homewor k pr obl em s et 2 s ol ut i ons

3.5. An Al film was deposited at a rate of ~1 m/min in vacuum at 25 C, and it was estimated that the oxygen
content of the film was 10
-3
. What was the partial pressure of oxygen in the system?

For this problem, you could use equation 3-24 on p. 116 directly if you get the units right. I find, however,
that I need to back up a bit to make the units work out more clearly. So, I used equation 2-8 on p. 61 for the
gas impingement flux, and the expression given for evaporant vapor impingement rate on p. 116.

a
=
N
A
P
2M
g
RT
( )
1
2
N
A

d
M
a
=
PM
a

d 2M
g
RT
( )
1
2

and we know that the ratio of the impingement rates is 10
-3
. This gives the following expression for the
oxygen gas pressure P:

P =
0.001

d 2M
g
RT
( )
1
2
M
a

P =
0.001 2.7g/cm
3
( )
1.667 10
6
cm/ s
( )
2 0.032kg/ mole ( ) 8.314J / mole K ( )298K
[ ]
1
2
26.98g/ mole

10
4
cm
2
m
2

and assuming my units work out, and I didnt make any calculation errors,

P = 2.110
4
Pa


3.6. In order to deposit films of the alloy YBa
2
Cu
3
, the metals Y, Ba, and Cu are evaporated from three point
sources. The latter are situated at the corners of an equilateral triangle whose side is 20 cm. Directly above
the centroid of the source array, and parallel to it, lies a small substrate; the deposition system geometry is
effectively a tetrahedron, each side being 20 cm long.
a. If the Y source is heated to 1740 K to produce a vapor pressure of 10
-3
torr, to what temperature must
the Cu source be heated to maintain film stoichiometry?
b. Rather than a point source, a surface source is used to evaporate Cu. How must the Cu source
temperature be changed to ensure deposit stoichiometry?
c. If the source configuration in part (a) is employed, what minimum O
2
partial pressure is required to
deposit stoichiometric superconducting oxide YBa
2
Cu
3
O
7
films by a reactive evaporation process?
The atomic weights are Y =89, Cu =63.5, Ba =137, and O =16.

NOTE: If you f ind a better way to work t his problem, please let us know!

a. For this problem, we know the desired ratio of Cu to Y based on the compound stoichiometry, and we
are concerned with the ratio of the fluxes of two atom types in the vapor stream above the melt. Thus, it
is a problem that deals with preferential vaporization, and we can apply Equation 3-11 to solve for a
desired vapor pressure of the Cu. It appears that, given the tetrahedral configuration, we can ignore all
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 2 OF 12
ENGR 3899



geometrical effects since the point sources are the same distance from the substrate and oriented in
the same manner. From the given stoichiometry, we know that we need a ratio of fluxes of Cu atoms to
Y atoms of 3:1. Lets assume that we can also arrange for a 1:1 molar ratio of Y to Cu in point sources,
i.e., X
Cu
=X
Y
. Lets also assume that the activity coefficients of Y and Cu are equal, i.e.,
Cu
=
Y
(this
may or may not be the case, but finding these values in the literature could be difficult).

Cu

Y
=

Cu
X
Cu
P
Cu
(0) M
Y
( )
1 2

Y
X
Y
P
Y
(0) M
Cu
( )
1 2
=
P
Cu
(0) M
Y
( )
1 2
P
Y
(0) M
Cu
( )
1 2
=
3
1


Rearranging and filling in some values, and solving for the vapor pressure of Cu gives:

P
Cu
(0) =
3P
Y
(0) M
Cu
( )
1 2
M
Y
( )
1 2
=
3 10
3
torr
( )
63.5g/ mole
( )
1 2
89g/ mole
( )
1 2
= 2.5 10
3
torr

From Figure 3-1, a temperature of about 1670 K is required to attain this vapor pressure for Cu.

b. Surface source implies that, at the same source temperature, the flux of Cu atoms will be greater that
that observed from a point source. Thus, the temperature of the source should be decreased to attain
the proper stoichiometry.
c. It seems like there should be a way to solve this problem by treating O
2
as an impurity and using Table
3-2, but I cant quite get it to work out that way. So, Im going to base my solution on the desired ratio
of the gas impingement fluxes and use Equations 2-8 and 2-9.


