Electronic Chemicals 總覽百科

Electronic Chemicals 1
Electronic Chemicals
Steve Daigle, Charles H. Kline & Co., Fairfield, New Jersey 07006, United States
Eric Vogelsberg, Charles H. Kline & Co., Fairfield, New Jersey 07006, United States
Biron Lim, Charles H. Kline & Co., Fairfield, New Jersey 07006, United States
Ian Butcher, Charles H. Kline & Co., Fairfield, New Jersey 07006, United States
1. Introduction . . . . . . . . . . . . . . . . 2 6.7. Ammonium Fluoride . . . . . . . . . . 17

2. Substrates . . . . . . . . . . . . . . . . . 3 6.8. Persulfates . . . . . . . . . . . . . . . . . 18
2.1. Silicon Wafers . . . . . . . . . . . . . . . 3 6.9. Other Acids and Etchants . . . . . . . 18
2.2. Other Semiconductor Substrates . . 4 7. Atmospheric Gases . . . . . . . . . . . 20
2.3. Printed Circuit Board Laminates . . 4 8. Photoresist Adjuncts . . . . . . . . . . 21
3. Packaging Materials . . . . . . . . . . 5 8.1. Photoresist Strippers . . . . . . . . . . 21
3.1. Ceramic Packaging Materials . . . . 5 8.2. Dry Film Photoresist Developers . . 22
3.2. Plastic Packaging Materials . . . . . . 6 8.3. Positive Photoresist Developers . . . 22
4. Plating Chemicals . . . . . . . . . . . . 7 8.4. Negative Photoresist Developers . . . 23
4.1. Electrolytic Gold Plating Chemicals 7 8.5. Photoresist Adhesion Promoters . . . 23
4.2. Electroless Copper Plating 9. Cleaners and Specialty Materials . . 24
Chemicals . . . . . . . . . . . . . . . . . 8 10. Specialty Gases . . . . . . . . . . . . . . 25
4.3. Electrolytic Copper Plating 10.1. Silicon Gases . . . . . . . . . . . . . . . 25
Chemicals . . . . . . . . . . . . . . . . . 9 10.2. Etchant Gases . . . . . . . . . . . . . . . 26
4.4. Electrolytic Tin – Lead Plating
10.3. Light-Emitting Diode Gases . . . . . 27
Chemicals . . . . . . . . . . . . . . . . . 10
11. Solvents . . . . . . . . . . . . . . . . . . . 28
4.5. Other Electrolytic Plating Chemicals 10
12. Masks . . . . . . . . . . . . . . . . . . . . 29
5. Photoresists . . . . . . . . . . . . . . . . 11
13. Dopants . . . . . . . . . . . . . . . . . . . 30
5.1. Dry Film Photoresists . . . . . . . . . . 11
13.1. Liquid Dopants . . . . . . . . . . . . . . 30
5.2. Liquid Positive and Negative Pho-
toresists . . . . . . . . . . . . . . . . . . . 12 13.2. Gas Dopants . . . . . . . . . . . . . . . . 31
5.3. Screening Inks . . . . . . . . . . . . . . 13 13.3. Solid Dopants . . . . . . . . . . . . . . . 31
6. Acids and Etchants . . . . . . . . . . . 13 14. Auxiliary Materials . . . . . . . . . . . 32
6.1. Sulfuric Acid . . . . . . . . . . . . . . . 13 14.1. Ceramic Substrates . . . . . . . . . . . 32
6.2. Hydrofluoric Acid . . . . . . . . . . . . 14 14.2. Liquid Crystals . . . . . . . . . . . . . . 32
6.3. Ammoniacal Solutions . . . . . . . . . 15 14.3. Conductive Inks and Pastes . . . . . . 32
6.4. Nitric Acid . . . . . . . . . . . . . . . . . 15 14.4. High-Purity Metals . . . . . . . . . . . 32
6.5. Hydrogen Peroxide . . . . . . . . . . . 16 14.5. Passivation Materials . . . . . . . . . . 33
6.6. Proprietary Peroxy and Sulfuric 14.6. Wafer Cleaners . . . . . . . . . . . . . . 33
Etchants . . . . . . . . . . . . . . . . . . 17 15. References . . . . . . . . . . . . . . . . . 33
1. Introduction auxiliary materials (Chap. 14)

cleaners (Chap. 9)
The chemicals and materials used to manufac- dopants (Chap. 13)
ture and package semiconductors and printed masks (Chap. 12)
circuit boards are considered electronic chemi- packaging materials (Chap. 3)
cals. The more than 100 different products used photoresists (Chap. 5)
in these applications are grouped into the fol- photoresist adjuncts (Chap. 8)
lowing 13 major product categories: plating chemicals (Chap. 4)
acids and etchants (Chap. 6) solvents (Chap. 11)
atmospheric gases (Chap. 7) specialty gases (Chap. 10)
c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a09 265
2 Electronic Chemicals
substrates (Chap. 2) 2. Substrates

Semiconductors are devices having a spe- A substrate is the base material in the manufac-
cific electronic circuit fabricated onto a single ture of semiconductor devices and printed circuit
square or rectangular piece of semiconducting boards. The semiconductor industry uses mate-
material such as silicon (→ Semiconductors). rials, such as silicon and gallium arsenide, which
The two main types of semiconductor devices are produced in single crystal form. Thin circular
are discrete devices and integrated circuits (IC). slices or wafers of these single crystal materials
Discrete devices contain only one active ele- serve as the substrate in manufacturing semicon-
ment, whereas integrated circuits contain mul- ductor devices.
tiple elements that act together to form a com- The printed circuit board industry uses ma-
plete electronic circuit. Since the semiconduc- terials known as laminates to act as the base in
tor industry began in 1947 with the invention of the production of circuit boards. Combinations
the transistor and was further enhanced by the of a resin with either paper or glass cloth form
invention of the integrated circuit in 1958, the the laminate, which is produced in thin sheets.
business has grown rapidly.
More than 100 manufacturers of semiconduc-
tor devices exist in the United States, includ- 2.1. Silicon Wafers
ing both merchant and captive producers. In-
ternational Business Machines (IBM), a captive Types and Grades. Silicon [7440-21-3]
producer, is believed to be the largest semicon- wafers are sold as either polished wafers or epi-
ductor manufacturer worldwide. Other impor- taxial wafers, i.e., wafers having an added silicon
tant semiconductor manufacturers include Texas layer over the surface, that has the same crys-
Instruments, Motorola, National Semiconduc- tallographic orientation as the wafer itself. All
tor, Intel, Fairchild, Signetics, AT & T, and Ad- wafers are manufactured with dopants embed-
vanced Micro Devices in the United States; ded in the silicon. Wafers positively doped with
Philips (Netherlands); Siemens (Federal Repub- boron or negatively doped with either antimony
lic of Germany); and NEC, Hitachi, Toshiba, and or phosphorus are available. Silicon wafers are
Fujitsu (Japan). also sold in two types of crystal lattices: (100)
and (111) orientations.
Printed circuit boards are plastic sheets
onto which conductive paths are formed in a spe- Production. The two major methods of
cific pattern for the purpose of interconnecting producing silicon wafers are the Czochral-
electronic components such as semiconductor ski method and the Floating Zone technique
devices, resistors, and capacitors. The circuitry (→ Crystal Growth).
can be formed on either one side or both sides of The Czochralski method is the most widely
the board, and several boards can be connected to used crystal growing process. Pure polycrys-
produce a multilayer board. The need for printed talline silicon is placed in a fused silica quartz
circuit boards is widespread, and they are either crucible. The material is heated to 1400 ◦ C in
produced captively by large consumers or pur- a protective atmosphere, usually argon, which
chased on the merchant market. melts the silicon and keeps it molten. A seed
Of the over 1000 individual manufacturers crystal of the desired crystal orientation is
of printed circuit boards in the United States, dipped into the melt. The single silicon crystal
two companies, IBM and Western Electric, is grown by rotating the seed and the crucible in
are by far the largest producers. Other im- opposite directions while withdrawing the seed.
portant manufacturers include Hewlett-Packard, The Floating Zone technique uses a rod of
Digital Equipment, Delco, Tyco Laboratories, polycrystalline silicon attached to a chuck at the
Hadco, and Photocircuits (United States); GEC top of an inert atmosphere chamber and a seed
(United Kingdom); Telefunken (Federal Repub- crystal attached to a shaft at the bottom of the
lic of Germany); Olivetti (Italy); Thompson- chamber. A heating coil located at the base of the
CSF (France); and NEC, Hitachi Chemical,
CMK, and Fujitsu (Japan) [4].
rod forms a molten zone, which is fused with the 2.2. Other Semiconductor Substrates
seed to begin crystal growth. Movement through
the molten zone purifies the polysilicon and es- Gallium arsenide [1303-00-0], GaAs, is a
tablishes the crystal structure. The molten sili- substrate produced by the Czochralski process
con is kept in place by surface tension, which from a molten mix of gallium and arsenic met-
limits the diameter of the pure silicon. als. It is sold as wafers, with diameters of 5.08
The major drawback of the Floating Zone and 7.62 cm being the most popular. Most GaAs
method in comparison to the Czochralski pro- is used as the base material for light-emitting
cess is the limited wafer diameter. The Floating diodes, although it does have applications with
Zone process can produce a maximum wafer other discrete devices, such as field-effect tran-
diameter of 7.6 cm, whereas wafer diameters sistors, Gunn diodes, and Schottky diodes. Gal-
up to 15.2 cm are feasible with the Czochralski lium arsenide is also an electrically fast sub-
method. Both processes add controlled amounts strate material and is of interest as a potential
of impurities or dopants during the growth pro- source for producing very-high-speed integrated
cess to create the necessary electrical proper- circuits.
ties within the silicon crystal structure. Dopants, Some of the more important suppliers of gal-
such as boron, are added to establish a positive lium arsenide include Sumitomo Electric Indus-
charge within the silicon; phosphorus and an- tries and Mitsubishi Monsanto (Japan), Mor-
timony are used to create a negatively charged gan Semiconductor (United States), and Wacker
material. In the Czochralski process, dopants are (Federal Republic of Germany).
typically added to the molten silicon as pure el-
ements or concentrated silicon solutions. The Silicon-on-sapphire (SOS) is produced by
Floating Zone method uses dilute phosphine or epitaxially depositing a thin silicon layer on a
diborane gas, which is added when the rod is sapphire substrate. It is sold as wafers, with the
in the molten zone or when the rod is initially 7.62 cm diameter variety being the most com-
manufactured. mon. As a substrate material, SOS is capable of
producing dense, high-speed devices that are re-
Quality Specifications. The dimension and sistant to radiation. However, its manufacture is
thickness specifications for polished silicon both difficult and expensive. Despite attempts to
wafers have been established by the Semi- develop SOS for commodity type devices, it re-
conductor Equipment and Materials Institute mains mainly as a material for specialty devices
(SEMI) [5]. in military applications.
The United States is the main market for SOS
Uses. Silicon is used as a substrate for dis- substrates as a result of its military applications.
crete semiconductor devices, such as diodes, Union Carbide and Sappikon are the major U.S.
rectifiers, and transistors, as well as for all types suppliers of SOS substrates. Small quantities of
of integrated circuits (IC). Wafers produced by SOS are used in Japan mainly by Toshiba, which
the Czochralski process are used primarily for supplies some of its internal requirements.
ICs and transistors, whereas those manufactured
by the Floating Zone method are used mainly for Gadolinium gallium garnet (GGG)
rectifiers and thyristors. [12024-36-1], Gd3 Ga5 O12 , is manufactured
from gadolinium oxide and gallium oxide by
Economic Aspects. The consumption of sil- the Czochralski method. Single-crystal GGG is
icon wafers in the United States was ca. available in wafer form with a typical diameter
3×109 cm2 in 1980. The demand in Western of 7.62 cm and thicknesses of 5 – 6 µm. The main
Europe during the same period was 0.742 application for GGG is as the substrate material
×109 cm2 . The leading suppliers worldwide of for magnetic bubble memories, a relatively new
silicon wafers are Wacker (Federal Republic of device that can store >106 bits of information.
Germany), Monsanto (United States), Shin-Etsu Gadolinium gallium garnet (GGG) is electri-
Handotai (Japan), and Dynamit Nobel (Italy). cally involatile; however, it is a relatively slow
electrical semiconductor. Unfortunately, the de-
mand for magnetic bubble memories has been 3. Packaging Materials

limited.
3.1. Ceramic Packaging Materials
2.3. Printed Circuit Board Laminates Ceramic materials are used to encase semicon-
ductor devices to protect the devices from the ad-
Laminates are used as the substrate for printing verse effects of moisture, atmospheric salt, and
electrical circuitry. They are composed of lay- high temperature (→ Ceramics, Electronic). Be-
ers of material compressed under heat and pres- cause ceramic packages provide a high degree of
sure to form a consistent electrical insulator. The hermaticity and reliability, ceramics are gener-
basic raw materials of the laminate include pa- ally used to package critical military, computer,
per and glass cloth, or glass mat bonded with and communication devices.
one of several resins, mainly phenolic, epoxy, or Most ceramics used in packaging are made
polyester. Circuit boards processed by the sub- from aluminum oxide [1344-28-1], Al2 O3 , al-
stractive method use laminates clad with cop- though beryllium oxide [1304-56-9], BeO, is
per foil, whereas the additive and semiadditive sometimes used. Aluminum oxide is very strong
methods use unclad laminates, and refractory and has a low dielectric constant,
which makes it suitable for most packaging ap-
Types and Grades. Laminates are manufac- plications. Beryllium oxide offers the unusual
tured specifically for circuit printing on both combination of high thermal and electric con-
sides (double-sided board) or an only one side ductivity. However, the high cost of this material
(single-sided board) and can be either rigid or limits its use to the most critical applications.
flexible in form. The types of laminates avail-
able commercially are given in Table 1 [6]. Types and Grades. Most ceramic packages
contain 94 wt % aluminum oxide, although other
Uses. Paper-based phenolic and composite compositions are available. The major types of
laminates are used as substrates for single-sided ceramic packages are (1) the metallized ceramic
and simple double-sided circuit boards. These dual in-line package (DIP), (2) the ceramic dual
boards are typically used for less critical con- in-line package (CERDIP), and (3) the chip car-
sumer items, such as electronic games, televi- rier. Other types include specialty beryllium ox-
sions, appliances, calculators, and automotive ide packages.
circuits. Glass-based epoxy and polyimide lam-
Uses. The type of ceramic package used with
inates are favored for complex double-sided
a semiconductor device depends on (1) the level
and multilayer boards that have applications
of hermetic seal desired, (2) the degree of relia-
with computers, communication equipment, and
bility required, (3) the amount of space alloted
other electronic devices requiring a high degree
to the device on the printed circuit board, and (4)
of reliability.
the total package cost. A ceramic package that is
metallized by cofiring the alumina powder with
Economic Aspects. Total demand for
tungsten forms the tightest hermetic seal of all
printed circuit board laminates in the United
types of packages, whether ceramic or plastic.
States was 20×106 m2 in 1980. The demand
However, this package is also the most expen-
in Western Europe was 15×106 m2 during the
sive, except for the seldom used beryllium oxide-
same period. The major laminate suppliers in-
type package. Because of their high reliability,
clude Norplex and Oak Laminates (both of
DIPs are most often used for devices used by the
which are part of Allied-Signal), Westinghouse,
military and for the more critical devices used in
and General Electric (United States); Dynamit
computers and communication equipment.
Nobel and Isola (Federal Republic of Germany);
The CERDIP, which has no metallization, of-
MAS (Italy); and Hitachi Chemical, Sumitomo
fers a compromise between the level of hermetic
Bakelite, and Matsushita Electric (Japan).
seal and package cost. As a result, the CERDIP
is favored for many computer and communica-
tion applications where a more hermetic seal is
Table 1. Standard laminate materials
NEMA MIL-P-13949E∗ Resin system Base Color Description

