Germanium

Germanium (pronEng|dʒɚˈmeɪniəm) is a chemical element with the symbol Ge and atomic number 32. It is a lustrous, hard, silver-white metalloid in the carbon group, chemically similar to its group neighbors tin and silicon. Germanium has five naturally occurring isotopes ranging in atomic mass number from 70 to 76. It forms a large number of organometallic compounds, including tetraethylgermane and isobutylgermane.

Because few minerals contain it in large concentration, germanium was discovered relatively late despite the fact that it is relatively abundant in the Earth's crust. In 1869, Dmitri Mendeleev predicted its existence and some of its properties based on its position on his periodic table and called the element ekasilicon. Nearly two decades later, in 1886, Clemens Winkler found it in the mineral argyrodite. Winkler found that experimental observations agreed with Mendeleev's predictions and named the element after his country, Germany.

Germanium is an important semiconductor material used in transistors and various other electronic devices. Its major end uses are fiber-optic systems and infrared optics, but is also used for polymerization catalysts, in electronics and in solar electric applications. Germanium is mined primarily from sphalerite, though it is also recovered from silver, lead, and copper ores. Some germanium compounds, such as germanium chloride and germane, can irritate the eyes, skin, lungs, and throat.

History

In his report on "The Periodic Law of the Chemical Elements", in 1869, Dmitri Mendeleev predicted the existence of several unknown elements, including one filling a gap in the carbon family, between silicon and tin. [ cite journal| first = Masanori | last = Kaji |title = D. I. Mendeleev's concept of chemical elements and "The Principles of Chemistry"|journal=Bulletin for the History of Chemistry|volume=27|issue=1|pages=4–16|year=2002|url=http://www.scs.uiuc.edu/~mainzv/HIST/awards/OPA%20Papers/2005-Kaji.pdf| format=pdf|accessdate = 2008-08-20 ] Because of its position in the table, he called it "ekasilicon (Es)" and assigned it an atomic weight of 72.

In the summer of 1885, in a mine near Freiberg, Saxony, a new mineral was found. It was named "argyrodite", because of its high silver content.Ref_label|A|a|none Clemens Winkler examined this new mineral and was able to isolate an element similar to antimony in 1886.cite journal | journal = Berichte der deutschen chemischen Gesellschaft | volume = 19 | issue = 1 | pages = 210–211 | title = Germanium, Ge, a New Nonmetal Element | language=German | first = Clemens | last = Winkler | authorlink = Clemens Winkler | year = 1887 | doi = 10.1002/cber.18860190156 | url = http://gallica.bnf.fr/ark:/12148/bpt6k90705g/f212.chemindefer | format= [http://dbhs.wvusd.k12.ca.us/webdocs/Chem-History/Disc-of-Germanium.html English translation] ] Before he published his results on the new element Winkler intended to name the element "neptunium", as the actual discovery of planet Neptune in 1846 had been preceded by mathematical prediction of its existence.Ref_label|B|b|none However, the name neptunium had already been given to an element (though not the element that today bears the name neptunium, discovered in 1940),Ref_label|C|c|none and instead, Winkler named the new metal "germanium" (from the Latin "Germania" for Germany) in honor of his fatherland. Because the element showed similarities with the elements arsenic and antimony, its place in the periodic table was under discussion, but the similarities between Mendeleev's ekasilicon and germanium confirmed its place. [cite journal | journal = The Manufacturer and Builder | url = http://cdl.library.cornell.edu/cgi-bin/moa/pageviewer?frames=1&coll=moa&view=50&root=%2Fmoa%2Fmanu%2Fmanu0018%2F&tif=00187.TIF | year = 1887| title = Germanium, a New Non-Metallic Element | pages =181| accessdate = 2008-08-20] With further material from 500 kg of ore from the mines in Saxony, Winkler could confirm the chemical properties of the new element in 1887.cite journal | first = Clemens | last = Winkler | title = Mittheilungen über das Germanium | journal = J. Prak. Chemie | volume= 34 | year = 1886 | pages=177–229 | doi = 10.1002/prac.18860340122 | url = http://gallica.bnf.fr/ark:/12148/bpt6k90797z/f185.table | language=German ] cite journal | first = Clemens | last = Winkler | journal = J. Prak. Chemie | volume = 36 | year = 1887 |pages = 177–209 | title = Mittheilungen über des Germanium. Zweite Abhandlung |doi = 10.1002/prac.18870360119 | url = http://gallica.bnf.fr/ark:/12148/bpt6k90799n/f183.table| accessdate = 2008-08-20| language=German ] [cite journal | first = O. | last = Brunck | title = Obituary: Clemens Winkler | journal = Berichte der deutschen chemischen Gesellschaft | volume= 39 | issue = 4 | year = 1886 | pages=4491–4548 | doi = 10.1002/cber.190603904164 | language=German ] He also determined an atomic weight of 72.32 by analyzing pure germanium tetrachloride (chem|GeCl|4), whilst Lecoq de Boisbaudran deduced 72.3 by a comparison of the lines in the spark spectrum of the element. [cite journal | title = Sur le poids atomique du germanium | first = M. Lecoq | last = de Boisbaudran | journal = Comptes rendus | year = 1886 | volume = 103 |pages = 452 | url = http://gallica.bnf.fr/ark:/12148/bpt6k3059r/f454.table | accessdate = 2008-08-20| language=French]

