UNIVERSITI PUTRA MALAYSIA

EFFECT OF STANUM DOPING AND HEAT TREATMENT ON Bi-Sr-Ca-Cu-O SUPERCONDUCTING CERAMICS

AZHAN BIN HASHIM @ ISMAIL

FSAS 1999 12

E FFECT O F STANUM DOPING AND H EAT TREATMENT ON Bi-Sr-Ca-Cu-O SUPERCONDUCTIN G CERAMICS

By

AZHAN BIN HASHIM (ii) ISMAIL

Thesis Submitted in Fulfilment of the Requirements for the Degree of Doctor of Philosophy in the

Faculty of Science and Environmental Studies Universiti Putra Malaysia

December 1999

D E DICA TIOl\S

To Assoc Prof Dr Halim, for h is pat ience, guidance and bel i ef in me

To mak, ayah and fam i l y , for their love and concern

To my wife, Aiza and my chi ldren, for their love, support and understanding

II

Abstract of thesis presented to the senate of Universiti Putra MalaysIa I n fulfilment of the requirements for the degree of Doctor of Phi losophy

EFFECT OF STANUM DOPING AND HEAT TREA TME:\,T ON Bi-Sr-Ca-Cu-O SUPERCOND UCTING CERAMICS

By

AZHAN B IN HASHIM ® ISMAIL

December 1 999

Chairman : Associate Professor Abdul Halim bin Shaari, Ph.D

Faculty : Science and Environmental Studies

The influence of Sn doping in calcium (Ca) and copper (Cu) sItes either

temperature for 30 hours soaking time were studied For Sn-free sample. heat

treatment improved the superconducting transition temperature, T C(R I)) from 1 00

K to 1 04 K, when the sintered sample was annealed at 820°C The hIghest T (il� 0)

of 1 04 K was observed for s Intered sample (x=O 02) with sImultaneous dOp111g

The heat treatment improved the T C(R�(J) from 60 K to 94 K for sample doped 111

Ca site when re-sintered at 855 °C and from 66 K to 1 00 K for sample doped wIth

Sn in Cu site when annealed at 840°C For simultaneous doping, the T C(R 0) dId

not change significantly after heat treatment except for sample with x=O 05 that

showed drastic improvement of T C(R=U) from 64 K (sintered) to above 1 00 K

III

From XRD analys Is, the volume of 2221 phase decreased as the �n

concentration mcreased Al l samples with Sn concentration above ,=0 I ()

contall1ed unknown peaks which con espond to the non-superconductmg pha�e

>\Ithough the lattice parameter of the samples shortened, the crystal lographic

�tructure remamed m the tetragonal form

A l l samples lI1dlcated the onset of d IamagnetIsm temperature at around

I 1 0 K showmg the presence of 2223 phase The volume of d IamagnetIC sh le ld l11g

decreased as the Sn concentration mcreased It was also observed that the heat

tl eatment process l lnproved the volume ot d iamagnetic shIeldmg m Sn-free and Sn-doped samples especIal ly for concentratIons of x=O 02 and \.= 0 0':;

I nterestmgly the shielded volume fOI Sn-doped samples m eu site \vlth

concentratIon ot x=O 20 and >..=0 25 mCI eased as the heat treatment tempel (ltUfe:

l11creased The couplIng peak, T p shifted to lower temperature a� the Sn

concentration l I1 creac;ed due to the enhancement of weak Imks The natul e ot the

\\ eak Imks due to the Josephson Junction m each dopl l lg mode based on the Sn

concentratIons was different For Sn-free and separately doped (\.= 0 02) samples

the Junctions were S-N-S type, wherea::. for higher concentration o f Sn, the ,\ eal-..

1 1 I1ks was domll 1ated by the S-I-S type For the s l lnultaneoush doped S-N-S

lunctlon seemed to domlllate I I I samples With O�x�O 1 0 Samples \\ Ith >..=0 0':; and

,= 0 I 0 �howed the transformation from S-l-S type to S-N-S type III thi S dopIn g

mode as compared to the other dopmg mode

1\

Abstrak tesi s yang dikemukakan kepada senat Universiti Putra Malaysia b agi memenuhi keperluan untuk ijazah Doktor Fal safah

KESAN PEND OPAN STANUM DAN RAWATAN HABA KE ATAS SERAMIK SUPERKOND UKTOR Bi-Sr-Ca-Cu-O

Oleh

AZHAN BIN HASH IM (iiJ, ISMA IL

Disember 1 999

Pengerusi : Profeso r Madya Abdul Halim Shaari, P h.D

Fakulti : Sains dan Pengaj ian Alam Sekitar

Kesan pendopan Sn pada tapak kals ium dan kupram samada secara

berasingan atau serentak terhadap s i stem B i-Sr-Ca-Cu-O [Bil ('Sr:(Cal_

pelbagai suhu dengan tempoh masa 30 jam telah dikaj i Untuk sampel tul in_

rawatan haba telah meningkatkan suhu peral ihan superkonduktoL T e(R 0) dari 1 00

