Applications of Spin Coating

Spin coating is used for many applications where relatively flat

substrates or objects are coated with thin layers of material. The material
to be made into the coating must be dissolved or dispersed into a solvent of
some kind and this coating solution is then deposited onto the surface and
spun-off to leave a uniform layer for subsequent processing stages and
ultimate use.
Some technologies that depend heavily on high quality spin coated layers
are
!hotoresist for defining patterns in microcircuit fabrication.
"ielectric#insulating layers for microcircuit fabrication $ polymers%
S&'% Si()% etc.
*agnetic disk coatings - magnetic particle suspensions% head
lubricants% etc.
+lat screen display coatings. - Antireflection coatings% conductive
o,ide% etc.
Compact "isks $ "-"% C" .&*% etc.
Television tube phosphor and antireflection coatings.
The )ey Stages in Spin Coating
Although different authors sometimes count things differently, there are four
distinct stages to the spin coating process. Stage 3 (flow controlled) and Stage 4
(evaporation controlled) are the two stages that have the most impact on final
coating thickness.
Stage &ne The first stage is the deposition of the coating fluid onto the
wafer or sustrate.
!t can e done using a no""le that pours the coating solution out, or it could e
sprayed onto the surface, etc. #sually this dispense stage provides a sustantial
e$cess of coating solution compared to the amount that will ultimately e
re%uired in the final coating thickness. &or many solutions it is often eneficial
to dispense through a su micron si"ed filter to eliminate particles that could
lead to flaws. Another potentially important issue is whether the solution wets
the surface completely during this dispense stage. !f not, then incomplete
coverage can result.
Stage Two The second stage is when the sustrate is accelerated up to its
final, desired, rotation speed.
This stage is usually characteri"ed y aggressive fluid e$pulsion from the wafer
surface y the rotational motion. 'ecause of the initial depth of fluid on the
wafer surface, spiral vortices may riefly e present during this stage( these
would form as a result of the twisting motion caused y the inertia that the top
of the fluid layer e$erts while the wafer elow rotates faster and faster.
)ventually, the fluid is thin enough to e completely co*rotating with the wafer
and any evidence of fluid thickness differences is gone. #ltimately, the wafer
reaches its desired speed and the fluid is thin enough that the viscous shear drag
e$actly alances the rotational accelerations.
Stage Three The third stage is when the sustrate is spinning at a
constant rate and fluid viscous forces dominate fluid thinning ehavior.
This stage is characteri"ed y gradual fluid thinning. &luid thinning is generally
%uite uniform, though with solutions containing volatile solvents, it is often
possile to see interference colors +spinning off+, and doing so progressively
more slowly as the coating thickness is reduced. )dge effects are often seen
ecause the fluid flows uniformly outward, ut must form droplets at the edge
to e flung off. Thus, depending on the surface tension, viscosity, rotation rate,
etc., there may e a small ead of coating thickness difference around the rim
of the final wafer. ,athematical treatments of the flow ehavior show that if
the li%uid e$hiits -ewtonian viscosity (i.e. is linear) and if the fluid thickness
is initially uniform across the wafer (aleit rather thick), then the fluid
thickness profile at any following time will also e uniform *** leading to a
uniform final coating (under ideal circumstances).
Stage +our The fourth stage is when the sustrate is spinning at a constant
rate and solvent evaporation dominates the coating thinning ehavior.
As the prior stage advances, the fluid thickness reaches a point where the
viscosity effects yield only rather minor net fluid flow. At this point, the
evaporation of any volatile solvent species will ecome the dominant process
occurring in the coating. !n fact, at this point the coating effectively +gels+
ecause as these solvents are removed the viscosity of the remaining solution
will likely rise ** effectively free"ing the coating in place. (This ehavior was
used in the seminal work of ,eyerhofer (.. Appl. /hys. /0 (0123) 3113) where
he %uantified the coating thickness dependence on spin speed and viscosity and
its relationship to the evaporation rate.)