Winkler was able to prepare several new compounds of germanium, including the fluorides, chlorides, sulfides, germanium dioxide, and tetraethylgermanium, the first organogermane. With the physical data from these compounds—which corresponded with Mendeleev's predictions—it made the discovery an important confirmation of Mendeleev's idea of element periodicity. Here is a comparison between the prediction and Winkler's data:

Until the late 1930s, germanium was believed to be a poorly conducting metal.cite web|title=Germanium: From Its Discovery to SiGe Devices|author= Haller, E. E.| work=Department of Materials Science and Engineering, University of California, Berkeley, and Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, |url=http://www.osti.gov/bridge/servlets/purl/922705-bthJo6/922705.PDF| format=pdf| accessdate=2008-08-22] It did not become economically significant until after 1945, when its properties as a semiconductor were recognized as being valuable in electronics. It was only during World War II, in 1941, that germanium diodes began to supplant vacuum tubes in electronic devices. [cite web| author = W. K. | url = http://select.nytimes.com/gst/abstract.html?res=F30715FE3F5B157A93C2A8178ED85F478585F9 | publisher = NY Times | year = 1953| title = Germanium for Electronic Devices| accessdate=2008-08-22] [cite web | url = http://www.computerhistory.org/semiconductor/timeline/1941-semiconductor.html | title = 1941 - Semiconductor diode rectifiers serve in WW II | publisher = Computer History Museum| accessdate=2008-08-22] Its first major use was the point contact Schottky diodes for radar reception during WWII. The first silicon-germanium alloys were obtained in 1955. [cite web | url = http://www.sp.phy.cam.ac.uk/~SiGe/Silicon%20Germanium%20(SiGe)%20History.html | title = SiGe History | publisher = University of Cambridge| accessdate=2008-08-22] Before 1945, only a few hundred kilograms of the element were produced each year, but by the end of the 1950s, annual worldwide production had reached 40 metric tons.cite news|url=http://pubs.acs.org/cen/80th/print/germanium.html| year=2003| title=Germanium| first = Bethany | last = Halford| work= Chemical & Engineering News |publisher= American Chemical Society| accessdate=2008-08-22]

The development of the germanium transistor in 1948 [cite journal | journal = Physical Reviews | volume = 74 | pages = 230–231 | title = The Transistor, A Semi-Conductor Triode |first = J. | last = Bardeen | coauthor = Brattain, W. H.| year = 1948 | doi = 10.1103/PhysRev.74.230 ] opened the door to countless applications of solid state electronics. [cite web | title = Electronics History 4 - Transistors | url = http://www.greatachievements.org/?id=3967 | publisher = National Academy of Engineering | accessdate=2008-08-22] From 1950 through the early 1970s, this area provided an increasing market for germanium, but then high purity silicon began replacing germanium in transistors, diodes, and rectifiers.cite journal|title=Germanium—Statistics and Information| author=U.S. Geological Survey | year=2008 | journal=U.S. Geological Survey, Mineral Commodity Summaries | url=http://minerals.usgs.gov/minerals/pubs/commodity/germanium/ |quote=Select 2008| accessday=2008-08-28] Silicon has superior electrical properties, but requires much higher purity—a purity which could not be commercially achieved in the early days. [cite journal|journal=IEEE Transactions on Electron Devices | volume = ED-23 | issue = 7 | year = 1976 | month = July | title = Single Crystals of Germanium and Silicon-Basic to the Transistor and Integrated Circuit | first = Gordon K. | last = Teal |pages = 621–639 | url=http://ieeexplore.ieee.org/iel5/16/31752/01478478.pdf|doi=10.1109/T-ED.1976.18464]

Meanwhile, demand for germanium in fiber optics communication networks, infrared night vision systems, and polymerization catalysts increased dramatically. These end uses represented 85% of worldwide germanium consumption for 2000. The U.S. government even designated germanium as a strategic and critical material, calling for a 146 tons (132 t) supply in the national defense stockpile in 1987. Germanium differs from silicon in that the supply of silicon is only limited by production capacity, while that for germanium is limited by the shortage of exploitable sources. As a result, while silicon could be bought in 1998 for less than $10 per kg, the price of 1 kg of germanium was then almost $1800.

Characteristics

Under standard conditions germanium is a brittle, silvery-white, semi-metallic element. This form constitutes an allotrope technically known as "α-germanium", which has a metallic luster and a diamond cubic crystal structure, the same as diamond. At pressures above 120 kbar, a different allotrope known as "β-germanium" forms, which has the same structure as β-tin. Along with silicon, gallium, bismuth, antimony, and water, it is one of the few substances that expands as it solidifies (i.e. freezes) from its molten state.

