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Ptfe Nanoemulsions as Spin-On, Low Dielectric Constant Materials For Ulsi

Applications

Article  in  Materials Research Society symposia proceedings. Materials Research Society · January 2011
DOI: 10.1557/PROC-427-463

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 THIN POLYTETRAFLUOROETHYLENE ORGANOSILANE NANOCOMPOSITE
FILMS USED AS ULTRA LOW DIELECTRIC CONSTANT MATERIALS IN
MICROELECTRONICS
1 2 2
Shichun Qu', Tom Rosenmayer , Ping Xu , Perry Spevack
1. W. L. Gore and Associates, Inc., Eau Claire, WI
2. W. L. Gore & Associates, Inc., Elkton, MD.

ABSTRACT
Replacing the current on-chip dielectric materials such as silicon dioxide, which has a
dielectric constant of approximately 4.0, with low dielectric constant materials can greatly
improve the performance of high density VLSI device by reducing crosstalk and capacitive
delay. Polytetrafluoroethylene (PTFE) has the lowest dielectric constant (k < 2.0) of any full
density material, which makes it a promising candidate for this IC application. Pure PTFE thin
films cast from PTFE nanoemulsion containing sub-20nm PTFE particles, though thermally
stable, have some inherent sub-optimal properties. These include adhesion to other inorganic
materials and mechanical strength at high processing temperatures. In order to improve these
properties, we have developed a PTFE / silicon compound nanocomposite material. Initial tests
have shown that this nanocomposite material has significantly improved high temperature
mechanical properties and interfacial properties between the composite and inorganic materials
such as silicon, silicon oxide, silicon nitride and some metals. The surface roughness of the thin
film coatings is also reduced compared to pure PTFE thin film coatings. The coatings require no
separate adhesion promoter to be applied to the substrate prior to deposition. Characterization
work has been carried out with different techniques such as DMA, ToF-SIMS, XPS and AFM
with hydrofluoric acid (HF) selective etching, in order to understand this novel nanocomposite
and its surface and interfacial properties.

INTRODUCTION
As the microelectronics industry continues its trend towards progressively more demanding
applications, the need for low dielectric constant materials has become more important than ever.
Since as the size of the semiconductor device features shrinks without an accompanying
reduction in die size, the RC delay associated with materials and processes used in interconnects
contributes an increasingly large delay to signal propagation speed. To allow the industry to
realize continued device performance improvements, two basic approaches to RC time constant
reduction have been: reduction of "R" by the transition from aluminum-based to lower resistivity
copper-based interconnect metallization; and reduction of "C" by introduction of low dielectric
constant materials to replace Si0 2. In many cases, both paths are being taken simultaneously to
afford the largest possible benefit.
PTFE is well known for its ultra low dielectric constant at full density, which makes it a
promising candidate low-k material. Since 1995, W. L. Gore & Associates, Inc. has been
developing a proprietary PTFE nanoemulsion (SPEEDFILM TM ) for ultra thin film coating
applications. Previous work has proved that PTFE thin films cast from the Gore PTFE
nanoemulsion have very good thermal stability up to 400°C, excellent electrical properties, as
well as good chemical compatibility with all known chemicals currently used in the
semiconductor industry' 2. However, there were also some noticeable problems with the first
generation pure PTFE material. For example, in some occasions the instability of SiO 2 caps
layered on top of pure PTFE thin film coatings, such as blistering and wrinkling during high
temperature annealing, has been observed. In addition, an adhesion promoter is required prior to

