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(1)

V R

ËX ê s Æ X Øy ¢; c   \ ¥ Cu(In,Ga)Se 2 ° Ë Ñÿ  • ¤• «8 ý ö n ÚP X ì Ä — ¤V R Ë õ m Í ¿ k ÐT   ºV R Ë Ä Z ØV Ä

¼ ÿ

› # Ò · + ä  ÷ 7 B * > · ~ ç ¡* × <r ) · Pham Cong De · ‚ Ð=  ÷ 7 B

Â

Òí ß –@ /† < Ɠ §  ” ¸Ö 6 x ½ + Ël Õ ü t † < Æõ , x 9 € ª œ 627-706

¼

ÿ ›0 ï F¬ £ · T „ ‘ ž$ ß 

ô

 Dz D G K € ª œ@ /† < Ɠ §  ” ¸ì ø ͕ ¸^ ‰„  / B N,  Òí ß – 606-791

(2011¸   3 Z 4 7{ 9  ~ à Î6 £ §, 2011¸   4 Z 4 6{ 9  à º& ñ ‘ : r ~ à Î6 £ §, 2011¸   5 Z 4 6{ 9  > F  S X ‰& ñ )

‘ :

r ƒ  ½ ¨  H  € ª œô  Ç $ í  © œ “ : r • ¸\     7 £ x ‚ Ã Ì  ) a Cu(In,Ga)Se

2

( s  , CIGS) ~ à Ì} Œ •_  : £ ¤$ í õ  / å J – ÐÄ º~ ½ Ó

„

 ì  rF g l (GD-OES; glow discharge optical emission spectrometry)\  ¦ s 6   x # Œ ~ à Ì} Œ •_  U  ·s \    É r

"

é

¶ ™ èì  r Ÿ í ì  r$ 3    õ \  ¦ › ¸  % i  . CIGS ~ à Ì} Œ •“ É r 1 l x r 7 £ x µ 1 ρ © œq \  ¦ s 6   x # Œ 3é ß –>  / B N& ñ Ü ¼– Ð Mo/Ä » o

 l ó ø Í 0 A\  7 £ x ‚ à Ì÷ &% 3  . 2é ß –>  õ & ñ \ " f, $ í  © œ l ó ø Í“ : r • ¸\    É r CIGS ~ à Ì} Œ •_    & ñ $ í “ É r 450

C s 

\ " f  H (220)/(204) ~ ½ ӆ ¾ ÓÜ ¼– Ð, 500

C s  © œ\ " f  H (112) ~ ½ ӆ ¾ ÓÜ ¼– Ð Ä º‚   $ í  © œ % i  . ¢ ¸ô  Ç, $ í  © œ l  ó

ø Í “ : r • ¸ 7 £ x † < Ê\     CIGS ~ à Ì} Œ •_    & ñ w n  ß ¼l   H 7 £ x  % i  . à ºz   µm_  U  ·s ,  ú ª“ É r r ç ß –, F G p 

|

¾ Ó" é ¶ ™ èì  r$ 3 s  0 p x ô  Ç GD-OES\  ¦ CIGS ~ à Ì} Œ •ì  r$ 3 \   Ö ¸6   x “ ¦  % i Ü ¼ 9, l ” > r p | ¾ Óì  r$ 3 \   6   x ÷ &

 

H s  s “ : r| 9 | ¾ Óì  rF g l (SIMS) U  ·s  › ¸$ í ì  r$ 3    õ ü < q “ § % i  . GD-OES\  ¦ s 6   x # Œ CIGS ~ à Ì} Œ • _

 U  ·s  › ¸$ í `  ¦ › ¸ ô  Ç   õ , Cu, In, Ga x 9 Se " é ¶ ™ è ç  H{ 9  >  ì  r Ÿ í “ ¦ e ” 6 £ §`  ¦ S X ‰ “   % i  . 1é ß –>  450

C ü < 2é ß –>  550

C _  $ í  © œ“ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •Ü ¼– Ð ] j› ¸  ) a I € ª œ„  t   H €  • 8.12 %_  \ 



-t    ¨ 8 Š ´ òÖ  ¦`  ¦ ˜ Ð% i  .

Ù þ

˜d ” # Q: CIGS, U  ·s › ¸$ í , 1 l x r 7 £ x ‚ à Ìl , / å J – ÐÄ º~ ½ ӄ  ì  rF g l , ´ òÖ  ¦

Physical Properties and Depth Profiling of a Cu(In,Ga)Se 2 Absorber for Various Growth Temperature

K. Ahn · Y. M. Jeong · Y. H. Kang · P. C. De · C. R. Cho

Department of Nano-fusion Technology, Pusan National University, Miryang 627-706

H. S. Ahn · S. N. Yi

Department of Applied Science, Korea Maritime University, Busan 606-791 (Received 7 March 2011 : revised 6 April 2011 : accepted 6 May 2011)

This paper presents the results obtained from glow discharge optical emission spectrometry (GD- OES) depth profiling of Cu(In, Ga)Se

2

(CIGS) thin films prepared at various substrate temperatures.

The CIGS thin films were grown on molybdenum-coated soda-lime glass substrats by using a three- stage process with a co-evaporator system. For the substrate temperature (T

sub

) of the second stage. the CIGS thin films showed a (220)/(204)-preferred orientation at temperatures below 450

C and a (112)-preferred orientation at temperatures above 500

C. The grain size of the CIGS films increased with increasing T

sub

. The GD-OES depth profiling of the CIGS thin films prepared

-515-

(2)

at various T

sub

’s showed uniform distributions of all the elements through the CIGS film. These results were compared with the SIMS depth profiles for the CIGS thin films. A solar cell using a CIGS absorber layer prepared at the optimized T

sub

showed a conversion efficiency of about 8 %.