Germanium is a semiconductor. Zone refining techniques have led to the production of crystalline germanium for semiconductors that has an impurity of only one part in 10¹⁰,cite web|url=http://periodic.lanl.gov/elements/32.html|publisher=Los Alamos National Laboratory|title=Germanium|accessdate=2008-08-28] making it one of the purest materials ever obtained. [cite book |title=The Primordial Universe: 28 June - 23 July 1999 |editor=Binetruy, B. |author=Chardin, B. |chapter=Dark Matter: Direct Detection |publisher=Springer |year=2001 |isbn=3540410465 |pages=308] The first metallic material becoming a superconductor in the presence of an extremely strong electromagnetic field was a alloy of germanium with uranium and rhodium. The discovery was made in 2005. [cite journal | doi = 10.1126/science.1115498 | year = 2005|month=August | last =Lévy| first= F. | coauthors = Sheikin, I.; Grenier, B.; Huxley, Ad.|title=Magnetic field-induced superconductivity in the ferromagnet URhGe|volume=309|issue=5739|pages=1343–1346|pmid=16123293|journal=Science]

Pure germanium is known to spontaneously extrude very long screw dislocations, referred to as "germanium whiskers". The growth of these whiskers is one of the primary reasons for the failure of older diodes and transistors made from germanium, as, depending on what they eventually touch, they may lead to an electrical short. [cite journal| title = Morphology of Germanium Whiskers | first = E. I. | last = Givargizov | journal = Kristall und Technik | volume = 7 | issue = 1–3 |doi = 10.1002/crat.19720070107| pages = 37–41| year = 1972]

Chemistry

Elemental germanium oxidizes slowly to GeO₂ at 250 ^oC. [cite journal|doi=10.1016/S0169-4332(98)00251-7|title=KRXPS study of the oxidation of Ge(001) surface|year=1998|author=Tabet, N|journal=Applied Surface Science|volume=134|pages=275 ] Germanium is insoluble in dilute acids and alkalis but dissolves slowly in concentrated sulfuric acid and reacts violently with molten alkalis to produce germanates (chem| [GeO|3|] ²⁻). Germanium occurs mostly in the oxidation state +4 although many compounds are known with the oxidation state of +2.Greenwood&Earnshaw] Other oxidation states are rare, such as +3 found in compounds such as Ge₂Cl₆, and +3 and +1 observed on the surface of oxides, [cite journal|doi=10.1016/S0368-2048(98)00451-4|title=XPS study of the growth kinetics of thin films obtained by thermal oxidation of germanium substrates|year=1999|author=Tabet, N|journal=Journal of Electron Spectroscopy and Related Phenomena|volume=101-103|pages=233] or negative oxidation states in germanes, such as -4 in chem|GeH|4. Germanium cluster anions, (Zintl ions), such as Ge₄²⁻, Ge₉⁴⁻, Ge₉²⁻, [(Ge₉)₂] ⁶⁻ have been prepared by the extraction from e.g. alloys containing alkali metals and germanium in liquid ammonia in the presence of ethylenediamine or a cryptand. [cite journal|title=Oxidative Coupling of Deltahedral [Ge₉] ⁴⁻ Zintl Ions|first = Li | last = Xu | coauthors = Sevov, Slavi C.|journal=J. Am. Chem. Soc. | format = communication | year = 1999 | volume = 121| issue = 39 | pages = 9245–9246 | doi = 10.1021/ja992269s] The oxidation states of the element in these ions are not integers—similar to the ozonides O₃^-.

Two oxides of germanium are known: germanium dioxide (chem|GeO|2, germania) and germanium monoxide, (chem|GeO).cite book | last = Holleman | first = A. F. | coauthors = Wiberg, E.; Wiberg, N. | title=Lehrbuch der Anorganischen Chemie, 102nd ed. | publisher=de Gruyter | year=2007 | isbn=978-3-11-017770-1 | oclc = 145623740 180963521 219549154] The dioxide, GeO₂ can be obtained by roasting germanium sulfide (chem|GeS|2), and is a white powder that is only slightly soluble in water but reacts with alkalis to form germanates. The monoxide, (germanous oxide), can be obtained by the high temperature reaction of GeO₂ with Ge metal. The dioxide (and the related oxides and germanates) exhibits the unusual property of having a high refractive index for visible light, but transparency to infrared light. [cite journal | title = Infrared Transparent Germanate Glass-Ceramics | first = Shyam S. | last = Bayya | coauthors = Sanghera, Jasbinder S.; Aggarwal, Ishwar D.; Wojcik, Joshua A. | journal = Journal of the American Ceramic Society | volume = 85 | issue = 12 | pages= 3114–3116 | year = 2002] [cite journal | doi = 10.1007/BF00614256 | title = Infrared reflectance and transmission spectra of germanium dioxide and its hydrolysis products | year = 1975 |last = Drugoveiko | first = O. P. | journal = Journal of Applied Spectroscopy | volume = 22 | pages = 191 ] Bismuth germanate, Bi₄Ge₃O₁₂, (BGO) is used as a scintillator.cite journal | title = A Bismuth Germanate-Avalanche Photodiode Module Designed for Use in High Resolution Positron Emission Tomography | last = Lightstone | first = A. W. | coauthors = McIntyre, R. J.; Lecomte, R.; Schmitt, D. | journal = IEEE Transactions on Nuclear Science| year = 1986 | volume =33 | issue= 1 | pages = 456–459 | doi =10.1109/TNS.1986.4337142]

