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{{short description|Chemical element with atomic number 32}} | |||
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{{distinguish|geranium}} | |||
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{{infobox germanium}} | {{infobox germanium}} | ||
'''Germanium''' is a ] |
'''Germanium''' is a ]; it has ] '''Ge''' and ] 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to ]. It is a ] (more rarely considered a ]) in the ] that is chemically similar to its group neighbors silicon and ]. Like silicon, germanium naturally ] and forms complexes with ] in nature. | ||
Because it seldom appears in high concentration, germanium was |
Because it seldom appears in high concentration, germanium was found comparatively late in the ]. Germanium ranks 50th ]. In 1869, ] ] its existence and some of its ] from its position on his ], and called the element '''ekasilicon'''. On February 6, 1886, ] at Freiberg University found the new element, along with ] and ], in the mineral ]. Winkler named the element after Germany, his country of birth. Germanium is mined primarily from ] (the primary ore of ]), though germanium is also recovered commercially from silver, ], and ] ores. | ||
Elemental germanium is used as a semiconductor in ]s and various other electronic devices. Historically, the first decade of semiconductor electronics was based entirely on germanium. Presently, the major end uses are ] systems, ], ] applications, and ]s (LEDs). Germanium compounds are also used for ] catalysts and have most recently found use in the production of ]s. This element forms a large number of ]s, such as ], useful in ]. Germanium is considered a ].<ref>{{Cite journal |last1=Avarmaa |first1=Katri |last2=Klemettinen |first2=Lassi |last3=O’Brien |first3=Hugh |last4=Taskinen |first4=Pekka |last5=Jokilaakso |first5=Ari |date=June 2019 |title=Critical Metals Ga, Ge and In: Experimental Evidence for Smelter Recovery Improvements |journal=Minerals |language=en |volume=9 |issue=6 |pages=367 |doi=10.3390/min9060367 |bibcode=2019Mine....9..367A |doi-access=free}}</ref> | |||
Germanium is not thought to be an essential element for any living organism |
Germanium is not thought to be an essential element for any ]. Similar to silicon and aluminium, naturally-occurring germanium compounds tend to be insoluble in water and thus have little oral ]. However, synthetic soluble germanium salts are ], and synthetic chemically reactive germanium compounds with ]s and ] are irritants and toxins. | ||
== History == | == History == | ||
{{see also|History of the transistor}} | |||
<!--] | <!--] | ||
]|alt=Photo of a bust of a middle-aged man in a suit with a white short beard and gray moustache.]] THESE PHOTOS are hard to arrange due to the infobox; they are not essential for Germanium--> | ]|alt=Photo of a bust of a middle-aged man in a suit with a white short beard and gray moustache.]] THESE PHOTOS are hard to arrange due to the infobox; they are not essential for Germanium--> | ||
] | |||
In his report on ''The Periodic Law of the Chemical Elements'' in 1869, the Russian chemist Dmitri Ivanovich Mendeleev predicted the existence of several unknown ]s, including one that would fill a gap in the ] in his Periodic Table of the Elements, located between ] and ].<ref>{{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|date=2002|url=http://www.scs.uiuc.edu/~mainzv/HIST/awards/OPA%20Papers/2005-Kaji.pdf| format=PDF|accessdate = 2008-08-20}}</ref> Because of its position in his Periodic Table, Mendeleev called it ''ekasilicon (Es)'', and he estimated its ] to be about 72.0.<!-- Mendeleev studied several minerals in an unsuccessful search for this new element.<ref name="vdk">{{cite web| title = Elementymology & Elements Multidict: Germanium|first = Peter|last = van der Krogt|url = http://elements.vanderkrogt.net/element.php?sym=Ge| accessdate = 2008-08-20}}</ref> --> | |||
In his report on ''The Periodic Law of the Chemical Elements'' in 1869, the Russian chemist ] predicted the existence of several unknown chemical elements, including one that would fill a gap in the ], located between ] and ].<ref>{{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 |access-date=2008-08-20 |archive-url=https://web.archive.org/web/20081217080509/http://www.scs.uiuc.edu/~mainzv/HIST/awards/OPA%20Papers/2005-Kaji.pdf |archive-date=2008-12-17 |url-status=dead}}</ref> Because of its position in his periodic table, Mendeleev called it ''ekasilicon (Es)'', and he estimated its ] to be 70 (later 72).<!-- Mendeleev studied several minerals in an unsuccessful search for this new element.<ref name="vdk">{{cite web |title=Elementymology & Elements Multidict: Germanium |first=Peter |last=van der Krogt |url=http://elements.vanderkrogt.net/element.php?sym=Ge |access-date=2008-08-20}}</ref> --> | |||
In mid-1885, at a mine near ], a new ] was discovered and named '']'' because of |
<!-- ], discoverer of the element]] -->In mid-1885, at a mine near ], a new ] was discovered and named '']'' because of its high ] content.{{NoteTag|From Greek, ''argyrodite'' means ''silver-containing''.<ref>{{cite report |url=http://www.handbookofmineralogy.org/pdfs/argyrodite.pdf |publisher=Mineral Data Publishing |title=Argyrodite – {{chem|Ag|8|GeS|6}} |access-date=2008-09-01 |date= |archive-date=2016-03-03 |archive-url=https://web.archive.org/web/20160303221645/http://www.handbookofmineralogy.org/pdfs/argyrodite.pdf |url-status=live}}</ref>}} The chemist ] analyzed this new mineral, which proved to be a combination of silver, sulfur, and a new element. Winkler was able to isolate the new element in 1886 and found it similar to ]. He initially considered the new element to be eka-antimony, but was soon convinced that it was instead eka-silicon.<ref name="Winkle2" /><ref name="isolation">{{cite journal |journal=Berichte der Deutschen Chemischen Gesellschaft |volume=19 |issue=1 |pages=210–211 |title=Germanium, Ge, a New Nonmetal Element |language=de |first=Clemens |last=Winkler |author-link=Clemens Winkler |year=1887 |doi=10.1002/cber.18860190156 |url=http://gallica.bnf.fr/ark%3A/12148/bpt6k90705g/f212.chemindefer |url-status=dead |archive-url=https://web.archive.org/web/20081207033757/http://dbhs.wvusd.k12.ca.us/webdocs/Chem-History/Disc-of-Germanium.html |archive-date=December 7, 2008}}</ref> Before Winkler published his results on the new element, he decided that he would name his element ''neptunium'', since the recent discovery of planet ] in 1846 had similarly been preceded by mathematical predictions of its existence.{{NoteTag|Just as the existence of the new element had been predicted, the existence of the planet ] had been predicted in about 1843 by the two mathematicians ] and ], using the calculation methods of ]. They did this in attempts to explain the fact that the planet ], upon very close observation, appeared to be being pulled slightly out of position in the sky.<ref>{{cite journal |first=J. C. |last=Adams |bibcode=1846MNRAS...7..149A |title=Explanation of the observed irregularities in the motion of Uranus, on the hypothesis of disturbance by a more distant planet |journal=] |volume=7 |issue=9 |pages=149–152 |date=November 13, 1846 |doi=10.1093/mnras/7.9.149 |url=https://zenodo.org/record/1431905 |access-date=August 25, 2019 |archive-date=May 2, 2019 |archive-url=https://web.archive.org/web/20190502014753/https://zenodo.org/record/1431905/files/article.pdf |url-status=live |doi-access=free}}</ref> ] started searching for it in July 1846, and he sighted this planet on September 23, 1846.<ref>{{cite journal |first=Rev. J. |last=Challis |bibcode=1846MNRAS...7..145C |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 |issue=9 |pages=145–149 |date=November 13, 1846 |doi=10.1093/mnras/7.9.145 |url=https://zenodo.org/record/1431903 |access-date=August 25, 2019 |archive-date=May 4, 2019 |archive-url=https://web.archive.org/web/20190504065619/https://zenodo.org/record/1431903/files/article.pdf |url-status=live |doi-access=free}}</ref>}} However, the name "neptunium" had already been given to another proposed chemical element (though not the element that today bears the name ], which was discovered in 1940).{{NoteTag|R. Hermann published claims in 1877 of his discovery of a new element beneath ] in the periodic table, which he named ''neptunium'', after the Greek god of the oceans and seas.<ref>{{cite journal |title=Scientific Miscellany |journal=The Galaxy |volume=24 |issue=1 |date=July 1877 |page=131 |isbn=978-0-665-50166-1 |first=Robert |last=Sears |oclc=16890343}}</ref><ref>{{cite journal |title=Editor's Scientific Record |journal=Harper's New Monthly Magazine |volume=55 |issue=325 |date=June 1877 |pages=152–153 |url=http://cdl.library.cornell.edu/cgi-bin/moa/moa-cgi?notisid=ABK4014-0055-21 |access-date=2008-09-22 |archive-date=2012-05-26 |archive-url=https://archive.today/20120526215615/http://cdl.library.cornell.edu/cgi-bin/moa/moa-cgi?notisid=ABK4014-0055-21 |url-status=live}}</ref> However this ] was later recognized to be an ] of the elements ] and tantalum.<ref>{{cite web |title=Elementymology & Elements Multidict: Niobium |first=Peter |last=van der Krogt |url=http://elements.vanderkrogt.net/element.php?sym=Nb |access-date=2008-08-20 |archive-date=2010-01-23 |archive-url=https://web.archive.org/web/20100123002753/http://elements.vanderkrogt.net/element.php?sym=Nb |url-status=live}}</ref> The name "]" was later given to the synthetic element one step past ] in the Periodic Table, which was discovered by ] researchers in 1940.<ref>{{cite book |title=Nobel Lectures, Chemistry 1942–1962 |publisher=Elsevier |date=1964 |chapter=The Nobel Prize in Chemistry 1951: presentation speech |first=A. |last=Westgren |chapter-url=http://nobelprize.org/nobel_prizes/chemistry/laureates/1951/press.html |access-date=2008-09-18 |archive-date=2008-12-10 |archive-url=https://web.archive.org/web/20081210174205/http://nobelprize.org/nobel_prizes/chemistry/laureates/1951/press.html |url-status=live}}</ref>}} So instead, Winkler named the new element ''germanium'' (from the ] word, '']'', for Germany) in honor of his homeland.<ref name="isolation" /> Argyrodite proved empirically to be Ag<sub>8</sub>GeS<sub>6</sub>. | ||
Because this new element showed some similarities with the elements ] and antimony, its proper place in the periodic table was under consideration, but its similarities with Dmitri Mendeleev's predicted element "ekasilicon" confirmed that place on the periodic table.<ref name="isolation" /><ref>{{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 |page=181 |access-date=2008-08-20 |archive-date=2008-12-19 |archive-url=https://web.archive.org/web/20081219162737/http://cdl.library.cornell.edu/cgi-bin/moa/pageviewer?frames=1&coll=moa&view=50&root=%2Fmoa%2Fmanu%2Fmanu0018%2F&tif=00187.TIF |url-status=live}}</ref> With further material from 500 kg of ore from the mines in Saxony, Winkler confirmed the chemical properties of the new element in 1887.<ref name="Winkle2">{{cite journal |first=Clemens |last=Winkler |author-link=Clemens Winkler |journal=J. Prak. Chemie |volume=36 |issue=1 |date=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 |access-date=2008-08-20 |language=de |archive-date=2012-11-03 |archive-url=https://web.archive.org/web/20121103012004/http://gallica.bnf.fr/ark:/12148/bpt6k90799n/f183.table |url-status=live}}</ref><ref name="isolation" /><ref>{{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 |url=https://zenodo.org/record/1426200 |language=de |access-date=2020-06-07 |archive-date=2020-08-01 |archive-url=https://web.archive.org/web/20200801004057/https://zenodo.org/record/1426200 |url-status=live}}</ref> He also determined an atomic weight of 72.32 by analyzing pure ] ({{chem|GeCl|4}}), while ] deduced 72.3 by a comparison of the lines in the spark ] of the element.<ref>{{cite journal |title=Sur le poids atomique du germanium |first=M. Lecoq |last=de Boisbaudran |journal=Comptes Rendus |year=1886 |volume=103 |page=452 |url=http://gallica.bnf.fr/ark:/12148/bpt6k3059r/f454.table |access-date=2008-08-20 |language=fr |archive-date=2013-06-20 |archive-url=https://web.archive.org/web/20130620032945/http://gallica.bnf.fr/ark:/12148/bpt6k3059r/f454.table |url-status=live}}</ref> | |||
Winkler was able to prepare several new compounds of germanium, including ], ], ]<!--intentional link to DAB page-->, ], and ] (Ge(C<sub>2</sub>H<sub>5</sub>)<sub>4</sub>), the first organogermane.<ref name="Winkle2" /> The physical data from those compounds—which corresponded well with Mendeleev's predictions—made the discovery an important confirmation of Mendeleev's idea of element ]. Here is a comparison between the prediction and Winkler's data:<ref name="Winkle2" /> | |||
Because this new element showed some similarities with the elements ] and antimony, its proper place in the periodic table was under consideration, but its similarities with Dmitri Mendeleev's predicted element "ekasilicon" confirmed that place on the periodic table.<ref name="isolation" /><ref>{{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|date = 1887| title = Germanium, a New Non-Metallic Element|page =181| accessdate = 2008-08-20}}</ref> With further material from 500 kg of ore from the mines in Saxony, Winkler confirmed the chemical properties of the new element in 1887.<ref name="Winkle2">{{cite journal|first = Clemens|last = Winkler|authorlink = Clemens Winkler|journal = J. Prak. Chemie|volume = 36|issue = 1|date = 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}}</ref><ref name="isolation"/><ref>{{cite journal|first = O.|last = Brunck|title = Obituary: Clemens Winkler|journal = Berichte der deutschen chemischen Gesellschaft|volume= 39|issue = 4|date = 1886|pages=4491–4548|doi = 10.1002/cber.190603904164|language=German}}</ref> He also determined an atomic weight of 72.32 by analyzing pure ] ({{chem|GeCl|4}}), while ] deduced 72.3 by a comparison of the lines in the spark ] of the element.<ref>{{cite journal|title = Sur le poids atomique du germanium|first = M. Lecoq|last = de Boisbaudran|journal = Comptes rendus|date = 1886|volume = 103 |page = 452|url = http://gallica.bnf.fr/ark:/12148/bpt6k3059r/f454.table|accessdate = 2008-08-20| language=French}}</ref> | |||