PACS numbers: 73.61.J, 81.70.J, 81.15.E

Keywords: CIGS, Depth profile, Co-evaporator, GD-OES, Efficiency

I. " e  ] Ø

f ”

] X  …  ;s + þ A  ½ ™× ¼Ì “ sõ  Z  }“ É r F gf  ¨ à º > à º\  ¦ ”   Cu(In,Ga)Se

2

(CIGS) Ó ü t| 9 “ É r z  ´o – B H I € ª œ„  t \  q K 

$

 Ò q tí ß –s  0 p x “ ¦, Z  }“ É r \  -t    ¨ 8 Š ´ òÖ  ¦ M :ë  H \  p

A _  ~ à Ì} Œ •+ þ A I € ª œ„  t  í ß –\ O \ " f y Œ • F g`  ¦ ~ à Γ ¦ e ”   H F g f

 ¨ à º Ó ü t| 9 s  . CIGS ~ à Ì} Œ •_  ] j› ¸~ ½ ÓZ O \   H Cu, In, Ga x 9

Se F K5 Å q" é ¶ ™ è[ þ t`  ¦ s 6   x ô  Ç 1 l x r 7 £ x µ 1 ÏZ O (co-evaporation), ì

 r  ‚   7 £ x ‚ à ÌZ O (molecular beam deposition), „  l 7 £ x ‚ Ã Ì Z O

(Electrodeposition) x 9 Û ¼( '   ) a F K5 Å q ~ à Ì} Œ •_  ! s qE $ ™



o(selenization) 1 p x s  e ”   [1–4]. þ j   H National Renew- able Energy Lab. (NREL) _  Repins ƒ  ½ ¨ Õ ªÒ  ¨ \ " f 3é ß –

>

 7 £ x ‚ à ÌZ O `  ¦ s 6   x # Œ Cu, In, Ga x 9 Se " é ¶ ™ è\  ¦ 1 l x r  7 £ x µ 1 Ï r

&  ë ß –Ž  H CIGS I € ª œ„  t \ " f 19.9 %_   © œ Z  }“ É r \  - t

   ¨ 8 Š ´ òÖ  ¦`  ¦ ˜ Г ¦Ù þ ¡  [5]. ´ òÖ  ¦ s  Z  }“ É r CIGS F gf  ¨ à º 8

£

x`  ¦ ë ß –[ þ t l  0 AK " f  H CIGS ~ à Ì} Œ •_  grain ß ¼l  ß ¼“ ¦,

³

ð€    } 9 l   Œ •Ü ¼ 9, & h ] X ô  Ç „  l & h  : £ ¤$ í `  ¦ t “ ¦ e ” 

#

Q  “ ¦, s  Qô  Ç כ ¹™ è[ þ t“ É r CIGS ~ à Ì} Œ •_   o† < Æ& h  › ¸$ í s 



 $ í  © œ l ó ø Í “ : r • ¸ 1 p x \  _ K  ] j# Q½ + É Ã º e ”   [6–8]. Z  }“ É r l

ó ø Í “ : r • ¸\ " f $ í  © œ  ) a CIGS ~ à Ì} Œ •_   â Ä º, l ó ø ÍÜ ¼– РÒ' 

\ P

\  -t \  _ K   l   ) a ½ ¨$ í " é ¶ ™ è[ þ t _  ? /Â Ò S X ‰ í ß –\  _ ô  Ç



© œ   o (phase transformation)õ & ñ `  ¦ { 9 Ü ¼†   .   " f

´ ú

§“ É r ƒ  ½ ¨ [ þ t s  CIGS ~ à Ì} Œ • ? / U  ·s \    É r " é ¶ ™ è[ þ t _ 

›

¸$ í ì  r Ÿ í\  ¦ Auger „   ì  rF g l  (AES; Auger Electron Spectroscopy) ü < s  s “ : r| 9 | ¾ Óì  r$ 3 l (SIMS; Secondary Ion Mass Spectroscopy)\  ¦ s 6   x # Œ ˜ Г ¦ % i   [9, 10].

Õ

ª Q  s ü < ° ú  “ É r ì  r$ 3  © œq [ þ t“ É r { 9 ì ø Í& h Ü ¼– Ð ³ ð€   ì  r$ 3  s

  ³ ð€  \  @ /ô  Ç U  ·s  › ¸$ í ì  r$ 3 \  ´ ú §s   6   x ÷ &“ ¦, 1 atomic % s  _  p | ¾ Ó" é ¶ ™ è[ þ t s  Ÿ í† < ʝ ) a ¿ º î  r ~ à Ì} Œ •_ 

