717

PHYSICS AND APPLICATIONS OF

DIP COATING AND SPIN COATING

L. E. SCRIVEN
Department of Chemical Engineering & Materials Science and Center for Interfacial Engineering,
University of Minnesota, 421 Washington Ave. S.E., Minneapolis, MN 55455

ABSTRACT

Dip coating is a simple old way of depositing onto a substrate, especially small slabs and
cylinders, a uniform thin film of liquid for solidification into a coating. The basic flow is steady, and
in it film thickness is set by the competition among viscous force, capillary (surface tension) force and
gravity. Thickness and uniformity can be sensitive to flow conditions in the liquid bath and gas over-
head. The faster the substrate is withdrawn, the thicker the film deposited. This can be countered
by using volatile solutes and combining rapid enough drying with the basic liquid flow. Then the
physics grows more complicated, theoretical prediction of process performance more difficult, and con-
trol of the process more demanding. Outside product R & D labs it is far less often used in precision
coating manufacture than a variety of premetered coating methods.

Spin coating is a more recently developed way of getting onto piecemeal substrates, especially
small flat disks, a uniform thin liquid film for the same end. The basic flow is unsteady radial
drainage in which centrifugal and viscous forces so compete that ordinary (Newtonian) liquid of con-
stant viscosity tends toward a uniform film that grows ever thinner ever more slowly. Volatile sol-
vents are commonly used because conditions can often be found that adequately separate thinning by
spin-off from later thinning and solidification by drying. Thickness and uniformity, today theoreti-
cally predictable, are sensitive to speed, gas conditions, and rheology of concentrating, solidifying
liquid. For the rheology of photoresist coating in microelectronics, spin coating works well. For that
of suspension coatings in magnetic disk technology the process demands more careful control; actually
it is often modified.

INTRODUCTION

In research and development of materials which may find application as coated films and can be
deposited in a liquid state, laboratory scientists naturally turn to simple coating methods that do not
require sophisticated apparatus. Spray coating, dip or immersion coating, spin coating, and draw-
down coating are the methods most likely to be considered. Spray coating relies on accretion and
coalescence of multiple droplets and is usually rejected when the goal is a uniform film on a smooth
substrate. Drawdown coating, though quite common in the laboratories of some industries, requires
attention to mechanical tolerances and is generally harder to manage the lower the viscosity and the
thinner the wet film to be produced. So even if drawdown coating is considered it tends to lose out to
dip coating when substrates are flat or cylindrical, and to spin coating when they are disks, plates or
bowls. This appears to be as true as ever in the blossoming field of inorganic polymer coatings by
sol-gel routes.

Why and how do dip coating and spin coating work? How do the thickness and uniformity of
the wet films depend on the design and operating variables of these processes? On the properties of
the liquid? What are the limitations? Why is industrial production coating outside the laboratory so
often done with greatly modified or distinctly different processes? What is the relation of the drying
of the coated film to the process by which it is deposited?

Mat. Res. Soc. Symp. Proc. Vol. 121. c1988 Materials Research Society
718

PHYSICS OF DIP COATING

Dip coating, or immersion coating, is a batch process the end result of which is the application
of a thin film of some desired coating liquid or liquid-like slurry to a rigid slab or cylinder (or other
shapes when uniform film thickness is not critical); the film may or may not solidify during the dip
coating operation. Dip coating is also practiced as a continuous process when the substrate to be
coated is a long, flexible sheet or filament. The batch dip coating process can be divided into five
stages: immersion, start-up, deposition, drainage, and evaporation (see Fig. 1). The first three are
necessarily sequential; the third and fourth, concomitant; the fifth, evaporation of solvents from the
liquid, proceeds throughout the process unless precautions are taken.

The continuous dip coating process separates immersion from the other stages, relegates start-
up to a very short episode, hides drainage in the deposited film and restricts drying to the deposition
stage and afterward. So dip coating of a continuous sheet, or 'web,' is the process to consider first.

Continuous Process

At ( in Figure 1 (f), the web plunges into the coating bath. If the speed is not too great, most
of the gas originally in contact with the web is displaced by the coating liquid at the bath surface 1.
The submicroscopic region where that happens is called the dynamic wetting line. At higher speeds,
submicroscopic bubbles of the gas may be entrained at the web surface, only to dissolve subsequently.
With rising speed the amount of entrained gas increases until it becomes intolerable. This is the air
entrainment limit on coating speed, a fluid mechanical phenomenon. It is aggravated by making the
liquid viscosity greater or diminishing the surface tension; it may be affected by the topography of the
web but ordinarily rather little by surface composition.

