OVERVIEW _

Extracting and Refining Germanium

James E. Hoffmann

INTRODUCTION
Germanium products are well suited Feeds to the germanium conversion reaction usually arise from the treatment
for many advanced materials appli- of various smelter fumes in which germanium is present as the volatile compound
cations-lens blanks for infrared op- germanium monosulfide. Frequently, these fumes are refumed under reducing
tics, dioxide for electronic and catalyst conditions to produce a richer germanium-bearing concentrate. This concentrate
use, "intrinsic" metal for radiation de- is leached with sulfuric acid to dissolve the germanium values, and the germa-
tectors, and electronic grade tetrachlo- nium is recovered from this solution by tannin precipitation. After conversion to
ride for optical fibers. Before the oxide by ashing, a concentrate containing from 5-20% germanium, as ger-
undertaking these applications, how- manium dioxide, is produced. This concentrate is the feed to the conversion re-
ever, the germanium must first be action.
recovered. This article reviews the ger- The conversion reactions by which germanium in the feed-as either germa-
manium extraction and refining tech- nium dioxide or germanium sulfide-is converted to the crude germanium tet-
niques of the late 1950's and early 60's, rachloride via aqueous chemistry shown in Reactions 1 and 2:
as practiced by American Metal Cli-
GeS + 5Cl 2 + 4H 20 = GeCI. + H 2SO. + 6HCl (1)
max (now AMAX), and compares the
practices with the more recent devel- Ge0 2 + 4HCl = GeCI. + 2H 20 (2)
opments presented in current techni- The process considerations for these reactions include an acidity of 5.5-7.8 M
cal literature. Overall, there have been HCl; water formation; heating cycle; and chlorine environment. In performing
no major changes in the process chem- the conversion of germanium monosulfide to germanium tetrachloride, the oxi-
istry of germanium extraction and re- dation of the sulfide to sulfate must occur prior to distillation of the tetrachloride.
fining in the period surveyed. Otherwise, hydrogen sulfide may pass into the germanium tetrachloride product.
Significant changes have, however, Normally, the germanium present in the feed is in the form of germanium
taken place in the engineering of dioxide. This is readily converted to the tetrachloride by Reaction 2. Proper hy-
process plants for producing semicon- drochloric acid concentration and a chlorine environment are critical for effective
ductor grade germanium. The use of conversion of the oxide to the tetrachloride. Below an acidity of about 5.5 molar
zone refining for final purification of hydrochloric acid, virtually all the germanium is in the form of the oxide. At 7.8
germanium metal to semiconductor molar hydrochloric acid, all of the germanium is in the form of tetrachloride.
grade is still required and will prob- Dilution effects due to water formation during conversion must be considered in
ably continue for some time. Finally, computing acid requirements.
considerably more thermodynamic data To avoid the loss of anhydrous HCI from the concentrated (12N) acid used in
is available for predicting the optimal the conversion, it is important that Reaction 2 be initiated at a rather low tem-
germanium recovery conditions from perature (50 CC).
Once germanium tetrachloride is formed, the reaction temper-
smelter fumes than existed twenty years ature may be gradually increased to the boiling point of germanium tetrachloride.
ago. As a result, less experimental work Since the boiling point of germanium tetrachloride is less than that of 7.8 molar
should be required to optimize recov- hydrochloric acid, germanium tetrachloride may be distilled, leaving behind suf-
ery. ficient acid to prevent hydrolysis of residual germanium tetrachloride.
To prevent the co-distillation of volatile arsenic trichloride, chlorine is used to
convert the soluble arsenic to the pentavalent state from which it hydrolyzes to
the non-volatile compound, arsenic acid! (Figure 1).

