillator is a material that exhibits scintillation, the property of luminescence, when excited by ionizing radiation. Luminescent materials, when struck by an incoming particle, absorb its energy and scintillate (i.e. re-emit the absorbe ...
s, the activator impurities are typically chosen so that the emitted light is in the visible range or near-UV, where photomultipliers are effective. The holes associated with electrons in the conduction band are independent from the latter. Those holes and electrons are captured successively by impurity centers exciting certain
metastable state In chemistry and physics, metastability denotes an intermediate energetic state within a dynamical system other than the system's state of least energy. A ball resting in a hollow on a slope is a simple example of metastability. If the ball ...
s not accessible to the excitons. The delayed de-excitation of those metastable impurity states, slowed by reliance on the low-probability forbidden mechanism, again results in light emission (slow component). Phosphors are often
transition-metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
compounds or rare-earth compounds of various types. In inorganic phosphors, these inhomogeneities in the crystal structure are created usually by addition of a trace amount of
dopant A dopant, also called a doping agent, is a trace of impurity element that is introduced into a chemical material to alter its original electrical or optical properties. The amount of dopant necessary to cause changes is typically very low. Whe ...
s, impurities called '' activators''. (In rare cases
dislocation In materials science, a dislocation or Taylor's dislocation is a linear crystallographic defect or irregularity within a crystal structure that contains an abrupt change in the arrangement of atoms. The movement of dislocations allow atoms to s ...
s or other
crystal defect A crystallographic defect is an interruption of the regular patterns of arrangement of atoms or molecules in crystalline solids. The positions and orientations of particles, which are repeating at fixed distances determined by the unit cell pa ...
s can play the role of the impurity.) The wavelength emitted by the emission center is dependent on the atom itself and on the surrounding crystal structure.


