Table 5.1 Molar ratio of HCl/Ti in preparation conditions of titania sols
Temperature (℃)
Condition HCl／Ti
pH
─
─
50
60
70
80
A
0.2
2.8
B
0.4
1.3
─
─
─
60
70
80
C
0.8
0.5
─
40
50
60
─
─
D
1.6
-0.2
RT
40
50
─
─
─
E
3.2
RT
─
─
─
─
─
RT：Room temperature
─：Not prepared
Table 5.2 Condition A
Temperature (℃)
Time (hour)
50
60
70
80
1
×
×
×
×
2
×
×
×
×
3
×
×
×
×
○：Clear solution
4
×
×
×
×
△：Colloidal solution
5
×
×
×
×
×：Not peptized
6
×
×
×
×
Table 5.3 Condition B
Time (hour)
1
2
3
4
5
6
Temperature (℃)
60
△
△
△
＊
＊
＊
70
△
△
＊
＊
＊
＊
80
△
＊
＊
＊
＊
＊
○：Clear solution
△：Colloidal solution
×：Not peptized
＊：Gelation
60
△
＊
＊
＊
＊
＊
○：Clear solution
△：Colloidal solution
×：Not peptized
＊：Gelation
Table 5.4 Condition C
Time (hour)
1
2
3
4
5
6
Temperature (℃)
40
×
△
△
＊
＊
＊
50
△
△
＊
＊
＊
＊
159
Table 5.5 Condition D
Time (hour)
1
2
3
4
Temperature (℃)
RT
×
△
△
△
40
△
＊
＊
＊
50
△
＊
＊
＊
RT：Room temperature
○：Clear solution
△：Colloidal solution
×：Not peptized
＊：Gelation
Table 5.6 Condition E
Time (hour)
0.5
1
2
3
4
Temperature (℃)
RT
△
△
△
○
○
RT：Room temperature
○：Clear solution
△：Colloidal solution
×：Not peptized
＊：Gelation
160
Table 5.7 Fragmentation factor (PC)
H2O
m/z
16
17
18
PC
0.01
0.23
1
ここで用いたH2OのPCは，
第4章の付表の値とは異なっている
C2H4
m/z
13
14
25
26
27
28
29
PC
0.03
0.06
0.12
0.62
0.65
1
0.02
C2H6
m/z
14
15
25
26
27
28
29
30
PC
0.13
0.18
0.16
0.88
1.29
3.82
0.83
1.00
.
HCl
m/z
35
36
37
38
PC
0.17
1
0.05
0.32
C 2 H2
m/z
13
25
26
27
PC
0.06
0.2
1
0.03
161
C2H5OH
m/z
26
27
28
29
30
31
45
46
PC
0.50
1.45
0.42
1.42
0.36
6.06
2.08
1.00
Table 5.8 Chemical species corresponding to m/z 13∼30
m/z
Chemical species
m/z
13
CH，C，D
27
14
CH2，B，C
28
15
CH3，B
29
25
C2H，B，C，D
30
26
C2H2，A，B，C
Chemical species
C2H3，A，B，C，D
C2H4，A，B
C2H5，A，B，C
C2H6，A
A：Fragments of C2H5OH
B：Fragments of C2H6
C：Fragments of C2H4
D：Fragments of C2H2
162
Table 5.9 Firing processes of titania gel films in a vacuum condition
Gel film B
Evolved species
Gel film A
Physically
102℃
89℃
Adsorbed water
225℃
H2O(Ti-OH)
─
213℃
C2H5OH
─
about 210℃ and about 335℃
CxHy
─
─
NH3
─
HCl
Cl
about 220℃ and about 335℃about 175℃ and about240℃
─
─
Gel film C
78℃，91℃ and 128℃
─
─
─
107℃，134℃ and 157℃
about 117℃，about 140℃
and about 260℃
50∼1000℃
Table 5.10 Crystallization temperature of titania films and powders
Gel film A
Gel film B
Heating
TiCl4
Ti(OC2H5)4
condition
300∼400℃
in vacuum
200∼350℃
Film
300∼400℃
in air
200∼350℃
200∼300℃
Powder
in air
100∼200℃
Gel film C
Titanium
hydroxide
60℃
60℃
60℃
Table 5.11 Peak area of evolved species calculated from TPD curves of titania gel films
Peak area (A・℃)
Evolved species Temperature region
(℃)
Gel film A
Gel film B
Gel film C
Physically