CRUDE TETRACHLORIDE PURIFICATION

Figure 1 shows a schematic of the purification columns and the chemistry for
arsenic removal. The three commercial purification columns, made of pyrex R®,
are approximately 12 feet high, four inches in diameter, and packed with one
half-inch pyrex helices.
In operation, germanium tetrachloride, along with chlorine gas, is fed into the
top bottom third of the column. The germanium tetrachloride is volatilized and
ascends up the column against a countercurrent descending stream of seven
molar hydrochloric acid saturated with chlorine gas", The germanium tetrachlo-
ride distillate condenses on leaving and is revaporized prior to being introduced
into the next column. Three columns in series are employed. The volumetric ratio
of hydrochloric acid to germanium tetrachloride as liquids is approximately three
to one. The hydrochloric acid "bottoms" are cooled and pumped up into the res-
ervoir above the next column. The final bottoms are sent to general process
solutions storage.
These columns have shown themselves to be extremely effective purification
devices. Non-volatile impurities in the feed are rapidly washed out ofthe column
by the descending flow of hydrochloric acid. Slightly volatile impurities pass into
the hydrochloric acid layer and are carried out. Highly volatile constituents leave
the system with the chlorine gas. The columns operate with a liquid germanium
Czochralski-grown germanium crystals by tetrachloride vapor feed. Adiabatic operation minimizes thermal stresses in the
Metallurgie Hoboken-Overpelt. glass column walls, thus extending theirIife. Column throughput is limited by

42 JOURNAL OF METALS. June 1987

 Figure 1. The germanium tetrachloride pu-
rification column.
HCI
From Previous Stage
r CI2Gas
CI2 To Scrubber
L ..---:--.
HCI
Reservoir
CI2 Gas
GeCI2Vapor

r
GeCI4
Liquid

To Next GeCI4
Stage Reservoir
Crude r: GeCI4Feed
CI2 GaS

HCI
Heservolr
_ .......I'I;~, J'I,,.;.H.;.;C.;.;I...;T...;o..;.;Next Stage
Arensic Removal
As CI3 + CI2 ~ AsCls
As Cis + 4H20 ~ H3As04 + SHCI

vapor velocity. Despite the fact that this technology is 2D years old, it still appears
competent by today's standards.
Germanium tetrachloride vapor condensing from the last purification stage
does so in an atmosphere of chlorine gas and is substantially saturated with it.
Germanium tetrachloride, when saturated with chlorine, is a deep orange color.
When free of chlorine, it is clear. Chlorine is removed by refluxing the germa-
nium tetrachloride until the condensing vapors become clear at which point they
are swept with nitrogen gas to remove the last traces of chlorine.

PRODUCTION OF GERMANIUM DIOXIDE

Production of germanium dioxide from the tetrachloride involves hydrolysis of
germaniumtetrachloride to germanium dioxide, followed by filtration, washing,
drying, and calcination. The hydrolysis reactions are:
GeCl 4 + 4H 20 = H.Ge0 4 + 4HCI (3)
H 4Ge04 = Ge0 2 + 2H 20 (4)
In considering the hydrolysis reactions, it is important to remember that hy-
drolysis ceases at an acidity of approximately 7.8 M HCI. In 5.5 M HCI, soluble
germanium is present as germanic acid. In practice, a ratio of three grams of
water per gram of germanium tetrachloride yields a germanium dioxide recovery
of approximately 95% with the balance reporting as soluble germanic acid. To
achieve an acceptable bulk density, a minimum of 1.25 gms/cc, the rate of ger-
manium tetrachloride introduction, the reaction temperature, and the presence
of nucleation centers, has to be properly controlled". By operating at DOC and
allowing a small amount of material to precipitate and act as nucleation centers,
prior to introducing the bulk of the tetrachloride, both high yield and acceptable
bulk density can be achieved-,
Germanium dioxide is suction filtered on high purity polyvinyl chloride buch-
ner funnels. The hydrolysis step is the only process in which the + product is
exposed to plastics. However, since there is no recycle of the wash waters, con-
tamination is not a problem. Process water for hydrolysis, filtration and washing
is 15 megohm purity. Filtrates and all wash waters are consolidated and sent to

