GALLIUM SELENIDE ETCHANTS

GASE-0001
ETCH NAME: TIME:
TYPE: Mechanical, dislocation TEMP: RT
COMPOSITION:
x .... cleave
DISCUSSION:
GaSe, (0001) wafers cleaved and used in a study of dislocations. Authors say the material
can be either hexagonal-normal or hexagonal-rhombohedra1 in structure as an interlayered
atomic structure with the gallium layer showing weak van der Waal bonds. Cleaving will
create dislocations in the surface, and E-beam annealing is sufficient to create further defects
and dislocations. (Note: Single crystal cleaved surfaces normally show fine micro-structure
on surfaces as ledges, as well as other defects and dislocations. See general section on
(galena) lead sulfide, PbS with regard to such ledge-type surfaces.)
REF: Bainski, Z S et a1 - J Appl Phys, 34,469(1963)

GARNETS, M,M,(SiO,),
General: The general formula shown is for all natural garnets. There are only ten major
species of natural garnets, but several form isomorphous series or can have replacement
elements such that there are a large number of varieties or subspecies, many with individual
names to differentiate color or location occurrence. All garnets are found in the atypical
dodecahedron, (1 10) crystal form, though they may occur as a trapezohedron, (21 1) in
combination with the hexoctahedron, (321) - garnets being one of the few natural minerals
that occur with (321) type facets.
There are three prominent groups: (1) aluminum garnet; (2) iron garnet, and (3) chromium
garnet. Hardness ranges from H = 6.5-7.5 and specific gravity (density) varies between
G = 3.15-4.3 g/cm3. When a garnet is fused, it can both reduce in density and break
down into other minerals with loss of one or more constituent elements.
Garnets are usually an accessory, rock-making mineral with common occurrence in
certain rock types, such as chlorites, gneisses, or shists. Garnet is occasionally found in
massive beds, but more commonly as individual single crystals, sometimes hundreds of
small, deep red crystals (almandite, the iron garnet) in green chlorite beds, along with fine,
small octahedrons of coal black magnetite, Fe,O,.
There is one special form, not common to other minerals, called a "sand garnet", where
the crystal still retains its dodecahedra1 shape, but has been partly converted by compacted
sand grains, with only a small central core of pure garnet. Some sand garnets are 1 to 2 in.
in size. Such conversion is largely due to the low fusibility [(F = 3), 1200°C] of most
garnets and, under pressure and heat, many garnets are squeezed with elongation in the c-
axis direction, such that they are near-tabular in form.
Garnets have little use in metal processing except as lapping and polishing abrasives.
They have been used as precious and semiprecious gem stones since ancient times for their
range of colors and natural, highly reflective exterior facets. Some of the finest gem stones
still come from Southern Asia, the Malay Peninsula, and India. The deep red pyrope garnet
is top gem quality, but there are others that, depending upon color, also may be gem quality.
Cinnamon-stone (Glossularite) is noted for that color, yet may be white, pale green, amber,
honey-yellow, wine-yellow, rose-red, to emerald green. Spessartite is hyacinth-red to violet;
andradite, called common garnet, is most often deep red-black, yet can vary in color like
glossularite. Uvarovite, the chrome garnet, is a fine emerald green and, when it contains
lithium, called the lithium garnet, and is a fine violet color.
As a group, the garnets have a wider range of types, varieties, and subspecies than any
other single class of minerals.

© 1991 by CRC Press LLC

502 CRC Handbook of Metal Etchants

Technical Application: Natural garnets have had little use in Solid State processing other
than as lapping and polishing abrasives, but there are an increasing number of applications
for artificially developed and grown garnets.
The yttrium iron and yttrium aluminum garnet, YIG and YAG, respectively, were two
of the first Solid State laser and masar materials, the laser being more prominent. Note that
there are some natural garnets containing yttrium as a replacement element. Where the
natural garnet formula is shown as: M,M,(SiO,),, the artificial formula without silicon is
shown as: M,M,O,, or A,B,C,O,, and there are some special mixtures where M, and M,
contain two or more elements.
Where natural garnets are noted for their brilliant colors, the artificial garnets are usually
transparent, to slightly yellow-tan in color, and are available as oriented single crystal blanks
up to 3" in diameter.
The artificial garnets have light transmission and frequency characteristics similar to
those of quartz, and are used in a like manner as filter elements in microelectronic circuitry,
such as GGG garnets. An important application of iron containing garnets, such as YIG,
are in the fabrication of bubble memory computer devices with as much as a one million
bit capability.
Artificial garnets, when grown by molten flux methods, form as the atypical dodeca-
hedron, (110), but are limited in size to about 1". They also tend to be contaminated by
extraneous elements from the growth flux, such that repeatability control is difficult for
consistency in device fabrication. But, like in the growth of semiconductor materials, they
are now grown by the Czochralski (CZ) method as ingots up to 5 and 6" in diameter, and
also are grown by modified Czochralski, or Float Zone (FZ). Such ingots are most commonly
grown as (100) oriented, sliced, and used with that orientation.
Where garnet is used as an abrasive powder, the W-1 to W-12 types are widely used
in semiconductor wafer processing. The W-5 (15 pm) is a common "as received" lap finish.
The garnet particles are relatively soft (H = 6), tend to break down under lapping pressure,
such that a 600 grit abrasive may give a final finish closer to 400 grit.
Natural garnets have been the subject of much study for centuries, particularly in the
jewelry trade and today new artificial garnets are under development for a wide range of
applications.
Etching: H,PO,, HCl, halogens, variable with type garnet.

