Rhombohedral Phase Research Articles

New insights into the effect of glass addition on the piezoelectric and thermal stability properties of (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 Pb-free ceramic by defect engineering of MPB

Lead-free piezoceramics with superior piezoelectric properties don't meet the requirements of practical applications due to their lower phase transition temperature and poor thermal stability. In the present work, we report a new insight into the effect of glass phase on the piezoelectric, Curie temperature and thermal stability of (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 (BCZT) ceramic. Unlike traditional glass materials with more than 80% of B2O3 and SiO2 as glass formers, our approach is to fabricate a glass phase (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3-0.05B2O3 (abbreviate BBCZT) with the same elements and concentrations as the ceramic phase. The ceramics-doped glass samples with the composition [(1-x)BCZT-xBBCZT], where x=(0.0, 0.025, 0.05, 0.075 and 0.1 wt%), were sintered according to the glass phase content. The effect of BBCZT glass composition on the crystal structure, dielectric, ferroelectric and piezoelectric properties of BCZT was investigated in detail. X-ray diffraction revealed that the addition of glass phase causes a defect engineering of the tricritical triple point of BCZT ceramic, where the tetragonal (T) and rhombohedral (R) phases were suppressed by the addition of glass phase and the T-phase has completely vanished at x = 0.05. The maximum value of permittivity (ε = 4102) and converse piezoelectric coefficient (d*33 = 1150 Pm/V) were achieved for the 0.975BCZT-0.025BBCZT sample at ambient temperature. Furthermore, the diffusion coefficient (γ) and Curie temperature (Tc) were observed to increase beyond x = 0.025, indicating enhanced thermal stability of BCZT at high glass content. These results qualify that the addition of (BBCZT) can enhance piezoelectric properties, phase transition temperature and thermal stability of BCZT ceramic which can meet wide requirements of practical applications.

Phase transition behavior and electrical properties of (Bi0.97Sm0.03)ScO3-PbTiO3 textured ceramics MPB-modified by BaTiO3 templates for high temperature piezoelectric device applications

BaTiO3 (BT)-templated (1-x) (Bi0.97Sm0.03)ScO3-xPbTiO3 [(1-x)BSS-xPT] (0.60≤x≤0.64) ceramics were evaluated as to their phase transition behavior and electrical properties for high temperature piezoelectric devices. The morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases was obtained for template-free 0.36BSS-0.64PT ceramic. However, the addition of tetragonal BT to 0.36BSS-0.64PT resulted in a highly textured microstructure but degraded piezoelectric properties due to a shift of tetragonal-rich MPB. Compositional modification of 4 vol% BT-templated (1-x)BSS-xPT can restore good piezoelectric performance by enriching the BSS phase. Especially, the textured 0.38BSS-0.62PT ceramic with highly preferred (100) orientation exhibited excellent piezoelectric properties of d33 (719 pC/N), kp (61.8%), Qm (14), and g33 (45 × 10−3 Vm/N). In addition, the relaxor-like textured ceramic, having a high depolarization temperature of 373 °C, is highly promising for high temperature piezoelectric devices.

Al Doped into Si/P Sites of Na3Zr2Si2PO12 with Conducted Na3PO4 Impurities for Enhanced Ionic Conductivity.

Natrium superionic conductor (NASICON) is a promising solid-state electrolyte because of its high stability under air as well as its safety. Doping is an effective way to improve its ionic conductivity, but there is limited information about the explanation of the doping sites. In this work, Al-doped NASICONs are designed. When Al doping is 0.3 (NAl0.3ZSP), the ionic conductivity is the highest and is 5.08 × 10-5 S cm-1 at 30 °C, which is 3.3 times that of undoped NASICON. NAl0.3ZSP consists of a NASICON structure (monoclinic and rhombohedral phases), an amorphous glassy phase, and Na3PO4 impurities. After Al doping, more Si/P sites are occupied by Al; thus, the ratio of Na3PO4 impurities increases. Na3PO4 at the grain boundary is beneficial for grain boundary resistance decrease, contributing to the decrease of the total resistance. Our work first provides a detailed explanation of doped-Al sites and interprets their effects on ionic conductivity.

