£
? Ò ×T Æ X Øù p § Y 8 È X ¢ TiO 2 x ¢ø m É 8 ý ° Ç% iP Æ X Øy ¢; c  \ ¥ V ê s ¹ ÅT ì Å
-
!
HG B * > · ' Ö <( å M ∗
Â
Ò â @ / < Æ § Ó ü t o < Æõ , Â Òí ß 608-737
T
( å : c
Â
Òí ß õ < Æ% ò F < Æ §, Â Òí ß 614-822
», ê ¸
Â
Òí ß @ / < Æ § Ó ü t o < Æõ , Â Òí ß 609-735
(2005¸ 10 Z 4 25{ 9 ~ Ã Î6 £ §, 2005¸ 12 Z 4 9{ 9 þ j7 á x : r ~ Ã Î6 £ §)
Reverse micelle ~ ½ ÓZ O õ Solvothermal ~ ½ ÓZ O ` ¦ s 6 x # í H Ã ºô Ç TiO
2ü < F K5 Å q s : r` ¦ ' ô Ç TiO
2\ ¦
½
+ Ë$ í % i . ' ô Ç F K5 Å q s : r É r Mn, Co, Ni, Fe, Cr, Pb, Eu, Tb s 9, 0 l x ¸ H 2 % s . XRD, SEM, TEM` ¦ s 6 x # s [ þ t _ ½ ¨ ¸, ³ ð + þ AI , © s \ ¦ ¸ % i . ' ô Ç Mn, Co s : r É r TiO
2_ ©
s ü < { 9 _ $ í © ` ¦ 8 ú ¤ ô Ç ì ø Í , TiO
2\ ' ) a Eu, Tb s : r É r TiO
2_ © s \ ¦ t ¦ { 9 _
$ í © ` ¦ Ö ¼o > % i . Co, Ni, Pb, Eu, Tb s : r s ' ) a anatase © _ TiO
2\ " f H rutile Ð ©
o\ ¦ r H : r ¸\ " f D h Ðî r o½ + ËÓ ü t s $ 3 Ø ¦ ÷ &% 3 .
PACS numbers: 61.10,N
Keywords: TiO2, © s , ¸{ 9
I. " e  ] Ø
Titanium dioxide (TiO 2 ) H & ñ ½ ¨ ¸\ # Q t
l & h , F g < Æ& h , l o < Æ& h : £ ¤$ í ` ¦ t ¦ e # Q" f [1- 4], s \ @ /ô Ç ´ ú § É r ½ ¨ s À Ò# Q4 R M ® o . TiO 2 H & h Ü
¼ Ð anatase, brookite, rutile [ j t & ñ ½ ¨ ¸\ ¦ t
¦ e Ü ¼ 9 [5], anataseü < brookite ½ ¨ ¸ H ï r î ß & ñ & h
&
ñ © Ü ¼ Ð, rutile É r î ß & ñ ô Ç & ñ © Ü ¼ Ð · ú 94 R e [6-9].