grade
XXXP none phenolic paper opaque brown phenolic paper with no cold-punch
stipulation
XXXPC none phenolic paper opaque brown phenolic paper with punchability at or
above room temperature
FR-2 none phenolic paper opaque brown phenolic paper, punchable, with
flame-resistant (self-extinguishing) resin
system
FR-3 PX epoxy paper opaque cream epoxy resin, paper base with
flame-resistant resin system, cold
punching, and high insulation resistance
none none epoxy paper – glass opaque cream epoxy resin paper core with glass on the
composite laminate surface, self-extinguishing,
economical fabrication of paper base,
mechanical characteristics of glass
FR-6 none polyester glass mat opaque white polyester, random glass fiber,
flame-resistant, designed for
low-capacitance or high-impact
applications
G-10 GE epoxy glass translucent epoxy – glass, general purpose
green or white
FR-4 GF epoxy glass translucent epoxy – glass with self-extinguishing
green or white resin system
G-11 GP epoxy glass translucent high-temperature epoxy – glass with
green or white strength and electrical rentention at
elevated temperature
FR-5 GH epoxy glass translucent high-temperature epoxy – glass with
green or white flame-resistant resin system; strength
and electrical retention at elevated
temperature
polyimide glass translucent polyimide resin,
dark brown glass laminate with high continuous
operating temperature and high
property retention at high temperature,
low z-axis dimensional expansion
∗ Military designation.
desired than plastic can be obtained using a pack- nearly as tight as that of the DIP, but at < 50 %
age, but where cost limitations prevent use of a the cost.
DIP.
The chip carrier was developed to fulfill Economic Aspects. In 1980, ca. 2.2×109
the needs of systems manufacturers for (1) in- ceramic packages were used in the United States
creased package density, (2) better electrical per- for packaging semiconductor devices. At the
formance, and (3) more economical device pack- same time, ca. 87×106 ceramic packages were
aging. It has a metallized aluminum oxide ce- consumed. The two leading suppliers of ceramic
ramic substrate similar to that of a DIP. Its shape packages are Kyocera and NTK Technical Ce-
is square, whereas both the DIP and CERDIP ramics, both Japanese companies.
are rectangular. The square configuration of the
chip carrier reduces the space requirements on a
printed circuit board by 3 – 5 times compared to 3.2. Plastic Packaging Materials
that of the DIP and CERDIP. The square shape
also improves electrical performance by short- Plastic packaging materials are used to encase
ening the length of the electrical leads and by the finished semiconductor device, thus protect-
making the lead length more uniform over the ing the device from moisture, atmospheric salt,
entire package, thus permitting faster switching and high temperature. The four basic types of
times and improved system performance. Over- plastic materials used for this purpose are as fol-
all, the chip carrier produces a hermetic seal lows:
Epoxy molding resins are used primarily to complexity. Liquid potting compounds are used
package metal oxide semiconductor (MOS) and exclusively in this packaging process.
bipolar devices that require an inexpensive pack-
age while still receiving protection from the en- Economic Aspects. Worldwide consump-
vironment (→ Epoxy Resins). Epoxy resins of- tion of plastic packaging materials in 1980 is
fer low shrinkage and high strength, which help shown in Table 2. Epoxy-based molding com-
to prevent package cracking both on curing and pounds were the preferred product.
from the thermal shock.
Table 2. Worldwide consumption of plastic packaging materials in
Silicone molding resins are favored for pack- 1980
aging devices, such as power transistors, which
Product Consumption, 103 t
generate a great amount of heat. Silicone resins
are among the best of all polymeric materials for United Western Total
States Europe
operating at high temperature. They also have
excellent electrical properties, which change lit- Epoxy 10.0 1.4 11.4
tle with temperature. Silicone 1.1 0.2 1.3
Liquid potting 0.6 0.6
Silicone-epoxy resins are hybrids that at- Silicone – epoxy 0.2 0.2
tempt to combine the best qualities of each resin Total 11.9 1.6 13.5
while maintaining a low package cost. So far,
these resins have been used with some telecom- The major suppliers of epoxy molding com-
munication devices that seek a better hermetic pounds are Rohm & Haas and the Hysol Di-
seal than that from epoxy resins while maintain- vision of Dexter, both in the United States.
ing a package cost close to that of epoxy. Dow Corning (United States) is one of the most
Liquid potting compounds are generally important suppliers of silicone molding com-
used to package discrete devices such as tran- pounds.
sistors and diodes. These potting compounds
offer the lowest package cost, but also the least
amount of protection from the environment. 4. Plating Chemicals
Types and Grades. Plastic packaging mate- 4.1. Electrolytic Gold Plating Chemicals
rials are all sold as semiconductor-grade prod-
ucts. The molding resins are available in gran- Gold [7440-57-5] plating on printed circuit
ular form, whereas potting compounds are sold boards functions mainly as the surface metal for
as liquids. All products are marketed in ready- contact areas because of its high electrical con-
to-use form. ductivity and resistance to tarnish. Gold can also
function as a metal etch resist because of its re-
Uses. Two main processes are used for pack- sistance to all common circuit board etchants.
aging semiconductor devices. Electrolytic gold plating chemicals consist of
Transfer molding is the process of trans- gold salts, gold strikes, conductivity salts, and
ferring a hardenable material, under pressure, pH-adjusting salts.
from a pot or container into the mold that con- Gold salts, also known as gold plating pro-
tains the semiconductor device. This process is cesses, are proprietary formulations of either
economical for large-volume operations, but ini- potassium gold cyanide or alkaline noncyanide
tial facility construction and mold costs are high. gold in either powder or solution form. In addi-
All molding resins use this process for packag- tion to supplying gold metal for plating, these
ing devices. formulations often include brighteners to pro-
Potting consists of pouring a hardenable liq- duce a mirror finish or complexes of cobalt,
uid into a shell or housing, which remains as nickel, and indium for increased hardness and
an integral part of the package. This process wear resistance.
is also excellent for large-volume runs and re- Gold strikes are used to deposit a thin layer
quires minimal tooling. However, this process is of gold on other plated metals prior to the use
subject to limitations of both size and housing of a noncyanide gold plating solution or an elec-
troless gold plating process. The thin gold layer
improves the bonding of the noncyanide or elec- quirements can typically vary from 2.54 to
troless gold layers to the circuit board. 3.81 µm.
Conductivity salts allow gold plating baths to
operate at a lower voltage, thus increasing bath Economic Aspects. An estimated 5.3 kg of
efficiency; pH-adjusting salts are used to raise gold metal and formulation chemicals was con-
or lower the pH of the bath. sumed in the United States for electrolytic gold
plating on printed circuit boards. The major sup-
Production. All electrolytic gold baths and pliers of gold plating processes are Oxy Metal
strikes are prepared by mixing the conductiv- Industries, Engelhard, and Lea Ronal, all in the
ity salts in water and adding either the gold United States.
salt or gold strike to the solution. Some pH-
adjusting salts may be added initially to obtain
the proper pH. Once the bath is operating, only 4.2. Electroless Copper Plating
gold salts (and occasionally some pH-adjusting Chemicals
salts) are added to replenish the bath. Gold baths
are long lasting and are reformulated only once Electroless plating is used to deposit thin metal
or twice per year. Acid gold baths operate at a layers on nonmetallic surfaces without the use
temperature of 21 – 49 ◦ C with a pH of 3.5 – 4.0, of an electric current. Most electroless plating is
whereas alkaline noncyanide gold baths operate used for depositing copper [7440-50-8], which
at 32 – 54 ◦ C with a pH of 9.0 – 10.0 [7]. functions to metallize nonconductive surfaces
on printed circuit boards. Electroless copper
Types and Grades. Gold salts are available plating systems consist of a solution, a catalyst,
in three types and four grades (see Table 3), and an accelerator.
as defined by the U.S. Department of Defense Electroless copper solutions are usually a
specification MIL-G-45204 B Amendment 2 for proprietary two-component system. One com-
electrodeposited gold plating [7, p. 28]. The type ponent contains copper(II) salts and formalde-
of gold salt refers to the purity of the gold de- hyde, whereas the other contains sodium hy-
posit, whereas the grade refers to the hardness of droxide. When these solutions are combined in
the deposit as measured by the Knoop method. water, copper is reduced as follows [7]:
Table 3. Types and grades of gold salts
Type Gold purity Grade Knoop hardness

(min.), wt %
I 99.7 A 0 – 90 Electroless copper catalysts are proprietary

II 99.0 B 91 – 129 formulations containing both palladium chlo-
III 99.9 C 130 – 200 ride and tin(II) chloride. The palladium is es-
D 201
sential for initiating the copper reduction reac-
tion on a nonconductive surface. Once copper is
Gold concentration in the salts varies with deposited, the reaction is autocatalytic.
vendors, but most salts have concentrations of Electroless copper activators are propri-
ca. 67 %. etary formulations that increase the ability of
the palladium catalyst to reduce copper more
Uses. Electrolytic gold plating is used on rapidly and uniformly. The activator also im-
printed circuit boards for end uses such as com- proves adhesion of the electroless copper to the
puters, communications, and the military, all of base metal.
which require a high degree of reliability. The
thickness of plated gold varies among printed Production. All electroless or immersion
circuit board manufacturers. Western Electric plating is conducted by submerging the circuit
has developed a specification requiring a plated board into a prepared bath. Most electroless cop-
gold thickness of 1.27 µm. Specifications for per baths operate at a temperature of 21 – 27 ◦ C
other communication and computer companies with a pH of ca. 12 [7, p. 6]. The difference bet-
range from 0.762 to 2.03 µm and military re- ween electroless solutions and immersion solu-
tions is subtle but important. Electroless solu- sulfate, sulfuric acid, copper anodes, and pro-
tions contain a reducing agent that supplies elec- prietary brighteners, whereas the pyrophosphate
trons to reduce metal ions to the metallic state. process uses copper pyrophosphate, potassium
Theoretically, an electroless bath can proceed pyrophosphate, copper anodes, and proprietary
indefinitely. Immersion plating is accomplished additives.
by displacing one metal with another of lower Copper(II) sulfate [7758-98-7], CuSO4 , is
oxidation potential. As a result, plating ceases the source for copper ions, which are plated onto
when all the metal on a given substrate has been the board in an acidic copper bath. A chemi-
displaced. cally pure grade copper sulfate is usually rec-
ommended for plating.
Types and Grades. All electroless copper The function of sulfuric acid [7664-93-9],
plating chemicals are sold as a concentrate that H2 SO4 , is to increase the conductivity of the
requires dilution with water before it is ready for bath solution and to corrode the copper an-
use. Many suppliers have different dilution rates odes. Copper serves as the anode for the elec-
for the various electroless chemicals because of trical current and supplies copper to form cop-
the wide range of concentrations available. per sulfate as corrosion takes place in acid baths.
Acid copper baths require phosphorized anodes,
Uses. Electroless copper plating is used to whereas oxygen-free high conductivity or rolled
deposit metal on the nonconductive walls of phosphorized anodes are used in pyrophosphate
holes that are drilled in double-sided and mul- baths.
tilayer boards. The metallized holes allow the Copper and potassium pyrophosphate
printed circuitry to connect both sides of a board. [7320-34-5], K4 P2 O7 , are combined to form
Other electroless plating systems are employed potassium copper pyrophosphate, which serves
only occasionally for specific functions. Elec- as the source of copper ions in a pyrophosphate
troless nickel solutions and immersion tin or bath. Proprietary brighteners are added to the
tin – lead solutions can be used to inhibit corro- bath to increase grain refinement, hardness, dis-
sion and promote solderability on a completed tribution, and brightness of the plated copper.
circuit board. Electroless or immersion gold so- These additives are used to a much greater extent
lutions are used when electroplating is impracti- with acid copper systems than with pyrophos-
cal because of a lack of electrical continuity on phate systems.
the edge connectors.
Types and Grades. Copper sulfate is avail-
Economic Aspects. In 1980, ca. 6.1×106 L able in both technical and chemically pure
of electroless copper plating chemicals was used grades for use in electroplating and can be pur-
in the United States; half that amount was chased as a commodity or as a trade name in
consumed in Western Europe. MacDermid and either liquid or crystalline form. Copper sulfate
Shipley both in the United States, are the two is also sold in a dilute form mixed with sulfuric
major suppliers of these plating chemicals. acid and water for a ready-to-use bath solution.
Copper anodes are sold either as chips or rods.
Pyrophosphates are available as both solutions
4.3. Electrolytic Copper Plating and crystals and are usually bought as a trade
Chemicals name product. Proprietary brighteners are sold
as ready-to-use liquid concentrates.
Electrolytic copper plating chemicals are used
to deposit copper onto printed circuit boards. Uses. Both the acid copper and pyrophos-
Copper is widely accepted as a base conductor phate processes are used to deposit copper
metal in circuit board fabrication because of its on the printed circuit board to form the cir-
excellent electrical conductivity, low cost, high cuitry. The thickness of the plated copper varies
reliability, and good bonding with other metals. among circuit board manufacturers, but the typ-
The two most commonly used copper processes ical range is 2.54 – 5.08 µm, regardless of the
are acid sulfate and pyrophosphate. The chemi- plating process. Acid copper operates at a tem-
cals used in the acid sulfate process are copper perature of 18 – 32 ◦ C, whereas pyrophosphate
operates at 43 – 60 ◦ C and requires a pH of form Sn(BF4 )2 and Pb(BF4 )2 as corrosion takes

8.2 – 8.8. Typical bath compositions for acid place.
copper and copper pyrophosphate are as follows Boric acid [10043-35-3], H3 BO3 , is added to
[7, pp. 14, 16]: maintain bath stability by inhibiting the decom-
position of tetrafluoroborate. Two types of
Acid copper bath
Copper(II) sulfate 25 vol % brighteners are available: peptones and nonpep-
Sulfuric acid 10 vol % tone proprietary brighteners promote smooth,
Chloride ion 50 ppm
Brightener 0.6 vol %
fine-grain deposits.
Deionized water 74.4 vol %
Copper pyrophosphate bath Types and Grades. Lead and tin tetrafluo-
Copper(II) pyrophosphate 33.3 vol %
Potassium pyrophosphate 3.5 vol % roborates are available as liquid concentrates
Ammonium hydroxide 0.5 vol % with 50 % active material content, usually of
Brightener 0.09 vol % a chemically pure grade. Tin – lead anodes are
Deionized water 62.6 vol %
sold in both rod and nugget form with a min-
imal purity of 99.9 %. Brighteners are sold as
ready-to-use liquid concentrates.
Economic Aspects. In the United States, ca.
4.8×103 t of copper anodes and 5.7×103 m3 of Uses. Solder plating is typically used on
copper plating chemicals were consumed for double-sided boards and outer layers of multi-
electrolytic copper plating in 1980. The major layer boards. Solder is plated on top of the elec-
suppliers of the plating chemicals are Sel-Rex troplated copper to serve mainly as an etch resist
and Lea Ronal in the United States. Copper an- for the copper. The thickness of most tin – lead
odes are available from many suppliers, with deposits is 7.62 – 12.7 µm. Tin – lead baths usu-
such companies as AMAX, ASARCO, and Uni- ally operate at a temperature of 21 – 27 ◦ C [7,
vertical among the more important. p. 21].
Economic Aspects. In 1980, ca.

