O-o;

Problem 4.14:
Part 1:
Stoichiometric Table (Basis 1000 moles in)
Species In Out
WF6 45 45 ⋅ (1-X A )
H2 864 864 − 135 ⋅ X A
Ar 91 91
HF 0 270 ⋅ X A
W 0 Not included; deposits as solid
Total 1000 Total 1000 + 90 ⋅ X A

45 ⋅ (1-X A )
p WF6 = P×y WF6 = (1 mm Hg ) ⋅
1000 + 90 ⋅ X A
45 ⋅ (1-X A )
=
1000 + 90 ⋅ X A

864 − 135 ⋅ X A
p H2 = P×y H2 = (1 mm Hg ) ⋅
1000 + 90 ⋅ X A
864 − 135 ⋅ X A
=
1000 + 90 ⋅ X A

Part 2:
In – Out + Generation = 0 (balance on WF6)
The reaction takes place only on the top surface of the wafer. If the gas composition is the
same at every point in the vessel,
Generation=rA ⋅ A

However, since 1 mole of WF6 gives 1 mole of W,

Generation=-rW ⋅ A ,

In = FAo
Out = FAo ⋅ (1-X A )
 FAo - FAo ⋅ (1-X A ) + ( -rW ⋅ A ) = 0
FAo ⋅ X A = rW ⋅ A
A XA
=
FAo rW

Part 3:
π ⋅ 5.52
A= =23.76 cm 2
4
standard cc y Ao
FAo =660 ×
min standard cc
22400
mol
660 × 0.045 mol
=
22400 min
mol
=1.33 × 10-3
min
exp ( −8300 T ) ⋅ p 0.5
H 2 ⋅ p WF6
rw =
1+450 ⋅ p WF6

⎛ 864 − 135 ⋅ X A ⎞ ⎛ 45 ⋅ (1-X A ) ⎞

0.5

exp ( −8300 673) ⋅ ⎜ ⎟ ⋅⎜ ⎟

⎝ 1000 + 90 ⋅ X A ⎠ ⎝ 1000 + 90 ⋅ X A ⎠
=
⎛ 45 ⋅ (1-X A ) ⎞
1+450 ⋅ ⎜ ⎟
⎝ 1000 + 90 ⋅ X A ⎠

0.5
⎛ 864 − 135 ⋅ X A ⎞
4.4 × 10 ⋅ ( 45 ⋅ (1-X A ) ) ⋅ ⎜
−6
⎟
⎝ 1000 + 90 ⋅ X A ⎠ ⎛ sec ⎞
= ⋅ ⎜ 60 ⎟
21250 − 20160 ⋅ X A ⎝ min ⎠

0.5
⎛ 864 − 135 ⋅ X A ⎞
5.59 ×10 ⋅ (1-X A ) ⋅ ⎜
−7
⎟
⎝ 1000 + 90 ⋅ X A ⎠ mol
rw = ( Eqn. 1)
1-0.949 ⋅ X A cm 2 ⋅ min

Substitute into design equation;

 23.8 (cm2 ) X A (1
0.949X A ) (cm2
min/mole)
=
1.33x10 -3 (mole/min)
7
 864
135X A 0.5
5.59x10 (1
X A ) 
 1000 + 90X A 
X A (1
0.949X A )(1000 + 90X A )0.5
0.5
= 100x10
4 Eqn. 2
(1
X A )(864
135X A )

Solve Eqn. 2 for XA. Then substitute value of XA into Eqn. 1 to obtain rW. These
calculations were carried out in an Excel spreadsheet using GOALSEEK. See next page.

Values:
XA = 0.0093
rW = 8.66x10-9 (moles W/cm2-min)

NOTE: the conversion of the WF6 in the feed is quite low. A lot of WF6 will be wasted
unless WF6 in the reactor effluent is recovered and recycled. Even if WF6 is recovered
and recycled, any purge stream will probably have to be treated to remove residual WF6
before that stream is discharged into the atmosphere.
SOLUTION TO PROBLEM 4-14 (RD-26)

A = 23.7582744 cm^2
(A is the area of the wafer)
FA0 = 0.00132589 moles WF6/min
(FA0 is the molar feed rate of WF6 to the reactor)

USING GOALSEEK TO FIND THE VALUE OF XA THAT SATISFIES EQUATION 2:

xA f(xA) Constant Function f(xA)-Const.

0.00929552 0.01001663 0.01001655 8.0711E-05 8.07107E-08

f(xA)=xA*(1-0.949*xA)(1000+90*xA)^0.5/[(1-xA)(864-135xA)^0.5]
Constant=RHS of Equation 2, A*exp(-8300/T)*45/FA0
"Function" = 1000*(f(xA)-Constant)
(GOALSEEK was used to set "Function" = 0)
(The factor of 1000 in "Function" increases the sensitivity of the solution to xA)

CALCULATING rW and G FROM xA:

rW is calculated by substituting the value of xA into Equation 1
G is the linear growth rate of the tungsten film.
The reference article states that G = [5.72E+10]*rW.
This formula is used in the calculation below.
In Part 4 of the problem, a relationship between rW and G is derived.

T rW G
(K) (mole W/ (A/min)
cm^2-min)

673 8.6561E-09 495.127215

Part 4:

The linear growth rate (G) is calculated in the spreadsheet using a relationship
taken from the referenced publication:

G (Å/min) = 5.72x1010xrW

Let’s derive this relationship:

G (Å/min) =
rW(molesW/cm2–sec)x60(sec/min)x108(Å/cm)x183.4(g.W/moleW)x(1/19.4)(cm3/g.W)

G (Å/min) = rW(molesW/cm2–sec)x5.67x1010(sec-Å-cm2/min-moleW)

For rW = 8.66x10-9(molesW/cm2-sec)

G (Å/min) = 491

This agrees very closely with the results shown in Figure 5 of the referenced
publication!