375
Mat. Res. Soc. Symp. Proc. Vol. 581 ©2000 Materials Research Society
coating pure PTFE onto Si substrates. This extra coating step not only complicates the coating
process but also increases the chances of contaminating wafers.
In order to improve the high temperature mechanical property and interfacial integrity and
simplify the coating process, a PTFE/siloxane nanocomposite material was developed. Unlike
previous composite materials, however, there are some constraints that limit the possible types of
composites that could potentially be produced. First, the dielectric constant must remain low,
preferably below 2.2. Second, phase separation must be avoided, because the materials are
intended for integration into very fine metal structures, where line to line pitches could be less
than 0.5 microns. Any inhomogeneity could degrade the performance of the IC devices and thus
is unacceptable. Therefore, a composite that is homogeneous at molecular level must be
developed.
A new PTFE/siloxane composite material has been developed by adding a small amount (<
3wt%) of a siloxane into the Gore PTFE nanoemulsion during formulation. Once added, the
siloxane undergoes a series of reactions in the nanoemulsion. The color change from clear to
yellow is one of the most noticeable effects. However, the emulsion remains stable at either low
(8°C) or high temperature (50°C) for weeks. These accelerated aging processes indicate that the
shelf life of the emulsion could be months at room temperature. A series of tests have proved that
an adhesion promoter is no longer needed for coating this new PTFE/siloxane nanoemulsion.
Tests have also shown that coated films have higher per pass crack resistance (> 5pm, without
adhesion promoter) compared to the first generation pure PTFE coatings (- 1.5pm, with adhesion
promoter). Improved high temperature mechanical properties and better interfacial integrity
between the PTFE and Si0 2 hard masks have also been demonstrated.

EXPERIMENTAL
Several nanoemulsion samples with different PTFE/siloxane concentrations were prepared
together with control samples of pure PTFE. Then sub-micron thickness PTFE and
PTFE/siloxane films were spin coated onto Si wafers. Coatings were done on a SVG 8868 coater
track. Coated Si wafers were then scanned with a di-3 100 AFM after 250°C soft bake and
390"C sintering. Both soft bake and sintering were performed on the same SVG coater's hot
plate in air. A thin layer of Si0 2 was deposited in a PlasmaTherm's plasma enhanced chemical
vapor deposition (PECVD) tool. The stacked Si0 2/PTFE or PTFE composite samples were later
annealed on a 400"C hot plate for up to 120 minutes or when failure occured. Typical failures for
these type of stacks include blistering and haze caused by Euler buckling. AFM scans combined
with HF selective etching and XPS depth profiling were performed to investigate the surface and
interfacial properties.
ToF-SIMS and HF selective etching were combined to reveal possible microphase separation
inside the PTFE/siloxane thin film coatings.
Dynamic mechanical analysis (DMA) is a typical small strain e
experiment for measuring linear viscoelasticity of polymer melts.
As depicted in the drawings in Figure 1, a polymer sample is
sandwiched between two parallel plates. At the set temperature a
sinusoidal strain is introduced onto one plate, while the response __
stress is recorded from the other plate. Usually within a few cycles
of start-up, the stress will also oscillate sinusoidally at the same
frequency but in general will be shifted by a phase angle, 5, with
respect to the strain wave. The stress and strain relationship is
shown graphically in Figure 2 and described by the following M

mathematical expressions: Figure 1. Parallel plates

Y:=Y 0 sinaot and r= r0 sin(cott+) (1) and polymer melt.

376
 The stress wave may be decomposed into two
waves of the same frequency, thus:
r = r'+ -r"= r'
0 sin)a t + r"o cosco t (2)
tang = r"o/ r' (3) y
Here we get two dynamic moduli,
G'= r'o /ro, the in-phase elastic modulus. (4)
"r12 °'.' " ..."- "/ "••''
G"= r"o y/o, the out-of-phase viscous modulus. (5) T12
Also the tan of phase angle can be re-written as,
tang = G"IG' (6)
Normally a DMA experiment is performed in a
certain temperature range to obtain the temperature Time
dependent mechanical responses of the test materials.
For linear crystalline polymers a typical elastic Figure 2. Strain (y) and stress
modulus response curve is illustrated in Figure 3. wave curve (T), component stress
Characteristic transitions that can be observed are: the wave curves (r' and r") and strain
glass transition (Tg), the crystalline phase melting rate curve (y).
transition (Tm) and the melt flow transition (Tf). DMA
is also sensitive to picking up crosslink effects.
I