Role of V–V dimerization on electronic and magnetic properties of ilmenite-type CoVO3

Structural, electronic and magnetic properties of ilmenite-type CoVO3 have been explored via the generalized gradient approximation + effective Hubbard U eff correction, in the framework of density functional theory. Our results indicate that high temperature rhombohedral phase is metallic with oxidation states and electronic configurations Co2+ (), V4+ (), respectively, while low temperature triclinic phase, induced from spin-Peierls transition in the V–V dimerization manner, is insulating, maintaining charge and electronic states unchanged. Furthermore, the A-type antiferromagnetic ordering, where the ferromagnetic honeycomb layers are anti-aligned along the stacking axis, is identified to be the magnetic ground state for the low temperature phase, in nice agreement with experimental findings, analogous to CoTiO3. The unexpected intralayer ferromagnetic couplings can be attributed to the intraorbital t2g −t2g exchange coupling, which was assumed to be small earlier and ignored, but actually large in honeycomb cobaltates with 3d 7 electronic configuration. In addition, the computed magnetic moment on Co2+ ion ranges from 2.5 to 2.7 μ B, Hubbard U eff dependent, close to ideal S = 3/2 state, rather than the anticipated J eff = 1/2 state. Furthermore, the supplemental calculations, taking spin-orbit coupling (SOC) into account, uncover faint orbital moments of 0.21–0.27 μ B at the Co site, illustrating the insignificance of SOC. Except for the inevitable trigonal distortions, the excessive structural distortion triggered by the formation V–V dimerization, i.e. the breaking of trigonal symmetry around Co2+, further lifts the degeneracy of t 2g orbitals and increases crystal field splitting, driving it away from potential candidates for realizing Kitaev model physics.

Enhanced piezoelectric properties and strong red luminescence in Pr-doped Bi0.5Na0.5TiO3–BaTiO3 multifunctional ceramics

Multifunctional ceramics with the 0.93(Na0.5Bi0.5)1-xPr3+xTiO3-0.07BaTiO3 (abbreviated as BNBT-xPr, x = 0.00, 0.002, 0.004, 0.006, 0.008) were synthesized using the solid-phase reaction method. This study systematically investigated the phase structure, microstructure, dielectric, ferroelectric, piezoelectric, and photoluminescence properties. As the value of x increased, the ceramics underwent a transition from a co-existing rhombohedral (R) and tetragonal (T) phases to a T phase with a slight R distortion. In addition, the grain size decreased, and the relative density increased. The Pr3+ doping led to a decrease in the coercive field and an improved reversible phase transition, accompanied by a reduction in the depolarization temperature (Td) from 91 °C to 41 °C. The ceramic with x = 0.006 showed excellent piezoelectric properties, with a d33 = 201 pC/N and kp = 30.6%. Such properties were ascribed to the appropriate R/T phase ratio, increased relative density, decreased coercive field, and improved reversible phase transition. Moreover, under excitation at 451 nm, the ceramics exhibited bright red emission bands at 611 nm and 655 nm, corresponding to the transitions of 1D2→3H5 and 3P0→3F2, respectively. After polarization, the relative intensity of the emission peak at 655 nm significantly increased due to the changed lattice environment caused by the electric field. These Pr-doped BNBT ceramics demonstrated great potential in applications requiring electro-optic integration and coupling devices as multifunctional materials.