 â

Ä º ì  r$ 3 r ç ß –s  š ¸A    o    d ” t # Q  H ì  r$ 3 s  # Q 9 î

 r é ß –& h s  e ”  . Õ ª Q  s  Qô  Ç é ß –& h `  ¦ F G4 Ÿ ¤ l  0 Aô  Ç

~

½ ÓZ O Ü ¼– Ð ƒ  ½ ¨ [ þ t“ É r, é # Qo (bulk)  ¿ º î  r ~ à Ì} Œ •_  U  · s

 › ¸$ í `  ¦ / å J – ÐÄ º~ ½ ӄ   ‰ & ³ © œ`  ¦ s 6   x # Œ ì  r$ 3  “ ¦  

%

i  . GD-OES  H 1967¸   Grimm\  _ K  % ƒ6 £ § Ü ¼– Ð > hµ 1 Ï

÷

&% 3 “ ¦, 1973¸   Greeneõ  Whelan\  _ K  % ƒ6 £ § Ü ¼– Ð U  ·s 

›

¸$ í ì  r$ 3 \   6   x ÷ &% 3   [11]. GD-OES  H à º™ è\  ¦ Ÿ í† < Êô  Ç

—

¸Ž  H " é ¶ ™ è\  @ /ô  Ç ì  r$ 3 s  0 p x “ ¦, ± ú “ É r  Ž Ø  ¦ ô  Ç>  ({ 9 

E-mail: [email protected]

Fig. 1. (Color online) Schematic diagram of three stages temperature used for fabrication of CIGS thin film.

ì

ø Í& h Ü ¼– Ð 0.1 ∼ 50 ppm) x 9 Z  }“ É r Û ¼( ' Ö  ¦ \  _ K  100 µm  t  à ºœ í? /\  U  ·s  › ¸$ í ì  r$ 3 s  0 p x ô  Ç  © œ& h `  ¦ t 

“

¦ e ” Ü ¼ 9, ŠҖ Ð F K5 Å q Ó ü t| 9 _  › ¸$ í ì  r$ 3 \  ´ ú §s  s 6   x ÷ &

% 3  .

‘

: r ƒ  ½ ¨\ " f  H  € ª œô  Ç $ í  © œ l ó ø Í “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •\  @ /ô  Ç Ó ü t o & h  : £ ¤$ í `  ¦ › ¸  % i “ ¦, GD-OES

\

 ¦ s 6   x # Œ U  ·s \    É r › ¸$ í _     o\  ¦ 8 £ ¤& ñ % i  . ¢ ¸ ô

 Ç, þ j& h  › ¸| \ " f ] j› ¸  ) a CIGS ~ à Ì} Œ •\  @ /ô  Ç U  ·s › ¸$ í



  o\  ¦ SIMS ì  r$ 3   õ ü < q “ § % i Ü ¼ 9, I € ª œ„  t _  F g



 ¨ 8 Š ´ òÖ  ¦`  ¦ 8 £ ¤& ñ % i  .

II. ÷ m Ç] M öU ê s0 n É

CIGS ~ à Ì} Œ • $ í  © œ`  ¦ 0 AK  í  H • ¸ 99.999 %, ß ¼l  φ5 × 5 mm

3

“   Cu, In, Ga x 9 Se\  ¦ F K5 Å q 7 £ x µ 1 Ï" é ¶ Ü ¼– Ð  6   x 

%

i  . l ó ø ÍÜ ¼– Ѝ  H 5 × 5 cm

2

ß ¼l _  ]  t o Ú ÔD ! p(Mo)s  7

£

x ‚ Ã Ì  ) a Soda-lime Ä »o \  ¦  6   x % i “ ¦, # Œl " f Mo  H f ”  À

Ó+ þ A  Õ ªW 1à ԏ : r Û ¼( ' a AZ O Ü ¼– Ð 1 µm ¿ ºa – Ð 7 £ x ‚ à Ì÷ &

%

3  . CIGS ~ à Ì} Œ • 7 £ x ‚ à Ì`  ¦ 0 Aô  Ç 6   x l _  œ íl ”  / B N“ É r 7 × 10

−8

torr s  % i Ü ¼ 9, 7 £ x ‚ à ̷ ú š§ 4 “ É r 5 × 10

−6

torr% i  .

CIGS ~ à Ì} Œ •“ É r Fig. 1 \  ˜ Г    כ % ƒ! 3 , r ç ß –\    É r “ : r • ¸



  o\  ¦ 3 é ß –> – Ð  ¾ º# Q ] j› ¸÷ &% 3  . 1é ß –> \ " f In, Ga, x 9

Se F K5 Å q _  1 l x r  7 £ x µ 1 Ï\  _ K  l ó ø Í“ : r • ¸ 350

C \ " f

In

1−x

Ga

x

Se

y

8 £ x s  + þ A$ í ÷ &“ ¦, 2é ß –>  õ & ñ \  [ þ t # Ql  „  

(3)

Fig. 2. Surface morphologies and cross-sectional SEM images of CIGS thin films according to growth temper- ature at first and second stages, respectively. Tempera- tures denote first stage temperature/second stage tem- perature; (a) 350

C/450

C, (b) 350

C/500

C, (c) 350

C/550

C, (d) 400

C/450

C, (e) 400

C/500

C, (f) 400

C/550

C, (g) 450

C/450

C, (h) 450

C/500

C, (i) 400

C/550

C.

€



• 5ì  r ç ß – $ í  © œ “ : r • ¸\  ¦ 550

C – Ð `  ¦ 2 ; Ê ê, Cu ü < Se[ þ t

`

 ¦ 1 l x r  7 £ x µ 1 Ïô  Ç . s  Qô  Ç õ & ñ 1 l x î ß – In

1−x

Ga

x

Se

y

8 £ x õ  1

l

x r  7 £ x µ 1 Ï  ) a Cu ü < Se[ þ t s  ì ø Í6 £ x # Œ CIGS ~ à Ì} Œ •`  ¦ + þ A$ í ô

