Optimization of a Rapid Thermal Process by Measuring the Real-time Temperature of the Cu 2 ZnSnSSe 4 Absorption Layer

Optimization of a Rapid Thermal Process by Measuring the Real-time Temperature of the Cu ₂ ZnSnSSe ₄ Absorption Layer

Hyun-Jun Jo · Dae-Ho Son · Jin-Kyu Kang ^∗

Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu 711-873, Korea

Seoung-Jun Lee · In-Ho Bae

Department of Physics, Yeungnam University, Gyeongsan 712-749, Korea

Ki-Hong Kim

Department of Optometry & Vision Science, Catholic University of Daegu, Gyeongsan 712-702, Korea (Received 13 December 2013 : revised 2 January 2014 : accepted 6 March 2014)

Via an in-situ monitoring tool of phase change during CZTSSe crystallization, we measured the temperature of the Cu

2

ZnSn(SSe)

4

(CZTSSe) absorption layer during a selenization process with a rapid thermal process (RTP). The precursor of Cu/SnS/ZnS was prepared using a DC and RF sputtering process. On top of Cu/SnS/ZnS, Se was deposited by using a thermal evaporator.

We also measured the real-time temperature of the CZTS precursor layer by using a thermocouple placed on the surface of the precursor. Initially, the precursor temperature showed a drop of 50

^◦

C in 1 minute and returned to initial temperature after 2 minute. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were adopted to investigate the cause of the initial temperature drop.

The initial temperature drop was due to the growth of Cu

1−x

Se. Subsequently, Cu

2

Sn(SSe)

3

and Cu

2

ZnSn(SSe)

4

were formed and the temperature gradually returned to its initial value. Additional annealing after the temperature had returned to its initial value increased the XRD intensity of the ZnSSe peak.

PACS numbers: 61.10.Nz, 61.16.Bg, 66.30.Fq Keywords: CZTS, RTP, Secondary phase

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(2013¸   12 Z 4 13{ 9  ~ à Î6 £ §, 2014¸   1 Z 4 2{ 9  à º& ñ ‘ : r ~ à Î6 £ §, 2014¸   3 Z 4 6{ 9  > F  S X ‰& ñ ) 241

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\

 7 £ x ‚ Ã Ì % i Ü ¼ 9, s # Q" f Se`  ¦ \ P 7 £ x ‚ à Ìl \  ¦ s 6   x # Œ 7 £ x ‚ Ã Ì % i  . f  ¨ à º8 £ x ³ ð€  _  z  ´] j “ : r • ¸  H \ P „  @ / (thermocouple) “ : r • ¸> \  ¦ f  ¨ à º8 £ x _  ³ ð€  \  ] X 8 ú ¤ # Œ z  ´r ç ß –Ü ¼– Ð 8 £ ¤& ñ % i  . œ íl \  650

^◦

C  t   © œ 5

p

x ô  Ç f  ¨ à º8 £ x _  “ : r • ¸ s Ê ê 1ì  r1 l x î ß – €  • 50

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C | Ã Ì % i   2ì  r 1 l x î ß –  r   © œ5 p x # Œ œ íl  “ : r • ¸– Ð 4 Ÿ ¤ )

% i  . X-‚    r] X  (X-ray diffraction: XRD) x 9  Å Ò  „    ‰ & ³p  â (scanning electron microscope:

SEM) 8 £ ¤& ñ   õ – РÒ'  œ íl  “ : r • ¸ | à Ì_  " é ¶ “  s  Cu

^1−x

Se _  + þ A$ í \  _ ô  Ç  כ e ” `  ¦ S X ‰ “   % i  . s # Q" f Cu

2

Sn(SSe)

3

ü < Cu

2

ZnSn(SSe)

4

s  + þ A$ í ÷ &€  " f “ : r • ¸ & h    © œ5 p x # Œ œ íl  “ : r • ¸– Ð 4 Ÿ ¤ ) % i  . XRD

 

õ \ " f œ íl  “ : r • ¸ 4 Ÿ ¤ ) Ê ê\  \ P % ƒo  r ç ß –s  7 £ x  €   ZnSSe ’    ñ_  [ jl  7 £ x    H  כ `  ¦ S X ‰ “   

% i  .

