SS symmetry

Article
A Modified Equation for Thickness of the Film
Fabricated by Spin Coating
Un Gi Lee 1 , Woo-Byoung Kim 2 , Do Hyung Han 2 and Hyun Soo Chung 1, *
1 Department of Mathematics, Dankook University, Cheonan 31116, Korea; leewg@dankook.ac.kr
2 Department of Energy Engineering, Dankook University, Cheonan 31116, Korea;
woo7838@dankook.ac.kr (W.-B.K.); hans417@naver.com (D.H.H.)
* Correspondence: hschung@dankook.ac.kr




Received: 19 August 2019; Accepted: 10 September 2019; Published: 18 September 2019


Abstract: According to the equation for Newtonian fluids, the film thickness after spin coating is
determined by five parameters: angular velocity, spin coating time, viscosity, density of the coating
material, and initial thickness of the material before spin coating. The spin coating process is commonly
controlled by adjusting only the angular velocity parameter and the coating time in the Newtonian
expression. However, the measured coating thickness obtained is then compared to the theoretical
thickness calculated from the Newtonian fluid equation. The measured coating thickness usually varies
somewhat from the theoretical thickness; further details are described in Section 1. Thus, the Newtonian
fluid equation must be modified to better represent the actual film thickness. In this paper, we derive a
new formula for the spin coating film thickness, which is based on the equation for Newtonian fluids,
but modified to better represent film thicknesses obtained experimentally. The statistical analysis is
performed to verify our modifications.

Keywords: spin coating process; modified Newton’s formula; statistical analysis; curve estimated
function; polyhedron approximation

1. Introduction
In Ref. [1], Emslie, Bonner and Peck proposed differential equations in cylindrical polar coordinates
to calculate the thickness of Newtonian liquid on a rotating disk. They took cylindrecal polar coordinates
(r, θ, z) rotating with the spinning disk at angular velocity W. The z dependence of the radial velocity v of
the liquid at any point (r, θ, z) can be found by equating the viscous and centrifugal forces per unit volume:

∂2 v
−η = ρW 2 r, (1)
∂z2
where η is the viscosity and ρ the density of the liquid. Equation (1) may be integrated employing the
boundary conditions that v = 0 at the surface of the disk (z = 0) and ∂v/∂z = 0 at the free surface of the
liquid (z = h), where the shearing force must vanish. Hence,

1 1
− ρW 2 rz2 + ρW 2 rhz .


v= (2)
η 2

Symmetry 2019, 11, 1183; doi:10.3390/sym11091183 www.mdpi.com/journal/symmetry

Symmetry 2019, 11, 1183 2 of 20

The radial flow q per unit length of circumference is

ρW 2 rh3
Z h
q= vdz = . (3)
0 3η

In order to obtain a differential equation for h we apply the equation of continuity,

∂h ∂(rq)
r =− . (4)
∂t ∂r
Thus, via Equation (3),
∂h 1 ∂ 2 3
= −K (r h ), (5)
∂t r ∂r
ρW 2
where K = 3µ .
They obtained the solution which depends only on t. In this case, we have

dh
= −2Kh3 . (6)
dt
Hence, they obtained the general solution (7), the equation for thickness of the film fabricated by spin
coating, describes the film thickness obtained after the spin coating process

h0
h= r , (7)
4ρW 2 h20 t
1+ 3µ

where h0 is the initial thickness of the coating material [1–4]. Note that the final thickness of the film
is affected more by the angular velocity and time than by the other factors. Given that W = 30 π
× ω,
where ω is the number of revolutions per minute (RPM), the final thickness h of the film can be treated as
a two-variable function of t and ω [1–12].
Spin coating technology is useful in modern industrial society. However, it still relies on Formula (7),
which was introduced in the 1950s, to determine spin coating film thickness. Many companies that
deal with spin coating processes do not actually use the equation for thickness of the film fabricated
by spin coating (7) to determine spin coating thickness, due to the considerable discrepancy between
the theoretical and actual thickness values. Because of these differences in the spin coating process,
the traditional equation for thickness of the film fabricated by spin coating (7) was not used, but rather
the repetitive empirical formula has been used. Currently, many scholars are trying to reduce these
differences [13,14]. The disadvantages of our approach is that the empirical formula must be refreshed
whenever the experimental environment changes; additionally, this process tends to be costly and
time-consuming. Thus, a new mathematical formula is needed to describe the spin coating process
and resulting film thickness. In order to verify this, we are going to conduct an experiment to measure the
final thickness in the spin coating process. The experimental environment is given as follows:

(a) The viscous PDMS (Polydimethylsiloxane) coated on the glass (Sylagard 184, Dowcoaning) is using
the spin coating material.
(b) The substrate of size 2 × 2 cm2 is used to measure the film thickness at the center of the substrate,
and the substrate of size 3 × 3 cm2 is used to measure the overall thickness distribution of the
PDMS film.
Symmetry 2019, 11, 1183 3 of 20