Materials

Phosphors are usually made from a suitable host material with an added activator. The best known type is a copper-activated zinc sulfide (ZnS) and the
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
-activated zinc sulfide (''zinc sulfide
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
''). The host materials are typically
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
s, nitrides and oxynitrides,
sulfide Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds la ...
s, selenides,
halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a flu ...
s or silicates of
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
,
cadmium Cadmium is a chemical element with the Symbol (chemistry), symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12 element, group 12, zinc and mercury (element), mercury. Li ...
,
manganese Manganese is a chemical element with the Symbol (chemistry), symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of ...
,
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It ha ...
,
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
, or various
rare-earth metal The rare-earth elements (REE), also called the rare-earth metals or (in context) rare-earth oxides or sometimes the lanthanides (yttrium and scandium are usually included as rare earths), are a set of 17 nearly-indistinguishable lustrous silv ...
s. The activators prolong the emission time (afterglow). In turn, other materials (such as
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow t ...
) can be used to quench the afterglow and shorten the decay part of the phosphor emission characteristics. Many phosphor powders are produced in low-temperature processes, such as sol-gel, and usually require post-annealing at temperatures of ~1000 °C, which is undesirable for many applications. However, proper optimization of the growth process allows manufacturers to avoid the annealing. Phosphors used for
fluorescent lamp A fluorescent lamp, or fluorescent tube, is a low-pressure mercury-vapor gas-discharge lamp that uses fluorescence to produce visible light. An electric current in the gas excites mercury vapor, which produces short-wave ultraviolet, ult ...
s require a multi-step production process, with details that vary depending on the particular phosphor. Bulk material must be milled to obtain a desired particle size range, since large particles produce a poor-quality lamp coating, and small particles produce less light and degrade more quickly. During the firing of the phosphor, process conditions must be controlled to prevent oxidation of the phosphor activators or
contamination Contamination is the presence of a constituent, impurity, or some other undesirable element that spoils, corrupts, infects, makes unfit, or makes inferior a material, physical body, natural environment, workplace, etc. Types of contamination ...
from the process vessels. After milling, the phosphor may be washed to remove minor excess of activator elements. Volatile elements must not be allowed to escape during processing. Lamp manufacturers have changed compositions of phosphors to eliminate some toxic elements, such as
beryllium Beryllium is a chemical element with the symbol Be and atomic number 4. It is a steel-gray, strong, lightweight and brittle alkaline earth metal. It is a divalent element that occurs naturally only in combination with other elements to for ...
,
cadmium Cadmium is a chemical element with the Symbol (chemistry), symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12 element, group 12, zinc and mercury (element), mercury. Li ...
, or
thallium Thallium is a chemical element with the symbol Tl and atomic number 81. It is a gray post-transition metal that is not found free in nature. When isolated, thallium resembles tin, but discolors when exposed to air. Chemists William Crookes an ...
, formerly used. The commonly quoted parameters for phosphors are the
wavelength In physics, the wavelength is the spatial period of a periodic wave—the distance over which the wave's shape repeats. It is the distance between consecutive corresponding points of the same phase on the wave, such as two adjacent crests, tr ...
of emission maximum (in nanometers, or alternatively color temperature in
kelvin The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and ...
s for white blends), the peak width (in
nanometers 330px, Different lengths as in respect to the molecular scale. The nanometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: nm) or nanometer (American and British English spelling differences#-re ...
at 50% of intensity), and decay time (in
seconds The second (symbol: s) is the unit of time in the International System of Units (SI), historically defined as of a day – this factor derived from the division of the day first into 24 hours, then to 60 minutes and finally to 60 seconds each ...
). Examples: * Calcium sulfide with strontium sulfide with bismuth as activator, , yields blue light with glow times up to 12 hours, red and orange are modifications of the zinc sulfide formula. Red color can be obtained from strontium sulfide. *
Zinc sulfide Zinc sulfide (or zinc sulphide) is an inorganic compound with the chemical formula of ZnS. This is the main form of zinc found in nature, where it mainly occurs as the mineral sphalerite. Although this mineral is usually black because of various ...
with about 5 ppm of a
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
activator is the most common phosphor for the glow-in-the-dark toys and items. It is also called GS phosphor. *Mix of zinc sulfide and cadmium sulfide emit color depending on their ratio; increasing of the CdS content shifts the output color towards longer wavelengths; its persistence ranges between 1–10 hours. * Strontium aluminate activated by
europium Europium is a chemical element with the symbol Eu and atomic number 63. Europium is the most reactive lanthanide by far, having to be stored under an inert fluid to protect it from atmospheric oxygen or moisture. Europium is also the softest lan ...
, SrAl2O4:Eu(II):Dy(III), is a material developed in 1993 by Nemoto & Co. engineer Yasumitsu Aoki with higher brightness and significantly longer glow persistence; it produces green and aqua hues, where green gives the highest brightness and aqua the longest glow time. SrAl2O4:Eu:Dy is about 10 times brighter, 10 times longer glowing, and 10 times more expensive than ZnS:Cu. The excitation wavelengths for strontium aluminate range from 200 to 450 nm. The wavelength for its green formulation is 520 nm, its blue-green version emits at 505 nm, and the blue one emits at 490 nm. Colors with longer wavelengths can be obtained from the strontium aluminate as well, though for the price of some loss of brightness.


