Teresa Puig - Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, España.
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El lunes y martes 21 y 22 de mayo del 2018 realizamos un Simposio Internacional en la Fundación Ramón Areces, tratando el tema de la superconductividad y presión: una relación fructífera en el camino hacia la superconductividad a temperatura ambiente.
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Teresa Puig - Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, España.
- 1. HTS YBa2Cu3O7-x Coated Conductors: A reality and yet with emerging breakthroughs Teresa Puig Instituto de Ciencia de Materiales de Barcelona CSIC, Bellaterra, Spain Collaborators: X.Obradors, A. Palau, J. Gázquez, S. Ricart, M. Coll, X. Granados, Z. Li, C. Pop, N. Cha morro, B. Villarejo, F. Pino, F. Vallés, B. Mundet, L. Soler, J. Jareño, S. Rasi, J. Banchew ski, R. Guzmán (ICMAB) R. Yañez, J. Ros ( UAB) J. Farjas, P Roura (UG)
- 2. High Temperature Superconductors: YBa2Cu3O7-x Discovered in 1987 HTS materials with the highest potential for high current and high field applications (highest irreversibility line) No microscopic understanding (no theory) Laminar structure: high anisotropic properties CuO2 planes are the conduction planes Doped superconductor: oxygen stoichiometry determines carrier concentration (overdoped state is desired for higher Jc) Very important granularity effects (small ) : epitaxy is needed Complex vortex pinning due to high thermal fluctuations (high Tc, small and large )
- 3. Coated Conductors are a reality Metallic substrate (50-100 m) Buffers (0.5-1 m) YBa2Cu3O7 (2 m) Cu (50 m) + Ag protection (0.5-1 m) Km-length flexible epitaxial multilayer capable to carry 400 A/cm-w at 77K and 800 A/cm-w at 5 K & 30 T IBADs (ABAD): Ion Beam Assisted Deposited substrate & RABiTs: Rolling Assisted Biaxially Textured substrate NANOCOMPOSITES: Outstanding vortex pinning properites Growth methods: PLD, MOCVD, CSD Breakthroughs PLD ABAD
- 4. Nanotechnology engineering enables YBCO CC to improve at all regions
- 5. Nowadays CC are ready for commercialization Hastealloy Stainless steel Ni-based CeO2 Y2O3 YSZ MgO LMO … YBCO (Y,Gd)BCO GdBCO EuBCO +BZO, BHO We have a strong industry in CC manufacture
- 6. Nanostructured Coated Conductors Energy Future paradigm : cables, FCL, transformers, ... Large Electrical Motors and Generators: Wind Mills, Airplanes, Ships,.. High Energy Physics, Fusion, Ultrahigh Field NMR, … Ultra-High field even 30 T, 4.2K Design stage, some prototypes High field 3-5 T, 40-60K Much activity with prototypes Low and medium field 1-3 T, 77K Devices already in grid High Temperature Conductor High field Conductor Main challenge: Reduce “cost / performance ratio”, €/kAm Improved efficiency Higher power density and quality Higher magnetic fields Environmentally friendly
- 7. Ampacity HTS Cable 2 years installed in Essen grid 10 kV cable (+FCL) substituting 100 kV line (but also Airbus and NASA) EU project: Full scale 3.6 MW-direct- drive HTS wind generator EU- project: FCL for HVDC grids 1 kA – 50 kV
- 8. LTS (1 5 T) + YBCO (17 T) 32 T LTS-HTS Magnet Hoop stresses 400-440 MPa LTS + HTS (BSCCO-2223 (with Ni alloy reinforced) + REBCO) at Japan 1.3 GHz NMR Geneva PS SPS LHC Future Circular Collider (FCC) FCC-hh 100 TeV (c.o.m.) 100 km (80 km) 16 T (20 T) 6000 tons Nb3Sn + 3000 tons Nb-Ti (9000 tons LTS + 2000 tons HTS)CC- use also for Beam Screen Beam energy Dipole field Bending radius E[GeV]=0.3 x B[T] x [m]
- 9. Simultaneous deposition and growth (Case PLD, MOCVD) ReBCO Second phase (BaZrO3) Self-assembled spontaneous segregation of second nano-phases within the epitaxial YBCO matrix NANOCOMPOSITES: Outstanding push toward APC S. Kang, Science 311 (2006) J. Driscoll, Nat. Mat. 3(2004), Y. Yamada, APL 87(2005); B. Maiorov, Nat Mat 8 (2009); Epitaxial nanorods form simultaneous with YBCO inducing semicoherent interfaces Deposition Absorption Surface diffusion Self-assembly ReBa2Cu3O7 BaZrO3 BaHfO3 BaSnO3 … Vortex pinning mostly ascribed to nanorods and associated interfacial strain