Co-regulation of phase-domain structure in Bi0.5Na0.5TiO3- based ferroelectrics to optimize energy storage properties

Sodium bismuth titanate (BNT)-based dielectric capacitors with excellent energy storage performance play an important role in electronics industry. (Sr1.05Bi0.3)ScO3 (SBS) is introduced into 0.85Bi0.5Na0.5TiO3-0.15NaNbO3 (BNT-NN) to achieve co-regulation of phase and domain structure. With the introduction of SBS, the dominated pseudocubic phase accompanied by a small percentage of rhombohedral phase are tend to form, and thus induce nanodomain structure with high-density domain walls. Under the excitation of a bias voltage, the induced nanodomains are easier to switch and effectively reduce the residual polarization. Additionally, the homogeneous nanodomains with high-density domain walls will promote large negative built-in voltage which are favorable to rise of breakdown field strength, and thus, optimize the energy storage performance. The co-regulation of phase-domain structure provides an idea for designing ferroelectrics with good energy storage performance.

Giant strain performance of lead-free relaxor piezoceramics through synergistic compositional and defect engineering

For applications involving high-precision displacement actuators, piezoceramics exhibiting extensive strain and minimal hysteresis are much sought-after. However, achieving extensive strain concurrent with low hysteresis remains a formidable challenge. We hereby propose an innovative design approach, synergistically harnessing compositional and defect engineering, to concurrently boost the strain response and mitigate hysteresis in (Na0.5Bi0.5)TiO3 (NBT)-based ceramics. The defect dipoles are elaborately designed and introduced into the mixed rhombohedral (R) and tetragonal (T) phases system, which causing reversible domain switching, heightening recoverability of electric-field-induced phase transition and augmenting the electrostrictive effect. The synergy of defect dipoles leading to reversible domain switching and electric field-induced phase transitions is further validated via phase-field simulations. Ultimately, a giant strain of 0.62% with low hysteresis of 10.9% and correspondingly high d33* of 1033 pm V−1 were concurrently realized in the designed NBST(1-x)Mnx (x = 0.3%) specimen. This study opens up a feasible and effective way to design piezoelectric materials with both a giant strain and a narrow hysteresis in lead-free actuator materials.

Second Harmonic Generation Studies of Interfacial Strain Engineering in BaZr0.2Ti0.8O3

AbstractFilm ferroelectrics demonstrate large breakdown strength, high energy density, and many unique phenomena not found in bulk materials. In this investigation, a rhombohedral BaZr0.2Ti0.8O3 (BZT) solid solution and various film‐substrate misfit strains are utilized to optimize the energy storage performance of ferroelectric thick films. Optical second harmonic generation is applied in both reflection and transmission geometries to reveal the renovation of entangled rhombohedral and tetragonal phases in the BZT films under compressive misfit strains. It is shown that the interfacial strain between the BZT film and substrate introduces the tetragonal domains. The competition between the tetragonal and rhombohedral phases creates the self‐assembled, anisotropically strained morphotropic structures to effectively accommodate the elastic and electrical stress fields through inside the thick BZT film. The BZT films demonstrate exceptional energy storage performance because of the adaptable nano‐domain structure within the bulk of the BZT films and may be engineered to optimize the superior performance of BZT films in energy storage.

Effect of bismuth deficiency with K substitution for Na on piezoelectric properties and crystal structure of Bi0.5−x(Na0.8−yK0.2+y)0.5TiO3–3x/2 (0 ≤ x ≤ 0.015, 0 ≤ y ≤ 0.1) ceramics