Winkler was able to prepare several new compounds of germanium, including ]s, ]s, ]s, ], and ] (Ge(C<sub>2</sub>H<sub>5</sub>)<sub>4</sub>), the first organogermane.<ref name="Winkle2" /> The physical data from those compounds — which corresponded well with Mendeleev's predictions — made the discovery an important confirmation of Mendeleev's idea of element ]. Here is a comparison between the prediction and Winkler's data:<ref name="Winkle2" /> | |||
<div style="float: center; margin: 5px;"> | <div style="float: center; margin: 5px;"> | ||
{| class="wikitable" | {| class="wikitable" | ||
|- | |- | ||
! Property !! Ekasilicon !! Germanium | ! Property !! Ekasilicon<br />{{nobold|Mendeleev<br />prediction (1871)}} !! Germanium<br />{{nobold|Winkler<br />discovery (1887)}} | ||
|- | |- | ||
| atomic mass || 72.64 || 72. |
| atomic mass || 72.64 || 72.63 | ||
|- | |- | ||
| density (g/cm<sup>3</sup>) || 5.5 || 5.35 | | density (g/cm<sup>3</sup>) || 5.5 || 5.35 | ||
Line 44: | Line 45: | ||
| chloride density (g/cm<sup>3</sup>) || 1.9 || 1.9 | | chloride density (g/cm<sup>3</sup>) || 1.9 || 1.9 | ||
|}</div> | |}</div> | ||
Until the late 1930s, germanium was thought to be a poorly conducting ].<ref name="DOE">{{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}}</ref> Germanium did not become economically significant until after 1945 when its properties as an ]<nowiki/>semiconductor were recognized. During ], small amounts of germanium were used in some special ], mostly ]s.<ref>{{cite news| author = W. K.|url = http://select.nytimes.com/gst/abstract.html?res=F30715FE3F5B157A93C2A8178ED85F478585F9|publisher = NY Times| title = Germanium for Electronic Devices| accessdate=2008-08-22 | date=1953-05-10}}</ref><ref>{{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}}</ref> The first major use was the point-contact ]s for ] pulse detection during the War.<ref name="DOE" /> The first ] alloys were obtained in 1955.<ref>{{cite web|url = http://www.sp.phy.cam.ac.uk/~SiGe/Silicon%20Germanium%20(SiGe)%20History.html|title = SiGe History|publisher = ]| accessdate=2008-08-22}}</ref> Before 1945, only a few hundred kilograms of germanium were produced in smelters each year, but by the end of the 1950s, the annual worldwide production had reached 40 ]s.<ref name="acs">{{cite news|url=http://pubs.acs.org/cen/80th/print/germanium.html| date=2003| title=Germanium| first = Bethany|last = Halford| work= Chemical & Engineering News |publisher= American Chemical Society| accessdate=2008-08-22}}</ref> | |||
Until the late 1930s, germanium was thought to be a poorly conducting ].<ref name="DOE">{{cite journal |title=Germanium: From Its Discovery to SiGe Devices |author=Haller, E. E. |website=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 |access-date=2008-08-22 |date=2006-06-14 |archive-date=2019-07-10 |archive-url=https://web.archive.org/web/20190710154435/http://www.osti.gov/bridge/servlets/purl/922705-bthJo6/922705.PDF |url-status=live}}</ref> Germanium did not become economically significant until after 1945 when its properties as an ] semiconductor were recognized. During ], small amounts of germanium were used in some special ], mostly ]s.<ref>{{cite news |author=W. K. |url=http://select.nytimes.com/gst/abstract.html?res=F30715FE3F5B157A93C2A8178ED85F478585F9 |newspaper=The New York Times |title=Germanium for Electronic Devices |access-date=2008-08-22 |date=1953-05-10 |archive-date=2013-06-13 |archive-url=https://web.archive.org/web/20130613202934/http://select.nytimes.com/gst/abstract.html?res=F30715FE3F5B157A93C2A8178ED85F478585F9 |url-status=live}}</ref><ref>{{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 |access-date=2008-08-22 |archive-date=2008-09-24 |archive-url=https://web.archive.org/web/20080924135754/http://www.computerhistory.org/semiconductor/timeline/1941-semiconductor.html |url-status=live}}</ref> The first major use was the point-contact ]s for ] pulse detection during the War.<ref name="DOE" /> The first ] alloys were obtained in 1955.<ref>{{cite web |url=http://www.sp.phy.cam.ac.uk/~SiGe/Silicon%20Germanium%20(SiGe)%20History.html |title=SiGe History |publisher=University of Cambridge |access-date=2008-08-22 |url-status=dead |archive-url=https://web.archive.org/web/20080805204801/http://www.sp.phy.cam.ac.uk/~SiGe/Silicon%20Germanium%20%28SiGe%29%20History.html |archive-date=2008-08-05}}</ref> Before 1945, only a few hundred kilograms of germanium were produced in smelters each year, but by the end of the 1950s, the annual worldwide production had reached {{convert|40|MT|ST|lk=on|abbr=off}}.<ref name="acs">{{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 |access-date=2008-08-22 |archive-date=2008-05-13 |archive-url=https://web.archive.org/web/20080513180858/http://pubs.acs.org/cen/80th/print/germanium.html |url-status=live}}</ref> | |||
The development of the germanium ] in 1948<ref>{{cite journal|journal = Physical Review|volume = 74|issue = 2|pages = 230–231|title = The Transistor, A Semi-Conductor Triode |first = J.|last = Bardeen|author2=Brattain, W. H.| date = 1948|doi = 10.1103/PhysRev.74.230|bibcode = 1948PhRv...74..230B }}</ref> opened the door to countless applications of ].<ref>{{cite web|title = Electronics History 4 – Transistors|url = http://www.greatachievements.org/?id=3967|publisher = National Academy of Engineering|accessdate=2008-08-22}}</ref> 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 ]s.<ref name="usgs">{{cite journal|title=Germanium—Statistics and Information| author=U.S. Geological Survey|date=2008|journal=U.S. Geological Survey, Mineral Commodity Summaries|url=http://minerals.usgs.gov/minerals/pubs/commodity/germanium/ |quote=Select 2008| accessdate=2008-08-28}}</ref> For example, the company that became ] was founded in 1957 with the express purpose of producing silicon transistors. Silicon has superior electrical properties, but it requires much greater purity that could not be commercially achieved in the early years of ].<ref>{{cite journal|journal=IEEE Transactions on Electron Devices|volume = ED-23|issue = 7|date=July 1976|title = Single Crystals of Germanium and Silicon-Basic to the Transistor and Integrated Circuit|first = Gordon K.|last = Teal |pages = 621–639|doi=10.1109/T-ED.1976.18464}}</ref> | |||
The development of the germanium ] in 1948<ref>{{cite journal |journal=Physical Review |volume=74 |issue=2 |pages=230–231 |title=The Transistor, A Semi-Conductor Triode |first=J. |last=Bardeen |author2=Brattain, W. H. |year=1948 |doi=10.1103/PhysRev.74.230 |bibcode=1948PhRv...74..230B |doi-access=free}}</ref> opened the door to countless applications of ].<ref>{{cite web |title=Electronics History 4 – Transistors |url=http://www.greatachievements.org/?id=3967 |publisher=National Academy of Engineering |access-date=2008-08-22 |archive-date=2007-10-20 |archive-url=https://web.archive.org/web/20071020030644/http://www.greatachievements.org/?id=3967 |url-status=live}}</ref> 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 ]s.<ref name="usgs">{{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 |access-date=2008-08-28 |archive-date=2008-09-16 |archive-url=https://web.archive.org/web/20080916115005/http://minerals.usgs.gov/minerals/pubs/commodity/germanium/ |url-status=live}}</ref> For example, the company that became ] was founded in 1957 with the express purpose of producing silicon transistors. Silicon has superior electrical properties, but it requires much greater purity that could not be commercially achieved in the early years of ].<ref>{{cite journal |journal=IEEE Transactions on Electron Devices |volume=ED-23 |issue=7 |date=July 1976 |title=Single Crystals of Germanium and Silicon-Basic to the Transistor and Integrated Circuit |first=Gordon K. |last=Teal |pages=621–639 |doi=10.1109/T-ED.1976.18464 |bibcode=1976ITED...23..621T |s2cid=11910543}}</ref> | |||
Meanwhile, the demand for germanium for ] communication networks, infrared ] systems, and ] ] increased dramatically.<ref name="acs" /> These end uses represented 85% of worldwide germanium consumption in 2000.<ref name="usgs" /> The US government even designated germanium as a strategic and critical material, calling for a 146 ] (132 ]) supply in the national defense stockpile in 1987.<ref name="acs" /> | |||
Meanwhile, the demand for germanium for ] communication networks, infrared ] systems, and ] ] increased dramatically.<ref name="acs" /> These end uses represented 85% of worldwide germanium consumption in 2000.<ref name="usgs" /> The US government even designated germanium as a strategic and critical material, calling for a 146 ] (132 ]) supply in the national defense stockpile in 1987.<ref name="acs" /> | |||
Germanium differs from silicon in that the supply is limited by the availability of exploitable sources, while the supply of silicon is limited only by production capacity since silicon comes from ordinary sand and ]. While silicon could be bought in 1998 for less than $10 per kg,<ref name="acs" /> the price of germanium was almost $800 per kg.<ref name="acs" /> | Germanium differs from silicon in that the supply is limited by the availability of exploitable sources, while the supply of silicon is limited only by production capacity since silicon comes from ordinary sand and ]. While silicon could be bought in 1998 for less than $10 per kg,<ref name="acs" /> the price of germanium was almost $800 per kg.<ref name="acs" /> | ||
== Characteristics == | == Characteristics == | ||
Under ] germanium is a brittle, silvery-white, semi-metallic element.<ref name="nbb"/> This form constitutes an ] known as ''α-germanium'', which has a metallic luster and a ], the same as ].<ref name="usgs" /> At pressures above 120 ], it becomes a different allotrope known as ''β-germanium'' forms with the same structure as β-].<ref name="HollemanAF"/> Along with silicon, ], ], ], and ], it is one of the few substances that expands as it solidifies (i.e. ]) from the molten state.<ref name="HollemanAF"/> | |||
Under ], germanium is a brittle, silvery-white,<ref name="nbb" /> ]. This form constitutes an ] known as ''α-germanium'', which has a metallic luster and a ], the same structure as ] and ].<ref name="usgs" /> In this form, germanium has a ] of <math>19.7^{+0.6}_{-0.5}~\text{eV}</math>.<ref>{{Cite journal |last1=Agnese |first1=R. |last2=Aralis |first2=T. |last3=Aramaki |first3=T. |last4=Arnquist |first4=I. J. |last5=Azadbakht |first5=E. |last6=Baker |first6=W. |last7=Banik |first7=S. |last8=Barker |first8=D. |last9=Bauer |first9=D. A. |date=2018-08-27 |title=Energy loss due to defect formation from 206Pb recoils in SuperCDMS germanium detectors |journal=Applied Physics Letters |volume=113 |issue=9 |pages=092101 |doi=10.1063/1.5041457 |issn=0003-6951 |arxiv=1805.09942 |bibcode=2018ApPhL.113i2101A |s2cid=118627298}}</ref> At pressures above 120 ], germanium becomes the metallic allotrope ''β-germanium'' with the same structure as β-].<ref name="HollemanAF" /> Like silicon, ], ], ], and ], germanium is one of the few substances that expands as it solidifies (i.e. ]) from the molten state.<ref name="HollemanAF" /> | |||
Germanium is a ]. ] techniques have led to the production of crystalline germanium for semiconductors that has an impurity of only one part in 10<sup>10</sup>,<ref name="lanl">{{cite web|url=http://periodic.lanl.gov/32.shtml|publisher=Los Alamos National Laboratory|title=Germanium|accessdate=2008-08-28}}</ref> making it one of the purest materials ever obtained.<ref>{{cite book |title=The Primordial Universe: 28 June – 23 July 1999 |editor=Binetruy, B |author=Chardin, B. |chapter=Dark Matter: Direct Detection |publisher=Springer |date=2001 |isbn=3-540-41046-5 |page=308}}</ref> The first metallic material discovered (in 2005) to become a ] in the presence of an extremely strong ] was an ].<ref>{{cite journal|doi = 10.1126/science.1115498|date=August 2005|last =Lévy| first= F.|author2=Sheikin, I.|author3=Grenier, B.|author4=Huxley, A.|title=Magnetic field-induced superconductivity in the ferromagnet URhGe|volume=309|issue=5739|pages=1343–1346|pmid=16123293|journal=Science|bibcode = 2005Sci...309.1343L }}</ref> | |||
Germanium is a semiconductor having an ], as is crystalline silicon. ] techniques have led to the production of crystalline germanium for semiconductors that has an impurity of only one part in 10<sup>10</sup>,<ref name="lanl">{{cite web |publisher=Los Alamos National Laboratory |title=Germanium |url=http://periodic.lanl.gov/32.shtml |access-date=2008-08-28 |archive-date=2011-06-22 |archive-url=https://web.archive.org/web/20110622065850/http://periodic.lanl.gov/32.shtml |url-status=live}}</ref> | |||
making it one of the purest materials ever obtained.<ref> | |||
{{cite book |title=The Primordial Universe: 28 June – 23 July 1999 |editor=Binetruy, B |chapter=Dark Matter: Direct Detection |author=Chardin, B. |publisher=Springer |date=2001 |isbn=978-3-540-41046-1 |page=308}} | |||
</ref> | |||
The first semi-metallic material discovered (in 2005) to become a ] in the presence of an extremely strong ] was an ].<ref> | |||
{{cite journal |title=Magnetic field-induced superconductivity in the ferromagnet URhGe |last1=Lévy |first1=F. |last2=Sheikin |first2=I. |last3=Grenier |first3=B. |last4=Huxley |first4=A. |journal=Science |date=August 2005 |volume=309 |issue=5739 |pages=1343–1346 |pmid=16123293 |bibcode=2005Sci...309.1343L |doi=10.1126/science.1115498 |s2cid=38460998}} | |||
</ref> | |||
Pure germanium spontaneously |
Pure germanium is known to spontaneously extrude very long ]s, 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 ].<ref>{{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}}</ref> | ||
=== Chemistry === | === Chemistry === | ||
{{ |
{{Main article|Germanium compounds}} | ||
