Table 1.
Basic features of HTMC cuprates, CMR manganites and HLH solar perovskites in comparison.
| Features | HTSC cuprate perovskites | CMR manganite perovskites | Solar/hybrid lead halide perovskites |
|---|---|---|---|
| Key chemical elements configuration, ion size and framework bonding | Cu—O (d/p) Cu: [Ar]3d104s1 O: [He]2s22p4 68−71 pm for Cu(III)—Cu(I) 126 pm for O2− |
Mn—O (d/p) Mn: [Ar]3d54s2 O: [He]2s22p4 67−72 pm for Mn(IV)—Mn(III) 126 pm for O2− |
Pb—I (s/p, p/p) Pb: [Xe]4f145d106s26p2 I: [Kr]4d105s2 5p5 133 pm for Pb(II) 206 pm for I− |
| Functional properties | Superconductivity Diamagnetic |
Magnetoresistance Magnetic semiconductor / metallic |
Photoeffect Semiconductor |
| Carriers | Hole pairs (bosons, BCS pairs) | Electrons (spin–polarized) | Hole–electron pairs (excitons) |
| Metal oxidation state(s) | Mixed +2/+3 | Mixed +3/+4 | Fixed +2 |
| Conduction path | Flat CuO2 sheets (doped from charge reservoir) | Lined Mn–O–Mn chains (double exchange etc.) | Pb–I–Pb chains (“redox”) |
| Point defects | Disordered and ordered oxygen vacancies, cation antisites, homo- and heterovalent substitution in both cation and anion sublattices | Disordered oxygen vacancies, cation antisites, homo- and heterovalent substitution in both cation and anion sublattices | Mostly homovalent substitution in either cation or anion sublattices, iodine vacancies |
| Deviation from stoichiometry ratio | Large for oxygen, much smaller for the larger central cations and copper (wide range for proper substitutions) | Small for both oxygen and cations (wide range for proper substitutions) | Iodine stoichiometry (still unclear) (wide range for proper substitutions) |
| Carrier generation | Oxidation | Heterovalent substitutions | Light absorption |
| Local distortions | Jahn–Teller effect, ion mismatch | Jahn–Teller effect, ion mismatch | Ion mismatch |
| Microstructure required | Biaxial texturing, large grains, clean boundaries, no weak links | Intergrain tunneling (other requirements are not essential) | No pinholes, no charge traps at grain boundaries, large grains are better, no texture is required |
| Whiskers | Exist, no need | Exist, no need | Exist, possibly useful |
| Applications | Large grain ceramics, epitaxial thin films, heterostructures | Thin films, polycrystalline coatings | Polycrystalline thin films, heterostructures, quantum dots, single crystals |
| Best processing | Melt techniques (LAP, MTG, LPP, PDMG, IMC, GPM, CGMG, SLMG, PMP, TPP, GEORGE, QMG, OCMG, MPMG, QDR) and thin films (ASP/CVD/MOCVD/PVD/RaBiTS) | Ceramic sintering, thin films (CVD/MOCVD/PVD/ASP) | Thin films (solution/precipitation, CVD/PVD/ASP, RP-MAGIC) |
| Spinodal decomposition | Known, useful for pinning | Known, useless | Known, under study |
LAP, liquid assisted processing (crystallization or recrystallization with traces of melt); MTG, melt textured growth (melting and cooling process under constant pO2); LPP, liquid phase processing (melting and stepwise cooling); PDMG, platinum doped melt growth; IMC, isothermal melt crystallization (melting and crystallization by pO2 variation under constant temperature); GPM, gas pressure method (crystallization under elevated partial pressure of oxygen); CGMG, constant gradient melt growth (crystallization along the concentrational/spatial gradient of REE); SLMG, solid liquid melt growth (melting and cooling process of fine mixture of powders under constant pO2); PMP, powder melt process; TPP, two powder process; GEORGE, GEometrically-ORganized-Growth-Evaluation (crystallization along the geometrically created concentrational / spatial gradient of REE); QMG, quench melt growth; OCMG, oxygen controlled melt growth; MPMG, melt powder melt growth; QDR, quenched directional recrystallization; RP-MAGIC, reactive polyiodide melt assisted growth through in situ conversion; (MO) CVD, (metal-organic) chemical vapor deposition; PVD, physical vapor deposition; ASP, aerosol spray pyrolysis.