The piezoelectric properties and crystal structure of Bi0.5−x(Na0.8−yK0.2+y)0.5TiO3–3x/2 (0 ≤ x ≤ 0.015, 0 ≤ y ≤ 0.1) ceramics were characterized in this study. The crystal-structure refinement for Bi0.5−x(Na0.8K0.2)0.5TiO3–3x/2 was carried out using synchrotron X-ray diffraction data and Rietveld analysis and revealed the coexistence of rhombohedral (R3c) and tetragonal (P4mm) phases for the compositions with 0 ≤ x ≤ 0.015, although the fraction of these phases was almost independent of the composition x (49% for the rhombohedral phase and 51% for the tetragonal phase at x = 0.015). The Bi deficiency led to an increase in the lattice distortion of rhombohedral phase and a decrease in the that of tetragonal phase. The piezoelectric constant (d33) value decreased from 151.5 to 120.6 pC/N as x was increased from 0 to 0.015, and a shift of the depolarization temperature to higher temperatures was also confirmed by in situ d33 measurements. These results are attributed to an increase in the lattice distortion of rhombohedral phase enhanced by the Bi deficiency. The K substitution for Na in Bi0.485(Na0.8−yK0.2+y)0.5TiO2.9775 led to the formation of a morphotropic phase boundary (MPB) in the composition range 0 ≤ y ≤ 0.06, resulting in an increase in the fraction of the tetragonal phase. Although a decrease in the mechanical quality factor (Qm) was observed for K-rich compositions, the highest d33 value of 195.4 pC/N with a mechanical coupling factor of 32.9% was obtained for the Bi0.485(Na0.76K0.24)0.5TiO2.9775 (y = 0.04) ceramic because of the enhancement of the tetragonality in the MPB region, resulting in the onset of depolarization at ∼170 °C.

Positive and Negative Electrocaloric Effect in soft- and hard-doped commercial PZT ceramics

The electrocaloric properties of commercially modified Pb(Zr,Ti)O3- (PZT)-based soft and hard ceramics were investigated by the indirect estimation via measurement of temperature–electric field P (T,E) hysteresis loops. The adiabatic temperature change ΔT due to electrocaloric effects was estimated from the polarization change of these samples. Both positive and negative electrocaloric temperature change was obtained for all ceramics. The existence of the negative electrocaloric effect was related to the FE-FE field-induced phase transition, between rhombohedral and monoclinic phases that occur in PZT ceramics synthesized near the morphotropic phase boundary. The resulting negative electrocaloric temperature change reveals higher values for the hard-type ceramics (∼-1.5 K for PIC 300) than for the soft-type. Insignificant positive effect values were achieved for all ceramics. The highest values of positive ECE were recorded for PIC 155 (soft) and PIC 181 (hard) and are of the order of ΔT = 0.67 K. In this case, no correlation was observed between the type of PZT ceramics soft or hard.

Hard piezoelectric properties of lead‐free BiFeO3–BaTiO3 ceramics

AbstractHard piezoelectric properties are investigated in lead‐free BiFeO3–BaTiO3 (BF–BT) ceramics. Rhombohedral (R) phase ceramics of (1 – x)BF–xBT (x = 0.20–0.30) were prepared using a conventional solid‐state reaction and water‐quenching process. The R structure is observed in x = 0.20–0.275, and the R and tetragonal phases coexist at x = 0.30. The piezoelectric charge sensor coefficient (d33) and electromechanical planar coupling factor (kp) increase with increasing BT content, whereas the mechanical quality factor (Qm) decreases. The x = 0.20 ceramic shows the best hard piezoelectric properties: the highest Qm = 403 and the highest TC = 607°C. In contrast, x = 0.30 ceramic shows soft piezoelectric properties: d33 = 301 pC/N and kp = 0.33 with TC = 510°C. These results show that the BF–BT system in R‐phase‐rich region has good hard piezoelectric properties for transducer applications.

Impact of polymeric precursor and auto-combustion on the structural, microstructural, magnetic, and magnetocaloric properties of La0.8Sr0.2MnO3

