AbstractBi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10 superconducting pellet was prepared by solid state reaction. The epitaxial growth of Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10 films has been realized on Si (111) by pulse laser deposition (PLD) using Nd: YAG laser with 532nm, pulse duration of about 7 nsec and a current density (0.4 – 8) J/cm2, at different substrate temperature 300, 320, 350 and 400°C. All samples annealed at 820°C in vacuum furnace employing oxygen atmosphere with flow rate 2 lit/min and heating rate 15°C/min. The structure and morphology of the prepared samples was obtained by using x-ray diffractometer (XRD) and atomic force microscopy (AFM). The lattice constants of thin films samples were calculated using inter planer distance and Miller indices of the strong peaks in the XRD patterns. It has been observed that the enhancement of the transition temperature (Tc) for obtained films increase with increase of substrate temperature (Ts). The increase in Tc with the enhancement of substrate temperature could be explained to increasing the mobility of clusters and subsequently enhance the critical temperature

Hermiz, Ghazala Y.

Shakouli, Suzan M.

Suhail, Mahdi H.

Elsevier - Publisher Connector 

Effect of Substrate Temperature on Growth Bi1.6Pb0.4Sr2Ca2Cu2.4 Zn0.6O10 Thin Films Prepared by Pulsed Laser Deposition 

 Energy Procedia  36 ( 2013 )  881 – 887 
1876-6102 © 2013 The Authors. Published by Elsevier Ltd.
Selection and/or peer-review under responsibility of the TerraGreen Academy
doi: 10.1016/j.egypro.2013.07.101 
                  TERRAGREEN13 INTERNATIONAL CONFERENCE 
Effect of Substrate Temperature on Growth 
Bi1.6Pb0.4Sr2Ca2Cu2.4 Zn0.6O10 Thin Films Prepared by 
Pulsed Laser Deposition. 
 
                Ghazala Y.Hermiza,* , Mahdi H. Suhaila   and  Suzan M.Shakoulib 
 
a Department of Physics, College of Science University of Baghdad, Baghdad ,Iraq 
b Department of Physics, College of education  University of  Mustansiriyah , Baghdad ,Iraq 
 
____________________________________________________________________ 
Abstract 
 
Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10 superconducting pellet was prepared by solid state reaction. The epitaxial 
growth of Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10 films has been realized on Si (111) by pulse laser deposition (PLD) using Nd: 
YAG laser with 532 nm, pulse duration of about 7 nsec and a current density (0.4 – 8) J/cm2, at different substrate 
temperature 300, 320, 350 and 400 oC.  All samples annealed at 820oC in vacuum furnace employing oxygen 
atmosphere with flow rate 2 lit/min and heating rate 15oC/min. The structure and morphology of the prepared 
samples was obtained by using x-ray diffractometer (XRD) and atomic force microscopy (AFM). The lattice 
constants of thin films samples were calculated using inter planer distance and Miller indices of the strong peaks in 
the XRD patterns. It has been observed that the enhancement of the transition temperature (Tc) for obtained films 
increase with increase of substrate temperature (Ts). The   increase in Tc with the enhancement of substrate 
temperature could be explained to increasing the mobility of clusters and subsequently enhance the critical 
temperature. 
 
© 2013 The Authors. Published by Elsevier Ltd. 
Selection and/or peer-review under responsibility of the TerraGreen Academy. 
 