Rutile © _ TiO 2 H B Ä º î ß & ñ & h s ¦ 1 l q$ í s \ O # Q o © ¾ ¡ § _
" é ¶ « Ñ ` à Ô_ î ß « Ñ Ð ´ ú §s 6 x ÷ & ¦ e . Anatase
© _ TiO 2 H F g o < Æ 6 x` ¦ 9 [10], rutile © Ð F g8 ú ¤ B
´ òÖ ¦, l ¸ ¸ Z } É r כ Ü ¼ Ð · ú 94 R e # Q 6 £ x6 x 0
p x$ í s H Ó ü t| 9 s . Anatase © s brookite © _ TiO 2 nanocrystalline` ¦ \ P % o rutile Ð © s ô Ç H כ s
· ú 94 R e [11]. Õ ª Q { 9 ì ø Í& h Ü ¼ Ð ¸{ 9 _ ©
s H { 9 _ ß ¼l , ½ + Ë$ í ~ ½ ÓZ O , morphology 1 p x \ % ò ¾ Ó
`
¦ ~ Ã ÎÜ ¼Ù ¼ Ð [11-13] TiO 2 ¸{ 9 _ © s \ @ /ô Ç Ð
[ jô Ç ½ ¨ 9 כ ¹ . Hengzhong Zhang1 p x É r í H Ã º ô
Ç TiO 2 \ " f { 9 _ ß ¼l 14 nm s { 9 M : H anatase
© s î ß & ñ ¦ µ 1 ϳ ð % i Ü ¼ 9 [12], F K5 Å q s : r s ' ) a
∗
E-mail: [email protected]
TiO 2 ¸{ 9 H ' ô Ç F K5 Å q s : r _ 7 á x À Óü < 0 l x ¸,
|
¾ Ó 1 p x \ © s Ø Ô> è ß ¦ ´ ú § É r ½ ¨ [
þ
t s Ð ¦ % i [14-17]. TiO 2 _ © s \ @ /ô Ç ½ ¨ H
@
/Â Òì r sol-gel ~ ½ ÓZ O Ü ¼ Ð ½ + Ë$ í ô Ç TiO 2 \ ¦ @ / © Ü ¼ Ð % i Ü
¼ 9, { 9 Â Ò H ~ Ã Ì} ` ¦ ] j # © s \ ¦ ½ ¨ % i . : r
½ ¨\ " f H reverse micelle ~ ½ ÓZ O [19, 20]õ solvothermal
~
½ ÓZ O [21]` ¦ : x # í H Ã ºô Ç TiO 2 ü < Mn, Co, Ni, Fe, Cr, Pb, Eu, Tb 1 p x _ F K5 Å q s : r` ¦ ' ô Ç TiO 2 _ ¸ & ñ ì
r ´ ú ` ¦ reverse micelle ~ ½ ÓZ O õ solvothermal ~ ½ ÓZ O ` ¦ 6 x
# ½ + Ë$ í % i . ½ + Ë$ í ô Ç TiO 2 ¸ì r ´ ú ` ¦ # Q : r ¸
\
" f \ P % o % i Ü ¼ 9, x- r] X l (XRD, X’Pert-MPD, Philips), È Òõ & ³p â (TEM, JEM-2010, JEOL) 1 p x
`
¦ 6 x # © s x 9 { 9 _ ß ¼l o\ ¦ ½ ¨ % i .
II. ÷ m Ç] M ö U ê s0 n É õ m Í + s ÇÊ Ý
>
Ö ¸$ í ] j oleic acid (70 %, Aldrich)\ ¦ 0 l q anhy- drous toluene (99.8 %, Aldrich) 6 xÓ o\ F K5 Å q| 9 í ß oÓ ü t
`
¦ 0 l q Ó ü t` ¦ [ O # Q" f water-in-oil_ reverse micelle` ¦ + þ A
$ í
% i . Reverse micelle_ emulsion` ¦ y © > $ Ü ¼
"
f TiO 2 _ ½ ¨^ titanium tetraisopropoxide (TTIP,
-40-
97 %, Aldrich)\ ¦ ; ;y ' % i . TTIP\ ¦ ' ô Ç 6
xÓ o` ¦ 24 r ç ß 1 l x î ß y © > $ # Q ç H| 9 ô Ç 6 xÓ os ÷ & ¸ 2
¤ % i Ü ¼ 9 s õ & ñ \ " f toluene\ 6 x K ) a TTIP H re- verse micelle _ Ó ü t õ Ã º oì ø Í6 £ x ô Ç . ½ + Ë$ í \ 6 x ô Ç ¸
H r É r % o t · ú § ¦ 6 x % i . Ó ü t õ oleic acid, TTIP _ ] t q H 2.5 : 1 : 1 s 9, toluene\ @ /ô Ç TTIP _
0 l x ¸ H 13 mol % s . ' ô Ç y y _ F K5 Å q| 9 í ß % i ( M(NO 3 )x · yH 2 O, M = Cr 3+ , Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , Pb 2+ , Eu 3+ , Tb 3+ , 99 %, Aldrich) _ ª É r TTIP _ 2
% Ð % i . ½ + Ë$ í ô Ç reverse micelle_ emulsion` ¦ ^ ]
j ô Ç autoclave\ 60 % Ð G Ä º ¦ x 9 ` % i Ü ¼ 9, ì r { © 4 ◦ Cm 5 p x : r # 250 ◦ C t ` ¦ 2 ; Ê ê 24 r ç ß 1 l x î ß Ä »t
% i Í ty % i . È Ò" î ô Ç toluene 6 xÓ o 5 Å q \ Ñ ü æ
H } @ / ¸ ª _ g Ë > Ó ü t s + þ A$ í ÷ &% 3 Ü ¼ 9, s g Ë > Ó ü t É r ½ + Ë
$ í
) a TiO 2 ü < oleic acid Ó ü æ 5 g © I s . s 6 xÓ o` ¦ " é ¶ d
ì r o # 50 ◦ C Ð | ¸ # TiO 2 ¸{ 9 \ ¦ % 3 % 3 .