=
N
A
P
2MRT ( )
1
2
= 3.51310
22
P
MT
( )
1
2
atoms or molecules/cm
2
s

when P is in torr and T is in K.

I think we can ignore most of the information provided in the problem and simply determine the flux of
one atom type (Y, Ba, or Cu) and base the necessary O
2
flux on that number. Since we have all the
information on Y, lets go with that:

Y
= 3.51310
22
10
3
torr
( )
(89g/ mole)(1740K)
( )
1
2
= 8.927 10
16
atoms/cm
2
s

We need an O:Y ratio of 7:1, or an O
2
:Y ratio of 3.5:1. Assuming the oxygen gas is input at room
temperature (298 K), we have:

O
2
= 3.5
Y
= 3.124310
17
molecules/cm
2
s = 3.51310
22
P
O
2
(32g/ mole)(298K) ( )
1
2


P
O
2
= 8.7 10
4
torr

3.9 A tungsten evaporation source is rated at 1000 W and operates at 120 V. If the filament heater wire is 20
cm long and 0.75 mm in diameter, estimate the temperature (T) the source will reach when powered.
Compare your answer with an alternative estimate of the temperature assuming all of the input electrical
power dissipated is thermally radiated from the filament surface.

For the first part of the problem, simply plug all your known values into Equation 3-25 and solve for T.
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 3 OF 12
ENGR 3899




P = I
2
R =
V
2
R
=
V
2
(0) T T(0) [ ]
n
L A
c


T T(0)
[ ]
n
=
V
2
A
c
P(0)L
T = T(0)
V
2
A
c
P(0)L
1.2
= 293K
120V
( )
2
4
0.75 10
3
m
( )
2
1000W
( )
5.5 10
8
m
( )
0.20m
( )
1.2


T = T(0)
V
2
A
c
P(0)L
1.2
= 293K
120V
( )
2
4
0.75 10
3
m
( )
2
1000W
( )
5.5 10
8
m
( )
0.20m
( )
1.2
= 58, 700K

So, obviously this number is nonsense, since tungsten melts around 3700 K. Can you find an error in my
calculation?

For the second part of this problem, we simply need to plug numbers into Equation 3-26 and research a
value for the emissivity of tungsten. Using a quick Google search, I found a tungsten emissivity value of
about 0.4 at higher temperatures.


P =A
s
T
4
T(0)
4
( )


T =
P
A
s
+ T(0)
4
4 =
1000W
0.4 5.6 10
8
W m
2
K
4
( )
(0.75 10
3
m)(0.20m)
( )
+ 293
4
4
3100K

This number is a bit more reasonable!




3.10. Given: The specific energy for e-beam evaporation in a 100mm diameter water-cooled hearth for Zr,EZr, is
61.5 kWhr/kg. The thermal conductivity of Zr, Zr, is 30 W/Km (=0.3 W/Kcm). The average charge
thickness,l, is 1 cm.

Task: Compare EZr with that predicted in the book.

Solution: We need to calculate the power density terms on page 124 of the text. These terms give
the power losses associated with evaporating 1018 atoms/cm2s in W/cm2.

First convert EZr into PZr:




Then look up some constants:
o Heat of sublimation, H
s,Zr
, @ 298K: 600.8 kJ /mol (http://www.speclab.com/elements/zirconium.htm )
=3.75e24 eV/mol =6.2276 eV/atom
o Temperature of Source, Ts, from Table 3.3: 1987C =2260K
o Reference Temperature, T
0
, is room temperature: 293K

61.5
kW hr
Kg
Zr
|
\

|
.
|
10
18
atoms
cm
2
sec
( )
3600
sec
hr
( )
1.515 10
25 Kg
atom
|
\

|
.
|
Zr
10
3
W
kW
)
( )
= 33.5
W
cm
2
( )
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 4 OF 12
ENGR 3899



o Emissivity,
Zr
, at T
s,
http://www.osti.gov/energycitations/product.biblio.jsp?osti_id=5313392 I
assumed linear decay in the temperature range cited: 0.455
P
Zr
=P
Zr,s+
P
Zr,k+
P
Zr,r+
P
Zr,c
=0.16 H
s,Zr
+2.07e-5Ts +5.67e-12 (T
s
4
-T
0
4
) +
Zr
(T
s
-T
0
)/l:
1.00 +0.04 +67.28 +590 =658 W/cm
2

Conductance losses dominate, as stated in the text. Theoretical value is 20x the measured value.
The only way to bring these values in line with one another is to use a ridiculously low Ts.
I dont like this answer.