Elemental germanium oxidizes slowly to ] at 250 °C.<ref>{{cite journal|doi=10.1016/S0169-4332(98)00251-7|title=KRXPS study of the oxidation of Ge(001) surface|date=1998|author=Tabet, N|journal=Applied Surface Science|volume=134|issue=1–4|pages=275–282|bibcode = 1998ApSS..134..275T|last2=Salim|first2=Mushtaq A. }}</ref> Germanium is insoluble in dilute ] and ] but dissolves slowly in hot concentrated sulfuric and nitric acids and reacts violently with molten alkalis to produce ]s ({{chem||2−}}). Germanium occurs mostly in the ] +4 although many compounds are known with the oxidation state of +2.<ref name = "Greenwood">{{Greenwood&Earnshaw}}</ref> Other oxidation states are rare, such as +3 found in compounds such as Ge<sub>2</sub>Cl<sub>6</sub>, and +3 and +1 observed on the surface of oxides,<ref>{{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|first3=A.L|last3=Al-Oteibi|first2=M.A|date=1999|last2=Salim|author=Tabet, N|journal=Journal of Electron Spectroscopy and Related Phenomena|volume=101–103|pages=233–238}}</ref> or negative oxidation states in ]s, such as −4 in {{chem|GeH|4}}. Germanium cluster anions (] ions) such as Ge<sub>4</sub><sup>2−</sup>, Ge<sub>9</sub><sup>4−</sup>, Ge<sub>9</sub><sup>2−</sup>, <sup>6−</sup> have been prepared by the extraction from alloys containing alkali metals and germanium in liquid ammonia in the presence of ] or a ].<ref name = "Greenwood"/><ref>{{cite journal|title=Oxidative Coupling of Deltahedral <sup>4−</sup> Zintl Ions|first1 = Li|last1 = Xu|last2=Sevov| first2=Slavi C.|journal=J. Am. Chem. Soc.|date = 1999|volume = 121| issue = 39|pages = 9245–9246|doi = 10.1021/ja992269s}}</ref> The oxidation states of the element in these ions are not integers—similar to the ]s O<sub>3</sub><sup>−</sup>. | |||
Elemental germanium starts to oxidize slowly in air at around 250 °C, forming ] .<ref>{{cite journal |doi=10.1016/S0169-4332(98)00251-7 |title=KRXPS study of the oxidation of Ge(001) surface |date=1998 |author=Tabet, N |journal=Applied Surface Science |volume=134 |issue=1–4 |pages=275–282 |bibcode=1998ApSS..134..275T |last2=Salim |first2=Mushtaq A.}}</ref> Germanium is insoluble in dilute ] and ] but dissolves slowly in hot concentrated sulfuric and nitric acids and reacts violently with molten alkalis to produce ]s ({{chem||2−}}). Germanium occurs mostly in the ] +4 although many +2 compounds are known.<ref name = "Greenwood">{{Greenwood&Earnshaw}}</ref> Other oxidation states are rare: +3 is found in compounds such as Ge<sub>2</sub>Cl<sub>6</sub>, and +3 and +1 are found on the surface of oxides,<ref>{{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 |first3=A. L. |last3=Al-Oteibi |first2=M. A. |date=1999 |last2=Salim |author=Tabet, N |journal=Journal of Electron Spectroscopy and Related Phenomena |volume=101–103 |pages=233–238 |bibcode=1999JESRP.101..233T}}</ref> or negative oxidation states in ]s, such as −4 in {{chem|Mg|2|Ge}}. Germanium cluster anions (] ions) such as Ge<sub>4</sub><sup>2−</sup>, Ge<sub>9</sub><sup>4−</sup>, Ge<sub>9</sub><sup>2−</sup>, <sup>6−</sup> have been prepared by the extraction from alloys containing alkali metals and germanium in liquid ammonia in the presence of ] or a ].<ref name = "Greenwood" /><ref>{{cite journal |title=Oxidative Coupling of Deltahedral <sup>4−</sup> Zintl Ions |first1=Li |last1=Xu |last2=Sevov |first2=Slavi C. |journal=J. Am. Chem. Soc. |date=1999 |volume=121 |issue=39 |pages=9245–9246 |doi=10.1021/ja992269s|bibcode=1999JAChS.121.9245X }}</ref> The oxidation states of the element in these ions are not integers—similar to the ]s O<sub>3</sub><sup>−</sup>. | |||
Two ]s of germanium are known: ] ({{chem|GeO|2}}, germania) and ], ({{chem|GeO}}).<ref name="HollemanAF">{{cite book|last = Holleman|first = A. F.|author2=Wiberg, E.|author3=Wiberg, N.|title=Lehrbuch der Anorganischen Chemie|edition=102nd|publisher=de Gruyter|date=2007|isbn=978-3-11-017770-1|oclc = 145623740}}</ref> The dioxide, GeO<sub>2</sub> can be obtained by roasting ] ({{chem|GeS|2}}), and is a white powder that is only slightly soluble in water but reacts with alkalis to form germanates.<ref name="HollemanAF"/> The monoxide, germanous oxide, can be obtained by the high temperature reaction of GeO<sub>2</sub> with Ge metal.<ref name="HollemanAF"/> The dioxide (and the related oxides and germanates) exhibits the unusual property of having a high refractive index for visible light, but transparency to ] light.<ref>{{cite journal|doi = 10.1111/j.1151-2916.2002.tb00594.x|title = Infrared Transparent Germanate Glass-Ceramics|first = Shyam S.|last = Bayya|author2=Sanghera, Jasbinder S.|author3=Aggarwal, Ishwar D.|author4=Wojcik, Joshua A.|journal = Journal of the American Ceramic Society|volume = 85|issue = 12|pages= 3114–3116|date = 2002}}</ref><ref>{{cite journal|doi = 10.1007/BF00614256|title = Infrared reflectance and transmission spectra of germanium dioxide and its hydrolysis products|date = 1975 |last = Drugoveiko|first = O. P.|journal = Journal of Applied Spectroscopy|volume = 22|issue = 2|pages = 191–193|last2 = Evstrop'ev|first2 = K. K.|last3 = Kondrat'eva|first3 = B. S.|last4 = Petrov|first4 = Yu. A.|last5 = Shevyakov|first5 = A. M.|bibcode=1975JApSp..22..191D}}</ref> ], Bi<sub>4</sub>Ge<sub>3</sub>O<sub>12</sub>, (BGO) is used as a ].<ref name="BGO">{{cite journal|title = A Bismuth Germanate-Avalanche Photodiode Module Designed for Use in High Resolution Positron Emission Tomography|last = Lightstone|first = A. W.|author2=McIntyre, R. J.|author3=Lecomte, R.|author4=Schmitt, D.|journal = IEEE Transactions on Nuclear Science| date = 1986|volume =33|issue= 1|pages = 456–459|doi =10.1109/TNS.1986.4337142|bibcode = 1986ITNS...33..456L }}</ref> | |||
Two ]s of germanium are known: ] ({{chem|GeO|2}}, germania) and ], ({{chem|GeO}}).<ref name="HollemanAF">{{cite book |last=Holleman |first=A. F. |author2=Wiberg, E. |author3=Wiberg, N. |title=Lehrbuch der Anorganischen Chemie |edition=102nd |publisher=de Gruyter |date=2007 |isbn=978-3-11-017770-1 |oclc=145623740}}</ref> The dioxide, GeO<sub>2</sub>, can be obtained by roasting ] ({{chem|GeS|2}}), and is a white powder that is only slightly soluble in water but reacts with alkalis to form ]s.<ref name="HollemanAF" /> The monoxide, germanous oxide, can be obtained by the high temperature reaction of GeO<sub>2</sub> with elemental Ge.<ref name="HollemanAF" /> The dioxide (and the related oxides and germanates) exhibits the unusual property of having a high refractive index for visible light, but transparency to ] light.<ref>{{cite journal |doi=10.1111/j.1151-2916.2002.tb00594.x |title=Infrared Transparent Germanate Glass-Ceramics |first=Shyam S. |last=Bayya |author2=Sanghera, Jasbinder S. |author3=Aggarwal, Ishwar D. |author4=Wojcik, Joshua A. |journal=Journal of the American Ceramic Society |volume=85 |issue=12 |pages=3114–3116 |date=2002}}</ref><ref>{{cite journal |doi=10.1007/BF00614256 |title=Infrared reflectance and transmission spectra of germanium dioxide and its hydrolysis products |date=1975 |last1=Drugoveiko |first1=O. P. |journal=Journal of Applied Spectroscopy |volume=22 |issue=2 |pages=191–193 |last2=Evstrop'ev |first2=K. K. |last3=Kondrat'eva |first3=B. S. |last4=Petrov |first4=Yu. A. |last5=Shevyakov |first5=A. M. |bibcode=1975JApSp..22..191D |s2cid=97581394}}</ref> ], Bi<sub>4</sub>Ge<sub>3</sub>O<sub>12</sub> (BGO), is used as a ].<ref name="BGO">{{cite journal |title=A Bismuth Germanate-Avalanche Photodiode Module Designed for Use in High Resolution Positron Emission Tomography |last=Lightstone |first=A. W. |author2=McIntyre, R. J. |author3=Lecomte, R. |author4=Schmitt, D. |journal=IEEE Transactions on Nuclear Science |date=1986 |volume=33 |issue=1 |pages=456–459 |doi=10.1109/TNS.1986.4337142 |bibcode=1986ITNS...33..456L |s2cid=682173}}</ref> | |||
]s with other ]s are also known, such as the di] ({{chem|GeS|2}}), di] ({{chem|GeSe|2}}), and the ] (GeS), selenide (GeSe), and ] (GeTe).<ref name = "Greenwood"/> GeS<sub>2</sub> forms as a white precipitate when hydrogen sulfide is passed through strongly acid solutions containing Ge(IV).<ref name = "Greenwood"/> 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 Winkler to discover the element.<ref>{{cite journal|first =Otto H.|last = Johnson|title = Germanium and its Inorganic Compounds|journal = Chem. Rev.|date = 1952|volume= 3|issue =3| pages=431–469|doi = 10.1021/cr60160a002}}</ref> By heating the disulfide in a current of ], 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.<ref name="HollemanAF"/> Upon melting with ] and ], germanium compounds form salts known as thiogermanates.<ref>{{cite journal|doi=10.1039/a703634e|title=First synthesis of mesostructured thiogermanates|date=1997|last = Fröba|first = Michael |journal=Chemical Communications|issue=18|pages=1729–1730|last2=Oberender|first2=Nadine}}</ref> | |||
]s with other ]s are also known, such as the ] ({{chem|GeS|2}}) and ] ({{chem|GeSe|2}}), and the ] (GeS), ] (GeSe), and ] (GeTe).<ref name = "Greenwood" /> GeS<sub>2</sub> forms as a white precipitate when hydrogen sulfide is passed through strongly acid solutions containing Ge(IV).<ref name = "Greenwood" /> 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 Winkler to discover the element.<ref>{{cite journal |first=Otto H. |last=Johnson |title=Germanium and its Inorganic Compounds |journal=Chem. Rev. |date=1952 |volume=51 |issue=3 |pages=431–469 |doi=10.1021/cr60160a002}}</ref> By heating the disulfide in a current of ], 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.<ref name="HollemanAF" /> Upon melting with ] and ], germanium compounds form salts known as thiogermanates.<ref>{{cite journal |doi=10.1039/a703634e |title=First synthesis of mesostructured thiogermanates |date=1997 |last1=Fröba |first1=Michael |journal=Chemical Communications |issue=18 |pages=1729–1730 |last2=Oberender |first2=Nadine}}</ref> | |||
].|alt=Skeletal chemical structure of a tetrahedral molecule with germanium atom in its center bonded to four hydrogen atoms. The Ge-H distance is 152.51 picometers.]] | |||
Four tetra] are known. Under normal conditions GeI<sub>4</sub> is a solid, GeF<sub>4</sub> a gas and the others volatile liquids. For example, ], GeCl<sub>4</sub>, is obtained as a colorless fuming liquid boiling at 83.1 °C by heating the metal with chlorine.<ref name="HollemanAF"/> All the tetrahalides are readily hydrolyzed to hydrated germanium dioxide.<ref name="HollemanAF"/> GeCl<sub>4</sub> is used in the production of organogermanium compounds.<ref name = "Greenwood"/> All four dihalides are known and in contrast to the tetrahalides are polymeric solids.<ref name = "Greenwood"/> Additionally Ge<sub>2</sub>Cl<sub>6</sub> and some higher compounds of formula Ge<sub>''n''</sub>Cl<sub>2''n''+2</sub> are known.<ref name="HollemanAF"/> The unusual compound Ge<sub>6</sub>Cl<sub>16</sub> has been prepared that contains the Ge<sub>5</sub>Cl<sub>12</sub> unit with a ] structure.<ref>{{cite journal|title = The Crystal Structure and Raman Spectrum of Ge<sub>5</sub>Cl<sub>12</sub>·GeCl<sub>4</sub> and the Vibrational Spectrum of Ge<sub>2</sub>Cl<sub>6</sub>| last = Beattie|first = I.R.|author2=Jones, P.J.|author3=Reid, G.|author4=Webster, M.|journal = Inorg. Chem.|volume = 37|issue =23|pages = 6032–6034|date = 1998|doi =10.1021/ic9807341|pmid = 11670739}}</ref> | |||
].|alt=Skeletal chemical structure of a tetrahedral molecule with germanium atom in its center bonded to four hydrogen atoms. The Ge–H distance is 152.51 picometers.]] | |||
] (GeH<sub>4</sub>) is a compound similar in structure to ]. Polygermanes—compounds that are similar to ]s—with formula Ge<sub>''n''</sub>H<sub>2''n''+2</sub> containing up to five germanium atoms are known.<ref name = "Greenwood"/> The germanes are less volatile and less reactive than their corresponding silicon analogues.<ref name = "Greenwood"/> GeH<sub>4</sub> reacts with alkali metals in liquid ammonia to form white crystalline MGeH<sub>3</sub> which contain the GeH<sub>3</sub><sup>−</sup> ].<ref name = "Greenwood"/> The germanium hydrohalides with one, two and three halogen atoms are colorless reactive liquids.<ref name = "Greenwood"/> | |||
Four tetra] are known. Under normal conditions ] (GeI<sub>4</sub>) is a solid, ] (GeF<sub>4</sub>) a gas and the others volatile liquids. For example, ], GeCl<sub>4</sub>, is obtained as a colorless fuming liquid boiling at 83.1 °C by heating the metal with chlorine.<ref name="HollemanAF" /> All the tetrahalides are readily hydrolyzed to hydrated germanium dioxide.<ref name="HollemanAF" /> GeCl<sub>4</sub> is used in the production of organogermanium compounds.<ref name = "Greenwood" /> All four dihalides are known and in contrast to the tetrahalides are polymeric solids.<ref name = "Greenwood" /> Additionally Ge<sub>2</sub>Cl<sub>6</sub> and some higher compounds of formula Ge<sub>''n''</sub>Cl<sub>2''n''+2</sub> are known.<ref name="HollemanAF" /> The unusual compound Ge<sub>6</sub>Cl<sub>16</sub> has been prepared that contains the Ge<sub>5</sub>Cl<sub>12</sub> unit with a ] structure.<ref>{{cite journal |title=The Crystal Structure and Raman Spectrum of Ge<sub>5</sub>Cl<sub>12</sub>·GeCl<sub>4</sub> and the Vibrational Spectrum of Ge<sub>2</sub>Cl<sub>6</sub> |last1=Beattie |first1=I. R. |last2=Jones |first2=P.J. |last3=Reid |first3=G. |author4=Webster, M. |journal=Inorg. Chem. |volume=37 |issue=23 |pages=6032–6034 |date=1998 |doi=10.1021/ic9807341 |pmid=11670739}}</ref> | |||
] (GeH<sub>4</sub>) is a compound similar in structure to ]. Polygermanes—compounds that are similar to ]s—with formula Ge<sub>''n''</sub>H<sub>2''n''+2</sub> containing up to five germanium atoms are known.<ref name = "Greenwood" /> The germanes are less volatile and less reactive than their corresponding silicon analogues.<ref name = "Greenwood" /> GeH<sub>4</sub> reacts with alkali metals in liquid ammonia to form white crystalline MGeH<sub>3</sub> which contain the ] ].<ref name = "Greenwood" /> The germanium hydrohalides with one, two and three halogen atoms are colorless reactive liquids.<ref name = "Greenwood" /> | |||
] addition with an organogermanium compound.|alt=Skeletal chemical structures outlining an additive chemical reaction including an organogermanium compound.]] | |||
The first ] was synthesized by Winkler in 1887; the reaction of germanium tetrachloride with ] yielded ] ({{chem|Ge(C|2|H|5|)|4}}).<ref name="Winkle2" /> Organogermanes of the type R<sub>4</sub>Ge (where R is an ]) such as ] ({{chem|Ge(CH|3|)|4}}) and tetraethylgermane are accessed through the cheapest available germanium precursor ] and alkyl nucleophiles. Organic germanium hydrides such as ] ({{chem|(CH|3|)|2|CHCH|2|GeH|3}}) were found to be less hazardous and may be used as a liquid substitute for toxic ] gas in ] applications. Many germanium ]s are known: ] ]s, germylenes (similar to ]s), and germynes (similar to ]s).<ref>{{cite journal|title = Reactive intermediates in organogermanium chemistry|first = Jacques|last = Satge|journal = Pure & Appl. Chem.|volume = 56|issue = 1|pages = 137–150|date =1984|doi = 10.1351/pac198456010137}}</ref><ref>{{cite journal|title = Organogermanium Chemistry| first = Denis|last = Quane|author2=Bottei, Rudolph S.|journal = Chemical Reviews|volume = 63|issue = 4|pages = 403–442|date =1963|doi = 10.1021/cr60224a004}}</ref> The organogermanium compound ] was first reported in the 1970s, and for a while was used as a dietary supplement and thought to possibly have anti-tumor qualities.<ref name="toxic" /> | |||
