# Bubble Printing of Anisotropic Clay Nanotubes

Claire Hotton, Erwan Paineau, Eric H Hill

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Claire Hotton, Erwan Paineau, Eric H Hill. Bubble Printing of Anisotropic Clay Nanotubes. Advanced Optical Materials, 2025, 13 (25), 10.1002/adom.202500373. hal-05238499

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## Bubble Printing of Anisotropic Clay Nanotubes

Claire Hotton†*, Erwan Paineau†*, Eric H. Hill‡**

†Université Paris-Saclay, CNRS, Laboratoire de Physique des Solides, Orsay, 91405, France

E-mail: claire.hotton@universite-paris-saclay.fr; erwan-nicolas.paineau-lanone@cnrs.fr

‡Institute of Physical Chemistry, University of Hamburg, 20146 Hamburg, Germany; The
Hamburg Center for Ultrafast Imaging (CUI), 22761 Hamburg, Germany

E-mail: eric.hill@chemie.uni-hamburg.de

<figure><img src="image_2.png" /></figure>

## Abstract

The printing of colloidal particles with laser-driven microbubbles stands out as a powerful recent technique for rapid fabrication of assemblies with limited sample requirements and high spatial precision. However, controlling the structure of the resulting printed pattern remains a challenge with anisotropic particles, whose orientation can significantly impact the collective properties of the assembled structures. Herein, imogolite clay nanotubes with controlled dimensions and aspect ratios, that also display liquid-crystalline properties in suspension, were chosen as model 1D colloids. In the absence of laser movement, toroidal patterns were formed, with their size and shape strongly influenced by the electrostatic repulsion between nanotubes. Linear patterns printed under stage movement varied significantly depending on the movement speed and colloidal stability. Longer nanotubes in particular exhibited the formation of long filament bundles wrapping the microbubble in a radial orientation. However, insufficient electrostatic repulsion between nanotubes led to poor deposition. Interestingly, the liquid-crystalline dispersions were able to impart optical birefringence to the patterns themselves. This work provides a foundation for future studies on anisotropic nanomaterials, and reveals the potential of bubble printing to retain the light polarization properties of liquid crystalline colloids, which will advance future applications in sensing and devices.

**Keywords:** laser printing, directed assembly, material deposition, aspect ratio, imogolite nanotube
# 1. Introduction

The hierarchical assembly of colloidal particles on solid substrates is critical for functional material and device fabrication across various fields, such as electronics and photonics, where the precise nanoscale organization of building blocks imparts unique functional properties to the resulting material.[1,2] Achieving such hierarchical organization, particularly with anisotropic particles, remains a challenge in nanotechnology. To address this, various printing techniques have been developed, such as spin coating, casting, and inkjet printing.[3-7] While these methods offer scalability, they often suffer from limitations such as long processing times, high material consumption, and limited control over precise particle deposition in specific regions.

Recently, optically-directed and field-assisted assembly techniques have gained considerable attention for their ability to enhance control over particle positioning during the assembly process.[8-12] Among these, colloidal assembly controlled by a laser-induced microbubble, henceforth dubbed bubble printing, stands out as a promising technique for precise micropatterning of assemblies of colloidal particles on surfaces.[13-16] In this technique, a laser is focused on a plasmonic substrate or colloid, providing localized heating that generates a micrometric vapor bubble at the substrate-liquid interface.[17-19] Bubble formation and the resulting surface tension gradient drives Marangoni convection, drawing colloids toward the microbubble. Upon reaching the triple contact line at the bubble interface, a combination of forces, particularly capillary and van der Waals interactions, immobilize the particles on the substrate. Compared to other methods, bubble printing offers several distinct advantages: it allows for rapid fabrication, utilizes minimal material due to the convection-driven assembly, and provides the ability for freeform patterning with high precision, thanks to the ability to control the motion of the bubble with the laser.

