Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane

Until now, diverse polarization structures and topological domains are obtained in ferroelectric thin films or heterostructures, and the polarization switching and subsequent domain nucleation are found to be more conducive to building energy-efficient and multifunctional polarization structures.*

In the article “Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane” Jie Wang, Zhen Liu, Qixiang Wang, Fang Nie, Yanan Chen, Gang Tian, Hong Fang, Bin He, Jinrui Guo, Limei Zheng, Changjian Li, Weiming Lü and Shishen Yan introduce a continuous and periodic strain in a flexible freestanding BaTiO3 membrane to achieve a zigzag morphology. *

The authors successfully fabricated freestanding BTO membranes with a zigzag morphology using the water-solvation process. *

These films exhibited remarkable curvature-dependent long-range coherence and periodic distributions of polarization. Through experiments and phase-field simulations, Jie Wang et al. observed the presence of H–H and T–T polarization boundaries as well as the formation of large-scale chiral vortex domains. *

Interestingly, these singular polar structures could be induced by ultralow uniaxial and biaxial strains (≈0.5%), which is significantly lower than the previously reported values. The accumulation of charge was found to reduce the formation energy, making the singular polar structures more stable. *

This complicated polarization structure resulting from the morphological variation of the ferroelectric domain provides useful insights into the polarization structure and ferroelectric domain under strain engineering. *

The wrinkled ferroelectric oxides with different strained regions and correlated polarization distributions as well as tunable ferroelectricity can pave the way toward novel flexible electronics. *

Understanding the 3D polarization configuration of a wrinkled BTO membrane is crucial for revealing the relationship between the polarization structure and strain distribution.

To evaluate the polarization configuration, piezoresponse force microscopy (PFM) was employed to obtain the piezoresponse under both vertical and lateral modes (referred to as V-PFM and L-PFM, respectively), and the results are shown in Figure 2a from the article by Jie Wang et al. cited in this blogpost. *

The polarization structures in the freestanding wrinkled BTO membrane were characterized by a commercial scanning probe microscope (SPM).

When the conductive AFM probe (NanoWorld Arrow-EFM) with AC bias was in contact with the sample, the sample underwent regular expansions and contractions due to the inverse piezoelectric effect, which caused the AFM probe to oscillate with the sample.

The oscillation amplitude and phase signals were recorded, which corresponded to the piezoresponse strength and polarization orientation, respectively.

Dual AC resonance tracking PFM (DART-PFM) was used to track the shift in the contact resonance frequency caused by the surface roughness, avoid signal crosstalk, obtain more stable piezoelectric signals with higher sensitivity, and ensure the accuracy of data. The vertical deflection and torsional motion of the probe cantilever were used to detect the deformation of the sample, and the IP and OOP polarization components of the sample were obtained.

To determine the domain structures, both the vertical and lateral PFM images were recorded at different sample rotation angles. The local piezoresponse hysteresis loops were measured by fixing the PFM probe on the selected position and then applying a triangular-square waveform, accompanied with a small AC-driven voltage from the probe.

Electrostatic force microscopy (EFM) and scanning Kelvin probe force microscopy (SKPFM) are widely applied to obtain the surface potential of materials through a dual-channel method.

In the Nap mode, the first-line scanning is used to obtain the surface morphology information of the sample, and then the probe is lifted to a certain height to detect the long-range force (electrostatic force) signal. The operating principle of EFM can be simply interpreted as the phase difference imaging of probe vibration caused by the electrostatic force between the probe and sample. In SKPFM, a DC bias is applied to the conductive tip to balance the surface potential of the sample. The DC bias is equal to the potential difference between the tip and sample, thereby obtaining the relative surface potential distribution of the material. Therefore, EFM qualitatively reflects the potential properties of samples, and SKPFM quantifies the potential of samples.*

Figure 2 from Jie Wang et al. (2024), Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane:Domain structures of zigzag-wrinkled BTO film. a) Topographic image of wrinkled BTO film, giving rise to zigzag pattern. V-PFM and L-PFM amplitude and phase images for two different sample rotation angles of 0° and 90°. b) Line profiles of the height, OOP phase, and IP phase (0° and 90°) data (average over 6 pixels) along the red dotted lines in (a). c) Typical OOP and IP phase images overlapped on 3D morphology. The red and blue dotted curves indicate the position of the peak and valley, respectively. NanoWorld Arrow-EFM conductive AFM probes were used.
Figure 2 from Jie Wang et al. (2024), Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane:
Domain structures of zigzag-wrinkled BTO film. a) Topographic image of wrinkled BTO film, giving rise to zigzag pattern. V-PFM and L-PFM amplitude and phase images for two different sample rotation angles of 0° and 90°. b) Line profiles of the height, OOP phase, and IP phase (0° and 90°) data (average over 6 pixels) along the red dotted lines in (a). c) Typical OOP and IP phase images overlapped on 3D morphology. The red and blue dotted curves indicate the position of the peak and valley, respectively.