Binary compounds with other chalcogens are also known, such as the disulfide (chem|GeS|2), diselenide (chem|GeSe|2), and the monosulfide (GeS), selenide (GeSe), and Telluride (GeTe). GeS₂ forms as a white precipitate when hydrogen sulfide is passed through strongly acid solutions containing Ge(IV). The disulfide is appreciably soluble in water and in solutions of caustic alkalis or alkaline sulfides. Nevertheless, it is not soluble in acidic water, which allowed for Winkler to make the discovery of the element. [cite journal | first =Otto H. | last = Johnson | title = Germanium and its Inorganic Compounds | journal = Chem. Rev. | year = 1952 | volume= 3| pages=431 – 431 | doi = 10.1021/cr60160a002] By heating the disulfide in a current of hydrogen, the monosulfide (GeS) is formed. which sublimes in thin plates of a dark color and metallic luster, and is soluble in solutions of the caustic alkalis. Upon melting with alkaline carbonates and sulfur, germanium compounds form salts known as thiogermanates. [cite journal|doi=10.1039/a703634e|title=First synthesis of mesostructured thiogermanates|year=1997|last = Fröba | first = Michael |journal=Chemical Communications|pages=1729]

Four tetrahalides are known. Under normal conditions GeI₄ is a solid, GeF₄ a gas and the others volatile liquids. For example germanium tetrachloride, GeCl₄, is obtained as a colourless fuming liquid boiling at 83.1°C by heating the metal with chlorine. All the tetrahalides are readily hydrolysed to hydrated germanium dioxide. GeCl₄ is used in the production of organogermanium compounds. All four dihalides are known and in contrast to the tetrahalides are polymeric solids. Additionally Ge₂Cl₆ and some higher compounds of formula Ge_nCl_2n+2 are known. The unusual compound Ge₆Cl₁₆ has been prepared that contains the Ge₅Cl₁₂ unit with a neopentane structure. [cite journal | title = The Crystal Structure and Raman Spectrum of Ge₅Cl₁₂·GeCl₄ and the Vibrational Spectrum of Ge₂Cl₆| last = Beattie | first = I.R. | coauthors = Jones, P.J.; Reid, G.; Webster, M.; | journal = Inorg. Chem. | volume = 37 | issue =23 | pages = 6032–6034 | year = 1998 | doi =10.1021/ic9807341 S0020-1669(98)00734-4]

Germane (GeH₄) is a compound similar in structure to methane. Polygermanes—compounds that are similar to alkanes—with formula Ge_nH_2n+2 containing up to five germanium atoms are known. The germanes are less volatile and less reactive than their corresponding silicon analogues. GeH₄ reacts with alkali metals in liquid ammonia to form white crystalline MGeH₃ which contain the GeH₃⁻ anion. The germanium hydrohalides with one, two and three halogen atoms are colorless reactive liquids.

The first organogermanium compound was synthesised by Winkler in 1887; the reaction of germanium tetrachloride with diethylzinc yielded tetraethylgermane (chem|Ge(C|2|H|5|)|4). Organogermanes of the type R₄Ge (where R is an alkyl) such as tetramethylgermane (chem|Ge(CH|3|)|4) and tetraethylgermane are accessed through the cheapest available germanium precursor germanium tetrachloride and alkyl nucleophiles. Organic germanium hydrides such as isobutylgermane (chem|(CH|3|)|2|CHCH|2|GeH|3) were found to be less hazardous and may be used as a liquid substitute for toxic germane gas in semiconductor applications. Many germanium reactive intermediates are known: germyl free radicals, germylenes (similar to carbenes), and germynes (similar to carbynes). [cite journal | title = Reactive intermediates in organogermanium chemistry | first = Jacques | last = Satge | journal = Pure & Appl. Chem. | volume = 56 | issue = 1 | pages = 137–150 | year =1984 | doi = 10.1351/pac198456010137] [cite journal | title = Organogermanium Chemistry| first = Denis | last = Quane | coauthors = Bottei, Rudolph S. | journal = Chemical Reviews | volume = 63 | issue = 4 | pages = 403–442 | year =1963 | doi = 10.1021/cr60224a004] The organogermanium compound 2-carboxyethylgermasesquioxane was first reported in the 1970s, and for a while was used as a dietary supplement and thought to possibly have anti-tumor qualities.

Isotopes

Germanium has five naturally-occurring isotopes, ⁷⁰Ge, ⁷²Ge, ⁷³Ge, ⁷⁴Ge, and ⁷⁶Ge. Of these, ⁷⁶Ge is very slightly radioactive, decaying by double beta decay with a half-life of 1.58 × 10²¹ years. ⁷⁴Ge is the most common isotope, having a natural abundance of approximately 36%. ⁷⁶Ge is the least common with a natural abundance of approximately 7%.cite journal| last = Audi | first = G.| title = Nubase2003 Evaluation of Nuclear and Decay Properties| journal = Nuclear Physics A| volume = 729| pages = 3–128| publisher = Atomic Mass Data Center| year = 2003| doi=10.1016/j.nuclphysa.2003.11.001] When bombarded with alpha particles, the isotope ⁷²Ge will generate stable ⁷⁷Se, releasing high energy electrons in the process. Because of this, it is used in combination with radon for nuclear batteries.cite web|url=http://www.nuenergy.org/disclosures/AlphaFusionPatent_05-04-2007.pdf |title=Alpha Fusion Electrical Energy Valve |format=pdf |accessdate=2008-09-10 | publisher = Nu Energy Research Institute]

At least 27 radioisotopes have also been synthesized ranging in atomic mass from 58 to 89. The most stable of these is ⁶⁸Ge, decaying by electron capture with a half-life of 270.95 d. The least stable is ⁶⁰Ge with a half-life of 30 ms. While most of germanium's radioisotopes decay by beta decay, ⁶¹Ge and ⁶⁴Ge decay by β⁺ delayed proton emission. ⁸⁴Ge through ⁸⁷Ge also have minor β^- delayed neutron emission decay paths.