K kepada 1 04 K apab i la sampel yang di sinter telah di sepuhlindap pada suhu 820

"c. T C(R�()) tertinggi i aitu 1 04 K telah dicerap untuk sampel x=0.02 yang disinter

dan didopkan secara serentak . Rawatan haba telah meningkatkan T C(R-O) dan 60

K kepada 94 K untuk sampel yang didopkan pada tapak Ca apab i la di si nter

semula pada suhu 8 5 5 °C dan dari 66 K kepada 1 00 K untuk sampel \'ang

didopkan pada tapak Cu apab i la di sepuhl i ndap pada suhu 840 \'c. Untuk

pendopan secara serentak, T C(R-O) tidak berubah secara nyata selepas rawatan haba

kecuali bagi sampel x=0 .05 yang menunjukkan peningkatan drast ik T C(R-O) dari

64 K (s inter) kepada lebih 100 K .

\

Dari anal i s i s XRD, i s ipadu fasa 2223 berkurang apab i la kepekatan S n

meningkat . Semua sampel dengan kepekatan S n melebihi x=o 1 0 mengandungi

puncak-puncak yang tidak di ketahu i yang mana merujuk kepada fasa bukan

superkonduktor. Walaupun parameter kekisi-kekis i sampel d ipendekkan. struktur

hablur kekal dalam bentuk tetragonal.

Semua sam pel memperl ihatkan suhu peral ihan diamagnet di sekitar I 10 K

yang menunjukkan kehadiran fasa 2223. Is ipadu pemeri saian d iamagnetic

berkurang apab i l a kepekatan Sn bertambah. D iperhatikan juga rawatan haba telah

meningkatkan i sipadu pemerisaian diamagnet bagi sampel tulen dan sampel yang

didopkan dengan Sn terutama sekal i pada kepekatan x=O.02 dan x=O.05. Yang

menari knya. is ipadu pemerisaian di amagnet untuk sampel yang didopkan dengan

Sn pada tapak eu dengan kepekatan x=O.20 dan x=O.25, didapati meningkat

apabila suhu rawatan haba bertambah. Suhu puncak pepasangan. Tp telah

dianjakkan ke suhu yang lebih rendah apabila kepekatan Sn bertambah merujuk

kepada peningkatan ikatan l emah. S ifat ikatan lemah merujuk kepada simpang

Josephson bagi set i ap mod pendopan berdasarkan kepekatan Sn ada lah berbeza.

Untuk sampel tul i n dan sampel didopkan secara berasingan (x=002), simpangan

adalah jenis S-N-S, sebal iknya untuk kepekatan Sn yang leb ih t inggi, ikatan lemah

didominasi oleh jen i s S-I-S. Untuk pendopan secara serentak, s impang S-N-S

mendominasi sampel dengan O�x�O.lO. Sampel x=O.05 dan x=O.lO menunjukkan

transformasi dari jenis S-I-S kepada jen i s S-N-S pada mod pendopan in i apabi l a

dibandi ngkan dengan mod pendopan lain.

vi

ACKNOWLEDGE;\I ENTS

In the name of Al lah, the most GracIous and the most \/lerciful

Al l praise be to Al l ah the Almighty, for giving me the strength and \/Y I II to

WrIte and at l ast complete thi s thesi s

I am extremely grateful to my supervi sor, Associate P rofessor Dr Abdul

Hal im Shaari for, most of al l, be l ieving in me For al l the patIence. gUidance,

advice, ideas, critics, encouragement and continUOUS dIscuss IOn. my deepest

gratitude goes to you I also express my gratitude to my co-supervisor. �ssoc late

Professor Dr Kaida Khal id and AssocIate Professor Dr Sidek Abdul '\z\z fOJ

theIr comment, suggestIons and gU idance throughout the research \\ orh.

1 am very grateful for the financial assistance pro\ Ided through P ·\�C'\

and Intens ified Research Program in PriorIty Area (lRPA) \1\ specia l thanh.� go

to Dr S id ik S i long from Chemistry Department for 1m suggestion on the dry l llg

techl11que I am grateful to ASSOCiate Professor Dr Mansor Hashim. ASSOCIate

Professor Dr Wan Daud Wan Yusof and all the lecturers III the Ph\ S I CS

Department for their kind help and discussion

To Mr Ho, Mrs Aminah and MISS Azi l ah for their fa\ ours III SEM

exami nation Thanks a lot for a l l of you Not forgetti ng to my classmate, Abdul

Razak Ibrah im from USM and my close fri end, Ahmad Naz l im fro m UKM for

help ing me in carrying out the X-ray dIffraction analYS I S

\ 11

1 am extremely grateful to my fnend Dr S B M ohamed for 1m k ind help.

