Rutile V ê s8 ý TiO 2 x ¢ Ä Z Ø­ o ¶  ¥V R Ë õ m Í ö n ÚV R Ë Ä Z ØV Ä

Rutile V ê s8 ý TiO ₂
x ¢ Ä Z Ø­  o ¶  ¥V R Ë õ m Í ö n ÚV R Ë Ä Z ØV Ä



™

») ç . > · + ä : c* å  ^∗

Â

Òí ß –@ /† < Ɠ §
” ¸õ † < Æl Õ ü t† < Æ Ò,  Òí ß – 609-735

T g ` @+ Ö < · T „ ç ¡ 

Â

Òí ß –@ /† < Ɠ § Ó ü t o † < Æõ ,  Òí ß – 609-735



™

»ø ¶ B L · x · ‚ Ð=  ó j u

ô 

Dz D G l œ íõ † < Æt " é ¶ƒ  ½ ¨" é ¶,  Òí ß – 609-735 (2004¸   4 Z 4 1{ 9  ~ à Î6 £ §)

Ø

 ¦µ 1 ÏÓ ü t| 9 `  ¦ TiCl

4

– Ð  6   x # Œ à ºì  r K  ì ø Í6 £ x õ  | › ¸õ & ñ ë ß –Ü ¼– Ð rutile © œ_  TiO

2

” ¸   & ñ ì  r´ ú ˜

`

 ¦ ] j› ¸ % i  . ¢ ¸ô  Ç, à ºì  r K  ì ø Í6 £ x õ & ñ \ " f
 
  H µ 1 Ï\ P  Œ •6   x`  ¦ % 3 ] j l  0 AK  $ “ : r ì  r0 Al \ " f z 

´+ « >`  ¦ ”  ' Ÿ  % i  . “ §ì ø Í x 9  ™ D ¥½ + Ëõ & ñ Ü ¼– Ð ½ + Ë$ í ô  Ç ì  r´ ú ˜“ É r  € ª œô  Ç “ : r • ¸\ " f \ P % ƒo  ÷ &% 3 “ ¦, x-‚    r] X  ì

 r$ 3 l ü < Å Ò „   ‰ & ³p  â `  ¦ s 6   x # Œ   & ñ ½ ¨› ¸ü < { 9  — ¸€ ª œ`  ¦ 8 £ ¤& ñ % i  . TiO

2

ì  r´ ú ˜_    & ñ ½ ¨› ¸  H rutile  © œÜ ¼– Ð S X ‰ “   ÷ &% 3 “ ¦, { 9  — ¸€ ª œ“ É r | › ¸ì  r´ ú ˜õ  600

^◦

C  t  \ P % ƒo   ) a ì  r´ ú ˜\ " f p [ j { 9  [ þ t s  6 £ x

| 9

 ) a + þ AI % i Ü ¼ 9, 800

^◦

C s  © œ_  \ P % ƒo  “ : r • ¸\ " f grain_  ß ¼l   H 7 £ x  % i  . 100

^◦

C_  | › ¸ ì  r´ ú ˜

\

" f \ P % i † < Æ& h Ü ¼– Ð î ß –& ñ ô  Ç TiO

2

_  p [ j½ ¨› ¸\  ¦ È Òõ „   ‰ & ³p  â `  ¦ s 6   x # Œ › ' a¹ 1 Ï % i Ü ¼ 9, { 9  ß ¼l 



 H ½ ¨+ þ As  5 ∼ 10 nm, } Œ •@ /+ þ As  f ”  â 10 nm, U  ´s  45 ∼ 80 nm & ñ • ¸_  ß ¼l – Ð 8 £ ¤& ñ ÷ &% 3  .