 Ç . 2é ß –>  õ & ñ Ê ê CIGS ³ ð€  \   H # Œì  r _  Cuü < Se– Ð

“

 K  Ó  o © œ_  Cu

2

Se s   © œ`  ¦ + þ A$ í ô  Ç . 3é ß –>  õ & ñ \ " f Cu

2

Se s   © œ`  ¦ ] j  l  0 A # Œ, In, Ga,ü < Se F K5 Å q[ þ t

`

 ¦ 1 l x r  7 £ x µ 1 Ï # Œ þ j7 á x Ü ¼– Ð CIGS ~ à Ì} Œ •`  ¦ $ í  © œô  Ç . s  M

: $ í  © œ “ : r • ¸  H 2 é ß –> ü < 1 l x{ 9  >  Ä »t  % i  . CIGS ~ Ã Ì }

Œ

• 7 £ x ‚ Ã Ì „  ^ ‰ / B N& ñ é ß –> \ " f Se“ É r † ½ Ó © œ 7 £ x µ 1 Ïr & ï  r  .

s

  H Z  }“ É r l ó ø Í“ : r • ¸– Ð “  ô  Ç CIGS ~ à Ì} Œ •\ " f Se_  7 £ x µ 1 Ï

`

 ¦ ˜ ÐØ  æ l  0 AK " fs  .  € ª œô  Ç $ í  © œ l ó ø Í “ : r • ¸\    É r CIGS ~ à Ì} Œ •_  : £ ¤$ í `  ¦ › ¸  l  0 AK " f y Œ • é ß –> Z >  “ : r • ¸

\

 ¦  € ª œ >  [ O & ñ % i  . 1, 2é ß –> \ " f $ í  © œ “ : r • ¸\  ¦ y Œ • y

Œ

• 350 ∼ 450

C ü < 450 ∼ 550

C # 3 0 A ? /\ " f    o % i 

“

¦, 3é ß –> \ " f  H 2 é ß –> \ " fü < 1 l x{ 9  >  Ä »t  % i  . 7 £ x

‚ Ã

Ì÷ &  H ~ à Ì} Œ •_  ç  H{ 9 • ¸\  ¦ Z  } s l  0 AK " f r « Ñ\  ¦ 15 rpm _  5

Å

q • ¸– Ð { 9 & ñ >   r„   % i  .  € ª œô  Ç $ í  © œ “ : r • ¸\ " f 7 £ x

‚ Ã

Ì  ) a CIGS ~ à Ì} Œ •_    & ñ $ í , ³ ð€   + þ A © œ x 9 ~ à Ì} Œ •_  ¿ ºa 



 H X-‚    r] X l  (XRD; Phillips, X’pert pro)ü < „  > ~ ½ Ó



+ þ A Å Ò „   ‰ & ³p  â (SEM; Hitachi, S-4700)`  ¦ s 6   x 

#

Œ ì  r$ 3  % i  . ~ à Ì} Œ •_  › ¸$ í “ É r SEM  © œq \   ҂ Ã Ì  ) a \ 



-t ì  r í ß –ì  rF g l  (EDS)\  ¦ s 6   x # Œ 8 £ ¤& ñ % i  . U  ·s \ 



 É r ~ à Ì} Œ •_  › ¸$ í “ É r / å J – ÐÄ º~ ½ ӄ  ì  rF g l (GD-OES; Glow Discharge-Optical Emission Spectroscopy) [Jobin-Yvon, JY10000] ü < s  s “ : r| 9 | ¾ Óì  r$ 3 l (SIMS) [Cameca, mag- netic sector ims6f]\  ¦ s 6   x % i  . I € ª œ„  t  : £ ¤$ í ¨ î \  ¦

0

AK , AlZnO(AZO)/i-ZnO/CdS/CIGS/Mo/glass ½ ¨› ¸– Ð CIGS I € ª œ„  t \  ¦ ] j› ¸ % i Ü ¼ 9, AZO, i-ZnO x 9 CdS ~ Ã Ì }

Œ

•“ É r RF  Õ ªW 1à ԏ : r Û ¼( ' a AZ O õ  chemical bath depo- sition(CBD)Z O Ü ¼– Ð 7 £ x ‚ Ã Ì % i  . I € ª œ„  t    ¨ 8 Š : £ ¤$ í “ É r AM 1.5, 100 mW/cm

2

› ¸| \ " f ³ ðï  r q “ § I € ª œ„  t – Ð

˜

Ð& ñ ô  Ç Ê ê 8 £ ¤& ñ % i  .

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

Figure 2  H  € ª œô  Ç l ó ø Í “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •_ 

³

ð€  õ  é ß –€   SEM  ”  `  ¦   ? /% 3  . 1 é ß –> ü < 2é ß –>  õ 

&

ñ \ " f, $ í  © œ “ : r • ¸ Z  }`  ¦ à º2 Ÿ ¤ 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •“ É r   

†

< Ês   ç  H\ P s  \ O   H u x 9 ô  Ç   & ñ w n [ þ t – Ð ½ ¨$ í ÷ &% 3 Ü ¼ 9,

 

& ñ w n _  ß ¼l  7 £ x  % i  . — ¸Ž  H CIGS ~ à Ì} Œ •_  ¿ ºa   H

€



• 1.8 µm– Ð { 9 & ñ % i  . 1 é ß –>  “ : r • ¸_  7 á x À Óü <  H › ' a > 

\ O

s  450

C _  2é ß –>  $ í  © œ “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ • _

  â Ä º (Fig. 2(a,d,g), 500

C s  © œ\ " f 7 £ x ‚ Ã Ì  ) a CIGS

~ Ã

Ì} Œ •õ  q “ §K " f  © œ@ /& h Ü ¼– Ð   & ñ w n  ß ¼l   Œ •“ ¦, ~ à Ì} Œ • _

 ³ ð€  õ  ? / Ò\   Œ •“ É r l / B N s  ” > r F    H  כ `  ¦ SEM  ”   Ü

¼– РÒ'  S X ‰ “   % i  . 2é ß –>  õ & ñ _  $ í  © œ “ : r • ¸ 500

C s

 © œÜ ¼– Ð 7 £ x ½ + Éà º2 Ÿ ¤ CIGS ~ à Ì} Œ •_    & ñ w n  ß ¼l   H 7 £ x 

% i “ ¦,  Œ •“ É r l / B N s  \ O   H u x 9 ô  Ç ~ à Ì} Œ •s  + þ A$ í ÷ &% 3  . s 



 H 2 é ß –>  õ & ñ \ " f Cuü < Se 7 £ x µ 1 Ï" é ¶[ þ t s  523

C s  © œ_ 

$ í

 © œ “ : r • ¸\ " f Ó  o © œ_  Cu

2−x

Se ” > r F \  _ ô  Ç F   & ñ  o\  _

ô  Ç  כ Ü ¼– Ð ó ø Íé ß –  ) a   [12]. : £ ¤ y , Fig. 2(i)\ " f ˜ Г    כ

%

ƒ! 3 , 450

C _  1é ß –> \ " f_  $ í  © œ “ : r • ¸ü < 550

C _  2é ß –

>

\ " f_  $ í  © œ “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •s   © œ u x 9 

€  " f  H   & ñ w n  ß ¼l \  ¦ t   H  כ `  ¦ S X ‰ “   % i  .

Figure 3“ É r  € ª œô  Ç $ í  © œ l ó ø Í “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS

~ Ã

Ì} Œ •_  XRD  r] X  8 £ ¤& ñ   õ – Ð" f ½ ¨› ¸& h  : £ ¤$ í    o\  ¦



 ? /% 3  . 3é ß –>  õ & ñ `  ¦ : Ÿ x K  7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •_  — ¸

Ž

 H  r] X  x ß ¼[ þ t“ É r 1 é ß –>  õ & ñ \ " f $ í  © œ  ) a In

1−x

Ga

x

Se

y

 

& ñ  © œ x ß ¼ 0 Au ü < Ä »  % i   [13]. 2é ß –>  õ & ñ \ " f

$ í

 © œ “ : r • ¸\  ¦ 450

C – Ð “ ¦& ñ “ ¦ 1 é ß –> _  $ í  © œ “ : r • ¸\  ¦ y

Œ

•y Œ • 350, 400, 450

C – Ð    oô  Ç  â Ä º Fig. 3(a,d,g), $ í



© œ “ : r • ¸ 7 £ x † < Ê\     7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •_    & ñ w n “ É r (112) ü < q “ § # Œ (220)/(204) ~ ½ ӆ ¾ ÓÜ ¼– Ð Ä º‚   $ í  © œ   H

 כ

`  ¦ ^  ¦ à º e ”  . s   H 400 oC s  © œ_  1é ß –> _  $ í  © œ “ : r

•

¸\ " f (In,Ga)

2

Se

3

8 £ x s  & h ] X ô  Ç   & ñ w n  ß ¼l ü <   & ñ w n 

 â

> (grain boundary) + þ A$ í H † d \     2é ß –> \ " f 7 £ x µ 1 Ï

÷

&  H Cu ü < Se\  _ K  Ò q t$ í ÷ &  H Ó  o^ ‰ © œ_  Cu

2−x

Se \  _  K

 Cu S X ‰ í ß –s    & ñ w n   â > ü < columnar+ þ A_  (In,Ga)

2

Se

3

grain[ þ t \ " f ¸ ú ˜ { 9 # Q l  M :ë  H Ü ¼– Ð Ò q ty Œ •  ) a   [11]. 1é ß –

>

\ " f_  $ í  © œ “ : r • ¸\  › ' a > \ O s  500

C s  © œ_  2é ß –> 

(4)

Fig. 3. XRD patterns of CIGS thin films grown on Mo/soda-lime glass substrate at various substrate tem- peratures. Temperatures denote first stage tempera- ture/second stage temperature; (a) 350

C/450

C, (b) 350

C/500

C, (c) 350

C/550

C, (d) 400

C/450

C, (e) 400

C/500

C, (f) 400

C/550

C, (g) 450

C/450

C, (h) 450

C/500

C, (i) 400

C/550

C.

$ í

 © œ “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •“ É r (220)/(204) ˜ Ð   H (112) C † ¾ ÓÜ ¼– Ð Ä º‚   $ í  © œ % i “ ¦, l ó ø Í “ : r • ¸ 7 £ x † < Ê\ 



    & ñ $ í s  † ¾ Ó © œ÷ &  H  כ `  ¦ S X ‰ “   % i  . s   H 2 é ß –> 

\

" f Cu_  S X ‰ í ß –Ö  ¦ õ  CIGS ~ à Ì} Œ • $ í  © œÖ  ¦ s  500

C s

 © œ_  Z  }“ É r $ í  © œ “ : r • ¸\ " f Ø  æì  r ô  Ç \ P \  -t  / B N/ å L \  _  K

 (In,Ga)

2

Se

3

8 £ x ? / Җ Ð Cu S X ‰ í ß –s  " é ¶ Ö ¸ >  ”  ' Ÿ ÷ &# Q (112) Ä º‚   ~ ½ ӆ ¾ ÓÜ ¼– Ð CIGS ~ à Ì} Œ •s  7 £ x ‚ à Ì÷ &  H  כ Ü ¼– Ð ó ø Í é

ß –  ) a  . l ó ø Í “ : r • ¸ 7 £ x \    É r 7 £ x ‚ Ã Ì  ) a ~ à Ì} Œ •_    & ñ w n  ß ¼ l

 x 9   & ñ $ í † ¾ Ó © œ\  @ /ô  Ç SEM ³ ð€  /é ß –€   + þ A © œõ  XRD 8

£ ¤& ñ   õ  { 9 u    H  כ `  ¦ · ú ˜ à º e ”  .