(c) We fix the viscosity, density of coating material, initial thickness at 4000 cP, 965 kg/m3 and 0.105 cm.
Then, the rotation time is fixed at 300 s and the experiment is performed in 500 RPM units from 500
to 6000 RPM.
(d) The spin coating is performed by Spin coater ACE-200 (DongAh Trade Corp, Seoul, South Korea).
(e) Finally, we measure all samples thickness and thickness distribution to step measurement by surface
profiler DektakXT (Bruker, Karlsruhe, Germany).
(f) Thickness measurement is performed by measuring the thickness when the stylus of the DektakXT
passed through the coated film from the uncoated section of the substrate.
(g) We focus on a coating thickness range of 4 to 20 µm using experimental limits of ω = 1000, 2000 and
3000 and t = 300, 450 and 600 s. In these experimental conditions, the equation for thickness of the
film fabricated by spin coating is given by the formula:

1050
h(ω ) = √ (µm),
1 + 0.00116671ω 2

where µm is the micro meter, i.e., 1 µm = 10−6 µm.

Remark 1. PDMS is a non-Newtonian fluid and, in [15], the authors pointed out that a study on the realistic flow
for flattening of thickness through spin coating using non-Newtonian fluids. However, in [16], experiments were
conducted with non-Newtonian fluids to study the applicability of non-Newtonian fluids to Newtonian fluid law.
In this paper, the experiments were carried out using the most basic theory about the thickness of films made by the
spin coating and non-Newtonian fluids. Based on the results, Equation (7) was used to modify the new equation.

After conducting the experiment, we can find that the measured thickness (MT) is slightly different
from the theoretical thickness (TT). These differences are given by the Table 1 below.

Table 1. The thickness profile at each RPM and fixed time as 300 s.

RPM TT (µm) MT (µm)

500 61.38 52.99
1000 30.73 25.09
1500 20.49 15.36
2000 15.37 11.16
2500 12.30 8.53
3000 10.25 6.60
3500 8.78 5.30
4000 7.68 4.26
4500 6.83 3.92
5000 6.15 3.54
5500 5.59 2.80
6000 5.12 2.72

The existing equation for Newtonian fluids has five parameters: viscosity and density of material,
spin coating speed and time, and initial height of the material before spin starting. Due to these various
parameters, there is a difference in thickness to apply the existing equation to actual experiments.
Equation (7) is an ideal equation containing at least five variables. However, it does not include variables
such as the surface tension of the substrate. These variables and experimental conditions affect the
difference between the theoretical thickness and the actual thickness.
This paper introduces a modified equation for thickness of the film fabricated by spin coating
like Equation (7) that is based on curve estimation and polyhedron approximation. The mathematical
accuracy of the proposed formula is examined through a statistical analysis of thickness [17,18]. Finally,
the modified Newtonian fluid formula is used to construct an Excel-based thickness calculator for spin
Symmetry 2019, 11, 1183 4 of 20

coating applications. Here, we use the Statistical Package for Social Science (SPSS software, IBM Corp.,
Armonk, NY, USA) to estimate the curve and the polyhedron that best matches the experimental data.

2. A Modified Equation for Thickness of the Film Fabricated by Spin Coating via the
Curve Estimation
In this section, we establish the modified equation for thickness of the film fabricated by spin coating in
the spin coating process as a curve estimated function, and begin by referring to Table 1 above. From Table 1
in Section 1, the thickness calculated using the conventional theoretical equation and the thickness obtained
using a repetitive empirical formula differ considerably. Thus, the theoretical equation must be modified
with a curve estimated function to provide a more accurate calculated film thickness.

2.1. Fixed Time at 300 s

The estimation method is carried out through three steps. We shall explain this step by step.
Step 1. We use the Curve Estimation of the regression analysis from the SPSS to make a curve
estimate for the MT value of Table 1 above. There are 11 models available in the curve estimation menu.
Among these, we select five models with the possibility of being suitable for MT data. They are Logarithmic,
Inverse, Quadratic, Cubic and Power models. The results of the analysis are as follows (Figure 1).

Figure 1. Curve estimation for 300 s MT.

Symmetry 2019, 11, 1183 5 of 20

As shown in Figure 1 above, we can choose the power model and the inverse model based on the
value of the coefficient of determination. The estimated functions are given by the formulas

power : h power (ω ) = 111118.372 ω −1.2193

and
27472.2453
inverse : hinverse (ω ) = −2.3948 + .
ω
Both estimated functions are suitable for reducing the difference in film thickness mentioned above.
It is also possible to select and use what is applicable to each company. Then, we obtain Table 2 involving
the estimated function value and R2 (coefficient of determination) value with respect to the MT value.

Table 2. Estimated function value and R2 value for the MT value.