3.14 Given: Two small area sources 100 cm apart and 50 cm below a planar substrate. The source plane is
parallel to the substrate plane. The sources are operated at 1300K and the vapor pressure of element A
(in source A) is 10x that of element B in Source B. P
A
(0) =15P
B
(0) at 1500K.

Tasks: a) Find the distance along the substrate where the film is 60 at% A 40at% B.
b) Find the difference in the heats of vaporization of A & B, d =(H
e,B
- H
e,A
).


Solutions: a) , let =l
A
/h and =l
B
/h, so that
Assume M
A
=M
B
, so that d
0A
=10d
0B
. For the point is question, d
A
/d
B
=60/40, and l
A
+l
B
=100 or
l
A
/50+l
B
/50 =2 =+. Substitute d
0A
/d
0B
=10, (2- )
2
=
2
and d
A
/d
B
=1.5 and do some algebra:
, the positive root of this is =0.772, so that
l
B
=38.6 cm and l
A
=61.4 cm
b) P=P
0
exp(-H/RT); R=1.987 cal/mol-K. P
A
/P
B
=10 at 1300K and 15 at 1500K, so
a)
&
b)
Divide a) by b) and simplify to get d =(H
e,B
- H
e,A
) =-2.09x10
-5
cal/mol
100 cm
h=50 cm
l
A
l
B

2
2
0
1
1

+
=
h
l
d
d
( ) ( )
( )
( )
2
2
0
2
2
0
2
2
, 0
2
2
, 0
1
1
1
&
1

+
+
=
+
=
+
=
B
A
B
A B
B
A
A
d
d
d
d d
d
d
d
( ) ( ) 0 15 5 10 15 2 15 10
2
= + +
1 . 2583 /
0
0
1 . 2583 /
0
1 . 2583 /
0
exp
exp
exp
10
d
B
A
H
B
H
A
B
A
P
P
P
P
P
P
= = =


5 . 2980 /
0
0
5 . 2980 /
0
5 . 2980 /
0
exp
exp
exp
15
d
B
A
H
B
H
A
B
A
P
P
P
P
P
P
= = =


THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 5 OF 12
ENGR 3899



3.16 Given: A source initially at a distance, h, from a substrate. During deposition the source recedes a
distance h.
Task: Derive an expression for the fractional change in film thickness, d/d
0
, at any point along the film
substrate, l, as a function of h/h.
Solution: After time t the source has receded h so that the source to substrate distance is now h+h.
The fractional thickness equation (3-22) becomes:
Multiply the second term in the denominator by a judicious choice of 1 (h
2
/h
2
) to get:

2
2
0
1
1

+
+
=
h h
l
d
d
2
2
0
1
1
1

+
+
=
h
h
h
l
d
d
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 6 OF 12
ENGR 3899



Montgomery Chapter 3
Experiments with a Si ngl e Factor: The Analysis of Variance
Solutions


3-1 The tensile strength of portland cement is being studied. Four different mixing techniques can be used
economically. The following data have been collected:

Mixing
Technique Tensile Strength (lb/in
2
)
1 3129 3000 2865 2890
2 3200 3300 2975 3150
3 2800 2900 2985 3050
4 2600 2700 2600 2765

(a) Test the hypothesis that mixing techniques affect the strength of the cement. Use =0.05.

Design Expert Output
Response: Tensil e Strengthin lb/in^2
ANOVA for Sel ect ed Factorial Model
Anal ysis of vari ance table [Partial sum of squares]
Sum of Mean F
Source Squares DF Square Value Prob > F
Model 4.897E+005 3 1.632E+005 12.73 0.0005 significant
A 4.897E+005 3 1.632E+005 12.73 0.0005
Residual 1.539E+005 12 12825.69
Lack of Fit 0.000 0
Pure Error 1.539E+005 12 12825.69
Cor Total 6.436E+005 15

The Model F-value of 12.73 implies the model is significant. There is only
a 0.05% chance that a "Model F-Value" this large could occur due to noise.

