Shaping in the Third Direction: Colloidal Photonic Crystals with Quadratic Surfaces Self-Assembled by Hanging-Drop Method
Abstract
:1. Introduction
- (a)
- Show constant colors at different viewing angles (angular independence).
- (b)
- Both Bragg and grating diffraction contribute to the reflection.
- (c)
- Transmission spectra are not the inverse of the reflection.
- (d)
- Different crystal planes may contribute to the reflection.
2. Materials and Methods
2.1. Materials
- (a)
- Smooth and clean glass fibers: These common glass fibers were 5 cm long and ranged from 0.2 mm to 3 mm in diameter.
- (b)
- Microscope glass slides.
- (c)
- Copper and steel wires: These wires were also 5 cm long and had diameters ranging from 0.2 mm to 3 mm.
- (d)
- Steel spheres: These spheres were 5 mm in diameter.
- (e)
- PET (polyethyleneterephtalate) concavities: We obtained these concavities (with a diameter of 4 mm and a depth of 1.5 mm) from the edge of the packaging of a KD-JECT® III 1 mL syringe, KD Medical GMBH Hospital, Charlottenstrasse 65, 10117 Berlin, Germany.
2.2. Methods
2.2.1. Opal-Like Colloidal Photonic Crystal Self-Assembly
- (a)
- Opal-like colloidal photonic crystal on a fiber: We began by placing a glass or metallic fiber substrate either horizontally or at a 30–60° tilt angle using a small metallic burette clamp. Next, a droplet of 0.264 µm of SiO2 colloidal solution was carefully formed at the tip of a syringe. The droplet was gently transferred to the fiber: For horizontal substrates, it was touched somewhere along the fiber’s length. For tilted substrates, it was touched at the end of the fiber. If a larger drop volume was needed, additional droplets were added to the existing one hanging on the fiber. The droplet was allowed to dry under normal laboratory conditions, typically taking 30–60 min.
- (b)
- Opal-like colloidal photonic crystal on a metallic coil spring: A copper wire (0.3 mm in diameter) was wound around a fiber (2 mm in diameter) to create a coil spring with approximately 10 loops and a 1 mm distance between loops. The detached coil spring was then placed horizontally. A hanging 0.264 µm SiO2 colloidal drop was attached to the metallic coil spring, starting from its inside and gradually increasing the drop volume by adding more droplets. Finally, the drop was allowed to dry.
- (c)
- Opal-like colloidal photonic crystal on tangent metallic spheres: Two touching metallic spheres (each 5 mm in diameter) were fixed in a polystyrene thick film on a microscope glass slide (achieved by melting polystyrene flakes onto the glass slide). The glass slide was inverted and placed horizontally. A hanging 0.264 µm SiO2 colloidal drop was formed and attached to the spheres, hanging between them, and left to dry.
- (d)
- Opal-like colloidal photonic crystal self-assembled on a polymeric concavity: The PET sheet of the KD-JECT® III syringe packaging was placed in a horizontal position, its concavity pointing downwards. A hanging 0.264 µm SiO2 colloidal drop was formed and attached to the concavity and left to dry.
2.2.2. Polystyrene Inverse-Opal Superstructure Fabrication
- (a)
- Ellipsoid inverse-opal superstructure fabrication: A polystyrene (20.00 µm spheres) opal-like colloidal crystal has self-assembled on a horizontal fiber as in 2.2.1 (a). After drying, by keeping it in the same hanging position, a 0.264 µm SiO2 colloidal solution drop was gently transferred to its top. The SiO2 colloidal solution infiltrates and crystallizes between the polystyrene spheres. After polystyrene melting and infiltration (270 °C, 15 min), polystyrene solidification, SiO2 dissolution (25% HF), and water washing, a high-quality polystyrene inverse opal resulted.