PACS numbers: 61.10.Nz, 61.16.Bg, 66.30.Fq Keywords: CZTS, / å L5 Å q \ P % ƒo , s   © œ

I. " e  ] Ø

‰

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„

 t  20.3%_  Z  }“ É r   ¨ 8 Š ´ òÖ  ¦`  ¦ ˜ Г ¦ % i   [1]. ¢ ¸ ô

 Ç CdTe ~ à Ì} Œ • I € ª œ„  t  % i r  ´ ú §s  s 6   x ÷ &“ ¦ e ”  .  t

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_  é ß –& h `  ¦ t “ ¦ e ”  . s  Qô  Ç CIGS x 9  CdTe ~ à Ì} Œ • I

€ ª œ„  t _  é ß –& h `  ¦ F G4 Ÿ ¤ l  0 A # Œ þ j   H \  $ + þ A F K 5

Å q“   Znü < Sn`  ¦ s 6   x ô  Ç º ú ˜ ï
 p  o½ + ËÓ ü t (chalcogenide)“   Cu 2 ZnSnS 4 , Cu 2 ZnSnSe 4 ü < Cu <sup>2</sup> ZnSn(SSe) 4 f  ¨ à º8 £ x`  ¦ s  6

 

x ô  Ç ~ à Ì} Œ • I € ª œ„  t \  @ /ô  Ç ƒ  ½ ¨ ´ ú §s  s À Ò# Q4 R M ® o   [2–6]. s  Qô  Ç I-II-IV-VI7 á ¤  o½ + ËÓ ü t ~ à Ì} Œ • I € ª œ„  t   H $ 

+ þ A ~ à Ì} Œ • I € ª œ„  t – Ð ´ ú §s  Å Ò3 l q ~ à Γ ¦ e ” Ü ¼ 9 Õ ª ´ òÖ  ¦“ É r 11.1%  t  ² ú ˜$ í % i   [7]. ‰ & ³F  Cu ² ZnSnSe 4 (CZTS) f

 ¨ à º8 £ x _  ] j Œ •~ ½ ÓZ O Ü ¼– Ѝ  H ”  / B N x 9  q ”  / B N ~ ½ ÓZ O s   6   x

÷

&“ ¦ e ” Ü ¼ 9, ”  / B N`  ¦ s 6   x ô  Ç ~ ½ ÓZ O s  “ ¦´ òÖ  ¦ õ  @ /| ¾ ÓÒ q tí ß – _

 0 p x$ í s  Z  }“ É r  כ Ü ¼– Ð ó ø Íé ß –  ) a  . ”  / B N`  ¦ s 6   x ô  Ç f  ¨ à º 8

£

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l

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½

¨^ ‰\  ¦ s 6   x ô  Ç ! s qE $ ™ o ~ ½ ÓZ O s  @ /| ¾ ÓÒ q tí ß – / B N& ñ \  & h 6   x  l

 & h ½ + Ëô  Ç ~ ½ ÓZ O Ü ¼– Ð" f s \  @ / # Œ ´ ú §“ É r ƒ  ½ ¨ € 9 כ ¹ 



. ! s qE $ ™ o / B N& ñ _  “ : r • ¸  H f  ¨ à º8 £ x î  r ì ø Í _  S X ‰ í ß – o \ 

% ò

† ¾ Ó`  ¦ p u   H Õ ªY U“   ß ¼l  x 9    & ñ $ í \  % ò † ¾ Ó`  ¦ p u  9, r

ç ß –“ É r s   © œ_  + þ A$ í x 9  ~ à Ì} Œ •  Ò_  MoSe8 £ x _  ¿ ºa 

\

 ´ ú §“ É r % ò † ¾ Ó`  ¦ p • 2 ; . “ ¦´ òÖ  ¦ _  CZTS ~ à Ì} Œ • I € ª œ„  t 

∗

E-mail: [email protected]

\

 ¦ > hµ 1 Ï l  0 AK " f  H f  ¨ à º8 £ x _  : £ ¤$ í \   © œ ´ ú §“ É r % ò † ¾ Ó

`

 ¦ p u   H ! s qE $ ™ o / B N& ñ _  “ : r • ¸ü < r ç ß –`  ¦ þ j& h  o   H  כ s

 ×  æ כ ¹  .