DIP COATING

IMMERSION START-UP DEPOSITION & DRAINAGE

DRAINAGE EVAPORATION CONTINUOUS

Figure 1. Stages of dip coating processes: (a)-(e) batch; (f) continuous.

 719

Between (D and (® the moving web entrains liquid in fluid mechanical boundary layers, setting
.the bath into a melange of recirculating flows and carrying some of the liquid toward the film deposi-
tion region at ®. There the boundary layer on each side of the web splits in two. The innermost
part next to the web, is moving fast enough to accompany the web through the subambient pressure
atd and form the film lifted away by the web. The outermost part, under the curved meniscus, is
turned back into the bath. Between the two parts of the flow is a dividing stream surface. Where it
intersects the meniscus is a stagnation line at which the liquid does not move: to one side liquid is
being lifted by the web; to the other side liquid is falling back into the bath.

The thickness of the deposited film is related to the location of this streamline. Both are
governed by a competition of as many as six forces in the film deposition region at ( First is the
viscous drag upward on the liquid by the rising web; it is proportional to liquid viscosity A and web
speed U . Second is the force of gravity, g, downward on liquid above the level of the bath; it is
proportional to liquid density p . Third is the resultant force of surface tension a in the concavely
curved meniscus. That resultant force lowers the pressure in the liquid beneath the curved meniscus
(P Pambiiet - a/r, where r is the local radius of the meniscus). One consequence is a minor slowing
of the flow falling away from the region; the other is a net downward force on the liquid in the depo-
sition region. Fourth is the inertial force, or momentum flux, of the boundary layer liquid arriving at
the deposition region; that liquid has been accelerated by the web deeper in the bath and its momen-
tum flux grows roughly as the square root of the length I of the submerged vertical run (actually the
flux is about 0.66 VppUaI). The fifth force is the surface tension gradient, if any. More about it
below. The sixth force can only be important where the deposited film is under a micron thick. More
about it, too, below.

Often the inertial force is inconsequential in the competition. That is a useful situation, because
then the thickness of the deposited film is insensitive to the length of the submerged vertical run and
to most other features of flow in the bath, often including the way make-up liquid is added.

If among the three remaining contenders, viscous drag, gravity, and surface tension, the last is
overshadowed because liquid viscosity and web speed are high enough to hold meniscus curvature
down, then the deposited film thickness h is that at which viscous drag and gravity are in balance.
The drag force is proportional p U/h and the gravity force to pgh. Thus

t
h - c, ' 'U/pg (1)

Experiments in various conditions of baths indicate the proportionality constant is around 0.8 for
Newtonian liquids 2 On the other hand, when liquid viscosity and web speed are not high enough,
the competition becomes three-sided, but in such a way that the ratio of viscous drag to surface ten-
sion effect simply modulates the drag-gravity balance, as L. D. Landau & B. G. Levich ' were first to
show:

h 0.944 (2)

Experiments accord with this provided the 'capillary number' pU/a is less than 10-2 . Measure-
2
ments at higher values fit more refined approximate theories of the competition . Liquids with shear-
sensitive and concentration sensitive viscosity are successfully dip-coated. So are some viscoelastic
liquids. How the deposited film thickness depends on measured rheological parameters is not
4
accounted for well by the approximate theories that are available .

Actually modern computer-aided mathematics has made full theories of coating flows possi-
6 7
ble '-. Dip coating is among the methods receiving attention ,'.

The deposited film of course accompanies the web upward. Were gravity absent, all the liquid
720

would move at the web's speed. Gravity slows the liquid a bit, so that there is a velocity gradient
toward the web surface, and thus a graded viscous drag force. In this way gravity and viscous drag
strike a balance. To an observer traveling with the web, the liquid drains toward the bath, fastest at
the free surface and not at all at the web surface. This drainage action does not change the profile of
film thickness, because everywhere in the deposited film there is as much draining in from above as
draining out to below.