4.4. Electrolytic Tin – Lead Plating 1.4×103 m3 of tetrafluoroborates, acids, and
Chemicals brighteners was consumed in the United States
for electrolytic tin – lead plating in electronics,
Tin – lead or solder is electroplated onto the along with 1.1×103 t of tin – lead anodes. The
printed circuit board by using electrolytic more important suppliers of the plating chem-
tin – lead plating chemicals. The plated solder icals are General Chemical (formerly Allied),
serves two functions: as a metal etch resist for Sel-Rex, Lea Ronal, and Harshaw. By far, the
the copper circuitry and as a solderable sub- most important supplier of tin – lead anodes is
strate for subsequent soldering of components Alpha Metals.
to the board. Tin – lead plating baths consist of
anodes, lead and tin tetrafluoroborates, fluoro-
boric acid, boric acid, and brighteners. Fluo- 4.5. Other Electrolytic Plating
roboric and boric acid are discussed further in Chemicals
Chapter 6.
Lead (II) tetrafluoroborate [13814-96-5], Several other electrolytic plating processes are
Pb(BF4 )2 , and tin(II) tetrafluoroborate employed by the printed circuit board industry.
[13814-97-6], Sn(BF4 )2 , are the sources of Among the most important processes are nickel,
metal for deposition onto the board. Variations tin, and rhodium plating.
in the metal content of the bath can affect the
content of the deposition alloy. Nickel electroplating uses such products as
Fluoroboric acid [16872-11-0], HBF4 , in- nickel sulfamate or nickel sulfate, boric acid,
creases bath conductivity and corrodes the nickel bromide, nickel anodes, and propri-
tin – lead anodes. Tin – lead (Sn [7440-31-5], etary additives. Nickel sulfamate [13770-89-3],
Pb [7439-92-1]) serves as the anode for the Ni(SO3 NH2 )2 , is the primary source of nickel
electrical current and supplies tin and lead to metal ions in a nickel sulfamate bath, whereas
nickel sulfate [15244-37-8], NiSO4 , serves the primarily on the source of nickel ions. Typical
same function in a modified watts nickel bath. compositions for both baths are as follows:
Boric acid functions as a buffer and reduces
Nickel sulfamate bath
burning at high current densities. Nickel bro- Nickel sulfamate 28 vol %
mide [13462-88-9], NiBr2 , is used to minimize Boric acid 4 vol %
Nickel bromide 1 vol %
internal stress and cause corrosion of the nickel Proprietary additive as needed
anodes. Nickel [7440-02-0] serves as the anode Deionized water 67 vol %
for the electric current and provides additional Modified watts nickel bath
Nickel sulfate 23 vol %
nickel ions as corrosion takes place. Proprietary Boric acid 4 vol %
additives are used to reduce stress and impart a Nickel bromide 1 vol %
Proprietary additive as needed
semibright appearance to the deposit. Deionized water 72 vol %
Tin electroplating requires the use of tin

Tin plating on circuit boards has limited ap-
sulfate, sulfuric acid, tin anodes, and propri-
plication, mainly to promote solderability. The
etary brighteners. Tin(II) sulfate [7488-55-3],
increase in the cost of precious metal plating has
SnSO4 , acts as the source of tin ions. Sulfu-
caused some renewed interest in tin plating as a
ric acid increases bath conductivity, solubilizes
metal etch resist.
the tin salts, and corrodes the tin anodes. Tin
The use of rhodium plating on circuit boards
[7440-31-5] supplies additional tin ions through
is limited to edge connectors where a low-
corrosion and functions as the anode for the
resistance, long-wearing, oxide-free contact is
electric current. Proprietary brighteners serve
required. In this type of application, rhodium re-
to brighten and level the distribution of the de-
places gold as the plated metal [7, pp. 23 – 24].
posit.
Economic Aspects. The United States
Rhodium electroplating uses proprietary
printed circuit board industry consumed
rhodium salt solutions, sulfuric acid, and
45×103 kg of nickel anodes and 230 × 103 L of
platinized titanium anodes. The proprietary
nickel plating chemicals in 1980 for electrolytic
rhodium solutions supply the metallic rhodium
nickel plating. An additional 190 × 103 L of
as an ion and contain additives that reduce the
tin and rhodium plating chemicals was also
tensile stress of the deposit. Sulfuric acid in-
consumed that year. The largest nickel anode
creases the conductivity of the bath and the pla-
supplier is International Nickel, and the two
tinized titanium serves as the anode for the elec-
largest suppliers of nickel plating chemicals are
tric current.
Sel-Rex and Lea Ronal.
Types and Grades. All anodes are available
as either rods or nuggets and have a minimal
purity of 99.9 %. The proprietary additives for 5. Photoresists (→ Imaging Technology)
nickel, tin, and rhodium are all supplied as ready-
to-use liquid concentrates. The remaining com- 5.1. Dry Film Photoresists
modity chemicals are usually sold in liquid form
as either a technical or chemically pure grade. Dry film photoresists all work negatively and
consist of an acid-based photopolymer layer
Uses. Nickel plating is used on printed cir- sandwiched between a layer of polyester film on
cuit boards as an undercoat for both precious one side and either a polyolefin or a polyethylene
and nonprecious metals. Its main function is sur- sheet on the other side. Both cover sheets pro-
faces, such as switch and edge contacts, that nor- tect the photopolymer from damage by abrasion.
mally receive heavy wear. The nickel is plated The polyolefin or polyethylene sheet is removed
underneath a gold or rhodium plate and greatly as the resist is laminated to the printed circuit
increases wear resistance. There are two basic board. An ultraviolet source is used to expose
nickel plating baths, the nickel sulfamate bath the resist; the polyester sheet is then removed,
and the modified watts nickel bath, which differ and the resist is developed.
Ultraviolet light causes the photopolymer to sible because no swelling induced pattern defor-
polymerize and become insoluble in the devel- mation occurs.
oping solutions. After the dry film is developed,
the remaining material acts as an etch resist with Negative photoresists are azide-based pho-
print- and etch-type circuit boards and as a plat- topolymers that polymerize when exposed to ul-
ing resist with print-, plate-, and etch-type circuit traviolet light. The polymerized areas become
boards. Once the dry film is no longer needed, it insoluble in the organic developer solutions
is stripped from the board by a methylene chlo- while the nonexposed areas are dissolved. The
ride solution for solvent type film, or it is stripped remaining material acts as either an etching re-
by a highly alkaline solution (pH 13) at ca. 49 ◦ C sist or a plating resist, depending on the appli-
for aqueous and semiaqueous type films. This cation.
process is performed only once on a printed cir-
cuit board. Types and Grades. All liquid photoresists
are currently exposed using ultraviolet light.
Types and Grades. Three types of dry film They are generally supplied as 100 % active ma-
photoresists are employed commercially: (1) terials with standard kinematic viscosities of (2,
solvent, (2) semiaqueous, and (3) aqueous. The 6, 18, 30, and 70)×10−6 m2 /s for positive pho-
solvent types are developed by using 1,1,1- toresists, and for negative ones, (5, 30, 45, 50,
trichloroethane, and semiaqueous resists are de- 110, and 540)×10−6 m2 /s.
veloped by using proprietary water-based solu-
tions. Aqueous dry films are developed by us- Uses. Positive and negative photoresists are
ing solutions of sodium carbonate or trisodium applied to the semiconductor substrate as a liq-
phosphate. uid that is spun to form a uniform coating and
subsequently baked to a dry film. Once the pos-
Uses and Economic Aspects. Dry film itive resist is developed, the remaining material
photoresists are used exclusively by the printed acts as an etch resist to form the desired pat-
circuit board industry and are favored for both tern. After the etching is complete, the resist
multilayer and double-sided boards with dense is stripped from the semiconductor wafer. Once
circuitry. the negative photoresist is developed, it protects
In 1980, the United States printed circuit the area that it covers from being etched. After
board industry consumed ca. 1.9×106 m2 of dry the etching process is complete, the developed
film photoresists while Western Europe used photoresist is stripped from the semiconductor
9.1×106 m2 . The two main suppliers of this wafer. This process is typically repeated 8 – 9
product are Du Pont and Dynachem. times for metal oxide semiconductor (MOS) de-
vices and 10 – 12 times for bipolar devices.
Liquid photoresists can also be used as etch-
5.2. Liquid Positive and Negative ing resists for the manufacture of thin-film cir-
Photoresists cuits. However, these circuits are not classified
as semiconductor devices; therefore, the resists
Positive photoresists are based on the pho- used for this application are not included in the
tochemical conversion of an ortho diazoketone economic data.
to a carboxylic acid. On exposure to ultraviolet Liquid photoresists can be used as either a
light, these resists become less hydrophobic and plating or an etching resist on the inner layer of
are more easily attacked by the alkaline devel- multilayer printed circuit boards. The developed
oper. The remaining unexposed areas act as an resist prevents the etching or plating of base and
etch resist for the manufacture of integrated cir- precious metals on the areas that it covers. Typ-
cuits. One of the significant advantages of this ically, these resists are applied only once to the
type of photoresist is that instead of swelling the circuit board.
film and leaching out the solubilized materials,
as with negative resists, the developer removes Economic Aspects. Semiconductors are the
the exposed areas of the positive resist. As a re- major application for positive and negative pho-
sult, extremely-high-resolution images are pos- toresists, with the United States using 300 × 103
and 800 × 103 L, respectively, and Western Eu- Economic Aspects. In 1980, the United
rope using 76 × 103 and 95 × 103 L in 1980. The States used a total of 590 × 103 L of both ther-
three major suppliers of positive resists are Ship- mal and ultraviolet curing screening inks for
ley, Olin-Hunt, and Hoechst, with Kodak and printed circuit board production. At the same
Tokyo Ohka also active. The two leading suppli- time, Western Europe consumed 380 × 103 L
ers of negative resists are Olin-Hunt and Kodak, of screening inks. Hysol and Dynachem are
with E. Merck also active. suppliers in both regions, with Colonial, Nuz-
Dor, London Chemical, and Grace active in the
United States; Coates, Sericol, and Wiederhold
5.3. Screening Inks are active in Europe.
Screening inks are based primarily on