‘

: r ƒ  ½ ¨\ " f  H \ P „  @ / “ : r • ¸> \  ¦ „  ½ ¨^ ‰ ³ ð€  \  f ” ] X  ] X

8 ú ¤ # Œ r « Ñ_  “ : r • ¸    o\  ¦ z  ´r ç ß –Ü ¼– Ð 8 £ ¤& ñ † < ÊÜ ¼– Ð+ ‹

\ P

% ƒo  “ : r • ¸ü < r ç ß –\    É r f  ¨ à º8 £ x _    & ñ $ í s       H

 כ

`  ¦ › ¸  % i  . f  ¨ à º8 £ x _  : £ ¤$ í    o  H X-‚    r] X  (X- ray diffraction: XRD) x 9  Å Ò  „    ‰ & ³p  â (scanning electron microscope: SEM) 8 £ ¤& ñ `  ¦ : Ÿ x # Œ › ¸  % i  .

II. ÷ m Ç ] M ö

]

 t o Ú ÔD ! ps  7 £ x ‚ Ã Ì  ) a ™ è -$ 3  r Ä »o l ó ø Í (soda-lime glass substrate) 0 A\  Û ¼( ' a A (sputtering) ~ ½ ÓZ O Ü ¼– Ð Cu/SnS/ZnS „  ½ ¨^ ‰\  ¦ 7 £ x ‚ Ã Ì % i  . Cu  H DC Û ¼( ' a A

~

½ ÓZ O `  ¦, SnS ü < ZnS  H RF Û ¼( ' a A ~ ½ ÓZ O `  ¦  6   x # Œ 7 £ x

‚ Ã

Ì % i  . s  Ê ê Se`  ¦ \ P 7 £ x ‚ à Ìl  (thermal evaporator)\  ¦ s

6   x # Œ €  • 4 µm 7 £ x ‚ Ã Ì % i  . ] j Œ •  ) a „  ½ ¨^ ‰  H ½ + ɖ Ð



p Ï þ ›á Ô\  ¦ s 6   x ô  Ç / å L5 Å q \ P % ƒo   © œu \ " f \ P % ƒo  % i Ü ¼ 9, \ P % ƒo  / B N& ñ “ : r • ¸  H 650 ^◦ C s % 3  . \ P % ƒo  ×  æ \  Æ Ò

Se / B N/ å L“ É r \ O % 3  . ]  t o Ú ÔD ! ps  7 £ x ‚ Ã Ì  ) a ™ è - e ”  Ä »o l  ó

ø Í_   © œÂ Ò\  \ P „  @ / “ : r • ¸> \  ¦ f ” ] X  ] X 8 ú ¤ # Œ › ' a8 £ ¤ ô  Ç “ : r

•

¸\  ¦ l ì ø ÍÜ ¼– Ð / B N& ñ “ : r • ¸\  ¦ ] j# Q % i  . / B N& ñ · ú š§ 4 “ É r q 

 Ö

¸$ í Û ¼“   ArÜ ¼– Ð G 0 >”   x 9 ` ‚+ þ A / B N ç ß –\ " f 1l · ú šÜ ¼– Ð Ä

»t  % i  . \ P % ƒo  Ê ê Ar ì  r 0 Al \ " f  ƒ   Í ‰ ty Œ • % i  .

