Indium

Indium is a chemical element; its symbol is In and its atomic number is 49. It is a silvery-white post-transition metal and one of the softest elements. Chemically, indium is similar to gallium and thallium, and its properties are largely intermediate between the two. It was discovered in 1863 by Ferdinand Reich and Hieronymous Theodor Richter by spectroscopic methods and named for the indigo blue line in its spectrum.

Indium is used primarily in the production of flat-panel displays as indium tin oxide (ITO), a transparent and conductive coating applied to glass. It is also used in the semiconductor industry, in low-melting-point metal alloys such as solders and soft-metal high-vacuum seals. It is used in the manufacture of blue and white LED circuits, mainly to produce Indium gallium nitride p-type semiconductor substrates. It is produced exclusively as a by-product during the processing of the ores of other metals, chiefly from sphalerite and other zinc sulfide ores.

Etymology

The name comes from the Latin word indicum meaning violet or indigo. The word indicum means "Indian", as the naturally based dye indigo was originally exported to Europe from India.

Properties

Physical

thumb|left|Indium wetting the glass surface of a test tube

Indium is a shiny silvery-white, highly ductile post-transition metal with a bright luster. It is so soft (Mohs hardness 1.2) that it can be cut with a knife or be bitten into by human teeth. Indium also leaves a visible line like a pencil when rubbed on paper. It is a member of group 13 on the periodic table and its properties are mostly intermediate between its vertical neighbors gallium and thallium. As with tin, a high-pitched cry is heard when indium is bent – a crackling sound due to crystal twinning. The boiling point is 2072 °C (3762 °F), higher than that of thallium, but lower than gallium, conversely to the general trend of melting points, but similarly to the trends down the other post-transition metal groups because of the weakness of the metallic bonding with few electrons delocalized.

The density of indium, 7.31 g/cm³, is also greater than gallium, but lower than thallium. Below the critical temperature, 3.41 K, indium becomes a superconductor. Indium crystallizes in the body-centered tetragonal crystal system in the space group I4/mmm (lattice parameters: a = 325 pm, c = 495 pm): Indium has greater solubility in liquid mercury than any other metal (more than 50 mass percent of indium at 0 °C). Indium displays a ductile viscoplastic response, found to be size-independent in tension and compression. However it does have a size effect in bending and indentation, associated to a length-scale of order 50–100 μm, significantly large when compared with other metals.

Isotopes

Indium has 39 known isotopes, ranging in mass number from 97 to 135. Only two isotopes occur naturally as primordial nuclides: indium-113, the only stable isotope, and indium-115, which has a half-life of 4.41 years, four orders of magnitude greater than the age of the Universe and nearly 30,000 times greater than half-life of thorium-232. The half-life of ¹¹⁵In is very long because the beta decay to ¹¹⁵Sn is spin-forbidden. Indium-115 makes up 95.7% of all indium. Indium is one of three known elements (the others being tellurium and rhenium) of which the stable isotope is less abundant in nature than the long-lived primordial radioisotopes.

The stablest artificial isotope is indium-111, with a half-life of approximately 2.8 days. All other isotopes have half-lives shorter than 5 hours. Indium also has 47 meta states, among which indium-114m1 (half-life about 49.51 days) is the most stable, more stable than the ground state of any indium isotope other than the primordial. All decay by isomeric transition. The indium isotopes lighter than ¹¹³In predominantly decay through electron capture or positron emission to form cadmium isotopes, while the indium isotopes heavier than ¹¹³In predominantly decay through beta-minus decay to form tin isotopes. Gallium (indium's lighter homolog) is only rarely observed in the +1 oxidation state. Thus, although thallium(III) is a moderately strong oxidizing agent, indium(III) is not, and many indium(I) compounds are powerful reducing agents. While the energy required to include the s-electrons in chemical bonding is lowest for indium among the group 13 metals, bond energies decrease down the group so that by indium, the energy released in forming two additional bonds and attaining the +3 state is not always enough to outweigh the energy needed to involve the 5s-electrons. Indium(I) oxide and hydroxide are more basic and indium(III) oxide and hydroxide are more acidic. are reported for indium, reflecting the decreased stability of the +3 oxidation state:

Indium(III) compounds

thumb|right|upright=1|[[Indium trichloride|InCl₃ (structure pictured) is a common compound of indium.]]