A：60∼180
1.16×10-7
3.76×10-8
1.85×10-8
adsorbed water
B、C：60∼300
＊
180∼300
×
×
H2O(Ti-OH)
5.50×10-8
-9
C2H5OH
×
×
100∼300
5.22×10
-7
C 2 H4
100∼300
×
×
1.26×10
-8
C 2 H2
100∼300
×
×
2.05×10
NH3
60∼250
×
×
1.44×10-8
A：60∼400
HCl
1.96×10-8
2.39×10-9
3.41×10-9
B、C：60∼350
A：60∼500
H2
7.50×10-8
2.04×10-9
3.09×10-9
B、C：60∼300
-8
H
60∼400
2.52×10-8
9.53×10-9
4.12×10
×：Not observed
＊：Evolved H2O from Ti-OH
in the gel film
Table 5.12 Amount of molecules of evolved species calculated from peak areas
of TPD curves
Amount of molecules
Evolved species
Gel film A
Gel film B
Gel film C
Physically
16
2.52×1016
8.91×1015
3.99×10
adsorbed water
H2O(Ti-OH)
×
×
1.79×1016
15
C2H5OH
×
×
4.00×10
16
C 2 H4
×
×
4.98×10
15
C 2 H2
×
×
4.85×10
NH3
×
×
1.57×1016
15
HCl
2.83×1015
1.78×1015
3.92×10
H2
4.53×1015
3.18×1014
3.77×1014
H
△
─
─
×：Not observed
─：Not calculated
△：Not analyzed
163
Table 5.13 Amount of evolved species calculated from TPD curves of titania films
Amount (mole)
Evolved species
Gel film A
Gel film B
Gel film C
Physically
-8
-8
6.62×10
4.17×10
1.49×10-8
adsorbed water
H2O(Ti-OH)
×
×
2.97×10-8
-9
C2H5OH
×
×
6.64×10
-8
C2H4
×
×
8.27×10
-9
C2H2
×
×
8.06×10
-8
NH3
×
×
2.64×10
HCl
6.51×10-9
4.70×10-9
2.94×10-9
H2
7.53×10-9
5.28×10-10
6.27×10-10
H
△
─
─
×：Not observed
─：Not calculated
△：Not analyzed
Table 5.14 Amount of Ti in titania films
Film A
Film B
22
9
Weight (μg)
-7
Mole
4.60×10
1.88×10-7
Film C
8
1.67×10-7
Table 5.15 Molar ratio of evolved species to Ti calculated from TPD curves and
amount of Ti in titania films
Evolved species
Physically
adsorbed water
H2O(Ti-OH)
C2H5OH
C2H4
C2H2
NH3
HCl
H2
H
Molar ratio of evolved gases to Ti
Gel film A
Gel film B
Gel film C
0.144
0.222
-2
×
×
×
×
×
2.50×10-2
2.81×10-3
─
6.46×10
1.44×10-2
0.180
1.75×10-2
×
1.42×10-2
1.64×10-2
△
164
8.29×10-2
×
×
×
×
0.158
1.76×10-2
3.75×10-3
─
×：Not observed
─：Not calculated
△：Not analyzed
Table 5.16 Crystallization temperature and molar ratio of O to Ti in titania films
Crystallized temperature
Ti：O
Gel film A
Gel film B
Gel film C
Ti(OC2H5)4
300∼400℃
1.00：2.08
TiCl4
200∼350℃
1.00：2.00
Titanium hydroxide
60℃
1.00：2.00
165
N2 atmosphere
Ti(OC
5)4 4.56g (0.02 mol) + 99.5% C2H5OH 40ml
Ti(OC2H
2H5)4 4.56g (0.02 mol) + 99.5% C2H5OH 40ml
H2O 0.36g (0.02mol)
+
35% HCl 0.42g (4.0×10-3mol)
Standing at room temperature for one day
Titania
Titaniasol
sol
Fig. 5.1
Scheme of a titania sol preparation from Ti(OC2H5)4.
166
N2 atmosphere
-2
TiCl
10g
TiCl4 41.76g
1.76g(9.3×10
(9.3×10-2mol)
mol) ++ HH2O
2O 10g
35% HCl 0.05g (4.7×10-4mol)
Standing at room temperature for one day
Titania
Titaniasol
sol
Fig. 5.2
Scheme of a titania sol preparation from TiCl4.