PACS numbers: 61.46.+w, 81.20.Ka, 78.30.-j Keywords: Rutile TiO

2

,
” ¸ì  r´ ú ˜, à ºì  r K 

I. " e  ] Ø

þ

j  H, í ß –\ O l Õ ü t_  µ 1 ϲ ú ˜õ  † < Êa  y Œ •7 á x F « Ñ_  : £ ¤$ í `  ¦ > h

‚ 

 “ ¦    H ƒ  ½ ¨ ”  ' Ÿ ÷ &“ ¦ e ” Ü ¼ 9, s \     l ” > r _  F « Ñ ° ú t  3 l w   H Ä ºÃ ºô  Ç l 0 p x$ í F « Ñ\  @ /ô  Ç › ' a d ”  s

 Z  }  t “ ¦ e ”  .  € ª œô  Ç : £ ¤$ í õ  6 £ x6   x$ í s  e ”   H
” ¸ ì  r

´

ú ˜F « Ñl Õ ü t \  @ /K " f• ¸ ´ ú §“ É r ƒ  ½ ¨ ”  ' Ÿ ÷ &“ ¦ e ”   [1–

3]. Ã º ∼ Ã ºz   nm s  _  ç  H{ 9 ô  Ç ß ¼l _ 
” ¸ì  r´ ú ˜ Ó ü t| 9 

“

É r { 9  _  ß ¼l   Œ • f ” \     " é ¶  ü < f  ¨  ô  Ç  1 l x`  ¦

˜

Ðs >  ÷ &  H X <, q ³ ð€  & h s  Z  }  t Ù ¼– Ð é ß –0 A " é ¶  { © œ Z  }

“ É

r ³ ð€   \  -t \  ¦ t  9, „    { (valence band)ü < „  

•

¸„    { (conduction band)  s _  energy band gaps 

&

h

& h  7 £ x   ) a   [4].   " f, Ó ü t| 9  “ ¦Ä »_  F  g† < Æ& h ,  o† < Æ& h  x 9

 „   l & h  $ í | 9  1 p x“ É r s  Qô  Ç Ó ü t$ í Ü ¼– Ð “  K   8¹ ¡ ¤ / å L   ô 

Ç    o
 ± ú ˜  כ Ü ¼– Ð \ V © œ ) a  .

” ¸ß ¼l \ " f # Œ Q t  Ó ü t o & h  : £ ¤$ í s  ² ú ˜ t   H  כ [

þ

t ×  æ 
“   TiO

2

  H, ¨ 8 Š ⠕ 2 ; o& h “   F  g8 ú ¤ B  F « Ñü < „  l 

\

 -t  Ò q tí ß –`  ¦ 0 Aô  Ç I € ª œ„  t , _ þ v • ¸G ' p" f x 9  “ ¦“ : r í ß –™ èG ' p

∗

E-mail: [email protected]

Û

¼ü < Li-battery™ èF  1 p x \  6 £ x6   x s  0 p xô  Ç  כ Ü ¼– Ð · ú ˜ 94 R e ”

  [5–9]. : £ ¤ y ,  ü @‚  `  ¦ é ß –r v   H ´ òõ  Ä ºÃ º # Œ Ñ þ

˜Ò  o î ß –« Ñ6   x F « і Ð  6   x ÷ &  H TiO

2

_  rutile ½ ¨› ¸  H \ P 

%

i † < Æ& h Ü ¼– Ð î ß –& ñ  9,   É r F « Ñ\  q K  Ä »„   © œÃ ºü < Ï ã J ] X

Ò  ¦ s  Z  } “ ¦, l 2 £ §_  f  ¨‚ Ã Ì x 9  ‚ à ÌÒ  o§ 4 s  Ä ºÃ º½ + É ÷  rë ß –   m

  y © œí ß –s 
 y © œ% i l $ í ì  r0 Al \ " f• ¸  o† < Æ& h Ü ¼– Ð î ß –& ñ

# Œ F  g† < Æ6   x  ïh A, c ”  Û ¼e  ¦ o ' (splitter), q ì ø Í   ïh A} Œ • 1

p

x_  F  g# 3 0 Aô  Ç % ò % i \   6   x ÷ &“ ¦ e ”   [10–13]. 6 £ x6   x 0 p x

$ í

s  Z  }“ É r rutile ½ ¨› ¸_  TiO

₂

ì  r´ ú ˜ ] j› ¸~ ½ ÓZ O Ü ¼– Ѝ  H [ O 

`

…s à Ô(sulfate)ü < 9 þ t – Ð s × ¼\  ¦ s 6   xô  Ç / B Ng Ë >Z O  [14, 15], Ã

º\ P ½ + Ë$ í Z O  [16, 17], · ú ˜9  q  s × ¼\  ¦ s 6   xô  Ç _ " t-7 ‹ qZ O  [18, 19] 1 p x s  e ” t ë ß –, “ ¦“ : r, “ ¦· ú š, ì  r W 1 p x_  õ & ñ Ü ¼– Ð
” ¸ ì