RPM TT MT hinverse h power

500 61.375 52.991 52.550 56.876
1000 30.727 24.541 25.077 24.428
1500 20.490 15.357 15.920 14.900
2000 15.368 11.280 11.341 10.492
2500 12.295 8.528 8.594 7.992
3000 10.246 6.530 6.763 6.399
3500 8.783 5.301 5.454 5.303
4000 7.685 4.264 4.473 4.506
4500 6.831 3.920 3.710 3.903
5000 6.148 3.536 3.100 3.433
5500 5.589 2.801 2.600 3.056
6000 5.123 2.718 2.184 2.748
R2 0.999 0.997

As shown in Table 2 above, MT value and estimated function value are each somewhat different.
To compensate for this, we implement the next step.
Step 2. Let E300 denote the difference of the TT value and the MT value. That is to say, let
E300 = TT −MT. Then, we obtain Table 3 below.

Table 3. Estimated E300 value.

RPM TT MT E300
500 61.375 52.991 8.384
1000 30.727 24.541 6.186
1500 20.490 15.357 5.133
2000 15.368 11.280 4.089
2500 12.295 8.528 3.767
3000 10.246 6.530 3.716
3500 8.783 5.301 3.481
4000 7.685 4.264 3.421
4500 6.831 3.920 2.911
5000 6.148 3.536 2.612
5500 5.589 2.801 2.788
6000 5.123 2.718 2.406
Symmetry 2019, 11, 1183 6 of 20

We then perform the curve estimate for the E300 value by using the SPSS. We will use the Logarithmic
model and the Inverse model as selected in Step 1. The results of the analysis are as follows (Figure 2).

Figure 2. Curve estimation for E300 .

Thus, the estimated functions are given by the formulas

Logarithmic : h(ω ) = 21.83 − 2.253 ln(ω )

and
3214.8068
Inverse : h(ω ) = 2.41182 + .
ω
By using these functions, the estimated functions are given by the formulas

1050
hlog (ω ) = √ − 21.83 + 2.253 ln(ω )
1 + 0.00116671w2

and
1050 3214.8068
hinv (ω ) = √ − 2.41182 − .
1 + 0.00116671w2 ω
All four estimated functions given are suitable for reducing time and cost in the spin-coating process.
To reduce the difference further, the following comparisons are made. The data obtained by each functions
are given by the following Table 4 below.
Symmetry 2019, 11, 1183 7 of 20

Table 4. Data obtained by each estimated functions.

RPM TT MT hlog hinv

500 61.375 52.991 53.538 52.534
1000 30.727 24.541 24.462 25.100
1500 20.490 15.357 15.138 15.935
2000 15.368 11.280 10.665 11.349
2500 12.295 8.528 8.095 8.598
3000 10.246 6.530 6.456 6.763
3500 8.783 5.301 5.340 5.452
4000 7.685 4.264 4.543 4.469
4500 6.831 3.920 3.955 3.705
5000 6.148 3.536 3.510 3.093
5500 5.589 2.801 3.165 2.593
6000 5.123 2.718 2.895 2.176
R2 0.964 0.953

The function that the best describes the measured thickness (MT) value among the functions derived
in Steps 1 and 2 undergo several iterations until the smallest error (see Table 5) is achieved. Here, the sum
of squares error (SSE) is given. The red value for each RPM represents the smallest difference.

Table 5. The smallest error.

RPM MT-hinverse MT-h power MT-hlog MT-hinv

500 0.442 −3.885 −0.557 0.457
1000 −0.537 0.113 0.079 −0.560
1500 −0.563 0.457 0.219 −0.578
2000 −0.061 0.788 0.615 −0.069
2500 −0.066 0.536 0.434 −0.069
3000 −0.233 0.131 0.073 −0.233
3500 −0.153 −0.001 −0.039 −0.151
4000 −0.210 −0.243 −0.280 −0.206
4500 0.210 0.017 −0.035 0.215
5000 0.437 0.104 0.027 0.443
5500 0.201 −0.255 −0.364 0.208
6000 0.534 −0.031 −0.178 0.542
SSE 1.490 16.375 1.181 1.565

To test compliance, we decide to use function with the smallest SSE value to approximate MT value.
It is
1050
ht=300 (ω ) ≡ hlog (ω ) = √ − 21.83 + 2.253 ln(ω ). (8)
1 + 0.00116671w2
Step 3. We now establish the following hypothesis to test the function hlog and the consistency of MT
value. Let µ MT and µh be population means of MT values and the estimated function hlog , respectively.
Then, we formulate the following research hypothesis.

H0 : µ MT = µh ,

H1 : µ MT 6= µh .

To test this hypothesis, the results of the paired Samples t-test at a significant level α = 5% are as
follows (Figure 3).
Symmetry 2019, 11, 1183 8 of 20

(a) (b)

(c)

Figure 3. t-test.

Therefore, we accept the null hypothesis (H0 ) to obtain the statistical basis for estimating hlog as an
approximation of the MT value. From Steps 1 through 3, the best-estimated function corresponds to a fixed
time of 300 s; i.e., the function given by Equation (8) is the best curve estimate for a fixed time of 300 s.