Bubble printing methods have been employed for directed deposition on surfaces, enabling the formation of complex assemblies with materials including polymer microspheres[20], plasmonic gold nanoparticles[21], quantum dots[22], MXenes[23] and layered silicate clay platelets.[24] Additionally, bubble printing shows the capacity for directing synthesis at interfaces, facilitating deposition of conductor/isolator multilayers[25], catalytic metal oxides[26] and conductive polymers.[27] Together, this approach has enabled the production of functional devices
for sensing modalities such as Surface-Enhanced Raman Scattering (SERS)[21] and Fluorescence Resonance Energy Transfer (FRET),[24] among others. However, a fundamental understanding of nanoparticle assembly via bubble printing as a function of particle anisotropy remains elusive[10], despite the numerous applications where anisotropic nanoparticle orientation can significantly impact the properties and functional outcome of the resulting patterns.[28]

In this study, the bubble printing of 1D anisotropic particles is explored to gain insights into controlling the orientation of the assembled structures, as this remains a knowledge gap for this recent method. To address this, aluminogermanate double-walled imogolite clay nanotubes (Ge-DWINT; GeAl₂O₇H) offer an ideal 1D model system due to their highly controlled aspect ratios (length/diameter) with monodisperse nanometric diameters[29], colloidal stability due to the predominance of electrostatic repulsion[30] and their ability to spontaneously form liquid crystal phases, such as nematic[31,32] and hexagonal columnar phases[33], at volume fractions of less than 1%. This low concentration has the advantage of producing low-viscosity suspensions that would promote bubble displacement while leaving the system optically transparent over a wide spectral range. A key question we seek to address is how the organization of the initial Ge-DWINT suspension influences the arrangement and orientation of the printed pattern, which could have significant implications for achieving better control in the design of advanced printed assemblies. Patterned materials with controlled spatial variation of optical properties such as birefringence could find applications as phase gratings, photonics or sensing devices.

## 2. Results and discussion

Bubble printing was carried out by focusing a laser at the interface of a plasmonic gold nanoisland substrate and a colloidal dispersion of imogolite, as described in detail in the methods section (Figure S1). Bubble printing was performed using three different aspect ratios (AR = length/diameter) of Ge-DWINT (6, 84, 210 referred as -S, -M, -L hereafter) prepared in aqueous suspensions at a fixed ionic strength of 10⁻⁴ M in NaCl. The median length of these nanotubes is around 26, 368 and 919 nm respectively, while their diameter remained fixed around 4.3 nm, as reported previously (Figure S2).[34] Suspensions of Ge-DWINT were prepared at volume fractions ranging from 0.03% to 0.71%. Within this range, Ge-DWINT-M and Ge-DWINT-L suspensions transition from an isotropic state to a biphasic isotropic/nematic phase and eventually
to a hexagonal columnar phase at thermodynamic equilibrium (Figure S2).[30,34,35] In contrast, Ge-DWINT-S does not display any liquid-crystalline behavior, remaining in an isotropic phase. Beyond a critical volume fraction (0.5% - 0.7%), which depends on the aspect ratio[35], all suspensions transition into a glass-like state, characterized by stiffened nanotubes and nematic-like ordering. Printing was performed with suspensions across the entire range of volume fractions encompassing all phases Ge-DWINT nanotubes exhibit as a function of volume fraction.

First, printing without movement of the laser was studied. For all aspect ratios and volume fractions, the formation of a half-sphere or toroidal structure revealed the shape of the microbubble. From 1 to 30 seconds of irradiation, the inner diameter of the half-sphere remains relatively constant (1 µm for Ge-DWINT-L and around 2.5 µm for Ge-DWINT-M and -S), while the outer diameter increases (from 5 µm to 11 µm for Ge-DWINT-L and from 3.5 µm to more than 6 µm for Ge-DWINT-M and -S). The toroidal shape becomes increasingly pronounced, with a noticeable growth in the amount of material deposited, both in the width of the torus and in its height. The center of the half-sphere is essentially unmodified, indicating minimal or no patterning in this region due to the pinning of the bubble and optical pressure at the focal point of the laser spot, whereas the well-defined walls are composed of long filaments (Figure 1 and Figures S3-S5).
<figure><img src="image_3.png" /><figcaption>**Figure 1.** Scanning electron microscopy images of printed Ge-DWINT-S, Ge-DWINT-M, Ge-DWINT-L and Ge-DWINT-M at an ionic strength (IS) of $10^{-2}$ M (instead of $10^{-4}$ M for the previous) without laser movement with 1s, 3s, 5s, 10s and 30s of irradiation for each aspect ratios and at an initial volume fraction of $\phi = 0.3\%$.</figcaption></figure>

Ge-DWINT-L exhibits noticeably less defined edges compared to the other aspect ratios, which may be attributed to the length of the nanotubes, and consequently the filaments which they form. The presence of such filaments likely results from a network-like assembly formed at the bubble interface composed of overlapped bundles of nanotubes, which forms a web-like structure. During bubble printing, the local temperature at the point of laser irradiation under the laser power used herein (11.8 mW) can reach nearly 200°C,[36] which can lead to edge-edge aggregation of nanotube bundles and the formation of such filaments.[37] The assembly of nanotubes arising from the wrapping of filaments around the microbubble could be observed by SEM (Figure 2a-b). The corresponding polarized optical microscopy image (Figure 2c-d) shows birefringence with a characteristic Maltese cross, indicating that the nanotubes within the printed pattern have a radial orientation. Interestingly, only the dispersions displaying initial liquid-
crystalline phase were able to impart optical birefringence to the printed patterns themselves (Figure S6).

