Leibniz-Institut for

Solid State and

Materials Research
Dresden

High temperature
superconductors:
Properties and applications
Ruben Hühne

IFW Dresden
Institute for Metallic Materials
Superconducting Materials Group
1

Outline

• High temperature superconductors (HTSC)

which materials?

what are the basic properties?
Introduction

• Power applications of HTSC

what are possible applications?

what are the requirements for application?

• Development of conductor based on HTSC

Powder-in-tube technology (PIT)

YBCO coated conductors

• textured substrates: RABiTS

• textured buffers: IBAD

1
 Outline

Basic properties of HTSC • High temperature superconductors (HTSC)

which materials?

what are the basic properties?

• Power applications of HTSC

what are possible applications?

what are the requirements for application?

• Development of conductor based on HTSC

Powder-in-tube technology (PIT)

YBCO coated conductors

• textured substrates: RABiTS

• textured buffers: IBAD

Superconductivity
Discovery of Superconductivity
Liquification of Helium
Basic properties of HTSC

H. Kamerlingh Onnes, Leiden (1908)

Discovery of „Superconductivity“: ideal conductivity

Kamerlingh Onnes
H. Kamerlingh Onnes, Leiden (1911)

Many metals become superconducting at low temperatures

Temperature (K)

Liquid hydrogen: 20 K

Year of discovery

Step in the electrical resistivity of Hg:

critical temperature TC

4  Current transport without losses possible Cooling with liquid helium necessary

2
 High temperature superconductors

Basic properties of HTSC

77 K

Ba-La-Cu-O compound:
J. G. Bednorz, K. A. Müller, Z.
Physik, B 64 (1986) 189

Ba-La-Cu-O

Cooling with liquid nitrogen possible

compound TC (K)

YBa2Cu3O7-δ Y-123 92
commercial
potential Bi2Sr2CaCu2O8 Bi-2212 84
Bi2Sr2Ca2Cu3O10 Bi-2223 110
TlBa2Ca2Cu3O10 Tl-1223 125
5 HgBa2Ca2Cu3O10 Hg-1223 133

High temperature superconductors

BiSCCO REBCO
Bi(Pb)-2212 Bi(Pb)-2223 REBa2Cu3O7-x
Basic properties of HTSC

2212 ≈ (Bi,Pb)2Sr2CaCu2Ox (x ≈ 8) RE: Y, Nd, Er, Gd, Eu…

2223 ≈ (Bi,Pb)2Sr2Ca2Cu3Ox (x ≈ 10)
O

Ceramics: layered Cu
perovskite material
Ba
(2-dimensionality)
c = 11.68 Å

CuO2-planes
Y
responsible for
superconductivity

Properties show
high anisotropy

Ca
Bi
Sr b = 3.88 Å
Cu
O a = 3.83 Å

6 TC = 85 K TC = 110 K TC = 92 K

3
 High temperature superconductors

Anisotropy of the resistivity Dependence of the superconducting

Basic properties of HTSC properties on O doping

HTSC in magnetic fields

B(T) phase diagramm of type II superconductors

type II superconductor
Basic properties of HTSC

nc
Mixed phase
µ0HC2 (T) (Shubnikov)
µ0H (T)

sc
Meissner
phase magnetic field

µ0HC1 (T) TC
flux line
Cooper pair
T (K) density n
Φ0
type II TC (K) µ0HC2 (T) flux quantum
normal -15 2
Nb 9.3 0.3 conducting core penetration F 0 = 2 ·10 Tm
depth λ
Nb3Sn 18.0 24.5 shielding
Nb3Ge 23.2 38.0 currents magnetic field B

MgB2 39.0 17.0 r

Y-123 92.0 150 vortex coherence lenghth ξ
8
Bi-2223 110.0 108

4
 HTSC in magnetic fields
B(T) phase diagram of superconductors: critical fields
Basic properties of HTSC
HTS
sc
µ0Hirr nc
vortex
µ0H (T)

liquid
vortex
glass
µ0HC2
vortex
lattice applied magnetic field penetrates the
superconductor in form of vortices
µ0HC1
 current leads to Lorenz force on vortex
lines
T (K)
 movement of vortices leads to
Φ0 dissipation: Irreversibility line
 pinning of the vortices necessary for high
pointlike critical currents in magnetic fields
pinning  incorporation of nanoscaled pinning
centers centres

core diameter ~ 2ξ
9 vortex

HTSC in magnetic fields

Irreversibility line
Bi-2223 Properties of the vortices are dependant
Basic properties of HTSC

on the crystal structure of the material

YBCO

YBCO BSCCO-2223

CuO2
B CuO2
CuO2

d
CuO2
CuO2
CuO2
CuO2 d CuO2

CuO2
YBCO is the preferred
CuO2 CuO2
material for applications CuO2
at 77 K in higher CuO2 CuO2
magnetic fields
d~ 2ξ d > 2ξ
10 3D flux line 2D pancake vortices