Keywords:  Substrate temperature; PLD;, Thin film superconductors  
______________________________________________________________________ 
1. Introduction 
Bi-based superconductor compounds of the form Bi2Sr2Can-1CunO10, where n=1, 2, 3 gives the 
number of CuO2 layers, have been studied extensively by many groups. The superconducting phases in 
this material, known as (2201),(2212) and (2223) ,for n=1,2,3 with the critical temperature of 10-20K,60-
85K and 110K ,respectively [1] .According to previous studies, the n =2 phase was found more stable and  
 more easily obtained than the 2223 phase. The later phase can be obtained in stable form by doping the 
structure with a small amount of Pb. The Pb atoms are thought to reside at the Bi sites in the structure [2] 
_________________________________ 
*Corresponding author. .:E-mail address gyhermiz@yahoo.com: 
Available online at www.sciencedirect.com
 2013 The Authors. Published by Elsevier Ltd.
election and/or peer-review under responsibility of the TerraGreen Academy
ScienceDirect
Open access under CC BY-NC-ND license.
Open access under CC BY-NC-ND license.
882   Ghazala Y. Hermiz et al.  /  Energy Procedia  36 ( 2013 )  881 – 887 
           Pulsed Laser Deposition (PLD) is a physical vapor deposition (PVD) technique based on the 
evaporation of material by using a pulsed, highly energetic laser beam focused inside a vacuum chamber 
to strike a target of the desired composition. This versatile technique may be applied to profoundly 
different materials such as, metals, insulators, semiconductors and high-Tc superconductors. With the use 
of PLD, the stoichiometric transfer of these materials from a multicomponent target to a film on a 
substrate can be obtained entirely. Under the right experimental conditions, PLD also offers the potential 
for epitaxial thin film growth. In the previous decades, various fabrication techniques of the BSCCO 2212 
and 2223 superconductor thin film developed [3]. Among them, the pulse laser deposition (PLD) 
technique was found to be most favorable, and has been regarded as a versatile method to grow ceramic 
thin films. Laser evaporation offers the particular advantages that one may deposited films rapidly and 
without the need for sophisticated rate control and high vacuum equipment. Many researchers [3-5] have 
been working on this technique because the application of high Tc superconductors in microelectronics 
depends on the availability of high quality superconducting thin films. It has been found that the nominal 
composition and thermal treatment parameters such as annealing time, heat rate and substrate temperature 
play an important role in the formation of high Tc phases. Kim et al. [3] deposited thin films of Bi-Sr-Ca-
Cu-O on (100) cubic zirconia by laser ablation from a bulk superconducting target of nominal 
composition BiSrCaCu2Ox. They indicated that the film quality is affected by the substrate temperature 
and the annealing processes. The influence of the composition on the crystallographic properties of 
deposited Mg (M) O with (M=Al, Cr, Ti, Y, and Zr) films was studied by Saraiva et al [6]. using dual 
reactive magnetron sputtering to predict the stoichiometry of the deposited coatings, an analytical relation 
that states the deposition rate varies inversely as the square of the target-substrate distance was used [6]. 
Effect of annealing on superconducting properties of Bi1.6Pb0.4Sr2Ca2Cu2.2Zn0.8O10 thin films by pulsed 
laser deposition was investigated by Malike et al.[7]. Their results demonstrate that the transition 
temperature are related to the phase's evolution and formation of intergrowth, however nearly pure 2223 
phases were grown  when the  annealing temperature is equal to 820 °C and 860 °C. On the other side 
enhancement of the annealing temperature above 860 °C leads to the increases of low phase and 
disappear of high phase.  
 
     In this paper, studies were carried out to reveal the role of substrate temperature on the surface 
morphology, structure and electrical properties of the Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10 superconducting thin 
films. The substrate temperature plays a great role of linking the crystalline orientations of both the 
substrate crystal and the film. 
2. Experimental work 
Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10 pellet was prepared by solid state reaction. The conventional 
preparation of the bulk involves mixing together the oxides, carbonates or nitrates of the constituent 
elements, the mixture was milled in agate mortar for 1h to obtain a fine particle size and heating them to 
810oC (calcinations) to initiate the reaction for 24 h in order to get oxides from fly to off carbonates, 
nitrate, alkaline oxides through calcinations reaction, the production power mill for 30 minute, pressing 
the mixture at 0.5 GPa as a pellet shape with thickness for 3mm, 14mm diameter. A pellet enters to 
furnace for sintering about 140 h at 860oC.  A pellet was use as a target to grow a thin film at an optimal 
Si (111) with different substrate temperature (300, 320, 350 and 400oC) by PLD technique. PLD using 
Nd: YAG laser with 532 nm, pulse duration of about 7 nsec and a current density (0.4 – 8) J/cm2 was use 
with an oxygen back ground pressure of 2×10-3 mbar, number of pulses is 150 pulses. Energy density was 
focused on the target to generate plasma plume. Distance between target and substrate was 5cm. system 
was mounted in vacuum chamber 10-5 mbar. All samples annealed at 820oC in vacuum furnace 
employing oxygen atmosphere with flow rate 2 lit/min with heating rate 15oC/min .The BiPbSrCaCuZnO 
nanostructure film has been measured by an optical interferometric method [8]. Then realized the 
 Ghazala Y. Hermiz et al.  /  Energy Procedia  36 ( 2013 )  881 – 887 883
electrical resistivity measurement (using four – probe) which is  important study in superconductivity in 
order to evaluate the critical temperature Tc through measure the resistivity  ρ  as a function of 
temperature using this equation  
                                                  
