Germanium

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32 gallium ← germanium → arsenic
Si

Ge

Sn
Periodic Table - Extended Periodic Table
General
Name, Symbol, Number germanium, Ge, 32
Element category metalloids
Group, Period, Block 14, 4, p
Appearance grayish white
Standard atomic weight 72.64(1)  g·mol−1
Electron configuration [Ar] 3d10 4s2 4p2
Electrons per shell 2, 8, 18, 4
Physical properties
Phase solid
Density (near r.t.) 5.323  g·cm−3
Liquid density at m.p. 5.60  g·cm−3
Melting point 1211.40 K
(938.25 °C, 1720.85 °F)
Boiling point 3106 K
(2833 °C, 5131 °F)
Heat of fusion 36.94  kJ·mol−1
Heat of vaporization 334  kJ·mol−1
Specific heat capacity (25 °C) 23.222  J·mol−1·K−1
Vapor pressure
P(Pa) 1 10 100 1 k 10 k 100 k
at T(K) 1644 1814 2023 2287 2633 3104
Atomic properties
Crystal structure Face-centered cubic
Oxidation states 4, 2,
(amphoteric oxide)
Electronegativity 2.01 (Pauling scale)
Ionization energies
(more)
1st:  762  kJ·mol−1
2nd:  1537.5  kJ·mol−1
3rd:  3302.1  kJ·mol−1
Atomic radius 125  pm
Atomic radius (calc.) 125  pm
Covalent radius 122  pm
Miscellaneous
Magnetic ordering Diamagnetic
Thermal conductivity (300 K) 60.2  W·m−1·K−1
Thermal expansion (25 °C) 6.0  µm·m−1·K−1
Speed of sound (thin rod) (20 °C) 5400 m/s
Mohs hardness 6.0
CAS registry number 7440-56-4
Most-stable isotopes
Main article: Isotopes of germanium
iso NA half-life DM DE (MeV) DP
68Ge syn 270.8 d ε - 68Ga
70Ge 21.23% 70Ge is stable with 38 neutrons
71Ge syn 11.26 d ε - 71Ga
72Ge 27.66% 72Ge is stable with 40 neutrons
73Ge 7.73% 73Ge is stable with 41 neutrons
74Ge 35.94% 74Ge is stable with 42 neutrons
76Ge 7.44% 1.78×1021 y β-β- - 76Se
References

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

Because few minerals contain it in large amounts, germanium was discovered relatively late despite its high abundance in earth crust. In 1869, Dmitri Mendeleev predicted the existence of germanium and also predicted some of its properties based on its position on his periodic table; he called the element ekasilicon. Nearly two decades later, in 1886, Clemens Winkler found it in the mineral argyrodite, and the experimental observations were found to agree with Mendeleev's predictions.

Germanium, named for the country Germany, is an important semiconductor material used in transistors and various other electronic devices. Germanium is mined primarily from sphalerite, though it is also recovered from silver, lead, and copper ores. Some germanium compounds, such as germanium chloride and germane, can irritate the eyes, skin, lungs, and throat.

Contents

History

Dmitri Mendeleev predicted the existence of germanium in 1869. Dmitri Mendeleev predicted the existence of germanium in 1869. Clemens Winkler was the first to isolate germanium in 1886. Clemens Winkler was the first to isolate germanium in 1886.

In his report on The Periodic Law of the Chemical Elements, in 1869, Dmitri Mendeleev predicted the existence of several unknown elements, including a missing analogue in the silicon group. Because this was supposed to be just below silicon, he called it ekasilicon (Es) and assigned it an atomic weight of 72. Mendeleev studied several minerals, although unsuccessfully, seeking for this new element.