5
 Critical current density
Current-voltage characteristic of superconductors
n
I 
U ( I ) = U 0  
Basic properties of HTSC
 I0 

Critical current Ic is dependant on

temperature and magnetic field

Critical current density Jc:

Ic divided by cross section of the superconductor

Engineering current density Je:

11 Ic divided by cross section of complete conductor

Critical current density

Critical current density Anisotropy

Basic properties of HTSC

9
3x10

B = 1 T, φ = 0°
B = 4 T, φ = 0°
B = 1 T, φ = 90°
9 B = 4 T, φ = 90°
2x10
Jc (A/m )
2

9
1x10

0
-90 -45 0 45 90
θ (°)
12

6
 HTSC grain boundaries
Measurement
Basic properties of HTSC YBCO on bicrystals

Bi2212 Bi2223

Hilgenkamp et al., Rev. Mod. Phys. 74 (2002) 485

 High Jc in polycrystalline materials require strong biaxial texture

13

HTSC grain boundaries

Θ

Origin of Jc-limitation at grain boundaries:

 Microstructure:
Basic properties of HTSC

d=b/2sin(Θ/2) ≈ b/Θ
• Strain fields around dislocations, d
• Distorted areas in large angle grain Für b=0.38nm

boundaries Θ=8° ⇒ d=2.7nm

 Deviations from ideal stoichiometry (100) (100)

• regions with oxygen vacancies (010) (010)

• disorder
• localised states
 Symmetry of the order parameter
 Band bending due to interface
charging Depletion zone
KG Tcmax
 Direct suppression of pairing EL
mechanism TcKorn Tc
EF 0
EV
 Reason:
Extremly short coherence length
ξ and low charge carrier density λ TF d λ TF
14 in HTSC Hilgenkamp et al., Rev. Mod. Phys. 74 (2002) 485

7
 Other „new“ superconductors
MgB2

Phase known since the early 50‘s
Basic properties of HTSC
Jones et al., J. Am. Chem. Soc. 76 (1954) 1434
Fe-pnictides and -chalcogenides

Superconductivity discovered 2008
Kamihara et al., J. Amer. Chem. Soc. 130 (2008) 3296

Superconductivity discovered in 2001 LaO1-xFxFeAs Tc ~ 26 K

Nagamatsu et al., Nature 410 (2001) 63 GdO1-xFxFeAs Tc ~ 53 K
SmO1-xFxFeAs Tc ~ 55 K

Tc = 39 K: highest Tc for binary Ba1-xKxFe2As2 Tc ~ 38 K
superconductors FeSe1-xTex Tc ~ 15 K
…

no weak link behavior at grain

boundaries in contrast to cuprates

15 large coherence length ξab = 7-10 nm

Outline
Applications of superconductors

• High temperature superconductors (HTSC)

which materials?

what are the basic properties?

• Power applications of HTSC

what are possible applications?

what are the requirements for application?

• Development of conductor based on HTSC

Powder-in-tube technology (PIT)

YBCO coated conductors

• textured substrates: RABiTS

• textured buffers: IBAD

16

8
 Application of classical superconductors
Application in medical and analytical devices
Applications of superconductors
Medicine:
Magnetic Resonance
Imaging (MRI) of soft
tissues like organs,
cartilages, tendons etc.
>3000 t NbTi per year

Analytics:
Nuclear Magnetic Resonance
(MNR) spectroscopy
>500 t Nb3Sn per year

17

Application of classical superconductors

Magnets for research devices

Applications of superconductors

• Accelerators in particle physics

• Reactors for nuclear fusion

18

9
 Power applications of HTSC

Generator Cable Transformer Motor

Applications of superconductors

Higher current density  lower weight @ same power

Lower losses / higher efficiency

Environmental friendly

copper

19

Power applications of HTSC

Ship populsion motors
Applications of superconductors

20

10
 Power applications of HTSC
Superconducting cable
Applications of superconductors 350 m long cable at 34.5 kV and 800 A in real network
Made form BiSCCO and YBCO based conductors

21

Power applications of HTSC

Required properties for different power applications
Applications of superconductors

