Effect of Nb Doping on the Superconducting Properties of (Ru,Nb,Sn)Sr
2EuCu
2O
zHo Keun Lee
∗Department of Physics, Kangwon National University, Chuncheon 24341, Korea (Received 4 August 2015 : revised 12 August 2015 : accepted 13 August 2015)
Polycrystalline samples of (Ru1−xNbx) Sr2EuCu2Ozand (Ru0.8−xNbxSn0.2) Sr2EuCu2Ozwith 0
≤ x ≤ 0.4 were synthesized by using a solid state-state reaction method. The phase formation and the physical properties were investigated by means of X-ray diffraction and transport measurements.
Contrary to the observation of no superconductivity in Sn-free Nb-doped (Ru1−xNbx) Sr2EuCu2Oz
samples with x ≥ 0.2, a superconducting transition behavior was observed in the (Ru0.8−xNbxSn0.2) Sr2EuCu2Oz samples, and an onset superconducting transition temperatures Tc, of about 29 K and 35 K were observed for the x = 0.2 and 0.4 samples, respectively. The superconducting behaviors induced by Nb and Sn co-doping are discussed in conjunction with the changes in the hole concentration and the structure.
PACS numbers: 74.72.-h, 74.70.Pq, 74.62.Dh, 74.25.-q
Keywords: (Ru,Nb,Sn)Sr2EuCu2Oz, Nb/Sn co-doping, Superconductivity
Nb V ò & ÿ; c  \ ¥ (Ru,Nb.Sn)Sr
2EuCu
2O
z4 8 ý ¾ ¹ Åy ¢ ¤V R Ë
T
Ú£ Ó
∗y
©"é¶@/<Ƨ Ótüo<Æõ, ðr ; 24341
(2015¸ 8Z4 4{9 ~ÃÎ6§, 2015¸£ 8Z4 12{9 ú&ñ:r~ÃÎ6£§, 2015¸ 84 13{Z 9 >FSX&ñ)
(Ru1−xNbx)Sr2EuCu2Oz (Rux9 0.8−xNbxSn0.2)Sr2EuCu2Oz (x = 0 - 0.4)r¼#`¦¦©ìøÍ6£xZOܼ
Ð ½+Ë$í ¦ Nbu¨8\ Ér© +þA$í x9 í¸:¤$£í`¦ X- r]X x9 ú5Åx :£¤$í8£¤&ñܼР¸Ùþ¡. Õª
õ Sns ¸iç÷&t ·ú§r (RuÉ 1−xNbx)Sr2EuCu2O_ r¼#¸$í\"f x ≥ 0.2 âĺ í¸:£¤$ís'a 8
£
¤÷&t ·ú§Hכ õ @/q÷&> Sn s u¨8)a(Ru0.8−xNbxSn0.2) Sr2EuCu2Oz r¼_# âĺ í¸s :
£¤$ís'a8£¤&%÷3ܼ 9, x = 0.2 x9 0.4 {9 M: yy 29 K x 9 35 K_ í¸ s :¤$£í`¦Ð%i. Nb x9 Sn 1_lxr ¸içܼРĻµ1Ïa)í¸ :£¤$í o\¦r¼#_ f.Ë 0lx¸ o x ½9¨¸oü< > # 7H_ Ùþ
¡.
PACS numbers: 74.72.-h, 74.70.Pq, 74.62.Dh, 74.25.-q
Keywords: (Ru,Nb,Sn)Sr2EuCu2Oz, Nb/Sn 1lxr ¸iç, í¸ :£¤$í
∗E-mail: hklee221@kangwon.ac.kr
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.