In the summer of 1885, in a mine near Freiberg, Saxony, a new mineral was found. It was named argyrodite, because of its high silver content. Clemens Winkler examined this new mineral and was able to isolate an element similar to antimony in 1886. Before he published his results on the new element Winkler intended to name the element neptunium, as the actual discovery of Neptune in 1846 had been preceded by mathematical prediction of its existence.[b] However, the name Neptunium was already given to an element (though not the element that today bears the name Neptunium, discovered in 1940),[c] and instead, Winkler named the new metal germanium (from the Latin Germania for Germany) in honor of his fatherland. Due to the fact that the new element showed similarities with the elements arsenic and antimony, its place in the periodic table was under discussion, but the similarities between Mendeleev's ekasilicon and germanium confirmed its place. With further material from 500 kg of ore from the mines in Saxony, Winkler could confirm the chemical properties of the new element in 1887. He also determined an atomic weight of 72.32 by analysing pure chloride GeCl4, whilst 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 the fluorides, chlorides, sulfides, germanium dioxide and the first organogermane tetraethylgermanium. With the physical data from these compounds—which corresponded with Mendeleev's predictions— it made the discovery an important confirmation of Mendeleev's idea of element periodicity. Here is a comparison between the prediction and Winkler's data:

Property Ekasilicon Germanium
atomic mass 72 72.59
density (g/cm3) 5.5 5.35
melting point (°C) high 947
color gray gray
oxide type refractory dioxide refractory dioxide
oxide density (g/cm3) 4.7 4.7
oxide activity feebly basic feebly basic
chloride boiling point under 100°C 86°C (GeCl4)
chloride density (g/cm3) 1.9 1.9

Until the late 1930s, germanium was believed to be a poorly conducting metal. It did not become economically significant until after 1945, when its properties as a semiconductor were recognized as being valuable in electronics. It was only during World War II, in 1941, that germanium diodes began to supplant vacuum tubes in electronic devices. Its first major use were the point contact Schottky diodes for radar reception during WWII. The first silicon-germanium alloys were obtained in 1955. Before 1945, only a few hundred kilograms of the element were produced each year, but by the end of the 1950s, annual worldwide production had reached 40 metric tons.

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. Silicon has superior electrical properties, but requires much higher purity—a purity which could not be commercially achieved in the early days.

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

Characteristics

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

Germanium is a semiconductor. Zone refining techniques have led to the production of crystalline germanium for semiconductors that has an impurity of only one part in 1010, making it the element that has been obtained in the highest purity.

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

Simplified electronic structure of germanium Simplified electronic structure of germanium
See also: Category:Germanium compounds

Elemental germanium burns at a red heat,[clarify] is insoluble in hydrochloric acid, but dissolves in aqua regia, and is also soluble in molten alkalis. Germanium occurs mostly in the oxidation state +4. A few compounds are known with the oxidation state of +2, while the oxidation state +3 occurs only in the Ge26+ cation.

Two oxides of germanium are known, the dioxide (GeO2) (germania), being obtained by roasting the sulfide (GeS2), and treatment with nitric acid. It is a white powder, very slightly soluble in water, and possesses acid properties. By heating with a small quantity of magnesium it is converted into germanious oxide (GeO). The dioxide (and the similar compounds Ge2O3 and germanates) exhibits the unusual property of having a high refractive index for visible light, but transparent to infrared light.

Germane is similar to methane. Germane is similar to methane.

By heating the metal with chlorine, germanium tetrachloride (GeCl4 is obtained as a colourless fuming liquid boiling at 83.1°C. It is decomposed by water forming a hydrated germanium dioxide. Germane (GeH4) is a compound similar in structure to methane. Other inorganic germanium compounds have been described, including germanium dichloride (GeCl2), germanium telluride (GeTe), germanium iodides (GeI4 and GeI2), germanium chloroform (GeHCl3), as well as germanates such as bismuth germanate (Bi4Ge3O12).

Upon melting with alkaline carbonates and sulfur, germanium compounds form salts known as thiogermanates. If an excess of a mineral acid is added to a solution of an alkaline thiogermanate, germanium disulfide (GeS2) is obtained as a white precipitate. The disulfide can also be obtained by passing hydrogen sulfide through a solution containing hydrochloric acid and the dioxide. The disulfide is appreciably soluble in water and in solutions of caustic alkalis or alkaline sulphides. By heating the disulfide in a current of hydrogen, the monosulphide (GeS) is formed. This sublimes in thin plates of a dark color and metallic luster, and is soluble in solutions of the caustic alkalis. Germanium salts in general may be identified by the white precipitate disulfide formed in acid solutions, on passing hydrogen sulfide.