So though the deposited film does drain, the action is hidden. It does show through in a slightly
thinner film, and in a slight lag of the film surface behind the web speed. The drainage rate, q, in
volume per unit time per unit of web width, and the free surface speed, v,, are

q_= .P_.&h3 vs -f -P-&h2 (3)

This drainage rate is a debit on the maximum volumetric flux per unit width the web could be trans-
porting, namely Uh. Thus the film thickness would readjust slightly if the web were turned away
from vertical, as by angling it over a roller. (Then the final thickness would be hf, the solution of Uh
- q = Uhr - (pgcosO/2p) h3, where 0 is the inclination angle from vertical.)

The slower the web passes through the bath, the smaller the viscous drag force by which the
web lifts liquid, and the thinner the film that is deposited. There are limits to thinness, however.
One limit may be set by the sixth force, which is appreciable only in films under a micron thick.
Known as disjoining pressure, it stems from London-Van der Waals intermolecular forces and, in
ionic solutions, from electrostatic interionic forces ('electric double layer' forces). If the disjoining
pressure depends on film thickness in such a way that there is an equilibrium thickness, the liquid is
said to wet the web perfectly, and no thinner film than what is in equilibrium with the bath liquid
can be deposited; in other words, film thickness falls no more as web speed is further reduced'. If the
liquid is not perfectly wetting, as when the disjoining pressure is negative - and thus is a conjoining
pressure - there is a web speed below which viscous drag is overwhelmed and the film collapses as it
1
is formed; in other words, there is a speed below which the web emerges unwetted from the bath" .
Even at higher speeds the film that forms in this case is unstable with respect to dewetting, as men-
tioned again below.

Evaporation may set a limit. If the gas above the bath is not saturated with respect to all the
volatile components of the coating liquid, evaporation proceeds. To a first approximation evaporation
is controlled by conditions in the gas phase and so the evaporation rate is independent of liquid
depth. Consequently, what is a negligible evaporation rate from the bath surface may reduce the
thickness of the coated film with dramatic rapidity, removing the film altogether if it is entirely vola-
tile, or leaving only the nonvolatile components in some crystalline, glassy, or porous state - a
solidified coating. In other words, the slower the web speed, the thinner the film and the greater the
10
overlap of the deposition and drying stages of dip coating . Overlap can bring surface tension
gradient-driven flow into film formation, because differential evaporation of the more volatile
component(s) produces graded composition that may cause appreciable surface tension gradient, a
potent force in thin films. Of course the two stages can always be separated by supplying saturated
gas above the locale where the film is being deposited.

The thinner the film, the less likely is the evaporation rate to be independent of its thickness,
because chemical potentials come to depend on that thickness. The effect is analogous to the sensi-
tivity of vapor pressure to the capillary pressure within tiny liquid drops (the well-known Kelvin
effect): the vapor pressure of liquid in a submicron film appears to depend on the disjoining or con-
joining pressure. Indeed, to a given set of partial pressures of volatile components in the adjacent gas
may correspond an equilibrium film thickness - or even more than one equilibrium film thickness"1.

Heat is so readily available from the web beneath a thin film that evaporation is unlikely to cool
2
the liquid surface significantly" . The most significant factor in the rate of evaporation is the rate of
diffusion of vapor away from the liquid surface. This depends.exquisitely on how the gas moves inside
 721

of a millimeter away, because even a tiny bit of convection can greatly enhance diffusion. The com-
bined action is called convective diffusion and is often represented in this context by an empirical
'mass transfer coefficient,' k. That is, the rate of evaporation per unit area, m , is related to the
difference between the partial pressure of a volatile at local equilibrium with the liquid surface, p.,
and its partial pressure pi a little distance away where the gas is fairly well stirred by convection"':

m = k (p. - pi) (4)

In dip coating the movement of the liquid surface can strongly influence gas motions nearby.
Gas is carried upward by the rising film above the stagnation line, and more slowly downward and
outward below that line. But the slower the web, the more feeble these motions and the more
influential the usually gentle, irregular incursions of gas from larger-scale, uncontrolled currents in the
gas space above the bath. The reality in situations like dip coating is that the mass transfer
coefficient, k, and the mass transfer driving force, P. - pi, fluctuate with time across the film being
deposited, because of irregular, uncontrolled movements in the gas.

Batch Process

Dip coating is practiced as a batch process when the substrate consists of slabs, cylinders, or
other pieces that cannot conveniently be linked into a continuous train. Then all the stages have
starts and finishes as each piece passes through. But the middle of a stage may be close enough to a
steady state that it differs very little from the continuous version.