2.2. Fixed RPM at 1000

By the similar method as in Section 2.1, we can obtain the estimated function of the following case of
fixed RPM at 1000. Then, the estimated function is given by the formula

1050
hω =1000 (t) = √ − 22.2524 + 2.69 ln(t).
1 + 3.889t

We also can compare the TT value, the MT value and the estimated function value as the following
Table 6.

Table 6. Compared values when there is fixed RPM 1000.

TIME TT MT hw=1000
100 53.176 43.269 43.311
200 37.625 29.576 29.625
300 30.727 24.541 23.818
400 26.613 19.710 20.478
500 23.905 18.192 18.270
600 21.731 16.591 16.687
700 20.121 15.948 15.490
800 18.822 14.431 14.551

The statistical hypothesis test of the estimated function hω =1000 (t) is as follows. The results of the
paired Sample t-test to verify the homogeneity of the two groups, as shown in Step 3 of Section 2.1, are as
follows (Figure 4).
Symmetry 2019, 11, 1183 9 of 20

(a) (b)

(c)
Figure 4. t-test.

Therefore, we have a statistical basis to conclude that populations in both sample spaces are equal to
each other at a significant level α = 5%.

2.3. Other Cases

Through the process same as in cases 2.1 and 2.2 above, we obtain estimated functions for the time
fixed at 450 and 600 s and the RPM fixed at 2000 and 3000. First, when the time is fixed at 450 and 600, we
obtain estimated functions by setting the RPM as a variable as follows:

1050 4346.44
ht=450 (ω ) = √ − 1.9398 −
1 + 0.00175ω 2 ω

and
1050
ht=600 (ω ) = √ − 19.8476 + 2.104 ln(ω ).
1 + 0.00233342ω 2
Table 7 is about the value of MTt=450 and MTt=600 , and estimated function values.

Table 7. The thickness profile at t = 450 and t = 600.

RPM MTt =450 ht =450 MTt =600 ht =600

500 38.969 39.510 36.454 36.664
1000 20.242 18.806 16.591 16.418
1500 11.639 11.894 10.177 10.029
2000 8.309 8.436 7.133 7.012
2500 6.134 6.361 4.996 5.309
3000 5.216 4.978 4.493 4.243
3500 4.199 3.990 3.580 3.532
4000 2.989 3.248 3.002 3.037
4500 2.199 2.672 2.478 2.681

Results of the t-test for estimated function values and MT values are as follows (in Figure 5), respectively.
Symmetry 2019, 11, 1183 10 of 20

(a) (b)

(c)
Figure 5. t-test.

Therefore, we see that the mean of populations of estimated functions and MT values are the same at
a significant level α = 5%.
Next, when the RPM is fixed, we obtain estimated functions for the time parameter

1050 333.83446
hω =2000 (t) = √ − 3.2594 −
1 + 15.5561t t

and
1050
hω =3000 (t) = √ − 12.8084 + 1.60735 ln(t).
1 + 35.00132t
We get MTω =2000 , MTω =3000 and estimated values as shown in Table 8.

Table 8. The thickness profile at ω = 2000 and ω = 3000.

TIME MTω=2000 hω=2000 MTω=3000 hω=3000

100 19.908 20.015 12.224 12.340
200 13.986 13.893 8.493 8.257
300 11.280 10.996 6.530 6.606
400 9.240 9.206 5.662 5.695
500 7.977 7.978 5.265 5.118
600 7.133 7.052 4.493 4.719
700 5.984 6.325 4.472 4.430
800 5.703 5.735 4.235 4.210

The results of the t-test are as follows (in Figure 6):

Symmetry 2019, 11, 1183 11 of 20

(a) (b)

(c)
Figure 6. t-test.

In addition, we see that the mean of populations of estimated functions and MT values are the same
at a significant level α = 5%.

2.4. Summary of Section 2

From Sections 2.1–2.3, we derived a curve-estimated function for each case. Figure 7 shows that all
functions provided an estimate that was statistically equivalent to the MT values. These results suggest
that the estimated function can be induced for other RPMs and times.

Figure 7. Six curve estimated functions.

3. A Modified Equation for Thickness of the Film Fabricated by Spin Coating via the
Polyhedron Approximation
In Section 2, we obtained six estimated functions regarding t and ω. In this section, we are going to
establish the polyhedron approximation with respect to the modified equation for thickness of the film
fabricated by spin coating.
Symmetry 2019, 11, 1183 12 of 20

3.1. Polyhedron Approximation

We first take 13 points from a1 to a13 via the estimated functions obtained in Section 2. Using these
points, we can divide into 13 areas of the domain D = {(t, ω )|300 ≤ t < ∞, 1000 ≤ ω < ∞} as follows
(Figure 8):

Figure 8. Separated domain.

Now, let Di,j,k be the sub-area of D with ai , a j and ak as the vertex. Then, each area can be expressed
in Table 9:

Table 9. Each sub-area of domain.