Natural abundance

Germanium is created through stellar nucleosynthesis, mostly by the s-process in asymptotic giant branch stars. The s-process is a slow neutron capture of lighter elements inside pulsating red giant stars.cite journal | journal = The Astrophysical Journal Letters | volume = 578 | pages = L55–L58 | year = 2002 | doi = 10.1086/344473 | title = Discovery of Enhanced Germanium Abundances in Planetary Nebulae with the Far Ultraviolet Spectroscopic Explorer | first = N. C. | last = Sterling | coauthors = Dinerstein, Harriet L.; Bowers, Charles W.] Germanium has been detected in the atmosphere of Jupiter [cite journal| title= The tropospheric gas composition of Jupiter's north equatorial belt /NH₃, PH₃, CH₃D, GeH₄, H₂O/ and the Jovian D/H isotopic ratio| last = Kunde| first = V. | coauthors = Hanel, R.; Maguire, W.; Gautier, D.; Baluteau, J. P.; Marten, A.; Chedin, A.; Husson, N.; Scott, N. |journal = Astrophysical J.| volume= 263|year= 1982|pages= 443–467|doi=10.1086/160516] and in some of the most distant stars. [cite journal| journal=Nature | volume=423|issue= 29|date=2003-05-01| doi=10.1038/423029a | title=Astronomy: Elements of surprise| last = Cowan | first = John| pages=29] Its abundance in the Earth's crust is approximately 1.6 ppm.cite journal| doi = 10.1016/j.oregeorev.2005.07.034 | title = Metallogenesis of germanium—A review | first = R. | last = Höll | coauthors = Kling, M.; Schroll, E.| journal = Ore Geology Reviews | volume = 30 | issues = 3–4 | year = 2007| pages = 145–180] There are only a few minerals like argyrodite, briartite, germanite, and renierite that contain appreciable amounts of germanium, but no minable deposits exist for any of them. Nonetheless, none is mined for its germanium content. [cite web|url=http://www.resourceinvestor.com/pebble.asp?relid=31285|publisher=Resource Investor.com|accessdate=2008-09-09|title=Byproducts II: Another Germanium Rush? |first=Jack | last = Lifton|date=2007-04-26] Some zinc-copper-lead ore bodies contain enough germanium that it can be extracted from the final ore concentrate.

An unusual enrichment process causes a high content of germanium in some coal seams, which was discovered by Victor Mordechai Goldschmidt during a broad survey for germanium deposits.cite journal | journal = Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen, Mathematisch-Physikalische Klasse | title = Ueber das Vorkommen des Germaniums in Steinkohlen und Steinkohlenprodukten | last = Goldschmidt| first = V. M. | pages = 141–167| year = 1930 | url =http://resolver.sub.uni-goettingen.de/purl?GDZPPN002508303] cite journal | journal = Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen, Mathematisch-Physikalische Klasse | title = Zur Geochemie des Germaniums | last = Goldschmidt| first = V. M. | coauthors = Peters, Cl. | pages = 141–167 | url =http://resolver.sub.uni-goettingen.de/purl?GDZPPN002509180 | year = 1933] The highest concentration ever found was in the Hartley coal ash with up to 1.6% of germanium. The coal deposits near Xilinhaote Inner Mongolia contains estimated 1600 tonnes of germanium.

Production

Worldwide production in 2006 was roughly 100 tonnes of germanium. Currently, it is recovered as a by-product from sphalerite ores where it is concentrated in amounts of up to 0.3%, [cite journal|doi=10.1016/0016-7037(85)90241-8|title=Germanium geochemistry and mineralogy|year=1985|author=Bernstein, L|journal=Geochimica et Cosmochimica Acta|volume=49|pages=2409] especially from sediment-hosted, massive Zn–Pb–Cu(–Ba) deposits and carbonate-hosted Zn–Pb deposits. Figures for worldwide Ge reserves are not available, but in the US it is estimated to be around 500 tonnes. In 2007 35% of the demand was met by recycled germanium.

It is produced mainly from sphalerite, a zinc ore, but is also found in silver, lead, and copper ores. A source of germanium is fly ash of coal power plants which use coal from certain coal deposits with a large concentration of germanium. Russia and China used this as a source for germanium.cite journal | first = A. V. | last = Naumov | title = World market of germanium and its prospects | journal = Russian Journal of Non-Ferrous Metals | volume = 48 | issue = 4 | year = 2007 | doi = 10.3103/S1067821207040049 | pages =265–272] Russia's deposits are located in the far east of the country on Sakhalin island. The coal mines northeast of Vladivostok have also been used as a germanium source. The deposits in China are mainly located in the lignite mines near Lincang, Yunnan and coal mines near Xilinhaote, Inner Mongolia and are also used as germanium sources.