advice, guidance, critics, constructive suggest ion and fru itful d i SCUSS io n

throughout the work To my labmates, K P Lim, Saleh AI Khawaldeh, Malik,

Khabashi, K S Fong, Tal ib, Yu and lmad, thanks a lot for your kind help and

understanding regard ing thi s work

To my friends who never fai l to encourage me u ntIl the e nd, Abang Am,

A.jwad, Husni , Azhar, Saifu l, Hal im, Win, M ieza, Zolman and Kak Ana, my

special thanks go to al l of you I am very thankful to 1\11 Razak Harun, 1\1r

Nordll1, 1\1r Hamdan and other technical staff in the Phys i cs Department for the l l

technical favours To Mr Kamal, M r Hamzah and Mr Saiful from ABEX. IV1 r

Phi l Benua and M r Brad from Lakeshore USA, thank s a lot for your techmca\

as:-'lstants

To mak, ayah, brothers and si sters, their love and support to J-..eep me

gomg, and to my in- laws who have been concern about my study al l thi s whi l e -

thank you And last but not least, to my wife, Aiza and my children, SyakJr and

-\11 ah, thank you for your love, continuous support, encouragement and

understanding I dedicated thi s success to both of you too

\ 111

1 cel11fy that an Examination Committee has met on 29 December, 1 999 to conduct the final eXamInatlOn of Azhan bm HashIm @ I smaI l on h I S Doctor of Philosophy thes I s entIt led "Effect of Stanum Doping and Heat Treatment on 81-SI -Ca-Cu-O SuperconductIng CeramIcs" In accordance with UI1 IVersIt I PertaI1 lan I\la laysIa ( HIgher Degree) Act 1 980 and UI1IVerslt I Pertal1Ian MalaysIa (HIgheJ Degree) Regulat ions 1 98] The Committee recommends that the candIdate be awarded the relevant degree Members of the ExamII1at lon CommIttee are a " tol low"

JAMIL B IN SURA D I, Ph.D. PhYSICS Department, Faculty of SCIence and EnvIronmental StudIes, UI1IVersItl Putra M alays Ia (ChaIrman)

..\BDUL H ALIM BIN S HAARI, Ph.D . ..\. ""OClate ProfessOI PhYSICS Department, Faculty of SCIence and EnvIronmental StudI es, UmversItI Putra M alaysIa (l\l embel)

�AIDA B IN KHALlD, Ph.D. 1\ ""oclate Professor, Ph) "I C� Department F acuity of SCIence and EnvIronmental Studle" L Il IVer�lt l Putra MalaY" la (Member)

SIDEK BIN HAJ} ABDUL AZIZ, Ph.D . ..\. ,,�oclate Professor PhYSICS Department, F acuity of SCIence and EnvIronmental StudIes, UI1IVersItI Putra Malays Ia (Member)

l\I UHAMMAD BIN Y AHY A, Ph.D. PI ofessOI , PhYSICS Department, Faculty of SCIence and Technology, UI1 lVersIt I Kebangsaan M alays Ia, (Member)

I\,

Professor, Deputy Dean of Graduate School, Universiti Putra Malays ia

Date 3 1 DEC 7999

,

Thi s thesi s was submitted to the Senate of Universi t i Putra Malays i a and was accepted as fu l fil ment of the requirements for the degree of Doctor of Philosophy

A� KAMIS ANG, Ph.D. Associate Professor. Dean of Graduate S chool , Universiti P utra Malays ia

Date � JAN 200�

DECLARATION

I hereby declare that the thesis i s based on 111\' origi nal work except for quotat Ions and citations which have been duly acknowledged 1 al so declare that it has not been previously or concurrent ly submitted for any other degree at UPM or other i nstitutions .

BIN HASHIM @ ISMAIL)

:\11

TAB LE OF CONTENTS

DEDICATION -\BSTRACT -\BSTRA K -\CKNOW LEDGEMENTS -\PPROVAL SHEETS DECLARATION FORM L lSTOF TABLES LIST OF FIGURES L I ST OF P LATES LIST OF SYMBOLS AND ABREVIATIONS

CHAPTER

II

I I I

INTRODUCTION B aSIC Phenomena of the Superconductivity High T ( Superconductors (HTS ) The B I-Sr-Ca-Cu-O ( B SCCO) System The Role of Dop\11g 111 BS CCO System ApplI cat ion of Supel conductor ... Objecti ve of the The�I'" Layout of the Thesl'>

FUNDAl\IE:\ T -\L OF HTS AND TH EORIES Type I and T\ pe II Supel conductors

Tvpe I Type I I

Meissner - Och�enfeld Effect Theory of Tv,o-Fl lI Ids Gorter-Casimir P lppal d's Theory London B roth el's Theory

Theory of Gmzburg and Landau Abnkosov's Theory B ardeen-Cooper-Schneffer (BCS) Theory Granular Superconductivity 111 M agnet ic F ie lds