*Jie Wang, Zhen Liu, Qixiang Wang, Fang Nie, Yanan Chen, Gang Tian, Hong Fang, Bin He, Jinrui Guo, Limei Zheng, Changjian Li, Weiming Lü and Shishen Yan
Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane
Advanced Science, Volume 11, Issue 25, July 3, 2024, 2401657
DOI: https://doi.org/10.1002/advs.202401657

Open Access  The article “Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane” by Jie Wang, Zhen Liu, Qixiang Wang, Fang Nie, Yanan Chen, Gang Tian, Hong Fang, Bin He, Jinrui Guo, Limei Zheng, Changjian Li, Weiming Lü and Shishen Yan is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

Nanoscale resolved mapping of the dipole emission of hBN color centers with a scattering-type scanning near-field optical microscope

Color centers in hexagonal boron nitride (hBN) are promising candidates as quantum light sources for future technologies. *

In the article “Nanoscale resolved mapping of the dipole emission of hBN color centers with a scattering-type scanning near-field optical microscope “, Iris Niehues, Daniel Wigger, Korbinian Kaltenecker, Annika Klein-Hitpass , Philippe Roell, Aleksandra K. Dąbrowska, Katarzyna Ludwiczak, Piotr Tatarczak, Janne O. Becker , Robert Schmidt, Martin Schnell, Johannes Binder, Andrzej Wysmołek and Rainer Hillenbrand utilize a scattering-type near-field optical microscope (s-SNOM) to study the photoluminescence (PL) emission characteristics of such quantum emitters in metalorganic vapor phase epitaxy grown hBN. *

On the one hand, Iris Niehues et al. demonstrate direct near-field optical excitation and emission through interaction with the nanofocus of the AFM tip resulting in a subdiffraction limited tip-enhanced PL hotspot. *

On the other hand, the authors show that indirect excitation and emission via scattering from the AFM tip significantly increases the recorded PL intensity. This demonstrates that the tip-assisted PL (TAPL) process efficiently guides the generated light to the detector. *

Iris Niehues et al. apply the TAPL method to map the in-plane dipole orientations of the hBN color centers on the nanoscale. This work promotes the widely available s-SNOM approach to applications in the quantum domain including characterization and optical control. *

The investigation utilizes a scattering-type near-field optical microscope employing a metallized Arrow AFM tip ( NanoWorld Arrow-NCPt AFM probe) illuminated by monochromatic laser light. *

The AFM tip acts as an optical antenna, transforming the incident p-polarizedlight into a highly focused near field at the AFM tip apex, the so-called nanofocus. *

The nanofocus interacts with the sample leading to modified scattering from the AFM tip and encoding local sample properties.

In conventional s-SNOM operation, the elastically scattered light is recorded as function of sample position (note that the sample is scanned), yielding near-field optical images with a spatial resolution down to 10 nm. *

To supress background scattering, the AFM is operated in tapping mode and the detector signal is demodulated at a higher harmonic of the AFM tip’s oscillation frequency. *

In the article, Iris Niehues et al. use the s-SNOM instrument to study PL from individual hBN color centers. *

To that end, the inelastically tip-scattered light is recorded with a grating spectrometer coupled to a CCD camera. Note that signal demodulation has not been possible with the use of a CCD camera so far. It may be achieved employing a photomultiplier tube or similar. Importantly, the authors’ s-SNOM setup includes a high-quality, silver-protected off-axis parabolic mirror with a numerical aperture (NA) of 0.72, which optimizes the focusing and collection efficiency of the optical system and is crucial for the performed PL measurements. *

Characterization of photoluminescence mapping

In the specific experiments performed by “, Iris Niehues et al., the authors employ the near-field optical microscope in tapping mode, with low oscillation amplitudes between 20 nm and 30 nm, to detect PL signals influenced by the presence of the metallic AFM tip. *

They use standard metallic Arrow AFM tips (NanoWorld Arrow-NCPt) Throughout this study, Iris Niehues et al., use a 532 nm (2.33 eV) laser for the optical excitation of the hBN color centers. *

