Zinc Sulphide
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Zinc sulfide (or zinc sulphide) is an
inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
with the
chemical formula In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...
of ZnS. This is the main form of zinc found in nature, where it mainly occurs as the mineral
sphalerite Sphalerite (sometimes spelled sphaelerite) is a sulfide mineral with the chemical formula . It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in Sedimentary exhalative deposits, sedimen ...
. Although this mineral is usually black because of various impurities, the pure material is white, and it is widely used as a pigment. In its dense synthetic form, zinc sulfide can be
transparent Transparency, transparence or transparent most often refer to: * Transparency (optics), the physical property of allowing the transmission of light through a material They may also refer to: Literal uses * Transparency (photography), a still, ...
, and it is used as a window for visible optics and
infrared Infrared (IR), sometimes called infrared light, is electromagnetic radiation (EMR) with wavelengths longer than those of visible light. It is therefore invisible to the human eye. IR is generally understood to encompass wavelengths from around ...
optics.


Structure

ZnS exists in two main crystalline forms. This dualism is an example of polymorphism. In each form, the coordination geometry at Zn and S is tetrahedral. The more stable cubic form is known also as zinc blende or
sphalerite Sphalerite (sometimes spelled sphaelerite) is a sulfide mineral with the chemical formula . It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in Sedimentary exhalative deposits, sedimen ...
. The hexagonal form is known as the mineral
wurtzite Wurtzite is a zinc and iron sulfide mineral with the chemical formula , a less frequently encountered Polymorphism (materials science), structural polymorph form of sphalerite. The iron content is variable up to eight percent.Palache, Charles, Har ...
, although it also can be produced synthetically.. The transition from the sphalerite form to the wurtzite form occurs at around 1020 
°C The degree Celsius is the unit of temperature on the Celsius scale (originally known as the centigrade scale outside Sweden), one of two temperature scales used in the International System of Units (SI), the other being the Kelvin scale. The ...
. A tetragonal form is also known as the very rare mineral called polhemusite, with the formula .


Applications


Luminescent material

Zinc sulfide, with addition of few ppm of suitable activator, exhibits strong
phosphorescence Phosphorescence is a type of photoluminescence related to fluorescence. When exposed to light (radiation) of a shorter wavelength, a phosphorescent substance will glow, absorbing the light and reemitting it at a longer wavelength. Unlike fluo ...
. The phenomenon was described by
Nikola Tesla Nikola Tesla ( ; ,"Tesla"
''
cathode ray tube A cathode-ray tube (CRT) is a vacuum tube containing one or more electron guns, which emit electron beams that are manipulated to display images on a phosphorescent screen. The images may represent electrical waveforms ( oscilloscope), pictu ...
s through
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 to glow in the dark products. When
silver Silver is a chemical element with the Symbol (chemistry), symbol Ag (from the Latin ', derived from the Proto-Indo-European wikt:Reconstruction:Proto-Indo-European/h₂erǵ-, ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, whi ...
is used as activator, the resulting color is bright blue, with maximum at 450
nanometer 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 ...
s. Using
manganese Manganese is a chemical element with the 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 industrial alloy use ...
yields an orange-red color at around 590 nanometers.
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 pinkis ...
gives long-time glow, and it has the familiar greenish glow-in-the-dark. Copper-doped zinc sulfide ("ZnS plus Cu") is used also in
electroluminescent 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 from ...
panels. It also exhibits
phosphorescence Phosphorescence is a type of photoluminescence related to fluorescence. When exposed to light (radiation) of a shorter wavelength, a phosphorescent substance will glow, absorbing the light and reemitting it at a longer wavelength. Unlike fluo ...
due to impurities on illumination with blue or
ultraviolet Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nanometer, nm (with a corresponding frequency around 30 Hertz, PHz) to 400 nm (750 Hertz, THz), shorter than that of visible light, but longer than ...
light.


Optical material

Zinc sulfide is also used as an
infrared Infrared (IR), sometimes called infrared light, is electromagnetic radiation (EMR) with wavelengths longer than those of visible light. It is therefore invisible to the human eye. IR is generally understood to encompass wavelengths from around ...
optical material, transmitting from visible
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, tro ...
s to just over 12
micrometer Micrometer can mean: * Micrometer (device), used for accurate measurements by means of a calibrated screw * American spelling of micrometre The micrometre ( international spelling as used by the International Bureau of Weights and Measures; ...
s. It can be used planar as an
optical window The optical window is a range of wavelengths that are not blocked by the earth's atmosphere. The window runs from around 300 nanometers (ultraviolet-B) up into the range the human eye can detect, roughly 400–700 nm and continues up to approxim ...
or shaped into a
lens A lens is a transmissive optical device which focuses or disperses a light beam by means of refraction. A simple lens consists of a single piece of transparent material, while a compound lens consists of several simple lenses (''elements''), ...
. It is made as
microcrystalline A microcrystalline material is a crystallized substance or rock that contains small crystals visible only through microscopic examination. There is little agreement on the range of crystal sizes that should be regarded as microcrystalline, but th ...
sheets by the synthesis from
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 unde ...
gas and zinc vapour, and this is sold as
FLIR Forward-looking infrared (FLIR) cameras, typically used on military and civilian aircraft, use a thermographic camera that senses infrared radiation. The sensors installed in forward-looking infrared cameras, as well as those of other thermal ...
-grade (Forward Looking Infrared), where the zinc sulfide is in a milky-yellow, opaque form. This material when hot isostatically pressed (HIPed) can be converted to a water-clear form known as Cleartran (trademark). Early commercial forms were marketed as Irtran-2 but this designation is now obsolete.