 r´ ú ˜ ] j› ¸\  # Q 9¹ ¡ § s  e ”  . TiO

2

  H rutile(tetragonal), anatase(tetragonal), brookite(orthorhombic)_  3t  ½ ¨

›

¸\  ¦ t   H  כ Ü ¼– Ð · ú ˜ 94 R e ”  . { 9 ì ø Í& h Ü ¼– Ð rutile ½ ¨

›

¸  H anatase ½ ¨› ¸\ " f Z  }“ É r \ P % ƒo \  ¦ : Ÿ x K  % 3 `  ¦ à º e ” 



 [20]. þ j  H \   H à º\ P ½ + Ë$ í Z O Ü ¼– Ð 160

^◦

C s  \ " f í  H Ã

º rutile  © œ_  TiO

2

ì  r´ ú ˜\  @ /ô  Ç ˜ Г ¦ [21] e ” Ü ¼
, 4 Ÿ ¤

¸ ú

šô  Ç z  ´+ « >/ B N& ñ `  ¦  5 g    H ë  H ] j& h s  e ”  . Yang 1 p x

“ É

r / B Ng Ë >Z O  x 9  peptizing ~ ½ ÓZ O Ü ¼– Ð  © œ“ : r \ " f rutile ½ ¨› ¸_ 

-541-

TiO

2

ì  r´ ú ˜`  ¦ % 3 % 3 Ü ¼
, anatase ½ ¨› ¸ Ÿ í† < ʝ ) a TiO

2

ì  r

´

ú ˜s % 3   [22]. ¢ ¸ô  Ç  © œ“ : r  & ñ  o\  @ /ô  Ç ƒ  ½ ¨ ÷  rë ß –  m 



, nanoì  r´ ú ˜_  { 9  — ¸€ ª œõ  ß ¼l › ¸] X s  | 9 ×  æ ÷ &“ ¦ 1 " é ¶

&

h “   ì ø ͕ ¸^ ‰ nanorod x 9  nanofiber_  ] j› ¸ü < Õ ª[ þ t_  : £ ¤

$ í

ƒ  ½ ¨\  ´ ú §“ É r › ' a d ” s  | 9 ×  æ ÷ &“ ¦ e ”  .

‘

: r z  ´+ « >\ " f  H TiCl

4

6   xÓ  o`  ¦  6   x # Œ à ºì  r K  ì ø Í 6

£

x`  ¦ : Ÿ x K  \ P % ƒo  “ : r • ¸\    É r   & ñ  o ) a Rutile ½ ¨› ¸_  TiO

2

ì  r´ ú ˜`  ¦ ] j› ¸ % i Ü ¼ 9, ì  r´ ú ˜_  ½ ¨› ¸ x 9  + þ A © œ, Ra- man`  ¦ 8 £ ¤& ñ % i  .