Phosphor degradation

Many phosphors tend to lose efficiency gradually by several mechanisms. The activators can undergo change of valence (usually
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
), the
crystal lattice In geometry and crystallography, a Bravais lattice, named after , is an infinite array of discrete points generated by a set of discrete translation operations described in three dimensional space by : \mathbf = n_1 \mathbf_1 + n_2 \mathbf_2 + n ...
degrades, atoms – often the activators – diffuse through the material, the surface undergoes chemical reactions with the environment with consequent loss of efficiency or buildup of a layer absorbing either the exciting or the radiated energy, etc. The degradation of electroluminescent devices depends on frequency of driving current, the luminance level, and temperature; moisture impairs phosphor lifetime very noticeably as well. Harder, high-melting, water-insoluble materials display lower tendency to lose luminescence under operation. Examples: * BaMgAl10O17:Eu2+ (BAM), a plasma-display phosphor, undergoes oxidation of the dopant during baking. Three mechanisms are involved; absorption of oxygen atoms into oxygen vacancies on the crystal surface,
diffusion Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical ...
of Eu(II) along the conductive layer, and electron transfer from Eu(II) to absorbed oxygen atoms, leading to formation of Eu(III) with corresponding loss of emissivity. Thin coating of aluminium phosphate or lanthanum(III) phosphate is effective in creating a barrier layer blocking access of oxygen to the BAM phosphor, for the cost of reduction of phosphor efficiency. Addition of
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-to ...
, acting as a
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth met ...
, to
argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice a ...
in the plasma displays significantly extends the lifetime of BAM:Eu2+ phosphor, by reducing the Eu(III) atoms back to Eu(II). * Y2O3:Eu phosphors under electron bombardment in presence of oxygen form a non-phosphorescent layer on the surface, where electron–hole pairs recombine nonradiatively via surface states. * ZnS:Mn, used in AC thin-film electroluminescent (ACTFEL) devices degrades mainly due to formation of deep-level traps, by reaction of water molecules with the dopant; the traps act as centers for nonradiative recombination. The traps also damage the
crystal lattice In geometry and crystallography, a Bravais lattice, named after , is an infinite array of discrete points generated by a set of discrete translation operations described in three dimensional space by : \mathbf = n_1 \mathbf_1 + n_2 \mathbf_2 + n ...
. Phosphor aging leads to decreased brightness and elevated threshold voltage. * ZnS-based phosphors in CRTs and FEDs degrade by surface excitation, coulombic damage, build-up of electric charge, and thermal quenching. Electron-stimulated reactions of the surface are directly correlated to loss of brightness. The electrons dissociate impurities in the environment, the reactive oxygen species then attack the surface and form
carbon monoxide Carbon monoxide ( chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simpl ...
and
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
with traces of
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon ma ...
, and nonradiative zinc oxide and zinc sulfate on the surface; the reactive
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-to ...
removes
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...
from the surface as
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The under ...
, forming nonradiative layer of metallic
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
. Sulfur can be also removed as sulfur oxides. * ZnS and CdS phosphors degrade by reduction of the metal ions by captured electrons. The M2+ ions are reduced to M+; two M+ then exchange an electron and become one M2+ and one neutral M atom. The reduced metal can be observed as a visible darkening of the phosphor layer. The darkening (and the brightness loss) is proportional to the phosphor's exposure to electrons and can be observed on some CRT screens that displayed the same image (e.g. a terminal login screen) for prolonged periods. * Europium(II)-doped alkaline earth aluminates degrade by formation of color centers. * :Ce3+ degrades by loss of luminescent Ce3+ ions. * :Mn (P1) degrades by desorption of oxygen under electron bombardment. * Oxide phosphors can degrade rapidly in presence of fluoride ions, remaining from incomplete removal of flux from phosphor synthesis. * Loosely packed phosphors, e.g. when an excess of silica gel (formed from the potassium silicate binder) is present, have tendency to locally overheat due to poor thermal conductivity. E.g. :Tb3+ is subject to accelerated degradation at higher temperatures.


Applications


Lighting

Phosphor layers provide most of the light produced by
fluorescent lamp A fluorescent lamp, or fluorescent tube, is a low-pressure mercury-vapor gas-discharge lamp that uses fluorescence to produce visible light. An electric current in the gas excites mercury vapor, which produces short-wave ultraviolet, ult ...
s, and are also used to improve the balance of light produced by metal halide lamps. Various neon signs use phosphor layers to produce different colors of light. Electroluminescent displays found, for example, in aircraft instrument panels, use a phosphor layer to produce glare-free illumination or as numeric and graphic display devices. White LED lamps consist of a blue or ultra-violet emitter with a phosphor coating that emits at longer wavelengths, giving a full spectrum of visible light. Unfocused and undeflected cathode-ray tubes have been used as stroboscope lamps since 1958.


Phosphor thermometry

Phosphor thermometry Phosphor thermometry is an optical method for surface temperature measurement. The method exploits luminescence emitted by phosphor material. Phosphors are fine white or pastel-colored inorganic powders which may be stimulated by any of a variety of ...
is a temperature measurement approach that uses the temperature dependence of certain phosphors. For this, a phosphor coating is applied to a surface of interest and, usually, the decay time is the emission parameter that indicates temperature. Because the illumination and detection optics can be situated remotely, the method may be used for moving surfaces such as high speed motor surfaces. Also, phosphor may be applied to the end of an optical fiber as an optical analog of a thermocouple.