Nucleophilic addition with an organogermanium compound Nucleophilic addition with an organogermanium compound

The first organogermanium compound was synthesised by Winkler in 1887; the reaction of germanium tetrachloride with diethylzinc yielded tetraethylgermane (Ge(C2H5)4). Organogermanes of the type R4Ge (with alkyl (R) groups) such as tetramethylgermane (Ge(CH3)4) and tetraethylgermane are accessed through the cheapest available germanium precursor germanium tetrachloride and alkyl nucleophiles. Organic germanium hydrides such as isobutylgermane ((CH3)2CHCH2GeH3) 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).

Isotopes

Main article: Isotopes of germanium

Germanium has five naturally-occurring isotopes, 70Ge, 72Ge, 73Ge, 74Ge, and 76Ge. Of these, 76Ge is very slightly radioactive, decaying by double beta decay with a half-life of 1.58 × 1021 years. 72Ge is the most common isotope, having a natural abundance of approximately 28%. 76Ge is the least common with a natural abundance of approximately 7%.

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

When bombarded with alpha particles, the isotope 72Ge will generate stable 77Se, releasing high energy electrons in the process. Because of this, it is used in combination with radon for nuclear batteries.

Occurrence and production

Rinierite, one of the few germanium-containing minerals Rinierite, one of the few germanium-containing minerals

Natural abundance

Germanium abundance in the Earth's crust is at approximately 1.6 ppm. There are only a few minerals like argyrodite, briartite, germanite, and renierite that contain appreciable amounts of germanium, but no minable deposits exist for either of them. As a result, none is mined because of its germanium content. Some zinc-copper-lead ore bodies contain enough germanium that it can be extracted from the final ore concentrate.

A unusual enrichment process causes an high content of germanium in some coal seams, which was discovered by Victor Mordechai Goldschmidt during a broad survey for germanium deposits. The highest concentration ever found was in the Hartley coal ash with up to 1.6% of Germanium. The coal deposite near Xilinhaote Inner Mongolia contains estimated 1600 t of germanium.

Germanium was observed to be present in the atmosphere of Jupiter, and in some of the most distant stars.

Production

Year Cost
($/g)
1999 1,400
2000 1,250
2001 890
2002 620
2003 380
2004 600
2005 660
2006 880
2007 1240

Worldwide production in 2006 was roughly 100 t of germanium. Currently, it is recovered as a by-product from sphalerite ores where it is concentrated in amounts of up to 0.3%, especially from sediment-hosted, massive Zn–Pb–Cu(–Ba) deposits and carbonate-hosted Zn–Pb deposits. Figures for worldwide Ge reserves are not available, but in the US it is estimated to be around 500 t In 2007 35% of the demand was met by germanium from new scrap recycling.

Mining

It is produced mainly from sphalerite, a zinc ore, but is also found in silver, lead, and copper ores. A source for germanium is fly ash of coal power plants which use coal from certain coal deposits showing a large enrichment in germanium. Russia and China used this as a source for germanium. Russia's deposits are located in the far east of the country on Sakhalin island and in the coal mines northeast of Vladivostok and have been used as a germanium source. The deposits in China are mainly located in the lignite mines near Lincang, Yunnan and coal mines near Xilinhaote, Inner Mongolia and are also used as germanium source.

Recovery process

The ore concentrates are mostly sulfidic, they are converted to the oxides by heating under air, so called roasting.

GeS2 + 3O2 → GeO2 + 2SO2

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

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

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

GeO2 + 4H2 → Ge + 2H2O
GeO2 + C → Ge + CO2

The germanium for the steel production or other industrial processes is normally reduced by carbon.

Applications

A typical single-mode optical fiber, showing diameters of the component layers. Germania is the main constituent of the core part. A typical single-mode optical fiber, showing diameters of the component layers. Germania is the main constituent of the core part.

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

Fiber optics

The most notable physical characteristics of germania (GeO2) are its high index of refraction and its low optical dispersion. These make it especially useful for wide camera lens, microscopy, and for the core part of optical fibers. It also replaced titania as the silica dopant for silica fiber, eliminating the need for subsequent heat treatment, which made the fibers brittle. At the end of 2002 the fiber optics industry accounted for 60% of the annual germanium use in the United States, on a world wide scale this use is application accounts only for less than 10% of the consumption.