II. ÷ m Ç] M ö + s ÇÊ Ý õ m Í À X Ø8 ý

” ¸ß ¼l _  TiO

₂

ì  r´ ú ˜`  ¦ ] j› ¸ l  0 AK  titanium tetrachloride(TiCl

4

, Aldrich Co.)6   xÓ  o`  ¦ Ø  ¦µ 1 ÏÓ ü t| 9 – Ð 7 £ x À

Óà º(distilled water)\  ¦ 6   x B – Ð  6   x % i  . TiCl

⁴

ü < H

2

O _  à ºì  r K  ì ø Í6 £ x Ü ¼– Ð Ò q t$ í ÷ &  H TiO

2

_  „  ^ ‰& h “    o† < Æ ì

ø Í6 £ x`  ¦ d ”  (1)\ 
 ? /% 3  . d ”  (2) ∼ (4)  H TiCl

4

ü <

H

2

O_  [ j Ò& h “    o† < Æì ø Í6 £ xd ” s  . # Œl " f H

²

O_  H

⁺

0 l x

•

¸ 7 £ x  ½ + Éà º2 Ÿ ¤ TiCl

4

Ó ü t| 9 õ  à ºì  r K  ì ø Í6 £ x s  ¸ ú ˜ { 9 

#

Qè ß – . ë ß –€  • H

⁺

s “ : r € ª œs  & h “ É r  â Ä º\   H d ”  (2)ü < ° ú  s  TiOH

³⁺

ü < ° ú  s    ½ + Ë÷ &# Q e ” # Q à ºì  r K  ì ø Í6 £ x`  ¦ ~ ½ ÓK ô  Ç



.   " f ¢ - a„  ô  Ç à ºì  r K  ì ø Í6 £ x \  _ ô  Ç TiO

₂

ì  r´ ú ˜`  ¦ ]

j› ¸ l  0 AK " f  H  o† < Æ| ¾ ӏ : r ˜ Ð  ´ ú §“ É r € ª œ_  H

2

O  € 9  כ

¹   [23].

Ø

 ¦µ 1 ÏÓ ü t| 9 “   TiCl

₄

  H 7 £ x l · ú šs  Z  } “ ¦ 7 £ x À Óà ºü <_  à º ì

 r K ì ø Í6 £ x \ " f  o† < Æ& h  Ÿ íJ $ ™[ >  \  -t (chemical potential energy)  7 £ x  # Œ €  • 100

^◦

C s  © œ_  \ P s  µ 1 ÏÒ q t ) a  . — ¸

Ž

 H z  ´+ « > õ & ñ “ É r 0

^◦

C\  ¦ Ä »t ½ + É Ã º e ”   H $ “ : r © œu ü < ”  / B N

 ©

œI \ " f þ j@ /ô  Ç  o† < Æ& h  Ÿ íJ $ ™[ >  \  -t (chemical poten- tial energy)\  ¦ ± ú Æ Ò# Q TiO

2

6   xÓ  o`  ¦ 2 r ç ß – 1 l xî ß – “ §ì ø Í x 9 

™

D ¥½ + Ë ô  Ç Ê ê 100

^◦

C \ " f 6r ç ß – 1 l xî ß – | › ¸r &  | › ¸  ) a ì  r

´ ú

˜`  ¦ ] j› ¸ % i  .

T iCl

4

+ 2H

2

O → T iO

2

+ 4H

⁺

+ 4Cl

⁻

(1)

T iCl

4

+ H

2

O ↔ T iOH

³⁺

+ H

⁺

+ 4Cl

⁻

(2)

T iOH

³⁺

↔ T iO

²⁺

+ H

⁺

(3)

T iO

²⁺

+ H

2

O ↔ T iO

2

(hydrous) + 2H

⁺

(4)

TiO

2

ì  r´ ú ˜_    & ñ ½ ¨› ¸, ³ ð€  + þ A © œ x 9  Raman ”  1 l x — ¸× ¼

\

 ¦ 8 £ ¤& ñ l  0 AK  DAT   õ – РÒ'  “ : r • ¸\    É r l Ö  ¦ l 

Fig. 1. DTA analysis of TiO

₂

nano powder with varying temperature.

 

 o\  ¦ “ ¦ 9 # Œ \ P % ƒo  “ : r • ¸ › ¸| `  ¦ y Œ •y Œ • 400, 600, 800, 1000

^◦

C – Ð % i  .

|

› ¸  ) a ì  r´ ú ˜“ É r y Œ •y Œ •_  \ P % ƒo  “ : r • ¸\    É r    o\  ¦ › ' a

¹

1 Ï l  0 AK  \ P r   ì  r$ 3 Z O (differential thermal analysis, DTA) Ü ¼– Ð \ P % ƒo  “ : r • ¸› ¸| `  ¦ S X ‰ “   % i  . \ P % ƒo  “ : r • ¸

›

¸| \    É r   & ñ $ í “ É r Cu Kα ‚  `  ¦  6   x   H x-‚    r] X  l

(XRD, Rigaku RAD III)Ü ¼– Ð 8 £ ¤& ñ % i “ ¦, { 9   — ¸€ ª œ x 9

 ß ¼l   H Å Ò  „    ‰ & ³p  â (SEM, Hitachi S-4200)õ  È Ò õ

+ þ A „    ‰ & ³p  â (TEM, Jeol Jem 2010)Ü ¼– Ð › ' a¹ 1 Ï % i 



.