The ore concentrates are mostly sulfidic; they are converted to the oxides by heating under air, in a process known as roasting:

: GeS₂ + 3O₂ → GeO₂ + 2SO₂

Part of the germanium ends up in the dust produced during this process, while the rest is converted to germanates which are leached together with the zinc from the cinder by sulfuric acid. After neutralisation only the zinc stays in solution and the precipitate contains the germanium and other metals. After reducing the amount of zinc in the precipitate by the Waelz process the residing Waelz oxide is leached a second time. The dioxide is obtained as precipitate and converted with chlorine gas or hydrochloric acid to germanium tetrachloride, which has a low boiling point and can be distilled off:

: GeO₂ + 4HCl → GeCl₄ + 2H₂O: GeO₂ + 2Cl₂ → GeCl₄ + O₂

Germanium tetrachloride is either hydrolysed to the oxide (GeO₂) or purified by fractionated distillation and than hydrolysed.The highly pure GeO₂ is now suitable for the production of germanium glass. The pure germanium oxide is reduced by the reaction with hydrogen to obtain germanium suitable for the infrared optics or semiconductor industry:

: GeO₂ + 4H₂ → Ge + 2H₂O

The germanium for steel production and other industrial processes is normally reduced using carbon:cite journal | journal = Minerals Engineering | voulume = 17 | year = 2004 | pages = 393–402 | doi = 10.1016/j.mineng.2003.11.014 | title = Review of germanium processing worldwide | author = Moskalyk, R. R. | volume = 17]

: GeO₂ + C → Ge + CO₂

Applications

The major end uses for germanium in 2007, worldwide, were estimated to be: 35% for fiber-optic systems, 30% infrared optics, 15% for polymerization catalysts, and 15% for electronics and solar electric applications. The remaining 5% went into other uses such as phosphors, metallurgy, and chemotherapy.

Optics

The most notable physical characteristics of germania (GeO₂) are its high index of refraction and its low optical dispersion. These make it especially useful for wide-angle camera lenses, microscopy, and for the core part of optical fibers. [cite journal|title=Infrared Detector Arrays for Astronomy|journal=Annu. Rev. Astro. Astrophys. | year = 2007 |doi = 10.1146/annurev.astro.44.051905.092436 |last = Rieke | first = G.H.| volume = 45 | pages = 77] cite web| url =http://minerals.usgs.gov/minerals/pubs/commodity/germanium/220400.pdf | title = Germanium| first = Robert D. | last = Brown, Jr.| publisher = U.S. Geological Survey |format=pdf | year = 2000 | accessdate = 2008-09-22] It also replaced titania as the silica dopant for silica fiber, eliminating the need for subsequent heat treatment, which made the fibers brittle. [cite web | url = http://www.sri.com/policy/csted/reports/sandt/techin2/chp3.html | title = Chapter III: Optical Fiber For Communications | publisher = Stanford Research Institute | accessdate = 2008-08-22 ] At the end of 2002 the fiber optics industry accounted for 60% of the annual germanium use in the United States, but this use accounts for less than 10% of world wide consumption. GeSbTe is a phase change alloy used for its optic properties, such as in rewritable DVDs. [cite web|url=http://www.osta.org/technology/pdf/dvdqa.pdf |title=Understanding Recordable & Rewritable DVD First Edition |format=pdf |accessdate=2008-09-22| publisher = Optical Storage Technology Association (OSTA)]

Because germanium is transparent in the infrared it is a very important infrared optical material, that can be readily cut and polished into lenses and windows. It is especially used as the front optic in thermal imaging cameras working in the 8 to 14 micron wavelength range for passive thermal imaging and for hot-spot detection in military, night vision system in cars, and fire fighting applications. It is therefore used in infrared spectroscopes and other optical equipment which require extremely sensitive infrared detectors.

Electronics

The alloy silicon germanide (commonly referred to as "silicon-germanium", or SiGe) is rapidly becoming an important semiconductor material, for use in high speed integrated circuits. Circuits utilizing the properties of Si-SiGe junctions can be much faster than those using silicon alone. [cite journal|doi=10.1109/TED.2003.810484|title=SiGe HBT and BiCMOS technologies for optical transmission and wireless communication systems|year=2003 |last=Washio | first= K.|journal=IEEE Transactions on Electron Devices|volume=50|pages=656] Silicon-germanide is beginning to replace gallium arsenide (GaAs) in wireless communications devices. The SiGe chips, with high-speed properties, can be made with low-cost, well-established production techniques of the silicon chip industry.