So it is with immersion: Figure 1 (a). Depending on the shape of the leading end of the sub-
strate, excessive gas may be entrained in the start-up phase. Similarly, gas bubbles may be injected
into the bath in the wake of the trailing end as immersion is completed.

At the start-up of withdrawal (Fig. I (b)), liquid draining off the leading end and delay in the
development of viscous drag force contribute an end effect. Beneath the convexly curved meniscus
over the edges the surface tension resultant raises the pressure in the liquid and causes it to drain
away, so that the deposited film is soon thinnest at those edges. Moreover, the piece must rise
through some distance before viscous action accelerates the adjacent liquid so that the viscous drag
force approaches its steady state value, as in the continuous version. And even as the liquid is
accelerated upward by viscous action, gravity drains it downward relative to the surface of the sub-
strate. Unless drying concentrates nonvolatiles and arrests flow, this drainage action soon affects
more of the deposited film than does the start-up end effect. The main feature is that the deposited
film is exceptionally thin at the leading edges, but thickens, over some distance, following a parabolic
profile to the continuous deposition film.

Once the viscous drag force reaches full value, the thickness of the deposited film is governed by
the same steady-state competition of forces as in completely continuous coating. The balance between
viscous drag and gravity is just as well described by Eq. (1), and the three-sided balance with surface
tension by Eq. (2).

The drainage stage appears first in the end region at the top of the substrate, as already men-
tioned (Fig. I (c)). To an observer moving with the substrate, gravity drains liquid toward the bath.
Because everywhere in the end region the film above is already thinner, less liquid drains in from
above than drains out to below, and the film thins. With x the distance downward from the leading
edge and the drainage flux given by Eq. (3), the thinning action is described by a simple equation of
local conservation of liquid volume (or mass):
 722

Aoi
at [ PA
a- j = pgh
•0 2 Oh
&• (5)

There are two solutions. One is any constant value of thickness h : this is the solution that per-
tains to continuous dip coating. The other is a draining film with a parabolic thickness profile that
falls to zero at the leading edge:

h = T (6)
og t

This draining profile gives way to the constant thickness film of continuous dip coating at the place
x. where h , from Eq. (6), reaches the steady-state deposition thickness, as given by an appropriate
equation, e.g. Eq. (2) when withdrawal is slow enough.

Local conservation of liquid has another consequence. As the film changes thickness, the loca-
tion of any particular thickness h shifts down the substrate at a speed proportional to the square of
that thickness:

vx, (Oh/at) = &Vh2 (7)

S ft- (ah/lx), A

The elevation at which the parabolic profile reaches the constant thickness is Ut - x., where U is
the speed of withdrawing the substrate and t is the time since the leading edge left the bath. From
Eqs. (6) and (1) or (2) it follows that x. is a constant fraction of Ut. The drainage action continually
lengthens the parabolic profile in such a way that the end effect occupies a fixed fraction of the with-
4
drawn length, as Groenveld1 pointed out. For example, when a substrate is withdrawn at U - 2.5
8
mm/s from liquid of surface tension a = 25 dyn/cm, viscosity p = I cp, and density 1 gm/cm , the
capillary number is 10' and from Eq. (2) the steady-state film thickness h is 3.2 pm and extends
96% of the way to the leading edge. When withdrawal is halted, the continuing drainage extends the
parabolic profile downward, increasing the distance x. at a speed that is 4.1% of U according to Eq.
(7), i.e. at 0.1 mm/s (at the bottom, meanwhile, draining liquid accumulates in an unwanted swelling
from which drops may form and fall off: Fig. 1 (d)). These estimates are all for cases in which drying
appreciably alters neither the film thickness nor the viscosity of the liquid in it.

If the liquid does not wet the substrate perfectly there is a speed below which the substrate
emerges unwetted from the bath, as in the continuous process. On the other hand, rapid enough eva-
poration of volatile components from the deposited film may so raise its viscosity as to prevent it
from thinning locally and dewetting, or from draining further, before it finally solidifies (Fig. 1 (e)).
Too rapid evaporation may cause the film surface to solidify prematurely into a skin that slows subse-
quent drying.

