Surface Analysis and Correlation to Moisture Generation

from Cylinder Packages and Delivery Systems Used in

High Purity HBr and other Halide Acid Gases for CMOS
Device Manufacturing

A u g e r E le ctro n Sp e ctro sc o p y D e p th P ro fi le o f N i
lin e d 4 1 3 0 C r-M o S te e l C ylin d e r Aft e r >1 Y e a r H B r
E xp o s u re

C. Wyse, A. Seymour, L. Yao, J. Vininski,

M. Raynor, R. Torres
Matheson Tri-Gas
Longmont, CO 80501
Corrosion of metal components within a
corrosive gas distribution system, such as HCl and HBr, is
highly problematic for the semiconductor industry (1).
HBr is frequently used in the semiconductor industry as a
trench-etch for CMOS device manufacturing and is highly
corrosive. Corrosion can happen at any stage within a
distribution system, including inside the gas cylinder in
which the source material is stored. The quality of the gas
delivered and impurities found in the distribution system
are significantly affected by the material of construction
of the gas cylinder. Notable differences in gas purity are
found in gases delivered from Ni lined AISI 4130 Cr-Mo
steel and 316L stainless steel cylinders.
Corrosion of the cylinder and delivery
component surface can affect the lifetime of gas
distribution system components, the stability and
performance of a process, and the purity and performance
of the final product. Corrosion generates molecular and
particulate contaminants that compromise the integrity of
the distribution system as well as contaminate the final
product (2).
The corrosion resistance of different materials of
construction of the gas cylinder used to store corrosive
gas, has a significant impact on the moisture levels found
in the delivered gas. Tests of corrosion resistance of
various alloys were performed with hydrobromic acid and
anhydrous HBr.
Surface studies conducted on the inside wall of
the Ni lined AISI 4130 Cr-Mo steel cylinder, 316L SS,
and AISI 4130 Cr-Mo steel cylinders exposed to
anhydrous HBr >1year reveal significant differences..
Auger surface scan studies conducted on the inside
cylinder surfaces show that the nickel lined cylinder
contains a lower concentration of oxygen than the steel
cylinder (Figure 1).

Ni Lined AISI 4130 Cr-Mo Steel

HBr Cylinder
35.6% O2

AISI 4130 Cr-Mo Steel

HBr Cylinder
53.2% O2

Figure 1. AES Surface Oxide Survey of HBr Cylinders

after >1 yr HBr service.
Auger depth profiling studies also demonstrate that the
oxide layer on the nickel surface is significantly thinner
than on the steel surface (Figure 2).
Surface roughness and oxide
thickness/concentration of the gas cylinder directly affect
the quality of the gas. Oxide on the 4130 Cr-Mo steel and
316L SS cylinder surfaces provides more chemical
reagent for reaction with the corrosive gas, by which free
moisture is generated. Materials with higher surface

A u g e r E le ct ro n S p e ct ro sc o p y D e p t h P ro file o f 4 1 3 0 C r -M o
S te e l Cy lin d e r A f te r > 1Y e a r H B r E xp o s u re (C ylin d e r A )

Figure 2. Auger Depth Profiles of Ni lined (above) and

4130 Cr-Mo steel (below) cylinders.
roughness have more surface area available to react with
the corrosive gas. In addition, the increased surface area
associated with high surface roughness allows for more
adsorbed moisture to be stored on the cylinder wall, and
available as an impurity.
The oxide dependant moisture level is evidenced
by a cylinder depletion study conducted on two different
cylinders, one 4130 Cr-Mo steel and one nickel lined,
both filled with HBr. The total moisture levels delivered
during cylinder depletion from the nickel lined cylinder
were significantly lower than from the steel cylinder, even
when the cylinder is liquid dry.
Conclusions:
The research contained herein shows direct
visual and quantitative information on the corrosion
resistance of the various alloys used in gas cylinder
materials and the resulting moisture impurity levels found
in the delivered gas. The data demonstrates that high
surface area metal oxides can lead to increased vapor
phase moisture in HBr. Ni lined AISI 4130 Cr-Mo steel
HBr cylinders generate less moisture than steel alloy
cylinders due to reduced stoichiometric oxide
concentrations.
The results reported in this abstract demonstrate
that AISI 4130 Cr-Mo steel and 316L stainless steel
cylinders are inferior to Ni lined AISI 4130 Cr-Mo steel
cylinders with respect to moisture generation in corrosive
gases.
References:
1.) J. V. Martinez de Pinilos, P. J. Maroulis, D. M.
Drummer, Proceedings of the MICROCONTMINATION
Conference and Exposition, Santa Monica, CA, pp. 89104 (1986).
2.) S. D. Cheung, G. L. Mooney, Micro, 10, 59 (1995).