s
\ ¦ r 500 ◦ C, 3 r ç ß 1 l x î ß \ P % o # oleic acid 1 p x
½
+ Ë$ í õ & ñ \ " f D ¥ ½ + Ë ) a Ä »l Ó ü t| 9 ` ¦ ] j % i . 500 ◦ C \
"
f \ P % o ô Ç TiO 2 _ & ñ © õ { 9 _ ß ¼l H 250 ◦ C \
"
f ½ + Ë$ í ) a TiO 2 ü < o \ O % 3 . \ P % o : r ¸\ É r TiO 2 _ © o\ ¦ S X l 0 AK 500 ◦ C \ " f \ P % o ô Ç TiO 2 ì r ´ ú ` ¦ 600 ◦ C \ " f 900 ◦ C t 50 ◦ C ç ß Ü ¼ Ð y y
\ P % o % i . \ P % o H ¸¿ º 3 r ç ß 1 l x î ß 1 l x{ 9 >
% i . TiO 2 _ & ñ © õ { 9 _ ß ¼l H XRD, í ½ Ó F g 5
Å
q l XRD, TEM 1 p x _ 8 £ ¤& ñ ~ ½ ÓZ O Ü ¼ Ð S X % i . & ñ w n
ß ¼l (D A ) H XRD r] X pattern\ " f ½ ¨ô Ç anatase © _
(101) õ rutile © _ (110) _ x ß ¼ ÐÂ Ò' Scher- rer d D A = 0.94λ/BcosθB ` ¦ s 6 x # > í ß % i [22].
#
l " f θB = x ß ¼_ y s 9, B H x ß ¼_ FWHMs .
Fig. 1. TEM image and SAED pattern for Eu doped TiO 2 powders as synthesized at 250 ◦ C through reverse micelles and solvothermal method.
III. + s ÇÊ Ý õ m Í w ² o
Reverse micelle õ solvothermal ~ ½ ÓZ O Ü ¼ Ð ½ + Ë$ í ô Ç Eu s
: r` ¦ 2 % ' ô Ç TiO 2 _ È Òõ & ³p â õ ] j ô
Ç% ò % i r] X Á º] ( (SAED) H Fig. 1 õ ° ú . { 9 _ ß
¼l H 8 nms 9, anatase © s % 3 . F K5 Å q s : r` ¦ 2%
'
# ½ + Ë$ í ô Ç TiO 2 ü < í H Ã ºô Ç TiO 2 H _ ° ú É r { 9 ß
¼l ü < ç H{ 9 ô Ç { 9 ß ¼l ì r í\ ¦ t ¦ e % 3 Ü ¼ 9, ¸¿ º anatase © s % 3 . ½ + Ë$ í ô Ç TiO 2 _ © o\ ¦ \ P r ì r$ 3 Z O
(DTA), \ P Á º> ì r$ 3 Z O (TGA) 1 p x Ü ¼ Ð 8 £ ¤& ñ % i Ü ¼
© : r \ " f 900 ◦ C t _ : r ¸ # 3 0 A\ " f H Õ ª o\ ¦ S X
½ + É Ã º \ O % 3 . í H à ºô Ç TiO 2 ¸ì r ´ ú _ \ P % o : r ¸\
É r XRD H Fig. 2 ü < ° ú . \ P % o : r ¸ 7 £ x < Ê\
anatase & ñ © \ " f rutile & ñ © Ü ¼ Ð oK H כ
`
¦ ^ ¦ Ã º e . 700 ◦ C t H anatase © ` ¦ Ä »t % i Ü ¼ 9, 750 ◦ C Â Ò' rutile © s Ò q t$ í ÷ & ¦ 850 ◦ C \ " f anatase
© s f ` ¦ · ú Ã º e .
