P5-13B.

)Microelectronic devices are formed by first forming SiO2 on a silicon wafer by chemical vapor
deposition (Figure PS-13). This procedure is followed by coating the SiO 2 with a polymer called
a photoresist. The pattern of the electronic circuit is then placed on the polymer and the sample is
irradiated with ultraviolet light. If the polymer is a positive photoresist, the sections that were
irradiated will dissolve in the appropriate solvent, and those sections not irradiated will protect
the SiO2 from further treatment. The wafer is then exposed to strong acids, such as HF which
etch (1.e.. dissolve) the exposed SiO 2. It is extremely important to know the kinetics of the
reaction so that the proper depth of the channel can he achieved. The dissolution reaction is
SiO2 + 6HF H2SiF6 + 2H2O
From the foliowing initial rare data. determine the rate law.
Etching Rate (nm/min)
HF (wt%)

60
8

200
20

600
33

1000
40

1400
48

A total of 1000 thin wafer chips are to be placed in 0.5 dm 3 of 20% HF. If a spiral channel 10 m
wide and 10 m in length were to be etched lo a depth of 50 m on both sides of each wafer, how
long should the chips be left in the solution? Assume that the solution is well mixed.

Solution:
SiO2 + 6HF H2SiF6 + 2H2O
Ac s
M Ws

Ns

= moles of SiO2 =

Ac

= Cross-sectional area

Ps

= silicon dioxide density

MWs = molecular weight of silicon dioxide = 60.0

= depth of Si
wV
100 M W F

NF

= moles of HF =

= weight percentage of HF in solution

= density of solution

= volume of solution

MWF = molecular weight of HF = 20

Assume the rate law is -rs = k C F

d Ns
=r s V
dt

Mole balance:

Ac s d
wV
=k
V
M W s dt
100 V M W F

k MWs
d

=
V w
dt
100 Ac s M W F

k M Ws
d

= w , where =
V
dt
100 A c s M W F

ln

=ln + ln w
( d
dt )
ln

( )
d
dt

ln w

Where

( d
dt )

-16.629

-15.425

-14.32

-13.816

-13.479

2.079

2.996

3.497

3.689

3.871

is in m/min

From linear regression between ln

( d
dt )

and ln w , we got:

k MWs
1001.755 Ac s

MWF

Slope

Intercept

= ln = -20.462

9
= 1.2986 10

1.755

A c =( 10 106 m ) ( 10 m )( 2 sides )( 1000 wafers )=0.2m2

M W s=60 g/mol
s =2.32

g
=2.3210 6 g /m3
ml

g
=10 6 g/m 3
ml

M W F =20 g / gmol
3

V =0.5 dm =0.0005m

= 1.755

=1.2986 10

10 6 g /m 3
1.2986 10 =
20 g /gmol

k =3.224 10

m3
gmol

1.775

k (60 g /mol )
( 0.0005 m3 )
1.775
6
3
( 0.2 m ) ( 2.32 10 g/m ) ( 100 )
2

0.775

( )

min1

Final concentration of HF

52.316
( 0.2 )=0.107
5

Initial concentration of HW = 0.2 (given)

Mole balance for HF:

dNF
= 6
dt

dNs
dt

V dw

=6 k
V ; =1.775
100 M W F dt
100 M W F

10.7

20

dw

=6 k
1.775
100
M
WF
w

0.775 t

dt
0

1
1
1
0.775 =2.389 104 t
0.775
0.775 10.7
20

t=331 min