<figure><img src="image_4.png" /><figcaption>**Figure 2.** Scanning electron microscopy images of printed Ge-DWINT-M without laser movement with 20s of laser irradiation (a) without tilt and (b) with 70° tilt. Polarized optical microscopy images without (c) and with (d) a retardation filter of printed Ge-DWINT-M.</figcaption></figure>

The role of ionic strength on the printing of a Ge-DWINT-M suspension was also studied. Increasing the ionic strength from $10^{-4}$ M to $10^{-2}$ M causes the suspension to partially lose its colloidal stability due to the screening of electrostatic repulsion between the nanotubes [30,38]. Consequently, no hexagonal columnar phase is observed at 0.3% volume fraction under this ionic strength[30]. As shown in **Figure 1**, this results in the loss of cavity formation and thus of the assembly at the microbubble interface. In this case we only obtain a random accumulation of
nanotubes at the spot of the microbubble without the formation of oriented bundles. Then, interfacial assembly is directly linked to the colloidal stability of the suspension prior to printing.

The movement of the laser spot via a motorized XY stage allows spatial control, and printing of linear patterns. Printed patterns reveal the formation of 3D structures whose shapes depend strongly on the colloidal stability of the nanotube suspension as well as the movement speed of the laser beam. At high aspect ratio (Ge-DWINT-L), the formation of almost toroidal-shaped cavities for all initial volume fractions was observed (Figure 3 and Figure S7). This results in the periodic depinning of the microbubble from the surface during movement, which then leads to the deposition of matter adsorbed at the bubble interface at the triple contact line. SEM characterization showed that only the nanotubes printed onto the substrate remained adhered, and complete dome structures were not observed. This is likely due to the upper portion of the dome-like assemblies detaching under either cavitation forces or the drag force exerted by the moving bubble, which was directly observed to occur during printing in previous studies of bubble printing of gold nanoparticles.[21] The rinsing/drying of the substrates may also have damaged such structures. The center of the deposit contains minimal material, while the nanotubes are assembled into long filaments at the edges. The pattern shows different domains of birefringence under polarized optical microscopy (Figure 3b), indicating that the nanotubes should be oriented with a radial orientation (Figure 3e-f).
<figure><img src="image_5.png" /><figcaption>**Figure 3.** (a, c-e) Scanning electron microscopy images of printed Ge-DWINT-L (initial volume fraction φ = 0.3%) at different magnifications and (f) with a representation of the orientation of the image. Colors indicate different orientations, legend given in the bottom left. (b) Polarized optical microscopy image of printed Ge-DWINT-L.</figcaption></figure>

For intermediate aspect ratio (Ge-DWINT-M) and low aspect ratio (Ge-DWINT-S), the same kind of cavities is observed but with a smaller diameter (~ 3 µm compared to ~ 6 µm for Ge-DWINT-L) and with more clearly defined edges as depicted in **Figure 4a-d**. As expected, Ge-DWINT-M printed patterns also show different domains of birefringence in polarized optical
microscopy images (**Figure S8a**), suggesting the radial orientation of the nanotubes within the printed patterns. Interestingly, Ge-DWINT-S now exhibit slight birefringence during bubble movement, in contrast to the absence of birefringence observed in static conditions (**Figure S8b**). This is probably related to nanotube alignment induced by the shear flow. **Figure 4e-f** shows that the printed pattern is clearly different at high ionic strength. Discrete cavities are no longer observed and smearing of printed pattern is apparent, with an accumulation of nanotubes along the deposition line. This results in the loss of the assembly at the microbubble interface. The printed line exhibits consistent birefringence along its entire length, without variations in intensity across different domains, indicating a random alignment of nanotubes along the deposition line (**Figure S8c**).