] addition with an organogermanium compound|alt=Skeletal chemical structures outlining an additive chemical reaction including an organogermanium compound.]] | |||
Using a ligand called Eind (1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) germanium is able to form a double bond with oxygen (germanone).<ref>{{cite news|last=Broadwith|first=Phillip|title=Germanium-oxygen double bond takes centre stage|url=http://www.rsc.org/chemistryworld/News/2012/March/germanone-germanium-oxygen-double-bond-created.asp|accessdate=2014-05-15|newspaper=Chemistry World|date=25 March 2012}}</ref> | |||
The first ] was synthesized by Winkler in 1887; the reaction of germanium tetrachloride with ] yielded ] ({{chem|Ge(C|2|H|5|)|4}}).<ref name="Winkle2" /> Organogermanes of the type R<sub>4</sub>Ge (where R is an ]) such as ] ({{chem|Ge(CH|3|)|4}}) and tetraethylgermane are accessed through the cheapest available germanium precursor ] and alkyl nucleophiles. Organic germanium hydrides such as ] ({{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 ] applications. Many germanium ]s are known: ] ]s, ]s (similar to ]s), and germynes (similar to ]s).<ref>{{cite journal |title=Reactive intermediates in organogermanium chemistry |first=Jacques |last=Satge |journal=Pure Appl. Chem. |volume=56 |issue=1 |pages=137–150 |date=1984 |doi=10.1351/pac198456010137 |s2cid=96576323 |doi-access=free}}</ref><ref>{{cite journal |title=Organogermanium Chemistry |first=Denis |last=Quane |author2=Bottei, Rudolph S. |journal=Chemical Reviews |volume=63 |issue=4 |pages=403–442 |date=1963 |doi=10.1021/cr60224a004}}</ref> The organogermanium compound ] was first reported in the 1970s, and for a while was used as a dietary supplement and thought to possibly have anti-tumor qualities.<ref name="toxic" /> | |||
Using a ligand called Eind (1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) germanium is able to form a double bond with oxygen (germanone). Germanium hydride and germanium tetrahydride are very flammable and even explosive when mixed with air.<ref>{{cite news |last=Broadwith |first=Phillip |title=Germanium-oxygen double bond takes centre stage |url=http://www.rsc.org/chemistryworld/News/2012/March/germanone-germanium-oxygen-double-bond-created.asp |access-date=2014-05-15 |newspaper=Chemistry World |date=25 March 2012 |archive-date=2014-05-17 |archive-url=https://web.archive.org/web/20140517121351/http://www.rsc.org/chemistryworld/News/2012/March/germanone-germanium-oxygen-double-bond-created.asp |url-status=live}}</ref> | |||
=== Isotopes === | === Isotopes === | ||
{{main|Isotopes of germanium}} | {{main|Isotopes of germanium}} | ||
Germanium |
Germanium occurs in five natural ]s: {{SimpleNuclide|Germanium|70}}, {{SimpleNuclide|Germanium|72}}, {{SimpleNuclide|Germanium|73}}, {{SimpleNuclide|Germanium|74}}, and {{SimpleNuclide|Germanium|76}}. Of these, {{SimpleNuclide|Germanium|76}} is very slightly radioactive, decaying by ] with a ] of {{val|1.78|e=21|u=years}}. {{SimpleNuclide|Germanium|74}} is the most common isotope, having a ] of approximately 36%. {{SimpleNuclide|Germanium|76}} is the least common with a natural abundance of approximately 7%.<ref name="nubase">{{NUBASE 2003}}</ref> When bombarded with alpha particles, the isotope {{SimpleNuclide|Germanium|72}} will generate stable {{SimpleNuclide|Selenium|77|link=yes}}, releasing high energy electrons in the process.<ref name="72Ge" /> Because of this, it is used in combination with ] for ].<ref name="72Ge">Perreault, Bruce A. , US Patent 7800286, issued September 21, 2010. {{webarchive |url=https://web.archive.org/web/20071012103442/http://www.nuenergy.org/disclosures/AlphaFusionPatent_05-04-2007.pdf |archive-url=https://web.archive.org/web/20071012103442/http://www.nuenergy.org/disclosures/AlphaFusionPatent_05-04-2007.pdf |archive-date=2007-10-12 |url-status=live |date=October 12, 2007 |title=PDF copy }}</ref> | ||
At least 27 ]s have also been synthesized ranging in atomic mass from 58 to 89. The most stable of these is {{ |
At least 27 ]s have also been synthesized, ranging in atomic mass from 58 to 89. The most stable of these is {{SimpleNuclide|Germanium|68}}, decaying by ] with a half-life of {{val|270.95|u=days}}ays. The least stable is {{SimpleNuclide|Germanium|60}}, with a half-life of {{val|30|ul=ms}}. While most of germanium's radioisotopes decay by ], {{SimpleNuclide|Germanium|61}} and {{SimpleNuclide|Germanium|64}} decay by ] delayed ].<ref name="nubase" /> {{SimpleNuclide|Germanium|84}} through {{SimpleNuclide|Germanium|87}} isotopes also exhibit minor ] delayed ] decay paths.<ref name="nubase" /> | ||
=== Occurrence === | === Occurrence === | ||
{{category see also|Germanium minerals}} | {{category see also|Germanium minerals}} | ||
]|alt=A brown block of irregular shape and surface, about 6 cm in size.]] | |||
Germanium is created by ], mostly by the ] in ] stars. The s-process is a slow ] capture of lighter elements inside pulsating ] stars.<ref name="sterling">{{cite journal |journal=The Astrophysical Journal Letters |volume=578 |issue=1 |pages=L55–L58 |doi=10.1086/344473 |title=Discovery of Enhanced Germanium Abundances in Planetary Nebulae with the Far Ultraviolet Spectroscopic Explorer |first=N. C. |last=Sterling |author2=Dinerstein, Harriet L. |author3=Bowers, Charles W. |bibcode=2002ApJ...578L..55S |arxiv=astro-ph/0208516 |year=2002 |s2cid=119395123 |author2-link=Harriet Dinerstein}}</ref> Germanium has been detected in some of the most distant stars<ref>{{cite journal |journal=Nature |volume=423 |issue=29 |date=2003-05-01 |pmid=12721614 |doi=10.1038/423029a |title=Astronomy: Elements of surprise |last=Cowan |first=John |page=29 |bibcode=2003Natur.423...29C |s2cid=4330398 |doi-access=free}}</ref> and in the atmosphere of Jupiter.<ref>{{cite journal |title=The tropospheric gas composition of Jupiter's north equatorial belt /NH<sub>3</sub>, PH<sub>3</sub>, CH<sub>3</sub>D, GeH<sub>4</sub>, H<sub>2</sub>O/ and the Jovian D/H isotopic ratio |last=Kunde |first=V. |author2=Hanel, R. |author3=Maguire, W. |author4=Gautier, D. |author5=Baluteau, J. P. |author6=Marten, A. |author7=Chedin, A. |author8=Husson, N. |author9=Scott, N. |journal=Astrophysical Journal |volume=263 |date=1982 |pages=443–467 |doi=10.1086/160516 |bibcode=1982ApJ...263..443K}}</ref> | |||
Germanium's abundance ] is approximately 1.6 ].<ref name="Holl">{{cite journal |doi=10.1016/j.oregeorev.2005.07.034 |title=Metallogenesis of germanium – A review |first=R. |last=Höll |author2=Kling, M. |author3=Schroll, E. |journal=Ore Geology Reviews |volume=30 |issue=3–4 |date=2007 |pages=145–180}}</ref> Only a few minerals like ], ], ], ] and ] contain appreciable amounts of germanium.<ref name="usgs" /><ref>{{Cite journal |url=https://www.researchgate.net/publication/309583931 |title=The distribution of gallium, germanium and indium in conventional and non-conventional resources – Implications for global availability (PDF Download Available) |website=ResearchGate |doi=10.13140/rg.2.2.20956.18564 |access-date=2017-06-10 |last1=Frenzel |first1=Max |year=2016 |publisher=Unpublished |archive-date=2018-10-06 |archive-url=https://web.archive.org/web/20181006235214/https://www.researchgate.net/publication/309583931 |url-status=live}}</ref> Only few of them (especially germanite) are, very rarely, found in mineable amounts.<ref>{{cite journal |url=https://www.researchgate.net/publication/250273740 |title=Eyselite, Fe3+Ge34+O7(OH), a new mineral species from Tsumeb, Namibia |journal=The Canadian Mineralogist |volume=42 |issue=6 |pages=1771–1776 |date=December 2004 |doi=10.2113/gscanmin.42.6.1771 |first1=Andrew C. |last1=Roberts |bibcode=2004CaMin..42.1771R |display-authors=etal}}</ref><ref>{{Cite web |url=https://www.deutsche-rohstoffagentur.de/DERA/DE/Downloads/vortrag_germanium.pdf?__blob=publicationFile&v=2 |title=Archived copy |access-date=2018-10-06 |archive-date=2018-10-06 |archive-url=https://web.archive.org/web/20181006234914/https://www.deutsche-rohstoffagentur.de/DERA/DE/Downloads/vortrag_germanium.pdf?__blob=publicationFile&v=2 |url-status=live}}</ref><ref>{{Cite web |url=http://tupa.gtk.fi/raportti/arkisto/070_peh_76.pdf |title=Archived copy |access-date=2018-10-06 |archive-date=2020-03-20 |archive-url=https://web.archive.org/web/20200320190457/http://tupa.gtk.fi/raportti/arkisto/070_peh_76.pdf |url-status=live}}</ref><!--Ore found in the Pend Orielle Mine near ] has exceptionally high amounts of germanium.<ref>{{cite web |url=http://periodictable.com/Elements/032/index.html |title=Pictures, stories, and facts about the element Germanium in the Periodic Table |website=periodictable.com}}</ref><ref>{{Cite doi | 10.2307/30056827}}</ref>--> Some zinc–copper–lead ore bodies contain enough germanium to justify extraction from the final ore concentrate.<ref name="Holl" /> An unusual natural enrichment process causes a high content of germanium in some coal seams, discovered by ] during a broad survey for germanium deposits.<ref name="Gold1">{{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 |date=1930 |url=http://resolver.sub.uni-goettingen.de/purl?GDZPPN002508303 |access-date=2008-08-25 |archive-date=2018-03-03 |archive-url=https://web.archive.org/web/20180303165042/http://resolver.sub.uni-goettingen.de/purl?GDZPPN002508303 |url-status=live}}</ref><ref name="Gold2">{{cite journal |journal=Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen, Mathematisch-Physikalische Klasse |title=Zur Geochemie des Germaniums |last=Goldschmidt |first=V. M. |author2=Peters, Cl. |pages=141–167 |url=http://resolver.sub.uni-goettingen.de/purl?GDZPPN002509180 |date=1933 |access-date=2008-08-25 |archive-date=2008-12-01 |archive-url=https://web.archive.org/web/20081201115130/http://resolver.sub.uni-goettingen.de/purl/?GDZPPN002509180 |url-status=live}}</ref> The highest concentration ever found was in ] coal ash with as much as 1.6% germanium.<ref name="Gold1" /><ref name="Gold2" /> The coal deposits near ], ], contain an estimated 1600 ]s of germanium.<ref name="Holl" /> | |||
Germanium is created through ], mostly by the ] in ] stars. The s-process is a slow ] capture of lighter elements inside pulsating ] stars.<ref name="sterling">{{cite journal|journal = The Astrophysical Journal Letters|volume = 578|issue = 1|pages = L55–L58|date = 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|author2=Dinerstein, Harriet L.|author3=Bowers, Charles W.|bibcode=2002ApJ...578L..55S|arxiv = astro-ph/0208516 }}</ref> Germanium has been detected in the atmosphere of Jupiter<ref>{{cite journal| title= The tropospheric gas composition of Jupiter's north equatorial belt /NH<sub>3</sub>, PH<sub>3</sub>, CH<sub>3</sub>D, GeH<sub>4</sub>, H<sub>2</sub>O/ and the Jovian D/H isotopic ratio| last = Kunde| first = V.|author2=Hanel, R. |author3=Maguire, W. |author4=Gautier, D. |author5=Baluteau, J. P. |author6=Marten, A. |author7=Chedin, A. |author8=Husson, N. |author9= Scott, N. |journal = Astrophysical Journal| volume= 263|date= 1982|pages= 443–467|doi=10.1086/160516| bibcode=1982ApJ...263..443K}}</ref> and in some of the most distant stars.<ref>{{cite journal| journal=Nature|volume=423|issue= 29|date=2003-05-01| pmid=12721614| doi=10.1038/423029a|title=Astronomy: Elements of surprise| last = Cowan|first = John| page=29|bibcode = 2003Natur.423...29C }}</ref> Its abundance ] is approximately 1.6 ].<ref name="Holl">{{cite journal| doi = 10.1016/j.oregeorev.2005.07.034|title = Metallogenesis of germanium—A review|first = R.|last = Höll|author2=Kling, M.|author3=Schroll, E.| journal = Ore Geology Reviews|volume = 30|issue = 3–4|date = 2007| pages = 145–180}}</ref> There are only a few minerals like ], ], ], and ] that contain appreciable amounts of germanium, but no mineable deposits exist for any of them.<ref name="usgs" /><ref>{{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 |deadurl=yes |archiveurl=https://web.archive.org/web/20070612043415/http://www.resourceinvestor.com/pebble.asp?relid=31285 |archivedate=June 12, 2007 }}</ref><!--Ore found in the Pend Orielle Mine near ] has exceptionally high amounts of germanium.<ref>http://periodictable.com/Elements/032/index.html</ref><ref>{{Cite doi | 10.2307/30056827 }}</ref>--> Some zinc-copper-lead ore bodies contain enough germanium that it can be extracted from the final ore concentrate.<ref name="Holl" /> | |||
An unusual enrichment process causes a high content of germanium in some coal seams, which was discovered by ] during a broad survey for germanium deposits.<ref name="Gold1">{{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| date = 1930|url =http://resolver.sub.uni-goettingen.de/purl?GDZPPN002508303}}</ref><ref name="Gold2">{{cite journal|journal = Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen, Mathematisch-Physikalische Klasse|title = Zur Geochemie des Germaniums|last = Goldschmidt| first = V. M.|author2=Peters, Cl.|pages = 141–167|url =http://resolver.sub.uni-goettingen.de/purl?GDZPPN002509180|date = 1933}}</ref> The highest concentration ever found was in the ] coal ash with up to 1.6% of germanium.<ref name="Gold1" /><ref name="Gold2" /> The coal deposits near ], ], contain an estimated 1600 ]s of germanium.<ref name="Holl" /> | |||
== Production == | == Production == | ||