Sub-Area Domain
D1,2,3 {(t, ω )|300 ≤ t < 450, 1000 ≤ ω < 4000 − 20 3 t}
20
D2,3,5 {(t, ω )|300 ≤ t < 450, 4000 − 3 t ≤ ω < 2000}
D2,4,5 {(t, ω )|450 ≤ t < 600, 1000 ≤ ω < 5000 − 20 3 t}
D3,5,6 {(t, ω )|300 ≤ t < 450, 2000 ≤ ω < 5000 − 20 3 t}
D4,5,7 {(t, ω )|450 ≤ t < 600, 5000 − 203 t ≤ ω < 2000 }
D5,6,8 {(t, ω )|300 ≤ t < 450, 5000 − 203 t ≤ ω < 3000 }
D5,7,8 {(t, ω )|450 ≤ t < 600, 2000 ≤ ω < 6000 − 20 3 t }
D7,8,9 {(t, ω )|450 ≤ t < 600, 6000 − 203 t ≤ ω < 3000 }
D4,7,10 {(t, ω )|600 ≤ t < ∞, 1000 ≤ ω < 2000}
D7,9,11 {(t, ω )|600 ≤ t < ∞, 2000 ≤ ω < 3000}
D9,11,12 {(t, ω )|600 ≤ t < ∞, 3000 ≤ ω < ∞}
D8,9,12 {(t, ω )|450 ≤ t < 600, 3000 ≤ ω < ∞}
D8,9,13 {(t, ω )|300 ≤ t < 450, 3000 ≤ ω < ∞}

Let Ai be the intersection of the function values of ai for functions obtained in Section 2. We then
split the graph of the two-parameter function into a plane passing through three points as shown
below (Figure 9).
Symmetry 2019, 11, 1183 13 of 20

Figure 9. Planes.

Let Πi,j,k be the equation of plane passing through three points Ai , A j and Ak . Then, all equations of
the plane are as follows (Table 10).

Table 10. Equation of planes.

Plane Equation
Π1,2,3 t + 0.391529ω + 29.4118h − 1401.53 = 0
Π2,3,5 t + 0.677312ω + 64.2123h − 2349.91 = 0
Π2,4,5 t + 0.635932ω + 60.2894h − 2238.84 = 0
Π3,5,6 t + 0.295985ω + 64.2123h − 1547.26 = 0
Π4,5,7 t + 0.977515ω + 102.669h − 3276.9 = 0
Π5,6,8 t + 0.36767ω + 110.947h − 2127.51 = 0
Π5,7,8 t + 0.340246ω + 102.669h − 2002.36 = 0
Π7,8,9 t + 0.548209ω + 214.9h − 3207.38 = 0
Π4,7,10 t + 1.46929ω + 154.321h − 4623.61 = 0
Π7,9,11 t + 1.89665ω + 743.49h − 9620.82 = 0
Π9,11,12 t + 1.07435ω + 743.494h − 7153.9 = 0
Π8,9,12 t + 0.31053ω + 214.9h − 2494.34 = 0
Π6,8,13 t + 0.214127ω + 110.947h − 1666.86 = 0

Let hΠi,j,k (t, ω ) denote the new expression of plane with respect to t and ω. For example,

hΠ1,2,3 (t, ω ) = 47.652 − 0.0133ω − 0.034t

and
hΠ3,5,6 (t, ω ) = 24.096 − 0.0043ω − 0.0156t.

Using these, we obtain an approximate polyhedron function of the modified. Let

hΠ (t, ω ) = ∑ hΠi,j,k (t, ω )χDi,j,k , (9)

i,j,k
Symmetry 2019, 11, 1183 14 of 20

where ∑i,j,k means adding all the possible circumstances in Table 10 above. The function hΠ (t, ω ) is the
polyhedron approximation of the equation for thickness of the film fabricated by spin coating.

3.2. Verification of the Polyhedron Approximation

In this section, we try to perform statistical verification of the polyhedron approximation obtained
in Section 3.1. In order to do this, we first choose 14 points except a j ’s, denoted by b j ’s, in Figure 10.
These points b j are in the six curve estimation functions in Section 2. We are going to use these points to
determine if the polyhedron function hΠ (t, ω ) is an extension function with curve estimation functions.

Figure 10. Add Points for the verification.

We then obtain the following Table 11 below.

Table 11. Compared values.

bi Coordinates Curve appro Πi,j,k h Π ( bi )

b1 (400, 1000) 20.4781 Π1,2,3 20.7520
b2 (300, 1500) 15.1329 Π1,2,3 17.5020
b3 (500, 1000) 18.2702 Π2,4,5 18.3349
b4 (300, 2500) 8.0908 Π3,5,6 8.6660
b5 (700, 1000) 15.4906 Π4,7,10 15.9110
b6 (500, 2000) 7.9778 Π5,7,8 8.0531
b7 (400, 3000) 5.6956 Π6,8,13 5.7239
b8 (700, 2000) 6.3254 Π4,7,10 6.8300
b9 (600, 2500) 5.3086 Π7,9,11 5.6600
b10 (500, 3000) 5.1175 Π8,9,12 5.0570
b11 (300, 4500) 3.9517 Π6,8,13 3.7739
b12 (700, 3000) 4.4294 Π9,11,12 4.5120
b13 (450, 4500) 2.6720 Π6,8,13 2.4239
b14 (600, 4500) 2.6812 Π9,11,12 2.5420

We can perform the statistical analysis to see whether the polyhedron approximation is correct.
The results of the analysis are as follows (Figure 11):
Symmetry 2019, 11, 1183 15 of 20

(a) (b)

(c)
Figure 11. t-test.

