Tuning of Photoluminescence of Sr(Zr,Hf)O 3 :Cu by Using the Photo-excitation Energy

(1)

Tuning of Photoluminescence of Sr(Zr,Hf)O ₃ :Cu by Using the Photo-excitation Energy

Dongjae Lee · Yunsang Lee ^∗

Department of Physics, Soongsil University, Seoul 156-743, Korea (Received 26 May 2015 : revised 22 June 2015 : accepted 23 June 2015)

We investigated the visible emission of Cu-ion-doped Sr(Zr,Hf)O

3

at various photo-excition en- ergies. In the Cu-ion-doped SrZrO

3

(SZO:Cu), the peak position of the visible emission changed from 400 nm (violet) to 600 nm (yellow) as the photo-excitation wavelength was tuned from 220 nm to 375 nm. This tunable multicolor behavior depended on the concentration of the Cu-ion doping.

The Cu-ion-doped SrHfO

3

(SHO:Cu) show optical properties similar to those of SZO:Cu. For a qualitative analysis, we calculated the CIE chromaticity coordinates of our samples. Our results suggest that the tunable multicolor emission in SZO:Cu and SHO:Cu can be utilized for ultraviolet sensors.

PACS numbers: 78.20.-e, 78.20.Ci

Keywords: Sr(Zr,Hf)O

3

, Cu ion doping, Photo-excitation energy, Tunable emission color

° Ë

Ñ-# bM ; c .U ; c Â \ ¥ Sr(Zr,Hf)O ³ :Cu8 ý ° Ë Ñ® o° Ë Ñ V R Ëù m Ç ì Å

T

ò 6 B< · T * × < ç ¡ ^∗

Õ

ü æz ´@ / < Æ § Ó ü t o < Æõ , " fÖ ¦ 156-743

(2015¸ 5 Z 4 26{ 9 ~ Ã Î6 £ §, 2015¸ 6 Z 4 22{ 9 Ã º& ñ : r ~ Ã Î6 £ §, 2015¸ 6 Z 4 23{ 9 > F S X & ñ )

H ½ × ¼Ì s` ¦ ° ú H SrZrO

3

ü < SrHfO

3

Ó ü t| 9 \ " f 3d s F K5 Å q ½ ¨o s : r` ¦ ' # µ 1 Ï & ³÷ & H r

F g % ò % i _ µ 1 Ï F g: £ ¤$ í s F g # l \ -t \ ß ¼> _ > r < Ê` ¦ ½ ¨ % i . ½ ¨o s : r s ' ) a SrZrO

3

(SZO:Cu) _ â Ä º, F g- # l © ` ¦ 220 nm \ " f 375 nm Ð o µ 1 Ï F g Û ¼& 7 à Ô! 3 _ 0 Au 400 nm ( Ð Ò o)\ " f 600 nm ( ¸| ½ ÓÒ o) Ð 7 % 3 . s Qô Ç F g- # l \ -t \ É r µ 1 Ï F gÒ o_ o H ½ ¨o s

:

r _ ' | ¾ Ó\ Ø Ô> ' a8 £ ¤ ÷ &% 3 . ½ ¨o s : r s ' ) a SrHfO

3

(SHO:Cu) Ó ü t| 9 ¸ SZO:Cuü < Ä »

ô Ç F g < Æ & ³ © s Ð% i . & ñ | ¾ Ó& h ì r$ 3 ` ¦ 0 AK CIE t Ã º\ ¦ > í ß % i . SZO:Cuü < SHO:Cu\ " f / B N :

x& h Ü ¼ Ð ' a8 £ ¤ ÷ & H F g- # l \ -t \ É r µ 1 Ï F gÒ o ¸] X $ í É r ü @ G ' p" f\ Ö ¸6 x| ¨ c Ã º e ` ¦ כ s .

PACS numbers: 78.20.-e, 78.20.Ci

Keywords: Sr(Zr,Hf)O

3

, ½ ¨o s : r ' , F g # l \ -t , µ 1 Ï F gÒ o ¸] X $ í

∗

E-mail: [email protected]

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License

(http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in

any medium, provided the original work is properly cited.

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676 New Physics: Sae Mulli, Vol. 65, No. 7, July 2015

I. " e Â ] Ø

3d s F K5 Å q s : r É r F g < Æ& h Ö ¸$ í ] j Ð V , o Ö ¸6 x ÷ & ¦ e

[1]. s F K5 Å q s ' | ¨ c M :, é ß { 9 " é ¶ ? /\ " f H 1 l x { 9

ô Ç \ -t ï r 0 A\ ¦ ° ú H s F K5 Å q _ 3d ¸q » 1 Ï © I

Å

Ò _ 6 £ § s : r \ _ ô Ç crystal field\ _ K î ß 2 ; © I

) a . s M : ¸q » 1 Ï © I ç ß _ s \ -t r F g

% ò

% i \ K { © ÷ &# Q Ä ºÃ ºô Ç F g < Æ: £ ¤$ í ` ¦ Ðs > ) a . ª ô

Ç 3d s F K5 Å q \ @ /K ½ ¨ Ö ¸ µ 1 Ïy ' ÷ & ¦ e H X <, :

£

¤ y ½ ¨o s : r` ¦ ì ø Í ¸^ x 9 í ß oÓ ü t ] X ^ \ ' # :

£

¤ s ô Ç r F g µ 1 Ï F g` ¦ Ä » ¸ 9 H ½ ¨ Å Ò3 l q ~ Ã Î ¦ e

. ½ ¨o s : r` ¦ ' ô Ç II-IV ì ø Í ¸^ H Õ ª ½ ¨$ í " é ¶ è_ 7

á

x À Óü < ¸{ 9 _ ß ¼l \ ½ ¨o s : r \ _ ô Ç µ 1 Ï F g _

Ò os ¸] X ) a [2,3]. ZnO_ â Ä º ½ ¨o s : r _ ' Ð y

© ô Ç í2 ¤ µ 1 Ï F g` ¦ Ä » ¸½ + É Ã º e [4,5]. ¢ ¸ô Ç ½ ¨o s : r s '

) a F g < Æ& h & ñ $ 3 Ä » H UVC radiation dosimetry Ð

6 x s 0 p x o \ V © ¦ e [6]. { 9 ì ø Í& h Ü ¼ Ð ½ ¨o s

: r 3d ¸q » 1 Ï_ \ -t ï r 0 A H ñÛ ¼à Ô Ó ü t| 9 _ ½ × ¼Ì s

s \ 0 Au ô Ç [2].