167
N2 atmosphere
-2
TiCl
10g
TiCl4 41.76g
1.76g(9.3×10
(9.3×10-2mol)
mol) ++ HH2O
2O 10g
29％ Aqueous ammonia 2.36g (pH 9)
White
Whiteprecipitate
precipitate(Titanium
(Titaniumhydroxide
hydroxide) )
Filtration and Washed to pH 7
Titanium hydroxide + H2O 10g
35％ HCl (molar ratio of HCl / Ti=0.2∼3.2)
Heating
Temp.：room temperature ∼ 80℃
Time：１∼６h
Titania
Titaniasol
sol
Fig. 5.3
Scheme of a titania sol preparation from
titanium hydroxide.
168
Titania
Titaniasol
solsolutions
solutions
Substrate
・Si wafers after heating
at 550℃ for 30min in air
・Alkali-free glasses
Spin coating
Evaporation
Coating condition
500rpm/5sec⇒2000rpm/30sec
Evaporated with a rotary
evaporator
Condition
A：60℃/30min → 90℃/40min
B：60℃/60min
Titania
Titaniagel
gel films
films
Dried in a desiccator
for one day
Fired in an electric furnace
Titania
Titania films
films
Fig. 5.4
Titania
Titaniagel
gelpowders
powders
Preparation scheme of titania films
and gel powders.
169
Titania
Titaniagel
gelfilms
filmson
onaaSiSi wafer
wafer
Temperature
Temperatureprogrammed
programmed
desorption
apparatus
desorption apparatus
Load-lock chamber
Vacuumed for 10min
⇒ below 1×10−3 Pa
Analysis chamber
Elapsing for 20min
(3×10−8Pa)
Fired by infrared radiation
Temp.：200℃, 300℃, 350℃, 400℃
with a heating rate of 20℃/min
Titania
Titaniafilms
films
Fig. 5.5
Preparation scheme of titania films
in vacuum conditions.
170
10
20
○(004)
30
40
○(200)
○：Anatase
○(101)
171
Intensity / arb. units
Si(111)
50
60
70
80
2θ / deg.
Fig. 5.6 XRD pattern of a titania film prepared
from titanium hydroxide.
90
172
△
○：Anatase
△：NH4Cl
○(204)
△
○(105)
○(211)
(211)
(200)
○(200)
△
○(004)
(110)
(100)
○(101)
Intensity / arb. units
△
Titanium
hydroxide
TiCl4
10
20
30
40
50
60
70
80
Ti(OC2H5)4
90
2θ / deg.
Fig. 5.7 XRD patterns of titania gel powders.
173
10 nm
Fig. 5.8 TEM image of a titania gel powder prepared
from titanium hydroxide.
Intensity / arb. units
174
60℃ / 2h
10
20
30
40
50
60
70
80
90
2θ / deg.
Fig. 5.9 XRD pattern of a titania gel powder prepared from Ti(OC2H5)4.
175
○(301)
○(112)
○(310)
○(211)
○(220)
○(111)
○(210)
○(101)
○(110)
Intensity / arb. units
○：TiO2
Precipitate
(60℃ / 2h)
(a)
Gel
(60℃ / 30min)
10
20
30
40
50
60
70
80
(b)
90
2θ / deg.
Fig. 5.10 XRD patterns of a titania gel powder and precipitate
prepared from TiCl4.
(110)
(100)
△
△
10
20
30
40
50
(211)
△
(200)
176
Intensity / arb. units
△：NH4Cl
△
60
70
80
2θ / deg.
Fig. 5.11 XRD pattern of a titania gel powder synthesized
from titanium hydroxide without heating.
90
-9
Intensity / A (×10 )
3.00
2.40
m/z 18
m/z 28
1.80
177
1.20
m/z 46
m/z 36
0.60
0.00
50
200
350
500
650
800
Temperature /℃
Fig. 5.12 TPD curves of evolved species from titania gel film A.
-9
Intensity / A (×10 )
3.00
○
2.40
1.80
1.20
178
●
0.60
0.00
50
200
350
500
650
800
Temperature / ℃
Fig. 5.13 TPD curve of H2O evolved from titania gel film A.
179
Intensity / arb. units
○
H2O
538
536
534
◎
532
530
528
526
524
Binding Enery / (eV)
Fig. 5.14 XPS spectrum of O(1s) of titania gel film A.
522
180
Intensity / A (×10-10)
5.00
4.00
3.00
2.00
1.00
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.15 TPD curve of m/z 46(C2H5OH) from titania gel film A.
181
Intensity / A (×10 -9)
3.00
2.40
m/z 28
m/z 29
1.80
m/z 27
m/z 13
1.20
0.60
m/z 26
m/z 15
m/z 25
m/z 30
0.00
50
m/z 14
200
350
500
650
Temperature / ℃
800
Fig. 5.16 TPD curves of m/z 13∼
13∼30 from titania gel film A.