This shows that the significance value 0.152 is greater than the significance level value 0.05. Therefore,
we can not reject the null hypothesis h0 : µCurveappro = µhΠ . This means that values of Curveappro are
statistically equal to values of hΠ .

3.3. Summary of Section 3

We took points from a1 to a13 in the domain of f Π (t, ω ) using the six curves described in Section 2 to
find the approximate function for the binary function f (t, ω ). The domain was then divided into sub-areas
Di,j,k , passing through three points, ai , a j , and ak . We obtained equations of planes Πi,j,k passing through
Ai , A j , and Ak , corresponding to the MT values of ai , a j , and ak at each vertex of Di,j,k , respectively. We then
estimated the polyhedron approximation, hΠ (t, ω ), as shown in Equation (9). To assess the suitability of the
polyhedron approximation hΠ , we set 14 points of b1 , · · · , b14 in the domain D. The values listed in Table 12
were determined by substituting Curvea ppro and hΠ . Then, a paired sample t-test was performed between
Curvea ppro and hΠ values, i.e., the curve approximation data from Section 2 and the data obtained by
substituting the equation of polyhedron hΠ , respectively, to determine whether the mean was statistically
identical within 5% of the significance level. Our results revealed that the polyhedron approximation hΠ
contained six of the curves from Section 2; thus, our function provides a good approximation of the binary
function f (t, w).

4. Application: Target Verification

In this section, we try the target verification. We first set the target thickness and thus obtain the
required time or RPM for each cases. Finally, we again conduct an experiment. The maximum rotation
time for the Spin Coater ACE-200 is 999 s. Thus, the likelihood of error in the coating thickness estimations
below 4 µm and above 20 µm is high.
The following table shows the results obtained by using the curve estimation function obtained
in Section 2 when the RPM is fixed at ω = 1000, 2000 and 3000, and the rotation time t is fixed at
t = 300, 450 and 600, respectively (see Table 12).
Symmetry 2019, 11, 1183 16 of 20

Table 12. Compared values.

h(µm) ω t t ω
1000 - 300 4453
4 2000 1251 450 3493
3000 925 600 3150
1000 - 300 3692
5 2000 956 450 2990
3000 526 600 2623
1000 - 300 3181
6 2000 752 450 2613
3000 360 600 2265
1000 - 300 2809
7 2000 606 450 2321
3000 269 600 2002
1000 6194 300 2522
8 2000 498 450 2087
3000 211 600 1799
1000 3007 300 2294
9 2000 415 450 1896
3000 171 600 1637
1000 2062 300 2106
10 2000 350 450 1737
3000 143 600 1503
1000 749 300 1511
15 2000 174 450 1224
3000 71 600 1078
1000 418 300 1187
20 2000 100 450 945
3000 44 600 846

With regard to Table 12, we discuss the thickness value for the parameters specified. When the
RPM is fixed, there is no value at ω = 1000, as shown in the table. Because the function
hw=1000 (t) = √ 1050 − 22.2524 + 2.69 ln(t) has a local minimum value 7.847 at t = 9793.59, there is no
1+3.889t
value from 4 µm to 7 µm. Therefore, when a thickness of 4 µm to 7 µm is desired, a speed higher than
1000 RPM is required. Additionally, because the ACE-200 system has a maximum spin time of 999 s,
it cannot provide a thickness in the desired range of 8 µm to 10 µm when ω = 1000. We give the following
summary in Table 13:

Table 13. Suitable RPM with fixed rotation time.

Target Thickness (µm) Suitable RPM

11–20 less than 1000
7–10 1000–3000
4–6 more than 3000

In another experiment, the rotation time t is held fixed at t = 300, 450 and 600 s. To obtain the desired
thickness, as shown in Table 12, the RPM could be adjusted for the fixed time frame. In contrast to the
previous case in which the RPM was fixed, here we are able to adjust the RPM to produce the desired
Symmetry 2019, 11, 1183 17 of 20

thickness within the allowable range, given a fixed rotation time. Therefore, it appears to be more effective
to fix the rotation time t to obtain the target film thickness in spin coating processes.
Table 14 lists the thicknesses determined by substituting RPM for the rotation time t for each coating
thickness into hΠ from Section 3. To compare these values with MT values, we prepare three samples in
which the rotation time is fixed at 450 s. The MTt=450 values in the following table represent the average
values of the raw data of the three samples.