The recent rise in energy cost has improved the economics of solar panels, a potential major new use of germanium. Germanium is the substrate of the wafers for high-efficiency multijunction photovoltaic cells for space applications. Because germanium and gallium arsenide have very similar lattice constants, germanium substrates can be used to make gallium arsenide solar cells. [cite journal|doi=10.1002/pip.446|title=Space and terrestrial photovoltaics: synergy and diversity|year=2002|last=Bailey| first= Sheila G.|journal=Progress in Photovoltaics Research and Applications|volume=10|pages=399] The Mars Exploration Rovers and several satellites use triple junction gallium arsenide on germanium cells. [cite journal | doi = 10.1016/S0094-5765(02)00287-4| title = The performance of gallium arsenide/germanium solar cells at the Martian surface | year = 2004 | first = D. | last = Crisp | coauthors = Pathare, A.; Ewell, R. C.| journal = Progress in Photovoltaics Research and Applications | volume = 54 | issue = 2 | pages = 83–101 ]

Germanium-on-insulator substrates are seen as a potential replacement for silicon on miniaturized chips. Other uses in electronics include phosphors in fluorescent lamps, and germanium-base solid-state light-emitting diodes (LEDs). Germanium transistors are still used in some effects pedals by musicians who wish to reproduce the distinctive tonal character of the "fuzz"-tone from the early rock and roll era, most notably the Dallas Arbiter Fuzz Face. [cite journal | author = Szweda, Roy | year = 2005 | title = Germanium phoenix | journal = III-Vs Review | volume = 18 | issue = 7 | pages = 55 | doi = 10.1016/S0961-1290(05)71310-7 ]

Other uses

Germanium dioxide is also used in catalysts for polymerisation in the production of polyethylene terephthalate (PET).cite journal | last = Thiele | first = Ulrich K. | year = 2001 | title = The Current Status of Catalysis and Catalyst Development for the Industrial Process of Poly(ethylene terephthalate) Polycondensation | journal = International Journal of Polymeric Materials | volume = 50 | issue = 3 | pages = 387 – 394 |doi = 10.1080/00914030108035115 ] The high brilliance of the produced polyester is especially used for PET bottles marketed in Japan. However, in the United States, no germanium is used for polymerization catalysts. Due to the similarity between silica (SiO₂) and germanium dioxide (GeO₂), the silica stationary phase in some gas chromatography columns can be replaced by GeO₂. [cite journal | title = Germania-Based, Sol-Gel Hybrid Organic-Inorganic Coatings for Capillary Microextraction and Gas Chromatography | last= Fang| first=Li | coauthors =Kulkarni, Sameer; Alhooshani, Khalid; Malik, Abdul | journal = Anal. Chem. | volume = 79 | issue = 24 | pages = 9441–9451 | year = 2007 | doi = 10.1021/ac071056f ]

In recent years germanium has seen increasing use in precious metal alloys. In sterling silver alloys, for instance, it has been found to reduce firescale, increase tarnish resistance, and increase the alloy's response to precipitation hardening. A tarnish-proof sterling silver alloy, trademarked Argentium, requires 1.2% germanium. The material has a very high refractive index (4.0) and so needs to be anti-reflection coated. Particularly, a very hard special antireflection coating of diamond-like carbon (DLC), refractive index 2.0, is a good match and produces a diamond-hard surface that can withstand much environmental rough treatment. [cite journal | first = Alan H. | last =Lettington | doi = 10.1016/S0008-6223(98)00062-1 | title = Applications of diamond-like carbon thin films | volume = 36 | issue = 5–6 | year = 1998 | pages =555–560 | journal = Carbon ] [cite journal | first = Michael N. | last = Gardos | coauthors = Bonnie L. Soriano, Steven H. Propst | title = Study on correlating rain erosion resistance with sliding abrasion resistance of DLC on germanium | journal = Proc. SPIE, | volume = 1325 | pages = 99 | year = 1990 | doi = 10.1117/12.22449 | issue = Mechanical Properties]

High purity germanium single crystal detectors can precisely identify radiation sources—for example in airport security. [cite web | title = Performance of Light-Weight, Battery-Operated, High Purity Germanium Detectors for Field Use | first = Ronald | last = Keyser | coauthor = Twomey, Timothy; Upp, Daniel | url = http://www.ortec-online.com/papers/inmm_2003_keyser.pdf |format=pdf| accessdate = 2008-09-06 | publisher = Oak Ridge Technical Enterprise Corporation (ORTEC)] Germanium is useful for monochromators for beamlines used in single crystal neutron scattering and synchrotron X-ray diffraction. The reflectivity has advantages over silicon in neutron and high energy X-ray applications. [cite journal |doi=10.1142/S0218301396000062 |year=1996 |author=Ahmed, F. U. |journal=International Journal of Modern Physics E |volume=5 |pages=131|title = Optimization of Germanium for Neutron Diffractometers] Crystals of high purity germanium are used in detectors for gamma spectroscopy and the search for dark matter. [citejournal |doi=10.1016/j.nuclphysa.2005.02.155 |title=Astrophysical constraints from gamma-ray spectroscopy |year=2006 |last=Diehl|first= R. |journal=Nuclear Physics A |volume=777 |pages=70 ]

Certain compounds of germanium have low toxicity to mammals, but have toxic effects against certain bacteria.cite book| last = Emsley| first = John| title = Nature's Building Blocks| publisher = Oxford University Press| year = 2001| location = Oxford| pages = 506–510| isbn = 0-19-850341-5 ] This property makes these compounds useful as chemotherapeutic agents. [cite journal | first = Milan | last = Slavik | coauthors = Blanc, Oscar; Davis, Joan | title = Spirogermanium: A new investigational drug of novel structure and lack of bone marrow toxicity | journal = Investigational New Drugs | volume = 1 | issue = 3 | year = 1983 | doi = 10.1007/BF00208894 | pages = 225–234]

