26 CRC Handbook of Metal Etchants

METHODS OF ETCHING

There have been over 200 terms used in the literature to describe a method of etching,
and generally fall into one of the three format categories described in the previous section:
wet or dry chemical and electrolytic etching. The use of a molten flux, here, is considered
a form of wet chemical etching as the chemical flux is in liquid form, and also is used for
growing single crystals, such as garnets and ferrites.
In addition to the acid and base definition using the Sorensen pH scale with water neutral
at pH 7; acids with pH below 7; and bases (also called alkalies) above pH 7, there are many
other categories. Water itself can be considered an acid-like etching solution; alcohols and
solvents, though usually considered as cleaning solvents, can act as an etchant on certain
materials; molecular gases can be used in conjunction with acids or used alone, such as in
hydrogen firing; vacuum as a "vapor" etchant on certain materials; molecular gases can be
used in conjunction with acids or used alone, such as in hydrogen firing; vacuum and vapor
pressure in vacuum have been used as etching vehicles; thermal heat treatment, alone, or
with gases is used both as a part of material fabrication as well as to etch. The halogens
are an etchant category of their own, with the bromine-methyl alcohol (BRM) solutions in
wide use.
Some highly specialized methods include the use of pressure, ice, cryogenic fluids, and
even abrasives. The latter, for example, are used for surface cleaning. Wire-saw cutting is
another area used in conjunction with an acid, with an abrasive slurry or acid-slurry. Many
of the specialized methods or techniques are categorized under wet chemical etching (WCE)
using the wet format (WF).
The use of etching solutions is still referred to as a magic art rather than a science by
many people, particularly when it involves developing a new solution as, though known
chemicals are used, results are often obtained by trial and error: varying solution constituents;
varying constituent concentrations; temperature variations; different methods of application.
Other factors include the material being etched and its structure; chemical reactivity or
contamination involved.
With time and usage many solutions have become industrial standards, such as aqua
regia (3HC1:1HNO3). When it was first formulated in the Middle Ages in Europe, the
alchemists of the period thought it to be the universal etch for all metals and metallic
compounds which, as we know today, is far from the case. It was the first solution developed
that would etch gold, and also will dissolve metals of the platinum group — platinum,
indium, osmium. All of these metals etch slowly in comparison to gold in aqua regia, even
when used hot to boiling. It does etch a few other metals and compounds, can be either a
removal/polish or preferential solution and, on still other metals, is a surface cleaning solution
only. It is particularly useful for removal of heavy metals contamination on surfaces, e.g.,
copper, iron, etc. The aqua regia solution varies in constituent concentrations, and may be
diluted with water or alcohols.
Other acid mixtures have been developed for one material and a specific result, such as
CP4 — initially Camp #4 — developed as a light figure orientation etch for (100) oriented
germanium wafers, yet, even on germanium, it can be both a preferential or polishing
solution. The original solution was 15 ml HF:30 ml HNO3:15 ml HAc:0.6 ml Br2. Since
its development it has been used on several semiconductor materials and other metals and
compounds. Without bromine it is called CP4A, and is considered a better polishing etch
for either germanium or silicon than CP4. Further, as CP4-modified, the bromine has been
replaced with I2, Cu(NO2)3, Ag(NO2)3, etc. to improve preferential action for a particular
type of defect. And depending upon the material involved, CP4 may be applied as a surface
cleaning solution.
Nital and Picral — HNO3:EOH and (NO2)3C6H2OH:EOH, respectively, have long been
major solutions on iron, iron alloys and steels, both as polish and preferential etchants. The

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acid concentrations are varied, the ethanol replaced by methanol, and both solutions are
now used on other metals, such as the wide range of brass and bronze . . . both major
copper alloys since antiquity: bronze (the Bronze Age) around 5000 B.C.; brass in use by
the Egyptians, possibly, circa 3000 B.C.
The Sirtl etch (lHF:2CrO3), developed in the early 1960s, has been a major preferential
etchant for dislocation and defect development, initially on silicon, now on many other
metals and metallic compounds. Since its inception, a dozen other HF:CrO3-type solutions
have been developed for improved defect enhancement in general or for specific type defects.
It is interesting to note that like Sirtl etch, many of these solutions have been named after
their developers: Schimmel, Sopori, Wright, etc., to include variations and modifications
of their original formulations. These solutions are strictly preferential, as are many of the
*'iodine" etches — there are several iodine etches that have been developed over the years,
all called 'iodine etchant" although they are different formulas.
The HF:HNO3, HF:HNO3:H2O or HF:HNO3:HAc solutions are the original oxidation-
reduction etchants developed in the Solid State semiconductor industry for general removal,
polishing, and preferential attack on wafers, and are used on most metal and metallic
compounds. Heavily diluted with either water or acetic acid (HAc), they act as surface
cleaning, staining or passivating solutions. The mixture of HF:HNO3, high in either acid,
act as surface staining solutions.
There are a wide range of mixtures with H2O2 replacing HNO3 as the oxidizing
agent... the peroxide containing etches . . . with similar uses to those containing HNO3.
Another oxidizer type preferential solution is Killing's etch (HF:KMnO4) developed in the
iron and steel industry, and used on semiconductor wafers and other metals.
Caro's etch (1H2SO4:3H2O2) is primarily a surface cleaning solution on a wide range
of metals and metallic compounds, and there are many modifications of that base formula,
to include water dilution. These solutions should be handled with care as they become self-
heating upon being activated and, once reaction is initiated, will reach a constant boiling
level of about 175°C.
Sulfuric acid, H2SO4, alone, is a glass cleaner and conditioner, and has been long used
in preparing soda-lime glass plates for metallization as chrome glass masks for photolitho
graphy. It also is a general removal and polishing solution on many metals, particularly, as
an electrolytic etch in the metal industries. As a mixture of H2SO4:K2Cr2O7 it has long been
known as the "glass cleaner" solution in many laboratories, and it is an extremely powerful
oxidizer.
The two major alkalies, KOH and NaOH, have several applications depending upon
solution concentration, and/or temperature. A 2—10% mixture, at RT, is used for surface
cleaning. At 30—40% (RT to about 40°C, warm), good for general removal. As 20—50%
solutions, hot to boiling, they become increasingly preferential. As electrolytic solutions,
they are good for general removal, polishing, shaping, surface oxidation or selective struc
turing. As a molten flux, liquified pellets at 360°C, they are highly preferential and used
for dislocation development in silicon and other single crystals. Other molten fluxes, such
as carbonate and nitrate mixtures are applied as cleaning or etch solutions in general metals
processing. Still other fluxes are used in the growth of single crystals, such as ferrites and
garnets, and borax has already been mentioned as a flux for alloying.
The primary oxide or nitride remover is hydrofluoric acid, HF, applied as a concentrated
solution; or water, even alcohol or solvent diluted; used from RT to boiling; or as hot vapor.
Because of HF's rapid attack of oxides, buffered hydrofluoric acid (BHF) mixtures have
been developed to better control removal rates. A fairly standard solution is 1HF:1NH4F(4O%),
though there are other fluorine compounds used, such as KF and NaF, or NH4F.HF.
Concentrated, hot phosphoric acid, H3PO4, also is both an oxide and nitride removal
solution and, as it attacks silicon dioxide at a slower rate than it does silicon nitride, it can
be used as a stop-etch where the nitride is on top, and the reduced attack rate of the oxide