Glow-in-the-dark toys

In these applications, the phosphor is directly added to the
plastic Plastics are a wide range of synthetic or semi-synthetic materials that use polymers as a main ingredient. Their plasticity makes it possible for plastics to be moulded, extruded or pressed into solid objects of various shapes. This adapta ...
used to mold the toys, or mixed with a binder for use as paints. ZnS:Cu phosphor is used in glow-in-the-dark cosmetic creams frequently used for Halloween make-ups. Generally, the persistence of the phosphor increases as the wavelength increases. See also
lightstick A glow stick, also known as a light stick, chem light, light wand, light rod, and rave light, is a self-contained, short-term light-source. It consists of a translucent plastic tube containing isolated substances that, when combined, make light ...
for
chemiluminescence Chemiluminescence (also chemoluminescence) is the emission of light (luminescence) as the result of a chemical reaction. There may also be limited emission of heat. Given reactants A and B, with an excited intermediate ◊, : + -> lozenge - ...
-based glowing items.


Oxygen sensing

Quenching of the triplet state by O2 (which has a triplet ground state) as a result of Dexter energy transfer is well known in solutions of phosphorescent heavy-metal complexes and doped polymers. In recent years, phosphorescence porous materials(such as
Metal–organic framework Metal–organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. The organic ligands included are sometimes referred to as "stru ...
s and
Covalent organic framework Covalent organic frameworks (COFs) are a class of materials that form two- or three-dimensional structures through reactions between organic precursors resulting in strong, covalent bonds to afford porous, stable, and crystalline materials. COFs em ...
s) have shown promising oxygen sensing capabilities, for their non-linear gas-adsorption in ultra-low partial pressures of oxygen.


Postage stamps

Phosphor banded stamp {{no footnotes, date=February 2012 Phosphor bands were introduced on British stamps from 1959 as a replacement for the previous graphite lined stamps as an aid in the mechanical sorting of mail. The phosphor is applied in vertical bands, or more r ...
s first appeared in 1959 as guides for machines to sort mail. Around the world many varieties exist with different amounts of banding.
Postage stamp A postage stamp is a small piece of paper issued by a post office, postal administration, or other authorized vendors to customers who pay postage (the cost involved in moving, insuring, or registering mail), who then affix the stamp to the f ...
s are sometimes collected by whether or not they are "tagged" with phosphor (or printed on luminescent paper).


Radioluminescence

Zinc sulfide phosphors are used with
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
materials, where the phosphor was excited by the alpha- and beta-decaying isotopes, to create luminescent paint for dials of
watch A watch is a portable timepiece intended to be carried or worn by a person. It is designed to keep a consistent movement despite the motions caused by the person's activities. A wristwatch is designed to be worn around the wrist, attached ...
es and instruments ( radium dials). Between 1913 and 1950 radium-228 and radium-226 were used to activate a phosphor made of
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
doped zinc sulfide (ZnS:Ag), which gave a greenish glow. The phosphor is not suitable to be used in layers thicker than 25 mg/cm2, as the self-absorption of the light then becomes a problem. Furthermore, zinc sulfide undergoes degradation of its crystal lattice structure, leading to gradual loss of brightness significantly faster than the depletion of radium. ZnS:Ag coated spinthariscope screens were used by Ernest Rutherford in his experiments discovering
atomic nucleus The atomic nucleus is the small, dense region consisting of protons and neutrons at the center of an atom, discovered in 1911 by Ernest Rutherford based on the 1909 Geiger–Marsden gold foil experiment. After the discovery of the neutron ...
.
Copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
doped zinc sulfide (ZnS:Cu) is the most common phosphor used and yields blue-green light. Copper and
magnesium Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ...
doped zinc sulfide yields yellow-orange light. Tritium is also used as a source of radiation in various products utilizing tritium illumination.


Electroluminescence

Electroluminescence Electroluminescence (EL) is an optical and electrical phenomenon, in which a material emits light in response to the passage of an electric current or to a strong electric field. This is distinct from black body light emission resulting fro ...
can be exploited in light sources. Such sources typically emit from a large area, which makes them suitable for backlights of LCD displays. The excitation of the phosphor is usually achieved by application of high-intensity
electric field An electric field (sometimes E-field) is the physical field that surrounds electrically charged particles and exerts force on all other charged particles in the field, either attracting or repelling them. It also refers to the physical field ...
, usually with suitable frequency. Current electroluminescent light sources tend to degrade with use, resulting in their relatively short operation lifetimes. ZnS:Cu was the first formulation successfully displaying electroluminescence, tested at 1936 by
Georges Destriau Georges Destriau (1 August 1903 - 20 January 1960) was a French physicist and early observer of electroluminescence. Education and Research In 1926 Destriau became an engineer at the École Centrale des Arts et Manufactures in Paris. Thereafter h ...
in Madame Marie Curie laboratories in Paris. Powder or AC electroluminescence is found in a variety of backlight and night light applications. Several groups offer branded EL offerings (e.g. IndiGlo used in some Timex watches) or "Lighttape", another trade name of an electroluminescent material, used in electroluminescent light strips. The Apollo space program is often credited with being the first significant use of EL for backlights and lighting.