After spinning is stopped many applications re%uire that heat treatment or
+firing+ of the coating e performed (as for +spin*on*glass+ or sol*gel coatings).
4n the other hand, photoresists usually undergo other processes, depending on
the desired application5use.
6learly stages 3 and 4 descrie two processes that must e occurring
simultaneously throughout all times (viscous flow and evaporation). 7owever,
at an engineering level the viscous flow effects dominate early on while the
evaporation processes dominate later.
+luid +low 1ffects 2mportant for Spin Coating
+luid +low 3asics 42deal Case5
The starting point for much of the spin coating modeling was pulished
y )mslie, 'onner, and /eck 8.. Appl. /hys. 60 (0193) 393*3:;< (hereafter referred
to as )'/). Their seminal treatment is ased on assuming that flow has reached
a stale condition where the centrifugal and viscous forces are =ust in alance
(this is also the asis for most other modeling work * note that this does -4T
apply to the first stage of spin*up and e$cess solvent e$plusion). >hen the
centrifugal and viscous forces are in alance, this e%uation must e satisfied?
where " and r define a cylindrical coordinate system aligned with the a$is of
sustrate rotation, v is the fluid velocity in the radial direction (a function of
depth), and where is the fluid density, is the rotation rate in radians per
second, and is the viscosity in poise. >ith appropriate flow and velocity
oundary conditions, and considering a film that is initially uniform, the film
thickness as a function of time, h(t), was found to e?
where h
o
is the film thickness at time "ero (ut not physically meaningful
ecause of the first stage of unstale solution e$pulsion at early time), and @ is
a system constant defined as?
These e%uations are strictly valid only when @ is constant. 7owever, for spin
coating of sol*gel or other comple$ solutions this may not hold true during all
stages of spinning. 'oth viscosity and density are e$pected to increase as
evaporation progresses, so caution must e used when applying these
e%uations. !n their analysis, )'/ also showed that for early stages of fluid
thinning (efore evaporation ecomes important), the thinning rate would e
defined as?
At longer times, solvent evaporation ecomes an important contriution.
,eyerhofer was the first to estimate the effect of this on final coating thickness
8.. Appl. /hys. /0 (0123) 3113*3112<. A %uite reasonale appro$imation is that
evaporation is a constant throughout spinning, as long as the rotation rate is
held constant (see elow). Therefore, he simply added a constant evaporation
term to the e%uation aove. So, the governing differential e%uation ecame?
where +e+ is the evaporation rate 8ml5s5cm
;
< (this is effectively the contriution
to the interface velocity that is driven y the evaporation process alone).
!nstead of solving this e%uation e$plicitly, ,eyerhofer assumed that
early stages were entirely flow dominated, while later stages would e entirely
evaporation dominated. 7e set the transition point at the condition where the
evaporation rate and the viscous flow rate ecame e%ual. This can e thought of
as the fluid*dynamical +set+ point of the coating process. >hen these
assumptions are made, the final coating thickness, h
f
, is predicted to e?
where c
o
is the solids concentration in the solution. >hen the physically
applicale dependence of the evaporation rate on spin*speed was factored in,
this was successful in matching the regular e$ponents for the dependence of
final film thickness with spin speed. Aesearch has shown that the evaporation
rate should e constant
over the entire sustrate
and depend on rotation
rate according to?
where the proportionality constant, 6, must e determined for the specific
e$perimental conditions. This s%uare root dependence arises from the rate*
limiting*step eing diffusion through a vapor oundary layer aove the
spinning disk. !t should e noted that this results when airflow aove the
spinning sustrate is laminar.