182
Intensity / A (×10-10)
5.00
4.00
3.00
2.00
m/z 30
1.00
0.00
50
Fragment of C2H5OH
200
350
500
650
Temperature / ℃
800
Fig. 5.17 TPD curves of m/z 30 and fragment of C2H5OH from
titania gel film A.
183
Intensity / A (×10-10)
5.00
4.00
3.00
2.00
1.00
0.00
50
C2H6
m/z 30
Fragment of C2H5OH
200
350
500
Temperature / ℃
650
800
Fig. 5.18 TPD curves of C2H6, m/z 30 and fragment of C2H5OH
from titania gel film A.
184
Intensity / A (×10 -9)
3.00
2.40
m/z 28
1.80
1.20
Fragment of C2H6
0.60
Fragment of C2H5OH
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.19 TPD curves of m/z 28 and fragments of C2H6 and C2H5OH
from titania gel film A.
185
Intensity / A (×10 -9)
3.00
m/z 28
2.40
1.80
C2H4
1.20
Fragment of C2H6
Fragment of C2H5OH
0.60
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.20 TPD curves of C2H4, m/z 28 and fragments of C2H6
and C2H5OH from titania gel film A.
186
Intensity / A (×10-9)
3.00
2.40
Fragment of C2H5OH
1.80
m/z 26
1.20
Fragment of C2H4
0.60
Fragment of C2H6
0.00
50
200
350
500
Temperature / ℃
650
800
Fig. 5.21 TPD curves of m/z 26 and fragments of C2H4, C2H6
and C2H5OH from the titania gel film A.
187
Intensity / A (×10-9)
3.00
Fragment of C2H5OH
2.40
m/z 26
1.80
C2H2
1.20
Fragment of C2H4
0.60
Fragment of C2H6
0.00
50
200
350
500
Temperature / ℃
650
800
Fig. 5.22 TPD curves of C2H2, m/z 26 and fragments of C2H4, C2H6
and C2H5OH from titania gel film A.
188
Intensity / A (×10 -9)
3.00
2.40
1.80
C2H4
C2H5
1.20 CH
2
C2H3
C 2H
0.60 CH
C2H6
0.00
50
C2H2
CH3
200
350
500
Temperature / ℃
650
800
Fig. 5.23 TPD curves of CxHy (x=1∼
(x=1∼2, y=1∼
y=1∼6) species evolved
from titania gel film A.
189
Intensity / A (×10 -10)
3.00
2.40
1.80
m/z 38
1.20
m/z 36
○
m/z 37
0.60
m/z 35
●
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.24 TPD curves of HCl from titania gel film A.
190
Intensity / A (×10
-10
)
10.0
8.00
m/z 18
6.00
m/z 16
4.00
2.00
m/z 36
0.00
50
250
450
650
Temperature / ℃
850
Fig. 5.26 TPD curves of evolved species from titania gel film B.
191
Intensity / A (×10-10)
3.00
2.40
1.80
1.20
m/z 35
0.60
Fragment of H35Cl
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.25 TPD curves of m/z 35 and fragment of H35Cl
from titania gel film A.
192
Intensity / A (×10
-10
)
10.0
8.00
6.00
4.00
2.00
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.27 TPD curve of H2O from titania gel film B.
193
Intensity / A (×10-11)
10.0
8.00
6.00
4.00
●
m/z 38
2.00
○
m/z 36
m/z 37
m/z 35
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.28 TPD curves of HCl from titania gel film B.
194
Intensity / A (×10-11)
10.0
8.00
6.00
Fragment of H35Cl
4.00
m/z 35
2.00
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.29 TPD curves of m/z 35 and fragment of H35Cl
from titania gel film B.
195
Intensity / A (×10
-11
)
1.00
0.80
0.60
0.40
0.20
0.00
50
200
350
500
650
Temperature / ℃
800
Fig. 5.30 TPD curve of O from titania gel film B.
196
Intensity / A (×10
-10
)
5.00
m/z 17
4.00
3.00
m/z 16
m/z 18
2.00
m/z 35
m/z 36
1.00
0.00
50
200
350
500
650
800
Temperature / ℃
Fig. 5.31 TPD curves of evolved species from titania gel film C.
197
Intensity / A (×10-10)
5.00
4.00
3.00 ○
○
2.00
○
1.00
0.00
50
200
350
500
Temperature / ℃
650
Fig. 5.32 TPD curve of H2O from titania gel film C.