DIP COATING IN APPLICATIONS

Dip coating is a relatively simple way of depositing a thin film of liquid for solidification into
coating. A smoothly acting drive mechanism is needed to pull continuous web or to withdraw rigid
substrates at constant speed. A bath of great enough open area can be used that a simple level sensor
and flow controller together with an inexpensive pumping arrangement suffice to replenish the coating
liquid. Or, in the batch process, a smooth-walled cylindrical vessel of suitable material can be used so
that the open surface, or meniscus, descends without changing shape as liquid is deposited on the sub-
strate being withdrawn. With volatile solutes and adequately controlled evaporation the thin film can
be solidified during coating.
 723

There are complications, however. Liquid circulation is not controlled in the bath, so that the
liquid coated has resided there a variable time. Another consequence is that the flow in the boundary
layer on the moving substrate and in the film formation zone is subject to fluctuations that may cause
unacceptable local variations in coated film thickness. The exposed surface of the bath is like a drum-
head, ready to respond to disturbances with ripples that run to the film formation zone with similar
effect. So long as the coated film remains liquid and retains vertical orientation it is prey to sagging,
the (slow) amplification of thickness variations because thicker film drains faster than thinner film
(Eq. (7)). Hence to achieve desired quality in applications may require improving the drive mechan-
ism and replenishment arrangement, reducing or isolating other sources of mechanical and acoustic
vibrations, and insuring pinning or else smooth sliding of the liquid surface at the wall of the bath.

The exposed surface of the bath is also a receiver for adventitious particles dropping out of the
gas overhead. Most insidious are those with surface tension-lowering materials, for these cause sur-
face tension gradient that in turn drives local surface-spreading flow. In the film formation region
and on the formed film this mechanism can locally thin and even rupture the film. Tiny amounts of
surface tension-lowering or conjoining pressure-inducing materials on the substrate surface can be just
as fatal. Cleanliness is of course a key to successfully coating thin films of liquid, and new applica-
tions commonly require more than is anticipated.

Gas circulation over the bath is usually not controlled closely, so that there are irregular move-
ments some of which reach to the liquid surface and cause the rate of evaporation to fluctuate locally,
as noted in connection with the continuous process. In applications there may be benefits from
arranging controlled, laminar gas flow, cocurrent or countercurrent to the moving liquid surface.
There may be further benefits in managing the partial pressures of volatile components along the gas
flow, for instance to suppress a surface tension gradient in the film formation zone, to delay evapora-
tion until the film is fully formed, to slow the rate of concentration of a nonvolatile solute in the film,
or to delay the descent of evaporating micromenisci into the porespace of a particulate suspension. A
phenomenon to control, if it occurs, is periodic precipitation of the new phase when evaporation
supersaturates liquid in the film formation region or downstream. Transverse barring, or chatter-
marks, can arise from evaporation-driven instabilities as well as fluid mechanical ones and external
vibrations.

PREMETERED COATING

The slower the web or substrate is withdrawn, the lesser the viscous drag force by which the
web lifts liquid, and the thinner the film that is deposited. This behavior works against dip coating
in industrial practice: the thinner the coating wanted, the slower the production rate, the more sensi-
tive the process to external disturbances, the more difficult the attainment of quality, and the higher
the cost. A variety of alternative coating methods avoid the shortcomings of dip coating, though
each has its own limitations. They deliver liquid across the width of the web or around the perimeter
of the substrate uniformly at a controlled rate. Then the thickness of the deposited liquid film
provided it forms at all -- is just the feed rate per unit width divided by the web or substrate speed.
This is called premetered coating. It is usual in precision coating manufacture. A premetered coating
method closely related to dip coating is slot coating, diagrammed in Figure 2 (a).

The premetered liquid is delivered through a precisely machined slot arrangement in a coating
die, liquid being supplied uniformly across the width of the slot by a distribution chamber (not indi-
cated). The liquid fills the narrow gap between the die face and the moving web, and forms two free
surfaces, or menisci. One of these should attach (as shown) to the carefully machined downstream
edge of the die face. However it attaches, it curves and extends downstream as the exposed surface of
the liquid film. The second meniscus should attach (as shown) to the sharp upstream edge of the die
face. From there it curves across the gap and meets the moving web in a dynamic wetting line where
gas is displaced by coating liquid. The flowing liquid between the two menisci is called the coating
bead. The amount of liquid is far less than the inventory in a dip coating bath, and it has much less
free surface exposed to evaporation.
724

PREMETERING VS. DEMAND FEEDING

lb lI I l 4-

SLOT COATING SLOT COATING SLOT COATING DIP COATING

WITH 'VACUUM' WITHOUT *VACUUM' WITH 'SEAL' WITH 'SEAL'

Figure 2. Relation of slot coating to dip coating: (a)-(d) progression at constant substrate
speed.