+luid +low Complications
The flow ehavior descried aove ignores several effects that are
important for many coating solutions. As noted aove, the evaporation step is
critical in defining what the final coating thickness will e. 'ut, evaporation
occur ** y necessity ** from the top surface, and only some of the solution
components are volatile enough to evaporate to any sustantial degree. Thus,
there will necessarily e an enrichment of the non*volatile components in the
surface layer of the coating solution during the spinning process. The figure at
right illustrates that concept. 4ne of the key conse%uences is that this surface
layer will very likely have a higher viscosity than the unmodified starting
solution (this may simply e due to the higher concentration, ut might also
occur ecause of cross*linking effects, etc). >ith a higher viscosity, it will then
impede the flow characteristics set out aove, making it a difficult differential
e%uation to solve directly. And, this surface layer may have the secondary
result of reducing the evaporation rate. So oth the evaporation and flow
processes are coupled through the ehavior of the +skin+ that develops on the
top of the outwardly flowing solution during spin coating.
Another important effect is that some solutions are not +-ewtonian+ in
their viscosity5shear*rate relationships. Some solutions change viscosity
depending on what shear rate is used, thus depending on distance from the
center, the shear rate will e different and thus the flow ehavior. This can give
radial thickness variation that varies rather smoothly in a radial sense, as
pointed out y 'ritten and Thomas 8.. Appl. /hys. 78 (011;) 12;*121<.
Air +low 1ffects 2mportant for Spin Coating
Air +low 3asics 42deal Case5
The image at the right, from ,illsaps and
/ohlhausen, 8.. Aeronautical Sci., (019;) 0;B*0;:<
shows a schematic of the ideal airflow field aove
an infinitely large spinning disk. At the surface of
the disk there is a +no*slip+ condition so the
contacting air must e e$actly co*rotating *** hence
the flow vectors pointing essentially tangentially to
any point at a given radius (and proportional to the
distance from the center). At moderate distances
from the surface a centripetal acceleration must e
provided y the viscous effects( this condition is
thus maintained only when some outward radial air flow is also occurring. This
outward flow is alanced y some minor downdraft over the entire wafer. This
is a steady state configuration and does not include inertial effects included in
the +spin*up+ stages. This air flow pattern also only hold true so long as the
flow is laminar. A +oundary layer+ of uniform thickness thus e$ists over the
entire surface area of the spinning wafer? it is through this oundary layer that
evaporating solvent must diffuse. 'ecause the oundary layer is constant in
thickness over the wafer then the evaporation rate as a function of position is
predicted to also e constant.
Air +low Complications
The steady flow field descried aove is limited to cases where the flow
is laminar and where it is +steady+. !n fact, e$cept for very large wafers, most
spinning conditions C4 satisfy the constraint of having laminar flow. 7owever,
there can e un*steady oscillating instailities in the oundary layer near the
surface of the wafer. These form spiral shaped waves or rolls that are called
+)kman+ spirals. >ahal, et al 8Applied /hysics Detters 96 (0113) ;934*:< have
e$perimentally oserved )kman spirals (shown in the figure at right) for
nominally laminar conditions in spin coating. They claim that these instailities
can lead to coating thickness variations, ut have not e$plained >7E that
would e the case. Common "efects +ound :hen Spin
Coating
This is y no means an e$haustive list, ut ! try to highlight a numer of
defects5features that are characteristic of spin coated films.

Comets? These usually occur when relatively large solid particles impede
the normal flow patterns of the solution on the spinning wafer. )$cept during
+spin up+, the flow is normally smooth and radial in nature (having a gradient
in radial velocity governed y the applicale force alances and viscosity
constraints (see spin coating asics page). The presence of comets can e
reduced or eliminated y working in cleaner environments and y filtering
coating solutions as part of the dispense process.
)ach of the figures elow can e F44,)C y clicking in the figure
area for ;.9G enlargements. !n all cases the flow was from left to right and the
scale is the same for all photos. All are light microscopy photos so color
differences indicate different coating thickness at different locations. These
coating differences are most dramatic for the photo on the right.