White LEDs

White
light-emitting diode A light-emitting diode (LED) is a semiconductor Electronics, device that Light#Light sources, emits light when Electric current, current flows through it. Electrons in the semiconductor recombine with electron holes, releasing energy i ...
s are usually blue InGaN LEDs with a coating of a suitable material.
Cerium Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the +3 ...
(III)-doped YAG (YAG:Ce3+, or Y3Al5O12:Ce3+) is often used; it absorbs the light from the blue LED and emits in a broad range from greenish to reddish, with most of its output in yellow. This yellow emission combined with the remaining blue emission gives the "white" light, which can be adjusted to color temperature as warm (yellowish) or cold (bluish) white. The pale yellow emission of the Ce3+:YAG can be tuned by substituting the cerium with other rare-earth elements such as terbium and gadolinium and can even be further adjusted by substituting some or all of the aluminium in the YAG with gallium. However, this process is not one of phosphorescence. The yellow light is produced by a process known as scintillation, the complete absence of an afterglow being one of the characteristics of the process. Some rare-earth- doped
Sialon SiAlON ceramics are a specialist class of high-temperature refractory materials, with high strength at ambient and high temperatures, good thermal shock resistance and exceptional resistance to wetting or corrosion by molten non-ferrous metals, c ...
s are
photoluminescent Photoluminescence (abbreviated as PL) is light emission from any form of matter after the absorption of photons (electromagnetic radiation). It is one of many forms of luminescence (light emission) and is initiated by photoexcitation (i.e. photon ...
and can serve as phosphors.
Europium Europium is a chemical element with the symbol Eu and atomic number 63. Europium is the most reactive lanthanide by far, having to be stored under an inert fluid to protect it from atmospheric oxygen or moisture. Europium is also the softest lan ...
(II)-doped β-SiAlON absorbs in
ultraviolet Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation ...
and
visible light Light or visible light is electromagnetic radiation that can be perceived by the human eye. Visible light is usually defined as having wavelengths in the range of 400–700 nanometres (nm), corresponding to frequencies of 750–420 t ...
spectrum and emits intense broadband visible emission. Its luminance and color does not change significantly with temperature, due to the temperature-stable crystal structure. It has a great potential as a green down-conversion phosphor for white LEDs; a yellow variant also exists (α-SiAlON). For white LEDs, a blue LED is used with a yellow phosphor, or with a green and yellow SiAlON phosphor and a red CaAlSiN3-based (CASN) phosphor. White LEDs can also be made by coating near-ultraviolet-emitting LEDs with a mixture of high-efficiency europium-based red- and blue-emitting phosphors plus green-emitting copper- and aluminium-doped zinc sulfide . This is a method analogous to the way
fluorescent lamp A fluorescent lamp, or fluorescent tube, is a low-pressure mercury-vapor gas-discharge lamp that uses fluorescence to produce visible light. An electric current in the gas excites mercury vapor, which produces short-wave ultraviolet, ult ...
s work. Some newer white LEDs use a yellow and blue emitter in series, to approximate white; this technology is used in some Motorola phones such as the Blackberry as well as LED lighting and the original-version stacked emitters by using GaN on SiC on InGaP but was later found to fracture at higher drive currents. Many white LEDs used in general lighting systems can be used for data transfer, as, for example, in systems that modulate the LED to act as a beacon. It is also common for white LEDs to use phosphors other than Ce:YAG, or to use two or three phosphors to achieve a higher CRI, often at the cost of efficiency. Examples of additional phosphors are R9, which produces a saturated red, nitrides which produce red, and aluminates such as lutetium aluminum garnet that produce green. Silicate phosphors are brighter but fade more quickly, and are used in LCD LED backlights in mobile devices. LED phosphors can be placed directly over the die or made into a dome and placed above the LED: this approach is known as a remote phosphor. Some colored LEDs, instead of using a colored LED, use a blue LED with a colored phosphor because such an arrangement is more efficient than a colored LED. Oxynitride phosphors can also be used in LEDs. The precursors used to make the phosphors may degrade when exposed to air.