„

 ½ ¨^ ‰_  “ : r • ¸  H ¢ ¸   É r \ P „  @ / “ : r • ¸> \  ¦ ~ à Ì} Œ •_  ³ ð€  

\

 f ” ] X  ] X 8 ú ¤ # Œ z  ´r ç ß –Ü ¼– Ð › ' a ¹ 1 Ï % i  . \ P % ƒo  “ : r • ¸



 H 0, 1, 2, 3, 4, 5, 10ì  r Ü ¼– Ð    or (  Ü ¼ 9, ] j Œ •  ) a f  ¨ à º 8

£

x _  : £ ¤$ í “ É r X-‚    r] X  x 9  Å Ò  „    ‰ & ³p  â 8 £ ¤& ñ `  ¦ : Ÿ x

# Œ › ¸  % i  .

Fig. 1. (Color online) Temperatures of Mo-coated glass and sample.

III. + s ÇÊ Ý õ m Í À X Ø8 ý

Figure 1 \  5ì  r ç ß –_  / å L5 Å q \ P % ƒo  / B N& ñ ×  æ _  ] j# Q“ : r • ¸ ü < f  ¨ à º8 £ x _  8 £ ¤& ñ “ : r • ¸_     o\  ¦
 ? /% 3  . Se_  ’ < Hz  ´

`

 ¦ þ j@ /ô  Ç % 3 ] j l  0 A # Œ €  • 30 ^◦ C/s _  q “ §& h    É r 5 Å q

•

¸– Ð “ : r • ¸\  ¦  © œ5 p x r (   . 650 ^◦ C \ " f 5 min 1 l x î ß – \ P % ƒo 

\

 ¦ ô  Ç Ê ê Í ‰ ty Œ •r (   . Õ ªa Ë >\ " f
 
1 p w s  \ P % ƒo   © œu  _

 / B N& ñ “ : r • ¸  H 650 ^◦ C – Ð Ä »t ÷ &“ ¦ e ” Ü ¼
 f  ¨ à º8 £ x _  “ : r

•

¸  H % ƒ6 £ § 1ì  r ç ß – & h  & h Ü ¼– Ð 50 ^◦ C & ñ • ¸ | Ã Ì % i  

2ì  r ç ß – & h    © œ5 p x # Œ œ íl “ : r • ¸– Ð 4 Ÿ ¤ ) ô  Ç Ê ê { 9 & ñ ô  Ç “ : r

•

¸\  ¦ Ä »t  % i  . s  Qô  Ç f  ¨ à º8 £ x _  “ : r • ¸   o  H ~ à Ì} Œ •s 

\ P

% ƒo  r ç ß –\       & ñ $ í õ   o½ + ËÓ ü t _  ½ ¨$ í s     o 



 H  כ `  ¦ _ p ô  Ç . 7 £ ¤ œ íl _   o½ + ËÓ ü t õ 
×  æ _   o½ + ËÓ ü t _ 



© œI  " f– Ð  \  ¦  כ Ü ¼– Ð \ V8 £ ¤ ) a  . \ P % ƒo  r ç ß –\    É r f

 ¨ à º8 £ x _    & ñ $ í x 9   o½ + ËÓ ü t ½ ¨› ¸_     o\  ¦  [ jy  ƒ  ½ ¨

l  0 A # Œ \ P % ƒo  r ç ß –`  ¦    or (   . \ P % ƒo  r ç ß –“ É r



  o÷ &% 3 Ü ¼
 — ¸Ž  H r « Ñ[ þ t s  1 l x{ 9 ô  Ç ½ ¨ç ß –\ " f  H 1 l x{ 9 ô  Ç

“

: r • ¸    o\  ¦
 ? /% 3  . \ P % ƒo  r  Œ • 3ì  r Ê ê\   H r « Ñ_ 

“

: r • ¸ œ íl  “ : r • ¸– Ð 4 Ÿ ¤ ) % i Ü ¼ 9, s  Ê ê\   H  _  { 9 & ñ

>  Ä »t ÷ &% 3  .

Figure 2“ É r \ P % ƒo  r ç ß –    o\    É r XRD   õ s  .

„

 ½ ¨^ ‰\ " f  H Cu, SnS ü < ZnS_  ’    ñ ¸ ú ˜ › ' a8 £ ¤ ÷ &% 3  .