{ 9

ì ø Í& h Ü ¼– Ð TiO

2

_  DTA   õ   H 450

^◦

C s  © œ_  \ P % ƒ o

 “ : r • ¸ › ¸| \ " f ï  r î ß –& ñ  © œ“   TiO

₂

_  anatase © œs 
 

 9 €  • 800

^◦

C \ " f  H î ß –& ñ ô  Ç rutile © œs  + þ A$ í ÷ &  H  כ Ü ¼

–

Ð · ú ˜ 94 R e ”   [24]. Fig. 1“ É r | › ¸  ) a ì  r´ ú ˜_  “ : r • ¸    o

\

   É r  © œ    o x 9  # Œ Q t  \ P & h : £ ¤$ í    o\  ¦ 8 £ ¤& ñ 

Fig. 2. X-ray powder patterns of TiO

2

nano powders

with different annealing conditions at (a) dried powder

(100

^◦

C), (b) 400

^◦

C, (c) 600

^◦

C, (d) 800

^◦

C, and (e)

1000

^◦

C, 4 : Rutile phase of TiO

2

.

Fig. 3. The results of Raman spectroscopy for TiO

2

nano powders annealed at (a) dried powder (100

^◦

C), (b) 400

◦

C, (c) 600

^◦

C, (d) 800

^◦

C, (e) 1000

^◦

C, and (f) anatase phase.

l

 0 Aô  Ç DTA ì  r$ 3   õ s  . „  ì ø Í& h Ü ¼– Ð \ P & h : £ ¤$ í    o _  l Ö  ¦ l  f ” ‚  \  ¾ ú š> 
 z Œ ¤Ü ¼ 9, s  כ “ É r ì  r´ ú ˜_ 

“

: r • ¸   o\  @ /ô  Ç % ò † ¾ Ós   _  \ O 6 £ §`  ¦ _ p ô  Ç . €  • 450

◦

C ü < 800

^◦

C “ : r • ¸½ ¨ç ß –\ " f €  •ç ß –_  l Ö  ¦ l     o  H (d ”  1) \ " f ˜ Г    ü < ° ú  s  à ºì  r K  ì ø Í6 £ x Ê ê ï ß –# Œ Ó ü t| 9 “   H

⁺

, Cl

⁻

s “ : r[ þ t_  “ : r • ¸   o\    É r \ P ì  r K  ì ø Í6 £ x_  l # Œ

–

Ð K $ 3  % i  .

Fig. 2  H Å Ò# Q”   \ P % ƒo  “ : r • ¸ › ¸| \    É r XRD 8 £ ¤& ñ

 

õ s  . TiO

²

_  rutile © œs  800

^◦

C \ " f 1000

^◦

C ½ ¨› ¸

\

" f \ P % ƒo  “ : r • ¸ 7 £ x ½ + Éà º2 Ÿ ¤ x-‚    r] X x ß ¼ y © œ• ¸

&

t   H  כ `  ¦ · ú ˜ à º e ” % 3  .

|

› ¸  ) a ì  r´ ú ˜ x 9  \ P % ƒo  “ : r • ¸   o\  _ K " f TiO

²

_  anatase x 9  brookite  © œõ  ° ú  “ É r  © œ    o x 9  ï  r î ß –& ñ ô  Ç  © œ s


 
t  · ú §“ ¦ \ P % i † < Æ& h Ü ¼– Ð  © œ î ß –& ñ & h “   í  H à ºô  Ç rutile  © œ(JCPDS Card Files, No. 21-1276, a = 0.4593 nm, c = 0.2959 nm)ë ß –s 
 z Œ ™`  ¦ · ú ˜ à º e ” % 3  . s  כ

“ É

r Ø  æì  rô  Ç à ºì  r K  ì ø Í6 £ x õ & ñ \  _ K  î ß –& ñ & h “   rutile  © œ

Fig. 4. SEM images of TiO

2

nano powders annealed at (a) dried powder (100

^◦

C), (b) 400

^◦

C, (c) 600

^◦

C, (d) 800

^◦

C, and (e) 1000

^◦

C.