In this work, La0.8Sr0.2MnO3 (LSMO) nanopowders are synthesized using two different methods: Pechini (LSMO-PC) and auto-combustion (LSMO-AC). Nanoparticle sizes, structural, magnetic, and magnetocaloric properties were determined and compared. The X-ray diffraction confirms the coexistence of two phases; rhombohedral symmetry with space group R-3c and orthorhombic symmetry with space group Pbnm. The rhombohedral phase is dominant. The scanning electron microscope images show that LSMO-PC has larger nanoparticle sizes (∼495 nm) than LSMO-AC (∼195 nm). The samples exhibit ferromagnetic properties with distinct hysteresis loops and Curie temperatures of 340 K and 290 K for LSMO-PC and LSMO-AC, respectively. The variation of the magnetic entropy was measured indirectly using the Maxwell approach with increasing magnetic field. For LSMO-PC it reaches a maximum -ΔSM = 1.69 J/kg.K at 340 K and ΔH = 5 T. The associated adiabatic temperature change ΔTM is 1.04 K. While LSMO-PC demonstrates superior magnetic and magnetocaloric properties, LSMO-AC displays significant magnetocaloric thermal stability. The obtained values make LSMO-PC and LSMO-AC promising candidates for eco-friendly room-temperature magnetocaloric applications.

Microstructure, dielectric, and piezoelectric properties of BiFeO3–SrTiO3 lead‐free ceramics

AbstractBiFeO3–SrTiO3 (BF–ST) ceramics have been considered a novel class of lead‐free dielectric materials exhibiting notable dielectric constants and remarkable thermal stability. In this work, we fabricated a series of (1 − x)BF–xST (0.32 ≤ x ≤ 0.44) ceramics near the morphotropic phase boundary and comprehensively investigated their microstructure and electrical properties, which seeks to optimize the piezoelectric performance. As the ST content increases, a gradual reduction in the rhombohedral phase fraction is observed alongside a corresponding increase in the cubic phase fraction. Although x = 0.38, the maximum grain size of 5.66 μm is obtained, accompanied by a distinctive heterogeneous core–shell microstructure, which demonstrates a high remanent polarization of 51.2 μC/cm2 and a maximum d33 value of 72 pC/N. Furthermore, impedance spectroscopy analysis reveals the formation of a conductive core and a nonconductive shell within the sample. These findings highlight the potential of optimized BF–ST ceramics as promising alternatives to lead‐based piezoelectric materials, offering exceptional ferroelectric and piezoelectric properties.

Phase formation and structure in the solid solutions of the (1 – <i>х</i>)BiFeO<sub>3</sub>–<i>x</i>/2PbFe<sub>1/2</sub>NB<sub>1/2</sub>O<sub>3</sub>–<i>x</i>/2PbFe<sub>2/3</sub>W<sub>1/3</sub>O<sub>3</sub> system

The solid solutions of the (1 – х)BiFeO3–x/2PbFe1/2Nb1/2O3–x/2PbFe2/3W1/3O3 system in the concentration range 0.05 ≤ х ≤ 0.50 were produced by solid state method and sintering using conventional ceramic technology. In the range 0.25 x 0.35, a morphotropic phase transition from the rhombohedral phase to the cubic phase was found. The difference in symmetry when “scaling” the material is shown. The influence of PbFe1/2Nb1/2O3 and PbFe2/3W1/3O3 on the grain structure formation was established.

Synergy of morphotropic phase boundary and internal bias fields to achieve high d33 and d33* simultaneously in lead-free BNT-based ceramics

It is difficult to obtain high d33 and d33* simultaneously in one piezoelectric ceramic system via a conventional method due to the conflicting structure–properties responding mechanism between the direct piezoelectric and converse piezoelectric effects. In this work, a synergistic approach of constructing morphotropic phase boundary and introducing the internal bias fields in (Bi0.5Na0.5)TiO3 ceramics is proposed through Sr2+ and Li+ doping for mitigating the conflict between d33 and d33*. By this strategy, both high d33 (197 pC/N) and d33* (1500 p.m./V) are realized in Srx(Bi1-xNa0.97-xLi0.03)0.5TiO3 when x = 0.24. The large d33 stems from rhombohedral and tetragonal (R3c and P4bm) phase coexistence. The internal bias field introduced by defect dipoles tends to counteract the effects of depolarization field, thus greatly aiding the external fields with higher actual excitation fields. The superposition of internal bias field, depolarization field and external fields yields strong asymmetry bipolar strain curves, thereby contributing to the large d33*. Thus, this work opens a new door for developing lead-free ceramics with excellent piezoelectric performance.