`

ÐÚ ÔÛ ¼ s à Ô+ þ A ½ ¨ ¸\ ¦ ° ú H 4d, 5d s F K5 Å q í ß o Ó

ü t SrZrO ₃ ü < SrHfO 3 H ½ × ¼ ] X ^ Ð, & ³F V , o Ö ¸ 6

x ÷ & ¦ e H 3d s F K5 Å q í ß oÓ ü t õ Ä » > \ P % i < Æ& h Ü

¼ Ð î ß & ñ ¦ ] j ¸ 6 x s 9 ¦ : r : £ ¤$ í s Ä ºÃ º #

Ö

¸6 x$ í s H [ j b Û ¼ Ð" f_ : £ ¤f ç ` ¦ Ð [7,8].

4d/5d s F K5 Å q í ß oÓ ü t É r 3d s F K5 Å q í ß oÓ ü t \ q K ©

@

/& h Ü ¼ Ð É r l 6 £ §$ í ¸\ ¦ ° ú l M :ë H \ ½ × ¼Ì ss B Ä

º H : £ ¤f ç ` ¦ ° ú ¦ e [9]. \ V\ ¦ [ þ t # Q, 3d s F K5 Å q í ß o Ó

ü t SrTiO ₃ _ â Ä º ½ × ¼Ì ss 3.4 eVs t ë ß , SrZrO 3 _

½ × ¼Ì s É r 5.6 eV s 9 SrHfO ³ _ ½ × ¼Ì s É r 6.1 eV s . < É ª p

\ v > ¸ SrZrO 3 ü < SrHfO 3 H H ½ × ¼Ì s` ¦ ° ú ¦ e # Q ¸ He-Cd Laser ü < ° ú s UVA (λ = 325 nm ∼ 3.8 eV)\ _ K

"

f ¸ Ä ºÃ ºô Ç µ 1 Ï F g : £ ¤$ í ` ¦ Ð [10]. ¢ ¸ô Ç V , É r ½ × ¼Ì s

\

-t % ò % i \ < Ê ¸× ¼ + þ A$ í | ¨ c r \ < Ê ¸× ¼[ þ t ç ß _

g Ë >s & h # Q y < Ê ¸× ¼_ \ -t © I ½ ¨ì r ÷ &# Q ' a 8

£

¤| ¨ c 0 p x$ í s Z } . s H s F K5 Å q s ' ÷ &# Q µ 1 Ï F g: £ ¤

$ í

` ¦ Ð{ 9 M :, s F K5 Å q _ " é ¶ \ < Ê ¸× ¼[ þ t s

Ø Ô> + þ A$ í ÷ &# Q Z > & h F g < Æ$ í | 9 ` ¦ µ 1 Ï & ³½ + É Ã º e 6 £ §

`

¦ _ p ô Ç . s Qô Ç ½ ¨3 l q& h Ü ¼ Ð Ä ºo H ½ ¨o s : r` ¦ SrZrO 3 ü < SrHfO ³ Ó ü t| 9 \ ' # F g- # l © \ É r F

g < Æ$ í | 9 ` ¦ ½ ¨ % i . ½ ¨o s : r s ñÛ ¼à Ô Ó ü t| 9 ? /Â Ò

\

" f ¿ º > h_ " é ¶ \ ¦ ° ú ¦ s \ F g < Æ$ í | 9 s Ø Ô

>

µ 1 Ï & ³÷ &# Q, õ & h Ü ¼ Ð µ 1 Ï F gÒ os V , É r Û ¼& 7 à Ô! 3 % ò % i

\

" f ¸] X ÷ &# Q µ 1 Ï & ³H d` ¦ s K % i . & ñ | ¾ Ó& h ì r$ 3 ` ¦ 0

AK CIE t Ã º\ ¦ > í ß % i ¦, Ó ü t| 9 Z > , ' | ¾ ÓZ > Ð q § ì

r$ 3 % i . : r ½ ¨ H ½ ¨o s : r` ¦ F g < Æ& h Ö ¸$ í ] j Ð Ö ¸ 6

x ô Ç s _ ì ø Í ¸^ ½ ¨ü < q §½ + É M :, ½ × ¼Ì ss B Ä º H SrZrO 3 ü < SrHfO ³ \ s F K5 Å q s : r` ¦ ' D h Ðî r µ

1 Ï F g: £ ¤$ í s µ 1 Ï & ³÷ &# Q F g- èF Ð" f_ s 6 x 0 p x$ í s Z

} H כ ` ¦ Ð ¦ô Ç .

II. ÷ m Ç ] M ö

½

¨o s : r s ' ) a SrZrO 3 (SZO:Cu) ü < SrHfO ³ (SHO:Cu) r « Ñ H ¦ © ì ø Í6 £ xZ O Ü ¼ Ð ] j % i . $ , SrCO 3 ü < ZrO ² (HfO 2 )\ ¦ 1:1 q Ö ¦ Ð V , ¦, s ì r ´ ú ` ¦ 900

◦ C \ " f 12r ç ß ` ¦ è # SrZrO 3 (SrHfO ₃ ) © ` ¦ y y + þ

A$ í % i . Õ ª Ê ê ^ ] t \ x (x = 0.01 - 0.1)ë ß p u _ CuO\ ¦ V , ¦ ¦À Ò> [ O É r Ê ê\ , : \ Ï @ + þ AI Ð · ú § 4 ` ¦ ô Ç Ê

ê 1400 ^◦ C \ " f 48r ç ß è # SZO:Cu (SHO:Cu)\ ¦

½

+ Ë$ í % i [11].

r

« Ñ[ þ t _ ½ ¨ ¸\ ¦ ì r$ 3 l 0 AK , Bruker-AXS Discover D8 (λ = 1.5406 ˚ A)` ¦ 6 x # X r] X (XRD) z ´+ « >` ¦ Ã

º' % i . F g- # l \ -t Z > F g µ 1 Ï F g Û ¼& 7 à Ô! 3 ` ¦ 8 £ ¤& ñ

l 0 AK JASCO FP-8000 Series Spectrometer\ ¦ 6 x

% i . 6 x ô Ç F g- # l \ -t _ © (λ ex ) % ò % i É r λ ex

= 220 - 375 nm s . ¸ H F g < Æ8 £ ¤& ñ É r © : r \ " f '

% i .