vinyl – polymer resins, although other resins 6. Acids and Etchants
are also available. These inks are screened onto
a printed circuit board by forcing it through a Acids and etchants are used extensively by
stainless steel or polyester monofilament screen manufacturers of semiconductors and printed
that has a specific pattern that determines where circuit boards for operations such as cleaning
the ink is deposited. The inks act as either a and etching either wafers or copper-clad lami-
plating resist or an etching resist. Because of nates. Some of the most important products and
this end-use application, the screening ink must their applications are listed in Table 4.
be chemically resistant to the various cleaning,
plating, and etching solutions used in actual pro-
cessing operations, while maintaining viscosity 6.1. Sulfuric Acid
and thixotropic properties suitable for screen
printing. When the printing process is complete, Sulfuric acid (H2 SO4 ) is a corrosive, oily liquid
the ink is cured by either thermal drying or that is clear, cloudy, or fuming, depending on
ultraviolet light before being used as a resist. concentration (→Sulfuric Acid and Sulfur Tri-
oxide). Sulfur, the principal raw material em-
Types and Grades. There are two basic ployed in the manufacture of sulfuric acid, can
types of screening inks, thermally curable and be obtained from various sources, including (1)
ultraviolet curable, both of which can be soluble elemental sulfur, (2) stack gas emissions, (3) sul-
in either alkali or solvent. The inks are supplied furic acid sludge, and (4) pyrites and hydrogen
as 100 % active material and ready for immedi- sulfide gas.
ate use. New sulfuric acid is commonly manufactured
by the contact process. This procedure involves
Uses. Screening inks are used exclusively catalytic oxidation of sulfur dioxide (SO2 ) to
with printed circuit boards as either a plating sulfur trioxide (SO3 ), which is absorbed in wa-
resist or an etching resist. Alkali-soluble inks ter. Other manufacturing methods include the
are used primarily on print- and etch-type cir- chamber process, which offers slower rates of
cuit boards and can withstand acid-plating baths, production and a lower strength and quality acid,
but not alkaline cleaning steps. These inks are compared to that produced by the contact pro-
removed from the board by alkaline solutions cess.
such as sodium hydroxide. Solvent-soluble inks
Grades and Properties. Sulfuric acid is
are more versatile because they can withstand
produced commercially in a variety of strengths
all usual plating baths and cleaning steps. As a
for various industrial applications. Acids con-
result, these inks are more likely to be used with
taining up to 93.3 wt % H2 SO4 are measured
print, plate, and etch boards. Solvent inks are
in degrees Baume, while acid strengths of
removed from the board by the use of chlori-
93.4 – 100.0 wt % are measured in terms of per-
nated solvents such as 1,1,1-trichloroethane and
cent H2 SO4 . Sulfuric acid purchased by manu-
methylene chloride.
facturers of semiconductors is usually a semi-
conductor grade product assayed at 96 – 97 wt %
Table 4. Functions of acids and etchants
Products CAS registry Formula Applications
number Semiconductors Printed circuit boards
Acids
Acetic acid [64-19-7] CH3 COOH wafer etching of
metals
Boric acid [10043-35-3] H3 BO3 acid bath stabilization
Fluoroboric acid [16872-11-0] HBF4 tin – lead cleaner
Hydrochloric acid [7647-01-0] HCl wafer etching metal cleaner and regeneration
of copric chloride etchants
Hydrofluoric acid [7664-39-3] HF wafer etching
Nitric acid [7697-37-2] HNO3 wafer cleaning laminate cleaning
and etching
Phosphoric acid [7664-38-2] H3 PO4 wafer etching of metals metal cleaner
Sulfuric acid [7664-93-9] H2 SO4 wafer cleaning and cleaning and etching of laminate
resist stripping
Etchants
Ammoniacal solutions NH+
4 salts final copper etching
Ammonium fluoride [16099-75-5] NH4 F wafer etching
Buffered oxide wafer etching of
etchants MOS devices
Copper(II) chloride [7447-39-4] CuCl2 copper etching of inner
layer boards
Iron(III) chloride [7705-08-0] FeCl3 copper etching
Others
Hydrogen peroxide [7722-84-1] H2 O2 wafer etching and
photoresist stripping
Ammonium [7727-54-0] (NH4 )2 S2 O8 copper foil etching to provide
persulfate better adhesion of electroless
copper
Sodium persulfate [7775-27-1] Na2 S2 O8 same as above
acid. The SEMI (Semiconductor Equipment and ture with hydrogen peroxide to form Caro’s acid,
Materials Institute) specifications for sulfuric which is a wafer cleaner and resist stripper.
acid are available [5]. Printed Circuit Boards. Sulfuric acid is used
In addition to semigrade sulfuric acid, ex- as a (1) cleaner, (2) etchant, and (3) constituent
tremely low particulate products are also avail- of electrolytic copper plating baths. As a cleaner,
able to semiconductor manufacturers. These ma- the acid removes foreign contaminants formed
terials meet or exceed specifications for semi- from contact of an etchant of other material with
grade sulfuric acid while being virtually free of the laminate surface. For example, an ammo-
suspended matter. nium persulfate etch in contact with copper can
Manufacturers of printed circuit boards gen- produce copper ammonium sulfate, which can
erally purchase technical grade sulfuric acid. form a film on the board’s surface. This film is
Specifications for particulate content and purity readily removed by dipping the board in a sul-
of these products are not typically as high as furic acid bath prior to the next manufacturing
specifications for acid used by the semiconduc- step.
tor industry. Other applications for this electronic chem-
ical include acid – copper electrolytic plating,
Uses. During the manufacturing of semicon- whereby sulfuric acid is added to a copper sul-
ductors, the wafer is cleaned numerous times fate bath for anode corrosion to replenish the
with sulfuric acid to remove microscopic dust copper sulfate level of the solution while also
and other contaminants from the substrates sur- increasing bath conductivity.
face. For example, during the masking operation
alone, wafers may be cleaned several times be-
fore progressing to the next manufacturing step. 6.2. Hydrofluoric Acid
Other applications for sulfuric acid include mix- Hydrofluoric acid (HF) in the anhydrous form is
a fuming, corrosive liquid that can cause serious
burns on skin contact. The acid is manufactured Uses. Ammoniacal solutions are used only
by the reaction of sulfuric acid and fluorspar (cal- as final copper etchants by manufacturers of
cium fluoride) to produce hydrogen fluoride gas printed circuit boards. Early versions of alkaline
and calcium sulfate. After absorption in water, etchants, such as the ammoniacal solutions, were
the acid is concentrated by distillation, forming used for batch etching; the etch rates decreased
anhydrous hydrogen fluoride. Aqueous grades as the copper content in the etching solutions
are then made by dilution with water. increased. However, newer products were de-
veloped by adding oxidizing agents to speed the
Grades and Properties. Hydrofluoric acid etching rate and increase the copper capacity of
purchased by manufacturers of semiconduc- the solution at a constant temperature. Although
tors is often a semigrade product assayed at batch operations are still employed, continuous
48.8 – 49.2 % HF. Specifications for the semi- systems have become popular. A typical alkaline
conductor grade chemical according to SEMI etching installation operates continuously and in
are available [5]. a closed loop. System components include (1) a
Low particulate HF is also available to manu- standard spray etcher, (2) metering pumps, (3)
facturers of semiconductors. This acid meets or control modules, and (4) storage tanks.
exceeds the semiconductor grade specifications. As previously mentioned, various ammo-
nium compounds are important in formulating
Uses. Hydrofluoric acid is employed primar- ammoniacal solutions (Table 5). These ammo-
ily to etch conductive paths on the surface of the nium compounds serve to hold the copper be-
wafer. The acid is often mixed with ammonium ing etched in solution and to increase the etch
fluoride by the customer to form a buffered oxide rate. Other important components of these pro-
etch, particularly for MOS devices. Various con- prietary solutions include copper ions, which re-
centrations of ammonium fluoride and hydroflu- act with and dissolve the metal by oxidation,
oric acid are used for this purpose; however, a as indicated in Table 5. Generally the solutions
solution containing six parts of ammonium fluo- formulated with these chemicals are compati-
ride to one part of hydrofluoric acid is preferred ble with metals such as gold, nickel, silver, tin,
by most semiconductor fabricators. tin – nickel, and particularly tin – lead.
6.3. Ammoniacal Solutions 6.4. Nitric Acid
Ammoniacal solutions are proprietary formu- Nitric acid (HNO3 ) is strong, reactive, corrosive,
lations that typically contain a blend of vari- and colorless in pure (100 %) form. Pure ni-
ous ammonium-based compounds. For exam- tric acid is unstable and decomposes to nitrogen
ple, these proprietary solutions are generally dioxide, which gives concentrated solutions a
composed of hydroxides, chlorides, carbonates, yellow-brown color; thus, commercial products
phosphates, and nitrates of ammonia. The exact typically contain various proportions of water.
proportion of the individual chemicals to form Commercial production of nitric acid in-
the finished ammoniacal solution is kept confi- volves oxidation of ammonia first to form nitric
dential by the specialty suppliers. oxide, and then nitrogen dioxide, which is ab-
sorbed in water to give the acid. Concentrated
Grades and Properties. Ammoniacal solu- nitric acid is manufactured primarily by dehy-
tions are specifically formulated to meet the de- dration with sulfuric acid. In this procedure sul-
mands for copper etching set forth by the printed furic acid (98 – 99 %) is mixed with sulfur triox-
circuit board industry. These products generally ide (SO3 ) and 60 % nitric acid in a concentrator.
differ in formula mass, appearance, and other The sulfuric acid absorbs the water, resulting in
properties, depending on the proprietary prod- nitric acid of ≥ 95 % strength. The concentra-
uct analyzed. However, most blends have a pH tion of the remaining sulfuric acid ranges from
of 8 – 9 and a density of 12 g/cm3 . 60 to 70 %.
Table 5. Compounds important in formulating ammoniacal solutions
Component CAS registry Formula Function

number
Ammonium hydroxide [1336-21-6] NH4 OH holds copper in solution

Ammonium chloride [12125-02-9] NH4 Cl increases etch rate, copper holding capacity, and
solution stability
Ammonium carbonate [506-87-6] (NH4 )2 CO3 acts as a buffer, retains clean solder holes
Ammonium phosphate [7783-28-0] (NH4 )2 HPO4 retains clean solder
Ammonium nitrate [6484-52-2] NH4 NO3 increases etch rate and retains clean solder
Copper ion Cu2+ reacts with and dissolves metallic copper by acting
as an oxidizing agent
Sodium chlorate [7775-09-9] NaClO3 acts as an oxidizing agent that reacts with and
dissolves metallic copper
Grades and Properties. Nitric acid is oxidation of organic diketones. For example,
manufactured in several concentrations. Acids ethyl anthraquinone is hydrogenated to ethyl an-
containing up to 67.2 wt % nitric acid are de- thrahydroquinone, which is then oxidized to re-
scribed in degrees of Baume, whereas acids of generate the ethyl anthraquinone and hydrogen
70 – 95 wt % (or greater) concentration are com- peroxide.
monly referred to in terms of percent HNO3 .
The semiconductor grade of nitric acid used by Grades and Properties. Commercially,
manufacturers of semiconductors contains ca. aqueous solutions of hydrogen peroxide are
70 wt % HNO3 ; the SEMI specifications for this available in concentrations of 27 – 70 wt %.
acid are available [5]. Most of this material purchased by the semicon-
Grades of nitric acid with a low particulate ductor industry contains 30 – 32 wt % hydrogen
content are also available to the semiconductor peroxide. The SEMI specifications for hydrogen
industry. Manufacturers of printed circuit boards peroxide are available [5].
often buy an electronic- or technical-grade of ni- Grades of hydrogen peroxide with a low par-
tric acid. Specifications of particulate content for ticulate content are also available to semicon-
these products are generally inferior to those of ductor manufacturers. Technical grades are of-
acid purchased by the semiconductor industry. ten preferred by the producers of printed circuit
boards.
Uses. Nitric acid is used to clean foreign con-
taminants from the wafer’s surface during se- Uses. Hydrogen peroxide is commonly used
lected steps in the manufacture of semiconduc- by semiconductor manufacturers to clean wafer
tors. In addition, this material is also blended surfaces of foreign contaminants or to remove a
with other acids, such as acetic and hydrofluo- photoresist. Quite often sulfuric acid is mixed
ric acid, to etch away metals, such as tantalum, with hydrogen peroxide (4 : 1 ratio) to form
simply by reacting with them. Caro’s acid [7722-86-3], peroxymonosulfuric
During the manufacture of printed circuit acid, for maximum cleaning efficiency during
boards, the board itself is often cleaned. Nitric these operations.
acid is frequently used for this operation. Hydrogen peroxide is often purchased in-
dividually by manufacturers of printed circuit
boards to regenerate etching solutions of cop-
6.5. Hydrogen Peroxide per chloride. In this procedure, the laminate is
dipped into a copper chloride bath. The hydro-
Hydrogen peroxide (H2 O2 ) is a nonviscous, gen peroxide acts as an oxidizing agent to free
clear liquid with a faint blue-green color. Hy- chlorine ions, which etch copper from the lami-
drogen peroxide has a slightly sharp odor and is nate.
miscible in all proportions with water. In addition, manufacturers of printed circuit
Several manufacturing processes exist to boards add hydrogen peroxide to proprietary
make hydrogen peroxide; however, the current etchants based on sulfuric acid to etch copper
route involves successive hydrogenation and before electroless copper is deposited.
6.6. Proprietary Peroxy and Sulfuric Once the etchant is formulated by the manu-
Etchants facturer of printed circuit boards, it is then used
primarily to etch copper before electroless cop-
Proprietary etchants are based on either hydro- per is deposited. Because of the etching action of
gen peroxide or sulfuric acid. The formulations these products, electroless copper adheres more
contain specialty additives for stability. strongly to the copper foil on the laminate simply
Proprietary peroxy etchants are composed by its abrasive action. Sodium and ammonium
primarily of hydrogen peroxide. Special addi- persulfate etchants also compete with the peroxy
tives act as stabilizers to retard degradation of products in this end use.
the base chemical. The concentration of these In addition to acting as an etch, proprietary
additives is generally 1 – 4 wt % of the total peroxy etchants are used less extensively to re-
product. move unwanted copper from the board in a later
Proprietary sulfuric etchants usually con- production process, leaving the final circuitry
tain sulfuric acid. Specialty additives, primarily untouched. Other etchants used more frequently
stabilizers, extend the life of the product during in this application include ammoniacal solutions
etching procedures. and iron(III) and copper(II) chlorides.
Once the customer formulates the proprietary
Grades and Properties. Properties of the etchant with sulfuric acid or hydrogen peroxide
proprietary peroxy and sulfuric etchants depend (or both), the copper is etched by formation of
primarily on the base chemicals. For example, copper sulfate:
properties of the peroxy etchants are directly re-
lated to hydrogen peroxide, the base component. Cu + H2 O2 + H2 SO4 → CuSO4 + 2 H2 O
The relative molecular mass of hydrogen perox-
Cooling the etching solution to room tempera-
ide is 34 and its relative density is ca. 1.5 times
ture allows a pure grade of copper sulfate to be
that of water. Sulfuric acid, the base chemical for
extracted for reclamation of copper.
the sulfuric etchants, has a substantially higher
molecular mass of 98.1 and a density of ca. 1.83,
depending on the concentration.
6.7. Ammonium Fluoride
Uses. Before being used as an etchant by the
Ammonium fluoride (NH4 F) is a white crys-
printed circuit board industry, these proprietary
talline salt. It often has a strong ammonia odor
products may be further compounded by the cus-
because it tends to decompose to ammonia and
tomer, depending on the product purchased. For
the more stable ammonium hydrogen fluoride
example, a stabilized peroxy etchant requires
(NH4 F · HF). Ammonium fluoride can be pro-
the addition of water and sulfuric acid (tech-
duced easily by mixing aqueous ammonia with
nical or reagent grade) at the customer’s facil-
ammonium hydrogen fluoride in equimolar pro-
ity. A typical formulation of the finalized peroxy
portions.
product may contain 82 vol % water (deionized),
11 vol % sulfuric acid, and a 7 vol % proprietary
peroxy etchant. Grades and Properties. Ammonium fluo-
Conversely, a manufacturer of printed circuit ride employed by manufacturers of semiconduc-
boards buying stabilized sulfuric acid would add tors contains 40 wt % NH4 F. The SEMI specifi-
water and hydrogen peroxide to get the final for- cations for this material are available [5].
mulation.
In addition to stabilized hydrogen peroxide Uses. Ammonium fluoride is generally
or sulfuric acid, specialty additive formulations mixed with hydrofluoric acid by manufacturers
are also available. These products consist pri- of semiconductors to etch the surface of wafers,
marily of the same materials used to give sta- particularly those used to make MOS devices.
bility to the preceding base chemicals; however, These buffered oxide etches, made captively,
these products require addition of sulfuric acid often contain six parts of ammonium fluoride to
and hydrogen peroxide by the customer. one part of hydrofluoric acid.
6.8. Persulfates Na2 S2 O8 per liter of warm water. Small quanti-