Hydrides and halides

The hydride InH₃ has at best a transitory existence in ethereal solutions at low temperatures. It polymerizes in the absence of bases.

Chlorination, bromination, and iodination of In produce colorless InCl₃, InBr₃, and yellow InI₃. The compounds are Lewis acids, somewhat akin to the better known aluminium trihalides. Again like the related aluminium compound, InF₃ is polymeric.

Indium halides dissolves in water to give aquo complexes such as [In(H₂O)₆]³⁺ and [InCl₂(H₂O)₄]⁺. Similar complexes can be prepared from nitrates and acetates. Overall, the pattern is similar to that for aluminium(III). The analogous sesqui-chalcogenides with sulfur, selenium, and tellurium are also known.

The chemistry of indium pnictides (N, P, As, Sb) is also well known, motivated by their relevance to semiconductor technology. For applications in microelectronics, the P, As, and Sb derivatives are made by reactions of trimethylindium:

: (E = P, As, Sb)

Many of these derivatives are prone to hydrolysis.

Indium(I) compounds

Indium(I) compounds are not common. The chloride, bromide, and iodide are deeply colored, unlike the parent trihalides from which they are prepared. The fluoride is known only as an unstable gas. Indium(I) oxide black powder is produced when indium(III) oxide decomposes upon heating to 700 °C. and various subchalcogenides such as In₄Se₃. Several other compounds are known to combine indium(I) and indium(III), such as In^I₆(In^IIICl₆)Cl₃, In^I₅(In^IIIBr₄)₂(In^IIIBr₆), and In^IIn^IIIBr₄. and is polymeric, consisting of zigzag chains of alternating indium atoms and cyclopentadienyl complexes. Perhaps the best-known organoindium compound is trimethylindium, In(CH₃)₃, used to prepare certain semiconducting materials.

History

In 1863, German chemists Ferdinand Reich and Hieronymus Theodor Richter were testing ores from the mines around Freiberg, Saxony. They dissolved the minerals pyrite, arsenopyrite, galena and sphalerite in hydrochloric acid and distilled raw zinc chloride. Reich, who was color-blind, employed Richter as an assistant for detecting the colored spectral lines. Knowing that ores from that region sometimes contain thallium, they searched for the green thallium emission spectrum lines. Instead, they found a bright blue line. Because that blue line did not match any known element, they hypothesized a new element was present in the minerals. They named the element indium, from the indigo color seen in its spectrum, after the Latin indicum, meaning 'of India'.

Richter went on to isolate the metal in 1864. An ingot of was presented at the World Fair 1867. <!-- Until 1924, only approximately a gram of indium constituted the world's supply. --> Reich and Richter later fell out when Richter claimed to be the sole discoverer. The stable indium isotope, indium-113, is one of the p-nuclei, the origin of which is not fully understood; although indium-113 is known to be made directly in the s- and r-processes (rapid neutron capture), and also as the daughter of very long-lived cadmium-113, which has a half-life of about eight quadrillion years, this cannot account for all indium-113.

Indium is the 68th most abundant element in Earth's crust at approximately 50 ppb. This is similar to the crustal abundance of silver, bismuth and mercury. It very rarely forms its own minerals, or occurs in elemental form. Fewer than 10 indium minerals such as roquesite (CuInS₂) are known, and none occur at sufficient concentrations for economic extraction. Instead, indium is usually a trace constituent of more common ore minerals, such as sphalerite and chalcopyrite. From these, it can be extracted as a by-product during smelting. While the enrichment of indium in these deposits is high relative to its crustal abundance, it is insufficient, at current prices, to support extraction of indium as the main product. However, these amounts are not extractable without mining of the host materials (see Production and availability). Thus, the availability of indium is fundamentally determined by the rate at which these ores are extracted, and not their absolute amount. This is an aspect that is often forgotten in the current debate, e.g. by the Graedel group at Yale in their criticality assessments, explaining the paradoxically low depletion times some studies cite.]]

