Samarium monochalcogenides are chemical compounds with the composition SmX, where Sm stands for the
lanthanide
The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium (el ...
element
samarium
Samarium is a chemical element; it has symbol Sm and atomic number 62. It is a moderately hard silvery metal that slowly oxidizes in air. Being a typical member of the lanthanide series, samarium usually has the oxidation state +3. Compounds of s ...
and X denotes any one of three
chalcogen
The chalcogens (ore forming) ( ) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the rad ...
elements,
sulfur
Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...
,
selenium
Selenium is a chemical element; it has symbol (chemistry), symbol Se and atomic number 34. It has various physical appearances, including a brick-red powder, a vitreous black solid, and a grey metallic-looking form. It seldom occurs in this elem ...
or
tellurium
Tellurium is a chemical element; it has symbol Te and atomic number 52. It is a brittle, mildly toxic, rare, silver-white metalloid. Tellurium is chemically related to selenium and sulfur, all three of which are chalcogens. It is occasionally fou ...
, resulting in the compounds SmS, SmSe or SmTe. In these compounds, samarium formally exhibits
oxidation state
In chemistry, the oxidation state, or oxidation number, is the hypothetical Electrical charge, charge of an atom if all of its Chemical bond, bonds to other atoms are fully Ionic bond, ionic. It describes the degree of oxidation (loss of electrons ...
+2, whereas it usually assumes the +3 state, resulting in chalcogenides with the chemical formula Sm
2X
3.
Synthesis
Single crystals or polycrystals of samarium monochalcogenides can be obtained by reacting the metal with sulfur, selenium or tellurium vapors at high temperature.
[ Thin films can be obtained by magnetron ]sputtering
In physics, sputtering is a phenomenon in which microscopic particles of a solid material are ejected from its surface, after the material is itself bombarded by energetic particles of a plasma or gas. It occurs naturally in outer space, and c ...
electron beam physical vapor deposition
Electron-beam physical vapor deposition, or EBPVD, is a form of physical vapor deposition in which a target anode is bombarded with an electron beam given off by a charged tungsten filament under high vacuum. The electron beam causes atoms from the ...
, that is bombardment of samarium metal target with electrons in and appropriate gas atmosphere (e.g. hydrogen disulfide
Hydrogen disulfide is the inorganic compound with the formula . This hydrogen chalcogenide is a pale yellow volatile liquid with a camphor-like odor. It decomposes readily to hydrogen sulfide () and elemental sulfur.
Structure
The connection of ...
for SmS).[
]
Properties
Samarium monochalcogenides are black semiconducting
A semiconductor is a material with electrical conductivity between that of a conductor and an insulator. Its conductivity can be modified by adding impurities (" doping") to its crystal structure. When two regions with different doping levels ...
solids with rock-salt cubic crystal structure. Application of moderate hydrostatic pressure converts them into metals. Whereas the transition is continuous and occurs at about 45 and 60 kbar in SmSe and SmTe, respectively, it is abrupt in SmS and requires only 6.5 kbar. Similar effect is observed in monochalcogenides of another lanthanide, thulium
Thulium is a chemical element; it has symbol Tm and atomic number 69. It is the thirteenth element in the lanthanide series of metals. It is the second-least abundant lanthanide in the Earth's crust, after radioactively unstable promethium. It i ...
.[ This results in spectacular change in color from black to golden yellow when scratching or mechanically polishing SmS.][Eric Beaurepaire (Ed.]
Magnetism: a synchrotron radiation approach
Springer, 2006 p. 393 in the crystal volume. A hysteresis
Hysteresis is the dependence of the state of a system on its history. For example, a magnet may have more than one possible magnetic moment in a given magnetic field, depending on how the field changed in the past. Plots of a single component of ...
is observed, that is when the pressure is released, SmS returns to semiconducting state at much lower pressure of about 0.5 kbar.band gap
In solid-state physics and solid-state chemistry, a band gap, also called a bandgap or energy gap, is an energy range in a solid where no electronic states exist. In graphs of the electronic band structure of solids, the band gap refers to t ...
, which amounts at zero pressure to 0.15, 0.45 and 0.65 eV in SmS, SmSe and SmTe, respectively.[K. H. J. Buscho]
Concise encyclopedia of magnetic and superconducting materials
Elsevier, 2005 p. 318
At the transition pressure (6.5 kbar in SmS) the gap is still finite and the low resistivity originates from thermally activated generation of carriers across a narrow band gap. The gap collapses at about 20 kbar when SmS becomes a true metal. At this pressure, the material also changes from paramagnetic
Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, ...
to a magnetic state.[
The semiconductor-metal transition in samarium monochalcogenides requires application of pressure or presence of intrinsic stress, for example in thin films, and the reverse changes occur upon release of this stress. Such release can be triggered by various means, such as heating to about 200 °C]
Potential applications
The change in electrical resistivity in samarium monochalcogenides can be used in a pressure sensor or in a memory device triggered between a low-resistance and high-resistance state by external pressure, and such devices are being developed commercially. Samarium monosulfide also generates electric voltage upon moderate heating to about 150 °C that can be applied in thermoelectric power converters.other articles on this topic
References
{{Samarium compounds
Samarium(II) compounds
Chalcogenides