ties of phosphoric or sulfuric acid can be added
Ammonium persulfate (NH4 )2 S2 O8 and sodium on initial makeup for more aggressive cleaning
persulfate (Na2 S2 O8 ) employed by manufac- solutions.
turers of printed circuit boards are white crys-
talline materials with strong oxidizing charac-
teristics. These products are typically produced 6.9. Other Acids and Etchants
by electrolytic oxidation of the appropriate hy-
drogen sulfate salt. A variety of other acids and etchants are em-
ployed by manufacturers of semiconductors and
Grades and Properties. Both ammonium printed circuit boards in their production pro-
and sodium persulfates are high-purity salts cesses. Among the more important are acetic,
easily solubilized in water and other materials. phosphoric, and hydrochloric acids, whereas
The molecular mass of sodium persulfate is 238, other material, such as formulated buffered ox-
whereas that of ammonium persulfate is some- ide etches (BOE) and iron(II) chloride, are also
what less at 220. The amount of active oxygen significant.
differs between each product type, but generally
is 6 – 7 wt %. Acetic Acid (→ Acetic Acid). The three sig-
nificant processes employed to produce acetic
Uses. Persulfates are used by the printed cir- acid are (1) methanol carboxylation, (2) bu-
cuit board industry mostly as a cleaner and tane oxidation, and (3) acetaldehyde oxidation.
etchant prior to the deposition of electroless cop- Acetic acid purchased by manufacturers of semi-
per. Because they are strong oxidizing agents, conductors is usually a semigrade product as-
these products roughen or abrade the surface of sayed at 99.7 wt % CH3 COOH. The SEMI spec-
the board, enabling electroless copper to adhere ifications for acetic acid as used in phosphoric
more strongly without attacking resists or plas- etchants are available [5].
tics used as the circuitry base. Persulfates are Acetic acid is used by manufacturers of semi-
applied in either continuous or batch methods, conductors only where it is mixed with nitric and
depending on the customer’s operation. phosphoric acids to serve as a metal etchant.
Solutions based on persulfates have an etch Semigrade acetic acid sells for ca. $ 2.20/kg
rate of 0.76 – 2.5 nm/min, depending on the tem- ($ 1/lb.), and it is usually shipped in 2.3-kg (5-
perature and copper content of the solution, lb.) bottles, with six to a case.
which can be ≥ 7.8 mg/L. The persulfate con-
centration can also affect the etch performance Phosphoric Acid. (→ Phosphoric Acid and
of the finished persulfate solution. Phosphates) Phosphoric acid is a corrosive,
Ammonium persulfate can be used to etch syrupy liquid that can cause burns on contact
other metals besides copper, including materi- with the skin. It can be made by reacting ele-
als such as aluminum, beryllium, and brass. The mental phosphorus with oxygen to form phos-
ratio of the compounds in the mixture depends phorus oxides, which are then dissolved in water
on the customer’s operation. A 20 % solution to form the acid. An alternate process involves
is made simply by adding 0.2 kg of ammonium the reaction of acids such as sulfuric or nitric
persulfate per liter of water in a sump or dissolv- acid with phosphate rock to dissolve the calcium
ing tank. phosphate. Phosphoric acid purchased by manu-
Solutions are often catalyzed with materials facturers of semiconductors is usually a semi-
such as mercuric chloride to achieve optimal grade product assayed at 85 – 87 wt % H3 PO4 .
etch rates or phosphoric acid to eliminate in- The SEMI specifications for this chemical are
complete etching of copper next to solder-plated available [5].
conductors. Technical grades of phosphoric acid have
Sodium persulfate solutions are also pre- lower purity and a higher particulate content than
pared according to the customer’s preference. the semigrade products and as a result are used
For example, solutions often contain 0.15 kg of less frequently.
Manufacturers of semiconductors mix phos- Chromic – Sulfuric Acid Etchants.

phoric acid with nitric and acetic acids and use Chromic – sulfuric etchants are specially
the mixture as a metal etchant, whereas the blended products containing chromic and sul-
printed circuit board industry employs the acid furic acids with the exact proportion of each
by itself as a metal cleaner. Semigrade phos- component determined by the formulator. These
phoric acid sells for ca. $ 1.50/kg ($ 0.68/lb.), products are used sparingly by printed circuit
and it is usually packaged in 6.35-kg (14-lb.) board manufacturers to remove epoxy smears
bottles, with four to a case. Technical grade in the etch-back process and as a final copper
acid is somewhat less expensive at $ 0.46/kg etchant. Chromic – sulfuric blends usually cost
($ 0.21/lb). ca. $ 0.53/L ($ 2/gal).
Hydrochloric Acid. (→ Hydrochloric Acid) Boric Acid. (→ Boric Oxide, Boric Acid,
Hydrochloric acid is a strong, highly corrosive and Borates, Chap. 3.) Boric acid is used by
acid, primarily produced as a byproduct from the printed circuit board manufacturers for acid bath
manufacture of organochlorine chemicals. The stabilization. The cost of this product is ca.
semiconductor industry buys a semigrade prod- $ 0.14 kg ($ 0.30/lb).
uct assayed to contain a minimum of 37 wt %
acid. The SEMI specifications are available [5]. Buffered Oxide Etchants. Buffered oxide
In addition to semigrade acid, products with etchants (BOE) are specially blended products
an extremely low particulate content are also often containing six parts of ammonium fluo-
available to manufacturers of semiconductors. ride to one part of hydrofluoric acid. These prod-
Technical- or reagent-grade hydrochloric acid is ucts are used primarily as etchants, particularly
commonly employed by the printed circuit board for MOS devices, by semiconductor manufac-
industry. turers. Formulated BOE etchants purchased by
Hydrochloric acid is used primarily as a wafer this industry cost ca. $ 1.83/kg ($ 0.83/lb.) in
etchant by semiconductor manufacturers. The 1980. The SEMI specifications for this product
printed circuit board industry employs HCl as are available [5].
a metal cleaner and as a source of chlorine ions
for copper(II) chloride etchants. Semigrade acid Copper(II) Chloride. (→ Copper Com-
sells for ca. $ 1.28/kg ($ 0.58/lb.) in 4.54-kg (10- pounds, Chap. 4.) Copper(II) chloride etch-
lb.) containers, with four to a case, whereas ing solutions contain components such as hy-
technical-grade acid is considerably less expen- drochloric acid, sodium chloride, ammonium
sive at $ 0.18/kg ($ 0.08/lb). chloride, water, and copper(II) chloride crys-
tals. Specific formulations of these commodity
Fluoroboric Acid. (→ Boron Compounds, chemicals depend on performance results ex-
Chap. 2.) Fluoroboric acid with a density of ca. perienced by the individual manufacturer of
1.38 g/cm3 has properties similar to those of hy- printed circuit boards during final etching oper-
drofluoric acid, including a corrosive effect on ations. For example, chloride ions can be pro-
glass. This acid is used primarily by the printed vided by several sources, including hydrochloric
circuit board industry as a tin – lead cleaner, and acid, sodium chloride, or ammonium chloride,
the cost is ca. $ 1.32/kg ($ 0.60/lb). to solubilize the relatively insoluble copper(I)
chloride formed by the etching action of the
copper (II) chloride solution on copper. The use
Mixed Acid Etchants. Mixed acids are spe-
of such chloride ions assists in maintaining a
cially blended products usually containing ni-
stable etch rate. In addition, copper(I) chloride
tric, hydrofluoric, and acetic acids. Properties of
can be oxidized to copper(II) chloride by elec-
these products depend on the proprietary pro-
trolytic processes or by direct chlorination, as
portions of each component. A mixture of acids
follows:
is used by the semiconductor industry as a metal
etchant; cost ranges from $ 1.52 to $ 2.29/kg Cu2 Cl2 +Cl2 −→ 2 CuCl2
($ 0.69 to $ 1.04/lb). The SEMI specifications
for mixed acid etchants are available [5]. Copper(II) chloride solutions are used mostly
to etch inner layers of multilayer boards. These
solutions are also used to process print and etch Economic Aspects. Total demand for acids
boards. Resists, such as screening inks, dry film, and etchants by the electronics industry in the
and tin – nickel, are compatible with this etchant, United States was 169.6×103 t in 1980. The
whereas other materials, such as tin – lead and printed circuit board industry used 71 % of the
tin boards, are unsuitable. total (119.9×103 t), and the semiconductor in-
dustry consumed the balance. A breakdown of
Table 6. Consumption of acids and etchants in electronics in the
United States, 1980 consumption by product is given in Table 6.
The leading suppliers of semiconductor-
grade acids and etchants in the United States
Semicon- Printed Total are General Chemical, Ashland Chemical, and
ductors circuit
boards
Mallinckrodt. Technical-grade chemicals are
provided by numerous bulk chemical manufac-
Acids turers. Ammoniacal solutions are sold mainly
Sulfuric 16.8 27.2 44.0
Nitric 7.7 2.0 9.7 by Olin-Hunt, MacDermid, and Southern Cal-
Hydrochloric 1.4 7.7 9.1 ifornia Chemical. The three major suppliers of
Hydrofluoric 8.2 8.2
Proprietary 3.1 3.1
proprietary acid mixtures are Electrochemicals,
Phosphoric 1.7 1.3 3.0 Shipley, and MacDermid. The major supplier of
Acetic 2.3 2.3 persulfates in the United States is FMC.
Fluoroboric 2.1 2.1
Chromic – sulfuric 1.0 1.0
Mixed 0.5 0.5
Boric 0.4 0.4
Subtotal 38.6 44.8 83.4 7. Atmospheric Gases
Etchants
Ammoniacal Nitrogen [7727-37-9], N2 , bp −196 ◦ C, is a
solutions 48.1 48.1
Copper(II) chloride 12.2 12.2
chemically inert, odorless, colorless, tasteless,
Iron(III) chloride 8.1 8.1 diatomic gas (→ Nitrogen). It makes up 80 vol %
Hydrogen peroxide 5.4 1.4 6.8 of the air we breathe. Nitrogen reacts with other
Persulfates 5.3 5.3
Ammonium fluoride 3.7 3.7 elements only at high temperature and pressure.
Buffered oxide Nitrogen is produced in air-separation plants
etchants 2.0 2.0
Subtotal 11.1 75.1 86.2 by liquefaction and subsequent fractionation of
Total 49.7 119.9 169.6 air into its major components, i.e., nitrogen, oxy-
gen, and small amounts of argon. In some plants
small quantities of neon, krypton, and xenon
Iron(III) Chloride (→ Iron Compounds). may also be recovered, whereas other gases in
Iron(III) chloride etchants consist primarily of the air, such as carbon dioxide, helium, and hy-
FeCl3 in water with concentrations ranging from drogen, are usually vented. Generally, the most
28 to 42 wt %; wetting and antifoam agents also economical production ratio is 2.4 parts of ni-
are typically added. These solutions are widely trogen to 1 part of oxygen, with excess N2 used
used in the printed circuit board industry as fi- to clean alternate compressors within the plant.
nal etchants for copper, copper alloys, and steel. Grades and Properties. Nitrogen has a
In addition the iron(III) chloride etchant is com- molecular mass of 28.01 and a specific volume
patible with screening inks and photoresists, but of 0.862 m3 /kg. Typically, gas sold to the semi-
not with solder or tin-plated boards. conductor industry exceeds 99 % in purity. The
Solutions of iron(III) chloride formulated SEMI specifications for liquid nitrogen used in
with additives by specialty suppliers provide fast bulk by the semiconductor industry are available
and even etching, partly because of the addition [5].
of strong oxidizers and surface wetting agents. Uses. Nitrogen is essential in many produc-
Over the years, suppliers of these products have tion processes and is by far the most widely used
greatly extended the useful life and uniformity of atmospheric gas among manufacturers of semi-
etch rates provided by these products. Iron(III) conductors in the United States. For example, ni-
chloride etching solutions sold for ca. $ 0.18/L trogen is commonly found in furnaces, epi (epi-
($ 0.70/gal) or ca. $ 0.13/kg ($ 0.06/lb.) in 1980. taxial) reactors, and ion implanters as an inert
atmosphere to protect against impurities such as
oxygen. Additional uses for this versatile gas mercial oxygen is produced by fractional distil-
include serving as the transportation medium in lation of air.
air tracts and the driving force in air guns. Nitro- Types and Grades. Oxygen purchased by
gen is supplied to customers by several means, manufacturers of semiconductors is high in qual-
including (1) pipelines serving either single or ity with a minimal purity of 99.6 %.
multiple facilities, (2) air-separation plants lo- Uses. Oxygen is used by manufacturers of
cated on site, and (3) merchant bulk deliveries. semiconductors to produce passivation layers of
silicon dioxide on silicon substrates, particularly
Hydrogen [1333-74-0], H2 , is a colorless, for MOS devices. Additional uses of this gas in-
odorless, and tasteless gas that is lighter clude plasma stripping of photoresists.
than air and practically insoluble in water Economic Aspects. Consumption of the four
(→ Hydrogen). Commercial processes for hy- atmospheric gases discussed in this chapter is
drogen production include electrolysis, ammo- shown in Table 7.
nia dissociation, propane re-forming, partial ox- Table 7. Consumption of atmospheric gases by the semiconductor
idation of hydrocarbons, and steam re-forming industry, 1980
of natural gas. Gas Consumption, 106 m3
Types and Grades. Hydrogen purchased by
manufacturers of semiconductors generally has United Western
States Europe
a minimal purity of 99.9 % The SEMI specifi-
cations for impurity levels in bulk hydrogen are Nitrogen 1076.0 138.8
available [5]. Hydrogen 31.2 6.4
Argon 7.1 2.0
Uses. Hydrogen is used by the semiconduc- Oxygen 21.5 2.6
tor industry to create a reducing atmosphere, par-
ticularly in manufacturing bipolar devices. For These gases are typically sold by the same
example, with metals such as aluminum, any ox- companies. Several major suppliers are active
ide present can be reduced to seal the metallic in both the United States and Western Europe,
surface before becoming a component of the in- including Air Products, BOC/Airco, and L’Air
tegrated circuit. An additional, but less common, Liquide. The Linde Division of Union Carbide
application for hydrogen involves mixture of gas is an important supplier of atmospheric gases in
with carbon tetrafluoride for reactive ion etching the United States, and Messer Griesheim is a big
(RIE). supplier in the Federal Republic of Germany.
Argon [7440-37-1], Ar, bp −186 ◦ C, fp
−198.4 ◦ C is a colorless and odorless gas
(→ Noble Gases). Virtually all commercial pro- 8. Photoresist Adjuncts
duction of argon is the result of oxygenic sepa-
ration of atmospheric gases. 8.1. Photoresist Strippers
Types and Grades. Argon purchased by
manufacturers of semiconductors is almost Strippers are chemicals used to remove photore-
100 % pure. The SEMI specifications for the sist after the etching or plating process is com-
allowable impurity levels are available [5]. plete. Unlike developers, which remove solubi-
Uses. Argon is used primarily by the semi- lized photoresist, strippers remove the hardened
conductor industry as an inert atmosphere unsolubilized photoresist without damaging the
for growing single silicon cystals (→ Crystal underlying material.
Growth; → Silicon). Argon is also used as an
atmosphere during ion-implant procedures and Types and Grades. The three types of strip-
during annealing, a process to repair substrate pers for semiconductor photoresists are (1) oxy-
damage after ion implantation takes place. gen in a plasma state, (2) phenolic-based for-
mulations, and (3) nonphenolic formulations,
Oxygen [7782-44-7], O2 , is a colorless gas which are based on either sulfonic acid or
that forms oxides with all elements except some chromic acid. All of these products are sold as
of the noble gases (→ Oxygen). Almost all com- electronic-grade material. Strippers for printed
circuit board photoresists include commod- 8.2. Dry Film Photoresist Developers
ity chemicals, such as methylene chloride and
sodium hydroxide, as well as proprietary formu- Dry film photoresist developers are either
lations based on these chemicals. These printed solvent- or alkaline-based products that remove
circuit board strippers are available as technical- the soluble, nonexposed areas of the resist prior
grade materials. to the plating process.
Uses. Semiconductor photoresist stripping Types and Grades. The two types of dry
with oxygen is accomplished by placing the film developers are commodity solvents and pro-
wafers in a vacuum chamber, where the gas prietary formulations. Usually technical-grade
passes through a radio frequency electrode to 1,1,1-trichloroethane is the solvent used to de-
form a highly ionized gas or plasma. The plasma velop solvent-processable dry films. Propri-
contacts the photoresist, causing a chemical re- etary developers are used with aqueous- and
action that oxidizes the resist to ash; the resist semiaqueous-processable dry films.
ash is then rinsed from the water surface. On the
other hand, chemical resist stripping involves Uses. Dry film photoresists are developed by
immersion of the wafer in a stripping bath for immersing the printed circuit board in a solution
30 – 60 s. of aqueous developer. The time required for op-
All printed circuit board resists are stripped timum development varies with the thickness of
by immersion techniques. Solvent-based strip- the resist and the temperature of the bath, but
pers usually operate at room temperature and normally 30 – 60 s is needed.
require 1 – 2 min for complete photoresist re-
moval, while alkaline-based strippers operate at Economic Aspects. In 1980, the United
49 – 60 ◦ C and require from 30 s to 3 min for States printed circuit board industry used a to-
complete photoresist removal. tal of 14.8×106 L of dry film photoresist devel-
opers. Approximately 11.4×106 L consisted of
Economic Aspects. The total consumption 1,1,1-trichloroethane, and the balance was pro-
of strippers for electronics in the United prietary formulations. Dow and PPG are the ma-
States was 12.8×106 L in 1980. Of this total, jor suppliers of 1,1,1-trichloroethane, whereas
10.9×106 L was used by the printed circuit Du Pont and Dynachem are the major suppliers
board industry, as indicated in Table 8. of proprietary developers.
Table 8. Consumption of strippers by the electronics industry
Consumption, 106 L 8.3. Positive Photoresist Developers