Figure 1 from Iris Niehues et al. 2025 “Nanoscale resolved mapping of the dipole emission of hBN color centers with a scattering-type scanning near-field optical microscope” :Photoluminescence (PL) measurement of a single color center taken with an AFM tip. The images are shown with the same color bar for better comparison of the observed PL intensities. (a) PL intensity map without the tip showing a diffraction limited emission spot. (b) PL spectrum of the studied emitter recorded with an extended integration time inside the arc in (c). The zero-phonon line (ZPL) and optical phonon sidebands (PSBs) of 160 meV are marked as well as the broad background PL (black line). (c) PL map of the same emitter with the AFM tip showing two subdiffraction limit features marked as “dot” and “arc.” (d) Lineprofiles along the dashed lines in (a) in black and (c) in red (dark measurement, bright Gaussian fits). The fitted full widths at half maximum (FWHM) are 110 nm (dot), 209 nm (arc), and 1,418 nm (w/o tip). (e) Schematic of the interference between direct and indirect excitation/emission of the color center via the AFM tip (TAPL). Inset shows the nanofocus interaction at the location of the color center explaining the dot (TEPL). (f) Analytical reproduction of the TAPL arc in (c) applying the model in (e). NanoWorld Arrow-NCPt AFM probes with a platinum iridium coating were used.
Figure 1 from Iris Niehues et al. 2025 “Nanoscale resolved mapping of the dipole emission of hBN color centers with a scattering-type scanning near-field optical microscope” :
Photoluminescence (PL) measurement of a single color center taken with an AFM tip. The images are shown with the same color bar for better comparison of the observed PL intensities. (a) PL intensity map without the tip showing a diffraction limited emission spot. (b) PL spectrum of the studied emitter recorded with an extended integration time inside the arc in (c). The zero-phonon line (ZPL) and optical phonon sidebands (PSBs) of 160 meV are marked as well as the broad background PL (black line). (c) PL map of the same emitter with the AFM tip showing two subdiffraction limit features marked as “dot” and “arc.” (d) Lineprofiles along the dashed lines in (a) in black and (c) in red (dark measurement, bright Gaussian fits). The fitted full widths at half maximum (FWHM) are 110 nm (dot), 209 nm (arc), and 1,418 nm (w/o tip). (e) Schematic of the interference between direct and indirect excitation/emission of the color center via the AFM tip (TAPL). Inset shows the nanofocus interaction at the location of the color center explaining the dot (TEPL). (f) Analytical reproduction of the TAPL arc in (c) applying the model in (e).

*Iris Niehues, Daniel Wigger, Korbinian Kaltenecker, Annika Klein-Hitpass , Philippe Roell, Aleksandra K. Dąbrowska, Katarzyna Ludwiczak, Piotr Tatarczak, Janne O. Becker , Robert Schmidt, Martin Schnell, Johannes Binder, Andrzej Wysmołek and Rainer Hillenbrand
Nanoscale resolved mapping of the dipole emission of hBN color centers with a scattering-type scanning near-field optical microscope
Nanophotonics, vol. 14, no. 3, 2025, pp. 335-342
DOI: https://doi.org/10.1515/nanoph-2024-0554

Open Access  The article “Nanoscale resolved mapping of the dipole emission of hBN color centers with a scattering-type scanning near-field optical microscope” by Iris Niehues, Daniel Wigger, Korbinian Kaltenecker, Annika Klein-Hitpass , Philippe Roell, Aleksandra K. Dąbrowska, Katarzyna Ludwiczak, Piotr Tatarczak, Janne O. Becker , Robert Schmidt, Martin Schnell, Johannes Binder, Andrzej Wysmołek and Rainer Hillenbrand is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions

Kaolinite is one of the most abundant natural clay minerals within soils at the Earth’s surface and within rock units in the upper crust. *

The interface between aqueous solutions and the facets of kaolinite plays an important role in a wide range of technological applications including tribology, paper production, oil recovery, waste water treatment and medical devices. *

This is made possible by kaolinite’s layered structure, with its two basal surfaces -aluminol and siloxane-exhibiting different properties and reactivity. *

Both macroscopic and nanoscale studies point to a strong dependence of kaolinite’s surface properties on its local hydration structure. No experimental results, however, have systematically and comparatively investigated the hydration landscape of both basal facets to date. *

In the article “Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions”  Clodomiro Cafolla, Tai Bui, Tran Thi Bao Le, Andrea Zen, Weparn J. Tay, Alberto Striolo, Angelos Michaelides, Hugh Christopher Greenwell and Kislon Voïtchovsky combine high-resolution atomic force microscopy (AFM) imaging and force spectroscopy with classical molecular dynamics (MD) simulations to illustrate key differences in the hydration behaviour of the aluminol and siloxane facets of kaolinite particles immersed in water and NaCl solutions. *