800
198
Intensity / A (×10-10)
5.00
4.00
3.00
m/z 17
m/z 16
2.00
m/z 18
1.00
0.00
50
200
350
500
Temperature / ℃
650
800
Fig. 5.33 TPD curves of m/z 16, 17 and 18 from titania gel film C.
199
Intensity / A (×10
-11
)
5.00
4.00
3.00
2.00
1.00
0.00
50
200
350
500
650
800
Temperature / ℃
Fig. 5.34 TPD curve of m/z 15 from titania gel film C.
200
Intensity / A (×10-10)
5.00
4.00
m/z 17
3.00
NH3 (m/z 17−Fragment of H2O)
2.00
Fragment of H2O
1.00
0.00
50
200
350
500
Temperature / ℃
650
800
Fig. 5.35 TPD curves of NH3, m/z 17 and fragment of H2O
from titania gel film C.
201
Intensity / A (×10-10)
5.00
4.00
m/z 15／PC
3.00
NH3
2.00
1.00
0.00
50
200
350
500
Temperature / ℃
650
800
Fig. 5.36 TPD curves of NH3 and m/z 15／
15／PC from titania gel film C.
202
Intensity / A (×10-10)
5.00
4.00
m/z 16
3.00
NH2 (m/z 16− Fragment of H2O)
2.00
O (Fragment of H2O)
1.00
0.00
50
200
350
500
Temperature / ℃
650
Fig. 5.37 TPD curves of m/z 16, NH2 and fragment of H2O
from titania gel film C.
800
203
Intensity / arb. units
NH3×PC
NH2 (m/z 16−Fragment of H2O)
50
200
350
500
Temperature / ℃
650
800
Fig. 5.38 TPD curves of NH2 and NH3×PC from titania gel film C.
204
Trancemittance / arb. units
○
Prepared from
titanium hydroxide
Prepared from
TiCl4 (Blank)
4000 3500
2500
1500
Wavenumber / cm-1
500
Fig. 5.39 FT-IR spectra of titania gel powders
1.50
205
Intensity / A (×10
-10
)
m/z 35
m/z 37
1.20
0.90
m/z 36
0.60
0.30
0.00 50
○○
m/z 38
○
200
350
500
Temperature / ℃
650
800
Fig. 5.40 TPD curves of HCl and Cl from titania gel film C.
206
Intensity / A (×10 -11)
3.00
2.40
1.80
m/z 38
1.20
Fragment of H35Cl
0.60
0.00
50
200
350
500
Temperature / ℃
650
Fig. 5.41 TPD curves of m/z 38 and fragment of H35Cl
from titania gel film C.
800
207
Intensity / A (×10-10)
3.00
2.40
35Cl
1.80
37Cl
1.20
0.60
0.00
50
200
350
500
Temperature / ℃
650
800
Fig. 5.42 TPD curves of 35Cl and 37Cl from titania gel film C.
208
Intensity / A (×10-10)
3.00
2.40
m/z 35×Relative isotopic abundance
1.80
m/z 37
1.20
0.60
0.00
50
200
350
500
Temperature / ℃
650
Fig. 5.43 TPD curves of Cl from titania gel film C.
800
○(101)
300℃
10
20
Si(111)
30
40
○：Anatase
○(105)
○(200)
○(004)
209
Intensity / arb. units
Si(111)
50
400℃
60
70
2θ / deg.
Fig. 5.44 XRD patterns of titania films prepared
from titanium gel film A.
80
90
200℃
10
20
40
〇：Anatase
〇(105)
〇(211)
〇(004)
30
〇(200)
Si(111)
〇(101)
210
Intensity / arb. units
Si(111)
50
2θ/ deg.
350℃
60
70
Fig. 5.45 XRD patterns of titania films prepared
from titanium gel film B.
80
90
〇(101)
〇
〇(200)
211
Intensity / arb. units
〇：Anatase
Gel film C
100℃ / 30min
10
20
30
40
2θ/ deg.
50
60
Fig. 5.46 XRD patterns of titania films prepared
from titanium hydroxide.
212
Intensity / arb. units
Gel film A
100℃ / 30min
10
20
30
40
2θ / deg.
50
60
Fig. 5.47 XRD patterns of titania films synthesized
from Ti(OC2H5)4.
Intensity / arb. units
213
Gel film B
100℃ / 30min
10
20
30
40
2θ / deg.
50
60
Fig. 5.48 XRD patterns of titania films synthesized
from TiCl4.
Octahedron
Octahedron
ofofTiO
TiO6
6
C4h19 = I41/amd
214
：O ion
：Ti ion
Unit cell of anatase
Structure of anatase
Fig. 5.49 Structure of anatase and lattice of anatase.