Indium is produced exclusively as a by-product during the processing of the ores of other metals. Its main source material are sulfidic zinc ores, where it is mostly hosted by sphalerite. The exact process varies with the mode of operation of the smelter. Reserves and resources are not relevant for by-products, since they cannot be extracted independently from the main-products. Thus, major future increases in the by-product production of indium will be possible without significant increases in production costs or price. The average indium price in 2016 was 240/kg, down from 705/kg in 2014.

China is a leading producer of indium (290 tonnes in 2016), followed by South Korea (195 t), Japan (70 t) and Canada (65 t). Increased manufacturing efficiency and recycling (especially in Japan) maintain a balance between demand and supply. According to the UNEP, indium's end-of-life recycling rate is less than 1%.

Applications

Industrial uses

thumb|right|A magnified image of an [[TFT LCD|LCD screen showing RGB pixels. Individual transistors are seen as white dots in the bottom part.]]

In 1924, indium was found to have a valued property of stabilizing non-ferrous metals, and that became the first significant use for the element. The first large-scale application for indium was coating bearings in high-performance aircraft engines during World War II, to protect against damage and corrosion; this is no longer a major use of the element.

Indium(III) oxide and indium tin oxide (ITO) are used as a transparent conductive coating on glass substrates in electroluminescent panels. Indium tin oxide is used as an infrared radiation filter in low-pressure sodium-vapor lamps. The infrared radiation is reflected back into the lamp, which increases the temperature within the tube and improves the performance of the lamp. are semiconductors with useful properties: one precursor is usually trimethylindium (TMI), which is also used as the semiconductor dopant in II–VI compound semiconductors. Indium is used in photovoltaics as the semiconductor copper indium gallium selenide (CIGS), also called CIGS solar cells, a type of second-generation thin-film solar cell. Indium is used in PNP bipolar junction transistors with germanium: when soldered at low temperature, indium does not stress the germanium. Owing to its great plasticity and adhesion to metals, Indium sheets are sometimes used for cold-soldering in microwave circuits and waveguide joints, where direct soldering is complicated. Indium is an ingredient in the gallium–indium–tin alloy galinstan, which is liquid at room temperature and replaces mercury in some thermometers. Other alloys of indium with bismuth, cadmium, lead, and tin, which have higher but still low melting points (between 50 and 100&nbsp;°C), are used in fire sprinkler systems and heat regulators. Indium is added to some dental amalgam alloys to decrease the surface tension of the mercury and allow for less mercury and easier amalgamation.

Indium's high neutron-capture cross-section for thermal neutrons makes it suitable for use in control rods for nuclear reactors, typically in an alloy of 80% silver, 15% indium, and 5% cadmium. In nuclear engineering, the (n,n') reactions of ¹¹³In and ¹¹⁵In are used to determine magnitudes of neutron fluxes.

In 2009, Professor Mas Subramanian and former graduate student Andrew Smith at Oregon State University discovered that indium can be combined with yttrium and manganese to form an intensely blue, non-toxic, inert, fade-resistant pigment, YInMn blue, the first new inorganic blue pigment discovered in 200 years.

Medical applications

Radioactive indium-111 (in very small amounts) is used in nuclear medicine tests, as a radiotracer to follow the movement of labeled proteins and white blood cells to diagnose different types of infection. Indium compounds are mostly not absorbed upon ingestion and are only moderately absorbed on inhalation; they tend to be stored temporarily in the muscles, skin, and bones before being excreted, and the biological half-life of indium is about two weeks in humans. It is also tagged to growth hormone analogues like octreotide to find growth hormone receptors in neuroendocrine tumors.

Biological role and precautions

Indium has no metabolic role in any organism that has been studied. According to one overview, "[there is] no evidence of any health hazard from industrial use of indium."

Notes

References

Sources

External links

• Indium at The Periodic Table of Videos (University of Nottingham)
• Reducing Agents > Indium low valent
• NIOSH Pocket Guide to Chemical Hazards (Centers for Disease Control and Prevention)
• usgs.gov (Mineral Commodity Summaries 2025): Indium