Mn, Co, Ni, Fe, Cr, Pb, Eu, Tb 1 p x F K5 Å q s : r` ¦ y y 2 % ' ô Ç TiO 2 _ : r ¸\ É r rutile weight fraction É r Fig. 3 õ ° ú . rutile weight fraction É r XRD 8 £ ¤& ñ õ Ð Â
Ò' _ d ` ¦ s 6 x # > í ß % i Ü ¼ 9, anataseü < rutile_
& ñ © s D ¥ F ) a © I \ " f rutile © _ ª ` ¦ · p . d
\
" f IA H anatase © \ " f (101) _ & h ì r [ jl s ¦, IR
É r rutile © \ " f (110) _ & h ì r [ jl s . Fig. 3\ " f ü
< ° ú s Ni s : r` ¦ 2 % ' ô Ç TiO 2 _ © o H í H Ã ºô Ç TiO 2 _ © s ü < Ä » % i . Mnõ Co s : r` ¦ y y 2%
'
ô Ç TiO 2 H í H Ã ºô Ç TiO 2 Ð ± ú É r : r ¸ 700 ◦ C \
"
f rutile Ð © s l r # , 750 ◦ C \ " f H rutile _
Fig. 2. XRD patterns for pure TiO 2 nanoparticles sin-
tered at 500, 700, 750, 800, 850 and 900 ◦ C. A circle
represents anatase phase and a rectangle represents ru-
tile phase.
Fig. 3. Rutile weight fraction of pure and metal doped TiO 2 . The concentrations of the doped metal ions are 2
%, respectively.
weight fraction s 70 % s © Ü ¼ Ð 7 £ x < Ê` ¦ · ú Ã º e .
Fe s : r` ¦ 2 % ' ô Ç TiO 2 H 750 ◦ C \ " f rutile_ © s
l r # , 800 ◦ C{ 9 M : rutile weight fractions 20 %, 850 ◦ C{ 9 M : 70 %, 900 ◦ C{ 9 M : 100% Ð ÷ &% 3 Ü ¼ 9,
É r ;s F K5 Å q s : r` ¦ ' ô Ç TiO 2 \ q # : r ¸\
É
r © o ¢ - a ë ß > ' H d` ¦ · ú Ã º e . Cr s : r` ¦ 2 % ' ô Ç TiO 2 H 850 ◦ C{ 9 M : rutile Ð © o l r
% i .
