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(1)

N-] k ù  ¹ Å õ m Çy ¢õ u § P c tÀ W ¥ $ [ Ì ¦ R8 ý Bi 2 Te 3 8 ý ° ‚ Ǐ ¹ ŗ ¤V R Ë

<

K¦ _ ô >

C

F @ /† < Ɠ § õ † < Æl Õ ü t@ /† < Æ F g„   Ó ü to † < Æõ , @ /„   302-735 (2008¸   6 Z 4 27{ 9  ~ à Î6 £ §)

‘ :

r ƒ  ½ ¨\ " f  H Bi

2

Te

3

€ ª œ Ä ºÓ ü t½ ¨› ¸\ " f \ P „  $ í 0 p x`  ¦   & ñ   H Seebeck > à ºü < „  l „  • ¸• ¸[ þ t\  @ / ô



Ç € ª œ y Œ ™F K´ òõ ü < grain ´ òõ – Ð  Œ •6   x   H Ä ºÓ ü t; Ÿ ¤ ß ¼l \  @ /ô  Ç \ P „  • ¸• ¸\  ¦ “ : r• ¸   o\     ¶ ú ˜( R‘ : r



. “ ¦& ñ  ) a x 9 • ¸\ " f € ª œ y Œ ™F K´ òõ – Ð “   # Œ Seebeck > à º  H & t   „  l  „  • ¸• ¸  H € ª œ y Œ ™F K ´ òõ \  ß

¼>  % ò † ¾ Ó`  ¦ ~ à Ît  · ú §  H .   " f $  " é ¶ ½ ¨› ¸_  $ í 0 p xt à º 7 £ x  H € ª œ y Œ ™F K´ òõ – Ð “  ô  Ç Seebeck >  Ã

ºü < grain ´ òõ – Ð “  ô  Ç \ P „  • ¸• ¸_  > h‚  Ü ¼– Ð s À Ò# Qt  9, é ß –  & ñ õ   H  Ø Ô>  “ : r• ¸ 7 £ x½ + Éà º2 Ÿ ¤ &  t

  H ‰ & ³ © œ`  ¦ ˜ Ð# Œ ï  r .

PACS numbers: 66.70.+f, 68.60.D

Keywords: \P&h“ :£¤$í, \P„ $í0pxtú, \P„•¸•¸, \Pl„§4, ß¼l´òõ, €ªœyŒ™FK´òõ

I. " e  ] Ø



©

œ“ : r\ " f  Œ •1 l x   H \ P „  ™ è  (thermoelectric de- vices)\  ¦ z  ´‰ & ³ l 0 AK , š ¸A „   Ò'  (Bi,Sb,Te,Se)_  ¿ º- [

j כ ¹™ è[ þ t– Ð ½ ¨$ í  ) a ™ D ¥½ + ËÓ ü t (alloys)_  \ P & h “   : £ ¤$ í [ þ t

\

 @ /K  V , o  ƒ  ½ ¨÷ &# Q M ® o  [1–15]. { 9 ì ø Í& h Ü ¼– Ð \ P „  

™

è _  $ í 0 p x“ É r \ P „   $ í 0 p xt à º (Thermoelectric figure of merit)  Â ÒØ ԍ  H ZT=S

2

σ/κ (S− \ P l „  § 4  (Seebeck co- efficient), σ− „  l  „  • ¸• ¸ (electric conductivity), κ− \ P 

„



• ¸• ¸ (thermal conductivity))\  _ K    & ñ ÷ &  HX <, s 

$ í

0 p xt à º\  ¦ Z  }s l  0 AK   o½ + ËÓ ü t[ þ t`  ¦  € ª œô  Ç \ P & h “   › ¸

|

[ þ t\ " f ] j Œ •K  M ® o . Õ ª ×  æ\  @ /³ ð& h “   ] j Œ • ~ ½ ÓZ O s 

\ P

â ì2 £ § ~ ½ ÓZ O  (traveling heater method)õ  [16] ™ è  ~ ½ ÓZ O  (hot-pressing methods) [8, 11] s  . ™ è  Z O `  ¦  6   x   H ì



r´ ú ˜  F K (Powder metallurgy) “ É r \ P „   Ó ü t| 9 _  @ /| ¾ Ó] j



Œ

•\  e ” # Q" f y © œ§ 4 ô  Ç • ¸½ ¨s  9, ™ è  ÷ &  H Ó ü t| 9 _  p [ j½ ¨

›

¸\  ¦ ] j# Q   H  כ “ É r \ P „  $ í 0 p xõ  f ”    ) a .