Fig. 5. TEM images of rutile phase TiO

2

nano powder synthesized by hydrolysis reaction drying process at 100

◦

C.

_

 TiO

₂

 Ò q t$ í ÷ &% 3 6 £ §`  ¦ _ p ô  Ç . \ P % ƒo  “ : r • ¸ 7 £ x 

½ +

É Ã º2 Ÿ ¤  r] X x ß ¼_  þ j@ / ì ø Íu ; Ÿ ¤“ É r  Œ • t  9, s   H   & ñ



o & ñ • ¸ Z  }  t  
, ì  r´ ú ˜_    & ñ w n  ß ¼l  7 £ x ô  Ç  כ Ü

¼– Ð [ O " î ½ + É Ã º e ”  .

Raman ”  1 l x — ¸× ¼ 8 £ ¤& ñ Ü ¼– Ð Ò q t$ í  ) a Ó ü t| 9 _   o† < Æ& h    

½ +

Ë x 9  p [ j½ ¨› ¸ › ' a¹ 1 Ï x 9     o 1 p x`  ¦ & ñ S X ‰ >  · ú ˜ à º e ” 



. { 9 ì ø Í& h Ü ¼– Ð TiO

2

_    & ñ  © œ_  7 á x À Ó\ " f brookite  © œ_  Raman ”  1 l x — ¸× ¼  H 153 cm

⁻¹

, anatase  © œ_  Raman   õ 



 H 645, 512, 395 Õ ªo “ ¦ 143 cm

⁻¹

õ  rutile  © œ_  Raman

”

 1 l x — ¸× ¼  H 612, 447 Õ ªo “ ¦ 232 cm

⁻¹

Ü ¼– Ð ˜ Г ¦ ÷ &# Q& ’ 



 [24]. ‘ : r z  ´+ « >\ " f  H p [ j½ ¨› ¸ x 9  s “ : r[ þ t_   o† < Æ& h    

½ +

Ë © œI \  ¦ S X ‰ “   l  0 AK  \ P % ƒo  “ : r • ¸ › ¸| \    É r TiO

2

ì

 r´ ú ˜_  Raman ”  1 l x — ¸× ¼ 8 £ ¤& ñ   õ \  ¦ Fig. 3 \ " f
 ? /

% 3  .

|

› ¸ì  r´ ú ˜\ " f 1000

^◦

C  t  \ P % ƒo   ) a ì  r´ ú ˜[ þ t_  Raman

”

 1 l x — ¸× ¼  H rutile  © œ_  x ß ¼ë ß – › ' a8 £ ¤ ÷ &% 3 “ ¦, anatase © œ_ 

”

 1 l x — ¸× ¼  H › ' a8 £ ¤ ÷ &t  · ú §€ Œ ¤Ü ¼ 9, x ß ¼_  [ jl ü < 0 Au – Ð

˜

Ð  | › ¸ ì  r´ ú ˜\ " f_    & ñ + þ AI   _  ° ú Æ Ò# Q”    כ Ü ¼

–

Ð  € Œ • ) a  . s  Qô  Ç   õ   H x-‚    r] X ì  r$ 3 \ " f $ “ : r \ 

"

f ½ + Ë$ í  ) a ì  r´ ú ˜_  x ß ¼_  þ j@ / ì ø Íu ; Ÿ ¤ s  “ ¦“ : r \ P % ƒo   ) a ì

 r´ ú ˜˜ Ð   H s Ä »   & ñ $ í s  ± ú “ É r X <" f l “  ô  Ç l  ˜ Ð



  H
” ¸ß ¼l _  ì  r´ ú ˜ M :ë  H“    כ Ü ¼– Ð  « Ñ ÷ &# Q”   .

Fig. 6. (a) Observed growth habit of TiO

₂

, (b) Rutile of

TiO

₂

.