(glass transition)
ordered state
disordered state highly crosslinkedI

F
E momoderately crosslinked
E
slightly crosslinked
I uncrosslinked
I I .,.
Tg Tm
temperature
Figure 3. Schematic showing typical elastic modulus vs. temperature curve of a linear
crystalline polymer with characteristic transitions and the effects of crosslinking. The
shaded area is the actual test region.
For DMA measurements on pure PTFE and PTFE/siloxane composite materials,
nanoemulsion samples were baked sequentially at 105 °C, 250 °C and 390 °C to simulate a
standard coating process. Final powder samples were then pressed into thin disks for DMA
experiments. A Rheometric Scientific ARES-LS-M rheometer with 25 mm parallel plates at
about 0.8 mm gap was used to measure the viscoelastic properties of the PTFE and
PTFE/siloxane melts in the temperature range from 270 °C to 400 *C.

RESULTS AND DISCUSSION

AFM scans in Figure 4 show dramatic surface morphology changes due to the siloxane
addition. After a soft bake at 250 °C, pure PTFE shows rod-like PTFE aggregations, while the

377
PTFE/siloxane composite samples show no such phenomenon. The surface difference becomes
more obvious after high temperature sintering. The roughness of the composite sample is greatly
reduced, which was also observed and confirmed using optical microscopy.

2 ranve~sOWS2,rW Ras 7.W4n. Son 2 rakneW12O-nor Ra• 17592nS0

c d

i ranqet67: 7 S2M
n Ras 6.335m i 2 riigt 1 . 2 , af1 59
O? 5n

Figure 4. AFM scans of PTFE, PTFE/siloxane coatings. a). Pure PTFE after 250"C
soft bake; b) pure PTFE after 390"C sintering; c) PTFE/siloxane after 250"C soft
bake; d) PTFE/siloxane after 390"C sintering.
Optical micrographs taken after the Si0 2 capping and annealing procedures of both PTFE
and the PTFE/siloxane composite coatings are shown in Figure 5 below. In both cases, CVD
oxide caps about 300nm thick were layered on the top of pure PTFE or PTFE composite thin
films. The PTFE and PTFE composite films are about 500nm thick. The SiO 2/pure PTFE stack
actually failed (became hazy) after 20 minutes of annealing at 400"C, while the Si0 2/PTFE
composite stack survived even after 120 minutes. A 6:1 buffered HF solution was used to partly
remove the Si0 2 cap from the stack samples to expose the underlying PTFE or PTFE composite
surface. A Tencor profilometer was used to profile both the Si0 2 and PTFE or PTFE composite
surfaces yielding arithmetic roughness values of 33nm for the pure PTFE sample and 5nm for
the PTFE composite material.

Figure 5. a) Optical micrographs of a Si02/pure PTFE stack taken after annealing for 20
minutes at 400"C. b) Si0 2/PTFE composite stack after annealing for 120 minutes at
400"C. Oxide cap of both samples (shown on the left side of each figure) was removed
using HF.
DMA measurements on both pure PTFE powder and PTFE composite powder samples
quantified the differences observed in the oxide cap annealing test. As plotted in Figure 6, DMA
data of both samples' elastic moduli indicates that both samples have a melting transition at