Infrared optics

For a long time the major application for germanium was infra-red optics. Unlike most semiconductors, germanium has a small band gap, allowing it to efficiently respond to infrared light. It is therefore used in infrared spectroscopes and other optical equipment which require extremely sensitive infrared detectors. Its dioxide's index of refraction and dispersion properties make germanium useful in wide-angle camera lenses and in microscope objective lenses.

The characteristic of being transparent in the infrared makes germanium a very important infra-red optical material, that can be readily cut and polished into lenses and windows. It is especially used as the front optic in thermal imaging cameras working in the 8 to 14 micron wavelength range for passive thermal imaging and for hot-spot detection in military, night vision system in cars and fire fighting applications.

Polymerization catalyst

A PET soft drink bottle A PET soft drink bottle

Germanium dioxide is also used as a polymerisation catalyst for the production of polyethylene terephthalate. The high brilliance of the produced polyester is especially used for PET bottles marketed in Japan.

Electronics

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. Vintage effects pedals known to contain germanium transistors have shown marked increases in collector value for this reason alone.

The alloy silicon germanide (commonly referred to as "silicon-germanium", or SiGe) is rapidly becoming an important semiconductor material, for use in high speed integrated circuits. Circuits utilizing the properties of Si-SiGe junctions can be much faster than those using silicon alone. Silicon-germanide is beginning to replace gallium arsenide (GaAs) in wireless communications devices. The SiGe chips, with high-speed properties, can be made with low-cost, well-established production techniques of the silicon chip industry.

The recent rise in energy cost has improved the economics of solar panels, a potential major new use of germanium. Germanium is the substrate of the wafers for high-efficiency multijunction photovoltaic cells for space applications (Note: Germanium and gallium arsenide have very similar lattice constants and so germanium substrates can be used to make gallium arsenide solar cells.) The Mars Exploration Rovers and several satellites use triplejunction gallium arsenide on germanium cells.

Germanium-on-insulator substrates are seen as a potential replacement for silicon on miniaturized chips. Uses in phosphors in fluorescent lamps, and germanium-base solid-state light-emitting diodes (LEDs).

Other uses

In recent years germanium has seen increasing use in precious metal alloys. In sterling silver alloys, for instance, it has been found to reduce firescale, increase tarnish resistance, and increase the alloy's response to precipitation hardening. A tarnish-proof sterling silver alloy, trademarked Argentium, requires 1.2% germanium. The material has a very high refractive index (4.0) and so needs to be anti-reflection coated. Particularly, a very hard special antireflection coating of diamond-like carbon (DLC), refractive index 2.0, is a good match and produces a diamond-hard surface that can withstand much environmental rough treatment.

High purity germanium single crystal detectors can precisely identify radiation sources—for example in airport security. Germanium is useful for single crystal neutron or synchrotron X-ray monochromator for beamlines. 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.

Certain compounds of germanium have low toxicity to mammals, but have toxic effects against certain bacteria. This property makes these compounds useful as chemotherapeutic agents.

Due to the similarity between SiO2 and GeO2 silica (SiO2) the stationary phase in some gas chromatography columns can be replaced by GeO2.

Precautions

As early as 1922, doctors in the United States used the inorganic form of germanium to treat patients with anemia. It was used in other forms of treatments, but its efficiency has been dubious. Its role in cancer treatments has been debated. FDA research has concluded that germanium, when used as a nutritional supplement, "presents potential human health hazard".

Germanium is not thought to be essential to the health of plants or animals. Some of its compounds present a hazard to human health, however. For example, germanium chloride and germane (GeH4) are a liquid and gas, respectively, that can be very irritating to the eyes, skin, lungs, and throat. Germanium has little or no effect upon the environment because it usually occurs only as a trace element in ores and carbonaceous materials and is used in very small quantities in commercial applications.

Notes

  1. ^  Just as the existence of the new element was predicted, the existence of the planet was predicted in 1845 by the mathematicians John Couch Adams and Urbain Leverrier for the fact that Uranus was being pulled slightly out of position in its orbit. James Challis started searching for it in July 1846 and sighted the planet 23 September 1846.
  2. ^  R. Hermann published in 1877 claims of the discovery of a new element beneath tantalum, which he named neptunium. but this was later regarded as some mixture of niobium and tantalum. The name neptunium was eventually given to the synthetic element past uranium discovered in 1940.

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