Bean's M odel Cnt lca I Cun ent Den'>lty, h through AC Determ111atlon

LIT E RATU R E REVIEW Supel conduct ivity of B SCCO System Sample Preparations

Effect of S 1 I 1tenng Temperatu re/Tl 1ne Effect of Anneal 1 l 1g

Effect of DoplI1g 1I1 B SCCO S uperconductors

',II

Page

II III , VII 1'-

\,11 XVI \., III \,\,\,1

\. \."11

9 J )

1':;

16

IS

19

21

21

2-+

26

27

-ll

-l6

60

64

78

IV

V

VI

Effect of lnterst l t lal Dop1l1g Effect of Substitutional Dop1l1g

PREPARATION AND CHARACTERISATION TECHNIQUES Preparation Method

Chemical Powder Welgh1l1g Chemica l s M IX 1l1g Ca lcination IntermedI ate F Ir Ing Final S lntenng Heat Treatment Process

Charactensatlon Technique ReSistance Measurement AC M agnetic Susceptlbll Ity M easurement X-ray DIffractIon AnalysIs M Icrostructure AnalysI s

RESULTS AND DISCUSSION ReSI stance M easurement

Effect of Sn doping I II Ca sIte of B I I (,Pb04Sr2Ca2Cu,Q, Effect of Sn dopl llg 1 11 Cu site of B I I (,Pbo 4Sr2Ca2Cu,Q,) Effect of s lmultaneou<.., dopl Ilg of Sn 1 11 Ca and Cu �Ite�

X-ray DIffract IOn Analysl<; Effect of Sn doplIlg III Ca "Ite of B II (,Pb04Sr2C a2CulQ" Effect of Sn doping I II Cu sIte of B I I (,Pbo 4Sr2Ca2Cu,Q,) Effect of s Imul taneous dopll1g of Sn 111 Ca and Cu slte�

AC SusceptIbil I ty MeasUl ement Effect of Sn dopll1g I II Ca sIte of B I I (,Pbo 4Sr2Ca2Cu,Q" Effect of Sn doplI1g 111 Cu site of B I I (,Pbo 4Sr2Ca2Cu,Q" Effect of Simultaneous dop1 l1g of Sn In C a and Cu slte�

M lclostructural AnalysIs

CONCLUSIONS AND SUGGESTIONS FOR FUTURE WORK

'\1\

79 8)

96 96 97 9S 9')

101 102 10-+ 107 107 109 1 1-+ 1 1 -+

I I (1 1 1 6

1 11'

1 2-

I ) \ 1 -+ -

1-+7

1�-l

16[ 16S

I'''' 1-

18-+

200 21-+

ConclusIOns 228 Suggestion for Future Work

BIB LIOGRAPHY 2)4

�PPENDICES 244 24'i

VITA

A Uncertainties of the EqUipment and Calcu l at IOn

B P apers Published and Presented Throughout this Thes I s 246

248

"

Table

I I

1 2

I 1

LIST OF TABLES

Chronology of the de\ elopment on the superconductIvIty

L Ist of Nobel PrIze wI llner for thel l specIal contrIbut Ion on the superconductIvIty development

Insulat Ing parent. compounds and T ( of (HT S )

Page

4

10

2 1 Values of coherent length, �, penetratIon depth, Ie and GL parameter, K of varIOUS superconductors 1 1

2 2 ComparIson of energv gaps for varIOUS superconductors

The \ alues of Debye tempel atur e, 81) densIty of states, D(Er) and specIfic heat data fOl varIOUS supel conductors

17

2 4 The values of electron-phonon coup l I llg constants, Ie and Coulomb

1 I

, '} ) -

, , ) )

4 1

') I

� I epuls lOn between the electron� Pc '-to

The length of latt Ice pal ametel I II B SCCO supel conductI llg system ,)"

The �ummal bed re�L1 1 b on the etfect of \lI1tel I llg tempel ature and duratIon t Ime 72

The summal l sed resulh of the dopI llg el ements III Ca and Cu sItes 9<-1

EquIpment for the system of the resI stance measurement 1 08

SummarI sed data of TC(I< OJ (K) and Tco" (K) for samples doped wIth Sn III Ca sIte wIth varIOUS concentratIons of Sn and heat treatment temperatures ( S =s1 l 1tered, A = annealed and R S = re-s1 l 1tered) 1 21

SummarI sed data of T ((1< 0) (K) and T (Oil (K) for all samples doped wIth Sn In C li SIte \lvlth varIous concentratIons of Sn and heat treatment temperatul es ( S =SI lltel ed A = annealed and R S = re-sl l 1tered) 1 36

SummarI sed data of T (T< 0) (K) and T (Oil (K) for all samp les doped wIth Sn 111 Ca and Cu SItes With Val 10US concentratIons of Sn and heat treatment temperatures (S =sl l 1tered, A = anneal ed and R S = I e-S 1 l 1tel ed) 1 44

.:; 6

The length of l attice parameter and volume of umt cel l for a l l �amples doped with Sn I n Ca site