I
V
d
bt U                                                                                       (1) 
 Where b is width of sample (1cm), thickness (184.2±10 nm) depend on the number of pulses, d is 
distance between two point measure voltages (29.27x10-6 m), I is current flow through film surface (0.05 
mA). 
The structure of the prepared samples was obtained by using x-ray diffractometer (XRD) type 
(Philips) with the CuKα source. The lattice constants of thin films samples were calculated using inter 
planer distance d, and Miller indices h,k and l values of strong peaks in the XRD patterns according to: 
 
                            2
2
2
22
2 )(
1
c
l
a
kh
d
                                                                              (2) 
   
     Bragg law was used to find the lattice parameter c by taking the Miller indices of adjacent peak. The 
morphologies of the film were measured by atomic force microscopy (AFM) type origin USA   Model 
AA300-CSPM.                                                          
                          
3. Results and discussion  
         Fig (1) shows the resistivity as a function of temperature for films of Bi1.6 Pb0.4Sr2Ca2Cu2.4Zn0.6O10 
deposited at variable substrate temperature. It is found from this figure that the transition from normal 
state resistance to superconducting is not sharp and has tails, this may be attributed to the fluctuation of 
the oxygen content in grains and existence of multi phases 2223, 2212 and impurity phases as it is 
observed in the results of the x-ray diffraction.  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Fig 1: ρ-T curves  of Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10  thin films deposited at Ts: (a) 300°C, (b)320°C, (c)350°C and, (d)400°C   
884   Ghazala Y. Hermiz et al.  /  Energy Procedia  36 ( 2013 )  881 – 887 
 Fig.(2) shows the  Tc obtained under different substrate temperature 300, 320, 350 and 400 oC . The 
transition temperature as a function of substrate temperature was 95, 97, 110 and 112 K respectively. The 
reason of increase Tc with the enhancement of substrate temperature could be explained as follows: the 
heat increase the energy of adsorbed species over surface, and interact among themselves which lead to 
form clusters, these clusters collide with other to form bigger and becomes thermodynamically stable and 
grown in number as well as in size, this lead to increasing the mobility of clusters and subsequently 
enhance the critical temperature. Indeed heat treatment under high pressure of O2 enhances Tc  and 
improve the homogeneity of the crystals as indicated by  [9]  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Fig.2: Transition temperature as a function of substrate temperature 
 
        Fig.(3) Shows XRD patterns for films of Bi1.6Pb0.4Sr2 Ca2 Cu2.4 Zn0.6 O10  deposited at different 
substrate temperature. It has been observed that the intergrowth phase of 2212 and 2223 are obtained with 
the variation of the substrate temperature as pointed out by Ranno et al. [10]. Indeed  increase Ts does not 
causes re-evaporation  of Bi  in the films and thus leads to grow phase is between 2212 and 2223 , also 
film begin to melt away and drives  the calcium atoms to the 2212 phase , where, there exists a deficiency 
of calcium, there by forming the 2223 phase. X-ray diffraction patterns and Miller indices for specimens 
under study exhibit tetragonal structure, the indices in the patterns are taking and compared with, Primo et 
al. [11] and Koyama et al. [12]. 
    The lattice constants at different substrate temperature are listed in Table 1. It is interesting to note 
from this table, there is an increase in lattice parameter (a) with the increases of substrate temperature up 
to 350oC, while lattice constant (c) is nearly constant (from 320 oC to 400 oC). This behavior could be 
explained as follows: increases of the substrate temperature will increase the velocity of the particles 
traveling to the surface, this allowed  enough time for cluster to form .These nanoclusters, once attached 
to the film surface, would serve two possible purpose :( 1) they act themselves as seeding sites for island 
growth. (2) These larger species would certainly cause more strain on the film surface which lead to 
increase the growth in (a) parameter.  
 
