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The crystalline phase mixture and microstructure of SrO‐excess SrTiO3 powder sintered at 1350°C/4 h is analyzed using X‐ray diffractometry (XRD), and scanning and transmission electron microscopy (SEM and TEM). Second phases represented by Ruddlesden–Popper Sr3Ti2O7 (RP2) and Sr4Ti3O10 (RP3) coexist with SrTiO3 (ST), consistent with the SrO–TiO2 phase equilibrium diagram. Some ST grains contain inter‐grown RP2 lamellae that permits analysis of the ST‐RP2 interface. The ST‐RP2 boundary shared by (001)ST and (001)RP2, although containing a lattice mismatch, is accommodated by long‐range elastic strain. The crystallographic orientation relationships of ST and RP2 at the interface are determined by selected area diffraction patterns (SADP) and described by transformation matrices. The crystallographic shear structure across the ST–RP boundary exhibiting the characteristic α‐fringe pattern can be represented by a fault vector R = 1/2(111)ST.

We demonstrate ferroelectric switching in CeO2-doped Hf0.5Zr0.5O2 (HZCO) thin films and their applications for back-end-of-line (BEOL) compatible embedded memories. At low cerium oxide doping concentrations (2.0 -5.6 mol%), the ferroelectric orthorhombic phase is stabilized after annealing at temperatures below 400 ℃. HZCO ferroelectrics show reliable switching characteristics beyond 10 11 cycles in TiN/HZCO/TiN (MFM) capacitors, several orders magnitude higher than the identically processed Hf0.5Zr0.5O2 (HZO) capacitors, without sacrificing polarization and retention.Internal photoemission and photoconductivity experiments show that CeO2-doping introduces in-gap states in HZCO that are nearly aligned with TiN Fermi level, facilitating the electron injection through these states. The enhanced background conductivity, which may lead to more uniform thermal dissipation in the HZCO films, delays the irreversible degradation that leads to the device failures.