The length of l attIce parameter and volume of umt cel l for a l l \amples, which doped with S n lt1 Cu s i te

The length of l attlce parameter and volume of umt cel l for al l samples doped simul taneously with Sn In Ca and Cu site

.:; 7 Summan sed data of couplI ng peak temperature, T p, first onset

temperature of diamagnetism, T�n, phase lock-m temperature, T (1

and Josephson current, t, for B S CCO sampl es doped

166

with Sn In C a site 1 82

.:; 8 Summansed data of coupl I ng peak temperature, T p, first o nset

temperature of diamagnetism, T�n, phase lock-m temperature, T (1

and Josephson current, Ie, for BSCCO sampl es doped with Sn m Cu site 198

.:; 9 Summansed data of couplmg peak temperature, T p, first onset

temperature of diamagnetism, T�n , phase lock-m temperature T (I

and Josephson current, I" for s lmultaneow, doped samples 212

'\ \ 11

L I ST OF FIGURES

Fiuures � Page

1 1

1 2

1 4

21

J J

7 ' _ 1

Evolution of criti cal temperature, T l from 1 9 1 1 unti l 1 994 1

Qual itat ive behavIour of the resist i vity, p as a function of the temperatUl e, T (a) Normal conductor (b) Superconductor 6

(a) Fie ld distribution in the normal l y condu cting and the ideal l y conducting state with a homogeneous external m agnetic fie ld, H,. (b) Distribution of the magnetic fie ld in the ideall y conducting state after switching off the external magnetic fie ld, R. 7

F ield di stnbution, (a) In the normal l y conducting state with homogenous external magnetic fiel d, H,. (b) In the superconduct ing state with homogenous external magnetic fie ld, H.. (c) In the superconduct l l1g state with external magnetic, H,. sWitch off 8

M agnet isation curves of type I superconductors i n rel at ion to the external f ield, He 2J

Magnet l satlon curves of type II superconductors in rel ation to the external ficld, He 2--1

Exponential decay of a constant app l I ed magnetic fie ld B7(X) l l1 s lde the superconductOl 29

:2 --I A.. wave of l attice di stortion due to attractIOn to movl l1g el ectrons 1 11 normal and superconduct i ng states

26

2 7

The formation of Cooper pairs

Low field susceptlbi I Ity 4rrA. of sintered TI-2223 as a function of temperature

Intluenced of vanous appl i ed fields on sintered TI-222J sample

2 8 Schematic representation of the progression from the Meissner phase through the Abrikosov phase to glass phase or alternat ively, directly

35

4--1

44

to the Josephson phase with the increasing of appl ied fie ld . 45

:2 9 Imaginary component (X") of susceptibility as a function of temperature and appl i ed AC field for a bul k YBCO sample The appl i ed AC fie lds range in valu e (from right to l eft) , I Am-I (0 0 1 25 Oe ) to 800 Am-I ( 1 0 Oe ) .

,VIll

51

:2 10 B ean model detenmnatlon of cntl cal current density Jc as a functIOn of temperature for the data shown

') Crystal lographic structUi e of BI2Sr2Ca11C u11 1 0211 (, " sy'>tem With n = 0, 1 , and 2

, ') ) - Temperature-compOSition profi le 111 the (B I ,Pb hSr2CanCun 1 0(, 2n system

41 Graph of temperature CC) versus t ime ( hour) for furnace's final smtenng

4 2 Graph of temperature ("C) versus t ime (hours) for furnace's heat treatment

4') F low chart for fabncatlon of Sn-free and Sn-doped samples

44 SchematiC diagram of four-pomt probe resistance deVIce with temperature sensor used for measunng dc resist ivity/resistance

-+ ') Cross section view of the pnmary and secondary coI l s

46 SchematiC diagram of Scann l llg Electron M icroscope J OEL (JSM-6400) system

.:; NOl ll1al 1sed resi stance (RlR( I I()O")) as a function of temperatUie fOl �amples s1l1tered 111 air at 850 "c for 1 50 hours With vanous concentl dtions of Sn 1Il Bil (,Pbo 4S1 2(Cal ,Sn,hCu,O,)

.:; :2 NOl mal 1 sed l es lstance (RlR( l 100") as a function of tempel atU l e for samples annealed 111 aIr at 820 "c for 30 hours With vanous concentrations of Sn 111 BII (,Pbo 4Sr2(Cal ,Sn,hCu,Oi)

.:; ') N o l l l1al 1sed resi stance (R/R(l-100"») as a function of temperature fOI sample� annealed III arr at 830 "c tor 30 haUl S With val 10m concentrations of Sn 111 B I I (,Pbo 4Sr2 (Cal _,Sn,)2Cu1O,)

.:; 4 Normalised resi stance (RlR(I 100"» as a function of temperature fOl samples annealed 111 air at 840 "c for 30 hours With vanous concentrations of Sn 1Il B I I c,Pbo 4Sr2(Cal _,Sn,hCu,O,)

') 5 Normali sed resi stance (RlR( l 100"») as a funct ion of temperature for samples re-s1l1tered 1Il air at 85 5 "c for 30 hours With vanous concentrat Ions of Sn 1Il B I I c,Pbo 4SrZ(Cal -,Sn,hCu,O,)

') 6 T L(R 0) as a funct IOn of Sn concentration for B I I c,Pbo 4Sr2(Cal ,S nJzCu10() samples s1l1tered and heat treated at different temperature

'd'l.