About 118 ]s of germanium were produced in 2011 worldwide, mostly in China (80 t), Russia (5 t) and United States (3 t).<ref name="usgs" /> Germanium is recovered as a by-product from ] zinc ores where it is concentrated in amounts as great as 0.3%,<ref>{{cite journal |doi=10.1016/0016-7037(85)90241-8 |title=Germanium geochemistry and mineralogy |date=1985 |last=Bernstein |first=L. |journal=Geochimica et Cosmochimica Acta |volume=49 |issue=11 |pages=2409–2422 |bibcode=1985GeCoA..49.2409B}}</ref> especially from low-temperature sediment-hosted, massive ]–]–](–]) deposits and carbonate-hosted Zn–Pb deposits.<ref>{{Cite journal |title=Gallium, germanium, indium and other minor and trace elements in sphalerite as a function of deposit type – A meta-analysis |last1=Frenzel |first1=Max |date=July 2016 |journal=Ore Geology Reviews |doi=10.1016/j.oregeorev.2015.12.017 |last2=Hirsch |first2=Tamino |last3=Gutzmer |first3=Jens |volume=76 |pages=52–78 |bibcode=2016OGRv...76...52F}}</ref> A recent study found that at least 10,000 t of extractable germanium is contained in known zinc reserves, particularly those hosted by ], while at least 112,000 t will be found in coal reserves.<ref>{{multiref|{{Cite journal |title=On the geological availability of germanium |journal=Mineralium Deposita |date=2013-12-29 |issn=0026-4598 |pages=471–486 |volume=49 |issue=4 |doi=10.1007/s00126-013-0506-z |first1=Max |last1=Frenzel |first2=Marina P. |last2=Ketris |first3=Jens |last3=Gutzmer |bibcode=2014MinDe..49..471F |s2cid=129902592}}|{{Cite journal |title=Erratum to: On the geological availability of germanium |journal=Mineralium Deposita |date=2014-01-19 |issn=0026-4598 |page=487 |volume=49 |issue=4 |doi=10.1007/s00126-014-0509-4 |first1=Max |last1=Frenzel |first2=Marina P. |last2=Ketris |first3=Jens |last3=Gutzmer |bibcode=2014MinDe..49..487F |s2cid=140620827 |doi-access=free}}}}</ref> In 2007 35% of the demand was met by recycled germanium.<ref name="Holl" /> | |||
]|alt=A brown block of irregular shape and surface, about 6 cm in size.]] | |||
About 118 ]s of germanium was produced in 2011 worldwide, mostly in China (80 t), Russia (5 t) and United States (3 t).<ref name="usgs" /> Germanium is recovered as a by-product from ] ] ores where it is concentrated in amounts of up to 0.3%,<ref>{{cite journal|doi=10.1016/0016-7037(85)90241-8|title=Germanium geochemistry and mineralogy|date=1985|author=Bernstein, L|journal=Geochimica et Cosmochimica Acta|volume=49|issue=11|pages=2409–2422|bibcode = 1985GeCoA..49.2409B }}</ref> especially from low-temperature sediment-hosted, massive ]–]–](–]) deposits and carbonate-hosted Zn–Pb deposits.<ref>{{Cite journal|url = http://www.sciencedirect.com/science/article/pii/S0169136815302961|title = Gallium, germanium, indium and other minor and trace elements in sphalerite as a function of deposit type - A meta-analysis|last = Frenzel|first = Max|date = July 2016|journal = Ore Geology Reviews|doi = 10.1016/j.oregeorev.2015.12.017|pmid = |last2 = Hirsch|first2 = Tamino|publisher = Elsevier|last3 = Gutzmer|first3 = Jens|volume = 76|pages = 52–78}}</ref> A recent study found that at least 10,000 t of extractable germanium is contained in known zinc reserves, particularly those hosted by ], while at least 112,000 t is contained in coal reserves.<ref>{{Cite journal|title = On the geological availability of germanium|url = http://link.springer.com/article/10.1007/s00126-013-0506-z|journal = Mineralium Deposita|date = 2013-12-29|issn = 0026-4598|pages = 471–486|volume = 49|issue = 4|doi = 10.1007/s00126-013-0506-z|first = Max|last = Frenzel|first2 = Marina P.|last2 = Ketris|first3 = Jens|last3 = Gutzmer}}</ref><ref>{{Cite journal|title = Erratum to: On the geological availability of germanium|url = http://link.springer.com/article/10.1007/s00126-014-0509-4|journal = Mineralium Deposita|date = 2014-01-19|issn = 0026-4598|pages = 487–487|volume = 49|issue = 4|doi = 10.1007/s00126-014-0509-4|first = Max|last = Frenzel|first2 = Marina P.|last2 = Ketris|first3 = Jens|last3 = Gutzmer}}</ref> In 2007 35% of the demand was met by recycled germanium.<ref name="Holl" /> | |||
While it is produced mainly from ], it is also found in ], ], and ] ores. Another source of germanium is ] of coal power plants which use coal from some coal deposits with a large concentration of germanium. Russia and China used this as a source for germanium.<ref name="Naumov">{{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|date = 2007|doi = 10.3103/S1067821207040049|pages =265–272}}</ref> Russia's deposits are located in the far east of the country on ] Island. The coal mines northeast of ] have also been used as a germanium source. The deposits in China are mainly located in the ] mines near ], ]; coal mines near ], ] are also used.<ref name="Holl" /> | |||
<div style="float: right; margin: 5px;"> | <div style="float: right; margin: 5px;"> | ||
{|class="wikitable" | {|class="wikitable" style="font-size:85%; text-align:right;" | ||
!Year !! Cost<br />(]/kg)<ref><!--two sources in one here?-->{{ |
!Year !! Cost<br />(]/kg)<ref><!--two sources in one here?-->{{Cite book |title=USGS Minerals Information |url=http://minerals.usgs.gov/minerals/pubs/commodity/germanium/index.html#mcs |at=, , , , , |isbn=978-0-85934-039-7 |author=R.N. Soar |oclc=16437701 |date=1977 |access-date=2013-04-22 |archive-date=2013-05-07 |archive-url=https://web.archive.org/web/20130507125723/http://minerals.usgs.gov/minerals/pubs/commodity/germanium/index.html#mcs |url-status=live}}</ref> | ||
|- | |- | ||
|1999 || 1,400 | |1999 || 1,400 | ||
Line 120: | Line 128: | ||
|- | |- | ||
|2009 || 950 | |2009 || 950 | ||
|- | |||
|2010 || 940 | |||
|- | |||
|2011 || 1,625 | |||
|- | |||
|2012 || 1,680 | |||
|- | |||
|2013 || 1,875 | |||
|- | |||
|2014 || 1,900 | |||
|- | |||
|2015 || 1,760 | |||
|- | |||
|2016 || 950 | |||
|- | |||
|2017 || 1,358 | |||
|- | |||
|2018 || 1,300 | |||
|- | |||
|2019 || 1,240 | |||
|- | |||
|2020 || 1,000 | |||
|} | |} | ||
</div> | </div> | ||
While it is produced mainly from ], it is also found in ], ], and ] ores. Another source of germanium is ] of power plants fueled from coal deposits that contain germanium. Russia and China used this as a source for germanium.<ref name="Naumov">{{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 |date=2007 |doi=10.3103/S1067821207040049 |pages=265–272 |s2cid=137187498}}</ref> Russia's deposits are located in the far east of ] Island, and northeast of ]. The deposits in China are located mainly in the ] mines near ], ]; coal is also mined near ], ].<ref name="Holl" /> | |||
The ore concentrates are mostly ]; they are converted to the ]s by heating under air, in a process known as ]: | |||
The ore concentrates are mostly ]; they are converted to the ]s by heating under air in a process known as ]: | |||
: GeS<sub>2</sub> + 3 O<sub>2</sub> → GeO<sub>2</sub> + 2 SO<sub>2</sub> | : GeS<sub>2</sub> + 3 O<sub>2</sub> → GeO<sub>2</sub> + 2 SO<sub>2</sub> | ||
Some of the germanium is left in the dust produced, while the rest is converted to germanates, which are then leached (together with zinc) from the cinder by sulfuric acid. After neutralization, only the zinc stays in solution while germanium and other metals precipitate. After removing some of the zinc in the precipitate by the ], the residing Waelz oxide is leached a second time. The ] is obtained as precipitate and converted with ] gas or hydrochloric acid to ], which has a low boiling point and can be isolated by distillation:<ref name="Naumov" /> | |||
: GeO<sub>2</sub> + 4 HCl → GeCl<sub>4</sub> + 2 H<sub>2</sub>O | : GeO<sub>2</sub> + 4 HCl → GeCl<sub>4</sub> + 2 H<sub>2</sub>O | ||
: GeO<sub>2</sub> + 2 Cl<sub>2</sub> → GeCl<sub>4</sub> + O<sub>2</sub> | : GeO<sub>2</sub> + 2 Cl<sub>2</sub> → GeCl<sub>4</sub> + O<sub>2</sub> | ||
Germanium tetrachloride is either hydrolyzed to the oxide (GeO<sub>2</sub>) or purified by fractional distillation and then hydrolyzed.<ref name="Naumov" /> | Germanium tetrachloride is either hydrolyzed to the oxide (GeO<sub>2</sub>) or purified by fractional distillation and then hydrolyzed.<ref name="Naumov" /> The highly pure GeO<sub>2</sub> is now suitable for the production of germanium glass. It is reduced to the element by reacting it with hydrogen, producing germanium suitable for infrared optics and semiconductor production: | ||
The highly pure GeO<sub>2</sub> 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: | |||
: GeO<sub>2</sub> + 2 H<sub>2</sub> → Ge + 2 H<sub>2</sub>O | : GeO<sub>2</sub> + 2 H<sub>2</sub> → Ge + 2 H<sub>2</sub>O | ||
The germanium for steel production and other industrial processes is normally reduced using carbon:<ref name="Moska">{{cite journal|journal |
The germanium for steel production and other industrial processes is normally reduced using carbon:<ref name="Moska">{{cite journal |journal=Minerals Engineering |date=2004 |pages=393–402 |doi=10.1016/j.mineng.2003.11.014 |title=Review of germanium processing worldwide |issue=3 |author=Moskalyk, R. R. |volume=17 |bibcode=2004MiEng..17..393M}}</ref> | ||
: GeO<sub>2</sub> + C → Ge + CO<sub>2</sub> | : GeO<sub>2</sub> + C → Ge + CO<sub>2</sub> | ||
== Applications == | == Applications == | ||
The major end uses for germanium in 2007, worldwide, were estimated to be: 35% for ]s, 30% ], 15% ] catalysts, and 15% electronics and solar electric applications.<ref name="usgs" /> The remaining 5% went into such uses as phosphors, metallurgy, and chemotherapy.<ref name="usgs" /> | |||
] of the core silica (Item 1).<br /> | |||
1. Core 8 µm<br /> | |||
2. Cladding 125 µm<br /> | |||
3. Buffer 250 µm<br /> | |||
4. Jacket 400 µm|alt=A drawing of four concentric cylinders.]] | |||
The major end uses for germanium in 2007, worldwide, were estimated to be: 35% for ] systems, 30% ], 15% for ] catalysts, and 15% for electronics and solar electric applications.<ref name="usgs" /> The remaining 5% went into other uses such as phosphors, metallurgy, and chemotherapy.<ref name="usgs" /> | |||
=== Optics === | === Optics === | ||
] of the core silica (Item 1). {{olist | |||
The most notable physical characteristics of ] (GeO<sub>2</sub>) are its high ] and its low ]. These make it especially useful for ]es, ], and for the core part of ]s.<ref>{{cite journal|title=Infrared Detector Arrays for Astronomy|journal=Annual Review of Astronomy and Astrophysics|date = 2007 |doi = 10.1146/annurev.astro.44.051905.092436 |last = Rieke|first = G.H.| volume = 45|issue=1|pages = 77–115|bibcode=2007ARA&A..45...77R}}</ref><ref name="Brown">{{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|date = 2000|accessdate = 2008-09-22}}</ref> It also replaced ] as the silica ] for silica fiber, eliminating the need for subsequent heat treatment, which made the fibers brittle.<ref>{{cite web|url = http://ptgmedia.pearsoncmg.com/images/1587051052/samplechapter/1587051052content.pdf |title = Chapter III: Optical Fiber For Communications|publisher = Stanford Research Institute|accessdate = 2008-08-22}}</ref> 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 worldwide consumption.<ref name="Brown" /> ] is a ] used for its optic properties, such as in ].<ref>{{cite web|url=http://www.osta.org/technology/pdf/dvdqa.pdf|archiveurl=https://web.archive.org/web/20090419202545/http://www.osta.org/technology/pdf/dvdqa.pdf|archivedate=2009-04-19|title=Understanding Recordable & Rewritable DVD|edition=First |format=PDF |accessdate=2008-09-22| publisher = Optical Storage Technology Association (OSTA)}}</ref> | |||
|Core 8 µm | |||
|Cladding 125 µm | |||
|Buffer 250 µm | |||
|Jacket 400 µm | |||
}}]] | |||
The notable properties of ] (GeO<sub>2</sub>) are its high ] and its low ]. These make it especially useful for ]es, ], and the core part of ]s.<ref>{{cite journal |title=Infrared Detector Arrays for Astronomy |journal=Annual Review of Astronomy and Astrophysics |date=2007 |doi=10.1146/annurev.astro.44.051905.092436 |last=Rieke |first=G. H. |s2cid=26285029 |volume=45 |issue=1 |pages=77–115 |bibcode=2007ARA&A..45...77R}}</ref><ref name="Brown">{{cite web |url=http://minerals.usgs.gov/minerals/pubs/commodity/germanium/220400.pdf |title=Germanium |first=Robert D. Jr. |last=Brown |publisher=U.S. Geological Survey |year=2000 |access-date=2008-09-22 |archive-date=2011-06-08 |archive-url=https://web.archive.org/web/20110608071221/http://minerals.usgs.gov/minerals/pubs/commodity/germanium/220400.pdf |url-status=live}}</ref> It has replaced ] as the ] for silica fiber, eliminating the subsequent heat treatment that made the fibers brittle.<ref>{{cite web |url=http://ptgmedia.pearsoncmg.com/images/1587051052/samplechapter/1587051052content.pdf |title=Chapter III: Optical Fiber For Communications |publisher=Stanford Research Institute |access-date=2008-08-22 |archive-date=2014-12-05 |archive-url=https://web.archive.org/web/20141205210827/http://ptgmedia.pearsoncmg.com/images/1587051052/samplechapter/1587051052content.pdf |url-status=live}}</ref> At the end of 2002, the fiber optics industry consumed 60% of the annual germanium use in the United States, but this is less than 10% of worldwide consumption.<ref name="Brown" /> ] is a ] used for its optic properties, such as that used in ].<ref>{{cite web |url=http://www.osta.org/technology/pdf/dvdqa.pdf |archive-url=https://web.archive.org/web/20090419202545/http://www.osta.org/technology/pdf/dvdqa.pdf |archive-date=2009-04-19 |title=Understanding Recordable & Rewritable DVD |edition=First |access-date=2008-09-22 |publisher=Optical Storage Technology Association (OSTA)}}</ref> | |||
Because germanium is transparent in the infrared it is |
Because germanium is transparent in the infrared wavelengths, it is an important ] optical material that can be readily cut and polished into lenses and windows. It is especially used as the front optic in ] working in the 8 to 14 ] range for passive thermal imaging and for hot-spot detection in military, mobile ], and fire fighting applications.<ref name="Moska" /> It is used in infrared ]s and other optical equipment that require extremely sensitive ].<ref name="Brown" /> It has a very high ] (4.0) and must be coated with anti-reflection agents. Particularly, a very hard special antireflection coating of ] (DLC), refractive index 2.0, is a good match and produces a diamond-hard surface that can withstand much environmental abuse.<ref>{{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 |date=1998 |pages=555–560 |journal=Carbon |bibcode=1998Carbo..36..555L}}</ref><ref>{{cite journal |first=Michael N. |last=Gardos |author2=Bonnie L. Soriano |author3=Steven H. Propst |title=Study on correlating rain erosion resistance with sliding abrasion resistance of DLC on germanium |journal=Proc. SPIE |volume=1325 |page=99 |date=1990 |doi=10.1117/12.22449 |issue=Mechanical Properties |series=SPIE Proceedings |editor1-last=Feldman |editor1-first=Albert |editor2-last=Holly |editor2-first=Sandor |bibcode=1990SPIE.1325...99G |s2cid=137425193}}</ref> | ||
=== Electronics === | === Electronics === | ||
] alloys are rapidly becoming an important semiconductor material |