<figure><img src="image_6.png" /></figure>
**Figure 4.** Scanning electron microscopy images of printed (**a**-**b**) Ge-DWINT-S (initial volume fraction φ = 0.27%), (**c**-**e**) Ge-DWINT-M (initial volume fraction φ = 0.3%), and (**e**-**f**) Ge-DWINT-M (initial volume fraction φ = 0.3% with an ionic strength IS = 10⁻² M instead of 10⁻⁴ M), at different magnifications.

The influence of the laser speed was established for nanotubes of intermediate aspect ratio (Ge-DWINT-M). At low speed (10 µm/s), the printed particles consist of barchan dune-like quasitoroidal patterns with clearly defined edges (**Figure 5a,b,e,f and Video S1**). When the speed is increased to 30 µm/s (**Figure 5a,b,c,g and Video S2**), the diameter of the quasitoroidal wells become smaller (~2 µm compared to ~3 µm at lower speed). Further increase of the speed to 95 µm/s leads to a reduction in the formation of sidewalls and a thinner pattern consisting of half-wells with alternate facing directions (**Figure 5a,b,d,h**). At these speeds, the microbubble was observed oscillating from one side to another in the direction perpendicular to beam movement (**Video S3**). The lack of sidewalls at higher movement speed as opposed to the well-defined ones at low speed suggests that assemblies of nanotubes at the bubble interface do not have sufficient time to form. Instead, the nanotubes adsorb rapidly at the interface, causing the bubble to shift toward either side of the accumulating material. The variety of patterns observed at different laser speeds confirms that assembly occurs at the bubble interface before deposition onto the substrate. SEM images taken at a 70° tilt clearly reveal the cavities along the edges where the bubbles were formed (**Figure 5f,g,h**).
<figure><img src="image_7.png" /><figcaption>**Figure 5.** Scanning electron microscopy (SEM) images of printed Ge-DWINT-M without tilt (a-d) and with 70° tilt (e-h) at different laser speed from 10 µm/s (b,f) to 30 µm/s (c,g) and 95 µm/s (d,h). Panels (b,c,d) and (f,g,h) provide zoomed-in views of individual printed lines of (a) and (e) respectively.</figcaption></figure>

**3. Conclusions**

In summary, this study demonstrates the potential of bubble printing as an effective technique for the precise assembly of anisotropic 1D colloidal particles onto solid substrates. The printing can be achieved whatever the initial state of the colloidal suspension, from liquid to viscous arrested phases. The results reveal that key factors such as the aspect ratio of the nanotubes, ionic strength of the colloidal suspension, and laser movement speed significantly influence the alignment, stability, and morphology of the 3D printed patterns. The drag force exerted by the moving bubble allow the formation of long oriented filament wrapping the microbubble in a radial orientation due to the presence of sufficient electrostatic repulsion while the screening of electrostatic repulsion leads to poor deposition. The findings underscore the importance of controlling suspension properties and laser parameters to achieve desired nanoparticle
orientations, providing valuable insights for the development of functional materials in photonics, sensing, and other advanced applications. Ultimately, bubble printing emerges as a promising technique for fabricating complex, high-precision nanoparticle assemblies, with the potential to enhance material design and performance.

# 4. Materials and Methods

## Bubble printing experiments and setup

Plasmonic gold nano-island (AuNI) substrates were produced by depositing a 4 nm gold film on a glass coverslip by thermal deposition (Denton Vacuum, Moorestown, NJ) at a pressure of 9 × 10⁻⁶ Torr, followed by thermal annealing at 550°C for 2 h. A 0.12 mm imaging spacer (SecureSeal, Grace Biolabs, Bend, OR) containing a 0.9 cm well was adhered to the gold covered glass slip. A design was scratched into the AuNI substrate with tweezers so that the future printed patterns could be easily located. Afterwards, 15 µL of Ge-DWINTs suspension was pipetted into the circular well. A glass cover slip was placed on top and briefly pressed along the imaging spacer to ensure adhesion. The optical setup used for printing and spectroscopy consisted of an inverted optical microscope (Nikon Ti2-A) coupled to a 532 nm CW laser (Torus 532, Laser Quantum, Stockport, UK) that was passed through a 5× beam expander (GBE05-A, Thorlabs, USA) to fill the back of the microscope objective (60×, NA = 0.85, CFI Plan Fluor, Nikon) (Figure S1). An optical beam chopper (MC2000B-EC, Thorlabs, USA) operating at 5000 Hz was used for all printing experiments. After printing, the glass cover slip was removed and the sample was rinsed with distilled water and dried with compressed air.