Precautions

As early as 1922, doctors in the United States used the inorganic form of germanium to treat patients with anemia. [cite report|url=http://minerals.usgs.gov/minerals/pubs/commodity/germanium/220798.pdf|format=pdf|publisher=US Geologial Surveys|accessdate=2008-09-09| title = Comodity Survey:Germanium | first = Robert D. | last = Brown Jr.] It was used in other forms of treatments, but its efficiency has been dubious. Its role in cancer treatments has been debated. [cite web | url = http://www.cancer.org/docroot/ETO/content/ETO_5_3X_Germanium.asp | title = Germanium | publisher = American Cancer Society| accessdate = 2008-08-31 ] FDA research has concluded that germanium, when used as a nutritional supplement, "presents potential human health hazard".cite journal | last = Tao | first = S. H. | coauthors = Bolger, P. M. | year = 1997 | month = June | title = Hazard Assessment of Germanium Supplements | journal = Regulatory Toxicology and Pharmacology | volume = 25 | issue = 3 | pages = 211–219 | doi = 10.1006/rtph.1997.1098 ]

Germanium is not thought to be essential to the health of plants or animals. Some of its compounds present a hazard to human health, however. For example, germanium chloride and germane (GeH₄) are a liquid and gas, respectively, that can be very irritating to the eyes, skin, lungs, and throat. [cite journal | first = G.B. | last = Gerber | coauthors = Léonard, A.| year = 1997 | title = Mutagenicity, carcinogenicity and teratogenicity of germanium compounds | journal = Regulatory Toxicology and Pharmacology | volume = 387 | pages = 141–146 | doi = 10.1016/S1383-5742(97)00034-3 ] Germanium has little or no effect upon the environment because it usually occurs only as a trace element in ores and carbonaceous materials and is used in very small quantities in commercial applications.

Footnotes

1. Note_label|A|a|noneFrom Greek, "argyrodite" means "silver-containing". [cite report|url=http://www.handbookofmineralogy.org/pdfs/argyrodite.pdf|publisher="Mineral Data Publishing"| format=pdf|title=Argyrodite—chem|Ag|8|GeS|6|accessdate=2008-09-01]
2. Note_label|B|b|none Just as the existence of the new element was predicted, the existence of the planet Neptune was predicted around 1843 by the mathematicians John Couch Adams and Urbain Leverrier for the fact that Uranus was being pulled slightly out of position in its orbit. [cite journal | first=J. C. | last=Adams | url=http://adsabs.harvard.edu/cgi-bin/nph-bib_query?bibcode=1846MNRAS...7..149A&db_key=AST&data_type=HTML&format=&high=42c888df4622238 | title=Explanation of the observed irregularities in the motion of Uranus, on the hypothesis of disturbance by a more distant planet | journal=Monthly Notices of the Royal Astronomical Society | volume=7 | pages=149 | date=November 13, 1846 | accessdate=2008-02-18 | publisher=Blackwell Publishing] James Challis started searching for it in July 1846 and sighted the planet 23 September 1846. [cite journal | first=Rev. J. | last=Challis | url=http://adsabs.harvard.edu/cgi-bin/nph-bib_query?bibcode=1846MNRAS...7..145C&db_key=AST&data_type=HTML&format=&high=42c888df4622238 | title=Account of observations at the Cambridge observatory for detecting the planet exterior to Uranus | journal=Monthly Notices of the Royal Astronomical Society | volume=7 | pages=145–149 | date=November 13, 1846 | accessdate=2008-02-18 | publisher=Blackwell Publishing]
3. note_label|C|c|none R. Hermann published in 1877 claims of the discovery of a new element beneath tantalum, which he named "neptunium". [cite journal| title=Scientific Miscellany| journal= The Galaxy |volume= 24| issue= 1| month= July |year= 1877|pages= 131| isbn=0665501668| first =Robert | last = Sears | publisher=Siebert & Lilley| location=Columbus, O [hio] | oclc=16890343 243523661 77121148] [cite journal | title=Editor's Scientific Record| journal=Harper's new monthly magazine| volume= 55 | issue=325|month = June| year=1877 |pages= 152–153 |url = http://cdl.library.cornell.edu/cgi-bin/moa/moa-cgi?notisid=ABK4014-0055-21] But this was later regarded as some mixture of niobium and tantalum. [cite web| title = Elementymology & Elements Multidict: Niobium| first = Peter | last =van der Krogt | url = http://elements.vanderkrogt.net/elem/nb.html| accessdate = 2008-08-20] The name neptunium was eventually given to the synthetic element past uranium discovered in 1940. [cite book |title=Nobel Lectures, Chemistry 1942-1962 |publisher=Elsevier |year=1964 |chapter=The Nobel Prize in Chemistry 1951: presentation speech| first =A. | last =Westgren | url =http://nobelprize.org/nobel_prizes/chemistry/laureates/1951/press.html]

References

External links

* [http://www.webelements.com/webelements/elements/text/Ge/index.html WebElements.com – Germanium]