Cathode-ray tubes

Cathode-ray tubes produce signal-generated light patterns in a (typically) round or rectangular format. Bulky CRTs were used in the black-and-white household television (TV) sets that became popular in the 1950s, as well as first-generation, tube-based color TVs, and most earlier computer monitors. CRTs have also been widely used in scientific and engineering instrumentation, such as oscilloscopes, usually with a single phosphor color, typically green. Phosphors for such applications may have long afterglow, for increased image persistence. The phosphors can be deposited as either
thin film A thin film is a layer of material ranging from fractions of a nanometer ( monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films (a process referred to as deposition) is a fundamental step in many ...
, or as discrete particles, a powder bound to the surface. Thin films have better lifetime and better resolution, but provide less bright and less efficient image than powder ones. This is caused by multiple internal reflections in the thin film, scattering the emitted light. White (in black-and-white): The mix of zinc cadmium sulfide and zinc sulfide silver, the is the white P4 phosphor used in black and white television CRTs. Mixes of yellow and blue phosphors are usual. Mixes of red, green and blue, or a single white phosphor, can also be encountered. Red: Yttrium
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
-
sulfide Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds la ...
activated with europium is used as the red phosphor in color CRTs. The development of color TV took a long time due to the search for a red phosphor. The first red emitting rare-earth phosphor, YVO4:Eu3+, was introduced by Levine and Palilla as a primary color in television in 1964. In single crystal form, it was used as an excellent polarizer and laser material. Yellow: When mixed with cadmium sulfide, the resulting zinc cadmium sulfide , provides strong yellow light. Green: Combination of zinc sulfide with
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
, the P31 phosphor or , provides green light peaking at 531 nm, with long glow. Blue: Combination of zinc sulfide with few ppm of
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
, the ZnS:Ag, when excited by electrons, provides strong blue glow with maximum at 450 nm, with short afterglow with 200 nanosecond duration. It is known as the P22B phosphor. This material, zinc sulfide silver, is still one of the most efficient phosphors in cathode-ray tubes. It is used as a blue phosphor in color CRTs. The phosphors are usually poor electrical conductors. This may lead to deposition of residual charge on the screen, effectively decreasing the energy of the impacting electrons due to electrostatic repulsion (an effect known as "sticking"). To eliminate this, a thin layer of aluminium (about 100 nm) is deposited over the phosphors, usually by vacuum evaporation, and connected to the conductive layer inside the tube. This layer also reflects the phosphor light to the desired direction, and protects the phosphor from ion bombardment resulting from an imperfect vacuum. To reduce the image degradation by reflection of ambient light, contrast can be increased by several methods. In addition to black masking of unused areas of screen, the phosphor particles in color screens are coated with pigments of matching color. For example, the red phosphors are coated with
ferric oxide Iron(III) oxide or ferric oxide is the inorganic compound with the formula Fe2O3. It is one of the three main oxides of iron, the other two being iron(II) oxide (FeO), which is rare; and iron(II,III) oxide (Fe3O4), which also occurs naturall ...
(replacing earlier Cd(S,Se) due to cadmium toxicity), blue phosphors can be coated with marine blue ( CoO·''n'' ) or ultramarine (). Green phosphors based on ZnS:Cu do not have to be coated due to their own yellowish color.


Black-and-white television CRTs

The black-and-white television screens require an emission color close to white. Usually, a combination of phosphors is employed. The most common combination is (blue + yellow). Other ones are (blue + yellow), and (blue + green + red – does not contain cadmium and has poor efficiency). The color tone can be adjusted by the ratios of the components. As the compositions contain discrete grains of different phosphors, they produce image that may not be entirely smooth. A single, white-emitting phosphor, overcomes this obstacle. Due to its low efficiency, it is used only on very small screens. The screens are typically covered with phosphor using sedimentation coating, where particles suspended in a solution are let to settle on the surface.Lakshmanan, p. 54.