Mn 2+ , Co 2+ , Ni 2+ , Fe 3+ , Cr 3+ s : r É r 3d n _ ½ ¨
¸\ ¦ t H ;s F K5 Å q s : r s . Anatase, rutileõ ° ú É r C
0 AÃ º 6 octahedral ½ ¨ ¸\ " f Ti 4+ s : r _ ì ø Ít 2 £ §
É r 74.5 pm, Mn 2+ s : r É r 81 pm, Co 2+ s : r É r 79 pm, Ni 2+ s : r É r 83 pm, Fe 3+ s : r É r 69 pm, Cr 3+ s : r É r 75.5 pm s [23]. Fig. 3_ õ \ " f 2 s : r Mn, Co, Ni 1 p x s ' ) a TiO 2 H í H Ã ºô Ç TiO 2 \ q K " f © s
: r ¸ ± ú ° ú Ü ¼ 9, 3 s : r Fe, Cr 1 p x s ' ) a TiO 2 H í H Ã ºô Ç TiO 2 \ q K " f rutile Ð_ © s : r ¸
Z
}6 £ §` ¦ · ú Ã º e . ;s F K5 Å q s : r` ¦ ' ô Ç TiO 2 _ ©
s : r ¸ H ' ) a ;s F K5 Å q s : r _ ì ø Ít 2 £ § \ H f ] X & h Ü
¼ Ð ' a > t · ú §6 £ §` ¦ · ú Ã º e . Pb 2+ s : r` ¦ ' ô Ç TiO 2 H 850 ◦ C \ " f rutile Ð_ © s l r
% i Ü ¼ 9, 900 ◦ C{ 9 M : ¸ rutile weight fractions 30 % & ñ
¸% i . Eu 3+ , Tb 3+ s : r` ¦ y y 2 % ' ô Ç TiO 2 H 900
◦ C t anatase © ` ¦ Ä »t % i Ü ¼ 9, rutile Ð_ © o
t · ú § ¤ . C 0 AÃ º 6 octahedral ½ ¨ ¸\ ¦ s Ò ¦ M
: Ti 4+ s : r _ ì ø Ít 2 £ § É r 74.5 pm, Pb 2+ s : r É r 133 pm, Eu 3+ s : r É r 108.7 pm, Tb 3+ s : r É r 106.3 pm s [23].
TiO 2 \ ' ô Ç Pb 2+ , Eu 3+ , Tb 3+ s : r 1 p x É r Ti 4+ s : r
\
q K " f s : r _ ì ø Ít 2 £ § s ß ¼ ¦, ° ú t · ú § Ti 4+
Fig. 4. The XRD pattern of 2 % Tb doped TiO 2 powders sintered at 900 ◦ C. Solid circles represent anatase phase of TiO 2 . Structure of accompanied peaks with TiO 2 was identified as Tb 2 Ti 2 O 7 .
o \ u ¨ 8 ÷ &t · ú §Ü ¼ 9 TiO 2 _ © s \ ¦ t H ´ ò õ
\ ¦ · p כ s ½ + É Ã º e . Andrew Burns [14] 1 p x
É r Nd 3+ s : r` ¦ 1 - 3 % ' ô Ç TiO 2 \ ¦ sol-gel ~ ½ ÓZ O Ü ¼ Ð
½
+ Ë$ í # TiO 2 _ © o\ ¦ ½ ¨ % i . Õ ª[ þ t _ ½ ¨ õ
\ _ ½ + Ë$ í : r ¸ 850 ◦ C{ 9 M : rutile_ & ñ © s
z ¤ . : r ½ ¨\ " f H B ÐÀ Ó s : r` ¦ ' ô Ç TiO 2 \ ¦ 250 ◦ C \ " f ½ + Ë$ í # & ñ o ¦, & ñ o ) a TiO 2 \ ¦ \ P
%
o # © o\ ¦ S X % i Ü ¼Ù ¼ Ð Nd 3+ s : r s '
)
a gel` ¦ \ P % o # TiO 2 \ ¦ ½ + Ë$ í ô Ç Õ ª[ þ t õ H ] j õ & ñ s
Ø Ô . B ÐÀ Ó s : r[ þ t É r s : r ì ø Í â õ o < Æ& h $ í | 9 s
_ q 5 p w Ù ¼ Ð B ÐÀ Ó s : r` ¦ ' ô Ç TiO 2 _ © o
H q 5 p w ô Ç : r ¸\ " f ± ú כ Ü ¼ Ð Æ Ò& ñ ½ + É Ã º e . Õ ª Q
½ + Ë$ í ~ ½ ÓZ O _ s ü < & ñ w n _ ß ¼l H © oü < x 9 ] X ô
Ç ' a > e Ü ¼ 9 : r ½ ¨\ " f ½ + Ë$ í ô Ç TiO 2 sol-gel ~ ½ Ó Z O
Ü ¼ Ð ½ + Ë$ í ô Ç TiO 2 Ð 8 Z } É r : r ¸\ " f anatase © ` ¦ Ä
»t < Ê` ¦ · ú Ã º e . Fig. 4 H Tb 3+ s : r s 2 % ' ) a TiO 2 \ ¦ 900 ◦ C \ " f \ P % o ô Ç ì r ´ ú _ XRD patterns .