The following are the garnets discussed and presented in this section:

Boron Germanium, BGO

Calcium Aluminum Germanium, CAGG
Europium Scandium Iron, ESG
Gadolinium Gallium, GGG
Gadolinium Selenium Gallium, GSGG
Manganese Zinc Yttrium, MZYG
Natural Garnets, GAR
Strontium Gallium, SGG
Yttrium Aluminum, YAG
Yttrium Gallium, YGG
Yttrium Iron, YIG

© 1991 by CRC Press LLC

510 CRC Handbook of Metal Etchants

GERMANIUM, Ge
General: Does not occur in nature as a native element. It is a trace element in several
minerals, notably the iron pyrites, and is collected from flue dust during processing of pyrites
for the iron and sulfur content. Pyrite, FeS,, is a major source of iron ore, and representative
of the pyrite group as a class of minerals.
There are two known minerals containing germanium: argyrodite, 4Ag2S.GeS2 and
germanite, Cu,(Fe,Ge)S,. Neither mineral occurs in large quantity, but they are associated
with the pyrites which represent about 85% of the iron ore mined.
Germanium has had little or no use as a metal in industry until discovery of its semi-
conducting properties in the mid-1940s.
Technical Application: Germanium was the original semiconductor developed as a wire
point contact alloyed diode in the latter part of the 1940s and, by the early 1950s both
germanium and silicon, the two elemental semiconductors, had established the semiconductor
industry. It is now considered part of the Solid State industry, which includes electronics,
quartz crystals, and other allied technologies. Although silicon has become the primary
semiconductor, due to its more useful physical and electronic characteristics, germanium is
still fabricated as discrete alloyed or diffused devices, and is under development as a con-
stituent in thin film epitaxy, layered devices that contain other compound semiconductors
and materials, such as the heterostructure or heterojunction devices.
Both wafers and thin film epitaxy layers of germanium have been used in fabrication
of a variety of devices: tunnel diodes, low and high power diodes, varactor diodes, high
frequency transistors, solar cells and photodiodes-as a rod or barrel shaped unit, as a
lithium-drift alpha-particle radiation detector.
Evaporated germanium has been used in conjunction with photo resist lacquers or alone
as an etching and metallization mask on silicon and gallium arsenide. Although germanium
oxide, Ge203,has been grown and used as a surface protectant, it is not as stable and acid
resistant as silicon dioxide, SiO,. The same applies to germanium nitride, Ge3N, vs. silicon
nitride, Si,N,, though both the pure nitrides and oxynitrides have been studied, and they
form an isomorphous series between the two metals as both oxides and nitrides.
Germanium was initially grown as a single crystal ingot using the Bridgman method,
now called Horizontal Bridgman (HB). This produces a half-moon-shaped ingot and, as cut
wafers, are recognized by that shape. The method is still used for germanium and other
materials, such as compound semiconductors, but has a size limitation of about 2-3" square
area. For this reason, most semiconductor ingots are now grown by the Czochralski (CZ)
or Float Zone (FZ) methods with ingouwafer diameters a standard 3", and approaching
5-47"' Single crystal germanium has been the subject of much study, and is still under
development and study. Germanium/silicon single crystal ingots of varying proportional
concentrations have been grown and studied. It also is deposited as single crystal thin film
epitaxy; as polycrystalline layers, poly-Ge; as amorphous layers, a-Ge, which may be hy-
drogenated as a-Ge:H.
Etching: Soluble in hot H2S04, but no other single acids. Mixed acids: HF:HNO,;
HF:H,O, . . . with or without H,O, HAc, or other additives, alkali + halogen; halogens,
DCE ionized gases.

SELECTION GUIDE: Ge
(1) Br,:MeOH:
(i) Polish: GE-0038
(2) HF:
(i) Cleaning: GE-0064: -0126; -0284

© 1991 by CRC Press LLC