- 10. Self-assembled spontaneous segregation of second nano-phases within the epitaxial YBCO matrix NANOCOMPOSITES: Outstanding push toward APC Sequential deposition and growth (case CSD) 10-20 nm nanoparticles BaZrO3 BaHfO3 Ba2YTaO6 J. Guiterrez, T. Puig, Nat Mat 11 (2007) A. Llordés, T. Puig , Nat Mat 6 (2012) M. Miura, SUST 26 (2013) S. Engel, APL 90 (2007) precursor ReBCO Precursor deposition Nanoparticles formation ReBCO conversion and trapping of nanoparticles Random oriented nanoparticles form prior to YBCO growth inducing a defective matrix Vortex pinning mostly ascribed to distributed local lattice distortions (nanostrain) induced by the nanoparticles BaZrO3, BaHfO3, …
- 11. substrate 5 m Semi-dried gelified film substrate 1.6 m Fully pyrolyzed filmMetallorganic solution CSD process for Nanocomposites growth BaZrO3 BaHfO3 Ba2YTaO6 Grown YBCO nanocomposite YBa2Cu3O7 Y2O3 900 nm Intermediate phases and nucleation of YBCO film TFA-precursors 2 n m Epitaxial YBCO
- 12. 0 200 400 600 800 1000 1200 0 100 200 300 400 4 MA/cm 2 Nanocomposites 12% on CZO Low F solution (80% reduction) Spin pristine 3 MA/cm 2 IJP nanocomposites 12% IJP pristineIC(A/cm*width) Thickness (nm) Deposition of thick CSD films at ICMAB densification tension due to shrinkage substrate… … single deposition >1 m by ink jet printing LAO Epitaxial YBCO 77 K
- 13. BaZrO3 , Ba2YTaO6, Y2O3 or mixed compositions (randomly oriented nanoparticles) ss-Nanocomposites: Use of complex solutions for spontaneous segregation of nanoparticles (BaZrO3, BaHfO3, Ba2YTaO6, BaCeO3) pn-Nanocomposties: Colloidal solutions with preformed nanoparticles c 200 nm 5 n m5 n m BaZrO3 200 nm 5 nm BaHfO3 Solvothermal synthesis – (Autoclave)- 8-10 nm 4-5 nm Need to stabilize np in the alcoholic and ionic environment of YBCO precursor solution at high concentrations c
- 14. LAO pn-nanocomposites of non-reactive preformed BaZrO3 and BaHfO3 nanoparticles High homogeneity in Np dispersion at high Np concentrations. No reactivity. Randomly oriented. LAO BZO BZO BZO 20%M BZO 10 nm YBCO NC YBCO seed layer 20%M BHO 10 nm To be published Jc =3-5 MA/cm2 at 77 K
- 15. 0 5 10 15 20 25 0 2 4 6 [NP] (mol %) Jc SF (MA/cm 2 )@77K Spontaneous segregation Preformed np BZO-YBCO Tc is preserved with CSD nanocomposites Higher concentration of np without current blocking with pn-nanocomposites Colloidal solutions compatible with IJP and multideposition (demonstrated up to 1 m) 4 6 8 10 12 14 16 18 20 22 24 26 80 82 84 86 88 90 92 94 Tc(K) [Np] (% mol) Preformed np CSD nanocomposites: ss- and pn- nanocomposites
- 16. High performance of CSD-YBCO Nanocomposites High performance at all temperatures YBCO-TFA 65K 0 2 4 6 8 0 20 40 60 80 300 400 500 600 0 H (T) Pinningforce(GN/m 3 ) NANOCOMPOSITE 10K NANOCOMPOSITE 65K NANOCOMPOSITE 77K Nb-Ti 4.2K A. Llordés, et al. Nat. Mater , 11, 329 (2012), J. Gutierrez et al, Nat. Mater. 6, 367 (2007) P. Cayado, et al SUST (2015) K.De Keukeleere, etal AdvMatElectronics (2016) x5 x5 200 nm films 0,01 0,01 Pristine 10BZO5YO Preformed 12% BaHfO3 Preformed 13% ZrO2 77K 50K Jc (MA/cm 2 ) 0 H (T) 10K 1 x 50
- 17. YBCO+BZOPristine YBCO [010] 1nmY Ba Cu O CuO double chain (248 intergrowth Stacking faults) YBCO [010] BaZrO3 c eyy -10% 10% +2% -3% +2% Strong strain effects are generated at the partial dislocations Planar view BZO YBCO HAADF Y248 Y248 YBCO [001] Partial dislocation HR-STEM imaging Local compressive and tensile nanosized regions
- 18. New vortex pinning mechanism based on strain A.Llordés, T Puig., Nat Mat. (2012), J. Gutierrez, T. Puig, Nat. Mat. (2007) 0,05 0,10 0,15 0,20 0,25 0,0 0,5 1,0 BZO YO BCO BYTO F iso Pmax /F tot Pmax nanostrain % Vortex pinning is ascribed to distributed local lattice distortions (nanostrain) induced by the defects generated by the nanoparticles: Isotropic pinning Calculated from XRD Williamson-Hall plot Lower Jc anisotropy, eff =2-3