For the coating bead to exist at all the forces that act on it must be in balance, and the balance
5
must be stable to small upsets" . The main forces are the viscous drag of the web, surface tension
and gravity. The range of stable balance can be extended to higher web speed and thinner coated
film by contriving to reduce the gas pressure on the upstream side of the die (the bottom side as
shown). Maintaining a vacuum of as much as 10 cm of water and more in a chamber around the
upstream side is not uncommon in practice. The pressure difference makes a force that helps counter-
balance the viscous drag force. But the menisci must be able to curve sharply enough to sustain the
pressure difference, or vacuum, that is applied; consequently the gap must be narrow to produce thin
coating rapidly.

The relation to dip coating can be grasped from Fig. 2. If the vacuum is removed from the
upstream side of the bead, the menisci cannot curve as sharply and so to maintain the bead, the film
thickness and hence the supply rate must be raised: (b). The upstream meniscus can be effectively
removed by closing the upstream side of the gap to leave only a seal (though this leaves the web sur-
face vulnerable to marring and scratching): (c). The gap can then be widened out into a bath, with
further reduction of meniscus curvature and thickening of the deposited film. Now, however, the film
thickness is controlled by the force competition near the web and is little affected by the distant men-
iscus at the side wall. In place of precise premetering of the liquid, a cruder system can be used that
feeds when a falling liquid level demands it.

What bears remarking is that slot coating offers the possibility of coating the same film thick-
ness at higher speed, or alternatively of coating at the same speed a thinner film than dip coating
yields - and of doing so with superior control of the operation.

PHYSICS OF SPIN COATING

Spin coating is inherently a batch process the outcome of which is a solidified thin coating on a
rigid flat disk, plate, or slightly curved bowl or lens. The process can be divided into four stages:
deposition, spin-up, spin-off, and evaporation (see Fig. 3)13. The second may overlap the first but the
 725

first three stages are sequential. The fourth proceeds throughout the process unless, as is also true of
dip coating, precautions axe taken to delay the start of evaporation.

In the first stage an excess of liquid is delivered to the substrate at rest or spinning slowly. The
amount is far more than the coating to be produced would require. Liquid may be deposited as a
bolus on the axis or around the perimeter of the hole if the center of the substrate has been cut out.
Alternatively it may be delivered through an elevated port that moves radially over the substrate.
More about this below. In the second stage the liquid flows radially outward, driven by the centrifu-
gal force generated by the rotating substrate. This stage commonly occupies the seconds the sub-
strate is being spun up to full speed of several thousand revolutions per minute. Most of the gas ori-
ginally in contact with the substrate surface is displaced as the dynamic wetting line at the front of
the liquid advances radially outward.

In the third stage, Fig. 3 (c), excess liquid in the film that now covers the substrate flows radi-
ally to the perimeter, there accumulating temporarily in unwanted swellings from which droplets
form and fly off. If the substrate has a hole at its center, then from the hole's edge - the 'inner
diameter' of a 'disk' -drainage commences in the same way as it does in the batch dip coating pro-
cess. In the absence of a hole, spin-off flow thins the entire film more or less uniformly - except for
the edge effect at the 'outer diameter.' As the film thins, flow of the remaining liquid slows. One rea-
son is that the thinner the film, the much greater the resistance to flow. The other reason is that the
thinner the film, the greater the effect of evaporation in raising viscosity by concentrating the nonvo-
latile constituents that are to become the coating. Indeed, spin-off must slow to the extent that eva-
poration takes over as the chief mechanism of thinning, unless the gas overhead has been saturated
with the volatile components. The fourth stage is this thinning by evaporation. It generally contin-
ues after spin-off has been totally halted by solidification brought about by the concentrating of non-
volatile solutes and particulates.