þ

j  H\  (Bi

1−x

Sb

x

)

2

Te

3

“ ¦6   x^ ‰ (solid solution), ™ è  

^

‰,    & ñ \  @ /ô  Ç \ P & h “   : £ ¤$ í \  @ /K " f ™ D ¥½ + ˝ ) a í ß –ê ø Í — ¸ 4

S

q`  ¦ Ÿ í† < Ê   H „  • ¸@ /_  — ¸4 S q`  ¦  6   xK " f  € ª œô  Ç x_  $ í ì



rq \  @ /K " f ƒ  ½ ¨ % i  . ] j Œ • ) a Ó ü t| 9 \ " f þ j& h _  $ í 0

p

xt à º\  ¦ ° ú   H › ¸| [ þ t\  @ /K " f ƒ  ½ ¨ % i   HX <, $ í 0 p xt  Ã

º\  ¦ Z  }s l  0 AK " f  © œ ×  æכ ¹ô  Ç כ ¹™ è „   _  x 9 • ¸\  ¦

›

¸] X    H  כ s  9, s  כ “ É r l ” > r_  r « Ñ ] j Œ • ~ ½ ÓZ O Ü ¼– Ѝ  H B

Ä º # Q 9î  r  Œ •\ O s    H  כ s  · ú ˜ 94 R e ”  . Õ ªA " f : £ ¤

E-mail: je [email protected]

Z

>

y  ™ è  ^ ‰_   â Ä º\  \ P % ƒo \  ¦ : Ÿ xô  Ç x 9 • ¸› ¸] X õ   8Ô  ¦

#

Q grain ß ¼l \  ¦ › ¸] X  # Œ \ P „  • ¸• ¸\  ¦ ± ú Æ Ò# Q $ í 0 p xt à º

\



¦ Z  }s  9  H r • ¸ ´ ú §s  ' Ÿ K & ’ % 3   [17]. \ P „   $ í 0 p x : £ ¤

$ í

\ " f grain ´ òõ \  ¦ ˜ Ð 9€   Fig. 1\ " fü < ° ú  s  grain ß ¼ l

 1 µm s    H ÷ &# Q † < Ê`  ¦ ^  ¦ à º e ”  . Õ ª Q  grain ß

¼l _  › ¸] X – Ð ] j Œ • ) a    & ñ ™ è _   â Ä º \ P l „  § 4 s 



Œ

• t   H ì ø Í@ /‰ & ³ © œÜ ¼– Ð “   # Œ ™ è – Ð_  z  ´‰ & ³u  b  

#

Q& ’ % 3  .   " f $  " é ¶ ½ ¨› ¸\ – Ð_  \ P & h  : £ ¤$ í _  ƒ  ½ ¨

 ×  æכ ¹ >  ÷ &% 3 Ü ¼ 9, þ j  H\   H  ” ¸ ½ ¨› ¸_  \ P „  ™ è 

\

 @ /ô  Ç ƒ  ½ ¨  Ö ¸µ 1 Ï >  ”  ' Ÿ ÷ &“ ¦ e ”   [7,12–14,18,19].

‘ :

r ƒ  ½ ¨\ " f  H grain ´ òõ – Ð  Œ •6   x   H Ä ºÓ ü t; Ÿ ¤ ß ¼l \ 

@

/ô  Ç \ P „  • ¸• ¸_     o\  ¦ l Õ ü t # Œ $  " é ¶ ½ ¨› ¸\ " f_  $ í 0

p

x† ¾ Ó © œ`  ¦ l @ /½ + É Ã º e ” 6 £ §`  ¦ ] jr ô  Ç .  8    Bi

2

Te

3

_

 € ª œ Ä ºÓ ü t½ ¨› ¸\ " f “ : r• ¸   o\    É r \ P & h “   : £ ¤$ í _    



o\  ¦ › ¸  # Œ $  " é ¶ ½ ¨› ¸\ " f_  $ í 0 p xt à º   & ñ ÷ &  H

% i

† < ƛ ' a> \  ¦ › ¸  “ ¦, € ª œ y Œ ™F K´ òõ – Ð “  ô  Ç \ P „   $ í 0 p x t

à º_  : £ ¤$ í `  ¦ ¶ ú ˜( R˜ Ð ’ x .