Current limiter

Cable Generators,
106
Motors
Fusion magnets

105
Jc [A/cm²]

MRI magnets
104 Transformers
NMR-Spectrometer
10³ Typical YBCO
layer on technical
substrates at 77 K
10²
5 10 15 20

22 B [T]

11
 Application of HTSC

Main requirements on HTSL conductors for application

Applications of superconductors
• Mechanical flexible conductor (for coils etc.)
 metal-ceramic heterostructure

• High current transport capability at:

- highest application temperature (above 77 K)
- highest magnetic fields
 strongly textured superconductors
 defined incorporation of pinning centres

• Availability in long length

(several km necessary for demonstrators)

• Cheap production of long length necessary

 robust and fast methods
 low cost materials

• Other requirements for certain application:

- low ac-losses
- high mechanical strength
- reduced anisotropy
23

Outline

• High temperature superconductors (HTSC)

Preparation of HTSC conductors

which materials?

what are the basic properties?

• Power applications of HTSC

what are possible applications?

what are the requirements for application?

• Development of conductor based on HTSC

Powder-in-tube technology (PIT)

YBCO coated conductors

• textured substrates: RABiTS

• textured buffers: IBAD

24

12
 Powder-in-Tube (PIT) Technology
Preparation of BiSCCO and MgB2 conductors
Preparation of HTSC conductors
Precursor Deformation Thermal Treatment

Mixture of Precursor Drawing

Base Compounds

Ag -
• Sol-gel methods Tube

• Mechanical
alloying Bundling Drawing

e.g Bi-Pb-Sr-Ca-Cu-O
powder
with Bi-2223
composition
or
Rolling
Mg, B mechanically
alloyed
precursor

25 Cross section Longitudinal Section

PIT conductors
BiPbSrCaCuO (2223) PIT conductor MgB2 PIT conductor
Preparation of HTSC conductors

 available in long length
first long length available

 moderate performance (Jc < 60kA/cm2)
potential application at ~ 20 K
not applicable in magnetic fields at 77 K (boiling point of hydrogen)
too expensive (Ag)  combined with hydrogen
technology

MgB2

Nb

Cu

CuNi
600 m long
BSCCO tape
MgB2 multifilamentary conductor

26
Cross section of BSCCO tape with 61 filaments

13
 YBCO coated conductors
Application of YBCO for HTSC conductors
YBCO coated conductors
Advantage: high irreversibility Challenge: grain boundaries
fields at 77 K

Bi-2223
77K
YBCO 6
10

J (A/cm )
2
5
10

c
Y123

4
10

0 4 8 12 16
GB angle (°)

• Powder-in-tube technology does not work for YBCO

• Long length of highly textured YBCO conductors required

27 Growth of epitaxial YBCO on a textured template:

template: coated conductors

Preparation of YBCO coated conductors

Major processing routes for YBCO coated conductors
YBCO coated conductors

Rolling Assisted Biaxially Textured Ion Beam Assisted Deposition

Substrates (RABiTS) (IBAD)
Rolling and
Annealing
Ion beam
Ni, Cu
PLD, Sputtering PLD
Thermal evaporation e-beam
CVD,CSD Sputtering

Based on biaxially textured substrates Based on biaxially textured buffer layers

28

14
 RABiTS Approach
Rolling Assisted Biaxially Textured Substrates (RABiTS
(RABiTS))
YBCO coated conductors
Rolling Recrystallization Epitaxial Film
Deposition
Nickel

• Cold deformation >95% • Typical 900°C/1h • PLD

• Pure Ni • Ar/H2-atmosphere • E-beam
• Microalloyed Ni : • Sputtering
Ni-0.1at%Mn • CVD
• Alloyed Ni : • CSD
Ni-5at%W
Ni-7.5at%W
Ni-9at%W
Ni-9at%V
Ni-13at%Cr
• Composites :
Ni-W/Ni-Cr
29 (111)-pole figure of Ni-5at%W
Ni-W/Ni-W

Tape Processing I
Hot rolling

Induction furnace
YBCO coated conductors

Intermediate Ni bars

Special 4-
Final tape high mill
30 (up to 100 m)

15
 Tape Processing II
Continuous tape annealing Characterisation
Electron
Process gas Exhaust
backscattering
YBCO coated conductors
Tape
Exhaust diffraction
Tape
(EBSD)

Heating zone
B
Heating zone
Heating zone A
B

Reel

Gas
Reel, motorized

Gas
Continuous Tape Annealing
„Kikuchi pattern“

Local texture
information
„Texture maps“
31

YBCO coated conductors on RABiTS

Epitaxial deposition of buffer layers and YBCO
Necessary function of buffer layers:
YBCO coated conductors