I. " e  ] Ø
RuSr2RCu2O8 (Ru-1212)í¸^H CuBa2RCu2O7 (Cu-1212, R = Y ¢¸H BÐÀÓ "é¶è) > í¸^_ µ1Ï
|
[1] Êê u¨8\ @/ôÇ ´ú§rɽ¨\¦Ãº' H ×æ Cu-1212
í¸^_ Cu-O ^o Cu @/ Ru \¦u¨8 ¦ Ba
@
/ Sr`¦u¨8 # Bauernfeind 1px [2]\ _K %6£§Ü¼Ð
½
+Ë$í÷&%3. Õª[þtÉr¢¸ôÇ RuSr2(R2−xCex)Cu2O10 (Ru- 1222) > í¸^¸ ½+Ë$íÙ¡Üþ¼ 9, s[þt`¦ Ru> í¸
^
Ð Ô¦oĺ 9, Rs Sm, Eu, x9 Gd {9 âĺ\ëß éß{9
©s +þA$íHds ·ú94R e. Ru > í¸^\ :£¤Z>y
´ ú
§Ér 'a`d¦t>)a כÉrs[þt Ru> í¸^H e
>
:r¸ (Tc) 50 K s í¸ :£¤$í`¦ èq
÷
r m ls :r¸ (Tm) 100 K - 180 K ô
Ç y©$í:£¤$í¸ /BN>rÊs< Ц [3, 4]÷&%3l M:ëHs.
s
[þt $í í¸^_ Rux9 Cuo u¨8 ½¨ õH s
>\"f 'a8£¤÷&Hy©$íÉr RuO2 8£x\, Õªo¦ í
¸ :£¤$íÉr CuO2 8£x\ l H כ ܼР·ú9t¦ e.
:
£
¤y Cu o\ Zn`¦ u¨8ôÇ õ í¸ e>:r¸H y
è l&h s:r¸\H H %ò¾Ó`¦ put ·ú§H
כ
s 'a8£¤÷&%3 [5]. ÕªQ Ru 8£x_ l&h :£¤$í
o í¸ :£¤$í\ puH´òõHf "îSXy µ1ß)4R e
tH ·ú§ÉrI©Ð çßÅÒa). sH Ruo u¨8_ â Ä
º u¨8ܼРl&h :£¤$í_ o ÷r m f.Ë 0lx¸_
o\¦ Ä»µ1Ï # í¸ :¤$£í_ o¸ Ä»µ1Ïr~´ ú e l
M:ëHs. ÕªX< Ru-1222 >_ âĺ Ru @/ Nb`¦ 50% t u¨8 8¸ ls:r¸Hyè í
¸ e>:r¸_ oHÄBº &h6£§s Ц÷&#Q eܼ 9 [6, 7], sH Ru-1222 >_ âĺ í¸ü< ôÇ y©$í :£¤$í ç
ß_ © ñ6 xs Bĺ &h6£§`¦ trKïr. s\ @/q÷&
>
RuSr2RCu2Oz(R = Eu, Gd)> \"fH Ru@/ Nb`¦ u
¨8 í¸ e>:r¸ x9 ls :r¸ ¸¿º yè
<Ês ·ú94R eܼ 9 20% s©_ Nbs u¨8÷& e>:r
¸ 'a8£¤÷&t ·ú§6£§s Ц÷&#Q e [8, 9]. sQôÇ s
H u¨8\ Ér íßè|Ó_¾ o "é¶s |¨c ú eܼ
Ru @/ Nbx9 Sn`¦ u8¨ 8¸ Ru > í¸^ _
íßè|¾Ó_ oH_ \O6£§s ·ú94R e [7,10]. Õª o
# Nb u¨8¼ÜÐ'a8£¤÷&H¿º >çß_ í¸ :£¤$í_
sH, Ru_ (valence) ¿º > çß\ s e l
M:ëHܼРÆÒ&ñ÷&¦ e. XANES (X-ray absorption near-edge spectroscopy) z´+«>\ _ Ru-1212 x9 Ru- 1222>_ Ru yy 4.6 [11] x9 4.95 [12]Ð ìr$3
÷
&#Q s eܼ 9, sÐ K +5 _ Nbs u¨8÷& Ru-1212>_ âĺ Ru-1222 >\ qK f.Ë 0lx¸ yè
ß
¼l M:ëH\ Ru-1212 >_ í¸ :£¤$ís ß¼> t
Fig. 1. Temperature dependences of electrical resistivity for (Ru1−xNbx)Sr2EuCu2Oz(0 ≤ x ≤ 0.4) samples.