Response of DC biased magnetoelectric coupling in 0–3 type particulate lanthanum modified PZT-CFO composites

Magnetoelectric effect (ME) has been investigated in particulate ferroelectric (FE)-ferrimagnetic (FM) composites in the present work. The composition of ceramic composites has been tailored in terms of (1 - x) Pb0.4La0.6Zr0.6Ti0.4O3 (PLZT) – (x)CoFe2O4 (CFO) [x = 0, 0.2, 0.4, 0.6 and 1] in order to observe the magnetoelectric coupling. The FE-FM (PLZT-CFO) composites prepared using solid state route were investigated in terms of structural, morphological, dielectric, ferroelectric and magnetic properties. Well crystallized PLZT-CFO composites were observed with binary rhombohedral (R3m) and cubic (Fd3m) phase of PLZT and CFO, respectively, along with well-defined grains for both parent phases. The appearance of relaxor behaviour in prepared composites was revealed from temperature dependent dielectric study. The saturation (Ps) and remnant (Pr) polarizations were observed to be vary from 45µC/cm2 to 10µC/cm2 and 36µC/cm2 to 7 µC/cm2, with the increment in the CFO content from 0 % to 80 %, respectively. The emergence of long-range ferromagnetic ordering is revealed from M-H curves. It is evident from magnetization and polarization studies that each composite exhibits exceptional sensitivity to both the electric and magnetic fields. The magnetoelectric coefficient, is found to be initially rise with x and achieved maximal value of 450 µV/cm.Oe for 40 % CFO content. The obtained results indicate that almost equal number of weight proportion is required for achieving maximum strain transfer between FE-FM phases which is beneficial for future FE-FERAM devices. It is also perceptible that these novel composites may provide knowledge pathway for development of ME multifunctional device miniaturization.

Gd-doped BiFeO3 crystalline nanofibers for efficient rhodamine B in wastewater removal under simulated sunlight

This work synthesized a series of Gd-doped BiFeO3 (BGFO) hollow nanofibers by electrostatic spinning technique. The wall thickness of the hollow nanofibers was about 100 nm with an average grain size of 20 nm. The crystal structure distortion was found, and the BiFeO3 coexisted with rhombohedral and orthorhombic phases. The degradation efficiency of Gd-doped samples for RhB under simulated sunlight irradiation was higher than that of pure BiFeO3 nanofibers. Among them, the degradation rate of 10BGFO nanofibers on RhB was the fastest and reached 96.3% within 30 min. After five cycles, the removal efficiency could still be maintained at about 90%. The effects of temperatures, ions, concentrations, and water quality on the removal efficiency were studied in detail, and the possible photocatalytic degradation mechanism of BGFO nanofibers was also elaborated. With the increase of Gd doping, the band gap value gradually decreased, and the specific surface area was bigger, which effectively promoted the charge separation and could inhibit the complexation of photogenerated electrons and holes and produced more active substances (·O2-, h+). This study can provide a novel, reusable, flexible photocatalyst to purify dye wastewater.

A stable rhombohedral phase in ferroelectric Hf(Zr)1+xO2 capacitor with ultralow coercive field.

Hafnium oxide-based ferroelectric materials are promising candidates for next-generation nanoscale devices because of their ability to integrate into silicon electronics. However, the intrinsic high coercive field of the fluorite-structure oxide ferroelectric devices leads to incompatible operating voltage and limited endurance performance. We discovered a complementary metal-oxide semiconductor (CMOS)-compatible rhombohedral ferroelectric Hf(Zr)1+xO2 material rich in hafnium-zirconium [Hf(Zr)]. X-ray diffraction combined with scanning transmission electron microscopy reveals that the excess Hf(Zr) atoms intercalate within the hollow sites. We found that the intercalated atoms expand the lattice and increase the in-plane and out-of-plane stresses, which stabilize both the rhombohedral phase (r-phase) and its ferroelectric properties. Our ferroelectric devices, which are based on the r-phase Hf(Zr)1+xO2, exhibit an ultralow coercive field (~0.65 megavolts per centimeter). Moreover, we achieved a high endurance of more than 1012 cycles at saturation polarization. This material discovery may help to realize low-cost and long-life memory chips.