\ P

7 £ x ‚ à Ìl \  ¦ s 6   x # Œ 7 £ x ‚ à Ìô  Ç Se“ É r   & ñ $ í `  ¦ t t  3 l w

“ ¦ q & ñ | 9  © œI – Ð 7 £ x ‚ à Ì÷ &# Q ± ú ˜ – Ðî  r ’    ñ\  ¦ › ' a8 £ ¤ ½ + É Ã º

\ O

% 3 Ü ¼
 20 ∼ 35 ^◦ \    5 g ± ú “ ¦ V , > 
 z Œ ¤ . \ P % ƒo 

“

: r • ¸ t  5 p x“ : r Ê ê  – Ð Í ‰ ty Œ •ô  Ç 0 min \ P % ƒo _   â Ä º 30 ^◦

Fig. 2. (Color online) XRD results of samples as a func- tion of annealing time.



 H % ƒ\ " f  € ª œô  Ç s   © œ (secondary phase) [ þ t s 
 z Œ ¤ Ü

¼ 9, s [ þ t“ É r Cu ü < Ses  { 9 Â Ò ì ø Í6 £ x ô  Ç Cu 1−x Se x 9  6   xÖ 6 x Ê

ê 0 l q Ü ¼€  " f F   & ñ `  ¦ + þ A$ í ô  Ç “ ¦^ ‰ Se\  _ ô  Ç  כ Ü ¼– Ð Æ Ò

&

ñ  ) a  . ì ø Í6 £ x r ç ß –s   ú ª  SnSõ  ZnS  H p % ƒ ì ø Í6 £ x t  3

l

w # Œ › ' aº   ) a ’    ñ  f ” 
 
“ ¦ e ”  . 1 min \ P % ƒ o

_   â Ä º SnS_  ’    ñ   ”    כ Ü ¼– Ð ˜ Ð  SnS ~ à Ì} Œ •“ É r



_  — ¸¿ º Cu 1−x Se õ  ì ø Í6 £ x # Œ Cu 2 Sn(SSe) ₃ `  ¦ + þ A$ í ô  Ç

 כ

Ü ¼– Ð ˜ Ðs  9, SnSe ’    ñ• ¸ { 9 Â Ò › ' a8 £ ¤ ) a  . Õ ª Q
   f ”

 ZnS ’    ñ
 
  H  כ Ü ¼– Ð ˜ Ð  Cu ² ZnSn(SSe) 4   H + þ

A$ í ÷ &t  3 l w % i  . 2 ∼ 5 min t  \ P % ƒo  r ç ß –s  7 £ x 

½

+ Éà º2 Ÿ ¤ ZnS, ZnSe õ  Cu ² Sn(SSe) 3 ’    ñ_  [ jl  & h  

€



•K t €  " f Cu ² ZnSn(SSe) 4 ’    ñ_  ß ¼l  7 £ x  % i  .

0

A_    õ – РÒ'  Ä ºo   H  6 £ § õ  ° ú  “ É r    : r`  ¦ % 3 `  ¦ à º e ” 



. / å L5 Å q \ P % ƒo   © œu \  ¦  6   x # Œ \ P % ƒo \  ¦ ½ + É  â Ä º r « Ñ _

 „  ^ ‰\ " f 1 l x r \  ì ø Í6 £ x s  { 9 # Q
  H  כ s   m   \ P s 

K t   H  © œÂ Ò\ " f Ò'  & h  & h Ü ¼– Ð ì ø Í6 £ x s  { 9 # Q
" f   A

– Ð ”  ' Ÿ ô  Ç . \ P % ƒo  r ç ß –s  7 £ x ½ + Éà º2 Ÿ ¤ ]  t o Ú ÔD ! p ’    

ñ_  ß ¼l  7 £ x    H  כ “ É r ì ø Í6 £ x \  ‚ à Ð# Œ t  3 l w ô  Ç Se_  7

£

x µ 1 Ïõ  SnSeõ  ° ú  “ É r s   © œ_  7 £ x µ 1 ϖ Ð “   # Œ  © œÂ Ò ~ à Ì} Œ • _

 ¿ ºa  & h   · û ª & ’ l  M :ë  H s  .