H כ ܼР[O"î÷&#Q¸¦ e. sQôÇ ]jî`ߦРl 0
AK :r ½¨\"fH Ru-1212 >\ &h{©ôÇ f.Ë`¦ ¸içôÇ Ê
ê Nb`¦u¨8Ùþ¡`¦M: Ru-1222 >ü< Ä»ôÇ í¸ :£¤$í _
o eH\¦ÐÙþ¡. Ru-1212 >_ âĺ Ru @/
Sn` ¦ {9ÂÒ u¨8 f.Ë 0xl¸ 7£x|¨c ú e6£§s ·ú
94R eܼټР[9,10], :r½¨\"fH (Ru0.8−xNbxSn0.2) Sr2EuCu2Oz >_ í¸ :£¤$í\ @/K ½¨Ùþ¡.
II. ÷ m Ç ] M ö
r
¼#Ér ¦©ìøÍ6£xZOܼР½+Ë$íÙþ¡Ü¼ 9, íH¸ 99.9% s
©_ RuO2, Nb2O5, SnO2, SrCO3, Eu2O3, x9 CuO ì
r´ús s6 x÷&%3. r¼_# "î3lq¸$íÉr (Ru1−xNbx) Sr2EuCu2Oz x9 (Ru0.8−xNbxSn0.2)Sr2EuCu2Ozs%3ܼ 9, 900 - 980◦C\"f 7rçß |9è ìr0Al\"f \P%o ÷&
%
3ܼ 9, sÊê 1050◦CÐ \P)a lÐ\"f íßè\¦ fËo 9 5 rçß è ¦ s#Q"f 1050◦C\"f 10rçß è Êê
©:rܼР"fÍtÙþ¡. B \P%o ×æçß\ r¼#r ìÉrW x9 $í +þ
Aõ&ñ`¦'¬I. r¼#_ +©þA$í :£¤$íÉr Cu Kα`¦s 6
xôÇ X- r]Xl (X’pert-pro MPD)Ð 8£¤&ñ)a X<s'
\
¦ ½ÓܼРsÀÒ#Q&ܼ 9, q$½Ó x9 \Pl§4 :£¤$íÉr :
x_© 4 éß ]X]ZXO x9 pìrÓZ~½O`¦ s6x # 8£¤&ñ÷&
%
3. 4éß q$Ó 8½¤&£ñ\"fHË$½+í)anۼ߼+þA r¼#`¦ f
¹¢¤^ +þAIÐ ]XéßôÇ Êê ÉrÛ¦`¦s6 xK FG`¦
Fig. 2. X-ray diffraction patterns for (Ru0.8−xNbxSn0.2) Sr2EuCu2Oz (0 ≤ x ≤ 0.4) samples.
Ùþ
¡Ü¼ 9 10 mA_ ÀÓ\¦ fË9 8£¤&÷ñ&%3. 8£¤&ñÉr©:r
\
"f 10 K t 8£¤&ñ÷&%3.
III. ÷ m Ç] M ö+ s ÇÊ Ý õ m Í º8 ý
Fig. 1Ér (Ru1−xNbx)Sr2EuCu2Oz(0 ≤ x ≤ 0.4)¸$í r
¼#_ q$½Ó :¤$£í 8£¤&ñ õ\¦Ð#ïr. Nb`¦u¨8 t
·ú§Ér x = 0 r¼#_ âĺ í¸ s r:r¸ Tc
(onset) = 47 K,$½Ós 0s÷&H :r¸ Tc(zero) = 17 Kí
¸ s :£¤$`í¦Ð%i. s õHÉr½¨[þt\ _ K
Ц)a õü< Ä»ôÇ õs. Nb`¦u¨8ôÇ âĺ x
= 0.2 x9 x = 0.4 âĺ í¸ s :£¤$ís'a8£¤÷&t ·ú§
¤Ü¼ 9, ìø͸^&h q$½Ó :£¤$í`¦ Ð%i. Mclaughlin 1