Final film thickness is often found to be little affected by deposition and spin-up. The key to
spin coating is the spin-off stage. Apart from edge effects, a film of liquid tends to become uniform in
thickness as it thins by spin-off and, once uniform, to remain so as it thins further, provided its
viscosity is insensitive to shear and does not vary over the substrate. The reason for the strong ten-
dency to uniformity is the way the two main forces balance: they are the rotation-induced centrifugal
force, which drives radially outward flow, and the resisting viscous force, which acts radially inward.
Emslie et al." were the first to show that when these balance, the radial spin-off rate, q, in volume
per unit time per unit circumference at radius r, and the free surface speed, v,, are

q - pjrVv. 8 r (8)

Here w is the angular velocity. Film-thinning by spin-off is described by the equation of local conser-
vation of liquid volume (or mass):

(ýA]i = - -Lý (b 2'P-2 hS - Pw2r h2 JOh (

This differs from the analogous equation for dip coating, Eq. (5). It has three classes of solutions.

One is the evolution of a film that starts out with uniform thickness h.:

h(t) = h. (t0)
2
V.+ 4pw h.2t/3jp
726

STAGES OF THE BATCH SPINNING PROCESS

/
0
EoT
I EVAPORTO
SPIN-OFF

Figure 3. Stages of the spin coating process (after Ref. 13).

This means that as time t increases, an initially uniform film of constant viscosity remains uniform
and continues to thin. The second class of solutions is the evolution of films that start out only
mildly nonuniform, namely with slope that nowhere violates the condition - d In ho/d In r < 2/3.
As time goes on, these films tend monotonically toward uniformity and sooner or later follow Eq. (10)
closely. The third class is the evolution of films that start out more nonuniform than the foregoing
condition allows. These tend to develop a front of abrupt rise in film thickness that progresses radi-
ally outward, leaving behind a fairly uniform film that thereafter tends strongly to total uniformity.
A front of this sort can often be seen in the deposition stage, spin-up stage, or early in the spin-off
stage; usually it evolves into radially advancing fingers of thick film because a circular front is
unstable. In any case, the film ultimately tends toward uniformity in the spin-off stage, regardless of
its profile when it was deposited. Moreover, with viscosity in the range of I to 100 cp and angular
velocities in the range of 3000 to 8000 rpm, the time needed to thin a nonuniform 1 mm film to a
uniform 1 pm film is on the order of seconds to a minute or so (cf. Eq. (10)).

All of this stems from the dominance of centrifugal force and viscous shear force. The rapid
thinning quickly squelches any inertial forces other than centrifugal force that may be appreciable in
7
the early stages" . Upon spin-up the centrifugal force swamps the force of gravity, which has no part
anyway if the substrate is oriented horizontally. The strong tendency to uniformity also prevents sur-
face tension or disjoining pressure from causing any resultant forces (except at edges, steps, grooves
and pits), because these would require curvature or inclination, respectively, of the free surface of the
film. Surface tension gradient-force can enter only through contamination and differential evapora-
tion, as in dip coating. There is a new force to contend with, however. That is the viscous drag by
the gas overhead, which is set into motion by the spinning substrate. It turns out to have no appreci-
8
able effect on spin-off during spin coating) .

The spinning substrate acts on the gas as a centrifugal pump, drawing it in axially and
accelerating it into outwardly spiraling flow to the edge of the substrate, whence it departs radially.
This forced convection may be laminar, particularly if the substrate is small and closely surrounded
 727

by a housing; or it may be turbulent. In neither case is it feeble and irregular: it is forceful, directed,
and steady (excepting turbulent fluctuations, which if present are low in intensity and fine in scale
near the film surface). The nature of the flow is such that the mass transfer coefficient, k, is quite
uniform everywhere above the substrate. So to the extent that partial pressures of volatiles are uni-
form in the gas, the evaporation rate all over the substrate is uniform too (refer to Eq. (4)).

The thickness of a spin coating is the outcome of the delicate transition by which evaporation
takes over from spin-off. Nonvolatile constituents can leave the substrate solely by flow. Whatever
amounts of them are left when the film becomes so thin and viscous that flow halts, must remain as
9
the coating after all the volatiles have departed by evaporation. Recognizing this, Meyerhofer' con-
structed a crude model that is qualitatively correct in some important respects. In it spin-off of a uni-
form film proceeds with no evaporation whatsoever until the rate of film-thinning by flow falls to a
certain rate ePA/pA*, where PA is the mass of volatile solvent per unit volume, p1 is its initial value,
and e will soon be defined. From Eq. (9) the corresponding film thickness and elapsed time would be

h I )
2p9X
2
t3Pi=
8 4pw 2 (h2 3 5 (1

At that juncture flow abruptly ceases prematurely, and evaporation commences belatedly, at a con-
stant rate m = e that depends on gas-phase mass transfer alone, as by Eq. (4). When the last of the
solvent evaporates the final film thickness and total elapsed time would be

h -- A e2 tol = topisoS + h.pi3f" - (12)