Product Printed circuit Semiconductors Total
boards Positive photoresist developers are alkaline-
Solvent 8.3 8.3
based solutions that remove the soluble exposed
Alkaline 2.6 2.6 areas of the resist by an etching process. Devel-
Phenolic 1.5 1.5 opment of the resist is accomplished by either a
Nonphenolic 0.4 0.4
Total 10.9 1.9 12.8 spray or immersion technique.
Many companies supply photoresist strippers Types and Grades. The two types of pos-
for printed circuit boards, but the three largest itive photoresist developers are commodity
suppliers are Chemical Solvent, J & S Laborato- chemicals, such as sodium and potassium hy-
ries, and Inland Specialty Chemical. For semi- droxide, and proprietary alkaline-based formu-
conductor photoresist strippers, Industri-Chem lations. Electronic grades of sodium and potas-
is the major supplier of phenolic-based prod- sium hydroxide are normally used, while pro-
ucts, General Chemical is an important sup- prietary developers are available only in an elec-
plier of both phenolic and nonphenolic products, tronic grade.
and EKC Technology specializes in nonphenolic
products.
Uses. Semiconductor wafers can be either Uses. Usually electronic-grade xylene or

immersed in a developer solution or sprayed proprietary formulations are used to develop
with the solution. Immersion is favored with pos- photoresists on semiconductor wafers, although
itive photoresist developers because line resolu- some reagent-grade xylene is also used. Semi-
tion is usually better with this technique. The conductor wafers can either be immersed in a
developing time required for immersion is ca. developer solution or have the solution applied
1 min. Spray techniques offer faster speed than by spraying. Spray systems offer the benefit of
that obtained with the immersion method, with speed and provide a continuous flow of clean
a typical development time of 15 s. solvent, while batch immersion tends to give
Positive photoresists used on printed cir- finer resolution. The developing time with spray
cuit boards are usually developed by immersion systems ranges from 15 to 30 s compared with
techniques. 60 – 90 s for batch immersion.
Printed circuit boards using a Kodak or Hunt
Economic Aspects. In 1980, a total of negative resist can be developed either in a va-
704×103 L of positive photoresist developers por degreasing chamber using trichloroethylene
was consumed in the United States. Of the total, or by immersion in a proprietary developer. Dy-
643×103 L consisted of proprietary developers nachem resists are attacked by trichloroethyl-
and the rest were either sodium or potassium ene and must be developed by immersion in ei-
hydroxide. Proprietary developers are sold by ther 1,1,1-trichloroethane or a proprietary solu-
the photoresist supplier, Shipley, Hoechst, Olin- tion. Development time with a vapor degreaser
Hunt, and Kodak; firms such as Ashland Chem- ranges from 3 to 4 min, while immersion in a
ical, J. T. Baker, and General Chemical supply formulated developer usually requires 20 – 30 s.
semiconductor grade hydroxides. A vapor degreaser can develop many boards si-
multaneously, but immersion is usually done one
board at a time.
8.4. Negative Photoresist Developers
Economic Aspects. The use of negative pho-
Negative photoresist developers are either sol- toresist developers in the United States was
vent or solvent-based products that swell the 1.89×106 L in 1980, the vast majority being
photoresist film after the imaging process. The used in semiconductor applications. Xylene was
developer removes the soluble, unexposed area the preferred product, representing 90 % of all
of the resist by a leaching process. The resist is consumption, with proprietary formulations ac-
developed by either a spray or immersion tech- counting for most of the balance. Firms such
nique. A solvent rinse is used after the film is as Ashland Chemical, J. T. Baker, and General
developed to remove any residual developer and Chemical supply semiconductor-grade xylene.
to reduce swelling of the remaining photoresist. Photoresist manufacturers, including Olin Hunt,
Kodak, and E. Merck, supply the proprietary for-
Types and Grades. The two types of nega- mulations.
tive photoresist developers are commodity sol-
vents, such as xylene, 1,1,1-trichloroethane,
trichloroethylene (TCE), and stoddard solvent 8.5. Photoresist Adhesion Promoters
proprietary formulations. Both electronic-grade
and reagent-grade xylene is used by the elec- 1,1,1,3,3,3-Hexamethyldisilazane [999-97-3],
tronic industry, while only electronic-grade pro- (HMDS), (CH3 )3 SiNHSi(CH3 )3 , is an
prietary formulations are available. The propri- organosilicon compound that is used to promote
etary products are based on xylene, with stabi- adhesion of photoresists on silicon and silicon
lizers added. The printed circuit board indus- oxide surfaces during manufacture of semicon-
try usually uses technical-grade commodity sol- ductor devices. 1,1,1,3,3,3-Hexamethyldisila-
vents. The SEMI specifications for xylene are zane accomplishes increased photoresist adhe-
available [5]. sion by reacting with surface hydroxyl groups,
which normally repel photoresists, to form hex-
amethyldisiloxane, which does not repel pho- leading suppliers are PCR, KTI, Mallinckrodt,
toresists. and Ashland Chemical.
The three methods for applying HMDS to the
surface of the semiconductor substrate are evap-
oration, spinning it on, and complete immersion. 9. Cleaners and Specialty Materials
In the evaporative method, elevated tempera-
ture causes HMDS to vaporize and subsequently Tin – Lead Strippers. Tin – lead strippers
contact the wafer surface. This technique gen- are based mostly on hydrogen peroxide, a clear
erally uses 100 % active HMDS, although less liquid with a slightly sharp odor. Although not
concentrated solutions can also be used; a tray specifically identified, stabilizers are usually
of wafers can be treated simultaneously. Several included in the formulation to prevent degrada-
industry sources believe this method to be the tion of the base chemical. The average density
most cost effective of the three. of tin – lead strippers based on hydrogen perox-
The spin-on method applies the liquid HMDS ide is estimated to be 1.16 g/cm3 . Compositions
directly to the wafer just prior to applying the of the less frequently used products that are not
photoresist. This approach uses solvent mixtures based on peroxide are unavailable.
of HMDS, requiring that the solvent be compati- Uses. Manufacturers of printed circuit
ble with the photoresist thinner. Usually solvents boards frequently employ tin – lead stripping
such as xylene and stoddard solvent are used to remove tin – lead from edge connectors or
with negative resists, while ethylene glycol, fluo- tops without damaging the copper or laminate
rocarbon 113, or cellusolve acetate are used with itself. This procedure promotes adhesion of the
positive resists. Carbon tetrafluoride is compat- nickel plate on the copper surface prior to gold
ible with both types of resists. The spin-on tech- striking. Strippers currently available are capa-
nique provides a uniform coating of HMDS on ble of removing 0.013 mm of tin – lead in < 1
the wafer, but this method can treat only one min or up to 135 g of tin – lead per liter. Other
wafer at a time. products are specifically designed just to remove
Complete immersion requires dipping the tin to prevent subsequent poisoning of the nickel
wafer into a bath of HMDS and solvent. This plate by enhancing adhesion.
process is not widely used because it offers lit-
tle control over the amount of HMDS coated on Copper Cleaners. Copper cleaners are gen-
each wafer. erally acid- or alkaline-based products sold in
concentrate form. As expected, properties such
Types and Grades. 1,1,1,3,3,3-Hexa- as density and pH are directly related to the base
methyldisilazane is available in concentrations chemical. For example, the density of acid con-
ranging in activity from 5 to 100 %. In solu- centrates is ca. 1.08 g/cm3 and the pH is usually
tions, HMDS is normally mixed with solvents < 4. The exact amount of water or other solvents
such as xylene, stoddard solvent, ethylene gly- mixed with copper cleaners depends on operat-
col, and carbon tetrafluoride. All HMDS is sold ing results experienced by the individual opera-
as electronic-grade material, indicating that the tor at each company.
level of each metal impurity is < 1 ppm. Uses. The printed circuit board industry em-
ploys copper cleaners for a variety of jobs in-
Uses. The semiconductor industry uses cluding removal of organic and inorganic soils,
HMDS exclusively as an adhesion promoter. such as fingerprints, light oils, or tarnish, from
The use of HMDS to treat oxide surfaces is co- copper surfaces. Boards are generally sprayed
vered by a patent assigned to IBM [8]. Licenses or soaked with the copper cleaner followed by a
under this patent are available from IBM on rea- water rinse.
sonable terms and conditions.
Tin – Lead Cleaners. Tin – lead cleaners
Economic Aspects. In 1980, ca. 303×10 L 3 are generally acid-based products containing ad-
of 100 % active HMDS was consumed by the ditives to reduce degradation of components dur-
semiconductor industry in the United States. The ing adverse operating conditions. Some prod-
ucts are employed in full strength, and others
are frequently diluted with water before being Trichlorosilane [10025-78-2], SiHCl3 , is
applied. made by passing hydrogen chloride through
Properties of tin – lead cleaners vary by prod- silicon powder at a moderate temperature
uct, depending on the base chemicals. For exam- (280 – 300 ◦ C):
ple, densities of acid-based products can range
from 1.08 to 1.14 g/cm3 and the pH is typically 2 Si + 6 HCl −→ 2 SiHCl3 + 2 H2
< 1.
The manufacturing equipment used in this pro-
Economic Aspects. In 1980, the printed cir- cess is similar to that for the production of silicon
cuit board industry in the United States con- tetrachloride.
sumed 9.0×106 L of the following cleaners and The major application for trichlorosilane is as
specialties (in 106 L): a raw material for producing high-purity poly-
crystalline silicon, which eventually becomes
Tin – lead strippers 3.4 the polished silicon wafers used in semiconduc-
Tin – lead cleaners 3.0
Copper cleaners 2.6
tor production.
Dichlorosilane [4109-96-0], SiH2 Cl2 , is a

Numerous companies supply these products byproduct in the manufacture of trichlorosilane:
in the United States. The leading ones are
Chemelex, J & S Laboratories, MacDermid, En- Si + 2 HCl → SiH2 Cl2
thone, Argus International, and Electrochemi-
The only significant application for dichlorosi-
cals.
lane is as a source of polycrystalline silicon
and silicon nitride for epitaxial deposition in
the manufacture of semiconductors. However,
10. Specialty Gases Hemlock Semiconductor is conducting experi-
ments using dichlorosilane as a raw material for
10.1. Silicon Gases large-scale production of high-purity polycrys-
talline silicon.
Silicon gases are used to deposit silicon and sili-
con compounds onto silicon substrates by chem- Silane [7803-62-5], SiH4 , is produced by
ical vapor deposition. These deposits or epitaxial combining an ether solution of silicon tetrachlo-
layers are part of the finished semiconductor de- ride with an ether solution of lithium aluminum
vice. Four silicon gases are used to form the epi- hydride, as shown in the following equation:
taxial layers: silicon tetrachloride, trichlorosi-
lane, dichlorosilane, and silane. SiCl4 + LiAlH4 −→ SiH4 + LiCl + AlCl3
Silicon(IV) tetrachoride [10026-04-7], Silane is used largely as a raw material to form

SiCl4 , tetrachlorosilane, silicon(IV) chloride, other silicon-containing compounds, but it also
is manufactured as a liquid by an exothermic re- serves as a source of silicon for deposition of
action of silicon carbide with chlorine as given epitaxial layers.
in the following equation:
Types and Grades. The four silicon prod-
SiC + 2 Cl2 → SiCl4 + C ucts are all sold as compressed gases. Purity
levels of the gases vary among suppliers, but
The major use of SiCl4 is production of fumed all are available as semiconductor-grade ma-
silica, but other applications, include (1) syn- terial (> 99 % pure). The SEMI specification
thesis of silicon esters, (2) production of special for silicon tetrachloride and for silane (for both
glass for the electronics industry, and (3) pro- polysilium – silicon dioxide and silicon nitride
duction of high-purity silicon. applications) are available [5].
Uses and Toxicology. All four of the silicon Silane is considered one of the most danger-
gases can serve as a source for epitaxial silicon ous of the silicon gases to handle because it ig-
and silicon dioxide by chemical vapor deposi- nites on contact with air. However, the flame is
tion. Silane forms silicon by simple pyrolysis at relatively cool and no toxic fumes are known to
temperatures of 800 – 1000 ◦ C, as follows: be released. The ACGIH has established a TLV-
TWA of 5 ppm, 7 mg/m3 (no MAK has been es-
SiH4 → Si + 2 H2 tablished) [9]. The advantages of silane are that
it causes little or no pattern shift during forma-
The other gases form silicon deposits by hydro-
tion of epitaxial layers and that it operates at the
lysis and release of hydrogen chloride. Silicon
lowest temperature (800 – 1000 ◦ C) of all sili-
tetrachloride requires a temperature > 1200 ◦ C.
con gases. Silane also exhibits a layer growth
The reactions are as follows:
rate that is the easiest to control. As a result,
SiCl4 + 2 H2 −→ Si + 4 HCl
silane is important in the semiconductor indus-
try as the thickness of epitaxial layers decreases
SiHCl3 + H2 −→ Si + 3 HCl
with more sophisticated devices.
Both dichlorosilane and trichlorosilane of-
SiH2 Cl2 −→ Si + 2 HCl fer a compromise in characteristics between
silane and silicon tetrachloride. Dichloro- and
Epitaxial silicon dioxide layers are formed by trichlorosilane are corrosive and toxic, but do not
oxidation of silane; the other gases hydrolyze ignite when in contact with air. Both cause some
in a moist atmosphere. Reactions for these pro- pattern shift, but not as much as silicon tetrachlo-
cesses are as follows: ride, and both operate at temperatures between
1100 and 1200 ◦ C. Dichlorosilane is particularly
SiH4 + O2 −→ SiO2 + 2 H2 effective in producing thick epitaxial layers and
requires less processing time than silane.
SiHCl3 + 2 H2 O −→ SiO2 + 3 HCl + H2
Economic Aspects. The total United States
SiH2 Cl2 + 2 H2 O −→ SiO2 + 2 HCl + 2 H2 consumption of silicon gases for semiconduc-
tor fabrication was 108.9 t in 1980. Silicon tetra-
SiCl4 + 2 H2 O −→ SiO2 + 4 HCl
chloride represented the majority of the volume
Silane and dichlorosilane are also used to form as shown (in t):
epitaxial silicon nitride deposits for the passiva- Silicon tetrachloride 45.4
tion of semiconductor devices. In each case, the Silane 34
Dichlorosilane 22.7
silicon gas reacts with ammonia as the following Trichlorosilane 6.8
equations show:
3 SiH4 + 4 NH3 −→ Si3 N4 + 12 H2 The major suppliers of these products in the