px [8]Ér (Ru1−xNbx)Sr2GdCu2O8 >_ ½¨ õ \¦ :x K
Nb`¦ x = 0.15t u¨8 e>:r¸ (Tc(zero)) 29 K\"f 19 KÐ yè 9, x = 0.2 âĺ ìø͸^&h :
£¤$ís'a8£¤Hd`¦Ð¦ôÇ e. ¢¸ôÇ Williams 1px [9]Ér (Ru0.6Nb0.4)Sr2EuCu2O8 >_ Ä⺠ìø͸^&h q$½Ó :
£¤$í`¦Ðs 9, Nbs u8¨÷&t ·ú§Érâĺ Tc(onset) = 32 K. Tc(zero) = 12 K_ í¸ s\¦ ÐsH õ\¦Ð
¦Ùþ¡. "f :r½¨_ Nb u¨8\ Ér Fig. 1_ í
¸ :£¤$í_ oH Ru-1212 >_ âĺ Ru @/ Nbs 20%
s
© u¨8|¨c: Mí¸ :£¤$ísa8'£¤÷&t ·ú§HH 7áxA _
õü< Bĺ a%~Ér {9u\¦Ð. Fig. 1\ /åL)ar
¼
#_ ©:r \Pl§`4¦ 8£¤&ñôÇ õ x = 0, 0.2 x9 0.4 r
¼
#_ âĺ yy 78.9, 98.4 x 154.4 µV%9 i. ©:r \Pl
Fig. 3. Temperature dependences of electrical resistivity for (Ru0.8−xNbxSn0.2)Sr2EuCu2Oz (0 ≤ x ≤ 0.4) sam- ples.
§4õ CuO2 ¨î{©_ f.Ë0lx¸_ ©'a'a> [13]\ _
s[þt°úכÉr yy 0.066, 0.061, x9 0.027f.Ë0lx¸\ @/6£x
9, "f Nbs u¨8÷& r¼#_ f.Ë 0lx¸ yèHd
`
¦trôÇ.
Fig. 2H (Ru0.8−xNbxSn0.2)Sr2EuCu2Oz í¸^_ X- r]X X<s'\¦Ð#ïr. Fig. 2\ ³ðr)a ü< °ú s
@/ÂÒìr_ r]X xsß¼H Ru-1212½¨¸_ ©Ü¼Ð x9Q t
ú B^ ½+É Ãº e%3ܼ 9, þjè5pxZOܼР>íß)aa x9 c ©Ãº°úכÉr x = 0{9 M: 3.873(2) ˚A, 11.626(6) ˚A, x
= 0.2 {9 M: 3.856(3) ˚A, 11.588(10) ˚AÕªo¦ x = 0.4 {9 M
: 3.856(3) ˚A, 11.588(10) ˚A%i. Ru @/ Nb u¨8÷&
a x9 c ©Ãº°úכs 7£x<Ês ·ú94R e [7,14].
"f x = 0.2 ü< x = 0.4_ âĺ s[þt©Ãº °úכ_ 7£x
H Nb_ s:r¼lß (0.64 ˚A, CN = 6) Ru s:rß¼l (0.565 ˚A, CN = 6) Ð H כ [15]ܼР[O"î)a. ÕªQ
x = 0 r¼#s x = 0.2 Ð ©Ãº Hכ Ér Nb u
¨8\ Érs:rß¼l_ sÐ [O"îs #Q§>. Ru>\ Sns ¸iç|¨cM: q+þA&h ©Ãº o Ц)a &h s
eܼ 9 [16], ¾Ó Êê Ð &ñxô9Ç Ð 9כ¹ ¦ óøÍ é
ß)a.