Table 14. RPMs for the target thickness, polyhedron values and MT value.

h(µm) t ω hΠ (µm) MTt =450 (µm)

300 4453 3.863
4 450 3493 4.602 3.777
600 3150 4.432
300 3692 5.309
5 450 2990 5.271 4.956
600 2623 5.340
300 3181 6.280
6 450 2613 6.515 6.058
600 2265 6.271
300 2809 7.337
7 450 2321 7.479 6.390
600 2002 6.955
300 2522 8.571
8 450 2087 8.251 7.481
600 1799 8.981
300 2294 9.552
9 450 1896 9.757 8.587
600 1637 10.510
300 2106 10.360
10 450 1737 11.426 9.723
600 1503 11.783
300 1511 17.356
15 450 1224 16.813 15.163
600 1078 15.820
300 1187 21.665
20 450 945 − 21.872
600 846 −

Actually, this result indicates that the results in Sections 2 and 3 and the values observed by the
experiment are the same within the margin of error.

5. Conclusions

5.1. Importance of Results and Formulas in This Paper

Spin coating technology is useful in modern industrial society. However, it still relies on Formula (7),
which was introduced in the 1950s, to determine spin coating film thickness. This conventional approach
requires extensive time and experimentation to obtain the desired coating thickness, which increases
costs. Here, we propose an alternative to this conventional approach. Using the function hΠ , we can
estimate the desired coating thickness given the rotation time and RPM, according to the conditions of
the coating device. The coating thicknesses achieved using the proposed approach were within the error
Symmetry 2019, 11, 1183 18 of 20

range expected. In an example described in Section 4, we were able to obtain the coating thickness based
on a fixed rotation time and RPM, using the six functions developed in Section 2. Additionally, the binary
function hΠ (t, ω ) estimated in Section 3 allows users to simulate the desired thickness without having to
perform an actual experiment. As a result, many spin coating companies will save time and money using
the method implemented in this study.

5.2. Another Approach

Our original goal was to express the equation for thickness of the film fabricated by spin coating as a
new binary function. In Section 2, curved estimates were determined for each fixed variable, and, in Section
3.1, an approximation of the polyhedron function was acquired through the plane approximation method.
In the next research work, we will attempt to obtain an approximation of the equation for thickness of
the film fabricated by spin coating as a binary function of the curved estimate and polyhedron function.
In Section 3, we split the domain D using points a1 through a13 . Using a similar method, we obtained the
function hΠn with n-splitting points. Then, hΠ ≡ hΠ13 . By adding more splitting points, we can derive the
function f (t, ω ) as the limit of hΠn (t, ω ). That is,

h(t, w) = lim hΠn (t, ω ).

n→∞

5.3. Expected Results

In this study, we estimated the bivariate function h(t, ω ) by assuming rotation time and RPM as
independent variables, while the other factors remained fixed. However, the factors affecting the actual
coating thickness are h0 , ρ, and µ. Thus, the addition of other variables to the function formula should
improve the accuracy of the spin coating thickness prediction. Considering all of the factors that affect
thickness would make the formula too complex, but given that spin coating companies use fixed coating
materials, ρ and µ can be considered constants.
Therefore, in future studies, we will attempt to estimate a three-variable function h(t, ω, h0 ) by setting
the independent variables t, ω, and h0 .

5.4. Capture of the Thickness Calculator by the Excel Program

Based on the results of this study, we developed a thickness calculator using the Microsoft Office
Excel program (Microsoft Corp., Redmond, WA, USA). Here, we show screen shots of the initial
screen and application screen of the calculator. This calculator can predict the thickness without actual
experimentation. As you can see in Figures 12–14 below, they are shown for t = 150 and ω = 2700. We will
supply our calculator to companies free of charge, in order to help them achieve the desired coating
thickness in spin coating processes.

(a) Initial screen (b) Application screen

Figure 12. Calculator for t and RPM.
Symmetry 2019, 11, 1183 19 of 20

(a) Initial screen (b) Application screen

Figure 13. Calculator for RPM.

(a) Initial screen (b) Application screen

Figure 14. Calculator for t.

We finish this paper by giving a remark.

Remark 2. We are working on data at fixed conditions of 300 s, as well as different times or fixed RPM conditions,
and we will do further research. As shown in Figure 15 below, the experiment was conducted under different
conditions, and it was confirmed that the thickness was changed due to the parameters that were not considered in
the existing equation. For example, when the aging time is given after spin coating for a fixed condition of 300 s,
the thickness changes as shown in the attached figure and the equation, and the equation obtained through curve
estimation also changes. In addition, it is expected that process conditions for the manufacture of the desired thickness
can be derived simply. In addition, it will be possible to apply to other materials, and further experiments are planned.
A MODIFIED EQUATION FOR THICKNESS OF THE FILM FABRICATED BY SPIN COATING
23

15. Further
Figure10:
Figure Further research.
research

Author Contributions: Conceptualization, H.S.C. and W.-B.K.; method- ology, H.S.C.; software, U.G.L.; validation,
D.H.H., and W.-B.K.; formal analysis, H.S.C. and U.G.L.; data curation, D.H.H.; writing–original draft
preparation, H.S.C.
Acknowledgments
Funding: This research was supported by the Basic Science Research Program through the National Research
This research was supported by Basic Science Research Program through the
Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (2017R1E1A1A03070041).
National
The APC was funded byResearch Foundation of Korea (NRF) funded by the Ministry of Science,
2017R1E1A1A03070041.
ICT and Future Planning (2017R1E1A1A03070041). The authors would like to
expressThe
Conflicts of Interest: authors
their declare
gratitude no conflict
to the referee’soffor
interest.
their valuable comments and suggestions
which have improved the original paper.