III. + s ÇÊ Ý õ m Í w ² o

Fig. 1 É r x = 0.1 SZO:Cu _x=0.1 ü < SHO:Cu x=0.1 r « Ñ _

XRD θ-2θ Û ¼ ± p 8 £ ¤& ñ õ \ ¦ Ð# ï r . q §\ ¦ 0 AK SrZrO 3 ü < SrHfO 3 _ JCPDS X <s ' \ ¦ í < Ê % i . Õ ªa Ë >

\

" fü < ° ú s , SZO:Cuü < SHO:Cu r « Ñ[ þ t É r ½ ¨o '

÷

&t · ú § É r SrZrO 3 ü < SrHfO 3 ü < 1 l x{ 9 ô Ç ~ ½ Ó& ñ > ` ÐÚ Ô Û

¼ s à Ô_ XRD J ` ¦ Ð [12]. ¢ ¸ô Ç 0 p x ô Ç Ô ¦í H Ó

ü t SrCO ₃ , ZrO ₂ , HfO ₂ , CuO, CuO ₂ © _ XRD ñ

' a8 £ ¤ ÷ &t · ú § ¤ . s H © { © | ¾ Ó_ ½ ¨o s : r` ¦ '

8 ¸ í H Ã ºô Ç SrZrO ₃ ü < SrHfO 3 ° ú H ~ ½ Ó& ñ > ` Ð Ú

ÔÛ ¼ s à Ô ½ ¨ ¸ o t · ú § H H כ ` ¦ _ p ô

Ç .

½

¨o s : r _ ' \ _ ô Ç µ 1 Ï F g: £ ¤$ í _ o\ ¦ ¸ l

0 AK F g- # l \ -t (E ex ) \ É r F g µ 1 Ï F g Û ¼& 7 à Ô! 3

`

¦ 8 £ ¤& ñ % i . Fig. 2 H x = 0.1 ½ ¨o s : r ' r « Ñ SZO:Cu _x=0.1 _ © : r F g µ 1 Ï F g Û ¼& 7 à Ô! 3 ` ¦ Ð# ï r . F g-

#

l \ -t _ © (λ ex ) % ò % i É r λ ex = 220 - 375 nm s

. < É ª p \ v > ¸ λ ^ex \ SZO:Cu ^x=0.1 r « Ñ_ r F g µ

1 Ï F g: £ ¤$ í s ß ¼> o < Ês ' a8 £ ¤ ) a . $ , Fig. 2(a)\

(3)

Fig. 1. (Color online) X-ray diffraction (XRD) θ-2θ scans of (a) SrZrO ₃ :Cu and (b) SHO:Cu. For comparison, the JCPDS data of SrZrO ₃ (44-0161) and SrHfO ₃ (45-0211) are included.

"

f Ð# t 1 p w s , λ ex = 220 nm { 9 M : 400 nm Â Ò H \ " f Ð

Ò o_ y © ô Ç µ 1 Ï F g s ' a8 £ ¤ ) a . s Qô Ç & ³ © É r λ ex = 270 nm | ¨ c M : t Ä »t ) a . λ ^ex = 295 nm Ð U ´# Qt , 400 nm Â Ò H _ µ 1 Ï F g s | © A á ¤ Ü ¼ Ð s 1 l x " f 470 nm Â Ò H \ " f Ì º§ Â ô Ç | ½ ÓÒ o µ 1 Ï F g` ¦ Ð . λ ^ex \ ¦ 335 nm s © Ü ¼ Ð 8¹ ¡ ¤ U ´> , 470 nm_ | ½ ÓÒ o µ 1 Ï F g s y

è ¦, 600 nm_ ¸| ½ ÓÒ o µ 1 Ï F g s µ 1 Ï² ú > ) a . s ü <

° ú

s , SrZrO ³ :Cu x=0.1 r « Ñ H λ ex U ´# Qf \ µ 1 Ï F g

¸× ¼_ 0 Au 400 nm\ " f 470 nm, Õ ªo ¦ 600 nm Ð s 1

l

x " f, λ ex \ µ 1 Ï F gÒ os ¸] X ÷ & H < É ª p Ðî r F g < Æ

&

³ © ` ¦ Ð# ï r . s Qô Ç µ 1 Ï F gÒ o ¸] X $ í É r ½ ¨o s : r _ '

0 l x ¸ & h É r SZO:Cu x=0.01 \ " f ¸ Ä » > ' a8 £ ¤ ) a

.

E ex \ É r µ 1 Ï F gÒ o_ ¸] X $ í É r SHO:Cu \ " f ¸ ' a8 £ ¤ ½ + É Ã

º e . Fig. 3 H x = 0.1 SHO:Cu (SHO:Cu _x=0.1 ) _ µ 1 Ï F

g Û ¼& 7 à Ô! 3 ` ¦ Ð# ï r . λ ex = 250 nm{ 9 M : 400 nm Â Ò

H _ Ð Ò o µ 1 Ï F g s y © > ' a8 £ ¤ ) a . λ ^ex ` ¦ 280 nm Ð

Ë ¨ 400 nm Â Ò H _ µ 1 Ï F g s y è ¦ 450 nm Â Ò H _

| ½ ÓÒ o µ 1 Ï F g ¸× ¼õ 600 nm Â Ò H _ ¸| ½ ÓÒ o µ 1 Ï F g ¸

×

¼ & h & h µ 1 Ï² ú > ) a . λ ^ex = 365 nm Ð U ´# Qt 600 nm _ ¸| ½ ÓÒ o µ 1 Ï F g s Ä º[ j > ) a . Ä » ô Ç & ³ © É r

Fig. 2. Photoluminescence spectra of SZO:Cu x=0.1 with respect to the photo-excitation energy. The arrows mark the photo-excitation wavelength.