## Characterization of the printed patterns

Scanning electron microscopy (SEM) was performed with a Zeiss Supra55VP operating at an acceleration voltage of 4 keV without tilt and 10 keV with a 70° tilt. Samples were coated with a Au-Pd layer to avoid charging effects. The orientation analysis of the image was performed with the OrientationJ plugin in ImageJ.[39] Polarized optical microscopy (POM) was carried out on a BX51-P (Olympus, Japan) either without or with the use of a retardation filter (λ = 530 nm) placed at 45° with respect to the polarizers. The change of the interference colors from blue to red correspond to the orientation of the nanotube axis parallel to perpendicular to the slow axis of the retardation filter. Images were acquired with a sCMOS color camera (sCMEX-20, Euromex, Netherlands).
Synthesis of Ge-DWINT with different aspect ratio

The synthesis and characterization of Ge-DWINT with low, medium and large aspect ratio is detailed elsewhere.[34] Briefly, the synthesis consists in the co-condensation of Al and Ge precursors by the addition of a source of hydroxyl ions. In all cases, the initial Al concentration is fixed at 0.2 mol·L⁻¹. To obtain low aspect ratio Ge-DWINT (denoted as Ge-DWINT-S), the hydrolysis of the mixture of aluminum perchlorate nonahydrate (reagent grade, Alfa Aesar) and tetraethoxygermane (Sigma-Aldrich) is realized with NaOH (Sigma-Aldrich) in a polytetrafluoroethylene (PTFE) beaker. The final molar ratio of [Al]:[Ge]:[NaOH] equals to 2:1:4 [30]. The solution is then placed in an oven for 5 days at 95°C. The highest aspect ratio Ge-DWINT are obtained by replacing NaOH with urea (Sigma-Aldrich), leading to a ratio [Al]:[Ge]:urea equals to 2:1:2.[40] After mixing under stirring, the solutions are transferred into a PTFE-lined acid digestion vessel (Parr Instrument) for hydrothermal ageing under autogenous pressure at 140°C during 5 days (denoted as Ge-DWINT-M) and 20 days (denoted as Ge-DWINT-L), the time of aging allowing an increase of the average nanotube length.[41] After the hydrothermal treatment, all the recovered suspensions are purified by dialysis against ultrapure water using semipermeable membranes (Spectra/Por®, cutoff = 10 kDa) until the conductivity of the water bath decreases down to 0.5 mS·cm⁻¹. After this step, the membranes are placed into a 2L beaker containing a polyethylene glycol solution (20 g·L⁻¹, 20000 g·mol⁻¹, Sigma-Aldrich) to concentrate by osmotic stress the final suspensions. The ionic strength is controlled by the concentration of added NaCl (10⁻⁴ mol·L⁻¹ or 10⁻² mol·L⁻¹). After two weeks of osmotic stress, the suspensions are collected and their volume fractions φ (φ = C/ρ<sub>Ge-DWINT</sub> with C the solid concentration of Ge-DWINT and ρ<sub>Ge-DWINT</sub> the density of a nanotube taken as 3.6 g·cm⁻³) are determined by weight loss upon drying during 4h at 95°C. The characterization of the different batches by transmission electron microscopy (TEM), infrared spectroscopy and X-ray scattering has been reported in our previous work [34] (Figure S2).

**Supporting Information**

Videos of printing Ge-DWINT-M at different laser movement speeds; a schematic of the optical setup, TEM images and phase diagrams of Ge-DWINT-L,M,S; Additional SEM images; Additional polarized optical microscopy images. Supporting Information is available from the Wiley Online Library or from the author.
Acknowledgements

This work was supported by an Investissements d'Avenir grant from Labex PALM (ANR-10-LABX-0039-PALM) and financial support from the CNRS through the International Emerging Actions program (IEA00669, SECOWIN). This work is funded by the Cluster of Excellence ‘Advanced Imaging of Matter’ of the Deutsche Forschungsgemeinschaft (DFG) — EXC 2056 - project ID 390715994, and supported by the DFG project ID 447787198.

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Table of contents entry:

<figure><img src="image_8.png" /></figure>

Bubble printing patterns of lyotropic liquid crystal nanotubes form toroidal or linear patterns depending on laser movement and colloidal stability. Long nanotubes create radial filament bundles, while poor electrostatic repulsion hindered deposition. The printed structures exhibited birefringence, demonstrating bubble printing's potential to preserve liquid crystal optical properties for sensing and device applications.