Treatment Means (Adj ust ed, If Necessary)
Esti mat ed Standard
Mean Error
1-1 2971.00 56.63
2-2 3156.25 56.63
3-3 2933.75 56.63
4-4 2666.25 56.63

Mean Standard t for H0
Treatment Difference DF Error Coeff =0 Prob > |t |
1 vs 2 -185.25 1 80.08 -2.31 0.0392
1 vs 3 37.25 1 80.08 0.47 0.6501
1 vs 4 304.75 1 80.08 3.81 0.0025
2 vs 3 222.50 1 80.08 2.78 0.0167
2 vs 4 490.00 1 80.08 6.12 <0.0001
3 vs 4 267.50 1 80.08 3.34 0.0059

The F-value is 12.73 with a corresponding P-value of .0005. Mixing technique has an effect.

(b) Construct a graphical display as described in Section 3-5.3 to compare the mean tensile strengths for the four
mixing techniques. What are your conclusions?

625 56
4
7 12825
.
.
n
MS
S
E
y
. i
= = =
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 7 OF 12
ENGR 3899



2700 2800 2900 3000 3100
Tensile Strength
Scaled t Distribution
(3) (2) (1) (4)

Based on examination of the plot, we would conclude that
1
and
3
are the same; that
4
differs from
1
and
3
,
that
2
differs from
1
and
3
, and that
2
and
4
are different.

(c) Use the Fisher LSD method with a=0.05 to make comparisons between pairs of means.
495 174 85 6412 179 2
4
7 12825 2
2
4 16 025 0
2
. . . LSD
) . (
t LSD
n
MS
t LSD
, .
a N ,
E
= =
=
=

Treatment 2 vs. Treatment 4 =3156.250 - 2666.250 =490.000 >174.495
Treatment 2 vs. Treatment 3 =3156.250 - 2933.750 =222.500 >174.495
Treatment 2 vs. Treatment 1 =3156.250 - 2971.000 =185.250 >174.495
Treatment 1 vs. Treatment 4 =2971.000 - 2666.250 =304.750 >174.495
Treatment 1 vs. Treatment 3 =2971.000 - 2933.750 = 37.250 <174.495
Treatment 3 vs. Treatment 4 =2933.750 - 2666.250 =267.500 >174.495

The Fisher LSD method is also presented in the Design-Expert computer output above. The results agree with the
graphical method for this experiment.

(d) Construct a normal probability plot of the residuals. What conclusion would you draw about the validity of the
normality assumption?

There is nothing unusual about the normal probability plot of residuals.

THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 8 OF 12
ENGR 3899



Residual
Normal plot of residuals
-181.25 -96.4375 -11.625 73.1875 158
1
5
10
20
30
50
70
80
90
95
99

(e) Plot the residuals versus the predicted tensile strength. Comment on the plot.

There is nothing unusual about this plot.
22
Predicted
Residuals vs. Predicted
-181.25
-96.4375
-11.625
73.1875
158
2666.25 2788.75 2911.25 3033.75 3156.25

(f) Prepare a scatter plot of the results to aid the interpretation of the results of this experiment.

Design-Expert automatically generates the scatter plot. The plot below also shows the sample average for each
treatment and the 95 percent confidence interval on the treatment mean.
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 9 OF 12
ENGR 3899



Technique
One Factor Plot
1 2 3 4
2579.01
2759.26
2939.51
3119.75
3300
22

3-6 A pharmaceutical manufacturer wants to investigate the bioactivity of a new drug. A completely randomized
single-factor experiment was conducted with three dosage levels, and the following results were obtained.

Dosage Observations
20g 24 28 37 30
30g 37 44 31 35
40g 42 47 52 38

(a) Is there evidence to indicate that dosage level affects bioactivity? Use =0.05.

Minitab Output
One-way ANOVA: Activity versus Dosage

Analysis of Variance for Activity
Source DF SS MS F P
Dosage 2 450.7 225.3 7.04 0.014
Error 9 288.3 32.0
Total 11 738.9

There appears to be a different in the dosages.