JOURNAL OF METALS. June 1987 43

 GERMANIUM COMPOUNDS
Table I briefly reviews the major Germanium dioxide (Geo.,J is in- purification is best accomplished by
germanium compounds involved in the variably the compound [rorn which extractive distillation.
extraction and refining of the element. germanium metal is ultimately pro- Finally, germanium's melting point
T he high volatility of germanium duced by hydrogen red uction. (95SOC)-well above the temperatu re
monosulfide (GeS ) makes it possible to With a boiling point of 83.rc and at which germanium monoxide sub-
separate the compound from smelter immiscibility in aqueous hydrochloric limes-requires that reduction be
fume by subliming. However. the vol- acid. germanium tetrachloride (GeCl,) complete prior to melting.
atility of arsenious sulfide and. to a
Table I. German ium Compounds of Major Interest
lesser extent, lead sulfide are such that
the germanium-bea ring fume also GeS GeO GeO . Gee). Ge
contains these compounds. Atomic Weight 104.7 88.6 104.6 214.4 72.6
The volatility of germanium mon- Melting Point (eCl Sublimes Sublimes 1115 - 49.5 958
oxide (Ge O) restricts its reduction Boiling Point (eCl 430" 710* 83. 1 2700
temperature and. therefore. the rate of Specific Gra vity 3.3-4.0 4.70 1.86 5.35
germanium dioxide reduction to metal. "Sublima tio n Temperature

germanium recovery. Initial drying of the germanium dioxide is done at 100°C

and is followed by calcination at 300-400°C.

REDUCTION OF GERMANIUM DIOXIDE

The reactions for reducing germanium dioxide to germanium metal are:
Ge0 2 + H 2 = GeO + H 20 (5)
GeO + H 2 = Ge + H 20 (6)
The first step involves reducing germanium dioxide to the monoxide compound
while the second step reduces the monoxide to the metal. Because the germanium
monoxide intermediate sublimes at about 700°C, the process is constrained to a
rather low reduction temperature until substantially all of the germanium diox-
ide is reduced to metal". Because germanium is costly, operation at a low tem-
perature is mandated to ensure virtually 100% recovery. Although thermodynamic
considerations suggest modest hydrogen requirements, actual consumption is
high. The Ge0 2 is charged into a rectangular, high-walled graphite boat, within
a furnace controlled at a temperature of 650°C. Reduction in the boat requires
5-8 hours. At the end of the reduction period, the graphite boat still containing
the charge is moved to a hotter part of the furnace, and the temperature is taken
up to approximately 1000°C, causing the germanium to melt to a substantially
oxygen-free metal. Hydrogen enters through a fitting on one end of the high
purity graphite boat and the reduction products leave via a fitting at the other
side. This design enhances hydrogen diffusion into the charge, improving reduc-
tion time. Germanium recovery is usually between 98 and 99%.

PREMELTING AND ZONE REFINING

The final steps in the production of intrinsic semiconductor grade germanium
are premelting and zone refining. Premelting takes the germanium reduction
bars and, in effect, casts them to final customer shape, prior to zone refining, by
remelting in a resistance heated furnace under a reducing atmosphere. Six zone
refining passes are subsequently required to achieve acceptable purity",
After zone refining, the bars are pickled in CP-4, an acidic etchant, lapped or
slightly ground to provide a surface for electrical measurement, and subjected to
resistivity measurements using the two-point probe method. In the period sur-
veyed, the resistivity requirement for poly-crystalline, intrinsic, semiconductor
grade germanium was 40 ohm centimeters.

SOLUTION TREATMENT AND RECOVERY

Only half the hydrochloric acid present in commercial 12 molar hydrochloric
acid is available for conversion. The balance is required to maintain an acidity
high enough to prevent hydrolysis. Further, since hydrochloric acid forms an
azeotrope around six molar, there is no simple way to reconcentrate it. Vapori-
zation and delivery of anhydrous HCI gas would, however, allow the six molar
hydrochloric acid in the reactor to be reconstituted and used several times over.
This procedure would also allow the use of the azeotropic acid coming from the
bottom of the purification towers as feed to the germanium dioxide conversion
step.
Germanium recovery from process solutions is a rather expensive operation.
A photomicrograph of a typical germanium The process solutions include spent conversion liquors, acid from the purification
oxide grain. Germanium oxide is the batryoi- towers, and sump liquors-both alkaline and acidic-from scrubbers used to treat
dal multi-lobed grain in the center. Figure all vented gases. Germanium present .in etching solutions must be treated sep-
courtesy of the U.S. Bureau of Mines. arately due to the presence of fluorides. After compositing, the germanium con-

44 JOURNAL OF METALS. June 1987

tent of the solutions is precipitated either as slimy, voluminous calcium germanate
from a strongly alkaline solution, or, preferably, as a granular insoluble mag-
nesium germanate precipitable at a lower pH. In general, precipitation aims to
produce the preponderant fraction of the soluble germanium as germanium diox-
ide since this reduces acid consumption during conversion.