CIGS ~ à Ì} Œ •_  U  ·s \    É r " é ¶ ™ è ì  r Ÿ í\  ¦ › ¸  l  0 A K

" f,  ú ª“ É r r ç ß –(à ºz   œ í s ? /)? /\  ¿ º î  r( à ºz   µm s 

?

/) ~ à Ì} Œ •\  @ /ô  Ç U  ·s  › ¸$ í ì  r$ 3 s  0 p x ô  Ç GD-OES\  ¦ s  6

 

x # Œ ì  r$ 3 `  ¦ z  ´r  % i  . ‘ : r z  ´+ « >“ É r CIGS ~ à Ì} Œ •\  @ / ô

 Ç ³ ðï  r r « Ñ \ O l  M :ë  H \ , ï  r q   ) a CIGS r « Ñ\  @ / ô

 Ç & ñ S X ‰ ô  Ç & ñ | ¾ Ó ì  r$ 3 “ É r # Q§ > “ ¦, CIGS ~ à Ì} Œ •\  @ /ô  Ç & ñ

$ í

x 9 U  ·s \    É r " é ¶ ™ è_  ì  r Ÿ í\  ¦ › ¸  “ ¦  % i  .

Fig. 4  H  € ª œô  Ç $ í  © œ l ó ø Í “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ Ã Ì }

Œ

•\  @ /ô  Ç U  ·s \    É r › ¸$ í ì  r Ÿ í\  ¦ GD-OES\  ¦ s 6   x 

#

Œ 8 £ ¤& ñ ô  Ç   õ \  ¦   ? /% 3  . — ¸Ž  H r « Ñ\  @ /ô  Ç U  ·s  ì  r

$

3 \ " f CIGS ~ à Ì} Œ •õ  Mo ~ à Ì} Œ •ç ß –_  > €  “ É r Ì º§  >  ½ ¨ ì

 r ÷ &% 3 “ ¦, CIGS ~ à Ì} Œ •? /\  Cu, In, Ga x 9 Se " é ¶ ™ è ç  H { 9

 >  ì  r Ÿ í “ ¦ e ”   H  כ `  ¦ S X ‰ “   % i  . U  ·s \    É r › ¸

$ í

ì  r Ÿ í ì  r$ 3 \ " f CIGS ~ à Ì} Œ •_  ³ ð€   % ò % i \  Cu " é ¶ ™ è_ 

€

ª œs  y Œ ™™ èô  Ç  כ `  ¦ S X ‰ “   % i  . s  כ “ É r 2 é ß –>  õ & ñ \ " f

Fig. 4. (Color online) GD-OES depth profile of CIGS thin films deposited on Mo/soda-lime glass substrate with various substrate temperatures. Temperatures de- note first stage temperature/second stage temperature;

(a) 350

C/450

C, (b) 350

C/500

C, (c) 350

C/550

C, (d) 400

C/450

C, (e) 400

C/500

C, (f) 400

C/550

C, (g) 450

C/450

C, (h) 450

C/500

C, (i) 400

C/550

C.

Fig. 5. (Color online) SIMS depth profile and chemical composition analysis of the CIGS thin films deposited under first stage temperature of 450

C and second stage temperature of 550

C.

Cu ü < Se_  7 £ x µ 1 Ï\  _ K  Cu õ e ç “   CIGS ~ à Ì} Œ •s  + þ A

$ í

÷ & 9, Cuü < Se[ þ t _  õ e ç 7 £ x µ 1 Ï\  _ ô  Ç Cu

2−x

Se s   © œ ]

j \  ¦ 0 AK  3é ß –>  õ & ñ \ " f In, Ga x 9 Se[ þ t`  ¦ F 7 £ x µ 1 Ï 



 H õ & ñ \  _ K  ³ ð€  \  Cu  Ò7 á ¤ ô  Ç CIGS ~ à Ì} Œ •s  + þ A$ í

÷

&% 3 l  M :ë  H Ü ¼– Ð Ò q ty Œ •  ) a  . GD-OES U  ·s  ì  r$ 3 \ " f Cu, In, Ga ü < Se[ þ t s  Mo „  F G`  ¦ : Ÿ x K   Òì  r& h “   S X ‰ í ß –s  µ 1 ÏÒ q t ô

 Ç  כ Ü ¼– Ð ^  ¦ à º e ”  . Õ ª Q  s  Qô  Ç   õ   H, Z  }“ É r l 

(5)

Fig. 6. (Color online) Performance of CIGS solar cell fab- ricated using CIGS thin films deposited under first stage temperature of 450

C and second stage temperature of 550

C.

ó

ø Í “ : r • ¸– Ð “  ô  Ç CIGS ~ à Ì} Œ •õ  Mo „  F G  s  > €  \ " f_  intermixing ´ òõ , alloy formation_  › ¸½ + Ë, Mo 8 £ x _  ³ ð€  



} 9 l , Ô  ¦ç  H{ 9 ô  Ç Û ¼( ' a A\  _ K  µ 1 ÏÒ q t½ + É Ã º e ”   [14].