II. T  Â ] Ø

Ä

ºÓ ü tõ   © œ# 4 _  U  ´s  y Œ •y Œ • wü < b\  ¦ ° ú   H € ª œ  Ä ºÓ ü t½ ¨

›

¸_  \  -t  ï  r0 A[ þ t`  ¦ Kr¨onig-Penney — ¸4 S q`  ¦  6   xK " f



6 £ §õ  ° ú  s  > í ß – ) a  [19].

²

n

(k

x

, k

y

) = ~

2

k

x2

2m

x

+ ~

2

k

y2

2m

y

+ n~

2

π

2

2m

z

d (1)

-157-

(2)

PbTe F « Ñ  6   x÷ & 9, Ä ºo [ þ t_  > í ß – — ¸4 S q_   â Ä º ¿ º a

\  ¦ b = 100 ˚ ¼– Ð & ñ Ù þ ¡ . ^  ¦ç ¼ë ß – ~ ½ Ó& ñ d ” \  y Œ ™û Z r  ç

ß

–   H Z O  (the relaxation-time approximation) `  ¦ s 6   x

€   x ~ ½ ӆ ¾ ÓÜ ¼– Ð Ã º5 Å x÷ &  H Ó ü to & h “  >  à º[ þ t“ É r  6 £ §õ  ° ú   s

 Å Ò# Q”    [19].

σ = e

2

m

2d

k

B

T

πa~

2

G

1

) (2)

S = k

B

e

£ G

2

) − ζ

¤

(3)

G

n

= Z

0

τ

e

(x)y

n

exp(y − ζ

)

[1 + exp(y − ζ

)]

2

dy (4)

#

Œl " f ζ

kζ

BT

  H Ä »• ¸ ) a  o† < Æ& h “   Ÿ íJ $ ™[ >  (` …Ø Ôp  \ 



-t )s “ ¦, y = ~ω/k

B

T – Ð & ñ _ ÷ &“ ¦, k

b

  H ^  ¦ç ¼ë ß –  © œÃ º s

 . € ª œ/ B N_  à º5 Å x > à º[ þ t_   â Ä º  H ζ

\  (−ζ

− E

g

) – Ð

@

/^ ‰   H  כ õ  ° ú   . E

g

  H Bi

2

Te

3

Ó ü t| 9 _   ½ ™× ¼Ì “ s“  X <,

“ :

r• ¸_  † < Êà º– Ð  6 £ §õ  ° ú  “ É r › ' a> d ” `  ¦ ° ú   H . E

g

(T ) ≈ E

g

(Bi

2

Te

3

) −1.4 × 10

−4

T (eV) [20].





 \  @ /ô  Ç \ P „  • ¸• ¸  H  6 £ §õ  ° ú  s  Å Ò# Q”    [21].

κ

ph

= k

B

2

v ( k

B

θ

~ )

3

(I

1

+ I

22

I

3

) (5)

#

Œl " f I

1

, I

2

, I

3

  H  6 £ §õ  ° ú  s  Å Ò# Q”   .

I

1

= Z

θ/T

0

τ

c

y

4

exp(y) [exp(y) − 1]

2

dy I

2

= β

Z

θ/T

0

τ

c

τ

u

y

4

exp(y)

[exp(y) − 1]

2

dy (6)

I

3

= β Z

θ/T

0

1

τ

u

(1 − β τ

c

τ

u

) y

4

exp(y)

[exp(y) − 1]

2

dy (7)

#

Œl " f θ  H Debye “ : r• ¸s  . τ

u−1

  H Umklapp Ÿ í 7 H í ß –ê ø Í Ò



¦s “ ¦, τ

c−1

  H grain ´ òõ \  ¦ Ÿ í† < Ê   H „  ^ ‰ Ÿ í 7 H í ß –ê ø ÍÒ  ¦

`



¦    · p .