Fig. 3Ér (Ru0.8−xNbxSn0.2)Sr2EuCu2Oz_ q$½Ó :£¤
$í
8£¤&ñõ\¦Ð#ïr. Nb u¨8÷&t ·ú§Ér x = 0 r
¼#_ âĺ Tc(onset) = 46 K , Tc(zero) = 18 K\¦ Ð
%
i. "f Fig. 1_ õü< q§K^¦ M: Sn`¦u¨8
t
·ú§Ér RuSr2EuCu2Oz r¼#\ qK í¸ s:r¸ _
s Bĺ &hܼ 9, q$½Ó °úכs çß 7£x)a כ `¦
· ú
ú e. Õª!3\¸ Ô¦½¨ ¦ Nb`¦u¨8 Fig. 1\
"
f 'a8£¤)aÍøì¸^&h :£¤$íõH²úo í¸ s :£¤$í s
'a8£¤Hd`¦ Ð#ïr. :£¤y x = 0.4_ âĺ Tc (onset)
= 35 K, Tc (zero) = 14 K_ í¸ s :£¤$í`¦ Ð%i Ü
¼ 9, Nbs u¨8÷&t ·ú§Ér x = 0r¼#\ qK &ñ©©I _
q$½Ó °úכ¸ >'a8£¤÷&%3. ÕªQ x = 0.2 âĺ
¸ Tc (onset) = 29 K í¸ s :¤$£í`¦ Ð%iܼ Tc
(zero)H 8£¤&ñ%ò%i\"f 'a8£¤÷&t ·ú§¤. Nb u¨8\
É
r f.Ë 0lx¸_ o\¦ÆÒ&ñ l 0AK ©:r\Pl§4`¦ 8£¤
&
ñôÇ õ x = 0, 0.2 x9 0.4 r¼#_ âĺ yy 82.4, 100.6 x9
99.4 µV%i. s õH Sns u8¨÷&t ·ú§Érâĺü<
q
§KÐ x = 0 x9 0.2r¼_# âĺ Õª s Sn u
¨8ܼРf.Ë 0lx¸_ Ho \O6£§`¦rôÇ. ÕªQ x = 0.4 r¼#_ âĺH\Pl§4s ©@/&hܼР߼> y
è # Sn õ Nb_ 1lxr u¨8÷& Nb ëß u¨8ôÇ âĺ_ f
.Ë 0lx¸ yè ´òõ\¦ {9ÂÒ ©WrvH´òõ\¦Ä»µ1Ï H
כ
ܼР^¦ ú eܼ 9 sÐ K í¸ s :£¤$ís ¾Ó
©÷&H´òõ\¦4R¸H Üכ¼Ð [O"î)a. ôǼ# Fig. 3_ x = 0.2 ¼r#_ âĺ Sns u¨8÷&t ·ú§Ér Fig. 1_ x = 0.2 r¼#õ ©:r \Pl§_4 s &h6£§\¸ Ô¦½¨ ¦
í¸ s :¤$£í\H H s'a8£¤&Ù÷¼Ð sâĺ f.Ë 0
l
x¸ s ü@ ´òõ í¸ :£¤$\í Ð H %ò¾Ó`¦p u
Hכ ܼРÐ. :£¤y u8¨_ âĺ ²DGè&h Áº|9"f _
s > ÷& 9 s Áº|"9f :£¤$í_ ¾Ó© #ÂÒ
_ ²DGFo (localization)\ %òÓ`¾¦p5g í¸ :£¤$í
\
%ò¾Ó`¦puH Üכ¼Ð ·ú94R e [17,18]. ¢¸ôÇ Sn õ
Nbs 1lxr u8¨÷&%3`¦M: q+þA&h ©Ãº o
¸ í¸ :£¤$í_ oü< 'a÷&Hכ ܼРÐs 9 ¾ÓÊê
Ð ^>&h ½¨ ú'÷& Õª "é¶`¦Ð "îSXy
½+É Ãº e`¦ Üכ¼Ð \V©)a.