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28 CRC Handbook of Metal Etchants

effectively "stops" the reaction. With the oxide over the nitride, the oxide will act an etch
mask for photolithographic patterning of the nitride.
Hydrochloric acid (HC1) concentrated, water diluted, or diluted with alcohols, is used
as a general surface cleaner. As a hot vapor in epitaxy systems, it is the primary glass tube
and graphite susceptor cleaning method. In final rinse cleaning of semiconductor wafers,
say, prior to metallization, a two-step process is often used — dip in 50% HC1 and water
rinse — then dip in 50% HF, and final water rinse, then N2 blow dry.
The bromine-methanol (BRM) solutions are being widely used on many different metals
and metallic compounds as a chemical/mechanical (chem/mech) removal and polishing
solution at RT; for general polishing by immersion; or high concentrations of bromine as
preferential solutions. When a wafer is patterned with Apiezon-W (black wax), BRM so
lutions have been used for selective etching structure. Most polishing is done with solutions
of less than 5% Br2, and preferential etching between 5—20% concentration. In conjunction
with black wax patterning, solutions have been applied for thinning of specimens for trans
mission electron microscopy (TEM) study.
It should be noted that any chemical polish solution can be used for thinning, but a
reasonably slow solution that will produce a flat, planar surface is preferred. For thick
specimens, a rapid etch may be used for initial thickness reduction, followed by final thinning
with a slower more controllable etchant such as BRM. Iodine can replace the bromine in
BRM solutions with less evaporation loss, and similar results.
Ammonia, NH3 and ammonium hydroxide, NH4OH at standard liquid concentration are
the most widely applied neutralizes for acid waste sumps before disposal into sewer systems.
They may be the sole constituent of an etch on alkaline halides or as an additive constituent
in an etchant mixture. Both liquids can be used to neutralize acid burns on the skin, and
solid crystalline ammonia is the medical "smelling salts".
Water, alone, is a neutral solution (pH 7 on the Sorenson Scale), and the major quenching
medium following etching. It is considered the universal solvent in chemistry and geology
as, with time, it will eventually dissolve all compounds. In material processing, it can act
as an etching solution on water soluble compounds, such as the alkaline halides (NaCl, KC1,
etc.) and, when so applied, is referred to as an "acid" under TYPE in the formats. Sea
water, containing dissolved salts, either natural or artificially compounded, has been used
as an etchant for single crystal ice; as a quenching medium in metal processing; and even
used to etch single crystal sodium chloride (salt), itself ... the primary saline compound
in ocean water.
The "Chrome Etch" solutions contain cerric ammonium nitrate or sulfate, with or
without small amounts of HNO3, HC1, or H3PO4. They are commercially available as pre-
mixed solutions, and were developed specifically for the controlled etching of chromium
thin films on glass masks in the fabrication of chrome photo masks for photolithographic
processing. They are commonly used at 30°C. The masks are made with iron oxide in place
of chromium or nickel, today, for improved handling. The solutions used on chrome are
quite rapid with about 2000 A metallization, plus a 400—600 A anti-reflective (AR) coating
and the nitrate is preferred, as it has been shown that the sulfate solutions may leave an
unwanted film on the glass plate after etching. Note that these solutions also can be used
on nickel.
Though alcohols and solvents are mainly used for surface cleaning, often as a final rinse
following water quenching of an acid etch for their water absorbing qualities, they can act
as etchants on particular materials — in particular alkaline halide crystals.
The following methods of etching are in alphabetical order without regard to chemicals
and/or processes involved, and represent the wide variety of terms used throughout the
industrial cleaning and etching of materials.

© 1991 by CRC Press LLC