GD-OES\  ¦ s 6   x ô  Ç U  ·s  › ¸$ í ì  r$ 3    õ – РÒ'  S X ‰ “   ) a CIGS ~ à Ì} Œ •_  ¿ ºa   H SEM _  é ß –€   ”  \ " f S X ‰ “   ) a   õ  ü

< { 9 u  % i “ ¦, CIGS ~ à Ì} Œ • ] j› ¸õ & ñ \ " f $ í  © œ l ó ø Í “ : r

•

¸_     o CIGS ~ à Ì} Œ • ? /Â Ò " é ¶ ™ è ì  r Ÿ í\  % ò † ¾ Ó`  ¦ p u 



 H  כ Ü ¼– Ð Ò q ty Œ •  ) a  .

Figure 5  H ‘ : r ƒ  ½ ¨\ " f 1 é ß –>  450

C, 2 é ß –>  550

C _  þ j& h  o  ) a $ í  © œ “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •\  @ / ô

 Ç SIMS U  ·s  › ¸$ í ì  r$ 3    õ s  . CIGS ~ à Ì} Œ •“ É r U  ·s \ 



  Cu, In, Gaü < Se " é ¶ ™ è[ þ t s  ç  H{ 9  >  ì  r Ÿ í % i Ü ¼ 9, CIGS ~ à Ì} Œ • ³ ð€  % ò % i \ " f Cu_  † < Ê| ¾ Ós  y Œ ™™ è   H  כ `  ¦ S X ‰

“

  % i  . SIMSü < GD-OES ì  r$ 3    õ \ " f y Œ • " é ¶ ™ è\  @ / ô

 Ç  Ž Ø  ¦ l  y Œ ™• ¸ x 9  Ž Ø  ¦ ~ ½ ÓZ O \     µ 1 ÏÒ q tô  Ç Cu, In, Gaü <

Se[ þ t \  @ /ô  Ç x ß ¼[ jl  s  s ü @\   H U  ·s \    É r { 9 & ñ ô

 Ç " é ¶ ™ è ì  r Ÿ í_   ⠆ ¾ Ós  Ä »  % i  .   " f GD-OES U  · s

 › ¸$ í ì  r$ 3 `  ¦ : Ÿ x K  CIGS ~ à Ì} Œ •? / " é ¶ ™ è[ þ t _  ì  r Ÿ í & ñ • ¸

\

 ¦ S X ‰ “  ½ + É Ã º e ”   H  כ Ü ¼– Ð ó ø Íé ß –  ) a  . þ j& h _  $ í  © œ “ : r • ¸

\

" f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •_  " é ¶ ™ è| ¾ Ó`  ¦ EDS\  ¦ s 6   x # Œ ì  r

$

3 ô  Ç   õ , Cu/(In+Ga)ü < Ga/(In+Ga)_  " é ¶ ™ èq   H y Œ • y

Œ

• 1.15 x 9 0.31s % 3  .

Figure 6“ É r 2.5 × 2.5 cm

2

_  Mo/Ä »o  l ó ø Í 0 A\  þ j& h 



o  ) a $ í  © œ “ : r • ¸\ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •`  ¦ s 6   x # Œ €  

&

h

 0.47 cm

2

– Ð ] j Œ •  ) a CIGS I € ª œ„  t \  ¦    · p  כ s  .

þ

j& h  $ í  © œ “ : r • ¸\ " f ] j› ¸  ) a CIGS I € ª œ„  t   H > h~ ½ ӄ  · ú š 0.406 V, é ß –| à ̄  À Óx 9 • ¸ 36.6 mA/cm

2

, Ø  æz  ´• ¸ 58 % x 9   

¨ 8

Š ´ òÖ  ¦ 8.12 % _  : £ ¤$ í `  ¦ ˜ Ð% i  . s   H ‘ : r z  ´+ « >\ " f þ j& h  _

 $ í  © œ› ¸| \ " f 7 £ x ‚ à Ìô  Ç CIGS ~ à Ì} Œ •_    & ñ C † ¾ Ó,   & ñ $ í 7

£

x  x 9 grain ß ¼l  7 £ x ÷  r ë ß –  m   CdS, i-ZnO, AZO

~ Ã

Ì} Œ •_  þ j& h  7 £ x ‚ Ã Ì › ¸| \  _ ô  Ç CIGS ? / Ò\ " f Ò q t$ í  ) a

&

ñ / B N õ  „   [ þ t _  ± ú “ É r F   ½ + ËÖ  ¦ õ  Z  }“ É r s 1 l x • ¸\  l “   ô

 Ç  כ Ü ¼– Ð Ò q ty Œ •½ + É Ã º e ”  .