SHO:Cu _x=0.01 \ " f ¸ ' a8 £ ¤ ) a . s ü < ° ú s , E ex \ É r µ

1 Ï F gÒ o_ ¸] X $ í É r ½ ¨o s : r s ' \ _ K SrZrO ³ ü <

SrHfO 3 Ó ü t| 9 \ " f / B N: x& h Ü ¼ Ð ' a8 £ ¤ ÷ & H & ³ © e ` ¦ · ú Ã º e

.

z

´] j r y & h Ü ¼ Ð ' a8 £ ¤ ÷ & H µ 1 Ï F gÒ o` ¦ ì r$ 3 l 0 AK , F

g- # l \ -t \ É r µ 1 Ï F gÒ o` ¦ Ü ¼ Ð ¶ ú ( R Ð ¤ .

SZO:Cu ü < SHO:Cu Ä » ô Ç J ` ¦ Ðs Ù ¼ Ð, : r 7 Hë H

\

" f H SZO:Cu \ @ /K " f 7 H _ \ ¦ | 9 × æ % i . Fig. 4 H SZO:Cu r « Ñ\ ª ô Ç © _ y n C` ¦ ¸ # H µ

1 Ï F g` ¦ n t _ O B j Ð O É % ò ô Ç כ s . F g- # l © õ

½

¨o s : r ' | ¾ Ó\ µ 1 Ï F gÒ os ¸] X H d` ¦ ì r" î > S X

½ + É Ã º e . $ , ½ ¨o s : r ' | ¾ Ó x\ É r s p

t \ ¦ ¶ ú ( R Ð , x = 0.005 H © @ /& h Ü ¼ Ð | ½ ÓÒ o > \ P _

Ò o © s y © > è ß . λ ^ex = 220 nm \ " f H + þ A

&

h ê ø ÍÒ os Ðs ¦, λ ex s U ´# Q4 R" f λ ex = 375 nm

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678 New Physics: Sae Mulli, Vol. 65, No. 7, July 2015

Fig. 3. Photoluminescence spectra of SHO:Cu _x=0.1 with respect to the photo-excitation energy. The arrows mark the photo-excitation wavelength.

÷

& Ô É r y n C` ¦ { H Ñ þ Ò oF g s ' a8 £ ¤ ) a . x 7 £ x ½ + ÉÃ º 2

¤, Z } É r F g- # l \ -t % ò % i \ " f H & h Ð Ò o µ 1 Ï F g

`

¦ Ðs ¦, ± ú É r F g- # l \ -t \ " f H Å Ò S ! Ò o µ 1 Ï F g Ü ¼ Ð S X

@ /÷ &# Q, ì ø Í& h Ü ¼ Ð V , É r Ò o % ò % i _ µ 1 Ï F g Û ¼& 7 à Ô! 3 ` ¦

Ð# ï r . s H ½ ¨o s : r ' | ¾ Óõ F g- # l \ -t \

F g µ 1 Ï F gÒ os V , É r \ -t % ò % i \ " f ] j# Q | ¨ c Ã º e 6

£

§` ¦ _ p ô Ç .

&

ñ | ¾ Ó& h ì r$ 3 ` ¦ 0 AK SZO:Cuü < SHO:Cu_ Ò o ý

. Fig. 5(a)ü < Fig. 5(b) (Fig. 5_ ¢ , aA á ¤ J V , ) H SZO:Cu _x=0.01 ü < SZO:Cu x=0.1 _ Ò oý a³ ð\ ¦ Ð# ï r .

$

SZO:Cu x=0.01 _ â Ä º (Fig. 5(a)), λ ex = 220 - 295 nm{ 9 M :_ Ò oý a³ ð ³ ðï r | ½ ÓÒ o_ t & h \ H] X # 0

Au ¦, λ ex = 315 nm \ " f 7 £ x Ò oý a³ ð_ 0 A u

| ½ ÓÒ o % ò % i \ " f Ñ þ Ò o % ò % i Ü ¼ Ð s 1 l x < Ê` ¦ S X

½

+ ÉÃ º e . Fig. 5(b)\ " f Ðs H SZO:Cu x=0.1 _ â Ä º, SZO:Cu x=0.01 \ q K Ò oý a³ ð V , > ` 5 g4 R e ¦ Õ ª

% ò

Fig. 5(d) (Fig. 5 _ ¸ É rA á ¤ J V , ) É r SHO:Cu x=0.01 ü <

SHO:Cu x=0.1 _ Ò oý a³ ð\ ¦ Ð# ï r . SrHfO 3 :Cu 0.01 É r

Fig. 4. (Color online) Photos of SZO:Cu for x = 0.005, 0.01, 0.02, and 0.1 under irradiation of the λ ex = 220 - 375 nm light.

SZO:Cu _x=0.01 \ q K ± ú É r F g- # l \ -t \ _ ô Ç

¸| ½ ÓÒ o µ 1 Ï F g s µ 1 Ï² ú K e 6 £ §` ¦ · ú Ã º e . ì ø Í , SHO:Cu x=0.1 _ â Ä º, SZO:Cu ^x=0.1 \ q K Z } É r F g- # l

£

¤ ) a . s Qô Ç ' a8 £ ¤ õ [ þ t` ¦ 7 á x ½ + ËK Ð , F g- # l \ - t

ü < ½ ¨o s : r ' | ¾ Óõ 8Ô ¦ # Q & h ] X ô Ç Ó ü t| 9 × þ ` ¦ : x K

.

s

] j t 7 H _ ô Ç F g- # l \ -t \ É r µ 1 Ï F gÒ o_ ¸ ] X

$ í É r, µ 1 Ï F g Û ¼& 7 à Ô! 3 \ " f ^ ¦ Ã º e % 3 ~ 3t ¸× ¼ (400 nm, 480 nm Õ ªo ¦ 600 nm ¸× ¼) F g- # l \ -t \

í H & h Ü ¼ Ð " f H õ s . s Qô Ç : £ ¤ s

Ò8 £ ¤ ) a . í ß oÓ ü t \ ' ) a ½ ¨o s : r É r +1 õ +2_ " é ¶

\

< ' aº ) a µ 1 Ï F g s Z } É r \ -t \ " f ' a8 £ ¤ ) a . < É ª p \ v >

¸ ± ú É r F g- # l \ -t Ð µ 1 Ï F g` ¦ µ 1 Ï & ³r ~ ´ M :, Cu ²⁺ _

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Fig. 5. (Color online) CIE of the emission of (a) SZO:Cu x=0.01 , (b) SZO:Cu x=0.1 , (c) SHO:Cu x=0.01 , and (d) SHO:Cu x=0.1 .