IV. + s Ç Â ] Ø
:r ½¨\"fH (Ru1−xNbx)Sr2EuCu2Oz x9 (Ru0.8−xNbxSn0.2)Sr2EuCu2Oz (x = 0 - 0.4) r¼#
`
¦ ¦©ìøÍ6xZ£OܼР½+Ë$í ¦ ©+þA$í x9 í¸ :£¤$í`¦
½¨Ùþ¡. X- r]X ìr$ 3 õ Nbü< Sns 1lxr u¨8
)
a (Ru0.8−xNbxSn0.2)Sr2EuCu2Oz (x = 0 - 0.4) r¼# _
âĺ _ éß{9© r¼#s ½Ë$+íHd`¦ Ãú· º e%3. :£¤ y
Nbü< Sns 1lxr u¨8)a r¼#_ âĺ Nbëß u¨8ôÇ (Ru1−xNbx)Sr2EuCu2Oz r¼#õH ²úo í¸ s :
£¤$ís'a8£¤÷&%3. (Ru0.8−xNbxSn0.2) Sr2EuCu2Oz r
¼
#\"f x = 0.4 âĺ Tc(onset) = 35 K, Tc(zero) = 14 K_ í¸ s :£¤$í`¦ Ð%i. ôǼ# x = 0.2 r¼# _
âĺ Tc(onset) = 29 K í¸ s :£¤$í`¦ Ð%iܼ
Tc(zero)H 8£¤&ñ%ò%i\"f a8'£¤÷&t ·ú§¤. ©:r \P l
§4 :£¤$í 8£¤&ñ õH Nbü< Sn`¦ 1 lxr u¨8ôÇ âĺ _
í¸ :£¤$ís Nb ëß u8¨ôÇ r¼#_ :£¤$íõ ØÔ>
H כ Ér Sn u¨8´òõ\ _ôÇ f.Ë 0lx¸ o÷r m
u¨8\ Ér Áº|9"f:£¤$í 1px# ´òõ¸ ¦9÷&#Q
<Ê`¦]jrK ÅÒ%3.
P
c p 8 ý ò k >
:r ½¨H DzôDG½¨Féß (KRF-2012R1A1A2042519) õ
2014¸¸ y©"é¶@/<Ƨ <ÆÕtü½¨¸$íq_ t"é¶Ü¼Ð
½
¨÷&%3_þvm (õ]j ñ-120141498). :r½¨_ ú' ×æ XRD XRD 8£¤&ñÉr "©yé¶@/<Ƨ /BN1lxz´+«>z´_þv'a\"f ú '
÷&%3_þvm.
REFERENCES
[1] P. H. Hor, R. L. Meng, Y. Q. Wang, L. Cao and Z.
J. Huang et al., Phys. Rev. Lett. B 58, 1891 (1987).
[2] L. Bauernfeind, W. Widder and H. F. Braun, Phys- ica C 254, 151 (1995).
[3] I. Felner, U. Asaf, Y. Levi and O. Millo, Phys. Rev.
B 55, R3374 (1997).
[4] C. Bernhard, J. L. Tallon, Ch. Niedermayer, Th.
Blasius and A. Golnik et al., Phys. Rev. B 59, 14099 (1999).
[5] S. K. Goh, G. V. M. Williams and H. K. Lee, Curr.
Appl. Phys. 6, 515 (2006).
[6] H. K. Lee and Y. C. Kim, Int. J. Mod. Phys. B 17, 3682 (2003).
[7] H. K. Lee and G. V. M. Williams, Physica C 415, 172 (2004).
[8] A. C. Mclaughlin, V. Janowitz, J. A. McAllister and J. P. Attfield, Chem. Commun. 14, 1331 (2000).
[9] G. V. M. Williams, H. K. Lee and S. Kramer, Phys.
Rev. B 67, 104514 (2003).
[10] A. C. Mclaughlin and J. P. Attfield, Phys. Rev. B 60, 14605 (1999).
[11] R. S. Liu, L. -Y. Jang, H. -H. Hung and J. L. Tallon, Phys. Rev. B 63, 212507 (2001).
[12] G. V. M. Williams, L. -Y. Jang and R. S. Liu, Phys.
Rev. B 65, 064508 (2002).
[13] J. L. Tallon, C. Bernhard, H. Shaked, R. L. Hitter- man and J. D. Jorgensen, Phys. Rev. B 61, 12911 (1995).
[14] H. K. Lee and G. W. Kim, New Phys.: Sae Mulli 64, 952 (2014).
[15] R. D. Shannon, Acta Cryst. A 32, 751 (1976).
[16] N. Balchev, K. Nenkov, G. Mihova, B. Kunev and J. Pirov, Physica C 467, 174 (2007).
[17] J. P. Attfield, A. L. Kharmanov and J. A. McAllis- ter, Nature 394, 157 (1998).
[18] H. K. Lee, J. Supercond. Nov. Magn. 24, 1381 (2011).