Fig. 4“ É r \ P % ƒo  “ : r • ¸ › ¸| \    É r { 9  _  ß ¼l  x 9  — ¸€ ª œ

`

 ¦ › ' a¹ 1 Ï % i  . à ºì  r K  ì ø Í6 £ x Ü ¼– Ð þ j7 á x | › ¸  ) a rutile © œ _

 TiO

₂

  H p [ jô  Ç { 9  [ þ t s  " f– Ð 6 £ x| 9 ÷ &# Q e ” “ ¦, 600

^◦

C

\ P

% ƒo  “ : r • ¸\ " f• ¸ { 9  _  ß ¼l  x 9  — ¸€ ª œ_     o \ O   H 6

£ x| 9  ) a p [ jô  Ç { 9  [ þ t`  ¦ › ' a8 £ ¤ ½ + É Ã º e ”  . Õ ª Q
 800

^◦

C x 9

 1000

^◦

C \ " f \ P % ƒo   ) a ì  r´ ú ˜“ É r p [ jô  Ç { 9  [ þ t_  ß ¼l 

 7 £ x  % i “ ¦,   & ñ  o  ) a grain s  & f ” `  ¦ › ' a8 £ ¤ ÷ &% 3  .

s

 כ “ É r Fig. 2_  x-‚    r] X ì  r$ 3    õ \ " f \ P % ƒo  “ : r • ¸

7

£

x ½ + Éà º2 Ÿ ¤  r] X x ß ¼ y © œ• ¸ 7 £ x   9 ì ø Íg Ë :; Ÿ ¤ s  ×  ¦ # Q× ¼



 H  כ õ  q “ §K  ^  ¦ M :, ì  r´ ú ˜_    & ñ $ í õ    & ñ w n _  ß ¼l 

–

Ð 7 £ x ô  Ç  כ Ü ¼– Ð ¸ ú ˜ { 9 u  “ ¦ e ”  .

Fig. 5(a)  H \ P % ƒo  õ & ñ `  ¦  u t  · ú §“ É r \ P % i † < Æ& h Ü ¼– Ð î

ß –& ñ ô  Ç TiO

₂

_  rutile  © œ\  @ /ô  Ç { 9  _  — ¸€ ª œõ  ß ¼l \  ¦ È

Òõ „   ‰ & ³p  â  ”  Ü ¼– Ð › ' a¹ 1 Ïô  Ç Õ ªa Ë >s  . r « э  H 100

◦

C \ " f | › ¸ô  Ç ì  r´ ú ˜_  p [ j   & ñ + þ A`  ¦ S X ‰ “   l  0 AK  ‚  

× þ

˜÷ &% 3  .

Fig. 5(b) \ " f { 9  — ¸€ ª œ“ É r  Òì  r& h Ü ¼– Ð ½ ¨+ þ A x 9  } Œ •@ / + þ

A — ¸€ ª œ`  ¦ & ’  . (110)   ×  ¦ Á º] (  H } Œ •@ / » ¡ ¤ ~ ½ ӆ ¾ Óõ 

¨ î

' Ÿ  > 
 z Œ ¤“ ¦, [001]~ ½ ӆ ¾ Ó_  $ í  © œ5 Å q • ¸  H [110]~ ½ ӆ ¾ Ә Ð



   É r  כ Ü ¼– Ð [ O " î ½ + É Ã º e ”  . s  כ “ É r Fig. 6(a) \ 
 

 · p  כ % ƒ! 3  „  + þ A& h “   rutile  © œs  } Œ •@ /— ¸€ ª œÜ ¼– Ð $ í  © œ 



 H : £ ¤$ í M :ë  H“    כ Ü ¼– Ð s K ½ + É Ã º e ”   [25]. } Œ •@ / — ¸€ ª œ _

 rutile © œ“ É r c-» ¡ ¤ ~ ½ ӆ ¾ ÓÜ ¼– Ð $ í  © œ÷ &% 3 Ü ¼ 9, Fig. 6(b)  H (001)€  \ " f TiO

⁶

¼ 1 π  ^ ‰ ƒ    – Ð ½ ¨$ í  ) a rutile ½ ¨› ¸

y

Œ

•y Œ •_  ¼ 1 π  ^ ‰_  — ¸" fo  Òì  r \   ŠҘ Ð 9 c-» ¡ ¤ ~ ½ ӆ ¾ ÓÜ ¼– Ð



Ø Ô>  $ í  © œ÷ &# Q } Œ •@ /— ¸€ ª œs 
 
  H  כ Ü ¼– Ð [ O " î ½ + É Ã º e ”

 . { 9  ß ¼l   H ½ ¨+ þ A_   â Ä º f ”  â 5 ∼ 10 nm, g Ë > © œ+ þ A s

 10 nm, U  ´s  45 ∼ 80 nm & ñ • ¸% i  .