III. Ä Z ØV ÄÊ Ý ‚ º8 ý

>

í ß –\ " f  6   x ) a Bi

2

Te

3

€ ª œ Ä ºÓ ü t ½ ¨› ¸_  „   ü < € ª œ/ B N

\

 @ /ô  Ç Ä »´ ò| 9 | ¾ Ó[ þ t“ É r  © œ“ : r\ " f m

e

= 0.58 m

0

õ  m

h

= 1.07 m

0

Ü ¼– Ð 2 [Ù þ ¡“ ¦, m

0

  H  Ä »„    | 9 | ¾ Ó`  ¦    · p  [1, 2]. 0 A_    à º[ þ t`  ¦  6   xK " f “ : r• ¸    o\    É r \ P „  

Fig. 1. Thermal conductivity of Bi

2

Te

3

alloys for differ- ent grain sizes at 300 K.

Fig. 2. Thermal conductivities of quantum well with a width 1 µm and a single crystal of Bi

2

Te

3

for as a function of temperature.

:

£

¤$ í [ þ t`  ¦ à ºu & h Ü ¼– Ð > í ß – % i  . Fig. 2  H Ä ºÓ ü t ; Ÿ ¤s  1 µm\  ¦ ° ú   H Bi

3

Te

3

€ ª œ Ä ºÓ ü t ½ ¨› ¸ü < bulk \  @ /ô  Ç \ P „  

•

¸• ¸\  ¦ “ : r• ¸    o\       Í Ç x . ¿ º > _  \ P „  • ¸• ¸  H

“ :

r• ¸ 7 £ x\    É r  o† < Æ& h  Ÿ íJ $ ™[ > _     o– Ð “   # Œ \ P „  

•

¸• ¸  Œ • ”   . € ª œ Ä ºÓ ü t ½ ¨› ¸_   â Ä º\   H  © œ# 4 õ  Ä º Ó

ü

t  s \  y Œ ™F K÷ &  H Ÿ í 7 H_  ´ òõ \  ¦ grain ´ òõ – Ðë ß –  À Ò

% 3

 .   " f € ª œ  Ä ºÓ ü t\ " f_  „  ^ ‰ Ÿ í 7 H Ø  æ[  tÒ  ¦“ É r é ß –  

&

ñ

 â Ä º_  Ÿ í 7 H Ø  æ[  tÒ  ¦\  grain õ  Ÿ í 7 Hõ _  Ø  æ[  t ´ òõ ë ß –

`



¦ “ ¦ 9K " f > í ß –ô  Ç   õ s  9, Õ ªa Ë > © œ\ " f ¸ ú ˜ 2 ; & h ‚  Ü ¼

–

Ð ³ ðr  % i  .  © œ“ : r\ " f é ß –  & ñ _   â Ä º  H 1.7 W/K m

&

ñ

• ¸“  X <, € ª œ Ä ºÓ ü t_   â Ä º  H  _  1 W/K m & ñ • ¸– Ð € ª œ



y Œ ™F K´ òõ – Ð “   # Œ \ P „  • ¸• ¸  Œ • f ” `  ¦ · ú ˜ à º e ”  .

€ ª

œ  y Œ ™F K´ òõ – Ð “  ô  Ç  ½ ™× ¼ ½ ¨› ¸ü < „    x 9 • ¸ì  rŸ í_    



o Õ ªo “ ¦ grain ´ òõ – Ð “   # Œ € ª œ Ä ºÓ ü t ½ ¨› ¸_  \ P „  • ¸

•

¸ ß ¼>   Œ • f ” `  ¦ · ú ˜ à º e ”  .

(3)

Fig. 3. Resistivity and Seebeck coefficient for different well widths of Bi

3

Te

3

quantum well as a function of tem- perature.

Fig. 3“ É r  € ª œô  Ç ß ¼l _  € ª œ Ä ºÓ ü t ; Ÿ ¤`  ¦ ° ú   H ½ ¨› ¸\ " f

„



 _  q $ † ½ Óõ  \ P l „  § 4 \  @ /ô  Ç “ : r• ¸_     o\  ¦    Í

Ç

x . Fig. 3(a)\ " f ˜ Ð# Œt 1 p ws  “ : r• ¸ Z  }Ü ¼€   „   [ þ t õ

 Ÿ í 7 Hõ _  Ø  æ[  t ´ òõ  & t l  M :ë  H\  q $ † ½ Ós  & t 





H ‰ & ³ © œ`  ¦ ^  ¦ à º e ” t ë ß –, Ä ºÓ ü t ; Ÿ ¤_     o\  @ /ô  Ç q $ † ½ Ó _