')C)

1 0)

10"

1 06

10<)

I I')

I I ':;

1 17

1 19

1 19

1 21

121

j')' �)

-; 7

-; 8

-; q

-; 10

-; I I

.:; 12

.:; I 1

.:; 1 -+

.:; 1')

.:; 16

-; 1 7

.:; 18

-; 1 9

Tcm 0) as a function of s l ll tel ed and heat treatment for vanous

concentration of Sn III B I I (,Pbo 4Sr 2 (Ca I -,Sn,)2Cu,O()

Sn concentl atlon dependence of normal I sed resIdual res i stance fO J all "am ple<; '>111 teled 0 1 heat treated

S I I ltered and he�t -treated tempel ature dependence of normal I sed I eSldual res I"tance for al l sam ples with vanous concentration" of Sn

Normal t sed res istance (RiRo 100,,») as a function of temperature for samples s lntered 111 air at 85 0°C for 15 0 hours with vanous concentrations of Sn In BI I (,Pbo 4 Sr2Ca2 (CU I ,Sn,)101>

Normal t sed res istance ( RlR{I 100,,») as a function of temperature for samples annealed III air at 820 °C for 30 hours with vanous concentratIons of Sn In Bi l (,P bo 4Sr2C a2(Cu 1 ,Sn,)101>

'\01 m cll I �ed I e:,l '>tance (RlR( I 100,,») as a function of temperature fOI samples anneal ed \l1 air at 830° C for 10 hour� wIth van ou s concentrations of S n III B I I (,Pbo 4Sr2Ca2(CuI-,Sn,hOI>

l\JOJIllal I <;ed r e"I '>tance (RlRrI ,00,,») as a tunctlon of temperature fell samples annealed 111 air at 840°C for 1 0 hours wIth vanous concentl atlom of Sn III BI I (,Pbo 4Sr2 Ca2(CU 1-,Sn ,hO,)

'\ormal l "ec1 re"'htance (R. R( I ,riO,,») as a function of temperature fOJ �aI llples re-"I lltered I II a i r at 8')5 "c for 1 0 hours wi th vanou" concentl atlon" of Sn 111 BI I (' Pbo 4S1 2Ca2 (CU I ,SnJ1O ,)

T c (R 0) a� a fu nctlon of S n concentration for B I I (,Pbo4 Sr2Ca2 (CU r ,Sn,hO,) samples s l lltered and heat treated at d ifferent temperature

T li[( (!i a� a functIon of s l I1 tered and heat treatment for vanous concentr atlon� of Sn I I I BI I (,Pbo 4Sr 2Ca2(CU 1-,Sn,hOI> (S-slI1tered, A-annealed, R S-re-smtered)

Sn concentratIon dependence of normal I sed res idual resi stance for all samples s l I1tered 01 heat treated

S l I1 tered and heat-treated temperature dependence of normal Ised I eSldual resistance for all samples with vanous concentration of Sn (S-s l lltered A-annealed, R S-re-s l lltered)

N ormal t sed res i stance ( RlR(I ,00,,») as a function of temperature for samples sl l1tered 1 11 a ir at 85 0 °C for 15 0 hours with vanous concentratIOns of Sn 1I1 B I I (,Pbo 4Sr2(Ca[-,Sn,h(Cu I _,Sn,)101>

"

124

126

1 26

12 8

129

130

1 1 1

132

134

134

1 3 7

137

1 39

� 20 Norma l ised resistance (RiRCI-1()Oh») as a funct ion of temperature for samples annealed in air at 82 0 "c for 3 0 hours with \ arious concentrations of Sn in B i l r,Pbo 4 Sr 2 (Cal _,Sn,) z (Cu I _,SnJl0 ,) 139

� 21 NOI mal ised resI stance (RlR(l 100,,») as a function of temperature fOI samples annealed 111 air at 83 0 "c for 3 0 hours wIth \ arIOUS concentrations of Sn 111 B i l (,Pb04 Sr2( Ca l _,Sn,h (Cul_, Sn,),O " 1-+0

5 22 Normal i sed resistance (RlR(l-100,,») as a funct IOn of temperature for samples annealed in air at 840 "c for 3 0 hours with various

- 7" ) _J

� 24

5 25

.:; 26

':;27

5 28

:; 2 C)