 
 
 
 
 
 
92
96
100
104
108
112
116
300 320 340 360 380 400 420
T c
(K
) 
TS (oC) 
 Ghazala Y. Hermiz et al.  /  Energy Procedia  36 ( 2013 )  881 – 887 885
 
 
                         Fig.3: The XRD pattern of Bi1.6 pb0.4Sr2 Ca2 Cu2.4 Zn0.6 O10  thin films deposited at Ts300, 320, 350 and, 400°C 
 
 
 
 
Table 1: a and c lattice constants for Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6 O10 thin films deposited under different substrate temperature 
  
 
Ts(oC) 
 
a (nm) 
 
c (nm) 
 
300 
 
3.99 
 
37.33 
320 4.49 36.96 
350 4.62 36.96 
400 4.62 36.96 
      
     
 
 
886   Ghazala Y. Hermiz et al.  /  Energy Procedia  36 ( 2013 )  881 – 887 
Fig (4) shows the three dimensional views   AFM of Bi1.6 Pb0.4Sr2 Ca2 Cu2.4 Zn0.6 O10 thin films deposited 
at Ts equal to 300, 320, 350 and, 400°C.  From the AFM image, some out-growths exist on the surface of 
film. The width of the surface pits (average diameter), mean surface roughness (Ra) and the root mean 
square deviation value (RMS) of the samples carried out from AFM images are shown in Table (2). The 
film showed a rough surface. This mode may be correlated to the existence of clusters in the plasma. This 
can be explained by the different epitaxial growth modes with strong chemical bonds or weak physical 
interactions with Si (111). It has been observed that the interaction of film with substrate or the starting 
atomic layer of BiPbSrCaCuZnO may change with substrate temperature [14].   
   
 
 
 
 
 
 
Fig. 4: AFM of Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10  thin films deposited at Ts 300, 320, 350 and, 400°C 
 
Ts=300oC Ts=320
oC 
Ts=350oC Ts=400oC 
 Ghazala Y. Hermiz et al.  /  Energy Procedia  36 ( 2013 )  881 – 887 887
Table 2 :width of the surface pits (average diameter), average surface roughness and root mean square deviation of 
Bi1.6Pb0.4Sr2Ca2Cu2.4 Zn0.6 O10 thin films deposited at different substrate temperature. 
 
 
Ts(oC) 
 
Width of surface pits (nm) 
Average surface 
roughness(Ra) (nm) 
root mean square deviation 
(RMS)(nm) 
300 107.49 8.9 12.9 
320 164.23 12.6 16.2 
350 105.30 2.72 3.57 
400 69.19 1.8 2.32 
 
4. Conclusion  
            
            Bi1.6Pb0.4Sr2Ca2Cu2.4Zn0.6O10 pellet was prepared by solid state reaction. A pellet with thickness 
for 3mm and 14mm diameter was use as a target to grow a thin film at an optimal Si (111) at different 
substrate temperature (300, 320, 350 and 400oC) by PLD technique.  It has been observed that the 
intergrowth phase of 2212 and 2223 are obtained with the variation of the substrate temperature. AFM 
results reveal individual epitaxial domains posses. This was explaining by the different epitaxial 
growth modes with strong chemical bonds or weak physical interactions with Si (111). We can also be 
conclude that the increase of the substrate temperature lead to increases the growth in (a) parameter 
and enhance the activation energy of substrate atoms, which assist to attach the ablated atoms and 
subsequently increase the transition temperature. 
 
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Effect of Substrate Temperature on Growth Bi1.6Pb0.4Sr2Ca2Cu2.4 Zn0.6O10 Thin Films Prepared by Pulsed Laser Deposition

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