- 19. Bond Contraction Pairing : - tCuO : transfer integral between Cu d and O p orbitals - U : on-site Coulomb repulsion - t0 : half bandwidth Pair breaking energy: tCuO (1/dCuO 5) 0 2 8 )( 42 t U tCuO Nanostrain leads to unpaired nanoscale regions G. Deutscher, APL (2010) A. Llordes , T. Puig, et al., Nat. Mater 2012 Cu CuO New vortex pinning mechanism based on strain induced Cooper-pair suppression Isotropic-Strong pinning occurs by saving vortex line tension energy in a significant fraction of their length Additional pinning from Np is possible if they are in the 5 nm range Vortex bending accommodates to a 3D ramified network of localized isotropic nano-strained regions Tensile strain quenches pair formation vortex intergrowth Nanostrained regions
- 20. BZO Source of new atomic scale defects : Weak pinning contribution: Cu –O cation vacancies 2 VCu + 3 VO - DFT calculationsFaulted Y248 x2 VCu LAADF strain imaging J. Gázquez et al, Adv. Science 3 (2016)also confirmed by HR-EELS Z-contrast 1/ABFABF Cu O BaZrO3 YBCO [010] c
- 21. Annular Bright Field Imaging Z-contrast 1/ABF ✦O vacancies in the BaO plane!! The energy to introduce VO - at the BaO and CuO planes is similar (1.12 eV) Additional local structural distortions are observed: c –axis locally decreases
- 22. Jc aniso contribution dominant close to the IL Pinning properties of CSD YBCO nanocomposites H,T pinning strength diagrams Isotropic strong pinning mechanism dominates the phase diagram, Jc iso-strong Nanostrain pinning is key T.Puig et al., SUST 21 (2008); J. Plain et al, PRB 65 (2002); J.Gutierrez et al., Appl. Phys. Lett. 90 (2007), A. llordes et al, Nat Mat (2012) Jc iso-weak contribution present below 20 K
- 23. BaCO3 (s)+CuO (s)+Y2O3 Liquid-Solid reaction Fluorine free precursors • Faster diffusion-> faster growth rate (x100) • Highly simplified reactor • More enviromentally friendly • Compatible with IJP and pn-nanocomposites CSD-TLAG Transient Liquid Assisted Growth CuO + Ba1-xYxF2-yOy + Y2O3 (s) • Growth rate limited to 1nm/s Solid-Gas reaction HFH2O Trifluoroacetate precursors Standard CSD
- 24. CSD-Transient Liquid Assisted Growth High growth rate and low costof Nanocomposites : 15 20 25 30 35 40 45 50 55 60 0 1000 2000 3000 4000 5000 Quenched sample (332)Y2 O3 (431)Y2 O3 (622)Y2 O3 (400)Y2 O3 (222)Y2 O3 (440)Y2 O3 LAO Intensity(a.u.) 2(º) Amorphous liquid BaCuO2-CuO Twin boundaries 550nm 200 nm 2 nm at 48nm/sExtremely low porosity, Tc=90 K Jc(77K)= 3-5 MA/cm2 (x50 standard CSD) Approach towards ultrahigh fields : pn-Nanocomposites BZO BZO STO BZO 20 nm 5 n m5 n m BaHfO3
- 25. 2D detector BZO : 4 nm BHO : 5 nm BZO and BHO TLAG Nanocomposites
- 26. 0,01 0,1 1 10 5K Jc/MAcm-2 0H / T FF Pristine FF + 12% BZO FF + 12% BHO 0,01 0,1 1 0,1 1 5K Jc/Jc,max/MAcm-2 0H / T FF Pristine FF + 12% BZO FF + 12% BHO 0,01 0,1 1 0,001 0,01 0,1 1 77K Jc/MAcm-2 0H / T FF Pristine FF + 12% BZO FF + 12% BHO 1E-4 0,001 0,01 0,1 1 0,001 0,01 0,1 1 77KJc/Jc,max/MAcm-2 0H / T FF Pristine FF + 12% BZO FF + 12% BHO SQUID measurements Enhanced in-field properties of TLAG nanocomposites
- 27. CONCLUSIONS HTS have been an impressive nest of new knowledge with still many unknowns to be discovered Nanocomposites have been an outstanding solution for high and ultra- high field applications: Strain being the driving force Despite all initial difficulties, we have successfully manufactured km-length conductors and applications are here Low cost and fast growth manufacturing methodologies should fasten marketability Superconducting group at ICMAB
- 28. Uniform strain (macrostrain) Non-uniform strain (nanostrain) 2θ Crystal lattice strain XRD analysisCrystal lattice Diffraction line Microstructural defects ε = ∆d/d d-spacing fluctuations defects Semi-coherent interface incoherent interface Williamson-Hall plot may be used to analyse peak broadening crystal coherence volulme Misfit dislocation Lattice matching with strain relaxation