.:; 3 0

concentrations of Sn in B i l r,Pbo 4 Sr 2 (Cal - , S n,) z (Cuh Sn,hO " 1 42

Normal i sed resi stance (RlRn=100h» as a function of temperature for samp les re-s intered in air at 855 " C for 3 0 hours with a different concentrations of Sn in B i l r,Pbo 4 SrlC Cal_, Sn , ) z (CuI_,Sn,,j,O,, 142

T C(R 0) as a funct ion of Sn concentrat ion for samples B i l (,Pbo 4 Sr 2 (Cal -,Sn,) z( Cu l -,S n,),0" whI ch sintered and heat treated at different temperature l-L,

T C(R 0) as a function of sintered and heat treatment for varIOUS of Sn concentration in B il r,Pbo 4 Sr 2Ca2(C U1-,Sn,),O " ( S-sintered A-annealed, R S-re-sintered) 1-+-+

Sn concentrat ion dependence of normal ised resIdual resI stance for all samp les sintered or heat treated 1-+6

Sn concentratIon dependence of normal I sed res Idual I eSlstance for al l sampl es s intered or heat treated (S-sintered, A-annealed_ R S-re-sintered) 1-+(,

XRD pattern for B il (,Pbo 4 Sr 2 Ca2 Cu,O " samples doped \\ Ith Sn in Ca s i te sintered at 85 0°C for 1 50 hours 150

XRD pattern for BII r,Pbo 4Sr2Ca2 Cu,O ,) samples doped \\ Ith Sn 111 Ca s i te annealed at 820 "C for 3 0 hours 1 ':; 1

XRD pattern for Bil r,Pbo 4 Sr2 Ca2Cul0/) samples doped \\-Ith Sn in Ca s i te annealed at 83 0 " C for 3 0 hours 1 5 1

5 31 XRD pattern for Bil (,Pb04 Sr2Ca2 Cu,O " samples doped \\lth Sn in Ca s ite annealed at 840°C for 3 0 hours 1 �:

5 32 XRD pattern for B il (,Pb o 4 Sr 2Ca2Cu,O/) samples doped \\-l1h Sn 111 Ca s ite re-sintered a t 855 "c for 3 0 hours 152

5 33 Volume percentage of2223 high Tc -phase as a function of Sn concentration for al l samples doped with Sn in Ca site 15-+

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;; 34 XRD pattern for B i l (,Pbo 4 Sr2Ca2Cu,O,) samp les doped with Sn in Cu site, si ntered at 85 0°C for 1 50 hours 156

'i 1 5 XRD pattern for B i I (,Pbo 4 Sr 2Ca2 Cu10,) samp les doped with Sn in Cu site, annealed at 82 0°C for 30 hours 1 ;;7

'1 3 6 XRD pattern for B i I (iPbo 4 Sr 2Ca2Cu,O il samples doped with Sn in Cu site, annealed at 8 3 0°C for 3 0 hours 1 '17

5 3 7 XRD pattern for B i l (,Pbo 4 Sr 2Ca2Cu,O il samples doped with Sn in Cu site, annealed at 840°C for 3 0 hours 1 58

5 3 8 XRD pattern for B I I (,Pbo 4 Sr2Ca2CulOo samp les doped with Sn in Cu site, re-sintered at 855°C for 30 hours 1 58

;; 3 9 Concentration dependence of the volume percentage of 222 3 phase for samp les doped with Sn in Cu site 1 60

'i 40 XRD pattern for B i I (,Pbo 4 Sr2Ca2CU,Oi\ samples doped s imu ltaneously wi th Sn in Ca and Cu Sites, sintered at 85 0° C for 15 0 hours 1 63

'1 -l l XRD pattern for B i l (,Pbo 4 Sr2Ca2Cu,O,) samples doped simu ltaneously with Sn in Ca and Cu sites, annea led at 82 0°C for 3 0 hours 1 6-l

'1 -l:2 XRD pattern for B i l (,Pb04Sr2Ca2Cu,O ,) �amp les doped si multaneously with Sn in Ca and Cu Sites, annealed at 8 3 0°C for 3 0 hours 1 6-l

;; 43 XRD pattern for B i l (,Pbo 4Sr2Ca2Cu,O,) samples doped simultaneously with Sn in Ca and Cu s ites, annealed at 840°C for 3 0 hours 1 6"

5 44 XRD pattern for B i l (,Pbo 4 Sr2 Ca2 Cu,06 samples doped simu ltaneously with Sn in Ca and Cu s ites, re-sintered at 855°C for 3 0 hours 1 65

5 45 Concentration dependence of the volume percentage of22 23 phase for samp les doped simu ltaneously with Sn in Ca and Cu site 1 67

'i 46(a) The real part, X' of susceptib i l ity versu s temperature, T for \'arious ampl itude of appl ied magnetic fie ld for the Sn-free samp le 1 70

5 46(b) The i maginary part , X" of susceptib i l ity versu s temperature, T for various amp l itude of app l ied magnetic fie ld for the Sn-free sample 1 7 1