µ

H כ Ü ¼ Ð Ð . s X O 1 p w F g- # l \ -t \ É r µ 1 Ï F

g ~ ½ Ód _ s \ _ K V , É r r F g % ò % i _ Ò o ¸] X $ í s

0 p x ô Ç כ Ü ¼ Ð Ð .

IV. + s Ç Â ] Ø

: r ½ ¨\ " f H ½ ¨o s : r` ¦ ' ô Ç SrZrO ₃ ü < SrHfO 3

Ó

ü t| 9 \ " f r F g % ò % i _ µ 1 Ï F g: £ ¤$ í s F g # l \ -t \ ß

¼> _ > r < Ê` ¦ ' a8 £ ¤ % i . F g- # l \ -t \ ¦ UVC \ " f UVA Ð Ë ¨ µ 1 Ï F g Û ¼& 7 à Ô! 3 _ 0 Au 400 nm ( Ð Ò

o)\ " f 600 nm ( ¸| ½ ÓÒ o) Ð ¸] X ÷ &% 3 . s Qô Ç F g- # l

\

-t \ É r µ 1 Ï F gÒ o_ o H ü @ \ -t \ ¦ ì rZ >

# y > 8 £ ¤& ñ ½ + É Ã º e H כ ` ¦ _ p ô Ç . s Qô Ç

Ö

¸6 x| ¨ c Ã º e ` ¦ כ s .

ACKNOWLEDGEMENTS

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MOE) (No.2013R1A1A2012281).

REFERENCES

[1] P. A. Cox, Transition Metal Oxides: An Introduc- tion to Their Electronic Structure and Properties (Oxford, Clarendon, 1992).

[2] B. B. Srivastava, S. Jana and N. Pradhan, J. Am.

Chem. Soc. 133, 1007 (2010).

[3] J. H. Yu, S.-H. Kwon, Z. Petrasek, O. K. Park and S. W. Jun et al., Nat. Mater. 12, 359 (2013).

[4] R. Dingle, Phys. Rev. Lett. 23, 579 (1969).

[5] Z. A. Khan, A. Rai, S. R. Barman and S. Ghosh, Appl. Phys. Lett. 102, 022105 (2013).

[6] H. E. Hamzaoui, Y. Ouerdane, L. Bigot, G. Bouw- mans and B. Capoen et al., Opt. Express 20, 29751 (2012).

[7] J. K. Thomas, H. P. Kumar, R. Pazhani, S. Solomon and R. Jose et al., Mater. Lett. 61, 1592 (2007).

[8] F. Boschini, A. Rulmont, R. Cloots and R. Moreno, Ceram. Int. 35, 1007 (2009).

[9] Y. S. Lee, J. S. Lee, T. W. Noh, D. Y. Byun and K.

S. Yoo et al., Phys. Rev. B 67, 113101 (2003).

[10] J. W. Park, D. J. Lee, D. H. Kim and Y. S. Lee, J.

Korean Phys. Soc. 58, 316 (2011).

[11] D. J. Lee, D. H. Kim, M. H. Cho, and Y. S. Lee, J.

Korean Phys. Soc. 63, 2185 (2013).

[12] E. Mete, R. Shaltaf and S. Ellialtioglu, Phys. Rev.

B 68, 035119 (2003).

Tuning of Photoluminescence of Sr(Zr,Hf)O 3 :Cu by Using the Photo-excitation Energy

Tuning of Photoluminescence of Sr(Zr,Hf)O 3 :Cu by Using the Photo-excitation Energy

Dongjae Lee · Yunsang Lee ∗

Department of Physics, Soongsil University, Seoul 156-743, Korea (Received 26 May 2015 : revised 22 June 2015 : accepted 23 June 2015)

We investigated the visible emission of Cu-ion-doped Sr(Zr,Hf)O

at various photo-excition en- ergies. In the Cu-ion-doped SrZrO

(SZO:Cu), the peak position of the visible emission changed from 400 nm (violet) to 600 nm (yellow) as the photo-excitation wavelength was tuned from 220 nm to 375 nm. This tunable multicolor behavior depended on the concentration of the Cu-ion doping.

The Cu-ion-doped SrHfO

(SHO:Cu) show optical properties similar to those of SZO:Cu. For a qualitative analysis, we calculated the CIE chromaticity coordinates of our samples. Our results suggest that the tunable multicolor emission in SZO:Cu and SHO:Cu can be utilized for ultraviolet sensors.

PACS numbers: 78.20.-e, 78.20.Ci

Keywords: Sr(Zr,Hf)O

, Cu ion doping, Photo-excitation energy, Tunable emission color

° Ë

Ñ-# bM  ; c .U ; c  Â \ ¥ Sr(Zr,Hf)O 3 :Cu8 ý ° Ë Ñ®  o° Ë Ñ V R Ëù m Ç  ì Å 

T

 ò 6 B<  · T * × < ç ¡ ∗

Õ

ü æz ´@ / < Æ § Ó ü t o  < Æõ , " fÖ  ¦ 156-743

(2015¸  5 Z 4 26{ 9  ~ Ã Î6 £ §, 2015¸  6 Z 4 22{ 9  Ã º& ñ  : r ~ Ã Î6 £ §, 2015¸  6 Z 4 23{ 9  > F  S X & ñ )