- 29. 0 5 10 15 20 25 30 35 0,1 0,2 0,3 0,4 BZO YO BCO BYTO -nanostrain% Incoherent interface (m -1 ) pristine BZO 15%M BZO 10%M YO 15%M A. Llordés et al., Nat Mat, 11, 329 (2012) Random nanoparticles induce isotropic nanostrain Nanostrain determined by XRD Williamson-Hall plot analysis 77 K 0.05 0.10 0.15 0.20 0.25 0.0 0.5 1.0 BZO YO BCO BYTO F iso Pmax /F tot Pmax nanostrain % Nanostrain is controlled by random nanoparticles Local lattice strains control the isotropic pinning landscape of CSD-nanocomposites The highest isotropic performance ever found in any superconducting material
- 30. 45 90 135 180 0.1 1 5T Pristine 250nm 9T Pristine 250nm 5T 20BZO 700nm 9T 20BZO 700nm Jc /Jc (90º) [°] 5K 45 90 135 180 0.1 1 65K 5T Pristine 250nm 9T Pristine 250nm 5T 20BZO 700nm 9T 20BZO 700nm Jc /Jc (90º) [°] eff 5 𝒆𝒇𝒇 = 𝟓 Nanocomposite behaviour is preserved with thickness Smoother Jc(H) dependence and more isotropic behaviour 0 1 2 3 4 5 6 7 8 9 10 11 12 0,1 1 10 100 1000 5K 5K Ic (A/cm-w) 0 H||c [T] 77K 250 nm 750 nm 20% BZO 700 nm 250 nm 750 nm 20% BZO 700 nm 12% BZO 700-850 nm 1.2 m x 5 x10 To be published
Editor's Notes
- BCP: hole pairing mechanism is attributed to in-plane contraction of Cu-O bonds We propose a new vortex pinning mechanism were strain induces Cooper-pair suppression. A mechanism that is based on the contraction of the Cu-O bond to determine the pairing energy. Tensile strain decreases the overlapping of the Cud and Op orbitals and pair breaking is favourable. Being the transfer integral so much dependent on this Cu-O distance (power to the 5), small tensile strains of the order of 1% could do the job. Thus, essentially the Copper pair formation is suppressed in these nano-sized regions. Therefore, a new microscopic physical mechanism could account for the strong coupling of lattice strain and vortex pinning 3D ramified network of localized and highly strained nano-sized regions are responsible of the strong isotropic pinning Local vortex bending occurs to accommodate to the disordered nano-strained regions so vortices save line tension energy in a significant fraction of their length to achieve strong pinning BCP model could eventually explain our experiments as it correlates the nanostrain and the superconducting order parameter. In-plane Cu-O distances plays a key role in the pairing mechanism because hole pairing in adjacent Cu positions is made possible by the contraction of these bonds. Here I present a schematic representation of the vortex – dislocacions - strain coupling. Which can help to draw a better view of the microscopic origin of this coupling …. The ubiquitous (iubicuites) partial dislocations lead to a three dimensional ramified network of hightly strained and localized nano-sized regions, which are responsible for the vortex pinning properties observed in these nanocomposites, giving rise to a strong isotropic pinning.
- The vortex pinning analysis previously mentioned was here used to separate the different pinning contributions and helped us to identify that a new isotropic strong pinning contribution was dominating the phase diagram of the CSD nanocomposites. That isotropic random pinning was induced by nanostrain at high and low T and an anisotropic contribution was just left at the very high temperature close to the IL.
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- In fact, if we see these intergrowth now from a planar view of the ab plane, we can visualize the overall partial dislocation length, and quantify the huge increase of dislocation density achieved. 100 times higher than in pristine samples. By determining this accumulated strain by XRD analysis following the Williamson Hall plot analysis, we could demonstrate that the nanostrain was linearly increasing with the amount of incoherent interface and that in fact, this nanostrain tended to be isotropic.