Fig. 4 \ " fü < ° ú s Tb 3+ s : r` ¦ ' ô Ç TiO 2 H 900 ◦ C
\
" f Tb 2 Ti 2 O 7 (JCPDS 41-0363) s $ 3 Ø ¦ ÷ &% 3 . Eu 3+
s
: r` ¦ ' ô Ç TiO 2 H 900 ◦ C \ " f Eu 2 Ti 2 O 7 (JCPDS 23-1072) s , Pb 2+ s : r` ¦ ' ô Ç TiO 2 H 850 ◦ C \ " f PbTi 3 O 7 (JCPDS 45-0533), Co 2+ s : r` ¦ ' ô Ç TiO 2 H 700 ◦ C \ " f CoTiO 3 (JCPDS 15-0866), Ni 2+ s : r` ¦ '
ô Ç TiO 2 H 700 ◦ C \ " f NiTiO 3 (JCPDS 33-0960) s y y
$ 3 Ø ¦H d` ¦ S X % i . $ 3 Ø ¦ ) a Ó ü t| 9 É r TiO 2 anatase
© { 9 M : l r % i Ü ¼ 9, 8 Z } É r \ P % o : r ¸\
"
f ¸ ° ú É r © ` ¦ Ä »t % i . ¢ ¸ô Ç $ 3 Ø ¦ ) a Ó ü t| 9 \ " f ª s
: r _ s : r H ½ + Ë$ í õ & ñ \ " f ' ½ + É M :_ s : r ü < ° ú
. 7 £ ¤, Co 2+ , Ni 2+ , Pb 2+ s : r 1 p x s ' ) a TiO 2 \ " f H
anatase © \ " f rutile Ð © o l r H : r ¸\ " f
Fig. 5. Grain size evolution of anatase and rutile phases of TiO 2 as a function of the annealing temperature.
Open symbols represent anatase phase and solid sym- bols represent rutile phase.
© ì r o z ¤Ü ¼ 9, Eu 3+ , Tb 3+ s : r 1 p x É r TiO2 \ @ / ô
Ç solid solubility H ± ú TiO 2 \ ' ÷ &t · ú § ¦ © ì r o
< Ê` ¦ · ú Ã º e . Mn 2+ , Cr 3+ , Fe 3+ s : r` ¦ y y ' ô Ç TiO 2 \ " f H 900 ◦ C t TiO 2 s ü @_ É r Ó ü t| 9 s $ 3 Ø ¦
÷
&t · ú § ¤ . í H Ã ºô Ç TiO 2 ü < F K5 Å q s : r` ¦ ' ô Ç TiO 2 _
\ P
% o : r ¸\ É r & ñ w n _ ß ¼l o\ ¦ Fig. 5 \
?
/% 3 . Anatase © É r open symbol Ð, rutile © É r solid symbol Ð ³ ðr % i . \ P % o : r ¸ Z }` ¦ Ã º2 ¤ { 9 _ ß
¼l H 7 £ x ô Ç . Fig. 5\ " fü < ° ú s í H Ã ºô Ç TiO 2 H
&
ñ w n _ ß ¼l 50 nm rutile © \ " f î ß & ñ 9, Mn 2+ , Co 2+ s : r` ¦ 2% ' ô Ç TiO 2 H í H Ã ºô Ç TiO 2 Ð © s
: r ¸ ¸ ± ú ¦, & ñ w n ¸ / å L y $ í © < Ê` ¦ · ú Ã º e .