Fig. 3. SEM images of samples as a function of annealing time.

Fig. 4. (Color online) XRD results of samples with an- nealing time of 5 and 10 minute.

Figure 3“ É r \ P % ƒo  r ç ß –    o\    É r r « Ñ_  é ß –€   SEM



”  s  . 0 min  â Ä º SnSõ  ZnS 8 £ x _   â >   H Ì º§  > 

½

¨ì  r ÷ & 9, ~ à Ì} Œ •_  + þ AI – Ð ˜ Ð   f ”    É r Ó ü t| 9 õ _  ì ø Í6 £ x s

 { 9 # Q
t  · ú §“ É r  © œI s  . Õ ª Q
 Cuü < Se_   â > €   s

 Ì º§  t  · ú §“ É r  כ “ É r s „   XRD   õ \ " f Cu Seõ  _

 ì ø Í6 £ x Ü ¼– Ð “   # Œ Cu ^1−x Se ’    ñ
 è ß –  כ õ  ¸ ú ˜ { 9  u

ô  Ç . ¢ ¸ô  Ç Se_  ¿ ºa • ¸ 4 µm\ " f 2.78 µm– Ð y Œ ™™ è 

%

i  . 1 min s  Ê ê\   H y Œ • 8 £ x[ þ t _   â > \  ¦ Ì º§  >  › ' a8 £ ¤

t  3 l w % i Ü ¼ 9, 4 min s  Ê ê\   H Õ ªY U“  [ þ t`  ¦ S X ‰ “  ½ + É Ã

º e ” % 3  .

Figure 4  H \ P % ƒo  r ç ß –s  y Œ •y Œ • 5ü < 10 min“   r « Ñ_  XRD   õ s  . 10 min   õ \ " f s „  \  › ' a8 £ ¤ ½ + É Ã º \ O % 3 

~

  ZnSe ’    ñ\  ¦ › ' a8 £ ¤ % i  . s  כ “ É r \ P % ƒo  r ç ß –s  7 £ x 

Fig. 5. SEM images of samples with annealing time of 5 and 10 minute.

†

< Ê\     Sn_  ’ < Hz  ´s  7 £ x  “ ¦   õ & h Ü ¼– Ð Zn  H õ e ç s

 ÷ &# Q ï ß –# Œ Seõ  ì ø Í6 £ x # Œ ZnSe`  ¦ + þ A$ í % i l  M :ë  H s 



 [8].

Figure 5  H \ P % ƒo  r ç ß –s  y Œ •y Œ • 5ü < 10 min“   r « Ñ_  SEM   õ s  . \ P % ƒo  r ç ß –s  7 £ x ½ + Éà º2 Ÿ ¤ CZTSSe ~ Ã Ì }

Œ

•_  Õ ªY U“   ß ¼l   H 7 £ x  % i Ü ¼
 ]  t o Ú ÔD ! p 8 £ x _  ¿ ºa 



 H 575 nm \ " f 714 nm– Ð €  • 140 nm & ñ • ¸ 7 £ x  % i  .

Û

¼( ' a A`  ¦ s 6   x ô  Ç 7 £ x ‚ Ã Ì / B N& ñ \  _  # Œ 1 p x ç ß –  _  48 £ x Ü ¼

–

Ð ½ ¨ì  r ÷ &# Q ˜ Ðs ~   ]  t o Ú ÔD ! p_  8 £ x s  10 min \ P % ƒo \ 

"

f  H  A _  38 £ x _  ¿ ºa   H { 9 & ñ 
  © œÂ Ò 1> h 8 £ x _  ¿ ºa  ë

ß – 7 £ x  % i  . s  Qô  Ç   õ – РÒ'  ¿ ºa  7 £ x ô  Ç  © œÂ Ò



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