Electric field-temperature phase diagram and electrical properties of (1-x)Na0.5Bi0.5TiO3 - xK0.5Bi0.5TiO3 ceramics

Electrically and thermally induced transitions between ferroelectric and relaxor states are of great significance in Na1/2Bi1/2TiO3 (NBT)-based materials due to their remarkable similarity to electromechanical properties. However, an in-depth understanding of the family of this material remains challenging, primarily due to its structural complexity and diverse behaviour with or without the presence of an external electric field. For enhancing NBT-based ceramics and enabling the analysis of their electric field temperature (E-T) phase diagrams, it has been suggested that K0.5Bi0.5TiO3 (KBT) could be used as a dopant material. This study thoroughly examines the electrical, microstructural, and ferroelectric (FE) properties of (1-x)NBT-xKBT ceramics. The incorporation of KBT into NBT, inducing a change in structural symmetry, reveals the coexistence of rhombohedral and tetragonal phases (x ∼ 0.2), as confirmed by X-ray diffraction. Using a modified KWW function, electrical modulus (EM) analysis illustrates a non-Debye-type relaxation process. Moreover, it is observed that temperature influences the transition of the material among its ferroelectric (FE), ergodic (ER), and non-ergodic (NR) relaxor phases. This report proposes that the E-T phase diagram can serve as a valuable tool for determining optimal conditions and selecting materials for electromechanical and actuator-based applications.

Residual stress associated with crystalline phase transformation of 3–6 mol% yttria-stabilized zirconia ceramics induced by mechanical surface treatments

Monolithic dental prostheses made of 3–6 mol% yttria-stabilized zirconia (3–6YSZ) have gained popularity owing to their improved material properties and semi-automated fabrication processes. In this study, we aimed to evaluate the influence of mechanical surface treatments, such as polishing, grinding, and sandblasting, on the residual stress of 3–6YSZ used for monolithic prostheses in association with crystalline phase transformation. Plate specimens were prepared from five dental zirconia blocks: Aadva Zirconia ST (3YSZ), Aadva Zirconia NT (6YSZ), Katana HT (4YSZ), Katana STML (5YSZ), and Katana UTML (6YSZ). The specimens were either polished using 1, 3, or 9 μm diamond suspensions, ground using 15, 35, or 55 μm diamond discs, or sandblasted at 0.2, 0.3, or 0.4 MPa. The residual stress, crystalline phase, and hardness were analyzed using the cosα method, X-ray diffraction (XRD), and Vickers hardness test, respectively. Additionally, we analyzed the residual stress on the surfaces of monolithic zirconia crowns (MZCs) made of 4YSZ, 5YSZ, and 6YSZ, which were processed using clinically relevant procedures, including manual grinding, followed by polishing using a dental electric motor on the external surface, and sandblasting on the internal surface. Residual stress analysis demonstrated that grinding and sandblasting, particularly the latter, resulted in the generation of compressive residual stress on the surfaces of the plate specimens. XRD revealed that the ground and sandblasted specimens contained a larger amount of the rhombohedral phase than that of the polished specimens, which may be a cause of the residual stress. Sandblasting significantly increased the Vickers hardness compared to polishing, which may possibly be due to the generation of compressive residual stress. In the case of MZCs, compressive residual stress was detected not only on the sandblasted surface, but also on the polished surface. The difference in the residual stress between the plate and crown specimens may be related to the force applied during the automated and manual grinding and polishing procedures. Further studies are required to elucidate the effects of the compressive residual stress on the clinical performance of MZCs.