• Suppression of Ni diffusion into YBCO

(Ni degrades superconductivity)
• Suppression of uncontrolled O diffusion to
substrate (may lead to cracks and peeling off) (111)
• Texture transfer from substrate to superconductor
(cube textured YBCO)

Ni-5at%W RABiT substrate

YBCO (103)
CeO2
YSZ
Y2O3
Ni
YBCO coated conductor
architecture Cross section of coated conductor YBCO layer
32
Hühne, R. et al., Supercond. Sci. Technol. 20 (2007) 709

16
 YBCO coated conductors on RABiTS
Pulsed laser deposition - PLD
YBCO coated conductors
• high quality of layers
laser plume thermo • flexible method
target couple
• small substrates (typical 10 x 10 mm²)
• vacuum equipment necessary
• high costs
substrate heater
laser beam  ideal for research and development

Chemical solution deposition - CSD

Starting material dipcoating heat treatment
as organic • no vacuum necessary
compounds • easily scalable on long length
substrate
• high yield achievable
• large coating areas possible
precursor
A B C solution  ideal for industrial
processing

33

Preparation of YBCO coated conductors

Major processing routes for YBCO coated conductors
YBCO coated conductors

Rolling Assisted Biaxially Textured Ion Beam Assisted Deposition

Substrates (RABiTS) (IBAD)
Rolling and
Annealing
Ion beam
Ni, Cu
PLD, Sputtering PLD
Thermal evaporation e-beam
CVD,CSD Sputtering

Based on biaxially textured substrates Based on biaxially textured buffer layers

34

17
 Ionenstrahlunterstützte Deposition (IBAD)
Principle: Comparison to RABiTS approach
Substrate

Ionen-
YBCO coated conductors
 all kind of substrates possible
strahl  smaller grains and sharper textures
PLD
Evaporation compared to RABiTS  higher Jc
Sputtering  extremely fast texturing process for
IBAD-MgO or IBAD-TiN (within 10 nm!)
Target
 complex process
 smooth (polished) substrates
Preparation of textured buffer
necessary
layers
 vacuum equipment and on-line
control necessary

Typical IBAD coated conductor

architecture Superpower Inc.
(USA)
35 Available in length of > 1 km

Ion-beam assisted deposition (IBAD)

Materials for the IBAD process:
process:
 YSZ, CeO2, Pr6O11, Gd2Zr2O7...  MgO, TiN…
YBCO coated conductors

35 Cube texture in 10 nm thick IBAD-layers on

amorphous substrates
in-plane orientation [°FWHM]

30 IBALD-YSZ, 2,3 Å/s

additional epitaxial CeO2
IBALD-YSZ, 1,2 Å/s Wang et al. APL 71 (1997) 2955
25 additional epitaxial CeO2

20

15

10

5
divergence of the ion beam
Betz (1998)
0
0 1 2 3 4 5 6
YSZ-thickness [µm]

Ion beam improves in-plane texture Ion beam influences already the
through a growth selection process nucleation
 Slow process  Very fast process

36

18
 Optimization of YBCO coated conductors
Artificial pinning centres Reduction of ac-losses
• improvement of the critical current density • losses due to magnetization change
YBCO coated conductors
Jc in magnetic fields of ferromagnetic substrates
• incorporation of nanosized pinning sites:
• non-superconducting particles  development of RABiTS with
• growth defects through islands on
reduced ferromagnetism
the substrate • hysteretic losses in YBCO due to
• magnetic nanoparticles conductor geometry
7
critical current density Jc [A/cm²]

10  filamentation of conductors
MOD-YBCO 1.5 at.% Hf
MOD-YBCO 1 at.% Hf
6
10 MOD-YBCO 0.5 at.% Hf
MOD-YBCO

5
10 T = 77K
8
BIIc
0.15 mm
Pinning Force Density

7
Fp(10 N/m )

6
³

4
10 5
4
9

3 4 mm
2
3 1
10 0
0 2 4 6 8 10
magnetic field µ0H /T

0 2 4 6 8
magnetic field µ0H /T
• coupling losses in multilayer
37 systems
Engel, S. et al., Appl. Phys. Lett. 90 (2007) 102505

Summary

• HTSC are highly anisotropic, ceramic

superconductors

• HTSC are potential materials for different

applications using liquid nitrogen cooling
Summary

• Main challenge is to prepare flexible

conductors with high critical current
densities in higher magnetic fields on long
length

• Different approaches were developed to

realize such conductors:

Powder-in-tube technology

Coated conductors

38

19