'\ '''I

5 46( c) The relat ionship of coupl ing peak temperature, T I' with applied magnet ic fie ld for Sn-free sample

'i 48 (a) The real part, Z· and (b) The imagl l1ary part , X" of suscept ibil ity versus temperature, T at applied fiel d of [ 0 Oe

171

for the sl l1tered samples doped with Sn in Ca s ite [ 74

549 (a) The real part, X· and (b) The I maginary part, X" of susceptibi l ity versus temperature, T and at app lied fiel d of 1 0 Oe for the annealed samples at 820° C doped with Sn in Ca site 177

5 5 0 (a) The real part, X· and (b) The imaginary part, X" of susceptibility versus temperature, T at applied fiel d of I OOe for the annealed samples at 8 3 0°C doped with Sn in C a s ite 178

'i 51 (a) The real part, X· and (b) The l lnagl l1ary part, X" of susceptibilI ty versus temperature, T at appl ied field of I OOe for the annealed samples at 840°C doped with Sn in Ca site 179

'i 52 (a) The real part, X· and (b) The imaginary part, x" of susceptibility versus temperature, T at applied fi eld of 1 OOe fOI the re-sl lltered samples at 855 "c doped With Sn in Ca site 1 80

'i 53 The dependence of T" with Sn concentrat IOn at appl ied field of 1 0 Oe for all samples sll1tered and heat-treated doped with Sn In Ca si te 1 81

'i 'i4 The variat ion of J osephson current, L With Sn concentl atlon for all samples sintered and heat-treated doped with Sn in Ca site 18 1

5 55 ( a) The real part, X' and (b) The imaginary part, X" of susceptib I l ity versus temperature, T and appl ied with I OOe field for the sintered samples doped With Sn Il1 eu site 185

5 56 (a) The real part, X· and (b) The I magl11ary part, X" of susceptib i l Ity versus temperature, T and appl ied with I 0 Oe field for the annealed samples at 820 "c doped with Sn in C u s ite 190

.:; 'i7 ( a) The real part, X· and (b) The i magll1ary part, X" of susceptibil ity versus temperature, T and appl ied with I 0 Oe field for the anneal ed samples at 830 "c doped with Sn i n Cu site 19\

5 58 (a) The real part, X' and (b) The i maginary part, X" of susceptibi l ity versus temperature, T and app l ied with I 0 Oe field for the annealed samples at 840°C doped with Sn in Cu site 192

\. \,111

:; 'i9 (a) The real part, X' and (b) The imaginary part, X" of susceptib il ity versus temperature, T and appl ied with I OOe field for the re-sin tered samples at 8 5 5 "c doped with Sn In Cu s I te 1 93

:; 60 The dependence of TI' with Sn concen tration and app l ied wI th 1 0 Oe magnetic field for all samples sin tered and heat- treated doped wIth Sn 111 Cu site 1 94

:; 6 1 The temperature dependence of the I maginary part, X" of ac susceptibil ity and appl ied with various amp l itude of magnetic fie lds for Sn-doped sample with x=O 20 annealed at 840° C for 3 0 hours 19 4

:; 62 The temperature dependence of the imaginary part, X" of ac susceptibil ity and app l ied with various amp l itude of magnetic fields for Sn-doped sample with x=O 25 annealed at 840 "C for 3 0 hours 1 9'i

'i 63 The temperature dependence of the imaginary part, X" of ac susceptibil ity and app l ied with various amp l itude of magnetic fields for Sn-doped sample with x=O 20 re-s l ll tered at 8 5 5 DC for 3 0 hours 1 9 'i

'i 64 The temperature dependence of the I maginary part, X" of ac susceptibil ity and appl ted wIth various ampl itude of magnetic fi e lds for Sn-doped sample with x=O 25 re-sin tered at 855 ()C for 3 0 hours 1 %

.;; 6') The varIation of J osephson current, 1., wI th Sn concentratIon for all samples sintered and heat-treated 196

:'\ 66(a) The real part, X' of susceptibil ity versus temperature, T for applied field of 1 0 Oe for the sin tered samples doped with Sn simul taneously in Ca and Cu sites 20 I

:'\ 66(b) The I maginary p art, X" of susceptIbil ity versus temperature, T for appl ied fie ld of 1 0 Oe for the sintered samples doped with Sn simul taneousl y in Ca and Cu s ites 2 02

:'\ 6 7 (a) The real part, X' and ( b ) The imaginary part, X" of susceptibil ity versus temperature, T and appl ied with I 0 Oe field for the annealed samp les at 820 "c doped with Sn s imul taneous ly in Ca and Cu sites

:'\ 68 (a) The real part, X' and (b) The imaginary part, X" of susceptib il ity versus temperature, T and app l ied with I 0 Oe fi el d for the annealed samples at 8 3 0 "c doped with Sn s imu l taneous l y in Ca and Cu sites

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204

205