378
320°C, which is normal for the specific PTFE
10'- , ,
material. The pure PTFE sample starts
viscous flow at 360°C (elastic modulus drops
E
several orders of magnitude), while the PTFE
composite material can still maintain some
elasticity at even 400°C, which is the upper
temperature limit of the instrument. Based on
10' -v- pure PTFE
the sketch in Figure 3, it may be observed
E PTFE composite
that the PTFE composite material has a
moderately crosslinked structure. UHMW PTFE
Interestingly, the PTFE composite and an 10300 30 34 36 3 0 40
260 280 300 320 340 360 380 400
ultra high molecular weight (UHMW) PTFE
sample have comparable modulus values at temperature ['C]
400°C. It should be pointed out that the Figure 6. Elastic modulus measurements of
UHMW PTFE has Mn of 60x106 [g/mol], pure PTFE, PTFE composite and Ultra high
while our nanoemulsion PTFE has Mn of molecular weight (UJHMW) PTFE.
0.4x106 [g/mol]. The improvement of high
temperature mechanical properties of the nanoemulsion PTFE given the relatively low level of
siloxane additions is remarkable.
With the above DMA results, it is possible to explain what was observed in the Si0 2 capping
test. PECVD SiO 2 typically has a residual compressive stress. When the film stack is annealed
above the melt flow temperature of the PTFE, the PTFE can flow viscously. Over time, in this
case about 20 minutes, this viscous flow permits Euler buckling of the compressed Si0 2 film. In
the case of the PTFE/siloxane composite film, the melt flow temperature has been raised above
400°C and no flow occurs.
Optical micrographs taken after a HF selective etch results on pure PTFE and PTFE
composite thin films are shown in Figure 7. The pure PTFE sample shows no changes following
the treatment. The slight edge lift is due to HF attack at the adhesion promoter present at the
Si/PTFE interface. The PTFE composite material surface shows micron-sized craters. This
indicates the presence of silica-like material in the thin films. AFM was attempted to reveal
possible mechanisms for the appearance of craters, such as microphase separations caused by
silica clusters embedded in the PTFE matrix, but no such microphase separation was observed.
The craters are about 60nm deep on 500nm PTFE composite thin films.
a SAMV 'lo

Figure 7. Optical micrographs taken after HF selective etching on both pure PTFE
(a) and PTFE composite (b) thin films.
To investigate the possible microphase separation inside the PTFE composite films, ToF-
SIMS surface elemental analysis was carried out. Results are summarized in Figure 8. For as-
received sample surface mapping, hydrocarbons, fluorocarbon, and silicon were monitored
(Figure 8a). The PTFE composite surface is almost 100% fluorocarbon. The trace amounts of

379
hydrocarbon are likely caused by surface contamination during shipping and handling. A shallow
crater of about 50nm is then sputtered into the composite thin film. ToF-SIMS elemental
mapping of fluorocarbon, carbon and silicon is then performed on the bottom of the etched crater
(Figure 8b). Uniformly distributed silicon signal is detected inside the PTFE composite. The scan
is 100 microns by 100 microns. No microphase separation is observed. Quantitative XPS
analysis on the bottom gives surface concentration of silicon of 2%, which further confirmed the
ToF-SIMS observation.

Total ions Hydrocarbon/C Fluorocarbon Si

Figure 8. ToF-SIMS surface elemental mapping on as received PTFE composite thin film
surface (a) and 50nm deep inside the thin film (b).

CONCLUSIONS
A novel PTFE/siloxane nanocomposite material has been successfully developed with very
low inorganic material concentration. The new composite material shows much improved high
temperature mechanical properties demonstrated by Si0 2 capping and annealing tests and DMA.
Unlike other composite materials, this PTFE/siloxane composite is a true molecular level
composite material. No microphase separation is detected. A complete set of thin film
characterization relative to the IC dielectric applications is underway. More detailed results will
be published in several forthcoming papers.

ACKNOLEDGEMENTS
The authors acknowledge special contributions by fellow Gore associates Jami Riggs, John
Bartz, Huey Wu, Mike Zumbrum, Jack Hegenbarth. Thanks also go to Dr. Ken Batzar
(consultant), Scott Krahn (intern), Dr. Paul Vlasak, John Newman and Jim Gibson at Physical
Electronics, Inc.
REFERENCES
1. S. C. Sun in Low-DielectricConstantMaterialsII, edited by Andr6 Lagendijk, et al, (Mater.
Res. Soc. Proc. 443, Pittsburgh, PA, 1997), p. 85-90.
2. C. T. Rosenmayer, in Low-Dielectric Constant Materials III, edited by Carlye Case, et al,
(Mater. Res. Soc. Proc. 476, Pittsburgh, PA, 1997), p. 231-236.
3. C. W. Macosko, Rheology Principles,Measurements,and Applications, (Wiley-VCH, 1994).

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