Pigment

Zinc sulfide is a common
pigment A pigment is a colored material that is completely or nearly insoluble in water. In contrast, dyes are typically soluble, at least at some stage in their use. Generally dyes are often organic compounds whereas pigments are often inorganic compo ...
, sometimes called sachtolith. When combined with barium sulfate, zinc sulfide forms
lithopone Lithopone, C.I. Pigment White 5, is a mixture of inorganic compounds, widely used as a white pigment powder. It is composed of a mixture of barium sulfate and zinc sulfide. These insoluble compounds blend well with organic compounds and confer op ...
.Gerhard Auer, Peter Woditsch, Axel Westerhaus, Jürgen Kischkewitz, Wolf-Dieter Griebler and Marcel Liedekerke "Pigments, Inorganic, 2. White Pigments" in Ullmann's Encyclopedia of Industrial Chemistry 2009, Wiley-VCH, Weinheim.


Catalyst

Fine ZnS powder is an efficient
photocatalyst In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalyzed photolysis, light is absorbed by an adsorbed substrate. In photogenerated catalysis, the photocatalytic activity depends on the abil ...
, which produces hydrogen gas from water upon illumination. Sulfur vacancies can be introduced in ZnS during its synthesis; this gradually turns the white-yellowish ZnS into a brown powder, and boosts the photocatalytic activity through enhanced light absorption.


Semiconductor properties

Both sphalerite and wurtzite are intrinsic, wide-
bandgap 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 (i ...
semiconductor A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
s. These are prototypical
II-VI semiconductor Semiconductor materials are nominally small band gap insulators. The defining property of a semiconductor material is that it can be compromised by doping it with impurities that alter its electronic properties in a controllable way. Because of ...
s, and they adopt structures related to many of the other semiconductors, such as
gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
. The cubic form of ZnS has a
band 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 ...
of about 3.54
electron volt In physics, an electronvolt (symbol eV, also written electron-volt and electron volt) is the measure of an amount of kinetic energy gained by a single electron accelerating from rest through an electric potential difference of one volt in vacuum. ...
s at 300
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 phys ...
s, but the hexagonal form has a band gap of about 3.91 electron volts. ZnS can be doped as either an n-type semiconductor or a p-type semiconductor.


History

The
phosphorescence Phosphorescence is a type of photoluminescence related to fluorescence. When exposed to light (radiation) of a shorter wavelength, a phosphorescent substance will glow, absorbing the light and reemitting it at a longer wavelength. Unlike fluo ...
of ZnS was first reported by the French chemist Théodore Sidot in 1866. His findings were presented by
A. E. Becquerel Alexandre-Edmond Becquerel (24 March 1820 – 11 May 1891), known as Edmond Becquerel, was a French physicist who studied the solar spectrum, magnetism, electricity and optics. He is credited with the discovery of the photovoltaic effect, the ope ...
, who was renowned for the research on
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 ...
. ZnS was used by
Ernest Rutherford Ernest Rutherford, 1st Baron Rutherford of Nelson, (30 August 1871 – 19 October 1937) was a New Zealand physicist who came to be known as the father of nuclear physics. ''Encyclopædia Britannica'' considers him to be the greatest ...
and others in the early years of
nuclear physics Nuclear physics is the field of physics that studies atomic nuclei and their constituents and interactions, in addition to the study of other forms of nuclear matter. Nuclear physics should not be confused with atomic physics, which studies the ...
as a scintillation detector, because it emits light upon excitation by
x-rays 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 Picometre, picometers to 10 Nanometre, nanometers, corresponding to frequency, ...
or
electron beam Cathode rays or electron beam (e-beam) are streams of electrons observed in discharge tubes. If an evacuated glass tube is equipped with two electrodes and a voltage is applied, glass behind the positive electrode is observed to glow, due to ele ...
, making it useful for X-ray screens and
cathode ray tube A cathode-ray tube (CRT) is a vacuum tube containing one or more electron guns, which emit electron beams that are manipulated to display images on a phosphorescent screen. The images may represent electrical waveforms ( oscilloscope), pictu ...
s. This property made zinc sulfide useful in the dials of radium watches.


Production

Zinc sulfide is usually produced from waste materials from other applications. Typical sources include smelter, slag, and pickle liquors. As an example- the synthesis of
ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
from
methane Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Eart ...
requires a priori removal of
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 unde ...
impurities in the natural gas, for which
zinc oxide Zinc oxide is an inorganic compound with the formula . It is a white powder that is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cemen ...
is used. This scavenging produces zinc sulfide: :ZnO + H2S → ZnS + H2O


Laboratory preparation

It is easily produced by igniting a mixture 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 ...
and
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 formula ...
. Since zinc sulfide is insoluble in water, it can also be produced in a
precipitation reaction In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a super-saturated solution. The solid formed is called the precipitate. In case of an inorganic chemical reaction leading ...
. Solutions containing Zn2+ salts readily form a precipitate ZnS in the presence of
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 lar ...
ions (e.g., from H2S). :Zn2+ + S2− → ZnS This reaction is the basis of a
gravimetric analysis Gravimetric analysis describes a set of methods used in analytical chemistry for the quantitative determination of an analyte (the ion being analyzed) based on its mass. The principle of this type of analysis is that once an ion's mass has been ...
for zinc.


References


External links


Zinc and Sulfur
at ''
The Periodic Table of Videos ''Periodic Videos'' (also known as ''The Periodic Table of Videos'') is a video project and YouTube channel on chemistry. It consists of a series of videos about chemical elements and the periodic table, with additional videos on other topics i ...
'' (University of Nottingham)
Composition of CRT phosphors

University of Reading, Infrared Multilayer Laboratory
optical data

melting point {{Sulfides Sulfides
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 lar ...
II-VI semiconductors Luminescence Optical materials Phosphors and scintillators * Zincblende crystal structure Wurtzite structure type