Reduced-palette color CRTs

For displaying of a limited palette of colors, there are a few options. In beam penetration tubes, different color phosphors are layered and separated with dielectric material. The acceleration voltage is used to determine the energy of the electrons; lower-energy ones are absorbed in the top layer of the phosphor, while some of the higher-energy ones shoot through and are absorbed in the lower layer. So either the first color or a mixture of the first and second color is shown. With a display with red outer layer and green inner layer, the manipulation of accelerating voltage can produce a continuum of colors from red through orange and yellow to green. Another method is using a mixture of two phosphors with different characteristics. The brightness of one is linearly dependent on electron flux, while the other one's brightness saturates at higher fluxes—the phosphor does not emit any more light regardless of how many more electrons impact it. At low electron flux, both phosphors emit together; at higher fluxes, the luminous contribution of the nonsaturating phosphor prevails, changing the combined color. Such displays can have high resolution, due to absence of two-dimensional structuring of RGB CRT phosphors. Their color palette is, however, very limited. They were used e.g. in some older military radar displays.


Color television CRTs

The phosphors in color CRTs need higher contrast and resolution than the black-and-white ones. The energy density of the electron beam is about 100 times greater than in black-and-white CRTs; the electron spot is focused to about 0.2 mm diameter instead of about 0.6 mm diameter of the black-and-white CRTs. Effects related to electron irradiation degradation are therefore more pronounced. Color CRTs require three different phosphors, emitting in red, green and blue, patterned on the screen. Three separate electron guns are used for color production (except for displays that use beam-index tube technology, which is rare). The red phosphor has always been a problem, being the dimmest of the three necessitating the brighter green and blue electron beam currents be adjusted down to make them equal the red phosphor's lower brightness. This made early color TVs only usable indoors as bright light made it impossible to see the dim picture, while portable black-and-white TVs viewable in outdoor sunlight were already common. The composition of the phosphors changed over time, as better phosphors were developed and as environmental concerns led to lowering the content of cadmium and later abandoning it entirely. The was replaced with with lower cadmium/zinc ratio, and then with cadmium-free . The blue phosphor stayed generally unchanged, a silver-doped zinc sulfide. The green phosphor initially used manganese-doped zinc silicate, then evolved through silver-activated cadmium-zinc sulfide, to lower-cadmium copper-aluminium activated formula, and then to cadmium-free version of the same. The red phosphor saw the most changes; it was originally manganese-activated zinc phosphate, then a silver-activated cadmium-zinc sulfide, then the europium(III) activated phosphors appeared; first in an yttrium vanadate matrix, then in yttrium oxide and currently in yttrium oxysulfide. The evolution of the phosphors was therefore (ordered by B-G-R): *  –  –  *  –  –  *  –  –  (1964–?) *  –  –  or *  –  or  – 


Projection televisions

For projection televisions, where the beam power density can be two orders of magnitude higher than in conventional CRTs, some different phosphors have to be used. For blue color, is employed. However, it saturates. can be used as an alternative that is more linear at high energy densities. For green, a terbium-activated ; its color purity and brightness at low excitation densities is worse than the zinc sulfide alternative, but it behaves linear at high excitation energy densities, while zinc sulfide saturates. However, it also saturates, so or can be substituted. is bright but water-sensitive, degradation-prone, and the plate-like morphology of its crystals hampers its use; these problems are solved now, so it is gaining use due to its higher linearity. is used for red emission.