TECHNOLOGY UPDATE
With respect to converting crude oxides to germanium tetrachloride, studies
show that the kinetics of germanium tetrachloride distillation from process so-
lutions are improved by using a carrier gas such as air, nitrogen, or chlorine",
However, the greater gas volumes increase germanium loss because the dew
point of germanium tetrachloride in the gas is depressed. Undoubtedly, there is
some economical balance between the distillation rate and germanium loss. The
presence of ferric chloride in the solutions increases the viscosity of the solution
and reduces the distillation rate.
With respect to purification, the use of hydrogen peroxide" rather than chlorine
gas is suggested as an oxidant for trivalent arsenic. Generally, the use of ex-
tractive distillation with a flooded column for purification, a process substantially
identical with that used in the AMAX continuous process is described.
Other recent studies also feature some discussion of zone refining germanium
tetrachloride (melting point: -48.5°C)9. The speed at which the molten zones of
germanium tetrachloride traverses the frozen bar appears to be significantly
lower than those achieved while zone refining the metal. This may be attribut-
able to reduced diffusion rates at the low temperatures. This method may be
applicable for removing some impurities. In any case, however, the reduced metal
will probably have to be zone refined.
The use of hydrazine or hydroxylamine for reducing soluble chlorine has been
suggested for the removal of soluble chlorine from germanium tetrachloride".
Hydrolysis studies were performed using radioactive chlorine tracers to find out
whether the chlorine remaining in the final product came from unreacted tet-
rachloride or from the hydrochloric acid solution. As it turns out, it comes from
both".
References to the hydrolysis of germanium tetrachloride mention the need for
careful temperature control and the use of seeding through recycling of the oxide
precipitate".
With respect to reducing the oxide, a recent Japanese patent describes a two-
zone furnace. Its operation bears some similarity to the old AMAX procedure.
Since the volatility of germanium monoxide has not changed, reduction temper-
atures are still substantially the same as before". Some research has been done
on using carbon-carbon monoxide as reductants. At temperatures at which ef-
fective reduction occurs, however, most of the product is a volatile monoxide.
This is obviously the case since, had the reduction occurred at a low temperature,
the carbon boats used in the reduction would have been destroyed. In practice,
they are generally free of attack.
A technique for germanium recovery from process solutions suggests absorb-
tion onto an ion exchange resin, followed by eluting with concentrated hydro-
chloric acid to directly generate germanium tetrachloride. The germanium
tetrachloride is recovered from the eluant by solvent extraction of kerosene'",
This is an intriguing concept since it would allow the direct recovery of germa-
nium tetrachloride, eliminating the cost of neutralizing the process solutions as
well as the subsequent conversion process. Obviously, this concept warrants fur-
ther investigation.
References
1. u.s. Patent 2,811,418.
2. U.S. Patent 3,102,786. ABOUT THE AUTHOR • • • • •_
3. Ref Zh., Khim, 1971, Abstract No. 3B975.
4. Ref Zh., Khim, 1970, Abstract No. 16L162. James E. Hoffmann received his M.S. in
5. Japan Kokai 7493215. chemical engineering from NJIT. He is cur-
6. Met., ABM (Assoc. Brasil Matais), 23 (1967), pp. 825-828.
7. Khim., Tekhnol. Respub. Meshuedam. Nauch-Tekh. Sub., 2 (1965), pp. 78-82. rently a principal in the consulting firm of Jan
8. U.S.S.R. 508,478. H. Reimers and Associates USA Inc. Mr.
9. Mater. Vses. Soueshch. Metod. Poluch. Osobo Chist. Veshchestu, 1965 (pub. 1967), pp. 135-144. Hoffmann is also a member of TMS.
10. Czech. 137,346.
11. See Reference 4.
12. Uhr. Khim. Zh., 38 (2) (1972), pp. 215-218. If you want more information on this subject,
13. Tr. Vses. Nauch-Issled Inst. Miner. Syr'ya, No. 23 (1972), pp. 86-90. please circle reader service card number 59.

JOURNAL OF METALS. June 1987 45