- (b)
- Torus onto ellipsoid inverse-opal superstructure fabrication: A polystyrene (20.00 µm spheres) opal-like colloidal photonic crystal has self-assembled on a fiber as in 2.2.1 (a). After drying, by keeping it in the same hanging position, a 0.264 µm SiO2 colloidal solution drop was gently transferred to its top. The SiO2 colloidal solution infiltrates and crystallizes between the polystyrene spheres. After drying, a second 0.264 µm SiO2 or 0.384 µm SiO2 colloidal solution drop was gently transferred to its top. The second drop cannot infiltrate (all former holes between PS spheres are already filled with silica spheres) and forms a toroidal-shaped deposit on the ellipsoid surface. Melting infiltration and casting, followed by HF dissolution, give rise to an inverse-opal polystyrene colloidal photonic crystal of a special architecture.
2.3. Reproducibility
2.4. Investigations
3. Results and Discussion
3.1. Synthesis and Investigation of Quadratic Surface Colloidal Crystals
- (a)
- The tangential component of the weight of colloidal spheres (denoted as GT) confines the spheres within a compact colloidal crystal (Figure 1a).
- (b)
- The normal component of gravity (GN) generates a zero static frictional force (FF) between the spheres and the liquid/air interface. This allows the entire system to continuously reconfigure itself at the microscopic level (until it “freezes”), effectively creating a defect-free substrate (see Figure 1a).
- (a)
- Colloidal drop on a horizontal metallic coil spring (Figure 4f): This setup produces connected hyperboloids (Figure 4g) which exhibit an unexpected reflection of ambient light. The green rectangular spots represent light reflected from an ordinary white light source mounted on the ceiling, positioned three meters above the sample surface.
- (b)
- (c)
- Colloidal drop hanging inside a macroscopic concavity (Figure 4j): Consider the scenario depicted in Figure 4j (left): a colloidal drop deposited and hanging within a macroscopic concavity (a kind of freeform surface). Surprisingly, as we increased the drop volume beyond the concavity’s capacity, the liquid did not spill over the edge as expected. Instead, it descended, forming a massive drop (Figure 4j (right)). The interplay of adhesion, cohesion, and gravity balanced in an unexpected manner, yet meeting the necessary conditions for high-quality colloidal crystal formation: a large colloid volume acting as a reservoir, and the drop’s bottom surface free from contact.
3.2. Optical Phenomena in Quadratic Surface Colloidal Crystals
- (a)
- The reflectance band corresponding to (111) planes increases up to a certain point (at 2.5 mm), followed by a decrease as the distance increases.
- (b)
- At a specific distance between the sample and the probe, the reflection band associated with (200) planes appears for the curved colloidal crystals but not for the flat ones. Its intensity increases with the increasing distance from the probe for all crystal shapes.
- (c)
- The (111) peak position exhibits a small blue shift at greater distances from the probe, with the shift size increasing as the crystal curvature becomes more pronounced
3.3. Synthesis and Investigation of Shaped Super-Structured Inverted Opals
- (a)
- Inside infiltration (Figure 8f–g): In this case, the polystyrene reservoir is uniformly distributed within the silica crystalline structure volume.
- (b)
- Outside infiltration (Figure 9h,i): Here, the melted polystyrene must diffuse over a much longer distance (approximately 100 μm) through the silica crystalline structure. Notably, the tori in this scenario do not contain polystyrene spheres as reservoirs; instead, the polystyrene is provided from the ellipsoid.
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Conflicts of Interest
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Sandu, I.; Antohe, I.; Fleaca, C.T.; Dumitrache, F.; Urzica, I.; Dumitru, M. Shaping in the Third Direction: Colloidal Photonic Crystals with Quadratic Surfaces Self-Assembled by Hanging-Drop Method. Polymers 2024, 16, 1931. https://doi.org/10.3390/polym16131931
Sandu I, Antohe I, Fleaca CT, Dumitrache F, Urzica I, Dumitru M. Shaping in the Third Direction: Colloidal Photonic Crystals with Quadratic Surfaces Self-Assembled by Hanging-Drop Method. Polymers. 2024; 16(13):1931. https://doi.org/10.3390/polym16131931
Chicago/Turabian StyleSandu, Ion, Iulia Antohe, Claudiu Teodor Fleaca, Florian Dumitrache, Iuliana Urzica, and Marius Dumitru. 2024. "Shaping in the Third Direction: Colloidal Photonic Crystals with Quadratic Surfaces Self-Assembled by Hanging-Drop Method" Polymers 16, no. 13: 1931. https://doi.org/10.3390/polym16131931