Standard phosphor types


Various

Some other phosphors commercially available, for use as
X-ray An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10 picometers to 10  nanometers, corresponding to frequencies in the range 30&nb ...
screens, neutron detectors,
alpha particle Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay, but may also be prod ...
scintillator A scintillator is a material that exhibits scintillation, the property of luminescence, when excited by ionizing radiation. Luminescent materials, when struck by an incoming particle, absorb its energy and scintillate (i.e. re-emit the absorbe ...
s, etc., are: *Gd2O2S:Tb (P43), green (peak at 545 nm), 1.5 ms decay to 10%, low afterglow, high X-ray absorption, for X-ray, neutrons and gamma *Gd2O2S:Eu, red (627 nm), 850 μs decay, afterglow, high X-ray absorption, for X-ray, neutrons and gamma *Gd2O2S:Pr, green (513 nm), 7 μs decay, no afterglow, high X-ray absorption, for X-ray, neutrons and gamma *, green (513 nm), 4 μs decay, no afterglow, high X-ray absorption, for X-ray, neutrons and gamma *Y2O2S:Tb (P45), white (545 nm), 1.5 ms decay, low afterglow, for low-energy X-ray *Y2O2S:Eu (P22R), red (627 nm), 850 μs decay, afterglow, for low-energy X-ray *Y2O2S:Pr, white (513 nm), 7 μs decay, no afterglow, for low-energy X-ray * (HS), green (560 nm), 80 μs decay, afterglow, efficient but low-res X-ray * (HSr), red (630 nm), 80 μs decay, afterglow, efficient but low-res X-ray *CdWO4, blue (475 nm), 28 μs decay, no afterglow, intensifying phosphor for X-ray and gamma *CaWO4, blue (410 nm), 20 μs decay, no afterglow, intensifying phosphor for X-ray *MgWO4, white (500 nm), 80 μs decay, no afterglow, intensifying phosphor *Y2SiO5:Ce (P47), blue (400 nm), 120 ns decay, no afterglow, for electrons, suitable for photomultipliers *YAlO3:Ce (YAP), blue (370 nm), 25 ns decay, no afterglow, for electrons, suitable for photomultipliers *Y3Al5O12:Ce (YAG), green (550 nm), 70 ns decay, no afterglow, for electrons, suitable for photomultipliers * (YGG), green (530 nm), 250 ns decay, low afterglow, for electrons, suitable for photomultipliers *CdS:In, green (525 nm), <1 ns decay, no afterglow, ultrafast, for electrons *ZnO:Ga, blue (390 nm), <5 ns decay, no afterglow, ultrafast, for electrons *ZnO:Zn (P15), blue (495 nm), 8 μs decay, no afterglow, for low-energy electrons * (P22G), green (565 nm), 35 μs decay, low afterglow, for electrons * (P22G), green (540 nm), 35 μs decay, low afterglow, for electrons * (P20), green (530 nm), 80 μs decay, low afterglow, for electrons *ZnS:Ag (P11), blue (455 nm), 80 μs decay, low afterglow, for alpha particles and electrons *
anthracene Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the production of the red dye alizarin and other dyes. Anthracene is co ...
, blue (447 nm), 32 ns decay, no afterglow, for alpha particles and electrons *plastic (EJ-212), blue (400 nm), 2.4 ns decay, no afterglow, for alpha particles and electrons *Zn2SiO4:Mn (P1), green (530 nm), 11 ms decay, low afterglow, for electrons *ZnS:Cu (GS), green (520 nm), decay in minutes, long afterglow, for X-rays * NaI:Tl, for X-ray, alpha, and electrons * CsI:Tl, green (545 nm), 5 μs decay, afterglow, for X-ray, alpha, and electrons *6 LiF/ZnS:Ag (ND), blue (455 nm), 80 μs decay, for thermal neutrons * (NDg), green (565 nm), 35 μs decay, for
neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the atomic nucleus, nuclei of atoms. Since protons and ...
s *Cerium doped YAG phosphor, yellow, used in white LEDs for turning blue to white light with a broad spectrum of light


See also

*
Cathodoluminescence Cathodoluminescence is an optical and electromagnetic phenomenon in which electrons impacting on a luminescent material such as a phosphor, cause the emission of photons which may have wavelengths in the visible spectrum. A familiar example is ...
*
Laser A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word "laser" is an acronym for "light amplification by stimulated emission of radiation". The ...
*
Luminophore In chemistry, a luminophore (sometimes shortened to lumophore) is an atom or functional group in a chemical compound that is responsible for its luminescent properties. Luminophores can be either organic or inorganic. Luminophores can be furt ...
*
Photoluminescence Photoluminescence (abbreviated as PL) is light emission from any form of matter after the absorption of photons (electromagnetic radiation). It is one of many forms of luminescence (light emission) and is initiated by photoexcitation (i.e. photo ...


References


Bibliography

*


External links

{{Wiktionary
a history of electroluminescent displays

CRT Phosphor Characteristics
(P numbers)
Silicon-based oxynitride and nitride phosphors for white LEDs—A review


– RCA Manual, Fluorescent screens (P1 to P24)
Inorganic Phosphors Compositions, Preparation and Optical Properties, William M. Yen and Marvin J. Weber
Luminescence Lighting Display technology Optical materials