756 CRC Handbook of Metal Etchants

crystal structures even though the mineral appears to be only one form and yellow-orange
in color. The mineral plattnerite, PbO2, is the dioxide form.
In chemical processing, lead can be converted to litharge by heating in air above 600°C,
as can all other oxides of lead. Litharge has major use in the glass and pottery industries in
the making of flint glass (also called lead glass), and as a coloring agent in pottery glaze.
When mixed with glycerin it sets as a hard cement, and has been used as a two-part, colored
glue. "Red lead", a lead plumbate, Pb2Pb04, is the form used in flint glass, and the red-
orange undercoat on iron and steel for fencing and building construction as it is both stable
and inert under normal atmospheric conditions so it protects metals against weathering effects.
Because the lead-ion, Pb+ + , is poisonous, lead piping for drinking water (soft water),
lead paints, and leaded gasolines are being replaced due to the health hazard. Lead hydroxide,
Pb(OH)3, is the culprit, as it is fairly soluble in soft water and builds up in water piping.
Technical Application: Lead oxide is a IV—VI compound semiconductor with tetragonal
system structure rather than isometric-tetragonal, as are several other compound semicon
ductors. It has the typical (111) polarity of these compounds, such that wafers are normally
cut with the (100) orientation for device processing.
It has limited use as a semiconductor, in part due to its softness (H = 2—3, vs. H =
6—7 for most semiconductor materials). It has been grown as a single crystal ingot and as
single crystal platelets under pressure with two crystal structures depending upon pressure:
under 2200 psi, tetragonal; over 30,000 psi, orthorhombic, respectively, red-orange and
yellow-green in color. It has been grown as a single crystal epitaxy thin film and fabricated
as photoconductors.
Etching: Litharge is soluble in HNO3, alkalies and several chloride salts. Massicot is
soluble in alkalies.

LEAD OXIDE ETCHANTS

PBO-0001
ETCH NAME: TIME:
TYPE: Acid, removal TEMP:
COMPOSITION:
1 .... HAc
1 .... H2O2
DISCUSSION:
Pb specimens and single crystal ingots. Solution is a general cleaner and etchant for
lead and for removal of lead oxide.
REF: Snowden, K V — Phil Mag, 6,321(1961)

PBO-0002
ETCH NAME: TIME:
TYPE: Knife, cleave clean TEMP: RT
COMPOSITION:
x .... knife cut
DISCUSSION:
PbO single crystal plates grown at 400°C under pressure: (1) at less than 2200 psi,
structure is tetragonal and orange-red in color; (2) at greater than 30,000 psi structure is
orthorhombic and color is yellow-green. Grown in a quartz ampoule in an autoclave with
a slurry of NaOH 4- PbO — crystal platelets grow on ampoule sides. When the orthorhombic
form is cleaved with a scalpel some areas of specimen surfaces were converted to tetragonal.
REF: Keezer, R C et al — J Appl Phys, 39,2062(1968)

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PBO-0003
ETCH NAME: TIME:
TYPE: Acid, oxide removal TEMP:
COMPOSITION:
x .... HAc
x .... H2O2
DISCUSSION:
PbO, native oxide removed from lead. Solution used in cleaning lead telluride, PbTe2,
surfaces.
REF: Sato, Y et al — Jpn J Appl Phys, 2,688(1963)

PHYSICAL PROPERTIES OF LEAD NITRATE, Pb(NO3)2

Classification Nitrate
Atomic numbers 82, 7 & 8
Atomic weight 331.23
Melting point (°C) 470
Boiling point (°C)
Density (g/cm3)
Refractive index (n =) 1.782
Hardness (Mohs — scratch) 4—5
Crystal structure (isometric — normal) alpha (100) cube
(monoclinic — normal) beta (100) a-pinacoid
Color (solid) Colorless
Cleavage (octahedral/cubic) (lll)/(001)

LEAD NITRATE, Pb(NO3)2

General: Does not occur as a natural compound although some nitrate fertilizers may
be artificially compounded to contain trace lead. No present use in the metal industries, but
has chemical and medical applications.
Technical Application: The material has no use in Solid State device development, but
has been grown from solution in a structural study, and the effects of irradiation on the
development of NO3" and other radicals. Similar irradiation effects with development of
F~ centers have been done on fluorite, CaF2, natural crystals, and other transparent crystals,
e.g., NaCl, KC1, etc. as ionic and alkaline crystals.
Etching: Water, alcohols.