TiO 2 \ ' ) a Mn 2+ õ Co 2+ s : r É r anatase rutile Ð
© s H õ & ñ \ " f activation energy\ ¦ ± ú Æ Ò ¦ & ñ w n
s $ í © H כ ` ¦ 8 ú ¤ H % i ½ + É` ¦ H כ Ü ¼ Ð Æ Ò& ñ
½
+ É Ã º e . Eu 3+ , Tb 3+ s : r` ¦ ' ô Ç TiO 2 H í H Ã ºô Ç TiO 2 \ q # & ñ w n s Ö ¼o > $ í © 9 900 ◦ C t anatase © ` ¦ Ä »t ô Ç . í H Ã ºô Ç TiO 2 F K5 Å q s : r` ¦ '
ô
Ç TiO 2 nanocrystalline _ © o ½ ¨\ " f 900 ◦ C{ 9 M :
t anatase © ` ¦ Ä »t ô Ç H ½ ¨ õ H Ð ¦÷ &t · ú §
¦ e . [11-17] s : r ì ø Ít 2 £ § s Ti 4+ s : r _ 1.4 C Eu 3+ , Tb 3+ s : r 1 p x É r rutile Ð_ © o\ ¦ $ t ¦,
&
ñ w n _ $ í © ` ¦ } H כ Ü ¼ Ð s K ½ + É Ã º e .
IV. + s Ç Â ] Ø
í
H Ã ºô Ç TiO 2 ü < F K5 Å q s : r` ¦ ' ô Ç TiO 2 \ ¦ reverse mi- celle ~ ½ ÓZ O õ solvothermal ~ ½ ÓZ O ` ¦ s 6 x # ½ + Ë$ í % i .
½
+ Ë$ í : r ¸ H 250 ◦ C s 9, 24 r ç ß 1 l x î ß ½ + Ë$ í % i . ½ + Ë$ í ô
Ç TiO 2 { 9 _ ß ¼l H 8 nms 9, ' ô Ç F K5 Å q s : r _
7 á x À Ó\ ' a > \ O s ¸¿ º anatase © s % 3 . ' ô Ç F K5 Å q s
: r É r Mn, Co, Ni, Fe, Cr, Pb, Eu, Tb s 9, y y _ 0 l x
¸ H 2 % s . í H Ã ºô Ç TiO 2 \ " f H 750 ◦ C{ 9 M : rutile © s
Ò q t$ í ÷ &l r # , 850 ◦ C{ 9 M : rutile © Ü ¼ Ð ¢ - a y
s % i Ü ¼ 9, s M : & ñ w n _ ß ¼l H 50nm s % 3
. Mn, Co s : r` ¦ y y ' ô Ç TiO 2 H í H Ã ºô Ç TiO 2 Ð
± ú É r : r ¸\ " f © s % i Ü ¼ 9 & ñ w n ¸ Ø Ô> $ í ©
% i . Eu, Tb s : r s ' ) a TiO 2 H 900 ◦ C{ 9 M : t rutile Ð © s t · ú § ¤Ü ¼ 9 í H à ºô Ç TiO 2 \ q # { 9
_ $ í © ¸ Ö ¼o > z ¤ . Co, Ni, Pb, Eu, Tb s : r s
' ) a TiO 2 \ " f H rutile Ð © o\ ¦ r H : r ¸
\
" f CoTiO 3 , NiTiO 3 , PbTi 3 O 7 , Eu 2 Ti 2 O 7 , Tb 2 Ti 2 O 7 1
p
x _ D h Ðî r o½ + ËÓ ü t s $ 3 Ø ¦ ÷ &% 3 .
P
c p 8 ý ò k >
s
7 Hë H É r 2000 < Ƹ ¸ Â Ò â @ / < Æ § l $ í r < ÆÕ ü t ½ ¨q
\
_ # ½ ¨÷ &% 3 6 £ §.
Y
c p w à U Ø ô
[1] J. Reintjes and M. B. Schultz, J. Appl. Phys. 39, 5254 (1968).
[2] W. T. Geng and Kwang Kim, Phys. Rev. B68, 125203 (2003).