United States are the Linde Division of Union
3 SiH2 Cl2 + 4 NH3 −→ Si3 N4 + 6 HCl + 6 H2
Carbide, Liquid Carbonic, Matheson, Air Prod-
Silicon tetrachloride is the easiest of the silicon ucts, Scientific Gas Products, and Synthaton.
gases to handle. Although corrosive, it does not
ignite on contact with the atmosphere, nor is it
classified as toxic. Silicon tetrachloride has the 10.2. Etchant Gases
fastest layer growth rates and forms the thick-
est layers in the deposition of silicon and sili- Etchant gases are used to remove selected ar-
con dioxide, which is important in the manufac- eas of materials such as silicon, silicon diox-
ture of many linear type devices. It does cause ide, silicon nitride, glass, aluminum, and tan-
distortion pattern shift in the deposition of epi- talum during the processing of semiconduc-
taxial layers because of the chlorine radicals tor wafers. The most common gas used for
and requires the highest operating temperatures etching is carbon tetrafluoride [75-73-0], CF4 ,
(> 1200 ◦ C) of all silicon gases. tetrafluoromethane. It is a colorless, nontoxic,
stable gas, which can be used in pure form tetrafluoride as an etchant gas in 1980. An ad-
or mixed with oxygen to etch semiconduc- ditional 9100 kg of miscellaneous etchant gases,
tor wafers. Other gases that can be used as including silicon tetrafluoride, chlorine, hexaflu-
an etchant include silicon tetrafluoride (SiF4 ), oroethane, and perfluoropropane, was also con-
fluoroform (CHF3 ), hexafluoroethane (C2 F6 ), sumed. The only basic manufacturers of carbon
perfluoropropane (C3 F8 ), and chlorine (Cl2 ). tetrafluoride in the United States are Linde, Air
Products, and Du Pont. The Du Pont material is
Types and Grades. Carbon tetrafluoride is sold through such gas suppliers as Matheson and
sold as a compressed gas. It is usually available Scientific Gas Products.
with a minimum purity level of 99.7 %.
Uses. The etchant gases are employed in a 10.3. Light-Emitting Diode Gases
process known as plasma etching. A plasma re-
sembles a gas, but a fraction of the molecules or Light-emitting diode (LED) gases are used to
atoms are ionized and carry an electrical charge. deposit epitaxial layers of gallium arsenide, gal-
The plasma also contains a substantial quantity lium phosphide, and gallium arsenide phosphide
of free radicals, which are electrically neutral onto substrates of the same composition dur-
but highly reactive. The presence of ions and ing the manufacture of LED and miscellaneous
free radicals makes the plasma very reactive and, gallium-based semiconductor devices. Arsine
thus excellent for an etching process. [7784-42-1], AsH3 , and phosphine [7803-51-2],
A plasma etching system consists of three ba- H3 P, are two gases that are used for this pur-
sic units: (1) a reactor, which holds wafers dur- pose. Both gases are extremely toxic, and expo-
ing etching, (2) a radio-frequency (RF) genera- sure to concentrations of 1000 ppm for only a
tor, which supplies energy for creating plasmas few minutes is lethal. The TLV-TWA and MAK
inside the reactor, and (3) control equipment for for arsine are 0.05 ppm, 0.2 mg/m3 . For phos-
monitoring the etching process. Once the reac- phine, the TLV-TWA is 0.3 ppm, 0.4 mg/m3 ; the
tor is loaded with wafers, air is evacuated by a TLV-STEL is 1 ppm, 1 mg/m3 ; and the MAK is
mechanical pump. An etchant gas then enters the 0.1 mL/m3 , 0.15 mg/m3 [9], [10].
reactor and is ionized to form an etching plasma.
Fresh etchant gas flows into the reactor contin- Types and Grades. Both gases are available
uously during etching, while gaseous reaction as an LED-grade material, which has purity lev-
products are withdrawn from the reactor by a els of 99.99 – 99.9995 %. The SEMI specifica-
vacuum pump. tions for impurities in LED-grade phosphine are
The specific etchant gas or gas mixture used available [5].
for plasma etching depends on the type of ma-
terial to be processed. Examples of the various Uses. Arsine and phosphine are used to form
etchants that are used are listed in Table 9. epitaxial devices as LEDs and field-effect tran-
sistors (FETs). These gases can also be used
Table 9. Examples of etchants used for plasma etching
as dopants for the manufacture of semiconduc-
Etched material Substrate Gas etchant tor devices (see Chap. 13). Most LED manufac-
material turers utilize the gases in high percentage con-
Polycrystalline silicon dioxide CF4 /O2 or SiF4 /O2 centrations, 5 – 10 % for arsine and 5 – 15 % for
silicon phosphine, mixed with extremely high-purity
Silicon nitride silicon dioxide CF4 /O2 or SiF4 /O2
Silicon nitride silicon SiF4 /O2 hydrogen as the background gas. Some manu-
Silicon sapphire SiF4 /O2 facturers have begun to use a pure phosphine gas
Silicon nitride gold CF4 /O2
Tantalum silicon dioxide CF4 /O2
for growing epitaxial layers, but it is a relatively
Silicon CF4 small percentage of the total demand.
Silicon dioxide silicon CF4
Economic Aspects. In 1980, the United
States semiconductor industry used 4500 kg of
Economic Aspects. The United States semi- arsine and 1100 kg of phosphine for manufactur-
conductor industry used 91 000 kg of carbon ing light-emitting diodes. The most important
supplier of these LED-grade gases is Phoenix Trichloroethylene [79-01-6],

Research, now part of Union Carbide. TCE, ClCH=CCl2 , is a clear, water white,
volatile liquid that is completely miscible with
most organic solvents, but only slightly sol-
11. Solvents uble in water (→ Chlorinated Hydrocarbons,
Chap. 3.4.). The production of TCE is generally
Fluorocarbon solvents can be either a flu- accomplished by chlorination of ethylene, form-
orinated product or a blend of the fluoro- ing ethylene dichloride, which is then oxychlo-
chemical with alcohols such as ethanol or 2- rinated to form trichloroethylene. Manufactur-
propanol. One of the most commonly used mate- ers of semiconductors purchase this electronic
rials is 1,1,2-trichlorotrifluoroethane [76-13-1], chemical typically in a semigrade product as-
CCl2 F –CClF2 , which is a clear, dense, and sayed at 99 wt % TCE.
colorless liquid having a faint solvent odor The semiconductor industry consumes lim-
(→ Fluorine Compounds, Organic). ited quantities of trichloroethylene to clean
Manufacturers of semiconductors utilize flu- wafers; however, this industry also uses this
orocarbon solvents to clean wafers; the printed product as a chlorination source in crystal grow-
circuit board industry employs these products ing furnaces, whereby the chlorine minimizes
to remove grease from the boards. In addition, crystal defects. Manufacturers of printed circuit
manufacturers of printed circuit boards use fluo- boards use this material in metal cleaning and
rocarbon solvents in defluxing operations to re- degreasing operations.
move solder flux after the components are at-
tached. n-Butyl acetate [123-86-4],
CH3 COO(CH2 )3 CH3 , is produced by esterifica-
Isopropyl alcohol [67-63-0], CH3 CHOHCH3 , tion of acetic acid with n-butyl alcohol, using a
2-propanol, has many chemical and solvent catalyst, typically sulfuric acid. Manufacturers
properties similar to those of ethyl alcohol; it of semiconductors generally purchase a semi-
has a slight odor resembling a mixture of eth- grade product assayed at 99 wt %.
anol and acetone (→ Propanols). Production Manufacturers of semiconductors use n-butyl
of isopropyl alcohol is based on the reaction acetate as a rinse for negative resists to stop the
of propene and sulfuric acid to form isopropyl developing action.
hydrogen sulfate, with subsequent hydrolysis
to yield the alcohol and sulfuric acid. Isopropyl Methanol [67-56-1], CH3 OH, methyl alco-
alcohol purchased by manufacturers of semicon- hol, is produced from steam-re-formed natu-
ductors is usually a semigrade product assayed ral gas, which is compressed, catalytically con-
at 99.5 wt % CH3 CHOHCH3 . verted to crude methanol, and finally purified by
Manufacturers of semiconductors use isopro- distillation (→ Methanol). Purchases of metha-
pyl alcohol to clean wafers; the printed circuit nol by the semiconductor industry are typically
industry also employs this product in cleaning assayed at 99.9 wt % CH3 OH.
operations. Manufacturers of semiconductors use meth-
anol for wafer cleaning.
Acetone [67-64-1], CH3 COCH3 , is an
inflammable liquid that is low in toxicity com- 1,1,1-Trichloroethane [71-55-6], CH3 CCl3 ,
pared to other volatile solvents. Acetone is pro- is one of the least toxic chlorinated hydro-
duced by either oxidation of cumene or cat- carbons. The most popular route to manu-
alytic dehydrogenation of isopropyl alcohol facture this material is from vinyl chloride,
(→ Acetone). Acetone purchased by manufac- which is hydrochlorinated with hydrogen chlo-
turers of semiconductors is often a semigrade ride to form 1,1-dichloroethane and then ther-
product assayed at 99.5 wt % CH3 COCH3 . mally chlorinated to give 1,1,1-trichloroethane
The semiconductor industry uses acetone for (→ Chlorinated Hydrocarbons, Chap. 2.4.).
wafer cleaning, and manufacturers of printed cir-
cuit boards use the solvent to clean masks con-
taminated with dirt.
Semiconductor companies use this electronic printed onto a printed circuit board. Once
chemical for wafer cleaning and in crystal grow- printed, the mask is cured by using either heat
ing furnaces to reduce defects. Manufacturers of or ultraviolet light. After the mask is cured, it
printed circuit boards use this material in clean- acts as a solder resist, selectively protecting the
ing operations; however, its more important ap- circuitry during component soldering.
plication in this industry is to develop resists.
Types and Grades. Two types of screening
Types and Grades. The SEMI specifica- masks are available. One type can be cured ther-
tions for acetone, n-butyl acetate, methanol, mally, and the other type can be cured with ul-
trichloroethylene, and trichlorotrifluoroethane traviolet radiation. Both can be either permanent
are available [5]. or temporary resists. The masks are supplied as
100 % active material and are ready for use.
Economic Aspects. A total of 14.60×103 t
of solvents was used in the United States for Uses. Screening masks are used exclusively
electronic applications in 1980. Of the total, by the printed circuit board industry as a sol-
9.88×103 t was used in semiconductor applica- der resist. The mask is applied to the board by
tions and the balance was used in printed circuit forcing it through a stainless steel or polyester
boards, as shown in Table 10. monofilament screen. The screen pattern deter-
Table 10. Solvents used in printed circuit boards in 1980 mines where the mask is deposited on the board.
Once applied to the board, the mask is cured ei-
ther by heat or by ultraviolet light. After curing,
Semicon- Printed Total temporary masks can be removed from the board
ductors circuit with hot alkaline solutions of sodium hydroxide
boards
and water. Permanent solder masks are not made
Fluorocarbon solvents 0.68 1.13 1.81 to be removed after curing.
Isopropyl alcohol 2.22 0.91 3.13
Trichloroethylene 1.59 0.91 2.50
Acetone 1.72 1.09 2.81 Economic Aspects. A total of 852×103 L of
n-Butyl acetate 1.13 0.23 1.36 screening masks was consumed by the printed
Methanol 1.81 1.81
1,1,1-Trichloroethane 0.73 0.45 1.18 circuit board industry in the United States in
Total 9.88 4.72 14.60 1980. Of this total, ca. 85 % or 719×103 L were
thermally curing masks. The major suppliers of
The major suppliers of semiconductor-grade screening masks in the United States are Mac-
solvents are Ashland Chemical, General Chem- Dermid, Photocircuits, Mysol, Colonial, Lon-
ical, J. T. Baker, and Mallinckrodt. There are don Chemical, Grace, and Dynachem.
numerous suppliers of solvents to the printed
circuit board industry, including Du Pont, Dow, Dry Film Masks. Dry film solder masks
Shell, Union Carbide, PPG, and Exxon. consist of a photosensitive polymer layer sand-
wiched between a layer of polyester film on
one side and a polyolefin sheet on the other
12. Masks side. Both cover sheets protect the photopoly-
mer from damage by abrasion. The polyolefin
Solder Masks. Most solder masks are per- sheet is removed as the solder mask is lami-
manent and are intended to remain on the board; nated to the printed circuit board. Ultraviolet
thus, they are usually made of durable scratch- light selectively images the mask by polymer-
resistant material such as epoxy resins. Tempo- izing the exposed photopolymer, causing these
rary solder masks are normally used to protect areas to be insoluble in the developing solution.
gold contact fingers from being soldered; the The polyester sheet is removed just prior to im-
mask can be removed at a later date to expose mersion in the developing solution. After the de-
the gold contacts. veloping process, the dry film acts as solder re-
sist, protecting the circuitry during component
Screening Masks. Screening masks are pho- soldering.
tosensitive polymeric resins that are screen
Types and Grades. Currently, only two liquid at room temperature and solid compounds
types of dry film masks are available. One type that are dissolved in solvents to form solutions.
has a heat-resistant coating, and the other has The main difference between the two is the
a flame-retardant coating. Both products work method of application. The dopant – solvent so-
negatively and can be processed in solvent, usu- lutions are applied by spin-on techniques, while
ally with 1,1,1-trichloroethane. the pure liquids are applied by chemical vapor
deposition (CVD) techniques.
Uses. Dry film masks are used exclusively Orginally, all liquid dopants were formulated
by the printed circuit board industry and are for application by CVD techniques. This tech-
designed for boards with tight circuitry spac- nique uses a carrier gas, usually nitrogen, which
ings (≤ 0.3 mm). The developed dry film pro- bubbles through the liquid dopant and carries the
tects the circuitry from coming in contact with dopant vapor mixture into a furnace, where the
solder when components are assembled on the dopant diffuses into the wafer.
board. Later, spin-on techniques were developed.
This method uses several drops of the dopant
Economic Aspects. Dry film solder masks solution, which is placed directly on the wafer,
were introduced in 1979 by Du Pont. Therefore, spun to a uniform thickness, and dried to form a
consumption of these products in 1980 was low, dopant film. Once dry, the wafers are placed in
at 30 480 m2 . Du Pont, Dynachem, and Hercules a furnace operating between 1100 and 1300 ◦ C,
all offer dry film masks. where the diffusion process occurs.
Types and Grades. The two major classifi-