    o  H Z > – Ð s  ß ¼>     t  · ú §  H . s  כ “ É r € ª œ



 y Œ ™F K´ òõ  „   ü < Ÿ í 7 H[ þ t_  í ß –ê ø Í´ òõ \  Z > – Ð % ò † ¾ Ó

`



¦ Å Òt  · ú §  H   H  כ `  ¦ > p wô  Ç . Fig. 3(b)  H  € ª œô  Ç € ª œ  Ä

ºÓ ü t ; Ÿ ¤`  ¦ ° ú   H ½ ¨› ¸\  @ /ô  Ç \ P „  § 4 _  “ : r• ¸\  @ /ô  Ç    o

\



¦    · p . “ : r• ¸ Z  }`  ¦Ã º2 Ÿ ¤ Ø  æ[  t´ òõ  ´ ú § 4 R" f “ : r

•

¸ s – Ð “  ô  Ç „   [ þ t_  s 1 l xs  # Q 90 >t l  M :ë  H\  \ P 

„



§ 4 s  & f ” `  ¦ · ú ˜ à º e ”  . ¢ ¸ Ä ºÓ ü t ½ ¨› ¸  Œ •`  ¦Ã º2 Ÿ ¤ „  

_  \  -t  ï  r0 A Z  }“ ¦, „   ü < € ª œ/ B N_  ç ß –  • ¸ Y O # Q t

 9, ± ú “ É r \  -t  0 Au \ " f  o† < Æ& h “   Ÿ íJ $ ™[ > `  ¦ ° ú   H .

7

£

¤, ° ú  “ É r „    x 9 • ¸  © œ\ " f „   [ þ t_  y Œ ™F Ks  & t €   € ª œ



Ä ºÓ ü t ½ ¨› ¸_   8  H ”  $ í ì ø ͕ ¸^ ‰_  : £ ¤$ í `  ¦ ° ú >   ) a .

Õ

ª   õ – Ð \ P „  § 4 “ É r & t   H  כ s  .   õ & h Ü ¼– Ð \ P „  § 4 

Fig. 4. The figure of merit for different well widths of Bi

2

Te

3

quantum well with a carrier density of 5.8 × 10

17

cm

−3

as a function of temperature.

s

 „  l & h “   q $ † ½ Ә Ð  € ª œ y Œ ™F K ´ òõ \  @ /ô  Ç    o

 s

`›   & f ” `  ¦ · ú ˜ à º e ”  .

Fig. 4  H Ä ºÓ ü t ; Ÿ ¤s    É r € ª œ  Ä ºÓ ü t ½ ¨› ¸[ þ t\  @ /ô  Ç \ P 

„



 $ í 0 p xt à º_  “ : r• ¸ _ ” > r$ í `  ¦ ˜ Ð# ŒÅ ғ ¦ e ”  . é ß –  & ñ _ 

 â

Ä ºü <  H  Ø Ô>  “ : r• ¸ 7 £ x† < Ê\     $ í 0 p xt à º• ¸ 7 £ x

   HX <, s  כ “ É r \ P „  § 4 s  “ : r• ¸ 7 £ x\     7 £ x l  M

:ë  Hs  . „   [ þ t_  € ª œ  y Œ ™F K´ òõ  & | 9 à º2 Ÿ ¤ $ í 0 p xt  Ã

º• ¸ & t   H ‰ & ³ © œ`  ¦ ^  ¦ à º e ”   HX <, s  כ “ É r € ª œ  y Œ ™F K´ ò õ

\  @ /ô  Ç \ P l „  § 4  ´ òõ ü < grain ´ òõ – Ð “  ô  Ç \ P „  • ¸• ¸ _

    o– Ð l “  H † d`  ¦ · ú ˜ à º e ”  . # Œl \   H    e ” t  · ú § t

ë ß – $  " é ¶ ½ ¨› ¸{ 9 à º2 Ÿ ¤ þ j& h _  $ í 0 p xt à º\  @ /ô  Ç „    x

9

• ¸  H  Œ • f ” `  ¦ · ú ˜ à º e ” % 3  .