IV. + s Ç Â ] Ø

CIGS ~ à Ì} Œ •s  1 l x r 7 £ x µ 1 ÏZ O Ü ¼– Ð  € ª œô  Ç $ í  © œ “ : r • ¸_  3é ß –

>

 7 £ x ‚ à Ìõ & ñ Ü ¼– Ð ï  r q ÷ &% 3  . 1é ß –>  450

C ü < 2é ß –>  550

C \ " f 7 £ x ‚ Ã Ì  ) a CIGS ~ à Ì} Œ •“ É r (112) ~ ½ ӆ ¾ ÓÜ ¼– Ð Ä º‚   $ í  © œ

% i “ ¦, grain_  ß ¼l  7 £ x  x 9  â > €   y Œ ™™ è : £ ¤$ í `  ¦ ˜ Ð% i 



. s  Qô  Ç CIGS ~ à Ì} Œ •_  Cu/(In+Ga)ü < Ga/(In+Ga) › ¸

$ í

q   H y Œ •y Œ • 1.15ü < 0.31– Ð   z Œ ¤ . GD-OES\  ¦ s 6   x ô  Ç U

 ·s  › ¸$ í ì  r$ 3    õ , Cu, In, Gaü < Se " é ¶ ™ è[ þ t s  CIGS

~ Ã

Ì} Œ •? /\  ç  H{ 9  >  ì  r Ÿ í % i Ü ¼ 9, CIGS ~ à Ì} Œ • ³ ð€  % ò % i 

\

" f Cu € ª œ_  y Œ ™™ è x 9 CIGS ~ à Ì} Œ •õ  Mo > €   % ò % i \ " f intermixing ‰ & ³ © œ`  ¦ S X ‰ “   % i  . GD-OESü < SIMS  Ž Ø  ¦ l

_  y Œ ™• ¸ s \  _ K  8 £ ¤& ñ  ) a CIGS ~ à Ì} Œ • ½ ¨$ í " é ¶ ™ è_  x

ß ¼[ jl  s  s ü @\   H SIMS\  ¦ s 6   x ô  Ç U  ·s  › ¸$ í ì  r$ 3 

 

õ ü < { 9 u  % i  .   " f à º µm s  © œ_  ¿ º î  r ~ à Ì} Œ •

\

 @ /ô  Ç U  ·s  › ¸$ í ì  r$ 3 \  GD-OES_  s 6   x“ É r   É r ì  r$ 3 

~

½ ÓZ O \  q K  ì  r$ 3 _  ç ß –¼ #  o x 9 r ç ß –_  é ß –» ¡ ¤ 1 p x Ü ¼– Ð  € ª œ ô

 Ç ™ èF  & ñ $ í ì  r$ 3  x 9 > €   : £ ¤$ í ƒ  ½ ¨\  l # Œ½ + É  כ Ü ¼– Ð ó ø Í é

ß –  ) a  . CIGS I € ª œ„  t _  \  -t    ¨ 8 Š ´ òÖ  ¦“ É r 8.12 % s 

% 3  .

P

c p 8 ý ò k >

s

  7 Hë  H ¢ ¸  H $ " f  H 2008¸   & ñ  Ò(“ §¹ ¢ ¤ õ † < Æl Õ ü t  Ò)_  F

" é ¶ Ü ¼– Ð ô  Dz D G † < ÆÕ ü t”  < É ª F é ß –_  t " é ¶`  ¦ ~ à Î  à º' Ÿ  ) a ƒ  ½ ¨ e ”

 (KRF-2008-313-D00607).

Y

c p w Š à U Ø ”  ô

[1] Y. Hagiwara, T. Nakada and A. Kunioka, Sol. En- ergy Mater. Sol. Cells 67, 267 (2001).

[2] J. Muller, J. Nowoczin and H. Schmitt, Thin Solid Films 496, 364 (2006).

[3] T. Unold, U. Sieber and K. Ellmer, Appl. Phys. Lett.

88, 213502 (2006).

[4] A. M. Fernandez and R. N. Bhattacharya, Thin

Solid Films 474, 10 (2005).

(6)

[5] I. Repinsl, M. A. Contreras, B. Egaas, C. Dehart, J. Scharf, C. L. Perkins, B. To and R. Boufi, Prog.

Photovolt. Res. Appl. 16, 235 (2008).

[6] M. Ruckh, D. Schmid, M. Kaiser, R. Schaffler, T.

Walter and H. W. Schock, Sol. Energy Mater. Sol.

Cells 41, 335 (1996).

[7] F. Adurodija, J. Song, S. K, Kim, K. H. Kang, K.

H. Kang, K. H. Yoon and J. Song, J. Korean Phys.

Soc. 31, 796 (1997).

[8] J. Kessler, C. Chityuttakan, J. Scholdstrom and L.

Stolt, Thin Solid Films 431, 1 (2003).

[9] M. E. Calixto and P. J. Sebastian, Sol. Energy Mater. Sol. Cells 63, 335 (2000).

[10] G. Bilger, P. O. Grabitz and A. Strohm, Appl. Surf.

Sci. 231, 804 (2004).

[11] T. Mise and T. Nakada, Sol. Energy Mater. Sol.

Cells 93, 1000 (2009).

[12] T. Wada, N. Kohara, T. Negami and M. Nishitani, J. Mater. Res. 12, 1456 (1997).

[13] S. Chaistisak, A. Yamada and M. Konagai, Jpn. J.

Appl. Phys. 41, 507 (2002).

[14] T. Delsol, A. P. Samantilleke, N. B. Chaure, P. H.

Gardiner, M. Simmonds and I. M. Dharmadasa,

Sol. Energy Mater. Sol. Cells 82, 587 (2004).

수치

Fig. 1. (Color online) Schematic diagram of three stages temperature used for fabrication of CIGS thin film.
Fig. 2. Surface morphologies and cross-sectional SEM images of CIGS thin films according to growth  temper-ature at first and second stages, respectively
Fig. 4. (Color online) GD-OES depth profile of CIGS thin films deposited on Mo/soda-lime glass substrate with various substrate temperatures
Fig. 6. (Color online) Performance of CIGS solar cell fab- fab-ricated using CIGS thin films deposited under first stage temperature of 450 ◦ C and second stage temperature of 550 ◦ C.

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