 H  ½ × ¼Ì  s`  ¦ ° ú   H SrZrO

ü < SrHfO

Ó ü t| 9 \ " f 3d   s F K5 Å q  ½ ¨o  s  : r`  ¦ '   #  µ 1 Ï & ³÷ &  H  r

 F g % ò % i _  µ 1 Ï F g: £ ¤$ í s  F g # l  \  -t \  ß ¼>  _  > r  < Ê`  ¦   ½ ¨ % i  . ½ ¨o  s  : r s  '    ) a SrZrO

 :

r _  '  | ¾ Ó\     Ø Ô>   ' a8 £ ¤ ÷ &% 3  . ½ ¨o  s  : r s  '    ) a SrHfO

(SHO:Cu) Ó ü t| 9  ¸ SZO:Cuü < Ä »



ô  Ç F g  < Æ & ³ © s   Ð% i  . & ñ | ¾ Ó& h   ì  r$ 3 `  ¦ 0 AK  CIE t Ã º\  ¦ > í ß  % i  . SZO:Cuü < SHO:Cu\ " f / B N :

 x& h Ü ¼ Ð  ' a8 £ ¤ ÷ &  H F g- # l  \  -t \    É r µ 1 Ï F gÒ  o  ¸] X $ í  É r  ü @  G ' p" f\   Ö ¸6 x| ¨ c Ã º e  `  ¦  כ s  .

PACS numbers: 78.20.-e, 78.20.Ci

Keywords: Sr(Zr,Hf)O

, ½ ¨o  s  : r '  , F g # l  \  -t , µ 1 Ï F gÒ  o  ¸] X $ í

E-mail: [email protected]

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License

(http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in

any medium, provided the original work is properly cited.

676 New Physics: Sae Mulli, Vol. 65, No. 7, July 2015

I. " e Â ] Ø

3d   s F K5 Å q s  : r É r F g  < Æ& h  Ö ¸$ í ] j Ð V , o   Ö ¸6 x ÷ & ¦ e 

  [1].   s  F K5 Å q s  '   | ¨ c M :, é ß { 9  " é ¶  ? /\ " f  H 1 l x { 9

ô  Ç \  -t  ï  r 0 A\  ¦ ° ú   H   s F K5 Å q _  3d  ¸q » 1 Ï  © I 

Å

Ò  _  6 £ § s  : r \  _ ô  Ç crystal field\  _ K  î ß    2 ;  © I 

  ) a . s  M :  ¸q » 1 Ï  © I ç ß _    s  \  -t  r  F g

% ò

% i \  K { © ÷ &# Q Ä ºÃ ºô  Ç F g  < Æ: £ ¤$ í `  ¦  Ðs >   ) a .  ª  ô

 Ç 3d   s F K5 Å q \  @ /K    ½ ¨  Ö ¸ µ 1 Ïy    '  ÷ & ¦ e    H X <, :

£

¤ y  ½ ¨o  s  : r`  ¦ ì ø Í ¸^  x 9 í ß  oÓ ü t ] X   ^ \  '   #  :

£

¤ s ô  Ç r  F g µ 1 Ï F g`  ¦ Ä » ¸  9  H   ½ ¨ Å Ò3 l q ~ Ã Î ¦ e  

. ½ ¨o  s  : r`  ¦ '  ô  Ç II-IV ì ø Í ¸^   H Õ ª ½ ¨$ í " é ¶  è_  7

á

x À Óü <  ¸{ 9  _  ß ¼l \     ½ ¨o  s  : r \  _ ô  Ç µ 1 Ï F g _

 Ò  os   ¸] X  ) a  [2,3]. ZnO_   â Ä º ½ ¨o s  : r _  '   Ð y

© ô  Ç  í2  ¤ µ 1 Ï F g`  ¦ Ä » ¸½ + É Ã º e    [4,5]. ¢ ¸ô  Ç ½ ¨o  s  : r s  '

   ) a F g  < Æ& h   & ñ $ 3 Ä »  H UVC radiation dosimetry  Ð



6 x s  0 p x o   \ V ©   ¦ e    [6]. { 9 ì ø Í& h Ü ¼ Ð ½ ¨o  s

 : r 3d  ¸q » 1 Ï_  \  -t  ï  r 0 A  H ñÛ ¼à Ô Ó ü t| 9 _   ½ × ¼Ì  s



s \  0 Au ô  Ç  [2].

`

 ÐÚ ÔÛ ¼ s à Ô+ þ A ½ ¨ ¸\  ¦ ° ú   H 4d, 5d   s F K5 Å q í ß  o Ó

ü t  SrZrO 3 ü < SrHfO 3   H  ½ × ¼ ] X   ^  Ð,  & ³F  V , o   Ö ¸ 6

x ÷ & ¦ e    H 3d   s F K5 Å q í ß  oÓ ü t õ  Ä »  >  \ P % i  < Æ& h Ü

¼ Ð î ß & ñ  ¦ ] j ¸ 6 x s   9  ¦ : r : £ ¤$ í s  Ä ºÃ º # 

 Ö

¸6 x$ í s   H     [ j b  Û ¼ Ð" f_  : £ ¤f ç `  ¦  Ð   [7,8].

4d/5d   s F K5 Å q í ß  oÓ ü t É r 3d   s F K5 Å q í ß  oÓ ü t \  q K   © 

@

/& h Ü ¼ Ð    É r   l 6 £ §$ í  ¸\  ¦ ° ú l  M :ë  H \   ½ × ¼Ì  ss  B  Ä

º  H : £ ¤f ç `  ¦ ° ú  ¦ e    [9]. \ V\  ¦ [ þ t # Q, 3d   s F K5 Å q í ß  o Ó

ü t  SrTiO 3 _   â Ä º  ½ × ¼Ì  ss  3.4 eVs t ë ß , SrZrO 3 _ 



½ × ¼Ì  s É r 5.6 eV s  9 SrHfO 3 _   ½ × ¼Ì  s É r 6.1 eV s  . < É ª p

\  v >  ¸ SrZrO 3 ü < SrHfO 3   H  H  ½ × ¼Ì  s`  ¦ ° ú  ¦ e  # Q ¸ He-Cd Laser ü < ° ú s  UVA (λ = 325 nm ∼ 3.8 eV)\  _ K 