IV. + s Ç Â ] Ø





 : r& h Ü ¼– Ð € ª œ y Œ ™F K´ òõ – Ð “   # Œ \ P „   $ í 0 p xt à º  H B

Ä º  H ° ú כ`  ¦ | 9  à º e ”  . \ P „  • ¸• ¸  H Ä ºÓ ü t; Ÿ ¤ ß ¼l – Ð

“



 # Œ, \ P l „  § 4 “ É r € ª œ  y Œ ™F K ´ òõ – Ð “   # Œ $ í 0 p xt à º

>

h‚  \  ß ¼>  l # Œ t ë ß –,  © œ@ /& h Ü ¼– Ð q $ † ½ Ó_  > h‚  “ É r Õ

ª t  ß ¼t  · ú § .   " f $  " é ¶ ½ ¨› ¸_  \ P „   : £ ¤$ í “ É r Å

Җ Ð \ P „  • ¸• ¸ü < \ P l „  § 4 Ü ¼– Ð   & ñ ÷ &# Qt  9, é ß –  & ñ õ 





H  Ø Ô>  “ : r• ¸ Z  }`  ¦Ã º2 Ÿ ¤ \ P „   $ í 0 p x• ¸ 7 £ x† < Ê`  ¦ · ú ˜ à º e

”

 . \ P „  $ í 0 p x t à º\  ¦ † ¾ Ó © œr v   H ~ ½ ÓZ O Ü ¼– Ð € ª œ y Œ ™F K

´

òõ  ü @\ • ¸ „    x 9 • ¸\  ¦ › ¸] X    H ~ ½ ÓZ O • ¸ e ”  .   " f

$

 " é ¶ ½ ¨› ¸_   â Ä º \ P „  $ í 0 p x`  ¦ † ¾ Ó © œr v   H ~ ½ ÓZ O “ É r é ß –





& ñ _   â Ä º ˜ Ð   8  € ª œ$ í `  ¦ t m “ ¦ e ” 6 £ §`  ¦ · ú ˜ à º e ” 



.

(4)

[1] D.M. Rowe, CRC Handbook of Thermoelectrics (CRC Press, London, 1995).

[2] H. J. Goldsmid, Thermoelectric Refrigeration (Pion Ltd., London, 1986).

[3] G.E. Smith and R. Wolfe, J. Appl. Phys. 33, 841 (1962).

[4] M. A. Jim and A. Amith, Solid State Electron. 17, 1141 (1972).

[5] A. D. Belaya, S. A. Zayakin and V. S. Zemskov, J.

Adv. Matter. 1, 158 (1994).

[6] V. A. Kutasov, L. N. Luk’yanova and P. P. Kon- stantinov, Semiconductors. 34, 376 (2000).

[7] R. Venkatasubramanian, E. Siivola, T. Colpitts and B. Q’Quinn, Nature 413, 597 (2001).

[8] I. Yashima, H. Watanave, T. Ogisu, R. Tsukuda and S. Sato, Jpn. J. Appl. Phys. 37, 2472 (1998).

[9] K.-C. Je, H.-J. Im, D.-H. Kim, Y.-J. Kang, J.-S.

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(5)

Thermoelectric Properties of Low-dimensional n-type Bi 2 Te 3 Semiconductors

Koo-Chul Je

Department of Optical and Electrical Engineering,

College of Science and Technology, Paichai University, Taejeon 302-735 (Received 27 June 2008)

We investigate the quantum-confined thermoelectric properties of Bi

2

Te

3

quantum well structures as a function of temperature. The Seebeck coefficient is strongly improved by quantum confinement effects, and the thermal conductivity is improved by grain effects due to the well size. As a result, the figure of merit is enhanced. In contrast to the single-crystal system, the figure of merit for quantum-well structures increases with increasing temperature, and quantum confinement effects allow for more degrees of freedom for optimizing the figure of merit.

PACS numbers: 66.70.+f, 68.60.D

Keywords: Thermal properties, Thermoelectric figure of merit, Thermal conductivity, Seebeck coefficient, Grain effect, Quantum confinement effect

E-mail: je [email protected]

수치

Fig. 1. Thermal conductivity of Bi 2 Te 3 alloys for differ- differ-ent grain sizes at 300 K.
Fig. 4. The figure of merit for different well widths of Bi 2 Te 3 quantum well with a carrier density of 5.8 × 10 17 cm −3 as a function of temperature

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