(b) If it is appropriate to do so, make comparisons between the pairs of means. What conclusions can you draw?

Because there appears to be a difference in the dosages, the comparison of means is appropriate.

Minitab Output
Tukey's pairwise comparisons

Family error rate =0.0500
Individual error rate =0.0209

Critical value =3.95

Intervals for (column level mean) - (row level mean)

20g 30g

30g -18.177
4.177

40g -26.177 -19.177
-3.823 3.177

The Tukey comparison shows a difference in the means between the 20g and the 40g dosages.

(c) Analyze the residuals from this experiment and comment on the model adequacy.
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 10 OF 12
ENGR 3899




There is nothing too unusual about the residual plots shown below.

Residual
P
e
r
c
e
n
t
8 6 4 2 0 -2 -4 -6 -8
99
95
90
80
70
60
50
40
30
20
10
5
1
Normal Probability Plot of the Residuals
(response is Activity)


Fitted Value
R
e
s
i
d
u
a
l
46 44 42 40 38 36 34 32 30
8
6
4
2
0
-2
-4
-6
-8
Residuals Versus the Fitted Values
(response is Activity)

3-10 An experiment was run to determine whether four specific firing temperatures affect the density of a certain
type of brick. The experiment led to the following data:

Temperature Density
100 21.8 21.9 21.7 21.6 21.7
125 21.7 21.4 21.5 21.4
150 21.9 21.8 21.8 21.6 21.5
175 21.9 21.7 21.8 21.4

(a) Does the firing temperature affect the density of the bricks? Use =0.05.
THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 11 OF 12
ENGR 3899



No, firing temperature does not affect the density of the bricks. Refer to the Design-Expert output below.

Design Expert Output
Response: Density
ANOVA for Sel ected Fact orial Model
Anal ysis of vari ance table [Partial sum of squares]
Sum of Mean F
Source Squares DF Square Value Prob > F
Model 0.16 3 0.052 2.02 0.1569 not significant
A 0.16 3 0.052 2.02 0.1569
Residual 0.36 14 0.026
Lack of Fit 0.000 0
Pure Error 0.36 14 0.026
Cor Total 0.52 17

The "Model F-value" of 2.02 implies the model is not significant relative to the noise. There is a
15.69 % chance that a "Model F-value" this large could occur due to noise.

Treatment Means (Adj ust ed, If Necessary)
Esti mat ed Standard
Mean Error
1-100 21.74 0.072
2-125 21.50 0.080
3-150 21.72 0.072
4-175 21.70 0.080

Mean Standard t for H0
Treatment Difference DF Error Coeff =0 Prob > |t |
1 vs 2 0.24 1 0.11 2.23 0.0425
1 vs 3 0.020 1 0.10 0.20 0.8465
1 vs 4 0.040 1 0.11 0.37 0.7156
2 vs 3 -0.22 1 0.11 -2.05 0.0601
2 vs 4 -0.20 1 0.11 -1.76 0.0996
3 vs 4 0.020 1 0.11 0.19 0.8552

(b) Is it appropriate to compare the means using the Fisher LSD method in this experiment?

The analysis of variance tells us that there is no difference in the treatments. There is no need to proceed with
Fishers LSD method to decide which mean is difference.

(c) Analyze the residuals from this experiment. Are the analysis of variance assumptions satisfied? There is
nothing unusual about the residual plots.

Residual
Normal plot of residuals
-0.3 -0.175 -0.05 0.075 0.2
1
5
10
20
30
50
70
80
90
95
99
22
22
22
Predicted
Residuals vs. Predicted
-0.3
-0.175
-0.05
0.075
0.2
21.50 21.56 21.62 21.68 21.74

THIN FILMS MATERIALS and the DESIGN OF EXPERIMENTS HOMEWORK 2 SOLUTIONS, PAGE 12 OF 12
ENGR 3899



(d) Construct a graphical display of the treatments as described in Section 3-5.3. Does this graph adequately
summarize the results of the analysis of variance in part (b). Yes.
21.2 21.3 21.4 21.5 21.6 21.7 21.8
Mean Density
Scaled t Distribution
(125) (175,150,100)