"

f ¸ Ä ºÃ ºô  Ç µ 1 Ï F g : £ ¤$ í `  ¦  Ð   [10]. ¢ ¸ô  Ç V ,  É r  ½ × ¼Ì  s

\

Tuning of Photoluminescence of Sr(Zr,Hf)O ₃ :Cu by Using the Photo-excitation Energy

Dongjae Lee · Yunsang Lee ^∗

Ñ-# bM ; c .U ; c Â \ ¥ Sr(Zr,Hf)O ³ :Cu8 ý ° Ë Ñ® o° Ë Ñ V R Ëù m Ç ì Å

ò 6 B< · T * × < ç ¡ ^∗

ü æz ´@ / < Æ § Ó ü t o < Æõ , " fÖ ¦ 156-743

(2015¸ 5 Z 4 26{ 9 ~ Ã Î6 £ §, 2015¸ 6 Z 4 22{ 9 Ã º& ñ : r ~ Ã Î6 £ §, 2015¸ 6 Z 4 23{ 9 > F S X & ñ )

H ½ × ¼Ì s` ¦ ° ú H SrZrO

Ó ü t| 9 \ " f 3d s F K5 Å q ½ ¨o s : r` ¦ ' # µ 1 Ï & ³÷ & H r

F g % ò % i _ µ 1 Ï F g: £ ¤$ í s F g # l \ -t \ ß ¼> _ > r < Ê` ¦ ½ ¨ % i . ½ ¨o s : r s ' ) a SrZrO

:

r _ ' | ¾ Ó\ Ø Ô> ' a8 £ ¤ ÷ &% 3 . ½ ¨o s : r s ' ) a SrHfO

(SHO:Cu) Ó ü t| 9 ¸ SZO:Cuü < Ä »

ô Ç F g < Æ & ³ © s Ð% i . & ñ | ¾ Ó& h ì r$ 3 ` ¦ 0 AK CIE t Ã º\ ¦ > í ß % i . SZO:Cuü < SHO:Cu\ " f / B N :

x& h Ü ¼ Ð ' a8 £ ¤ ÷ & H F g- # l \ -t \ É r µ 1 Ï F gÒ o ¸] X $ í É r ü @ G ' p" f\ Ö ¸6 x| ¨ c Ã º e ` ¦ כ s .

, ½ ¨o s : r ' , F g # l \ -t , µ 1 Ï F gÒ o ¸] X $ í

3d s F K5 Å q s : r É r F g < Æ& h Ö ¸$ í ] j Ð V , o Ö ¸6 x ÷ & ¦ e

[1]. s F K5 Å q s ' | ¨ c M :, é ß { 9 " é ¶ ? /\ " f H 1 l x { 9

ô Ç \ -t ï r 0 A\ ¦ ° ú H s F K5 Å q _ 3d ¸q » 1 Ï © I

Ò _ 6 £ § s : r \ _ ô Ç crystal field\ _ K î ß 2 ; © I

) a . s M : ¸q » 1 Ï © I ç ß _ s \ -t r F g

% i \ K { © ÷ &# Q Ä ºÃ ºô Ç F g < Æ: £ ¤$ í ` ¦ Ðs > ) a . ª ô

Ç 3d s F K5 Å q \ @ /K ½ ¨ Ö ¸ µ 1 Ïy ' ÷ & ¦ e H X <, :

¤ y ½ ¨o s : r` ¦ ì ø Í ¸^ x 9 í ß oÓ ü t ] X ^ \ ' # :

¤ s ô Ç r F g µ 1 Ï F g` ¦ Ä » ¸ 9 H ½ ¨ Å Ò3 l q ~ Ã Î ¦ e

. ½ ¨o s : r` ¦ ' ô Ç II-IV ì ø Í ¸^ H Õ ª ½ ¨$ í " é ¶ è_ 7

x À Óü < ¸{ 9 _ ß ¼l \ ½ ¨o s : r \ _ ô Ç µ 1 Ï F g _

Ò os ¸] X ) a [2,3]. ZnO_ â Ä º ½ ¨o s : r _ ' Ð y

© ô Ç í2 ¤ µ 1 Ï F g` ¦ Ä » ¸½ + É Ã º e [4,5]. ¢ ¸ô Ç ½ ¨o s : r s '

) a F g < Æ& h & ñ $ 3 Ä » H UVC radiation dosimetry Ð

6 x s 0 p x o \ V © ¦ e [6]. { 9 ì ø Í& h Ü ¼ Ð ½ ¨o s

: r 3d ¸q » 1 Ï_ \ -t ï r 0 A H ñÛ ¼à Ô Ó ü t| 9 _ ½ × ¼Ì s

s \ 0 Au ô Ç [2].

ÐÚ ÔÛ ¼ s à Ô+ þ A ½ ¨ ¸\ ¦ ° ú H 4d, 5d s F K5 Å q í ß o Ó

ü t SrZrO ₃ ü < SrHfO 3 H ½ × ¼ ] X ^ Ð, & ³F V , o Ö ¸ 6

x ÷ & ¦ e H 3d s F K5 Å q í ß oÓ ü t õ Ä » > \ P % i < Æ& h Ü

¼ Ð î ß & ñ ¦ ] j ¸ 6 x s 9 ¦ : r : £ ¤$ í s Ä ºÃ º #

Ö

¸6 x$ í s H [ j b Û ¼ Ð" f_ : £ ¤f ç ` ¦ Ð [7,8].