Germanium can be alloyed with ], and ] alloys are rapidly becoming an important semiconductor material for high-speed integrated circuits. Circuits using the properties of Si-SiGe ]s can be much faster than those using silicon alone.<ref>{{cite journal |doi=10.1109/TED.2003.810484 |title=SiGe HBT and BiCMOS technologies for optical transmission and wireless communication systems |date=2003 |last=Washio |first=K. |journal=IEEE Transactions on Electron Devices |volume=50 |issue=3 |pages=656–668 |bibcode=2003ITED...50..656W}}</ref> The SiGe chips, with high-speed properties, can be made with low-cost, well-established production techniques of the ] industry.<ref name="usgs" /> | ||
High efficiency ]s are a major use of germanium. Because germanium and ] have nearly identical ], germanium substrates can be used to make gallium-arsenide ]s.<ref>{{cite journal |doi=10.1002/pip.446 |title=Space and terrestrial photovoltaics: synergy and diversity |date=2002 |last1=Bailey |first1=Sheila G. |journal=Progress in Photovoltaics: Research and Applications |volume=10 |issue=6 |pages=399–406 |last2=Raffaelle |first2=Ryne |last3=Emery |first3=Keith |hdl=2060/20030000611 |bibcode=2002sprt.conf..202B |s2cid=98370426 |hdl-access=free}}</ref> Germanium is the substrate of the wafers for high-efficiency ]s for space applications, such as the ]s, which use triple-junction gallium arsenide on germanium cells.<ref>{{cite journal |doi=10.1016/S0094-5765(02)00287-4 |title=The performance of gallium arsenide/germanium solar cells at the Martian surface |date=January 2004 |first=D. |last=Crisp |author2=Pathare, A. |author3=Ewell, R. C. |journal=Acta Astronautica |volume=54 |issue=2 |pages=83–101 |bibcode=2004AcAau..54...83C}}</ref> High-brightness LEDs, used for automobile headlights and to backlight LCD screens, are also an important application.<ref name="usgs" /> | |||
The recent rise in energy cost has improved the economics of ]s, a potential major new use of germanium.<ref name="usgs" /> Germanium is the substrate of the wafers for high-efficiency ]s for space applications. | |||
Germanium-on-insulator (GeOI) substrates are seen as a potential replacement for silicon on miniaturized chips.<ref name="usgs" /> CMOS circuit based on GeOI substrates has been reported recently.<ref>{{cite journal |first1=Heng |last1=Wu |first2=Peide D. |last2=Ye |date=August 2016 |title=Fully Depleted Ge CMOS Devices and Logic Circuits on Si |journal=] |volume=63 |issue=8 |pages=3028–3035 |doi=10.1109/TED.2016.2581203 |bibcode=2016ITED...63.3028W |s2cid=3231511 |url=https://engineering.purdue.edu/~yep/Papers/TED_Ge%20Fully%20Depleted%20CMOS_2016.pdf |access-date=2019-03-04 |archive-date=2019-03-06 |archive-url=https://web.archive.org/web/20190306044456/https://engineering.purdue.edu/~yep/Papers/TED_Ge%20Fully%20Depleted%20CMOS_2016.pdf |url-status=live}}</ref> Other uses in electronics include ]s in ]s<ref name="lanl" /> and solid-state light-emitting diodes (LEDs).<ref name="usgs" /> Germanium transistors are still used in some ]s by musicians who wish to reproduce the distinctive tonal character of the ] from the early ] era, most notably the ].<ref>{{cite journal |author=Szweda, Roy |date=2005 |title=Germanium phoenix |journal=] |volume=18 |issue=7 |page=55 |doi=10.1016/S0961-1290(05)71310-7}}</ref> | |||
Because germanium and ] have very similar lattice constants, germanium substrates can be used to make gallium arsenide ]s.<ref>{{cite journal|doi=10.1002/pip.446|title=Space and terrestrial photovoltaics: synergy and diversity|date=2002|last=Bailey| first= Sheila G.|journal=Progress in Photovoltaics Research and Applications|volume=10|issue=6|pages=399–406|last2=Raffaelle|first2=Ryne|last3=Emery|first3=Keith}}</ref> The ]s and several satellites use triple junction gallium arsenide on germanium cells.<ref>{{cite journal|doi = 10.1016/S0094-5765(02)00287-4| title = The performance of gallium arsenide/germanium solar cells at the Martian surface|date = 2004|first = D.|last = Crisp|author2=Pathare, A.|author3=Ewell, R. C.| journal = Acta Astronautica |volume = 54|issue = 2|pages = 83–101|bibcode = 2004AcAau..54...83C }}</ref> | |||
Germanium has been studied as a potential material for implantable bioelectronic sensors that are ] in the body without generating harmful hydrogen gas, replacing ]- and ]-based implementations.<ref>{{ cite journal |last1=Zhao |first1=H. |last2=Xue |first2=Z. |last3=Wu |first3=X. |display-authors=2 |date=21 July 2022 |title=Biodegradable germanium electronics for integrated biosensing of physiological signals. |journal=npj Flexible Electronics |volume=6 |at=63 |doi=10.1038/s41528-022-00196-2 |s2cid=250702946 |doi-access=free}}</ref> | |||
Germanium-on-insulator substrates are seen as a potential replacement for silicon on miniaturized chips.<ref name="usgs" /> Other uses in electronics include ]s in ]s,<ref name="lanl" /> and germanium-base solid-state light-emitting diodes (LEDs).<ref name="usgs" /> Germanium transistors are still used in some ]s by musicians who wish to reproduce the distinctive tonal character of the ] from the early ] era, most notably the ].<ref>{{cite journal|author = Szweda, Roy|date = 2005|title = Germanium phoenix|journal = ]|volume = 18|issue = 7|page = 55|doi = 10.1016/S0961-1290(05)71310-7}}</ref> | |||
=== Other uses === | === Other uses === | ||
] ]|alt=Photo of a standard transparent plastic bottle.]] | ] ]|alt=Photo of a standard transparent plastic bottle.]] | ||
Germanium dioxide is also used in ]s for ] in the production of ] (PET).<ref name="Thiele">{{cite journal |last=Thiele |first=Ulrich K.|date=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}}</ref> The high brilliance of |
Germanium dioxide is also used in ]s for ] in the production of ] (PET).<ref name="Thiele">{{cite journal |last=Thiele |first=Ulrich K. |date=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 |s2cid=98758568}}</ref> The high brilliance of this polyester is especially favored for PET bottles marketed in Japan.<ref name="Thiele" /> In the United States, germanium is not used for polymerization catalysts.<ref name="usgs" /> | ||
Due to the similarity between silica (SiO<sub>2</sub>) and germanium dioxide (GeO<sub>2</sub>), the silica stationary phase in some ] columns can be replaced by GeO<sub>2</sub>.<ref>{{cite journal |title=Germania-Based, Sol-Gel Hybrid Organic-Inorganic Coatings for Capillary Microextraction and Gas Chromatography |last1=Fang |first1=Li |last2=Kulkarni |first2=Sameer |last3=Alhooshani |first3=Khalid |last4=Malik |first4=Abdul |journal=Anal. Chem. |volume=79 |issue=24 |pages=9441–9451 |date=2007 |doi=10.1021/ac071056f |pmid=17994707}}</ref> | |||
In recent years germanium has seen increasing use in precious metal alloys. In ] alloys, for instance, it has been found to reduce ], increase tarnish resistance, and increase the alloy's response to precipitation hardening. A tarnish-proof sterling silver alloy, trademarked ], contains 1.2% germanium.<ref name="usgs" /> | |||
In recent years germanium has seen increasing use in precious metal alloys. In ] alloys, for instance, it reduces ], increases tarnish resistance, and improves precipitation hardening. A tarnish-proof silver alloy trademarked ] contains 1.2% germanium.<ref name="usgs" /> | |||
High purity germanium single crystal ]s can precisely identify radiation sources—for example in airport security.<ref>{{cite web |title=Performance of Light-Weight, Battery-Operated, High Purity Germanium Detectors for Field Use |first1=Ronald |last1=Keyser |last2=Twomey |first2=Timothy |last3=Upp |first3=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) |archiveurl=https://web.archive.org/web/20071026162911/http://www.ortec-online.com/papers/inmm_2003_keyser.pdf |archivedate=October 26, 2007 |deadurl=yes}}</ref> Germanium is useful for ] for ]s used in ] ] and ] diffraction. The reflectivity has advantages over silicon in neutron and ] applications.<ref>{{cite journal |doi=10.1142/S0218301396000062 |date=1996 |journal=International Journal of Modern Physics E |volume=5 |issue=1 |pages=131–151 |title=Optimization of Germanium for Neutron Diffractometers |bibcode=1996IJMPE...5..131A |last1=Ahmed |first1=F. U. |last2=Yunus |first2=S.M. |last3=Kamal |first3=I. |last4=Begum |first4=S. |last5=Khan |first5=Aysha A. |last6=Ahsan |first6=M.H. |last7=Ahmad |first7=A.A.Z. }}</ref> Crystals of high purity germanium are used in detectors for ] and the search for ].<ref>{{cite journal |doi=10.1016/j.nuclphysa.2005.02.155 |title=Astrophysical constraints from gamma-ray spectroscopy |date=2006 |last=Diehl |first=R. |journal=Nuclear Physics A |volume=777 |pages=70–97 |last2=Prantzos |first2=N |last3=Vonballmoos |first3=P |arxiv=astro-ph/0502324 |bibcode=2006NuPhA.777...70D}}</ref> | |||
Germanium crystals are also used in X-ray spectrometers for the determination of phosphorus, chlorine and sulfur.<ref>Eugene P. Bertin, Principles and practice of X-ray spectrometric analysis, Chapter 5.4-Analyzer crystals, Table 5.1, p. 123; Plenum Press,1970</ref> | |||
] made of single crystal high-purity germanium can precisely identify radiation sources—for example in airport security.<ref>{{cite web |title=Performance of Light-Weight, Battery-Operated, High Purity Germanium Detectors for Field Use |first1=Ronald |last1=Keyser |last2=Twomey |first2=Timothy |last3=Upp |first3=Daniel |url=http://www.ortec-online.com/papers/inmm_2003_keyser.pdf |access-date=2008-09-06 |publisher=Oak Ridge Technical Enterprise Corporation (ORTEC) |archive-url=https://web.archive.org/web/20071026162911/http://www.ortec-online.com/papers/inmm_2003_keyser.pdf |archive-date=October 26, 2007 |url-status=dead}}</ref> Germanium is useful for ] for ]s used in ] ] and ] diffraction. The reflectivity has advantages over silicon in neutron and ] applications.<ref>{{cite journal |doi=10.1142/S0218301396000062 |date=1996 |journal=International Journal of Modern Physics E |volume=5 |issue=1 |pages=131–151 |title=Optimization of Germanium for Neutron Diffractometers |bibcode=1996IJMPE...5..131A |last1=Ahmed |first1=F. U. |last2=Yunus |first2=S. M. |last3=Kamal |first3=I. |last4=Begum |first4=S. |last5=Khan |first5=Aysha A. |last6=Ahsan |first6=M. H. |last7=Ahmad |first7=A. A. Z.}}</ref> Crystals of high purity germanium are used in detectors for ] and the search for ].<ref>{{cite journal |doi=10.1016/j.nuclphysa.2005.02.155 |title=Astrophysical constraints from gamma-ray spectroscopy |date=2006 |last1=Diehl |first1=R. |journal=Nuclear Physics A |volume=777 |issue=2006 |pages=70–97 |last2=Prantzos |first2=N. |last3=Vonballmoos |first3=P. |arxiv=astro-ph/0502324 |bibcode=2006NuPhA.777...70D |citeseerx=10.1.1.256.9318 |s2cid=2360391}}</ref> Germanium crystals are also used in X-ray spectrometers for the determination of phosphorus, chlorine and sulfur.<ref>Eugene P. Bertin (1970). ''Principles and practice of X-ray spectrometric analysis'', Chapter 5.4 – Analyzer crystals, Table 5.1, p. 123; Plenum Press</ref> | |||
=== Inorganic germanium and medical aspects === | |||
Germanium is emerging as an important material for ] and spin-based ] applications. In 2010, researchers demonstrated room temperature spin transport<ref>{{Cite journal |last1=Shen |first1=C. |last2=Trypiniotis |first2=T. |last3=Lee |first3=K. Y. |last4=Holmes |first4=S. N. |last5=Mansell |first5=R. |last6=Husain |first6=M. |last7=Shah |first7=V. |last8=Li |first8=X. V. |last9=Kurebayashi |first9=H. |date=2010-10-18 |title=Spin transport in germanium at room temperature |journal=Applied Physics Letters |volume=97 |issue=16 |page=162104 |doi=10.1063/1.3505337 |issn=0003-6951 |bibcode=2010ApPhL..97p2104S |url=https://eprints.soton.ac.uk/271616/1/Gespin.pdf |access-date=2018-11-16 |archive-date=2017-09-22 |archive-url=https://web.archive.org/web/20170922180043/https://eprints.soton.ac.uk/271616/1/Gespin.pdf |url-status=live}}</ref> and more recently donor electron spins in germanium has been shown to have very long ]s.<ref>{{Cite journal |last1=Sigillito |first1=A. J. |last2=Jock |first2=R. M. |last3=Tyryshkin |first3=A. M. |last4=Beeman |first4=J. W. |last5=Haller |first5=E. E. |last6=Itoh |first6=K. M. |last7=Lyon |first7=S. A. |date=2015-12-07 |title=Electron Spin Coherence of Shallow Donors in Natural and Isotopically Enriched Germanium |journal=Physical Review Letters |volume=115 |issue=24 |pages=247601 |doi=10.1103/PhysRevLett.115.247601 |pmid=26705654 |arxiv=1506.05767 |bibcode=2015PhRvL.115x7601S |s2cid=13299377}}</ref> | |||
Inorganic germanium and organic germanium are different chemical compounds of germanium and their properties are different. | |||
== Strategic importance == | |||
Germanium is not thought to be essential to the health of plants or animals.<ref name=acs/> Germanium in the environment has little or no health impact. This is primarily because it usually occurs only as a trace element in ores and ]aceous materials, and is used in very small quantities that are not likely to be ingested, in its various industrial and electronic applications.<ref name="usgs" /> For similar reasons, germanium in end-uses has little impact on the environment as a biohazard. Some reactive intermediate compounds of germanium are poisonous (see precautions, below).<ref name="Brown Jr">{{cite report|url=http://minerals.usgs.gov/minerals/pubs/commodity/germanium/220798.pdf|format=PDF|publisher=US Geological Surveys|accessdate=2008-09-09| title = Commodity Survey:Germanium|first = Robert D.|last = Brown Jr.}}</ref> | |||
Due to its use in advanced electronics and optics, Germanium is considered a ] (by e.g. the ]), essential to fulfill the ]. As ] controls 60% of global Germanium production it holds a dominant position over the world's supply chains. | |||
On 3 July 2023 China suddenly imposed restrictions on the exports of germanium (and ]), ratcheting up trade tensions with Western allies. Invoking "national security interests," the ] informed that companies that intend to sell products containing germanium would need an export licence. The products/compounds targeted are: germanium dioxide, germanium epitaxial growth substrate, germanium ingot, germanium metal, germanium tetrachloride and zinc germanium phosphide. It sees such products as "dual-use" items that may have military purposes and therefore warrant an extra layer of oversight.{{cn|date=April 2024}} | |||
