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ion-implanted resists
Georgy K. Vinogradova) and Vladimir M. Menagarishvili
MC Electronics Co. Ltd., 907-8 Shimoimasuwa, Shiranecho Yamanashi 400-02, Japan
~Received 26 March 1998; accepted 16 October 1998!
A kinetics of surface transformations and ashing of high energy high dose As1 implanted resists was
studied. Continuous bulk polymer structures, having minimum cross-sectional dimensions 10–30
times larger than the initial resist thickness, were found. These structures, named as giant folds, are
formed as a result of heating and melting of the normal polymer resist sublayer and its interaction
with a mechanically deformed implanted resist layer. The giant folds are responsible for the most
difficult to remove surface remaining features of ion implanted resists processed in downstream gas
discharge ashers. It is shown that the main problem of dry ashing of ion implanted resists of this type
is the flow patterns of the normal resist sublayer, not the hard implanted surface layer itself.
© 1999 American Vacuum Society. @S0734-211X~99!00601-0#
95 J. Vac. Sci. Technol. B 17„1…, Jan/Feb 1999 0734-211X/99/17„1…/95/6/$15.00 ©1999 American Vacuum Society 95
96 G. K. Vinogradov and V. M. Menagarishvili: Observations on the formation and ashing of giant folds 96
are usually larger than the residue. They commonly have II. EXPERIMENT
smoothed elongated, T- and triangle-, complex-, and group-
The 8 in. wafers with 300 Å thermal oxide and As ~40
shaped patterns. The size can vary from a few microns up to keV, 531015 cm22! ion implanted positive resists of about
millimeters. Typical complex patterns like rings, bracelets, 1.2 mm thickness were mainly used because such resist pro-
necklaces, chains, etc. are well known. Downstream I/I ash- duces very hard to remove remaining polymer. This I/I resist
ing takes usually a long time, from minutes to hours, al- differs from the P1 type in the fact that the hard skin of As1
though it never guarantees final removability of the remain- implanted resist is essentially thinner. However, the studied
ing polymer. It is important to underline that the remaining As1 resist shows lower removability than that of the P1 type.
polymer cannot be removed by any wet process including Ashing was performed in a downstream chamber of a
those capable of etching a wafer itself. The remaining poly- novel capacitively balanced full wave or lambda resonator
mer has an excellent intact interface with the wafer surface. (l-R) inductive discharge4 utilizing transmission line prop-
It would be worth mentioning that the group patterns of erties of an induction coil and having virtually 100% energy
both residue and remaining features look essentially similar efficiency operating without a matching box. Typical dis-
since both reflect the surface history from the very beginning charge conditions were: 3 slm ~standard liters per minute!
stage of the popping patterns. However, it must be remem- pure oxygen gas flow rate, 1.38 Torr pressure, 2 kW ab-
bered that the popping pattern itself does not determine the sorbed radio frequency ~rf! power at 27 MHz, 270 °C wafer
platen temperature. The wafers were thoroughly inspected
nature of the material composing the residue and remaining
after every processing step with an optical Olympus
polymer.
BH3MJL and electron scanning SEM-6301F JEOL field
It is commonly accepted that the problem of I/I resist
emission microscopes.
ashing is associated with the hard to remove remaining. It is
also commonly believed that the origin of the remaining is
the hard skin of the initial resist modified by ion implanta- III. RESULTS AND DISCUSSION
tion. There are several hypotheses concerning the nature of
There is no secondary rf capacitive plasma5 in the l-R
these hard to remove features. One of them counts on the
discharge downstream chamber under the ashing conditions.
popping phenomena since the remaining patterns always
The ashing rate of normal resist up to about 10 mm/min was
look as if they were reproducing the popping patterns. The
achieved at a wafer temperature of about 270 °C. It falls
problem of low removability of the remaining polymer is down to about 40 Å/min at room temperature thus revealing
commonly supposed to be solely based on the hardness of that any noticeable surface activation by energetic positive
the I/I modified top layer resist. It seems to be a very rea- ions does not exist. The positive ion current density on the
sonable suggestion since the underlying normal resist film wafer surface does not exceed about 1 mA/cm2 and ion en-
does not exhibit any difficulty for oxygen ashing. The under- ergy is lower than 20 V as measured by flat surface electro-
lying normal resist layer remains untouched by the ion bom- static probes.5 Hence, the ashing should be considered as a
bardment. true thermally activated oxidation by dissociated oxygen.
The splinters of the hard polymer skin generate some part To begin with, we studied the microscopic surface mor-
of the remaining polymer. Such pieces of hard skin falling phological transformation of the I/I resist under elevated
one onto another produce double and triple sandwiches temperatures and atmospheric pressure. The substrates
which is why the two step dry process was proposed in order heated up to 130–150 °C showed bubbles and broken skin
to overcome the problems associated with popping.3 The first patterns. Typically, the hard skin was peeled off from the
plasma ashing step was proposed in order to eliminate the sublayer. Sometimes, the peeled off hard skin was picking
hard skin under the temperature well below the popping parts of the softened sublayer from the wafer surface. The
threshold in a capacitively biased discharge. The second step broken parts of the skin almost never flew away from the
can be utilized in any high temperature asher. wafer.
Practically all published studies on the I/I resist ashing The behavior of the I/I resist changes when the tempera-
ture exceeds about 150 °C. Figure 1~a! shows the I/I resist
assumed that the hard skin itself is responsible for the hard to
heated up at 270 °C. There are numerous surface folds cre-
remove remaining polymer. However, the mechanism of I/I
ated by the hard skin. The underlying layer of normal poly-
remaining polymer formation was not established. This com-
mer in open areas is very smooth and usually invisible but
plicated phenomenon has been studied ‘‘statistically,’’ as can be easily distinguished by scratching. The color photo-
process results. Some attempts to disclose the molecular graphs of this pattern clearly show that the normal resist was
structure of the hard layer and material transformations were melted. Then the forces of surface tension, which depend on
focused too much on the hypothesis of a hard to remove the surface energy of all contacting materials ~wafer, top
surface skin or crust. Here we present a closer microscopic hard skin surface, bottom hard skin surface, and the normal
look at the surface phenomenon that makes clear the physical resist sublayer! affect it. The hard skin can be easily distin-
mechanism of the genesis of final remaining polymer. The guished by mechanical probing with a fine quartz fiber. This
mechanism follows straightforward from the kinetic observa- sample was then placed in the l-R asher for further process-
tions. ing.
FIG. 5. Typical residue on the wafer surface after the downstream oxygen
ashing of As1 implanted resist. The web composing the residue is wettable
and highly reactive in atmosphere.