4d/5d s F K5 Å q í ß oÓ ü t É r 3d s F K5 Å q í ß oÓ ü t \ q K ©

/& h Ü ¼ Ð É r l 6 £ §$ í ¸\ ¦ ° ú l M :ë H \ ½ × ¼Ì ss B Ä

º H : £ ¤f ç ` ¦ ° ú ¦ e [9]. \ V\ ¦ [ þ t # Q, 3d s F K5 Å q í ß o Ó

ü t SrTiO ₃ _ â Ä º ½ × ¼Ì ss 3.4 eVs t ë ß , SrZrO 3 _

½ × ¼Ì s É r 5.6 eV s 9 SrHfO ³ _ ½ × ¼Ì s É r 6.1 eV s . < É ª p

\ v > ¸ SrZrO 3 ü < SrHfO 3 H H ½ × ¼Ì s` ¦ ° ú ¦ e # Q ¸ He-Cd Laser ü < ° ú s UVA (λ = 325 nm ∼ 3.8 eV)\ _ K

f ¸ Ä ºÃ ºô Ç µ 1 Ï F g : £ ¤$ í ` ¦ Ð [10]. ¢ ¸ô Ç V , É r ½ × ¼Ì s

-t % ò % i \ < Ê ¸× ¼ + þ A$ í | ¨ c r \ < Ê ¸× ¼[ þ t ç ß _

g Ë >s & h # Q y < Ê ¸× ¼_ \ -t © I ½ ¨ì r ÷ &# Q ' a 8

¤| ¨ c 0 p x$ í s Z } . s H s F K5 Å q s ' ÷ &# Q µ 1 Ï F g: £ ¤

` ¦ Ð{ 9 M :, s F K5 Å q _ " é ¶ \ < Ê ¸× ¼[ þ t s

Ø Ô> + þ A$ í ÷ &# Q Z > & h F g < Æ$ í | 9 ` ¦ µ 1 Ï & ³½ + É Ã º e 6 £ §

¦ _ p ô Ç . s Qô Ç ½ ¨3 l q& h Ü ¼ Ð Ä ºo H ½ ¨o s : r` ¦ SrZrO 3 ü < SrHfO ³ Ó ü t| 9 \ ' # F g- # l © \ É r F

g < Æ$ í | 9 ` ¦ ½ ¨ % i . ½ ¨o s : r s ñÛ ¼à Ô Ó ü t| 9 ? /Â Ò

" f ¿ º > h_ " é ¶ \ ¦ ° ú ¦ s \ F g < Æ$ í | 9 s Ø Ô

µ 1 Ï & ³÷ &# Q, õ & h Ü ¼ Ð µ 1 Ï F gÒ os V , É r Û ¼& 7 à Ô! 3 % ò % i

" f ¸] X ÷ &# Q µ 1 Ï & ³H d` ¦ s K % i . & ñ | ¾ Ó& h ì r$ 3 ` ¦ 0

AK CIE t Ã º\ ¦ > í ß % i ¦, Ó ü t| 9 Z > , ' | ¾ ÓZ > Ð q § ì

r$ 3 % i . : r ½ ¨ H ½ ¨o s : r` ¦ F g < Æ& h Ö ¸$ í ] j Ð Ö ¸ 6

x ô Ç s _ ì ø Í ¸^ ½ ¨ü < q §½ + É M :, ½ × ¼Ì ss B Ä º H SrZrO 3 ü < SrHfO ³ \ s F K5 Å q s : r` ¦ ' D h Ðî r µ

1 Ï F g: £ ¤$ í s µ 1 Ï & ³÷ &# Q F g- èF Ð" f_ s 6 x 0 p x$ í s Z

} H כ ` ¦ Ð ¦ô Ç .

¨o s : r s ' ) a SrZrO 3 (SZO:Cu) ü < SrHfO ³ (SHO:Cu) r « Ñ H ¦ © ì ø Í6 £ xZ O Ü ¼ Ð ] j % i . $ , SrCO 3 ü < ZrO ² (HfO 2 )\ ¦ 1:1 q Ö ¦ Ð V , ¦, s ì r ´ ú ` ¦ 900

◦ C \ " f 12r ç ß ` ¦ è # SrZrO 3 (SrHfO ₃ ) © ` ¦ y y + þ

A$ í % i . Õ ª Ê ê ^ ] t \ x (x = 0.01 - 0.1)ë ß p u _ CuO\ ¦ V , ¦ ¦À Ò> [ O É r Ê ê\ , : \ Ï @ + þ AI Ð · ú § 4 ` ¦ ô Ç Ê

ê 1400 ^◦ C \ " f 48r ç ß è # SZO:Cu (SHO:Cu)\ ¦

+ Ë$ í % i [11].

« Ñ[ þ t _ ½ ¨ ¸\ ¦ ì r$ 3 l 0 AK , Bruker-AXS Discover D8 (λ = 1.5406 ˚ A)` ¦ 6 x # X r] X (XRD) z ´+ « >` ¦ Ã

º' % i . F g- # l \ -t Z > F g µ 1 Ï F g Û ¼& 7 à Ô! 3 ` ¦ 8 £ ¤& ñ

l 0 AK JASCO FP-8000 Series Spectrometer\ ¦ 6 x

% i . 6 x ô Ç F g- # l \ -t _ © (λ ex ) % ò % i É r λ ex

= 220 - 375 nm s . ¸ H F g < Æ8 £ ¤& ñ É r © : r \ " f '

% i .

III. + s ÇÊ Ý õ m Í w ² o

Fig. 1 É r x = 0.1 SZO:Cu _x=0.1 ü < SHO:Cu x=0.1 r « Ñ _

XRD θ-2θ Û ¼ ± p 8 £ ¤& ñ õ \ ¦ Ð# ï r . q §\ ¦ 0 AK SrZrO 3 ü < SrHfO 3 _ JCPDS X <s ' \ ¦ í < Ê % i . Õ ªa Ë >

" fü < ° ú s , SZO:Cuü < SHO:Cu r « Ñ[ þ t É r ½ ¨o '

&t · ú § É r SrZrO 3 ü < SrHfO 3 ü < 1 l x{ 9 ô Ç ~ ½ Ó& ñ > ` ÐÚ Ô Û

¼ s à Ô_ XRD J ` ¦ Ð [12]. ¢ ¸ô Ç 0 p x ô Ç Ô ¦í H Ó

ü t SrCO ₃ , ZrO ₂ , HfO ₂ , CuO, CuO ₂ © _ XRD ñ

' a8 £ ¤ ÷ &t · ú § ¤ . s H © { © | ¾ Ó_ ½ ¨o s : r` ¦ '

8 ¸ í H Ã ºô Ç SrZrO ₃ ü < SrHfO 3 ° ú H ~ ½ Ó& ñ > ` Ð Ú