PA 2p, +PA

Formulas (11) and (12) account for observed trends with initial solvent content, viscosity, spin
speed, and solvent partial pressure in the gas, but not for the effects of overlapping spin-off and eva-
poration, the rise of viscosity as evaporation proceeds, etc. Meyerhoferi' and others have constructed
more elaborate approximations. Modern computer-aided mathematics has made a full 2theory of spin
2
coating possible12'", and in a limited test its predictions match measurements closely1 . The theory
also bears on coating of substrates that are not smooth, but stepped, grooved, or pitted.

SPIN COATING IN APPLICATIONS

Two major uses are in microelectronics manufacture, for photoresist coatings from solution onto
smooth and micro-rough substrates; and in magnetic memory technology, for particulate coatings
from suspension onto rigid disks. If photoresist polymer solution is kept dilute enough it remains
close to Newtonian during spin-off, so that the strong tendency to uniform film thickness can be
exploited. If the solution becomes concentrated enough to be shear-sensitive, the tendency degrades.
Shear rates are lower toward the center, or the inner diameter, and % shear-thinning liquid tends to
have a higher effective viscosity and form a thicker coating there. Likewise do the often strongly
shear-thinning suspensions of colloidal magnetic particles. For this as well as other reasons - among
them control of edge effects and leveling or 'planarization' over steps, grooves and pits - systems
have been developed for delivering to the substrate the liquid in a fine stream from an elevated port
on an arm the radial motion of which can be programmed, rather as a robot arm. Such devices for
greatly modifying spin coating in order to wrest control from the intrinsic physics first came into use
20
in magnetic memory technology and more recently in microelectronics processing .

Other complications abound. The delicate transition from spin-off to evaporation and thus the
thickness and uniformity of the coating can be influenced locally on the substrate by altering the gas
flow, for example by mounting close-fitting side walls, covers, or a complete enclosure. The whole
course of evaporation as well as the transition can be controlled by managing the partial pressures of
solvents in the gas, which may call for programmed gas mixing and delivery. The potential advan-
tages include avoiding unwanted skin formation or premature precipitation of a polymer-rich phase
by too rapid evaporation. These phenomena can lead not only to slowed evaporation but also to
yielding and cracking in the centrifugally stressed, solidifying surface layer. Programming the gas
saturation appears to be a potent way of heightening control of the spin coating process.
728

Spin-up and spin-off are subject to flow instabilities. A radial fingering pattern from break-up
of a front or surge wave may persist in the way particles are packed in the coating. Finely spaced
21
radial striations, or 'spokes,' sometimes appear during spin-off of suspensions . Mist formation by
droplets detaching from the unstable accumulation of liquid at the perimeter, or outer diameter, can
be a problem if gas flow is inadequately controlled. So too can be mist from splashing during inept
delivery during the deposition stage. Contamination from either the gas phase or the substrate sur-
face is no less deleterious than in dip coating.

Spin coating owes its utility to the manner in which centrifugal force drives radial film flow of a
batch of viscous liquid toward uniformity, and to the ease of varying centrifugal force. Thinner coat-
ings can be achieved in the same time by raising the spin rate or, in some circumstances, by diluting
the liquid to lower its viscosity. For the simplest version of the process what is needed is a good,
constant-speed motor with a selection of speeds. More often in practice, however, controls are needed
that permit programming spin sequences precisely. Though batch in character, the process is quick,
and it can be mechanized into production lines. Consequently the technology, though more recently
developed than that of precision dip coating, is more advanced. Both can be considered for compact,
flat substrates, but each lends itself to particular shapes.

ACKNOWLEDGEMENT

Much of this paper is drawn from collaborative research with D. E. Bornside, S. A. Brandt, L.
Sartor, A. A. Servida, and Professors H. T. Davis and C. W. Macosko, to all of whom the writer is
indebted. He is grateful to Professor E. J. Cussler for helpful discussion. Portions of the research
have been supported by 3M Company, Control Data Corporation, and Exxon Research & Engineering
Company.

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