Sol*gel /FT on Silicon wafer
Sol*gel /DFT ;59B59B on conductive*
o$ide*coated glass. ;BBBA/, spinning
speed. Tiny 'aTi4
3
seeding particles in
suspension. (more visile in close*up).
Sol*Hel Silica*titania on silicon.
0BBBA/, spinning speed. -ominal
coating thickness I 3BBnm.

Striations?Striations are radially oriented lines of thickness variation in the
as*coated film. #sually they are %uite smoothly varying thickness variations
with a spacing or periodicity in the 9B*;BB micron range, or so. Their
orientation corresponds the direction of ma=or fluid flow (which is running
hori"ontally in ; of the 3 the optical micrographs shown elow). Their
occurance is thought to arise ecause of evaporation driven surface tension
effects. The early evaporation of light solvents can cause an enrichment of
water and5or other less volatile species in the surface layer. !&, the surface
tension of this layer is larger than the starting solution (and what still e$ists at
deeper levels), then an instaility e$ists where the higher surface tension
actually draws material in at regular intervals and the spaces in*etween are
more ale to evaporate, and surface relief develops. This is essentially due to
the ,arangoni effect which governs the development of structures in the
drainage patterns of wine down the sides of a wine glass? ethanol evaporates
first leaving an ethanol*depleted wine layer that gathers into rivulets and drains
down the glass wall.

Sol*Hel Silica*titania.
0BBBA/, * nominal thicknessI3BBnm.
Sol*Hel /FT viewed near edge.
3BBBA/, * average thickness not
resolved in ellipsometry
Sol*Hel /FT viewed at center. Same
sample as figure to left. Aadial flow of
fluid stretches out the cellular features
shown aove.
)vaporation driven surface tension effects can create striations the following
way?
The evaporation process makes the top layer have a different composition and
therefore a different surface tension. The top surface then can ecome unstale
to +long wavelength+ perturations that grow unstaly. The e$act conditions
that control what is stale and what is unstale are still not well known. 4ur
preliminary model is that you would like the evaporation process to e driving
the local surface tension to lower values and that this would tend to staili"e the
system. This is currently eing tested on a numer of sol*gel and polymer
coating systems.
Chuck *arks? These patterns can e created y thermal +communication+
etween the solution on top of the wafer and the metal vacuum chuck on the
ack side of the wafer (see 6huck ,arks page for more detailed e$planation).
Thus, the thermal conductivity of the sustrate material is very important as is
the thermal driving force (mainly evaporative cooling, ut could also e due to
temperature differences etween solution and sustrate and chuck....). The
figure at right has a single layer sol*gel*derived coating on a glass
sustrate.Silicon wafers, ecause of their higher thermal conductivity, will
usually have smaller thickness differences compared to glass or plastic.
1nvironmental Sensitivity >hen making coatings in the amient
environment, it is possile for the surroundings to have an influence on the
coating %uality. 4ne critical variale is the humidity of the surrounding air. &or
many solutions, water can play an important role in the chemistry of the
solution itself, so when varying amounts of water are present in the
surroundings then varying coating %uality can result. This can manifest itself as
coating roughness, microcracking of the coating upon further drying,
e$aggerated striation formation in the coating, etc. 4viously, close control of
the environment around the spin coater is crucial.
:afer 1dge 1ffects The edges of the sustrate will always e areas of
concern. !f etter uniformity can e maintained out to the edges then more area
can e used for device farication. The edges are prolems for several reasons.
&irst, surface tension effects make it difficult for solution that is flowing
radially outward to detach from the wafer. Thus a small +ead+ of li%uid can
stay attached around the entire perimeter and result in thicker coatings in this
rim "one. !n addition, if sustrates are not e$actly round and especially if they
are s%uare or rectangular, then the air flow over the protruding parts (corners)
will e pertured. Although the flow may still e laminar, it will have different
flow history and will usually result in non*uniformity in coating thickness in
these corner areas.