This combined approach allows the authors to overcome the limitations of each technique via the advantages of the other. Specifically, AFM images highlight the differences in the first hydration layer of each facet and serve as a basis for force spectroscopy measurements of the full hydration profile at a given location. *

Water densities extracted from MD help interpret the AFM results, both in the absence and in the presence of added Na+ ions. *

Complementary AFM spectroscopy measurements show an excellent agreement between the conservative component and MD’s water density profiles, with discrete hydration layers on both facets and little sensitivity to added ions. *

The dissipative component of the measured AFM tip-sample interactions is more sensitive to the presence of ions, with MD suggesting a link with the local water dynamics and transient instabilities between stable hydration layers. *

These effects are facet-dependant and more pronounced on the aluminol facet where the first water layer is better defined. Increasing the salt concentration allows hydrated ions to form more stable layers, with hints of organised ionic domains. *

The results provide unique insights into both the equilibrium molecular structure and dynamics of the kaolinite facets, potentially informing applications involving interfacial processes. *

The AFM experiments were conducted at 25 ± 0.1 °C using a commercial atomic force microscope equipped with temperature control.
NanoWorld Arrow-UHF silicon AFM probes were used.
The AFM cantilevers were thoroughly washed with pure water (20 times with 100 μl) and then with the solution of interest (40 times with 100 μl).
Experiments were performed at near neutral pH 5.8. This ensured that only the metal ions of interest were present on the AFM cantilever. Thorough cleaning procedures were implemented to avoid any possible sources of contamination. *

During the measurements, the AFM cantilever and the sample were fully immersed in the aqueous ionic solution of interest. The thermal spectrum of the AFM cantilever was used to perform the flexural calibration of the AFM cantilevers. The AFM probes were found to have a flexural spring constant in the range 1.0–4.0 N/m and a resonance frequency of ∼400–900 kHz in water. These values agree with the nominal range and the literature. The AFM cantilever oscillation was photo-thermally driven to ensure greater stability, making sure that the frequency response remained unaffected by any spurious contributions due to the noise produced by mechanical coupling with other experimental components of the system. *

Fig. 2 from Clodomiro Cafolla et al. 2024 “Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions”:Representative experimental (AFM) and computational (MD) images of both kaolinite facets. For each image, the corresponding atomic arrangement of the facet is superimposed to scale. The green triangle highlights the brightest periodic features appearing in both AFM and MD, showing a good agreement. The MD images represent the density distribution of the first hydration layer over each facet. The insets show the Fast Fourier Transform (FFT) of each image and highlight the first (red), second (orange) and third (cyan) order intensity peaks. The MD results represent a 2D projection for the water oxygen density in the first hydration layer averaged over 3 ns. The scale bar represents 1 nm. The AFM colour scale bar represents a height variation of ∼0.3 nm; the MD colour scale is based on a density range at a fixed height (first hydration layer). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.) NanoWorld Arrow-UHF silicon AFM probes were used.
Fig. 2 from Clodomiro Cafolla et al. 2024 “Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions”:
Representative experimental (AFM) and computational (MD) images of both kaolinite facets. For each image, the corresponding atomic arrangement of the facet is superimposed to scale. The green triangle highlights the brightest periodic features appearing in both AFM and MD, showing a good agreement. The MD images represent the density distribution of the first hydration layer over each facet. The insets show the Fast Fourier Transform (FFT) of each image and highlight the first (red), second (orange) and third (cyan) order intensity peaks. The MD results represent a 2D projection for the water oxygen density in the first hydration layer averaged over 3 ns. The scale bar represents 1 nm. The AFM colour scale bar represents a height variation of ∼0.3 nm; the MD colour scale is based on a density range at a fixed height (first hydration layer). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

*Clodomiro Cafolla, Tai Bui, Tran Thi Bao Le, Andrea Zen, Weparn J. Tay, Alberto Striolo, Angelos Michaelides, Hugh Christopher Greenwell and Kislon Voïtchovsky
Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions
Materials Today Physics, Volume 46, August 2024, 101504
DOI: https://doi.org/10.1016/j.mtphys.2024.101504

Open Access The article “Local probing of the nanoscale hydration landscape of kaolinite basal facets in the presence of ions” by Clodomiro Cafolla, Tai Bui, Tran Thi Bao Le, Andrea Zen, Weparn J. Tay, Alberto Striolo, Angelos Michaelides, Hugh Christopher Greenwell and Kislon Voïtchovsky is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.