III. + s Ç Â ] Ø

Ø

 ¦µ 1 ÏÓ ü t| 9 – Ð TiCl

4

`  ¦ s 6   x # Œ à ºì  r K  ì ø Í6 £ x õ & ñ ë ß –Ü ¼

–

Ð
” ¸ß ¼l _  TiO

₂

ì  r´ ú ˜`  ¦ ] j› ¸ % i  . Z  }“ É r “ : r • ¸_ 

\ P

% ƒo \  _ K  ] j› ¸÷ &  H rutile  © œ_  TiO

₂

\  q K , \ P % ƒ o

 õ & ñ `  ¦  u t  · ú §“ ¦ ] j› ¸  ) a ì  r´ ú ˜“ É r í  H à ºô  Ç rutile © œ_  TiO

₂

ì  r´ ú ˜s  ” > r F † < Ê`  ¦ p [ j½ ¨› ¸ì  r$ 3 , + þ A © œì  r$ 3 , Raman

”

 1 l x — ¸× ¼ 8 £ ¤& ñ Ü ¼– РÒ'  S X ‰ “   % i  . TiO

2

” ¸ì  r´ ú ˜_ 

 

& ñ — ¸€ ª œ“ É r | › ¸ô  Ç ì  r´ ú ˜\ " f c-» ¡ ¤ ~ ½ ӆ ¾ Ó_  } Œ •@ / — ¸€ ª œÜ ¼

–

Ð $ í  © œ÷ &% 3 Ü ¼ 9, { 9  ß ¼l   H 5 ∼ 10 nm ß ¼l % i  .

P c

p 8 ý ò k >

‘

: r ƒ  ½ ¨  H † < ÆÕ ü t”  < É ª F é ß – í  H à ºl œ íƒ  ½ ¨Õ ªÒ  ¨(KRF- 2002-070-C00033)_  t " é ¶ Ü ¼– Ð Ã º' Ÿ ÷ &% 3 6 £ §.

Y c

p w Š à U Ø ”  ô

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Physical Properties and Synthesis of a Rutile Phase TiO ₂ Nanopowder

S.-J. Kim and S.-Y. Jeong

^∗

School of Nano Science and Technology, Pusan National University, Busan 609-735

H.-J. Lee and S. A. Lee

Department of Physics, Pusan National University, Busan 609-735

J. P. Kim and C. R. Cho

Busan Branch, Korea Basic Science Institute, Busan 609-735 (Received 1 April 2004)

Rutile phase TiO

2

nanocrystals were synthesized by using only a hydrolysis reaction and dry process. To exclude the effects of an exothermic reaction during hydrolysis, we performed the process at low temperature, nearly 0

^◦

C. The powder, which had been synthesized only by mixing and stirring, was heat treated at several temperatures from 100

^◦

C to 1000

^◦

C. The structure and the morphology were investigated through the X-ray diffraction and scanning electron microscop, respectively. Although the temperatures of heat treatment were different, the structures of all powders had the same rutile phase. The particles were agglutinated in the powders which had been heat treated from 100

^◦

C to 600

^◦

C and the grain sizes were measured in the powders annealed above 800

^◦

C. Finally, we show that rutile TiO

2

, annealed at 100

^◦

C has thermodynamically stable state and that the diameters and the length of nano-particles are in the ranges of 5 ∼ 10 nm and 45 ∼ 80 nm, respectively.

PACS numbers: 61.46.+w, 81.20.Ka, 78.30.- Keywords: Rutile TiO

2

, Nanoparticle, Hydrolysis

∗

E-mail: [email protected]