References
[1] C.-C. Chang, C.-L. Pai, W.-C. Chen, S.A. Jenekhe, Spin coating of conjugated polymers for
electronic and optoelectronic applications, Thin solid films, 479 (2005) 254-260.
[2] A.G. Emslie, F.T. Bonner, L.G. Peck, Flow of a viscous liquid on a rotating disk, Journal of
Applied Physics, 29 (1958) 858-862.
[3] W.W. Flack, D.S. Soong, A.T. Bell, D.W. Hess, A mathematical model for spin coating of
polymer resists Journal of Applied Physics, 56 (1984) 1199-1206.
[4] Y.-Y. Huang, K.-S. Chou, Studies on the spin coating process of silica films, Ceramics inter-
national, 29 (2003) 485-493.
Symmetry 2019, 11, 1183 20 of 20

References
1. Emslie, A.G.; Bonner, F.T.; Peck, L.G. Flow of a viscous liquid on a rotating disk. J. Appl. Phys. 1958, 29, 858–862.
[CrossRef]
2. Huang, Y.-Y.; Chou, K.-S. Studies on the spin coating process of silica films. Ceram. Int. 2003, 29, 485–493.
[CrossRef]
3. Sahu, N.; Parija, B.; Panigrahi, S. Fundamental understanding and modeling of spin coating process: A review.
Indian J. Phys. 2009, 83, 493–502. [CrossRef]
4. Tyona, M. A theoritical study on spin coating technique. Adv. Mater. Res. 2013, 2, 195–208. [CrossRef]
5. Chang, C.-C.; Pai, C.-L.; Chen, W.-C.; Jenekhe, S.A. Spin coating of conjugated polymers for electronic and
optoelectronic applications. Thin Solid Films 2005, 479, 254–260. [CrossRef]
6. Flack, W.W.; Soong, D.S.; Bell, A.T.; Hess, D.W. A mathematical model for spin coating of polymer resists.
J. Appl. Phys. 1984, 56, 1199–1206. [CrossRef]
7. Jenekhe, S.A.; Schuldt, S.B. Coating flow of non-Newtonian fluids on a flat rotating disk. Ind. Eng. Chem. Fund.
1984, 23, 432–436. [CrossRef]
8. Norrman, K.; Ghanbari-Siahkali, A.; Larsen, N. 6 Studies of spin-coated polymer films. Annu. Rep. Sect. C
(Phys. Chem.) 2005, 101, 174–201. [CrossRef]
9. Schwartz, L.W.; Roy, R.V. Theoretical and numerical results for spin coating of viscous liquids. Phys. Fluids 2004,
16, 569–584. [CrossRef]
10. Shimoji, S. Numerical analysis of the spin-coating process. J. Appl. Phys. 1989, 66, 2712–2718. [CrossRef]
11. Vorotilov, K.; Petrovsky, V.; Vasiljev, V. Spin coating process of sol-gel silicate films deposition: Effect of spin
speed and processing temperature. J. Sol-Gel Sci. Technol. 1995, 5, 173–183. [CrossRef]
12. Yonkoski, R.; Soane, D. Model for spin coating in microelectronic applications. J. Appl. Phys. 1992, 72, 725–740.
[CrossRef]
13. Natsume, Y.; Sakata, H. Zinc oxide films prepared by sol-gel spin-coating. Thin Solid Films 2000, 372, 30–36.
[CrossRef]
14. Shih, T.-K.; Chen, C.-F.; Ho, J.-R.; Chuang, F.-T. Fabrication of PDMS (polydimethylsiloxane) microlens and
diffuser using replica molding. Microelectron. Eng. 2006, 83, 2499–2503. [CrossRef]
15. Pavlidis, M.; Dimakopoulos, Y.; Tsamopoulos, J. The effect of viscoelastic properties under creeping flow.
J. Non-Newton. Fluid Mech. 2010, 165, 576–591. [CrossRef]
16. Lindner, A.; Bonn, D.; Meunier, J. Viscous fingering in a shear-thinning fluid. Phys. Fluids 2000, 12, 256–261.
[CrossRef]
17. Hogg, R.V.; McKean, J.W.; Craig, A.T. Introduction to Mathematical Statistics, 7th ed.; Pearson Education, Inc.:
New York, NY, USA, 2013.
18. Weinberg, G.H.; Schumaker, J.A. Statistics an Intuitive Approach, 2nd ed.; Books/Cole Publishing Company, Inc.:
Herndon, VA, USA, 1969.

c 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).