Germanium supplements, made from both organic and inorganic germanium, have been marketed as an ] capable of treating ] and ].<ref name=acs/> There is however no ] of benefit, and instead some evidence that such supplements are actively harmful.<ref name="American Cancer Society">{{cite book |publisher=] |title=American Cancer Society Complete Guide to Complementary and Alternative Cancer Therapies |edition=2nd |year=2009 |isbn=9780944235713 |editor=Ades TB |pages=360–363 |chapter=Germanium}}</ref> | |||
The new dispute opened a new chapter in the increasingly fierce technology race that has pitted the United States, and to a lesser extent Europe, against China. The ] wants its allies to heavily curb, or downright prohibit, advanced electronic components bound to the Chinese market to prevent Beijing from securing global technology supremacy. China denied any tit-for-tat intention behind the Germanium export restrictions.<ref>, Euronews, 4 July 2023.</ref><ref>, CNN, 3 July 2023.</ref><ref>, Reuters, 4 July 2023.</ref> | |||
Other germanium compounds have been administered by alternative medical practitioners as non-FDA-allowed injectable solutions. Soluble inorganic forms of germanium used at first, notably the citrate-lactate salt, led to a number of cases of ] dysfunction, ] and peripheral ] in individuals using them on a chronic basis. Plasma and urine germanium concentrations in these individuals, several of whom died, were several orders of magnitude greater than ] levels. A more recent organic form, beta-carboxyethylgermanium sesquioxide (]), has not exhibited the same spectrum of toxic effects.<ref>{{cite book|author=Baselt, R. |title=Disposition of Toxic Drugs and Chemicals in Man|edition=8th|publisher=Biomedical Publications|place=Foster City, CA|date=2008|pages=693–694}}</ref> | |||
Following China's export restrictions, Russian state-owned company ] announced an increase in germanium production to meet domestic demand.<ref>{{Cite web |url=https://asia.nikkei.com/Economy/Trade/Russian-firm-says-ready-to-boost-germanium-output-for-domestic-use |title=Russian firm says ready to boost germanium output for domestic use |agency=Reuters |date=2023-07-05 |access-date=2023-07-09 |archive-date=2023-07-24 |archive-url=https://web.archive.org/web/20230724221011/https://asia.nikkei.com/Economy/Trade/Russian-firm-says-ready-to-boost-germanium-output-for-domestic-use |url-status=dead}}</ref> | |||
] research has concluded that inorganic germanium, when used as a ], "presents potential human ]".<ref name="toxic">{{cite journal|last = Tao|first = S. H.|author2=Bolger, P. M.|date=June 1997|title = Hazard Assessment of Germanium Supplements|journal = ]|volume = 25|issue = 3|pages = 211–219|doi = 10.1006/rtph.1997.1098|pmid = 9237323}}</ref> | |||
== Germanium and health == | |||
Certain compounds of germanium have low toxicity to ]s, but have toxic effects against certain ].<ref name="nbb">{{cite book| last = Emsley| first = John| title = Nature's Building Blocks| publisher = Oxford University Press| date = 2001| location = Oxford| pages = 506–510| isbn = 0-19-850341-5}}</ref> | |||
Germanium is not considered essential to the health of plants or animals.<ref name="American Cancer Society" /> Germanium in the environment has little or no health impact. This is primarily because it usually occurs only as a trace element in ores and ]aceous materials, and the various industrial and electronic applications involve very small quantities that are not likely to be ingested.<ref name="usgs" /> For similar reasons, end-use germanium has little impact on the environment as a biohazard. Some reactive intermediate compounds of germanium are poisonous (see precautions, below).<ref name="Brown Jr">{{cite report |url=http://minerals.usgs.gov/minerals/pubs/commodity/germanium/220798.pdf |publisher=US Geological Surveys |access-date=2008-09-09 |title=Commodity Survey:Germanium |first=Robert D. Jr. |last=Brown |date= |archive-date=2018-03-04 |archive-url=https://web.archive.org/web/20180304113236/https://minerals.usgs.gov/minerals/pubs/commodity/germanium/220798.pdf |url-status=live}}</ref> | |||
Germanium supplements, made from both organic and inorganic germanium, have been marketed as an ] capable of treating ] and ].<ref name="acs" /> There is, however, no ] of benefit; some evidence suggests that such supplements are actively harmful.<ref name="American Cancer Society">{{cite book |publisher=American Cancer Society |title=American Cancer Society Complete Guide to Complementary and Alternative Cancer Therapies |edition=2nd |year=2009 |isbn=978-0944235713 |editor=Ades TB |pages= |chapter=Germanium |chapter-url=https://archive.org/details/americancancerso0000unse/page/360}}</ref> ] (FDA) research has concluded that inorganic germanium, when used as a ], "presents potential human ]".<ref name="toxic">{{cite journal |last=Tao |first=S. H. |author2=Bolger, P. M. |date=June 1997 |title=Hazard Assessment of Germanium Supplements |journal=] |volume=25 |issue=3 |pages=211–219 |doi=10.1006/rtph.1997.1098 |pmid=9237323 |url=https://zenodo.org/record/1229957 |access-date=2019-06-30 |archive-date=2020-03-10 |archive-url=https://web.archive.org/web/20200310041729/https://zenodo.org/record/1229957 |url-status=live}}</ref> | |||
== Precautions for chemically reactive germanium compounds == | |||
Some of germanium's artificially-produced compounds are quite reactive and present an immediate hazard to human health on exposure. For example, ] and ] (GeH<sub>4</sub>) are a liquid and gas, respectively, that can be very irritating to the eyes, skin, lungs, and throat.<ref name="Gerber 1997 141–146">{{cite journal|first = G.B.|last = Gerber|author2=Léonard, A.| date = 1997|title = Mutagenicity, carcinogenicity and teratogenicity of germanium compounds|journal = Regulatory Toxicology and Pharmacology|volume = 387|issue = 3|pages = 141–146|doi = 10.1016/S1383-5742(97)00034-3}}</ref> | |||
Some germanium compounds have been administered by alternative medical practitioners as non-FDA-allowed injectable solutions. Soluble inorganic forms of germanium used at first, notably the citrate-lactate salt, resulted in some cases of ] dysfunction, ], and peripheral ] in individuals using them over a long term. Plasma and urine germanium concentrations in these individuals, several of whom died, were several orders of magnitude greater than ] levels. A more recent organic form, beta-carboxyethylgermanium sesquioxide (]), has not exhibited the same spectrum of toxic effects.<ref>{{cite book |author=Baselt, R. |title=Disposition of Toxic Drugs and Chemicals in Man |edition=8th |publisher=Biomedical Publications |place=Foster City, CA |date=2008 |pages=693–694}}</ref> | |||
Certain compounds of germanium have low toxicity to ]s, but have toxic effects against certain ].<ref name="nbb">{{cite book |last=Emsley |first=John |title=Nature's Building Blocks |publisher=Oxford University Press |date=2001 |location=Oxford |pages=506–510 |isbn=978-0-19-850341-5}}</ref> | |||
=== Precautions for chemically reactive germanium compounds === | |||
While use of germanium itself does not require precautions, some of germanium's artificially produced compounds are quite reactive and present an immediate hazard to human health on exposure. For example, ] and ] (GeH<sub>4</sub>) are a liquid and gas, respectively, that can be very irritating to the eyes, skin, lungs, and throat.<ref name="Gerber 1997 141–146">{{cite journal |first=G. B. |last=Gerber |author2=Léonard, A. |date=1997 |title=Mutagenicity, carcinogenicity and teratogenicity of germanium compounds |journal=Regulatory Toxicology and Pharmacology |volume=387 |issue=3 |pages=141–146 |doi=10.1016/S1383-5742(97)00034-3 |pmid=9439710 |bibcode=1997MRRMR.387..141G}}</ref> | |||
== See also == | == See also == | ||
* ] | * ] | ||
* ] | * ] | ||
* ] | |||
== Notes == | |||
{{NoteFoot}} | |||
== References == | |||
{{Reflist}} | |||
== External links == | |||
{{EB1911 poster|Germanium}} | |||
* at '']'' (University of Nottingham) | |||
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== Footnotes == | |||
{{Reflist|group=n}} | |||
== References == | |||
{{Reflist|30em}} | |||
== External links == | |||
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Latest revision as of 18:33, 18 December 2024
Chemical element with atomic number 32 Not to be confused with geranium. Chemical element with atomic number 32 (Ge)Germanium is a chemical element; it has symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid (more rarely considered a metal) in the carbon group that is chemically similar to its group neighbors silicon and tin. Like silicon, germanium naturally reacts and forms complexes with oxygen in nature.
Because it seldom appears in high concentration, germanium was found comparatively late in the discovery of the elements. Germanium ranks 50th in abundance of the elements in the Earth's crust. In 1869, Dmitri Mendeleev predicted its existence and some of its properties from its position on his periodic table, and called the element ekasilicon. On February 6, 1886, Clemens Winkler at Freiberg University found the new element, along with silver and sulfur, in the mineral argyrodite. Winkler named the element after Germany, his country of birth. Germanium is mined primarily from sphalerite (the primary ore of zinc), though germanium is also recovered commercially from silver, lead, and copper ores.
Elemental germanium is used as a semiconductor in transistors and various other electronic devices. Historically, the first decade of semiconductor electronics was based entirely on germanium. Presently, the major end uses are fibre-optic systems, infrared optics, solar cell applications, and light-emitting diodes (LEDs). Germanium compounds are also used for polymerization catalysts and have most recently found use in the production of nanowires. This element forms a large number of organogermanium compounds, such as tetraethylgermanium, useful in organometallic chemistry. Germanium is considered a technology-critical element.
Germanium is not thought to be an essential element for any living organism. Similar to silicon and aluminium, naturally-occurring germanium compounds tend to be insoluble in water and thus have little oral toxicity. However, synthetic soluble germanium salts are nephrotoxic, and synthetic chemically reactive germanium compounds with halogens and hydrogen are irritants and toxins.
History
In his report on The Periodic Law of the Chemical Elements in 1869, the Russian chemist Dmitri Mendeleev predicted the existence of several unknown chemical elements, including one that would fill a gap in the carbon family, located between silicon and tin. Because of its position in his periodic table, Mendeleev called it ekasilicon (Es), and he estimated its atomic weight to be 70 (later 72).
In mid-1885, at a mine near Freiberg, Saxony, a new mineral was discovered and named argyrodite because of its high silver content. The chemist Clemens Winkler analyzed this new mineral, which proved to be a combination of silver, sulfur, and a new element. Winkler was able to isolate the new element in 1886 and found it similar to antimony. He initially considered the new element to be eka-antimony, but was soon convinced that it was instead eka-silicon. Before Winkler published his results on the new element, he decided that he would name his element neptunium, since the recent discovery of planet Neptune in 1846 had similarly been preceded by mathematical predictions of its existence. However, the name "neptunium" had already been given to another proposed chemical element (though not the element that today bears the name neptunium, which was discovered in 1940). So instead, Winkler named the new element germanium (from the Latin word, Germania, for Germany) in honor of his homeland. Argyrodite proved empirically to be Ag8GeS6.
Because this new element showed some similarities with the elements arsenic and antimony, its proper place in the periodic table was under consideration, but its similarities with Dmitri Mendeleev's predicted element "ekasilicon" confirmed that place on the periodic table. With further material from 500 kg of ore from the mines in Saxony, Winkler confirmed the chemical properties of the new element in 1887. He also determined an atomic weight of 72.32 by analyzing pure germanium tetrachloride (GeCl
4), while Lecoq de Boisbaudran deduced 72.3 by a comparison of the lines in the spark spectrum of the element.
Winkler was able to prepare several new compounds of germanium, including fluorides, chlorides, sulfides, dioxide, and tetraethylgermane (Ge(C2H5)4), the first organogermane. The physical data from those compounds—which corresponded well with Mendeleev's predictions—made the discovery an important confirmation of Mendeleev's idea of element periodicity. Here is a comparison between the prediction and Winkler's data:
Property | Ekasilicon Mendeleev prediction (1871) |
Germanium Winkler discovery (1887) |
---|---|---|
atomic mass | 72.64 | 72.63 |
density (g/cm) | 5.5 | 5.35 |
melting point (°C) | high | 947 |
color | gray | gray |
oxide type | refractory dioxide | refractory dioxide |
oxide density (g/cm) | 4.7 | 4.7 |
oxide activity | feebly basic | feebly basic |
chloride boiling point (°C) | under 100 | 86 (GeCl4) |
chloride density (g/cm) | 1.9 | 1.9 |
Until the late 1930s, germanium was thought to be a poorly conducting metal. Germanium did not become economically significant until after 1945 when its properties as an electronic semiconductor were recognized. During World War II, small amounts of germanium were used in some special electronic devices, mostly diodes. The first major use was the point-contact Schottky diodes for radar pulse detection during the War. The first silicon–germanium alloys were obtained in 1955. Before 1945, only a few hundred kilograms of germanium were produced in smelters each year, but by the end of the 1950s, the annual worldwide production had reached 40 metric tons (44 short tons).
The development of the germanium transistor in 1948 opened the door to countless applications of solid state electronics. 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. For example, the company that became Fairchild Semiconductor was founded in 1957 with the express purpose of producing silicon transistors. Silicon has superior electrical properties, but it requires much greater purity that could not be commercially achieved in the early years of semiconductor electronics.