LEAD NITRATE ETCHANTS

PBNO-0001
ETCH NAME: Water TIME:
TYPE: Solvent, polish TEMP: RT
COMPOSITION:
(l)x .... H2Oor (2)x .... EOH
DISCUSSION.
Pb(NO3)2 grown as single crystals by slow cooling from a water solution. Crystals were
triangular with a (111) base, and were cubic space group T6n with trigonal axes. Crystals
were studied after irradiation to develop for NO3~, NO2~, and O3~ centers. Solutions shown
used to polish specimens prior to irradiation.
REF: Tagaya, K & Kitagawa, U — JpnJ Appl Phys, 23,116(1984)

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758 CRC Handbook of Metal Etchants

PHYSICAL PROPERTIES OF LEAD SELENIDE, PbSe

Classification Selenide
Atomic numbers 82 & 34
Atomic weight 286.15
Melting point (°C) 1065
Boiling point (°C)
Density (g/cm3) 7.6—8.8
Hardness (Mohs — scratch) 2—3
Crystal structure (isometric — normal) (100) cube
Color (solid) Lead-grey/bluish
Cleavage (cubic) (001)

LEAD SELENIDE, PbSe

General: Occurs as the natural mineral clausthalite, PbSe, which may contain traces of
both mercury and platinum. It looks much like galena, PbS, though with a slightly more
bluish cast of color. It is found in small quantities associated with hematite, Fe2O3, a primary
iron ore, and there are several additional minerals with individual names that contain claus
thalite as part of mixed crystals. Due to scarcity, it has no major use in industry other than
as a minor ore of selenium and lead.
Technical Application: The material is a IV—VI compound semiconductor with the
sphalerite, ZnS, atypical isometric-tetragonal structure. It is a polar compound with (11 l)Pb
and (TTT)Se wafer surfaces and, because of the difference in etching characteristics of (111)
polar surfaces, is normally used with the (100) surface orientation to obviate the polarity
effect. As with several of the compound semiconductors, it was originally grown by the
Horizontal Bridgman (HB) technique as a single crystal but now is more commonly grown
by the Czochralski (CZ) method. Vapor Phase Epitaxy (VPE) has been used to grow single
crystal thin films.
It has the same softness problem (H = 2—3) as does lead oxide, PbO, so has not been
widely used as a semiconductor ingot-grown product, though epitaxy thin films have been
used to fabricate laser devices. Note that selenium and several of its salts are poisonous.
Etching: Easily soluble in halogens and HNO3. Electrolytically with alkalies.

LEAD SELENIDE ETCHANTS

PBSE-OOOla
ETCH NAME: Nitric acid TIME:
TYPE: Acid, removal TEMP:
COMPOSITION: RATE: 0.37 mg/min
x .... HNO3
DISCUSSION:
PbSe, (100) wafers and other orientations. Author calls solution an immersion etch for
PbSe, PbTe, and PbS.
REF: Swets, D E — J Electrochem Soc, 131,172(1984)

PBSE-OOOlb
ETCH NAME: Hydrogen bromide TIME: 3 min
TYPE: Halogen, polish TEMP: RT
COMPOSITION:
x .... HBr

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DISCUSSION:
PbSe, (100) wafers and other orientations. Used as an immersion polish etch on PbSe,
PbTe, and PbS. Also used as a jet/spray etch from a squirt bottle followed with water jet/
spray quenching.
REF: Ibid.

PBSE-OOOlc
ETCH NAME: Hydrogen bromide, dilute TIME:
TYPE: Electrolytic, polish TEMP:
COMPOSITION: ANODE: PbSe
1 .... HBr CATHODE:
3 .... H2O POWER: 20 mA/cm2
50—100 mV
RATE: 0.2 p,m/min
DISCUSSION:
PbSe, (100) wafers and other orientations. Solution used to electropolish both PbSe and
PbS. Leaves a yellow film on the surface that can be removed with a dip in nitric acid.
REF: Ibid.

PBSE-0002
ETCH NAME: TIME:
TYPE: Electrolytic, polish/thin TEMP:
COMPOSITION: ANODE: PbSe
5 .... 45% KOH CATHODE:
1 .... H2O2 POWER:
5 .... ethylene glycol (EG)
DISCUSSION:
PbSe, (100) wafers used in a study of dislocations and structure. Solution used to thin
specimens for TEM study.
REF: Abrams, H & Tauber, R N — J Electrochem Soc, 116,103(1969)
PBSE-0003: Gatos, H C & Lavine, M C — Prog Semicond, 9,1(1965)
PbSe, (100) wafers and other orientations. Solution used as a wet chemical etch at 40°C,
3 min.

PBSE-0004
ETCH NAME: Nitric acid, dilute TIME:
TYPE: Acid, cleaning TEMP: RT
COMPOSITION:
1 .... HNO3
5 .... H2O
DISCUSSION:
PbSe, (100) cleaved wafers. A study of electron and hole mobility between RT and 4.2
K. Material has NaCl cubic structure. Solution can be used to lightly clean surfaces. PbS
and PbTe also studied.
REF: Allgaier, R S — Scanlon, W W — Phys Rev, 111,1029(1958)
PBSE-0005: Allgaier, R S — Phys Rev, 112,828(1958)
PbSe, (100) cleaved wafers. A study of magnetoresistance at 295,77, and 4.2 K. Solution
can be used to clean surfaces. PbS and PbTe also studied.

© 1991 by CRC Press LLC