13. Dopants cations of liquid dopants are inorganic- and
organometallic-based compounds. Within the
Dopants are materials that enhance the ability of inorganic class, the four main types of doping
a semiconductor to conduct electricity by selec- compounds are based on phosphorus, boron, an-
tively forming positively and negatively charged timony, or arsenic. The most common inorganic
areas within the substrate. liquid dopants, with the method of application
As the dopant contacts the substrate, dopant and available purity grades, are shown in Ta-
atoms, such as phosphorus or boron, begin to ble 11.
replace semiconductor atoms, such as silicon, The organometallic dopants consist of com-
in the crystal structure. Electric charges form pounds such as diethylzinc, dimethylcadmium,
because the change of atoms also changes the diethyltelluride, and trimethylgallium. These
number of valence electrons that are available in products are available as electronic-grade ma-
the substrate. Replacing a silicon atom, which terials that have a purity in excess of 99.9 % and
has four valence electrons, with a boron atom, are formulated for use by CVD techniques.
which has only three valence electrons, produces
a positively charged area because of the absence Uses. The spin-on type of liquid dopants are
of one electron. Conversely, replacing a silicon formulated into several different products by
atom with a phosphorus atom, which has five va- varying the dopant concentration of the solution.
lence electrons, produces a negatively charged These variations cause different concentrations
area because of an excess of one electron. This of dopant atoms per unit area in the semicon-
imbalance of electrons allows better conduction ductor substrate.
of electricity through the semiconductor mate- Phosphorus, antimony, and arsenic com-
rial. pounds are examples of dopants that produce
negatively charged sites (n-type dopant); boron,
aluminum, indium, and gallium compounds are
13.1. Liquid Dopants examples of dopants that produce positively
charged sites (p-type dopant).
Liquid dopants are compounds that contact
semiconductor substrates to produce charged ar-
eas. These liquids include compounds that are
Table 11. Most common inorganic liquid dopants
Product CAS registry Formula Method of Purity grades, wt %

number application
Phosphorus oxychloride [10025-87-3] POCl3 CVD ∗ 99.995, 99.999, 99.9999

Phosphorus tribromide [7789-60-8] PBr3 CVD ∗ 99.995, 99.9999
Phosphorus pentaoxide [1314-56–3] P2 O 5 spin-on 99.99
Boron tribromide [10294-33-4] BBr3 CVD ∗ 99.99, 99.995, 99.999, 99.9999
Antimony trioxide [1309-64-4] Sb2 O3 spin-on 99.99
Arsenic trioxide [1327-53-3] As2 O3 spin-on 99.99
Antimony trichloride [10025-91-9] SbCl3 CVD ∗ 99.995, 99.9999
∗ Chemical vapor deposition.
Economic Aspects. In 1980, almost 6300 kg tor substrate and within such epitaxial layers as
of liquid dopants was consumed in the United polysilicon and silicon nitride. Arsine and phos-
States for semiconductor fabrication. Of this to- phine are examples of dopants that produce neg-
tal, ca. 2300 kg was supplied as CVD dopants atively charged sites (n-type dopant); diborane is
and the remainder as spin-on dopants. The two an example of a dopant that produces positively
leading suppliers of CVD dopants are J. C. Schu- charged sites (p-type dopant).
macher, now part of Air Products, and Apache
Chemical, now part of Olin-Hunt. The important Economic Aspects. The total consumption
suppliers of spin-on dopants are Emulstone, Dif- of gas dopants in the United States for semicon-
fusion Technology, and General Chemical. ductor fabrication was 2300 kg as 100 % active
material in 1980. The four largest suppliers of
these products in the United States are Math-
13.2. Gas Dopants eson, Linde, Scientific Gas Products, and Air
Products.
The three primary doping gases are arsine
[7784-42-1], AsH3 ; diborane [19287-45-7],
B2 H6 ; and phosphine [7803-51-2], H3 P. All
13.3. Solid Dopants
three are colorless, highly toxic, and flammable.
Traditionally, the gas mixture is pumped into
Solid dopants, either in crystalline, powder, or
a furnace operating at a temperature between
wafer form, contact semiconductor substrates to
900 and 1300 ◦ C and is introduced into the sub-
produce positively or negatively charged sites.
strate by diffusion. A newer technique, called
Usually these dopants are compounds of met-
ion implantation, operates at room temperature
als such as arsenic, antimony, boron, and phos-
and is gaining popularity for doping of the semi-
phorus.
conductor substrate.
Types and Grades. An electronic grade of Types and Grades. The two main types of
dopant is used, requiring a minimum of solid dopants are boron and phosphorus com-
99.995 % purity. Gas dopants are typically pounds. These materials are available in grades
mixed, usually with nitrogen as the carrier gas, varying in purity from 99.9 to 99.999 % and are
although 100 % phosphine is sometimes used. ready for immediate use.
The concentration of dopant gas in the mixture
ranges from 5 to 50 000 ppm with the exception Uses. The boron compounds are examples
of diborane, whose concentration only ranges of dopants that produce positively charged sites
from 5 to 10 000 ppm. The SEMI specifications (p-type dopant) and the arsenic, antimony, and
for electronic-grade arsine and phosphine are phosphorus compounds are examples of dopants
available [5]. that produce negatively charged sites (n-type
dopants).
Uses. Dopant gases are used to produce se-
lectively charged areas within the semiconduc-
Crystalline or powder-type solid dopants are 14.2. Liquid Crystals

sublimed and pumped into the diffusion reac-
tor, where the material diffuses into the semi- Liquid crystals are used in conjunction with
conductor substrate, doping the desired areas. semiconductor devices in applications such
Most boron solids, particularly boron nitride, are as watches, calculators, and electronic games
available in wafer form and are placed inside the (→ Display Technology). Although not a semi-
diffusion reactor beside the semiconductor sub- conductor device, the liquid crystal serves as a
strate. The boron sublimes and travels a rela- display or read-out that rivals the light-emitting
tively short distance to contact the substrate. Ion diode, which is a semiconductor device. The
implantation may eventually be an alternate ap- liquid crystal operates by applying an electric
plication method, and some semiconductor de- charge, which changes the molecular orientation
vice manufacturers are experimenting with this of the liquid. Light passing through the crystal
process. is scattered or reflected where the charge is ap-
plied, thereby forming the display. This process
Economic Aspects. In 1980, ca. 860 kg of allows very little current consumption by the liq-
solid dopants were consumed by the United uid crystal display, which is its main advantage
States semiconductor industry. Mallinckrodt is over the light-emitting diode.
the leading supplier for the phosphorus, arsenic,
and antimony compounds, and Carborundum is
14.3. Conductive Inks and Pastes
the leading supplier of boron nitride.
Conductive inks and pastes are screened onto a
ceramic substrate to form the conductors, resis-
14. Auxiliary Materials tors, and capacitors in thick-film circuits. Thick-
film conductors are made from precious metal
A host of auxiliary materials, including ceramic pastes or inks, such as gold, silver, platinum, and
substrates for thick- and thin-film circuits, liquid palladium, either separately or in combination.
crystals, conductive inks and pastes, high-purity Resistors and capacitors use pastes that consist
metals, wafer cleaners, and passivation materi- of glass dielectric materials and metal or semi-
als, are used in the manufacture of electronic conducting compounds. The pastes and inks are
devices. deposited on the substrate by a stencil screen
process and are then fired in a furnace, where the
composition of the material determines the final
14.1. Ceramic Substrates characteristics of the circuit. Other components,
such as integrated circuits or discrete semicon-
Ceramic substrates of high-purity alumina ductor devices, can be added to the thick-film
(Al2 O3 ) are used as the base material in the assembly to form a hybrid circuit device.
manufacture of thick- and thin-film circuits
(→ Ceramics, Electronic). The alumina content
of substrates used for thick films ranges from 14.4. High-Purity Metals
94 to 96 %; most thin-film circuits use ceramics High-purity metals have applications with both
having an alumina content of > 99 %. semiconductor devices and thin-film hybrid cir-
Because most thick- and thin-film circuits are cuits. Aluminum and aluminum alloys (mainly
designed for specific purposes, the shape and tantalum) are used exclusively to form metal-
size of the ceramic base is made to meet con- lized areas on integrated circuit devices. Pre-
sumer specifications. Consumers are typically cious metals, such as palladium and platinum,
semiconductor manufacturers that use thick- and are used to form conductive paths in thin-film
thin-film circuits for resistor networks and hy- hybrid circuits. All the metals used have purity
brid circuits, thus augmenting the capabilities of levels ranging from 99.9999 to 99.99999 %.
the semiconductor devices. The two methods for depositing the metal
onto the substrate are sputtering and evapora-
tion. Evaporation is the simpler technique and
involves placing the substrate and the metal while such cleaners also protect against edge
source in a ball jar under vacuum. The metal fracturing.
is vaporized by heat and then moves in all di-
rections within the chamber and deposits on the
substrate. 15. References
Sputtering uses the metal source as a cathode
target, which is bombarded by ions of an inert General References
gas. This causes the metal to be deposited on the 1. E. D. Feit (Harris Semiconductor Group),
substrate surface. C. W. Wilkins, Jr. (Bell Laboratories) (eds.):
Polymer Materials for Electronic Applications,
Am. Chem. Soc., Washington, D.C., 1982.
14.5. Passivation Materials 2. E. R. Howells (ed.): Technology of Chemicals
and Materials for Electronics, Society of
Passivation materials protect the finished semi- Chemical Industry, London 1984.
conductor device from damage by environmen- 3. L. F. Thompson (Bell Laboratories), C. G.
tal factors such as dust, humidity, and tempera- Willson (IBM Research Laboratory), M. J.
ture. The passivator is applied as the final layer Bowden (Bell Laboratories) (eds.):
Introduction to Microlithography, Am. Chem.
on the semiconductor device. Several types of
Soc., Washington, D.C., 1983.
materials can be used to form passivation layers,
such as silicon nitride formed by the reaction of
Specific References
silane and ammonia gases, and polyimide coat- 4. S. R. Daigle, M. S. Rappaport, J. Diffenthal, C.
ings. Only the polyimide material is discussed J. Listner in A. A. Boccone (ed.): Electronic
in this section; the previously mentioned gases Chemicals, United States, Western Europe,
are covered in Chapter 10. and Japan, Charles H. Kline & Co., Fairfield,
The polyimide material is sold as a polyamic N.J., 1981.
acid solution, which is converted by heat to a 5. Semi-Standards Committee Chemical Section
stable polyimide coating. The material can be (ed.): Book of Semi-Standards, vol. 1,
applied to the wafer by screening, spraying, dip- Semiconductor Equipment & Materials
ping, or a spin-on method. The polyimide forms Institute, Mountain View, Calif., 1982,
a tough, temperature-resistant coating without pp. C1. STD. 1 – 22, C2. STD. 1 – 3, C.3
pin holes and seems to have an advantage over STD 1 – 11.
silicon nitride with devices having many stepped 6. C. G. Henningsen in C. F. Coombs (ed.):
layers. In addition, the polyimide can be used Printed Circuits Handbook, McGraw-Hill,
with a photoresist to expose metallized contact New York 1979, Section 7, pp. 2 – 18.
areas on the device while the polyimide protects 7. R. J. Bahn in C. F. Coombs (ed.): Printed
the rest of the chip. Circuits Handbook, McGraw-Hill, New York
1979, Section 7, p. 5.
8. IBM, US 3 549 368, 1970 (R. H. Collins, F. T.
Deverse).
14.6. Wafer Cleaners 9. ACGIH (ed.): Threshold Limit Values (TLV)
and Biological Exposure Indices, ACGIH,
Wafer cleaners can be hydrophilic polymers Cincinnati, Ohio, 1986 – 1987.
or surfactant materials that are either sprayed, 10. DFG (ed.): Maximum Concentrations at the
dipped, or spun onto the wafers. These materi- Workplace (MAK), VCH Verlagsgesellschaft,
als remove particles from the substrate surface Weinheim 1986.

Electronic Chemicals 總覽百科

Uploaded by

Copyright:

Available Formats

Electronic Chemicals 總覽百科

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Electronic Chemicals 總覽百科

Uploaded by

Copyright:

Available Formats

Electronic Chemicals 1

1. Introduction . . . . . . . . . . . . . . . . 2 6.7. Ammonium Fluoride . . . . . . . . . . 17

1. Introduction auxiliary materials (Chap. 14)

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

substrates (Chap. 2) 2. Substrates

mand for magnetic bubble memories has been 3. Packaging Materials

NEMA MIL-P-13949E∗ Resin system Base Color Description

Type Gold purity Grade Knoop hardness

I 99.7 A 0 – 90 Electroless copper catalysts are proprietary

operates at 43 – 60 ◦ C and requires a pH of form Sn(BF4 )2 and Pb(BF4 )2 as corrosion takes

Economic Aspects. In 1980, ca.

Tin electroplating requires the use of tin

Screening inks are based primarily on

Products CAS registry Formula Applications

number Semiconductors Printed circuit boards

6.3. Ammoniacal Solutions 6.4. Nitric Acid

Component CAS registry Formula Function

Ammonium hydroxide [1336-21-6] NH4 OH holds copper in solution

6.8. Persulfates Na2 S2 O8 per liter of warm water. Small quanti-

Manufacturers of semiconductors mix phos- Chromic – Sulfuric Acid Etchants.

Consumption, 106 L 8.3. Positive Photoresist Developers

Uses. Semiconductor wafers can be either Uses. Usually electronic-grade xylene or

Dichlorosilane [4109-96-0], SiH2 Cl2 , is a

Silicon(IV) tetrachoride [10026-04-7], Silane is used largely as a raw material to form

3 SiH4 + 4 NH3 −→ Si3 N4 + 12 H2 The major suppliers of these products in the

supplier of these LED-grade gases is Phoenix Trichloroethylene [79-01-6],

Types and Grades. The two major classiﬁ-

Product CAS registry Formula Method of Purity grades, wt %

Phosphorus oxychloride [10025-87-3] POCl3 CVD ∗ 99.995, 99.999, 99.9999

∗ Chemical vapor deposition.

Crystalline or powder-type solid dopants are 14.2. Liquid Crystals

You might also like