Meanwhile, the demand for germanium for fiber optic communication networks, infrared night vision systems, and polymerization catalysts increased dramatically. These end uses represented 85% of worldwide germanium consumption in 2000. The US government even designated germanium as a strategic and critical material, calling for a 146 ton (132 tonne) supply in the national defense stockpile in 1987.
Germanium differs from silicon in that the supply is limited by the availability of exploitable sources, while the supply of silicon is limited only by production capacity since silicon comes from ordinary sand and quartz. While silicon could be bought in 1998 for less than $10 per kg, the price of germanium was almost $800 per kg.
Characteristics
Under standard conditions, germanium is a brittle, silvery-white, semiconductor. This form constitutes an allotrope known as α-germanium, which has a metallic luster and a diamond cubic crystal structure, the same structure as silicon and diamond. In this form, germanium has a threshold displacement energy of . At pressures above 120 kbar, germanium becomes the metallic allotrope β-germanium with the same structure as β-tin. Like silicon, gallium, bismuth, antimony, and water, germanium is one of the few substances that expands as it solidifies (i.e. freezes) from the molten state.
Germanium is a semiconductor having an indirect bandgap, as is crystalline silicon. Zone refining techniques have led to the production of crystalline germanium for semiconductors that has an impurity of only one part in 10, making it one of the purest materials ever obtained. The first semi-metallic material discovered (in 2005) to become a superconductor in the presence of an extremely strong electromagnetic field was an alloy of germanium, uranium, and rhodium.
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.
Chemistry
Main article: Germanium compoundsElemental germanium starts to oxidize slowly in air at around 250 °C, forming GeO2 . Germanium is insoluble in dilute acids and alkalis but dissolves slowly in hot concentrated sulfuric and nitric acids and reacts violently with molten alkalis to produce germanates (
). Germanium occurs mostly in the oxidation state +4 although many +2 compounds are known. Other oxidation states are rare: +3 is found in compounds such as Ge2Cl6, and +3 and +1 are found on the surface of oxides, or negative oxidation states in germanides, such as −4 in Mg
2Ge. Germanium cluster anions (Zintl ions) such as Ge4, Ge9, Ge9, have been prepared by the extraction from alloys containing alkali metals and germanium in liquid ammonia in the presence of ethylenediamine or a cryptand. 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 (GeO
2, germania) and germanium monoxide, (GeO). The dioxide, GeO2, can be obtained by roasting germanium disulfide (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 elemental Ge. 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. Bismuth germanate, Bi4Ge3O12 (BGO), is used as a scintillator.
Binary compounds with other chalcogens are also known, such as the disulfide (GeS
2) and diselenide (GeSe
2), and the monosulfide (GeS), monoselenide (GeSe), and monotelluride (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 Winkler to discover the element. 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.
Four tetrahalides are known. Under normal conditions germanium tetraiodide (GeI4) is a solid, germanium tetrafluoride (GeF4) a gas and the others volatile liquids. For example, germanium tetrachloride, GeCl4, is obtained as a colorless fuming liquid boiling at 83.1 °C by heating the metal with chlorine. All the tetrahalides are readily hydrolyzed 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 GenCl2n+2 are known. The unusual compound Ge6Cl16 has been prepared that contains the Ge5Cl12 unit with a neopentane structure.
Germane (GeH4) is a compound similar in structure to methane. Polygermanes—compounds that are similar to alkanes—with formula GenH2n+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 synthesized by Winkler in 1887; the reaction of germanium tetrachloride with diethylzinc yielded tetraethylgermane (Ge(C
2H
5)
4). Organogermanes of the type R4Ge (where R is an alkyl) such as tetramethylgermane (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 ((CH
3)
2CHCH
2GeH
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). 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.
Using a ligand called Eind (1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) germanium is able to form a double bond with oxygen (germanone). Germanium hydride and germanium tetrahydride are very flammable and even explosive when mixed with air.
Isotopes
Main article: Isotopes of germaniumGermanium occurs in five natural isotopes:
Ge
,
Ge
,
Ge
,
Ge
, and
Ge
. Of these,
Ge
is very slightly radioactive, decaying by double beta decay with a half-life of 1.78×10 years.
Ge
is the most common isotope, having a natural abundance of approximately 36%.
Ge
is the least common with a natural abundance of approximately 7%. When bombarded with alpha particles, the isotope
Ge
will generate stable
Se
, releasing high energy electrons in the process. Because of this, it is used in combination with radon for nuclear batteries.
At least 27 radioisotopes have also been synthesized, ranging in atomic mass from 58 to 89. The most stable of these is
Ge
, decaying by electron capture with a half-life of 270.95 days. The least stable is
Ge
, with a half-life of 30 ms. While most of germanium's radioisotopes decay by beta decay,
Ge
and
Ge
decay by
β
delayed proton emission.
Ge
through
Ge
isotopes also exhibit minor
β
delayed neutron emission decay paths.
Occurrence
See also: Category:Germanium mineralsGermanium is created by 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. Germanium has been detected in some of the most distant stars and in the atmosphere of Jupiter.
Germanium's abundance in the Earth's crust is approximately 1.6 ppm. Only a few minerals like argyrodite, briartite, germanite, renierite and sphalerite contain appreciable amounts of germanium. Only few of them (especially germanite) are, very rarely, found in mineable amounts. Some zinc–copper–lead ore bodies contain enough germanium to justify extraction from the final ore concentrate. An unusual natural enrichment process causes a high content of germanium in some coal seams, discovered by Victor Moritz Goldschmidt during a broad survey for germanium deposits. The highest concentration ever found was in Hartley coal ash with as much as 1.6% germanium. The coal deposits near Xilinhaote, Inner Mongolia, contain an estimated 1600 tonnes of germanium.
Production
About 118 tonnes of germanium were produced in 2011 worldwide, mostly in China (80 t), Russia (5 t) and United States (3 t). Germanium is recovered as a by-product from sphalerite zinc ores where it is concentrated in amounts as great as 0.3%, especially from low-temperature sediment-hosted, massive Zn–Pb–Cu(–Ba) deposits and carbonate-hosted Zn–Pb deposits. A recent study found that at least 10,000 t of extractable germanium is contained in known zinc reserves, particularly those hosted by Mississippi-Valley type deposits, while at least 112,000 t will be found in coal reserves. In 2007 35% of the demand was met by recycled germanium.
Year | Cost ($/kg) |
---|---|
1999 | 1,400 |
2000 | 1,250 |
2001 | 890 |
2002 | 620 |
2003 | 380 |
2004 | 600 |
2005 | 660 |
2006 | 880 |
2007 | 1,240 |
2008 | 1,490 |
2009 | 950 |
2010 | 940 |
2011 | 1,625 |
2012 | 1,680 |
2013 | 1,875 |
2014 | 1,900 |
2015 | 1,760 |
2016 | 950 |
2017 | 1,358 |
2018 | 1,300 |
2019 | 1,240 |
2020 | 1,000 |
While it is produced mainly from sphalerite, it is also found in silver, lead, and copper ores. Another source of germanium is fly ash of power plants fueled from coal deposits that contain germanium. Russia and China used this as a source for germanium. Russia's deposits are located in the far east of Sakhalin Island, and northeast of Vladivostok. The deposits in China are located mainly in the lignite mines near Lincang, Yunnan; coal is also mined near Xilinhaote, Inner Mongolia.
The ore concentrates are mostly sulfidic; they are converted to the oxides by heating under air in a process known as roasting:
- GeS2 + 3 O2 → GeO2 + 2 SO2
Some of the germanium is left in the dust produced, while the rest is converted to germanates, which are then leached (together with zinc) from the cinder by sulfuric acid. After neutralization, only the zinc stays in solution while germanium and other metals precipitate. After removing some of the 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 isolated by distillation:
- GeO2 + 4 HCl → GeCl4 + 2 H2O
- GeO2 + 2 Cl2 → GeCl4 + O2
Germanium tetrachloride is either hydrolyzed to the oxide (GeO2) or purified by fractional distillation and then hydrolyzed. The highly pure GeO2 is now suitable for the production of germanium glass. It is reduced to the element by reacting it with hydrogen, producing germanium suitable for infrared optics and semiconductor production:
- GeO2 + 2 H2 → Ge + 2 H2O
The germanium for steel production and other industrial processes is normally reduced using carbon:
- GeO2 + C → Ge + CO2
Applications
The major end uses for germanium in 2007, worldwide, were estimated to be: 35% for fiber-optics, 30% infrared optics, 15% polymerization catalysts, and 15% electronics and solar electric applications. The remaining 5% went into such uses as phosphors, metallurgy, and chemotherapy.
Optics
The notable properties 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 the core part of optical fibers. It has replaced titania as the dopant for silica fiber, eliminating the subsequent heat treatment that made the fibers brittle. At the end of 2002, the fiber optics industry consumed 60% of the annual germanium use in the United States, but this is less than 10% of worldwide consumption. GeSbTe is a phase change material used for its optic properties, such as that used in rewritable DVDs.
Because germanium is transparent in the infrared wavelengths, it is an 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 range for passive thermal imaging and for hot-spot detection in military, mobile night vision, and fire fighting applications. It is used in infrared spectroscopes and other optical equipment that require extremely sensitive infrared detectors. It has a very high refractive index (4.0) and must be coated with anti-reflection agents. 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 abuse.
Electronics
Germanium can be alloyed with silicon, and silicon–germanium alloys are rapidly becoming an important semiconductor material for high-speed integrated circuits. Circuits using the properties of Si-SiGe heterojunctions can be much faster than those using silicon alone. The SiGe chips, with high-speed properties, can be made with low-cost, well-established production techniques of the silicon chip industry.
High efficiency solar panels are a major use of germanium. Because germanium and gallium arsenide have nearly identical lattice constant, germanium substrates can be used to make gallium-arsenide solar cells. Germanium is the substrate of the wafers for high-efficiency multijunction photovoltaic cells for space applications, such as the Mars Exploration Rovers, which use triple-junction gallium arsenide on germanium cells. High-brightness LEDs, used for automobile headlights and to backlight LCD screens, are also an important application.
Germanium-on-insulator (GeOI) substrates are seen as a potential replacement for silicon on miniaturized chips. CMOS circuit based on GeOI substrates has been reported recently. Other uses in electronics include phosphors in fluorescent lamps and 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.
Germanium has been studied as a potential material for implantable bioelectronic sensors that are resorbed in the body without generating harmful hydrogen gas, replacing zinc oxide- and indium gallium zinc oxide-based implementations.
Other uses
Germanium dioxide is also used in catalysts for polymerization in the production of polyethylene terephthalate (PET). The high brilliance of this polyester is especially favored for PET bottles marketed in Japan. In the United States, germanium is not 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.
In recent years germanium has seen increasing use in precious metal alloys. In sterling silver alloys, for instance, it reduces firescale, increases tarnish resistance, and improves precipitation hardening. A tarnish-proof silver alloy trademarked Argentium contains 1.2% germanium.
Semiconductor detectors made of single crystal high-purity germanium can precisely identify radiation sources—for example in airport security. 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. Crystals of high purity germanium are used in detectors for gamma spectroscopy and the search for dark matter. Germanium crystals are also used in X-ray spectrometers for the determination of phosphorus, chlorine and sulfur.
Germanium is emerging as an important material for spintronics and spin-based quantum computing applications. In 2010, researchers demonstrated room temperature spin transport and more recently donor electron spins in germanium has been shown to have very long coherence times.
Strategic importance
Due to its use in advanced electronics and optics, Germanium is considered a technology-critical element (by e.g. the European Union), essential to fulfill the green and digital transition. As China controls 60% of global Germanium production it holds a dominant position over the world's supply chains.
On 3 July 2023 China suddenly imposed restrictions on the exports of germanium (and gallium), ratcheting up trade tensions with Western allies. Invoking "national security interests," the Chinese Ministry of Commerce informed that companies that intend to sell products containing germanium would need an export licence. The products/compounds targeted are: germanium dioxide, germanium epitaxial growth substrate, germanium ingot, germanium metal, germanium tetrachloride and zinc germanium phosphide. It sees such products as "dual-use" items that may have military purposes and therefore warrant an extra layer of oversight.
The new dispute opened a new chapter in the increasingly fierce technology race that has pitted the United States, and to a lesser extent Europe, against China. The US wants its allies to heavily curb, or downright prohibit, advanced electronic components bound to the Chinese market to prevent Beijing from securing global technology supremacy. China denied any tit-for-tat intention behind the Germanium export restrictions.
Following China's export restrictions, Russian state-owned company Rostec announced an increase in germanium production to meet domestic demand.
Germanium and health
Germanium is not considered essential to the health of plants or animals. Germanium in the environment has little or no health impact. This is primarily because it usually occurs only as a trace element in ores and carbonaceous materials, and the various industrial and electronic applications involve very small quantities that are not likely to be ingested. For similar reasons, end-use germanium has little impact on the environment as a biohazard. Some reactive intermediate compounds of germanium are poisonous (see precautions, below).
Germanium supplements, made from both organic and inorganic germanium, have been marketed as an alternative medicine capable of treating leukemia and lung cancer. There is, however, no medical evidence of benefit; some evidence suggests that such supplements are actively harmful. U.S. Food and Drug Administration (FDA) research has concluded that inorganic germanium, when used as a nutritional supplement, "presents potential human health hazard".
Some germanium compounds have been administered by alternative medical practitioners as non-FDA-allowed injectable solutions. Soluble inorganic forms of germanium used at first, notably the citrate-lactate salt, resulted in some cases of renal dysfunction, hepatic steatosis, and peripheral neuropathy in individuals using them over a long term. Plasma and urine germanium concentrations in these individuals, several of whom died, were several orders of magnitude greater than endogenous levels. A more recent organic form, beta-carboxyethylgermanium sesquioxide (propagermanium), has not exhibited the same spectrum of toxic effects.
Certain compounds of germanium have low toxicity to mammals, but have toxic effects against certain bacteria.
Precautions for chemically reactive germanium compounds
While use of germanium itself does not require precautions, some of germanium's artificially produced compounds are quite reactive and present an immediate hazard to human health on exposure. For example, Germanium tetrachloride and germane (GeH4) are a liquid and gas, respectively, that can be very irritating to the eyes, skin, lungs, and throat.
See also
Notes
- From Greek, argyrodite means silver-containing.
- Just as the existence of the new element had been predicted, the existence of the planet Neptune had been predicted in about 1843 by the two mathematicians John Couch Adams and Urbain Le Verrier, using the calculation methods of celestial mechanics. They did this in attempts to explain the fact that the planet Uranus, upon very close observation, appeared to be being pulled slightly out of position in the sky. James Challis started searching for it in July 1846, and he sighted this planet on September 23, 1846.
- R. Hermann published claims in 1877 of his discovery of a new element beneath tantalum in the periodic table, which he named neptunium, after the Greek god of the oceans and seas. However this metal was later recognized to be an alloy of the elements niobium and tantalum. The name "neptunium" was later given to the synthetic element one step past uranium in the Periodic Table, which was discovered by nuclear physics researchers in 1940.
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External links
- Germanium at The Periodic Table of Videos (University of Nottingham)
- Definitions from Wiktionary
- Media from Commons
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