[3] S. J. Tauster, S. C. Fung and R. L. Garten, J. Am.
Chem. Soc. 100, 170 (1978).
[4] D. J. Dwyer, S. D. Cameron and J. Gland, Surf. Sci.
159. 430 (1985).
[5] Shang - Di Mo and W. Y. Ching, Phys. Rev. B51, 13023 (1995).
[6] X. Ding and X. Liu, J. Mater. Res. 13(9), 2556 (1998).
[7] H. Zhang and J. F. Banfield, J. Mater. Res. 15, 437 (2000).
[8] A. Amorelli, J. C. Evans and C. C. Rowlands, J.
Chem. Soc., Faraday Trans. 1, 85, 4031 (1989).
[9] R. J. Knnedy and P. A. Stampe, J. Crystal Growth 252, 333 (2003).
[10] A. Fujishima and K. Honda, Nature 238, 37 (1972).
[11] Yi Hu, H.-L. Tsai and C.-L. Huang, J. Eur. Cer.
Soc. 23, 691 (2003).
[12] Hengzhong Zhang and Jillian F. Banfield, J. Mater.
Chem. 8, 2073 (1998).
[13] Hengzhong Zhang and Jillian F. Banfield, J. Phys.
Chem. B 104, 3481 (2000).
[14] Andrew Burns, G. Hayes, W. Lia, J. Hirvonen, J.
Derek Demareed and S. Ismat Shah, Mater. Sci.
Eng. B 111, 150 (2004).
[15] J. Arbiol, J. Cerda‘ , G. Dezanneau, A. Cirera, F.
Peiro´ , A. Cornet and J. R. Morante, J. Appl. Phys.
92, 854 (2002).
[16] Yu-Hong Zhang and Armin Reller, Mater. Sci. Eng.
C 19, 323 (2002).
[17] S. Mahanty, S. Roy and Suchitra Sen, J. Crystal Growth 261, 77 (2004).
[18] R. Arroyo, G. Cordoba, J. Padilla and V. H. Lara, Mater. Lett. 54, 397 (2002).
[19] S. D. Romano and D. H. Kurlat, Chem. Phys. Lett.
323, 93 (2000).
[20] T. Hyeon, S. S. Lee, H. Park, Y. Chung, and H. B.
Na, J. Am. Chem. Soc. 123, 12798 (2001).
[21] Y. V. Kolen’ko, A. A. Burukhin, B. R. Churagulov and N. N. Oleynikov, Mater. Lett. 57, 1124 (2003).
[22] B. D. Cullity, Elements of X-ray Diffraction, 2nd ed.
(Addison-Wisley, Reading, MA, 1978).
[23] Chemistry : WebPeriodic Elements Table, http://
www.webelements.com/.
Annealing Effect on the Phase Transformation of Metal-Ion-Doped TiO 2 Nanoparticles
Il-Min Kwon and Byung Kee Moon ∗
Department of Physics, Pukyong National University, Busan 608-737
Beong-Sae Lee
Busan Science Academy, Busanjin-gu, Busan 614-103
Chung-Sik Kim
Department of Physics, Pusan National University, Busan 609-735 (Received 25 October 2005, in final form 9 December 2005)
Metal-ion-doped and pure TiO
2nanoparticles were prepared by using reverse micelles and a solvothermal process. Mn, Co, Ni, Fe, Cr, Pb, Eu, and Tb ions were doped into TiO
2nanoparticles, and the amount of doping was 2 % for all the metal ions. The crystalline structures, surface morphologies and phase transitions were investigated according to annealing process by using X- ray diffraction, scanning electron microscopy, and trans mission electron microscopy. Doing with Mn and Co ions was observed to promote a phase transformation from anatase to rutile and enhance the grain growth, whereas doing with Eu and Tb ions was observed to prevent phase the transformation and to inhibit grain growth in the annealing process of the synthesized TiO
2nanoparticles.
PACS numbers: 61.10,N
Keywords: TiO2, Phase transition, Nanoparticle, Mmetal ion doping
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