The two-photon laser ablation of TiO2 photocatalyst using intense ultrashort titanium sapphire laser was investigated experimentally and theoretically aiming at the enhancement of photocatalytic reaction. The black surfacing of the TiO2 photocatalyst crystal was successfully achieved by drilling a large number of conical microholes with two-photon laser ablation. The ablated surface has a roughness of submicrometer order, and no heat-affected zone was observed. The simple equation is developed to explain two-photon ablation process of the TiO2 photocatalyst and the dependence of the ablation characteristic on the pulse duration. A maximization procedure of the ablated surface area is achieved and the optimization of laser parameters is shown for dense integration of ablated conical holes to increase the surface area.
Laser ablation in liquids (LAL) offers
a facile technique to develop
a large variety of surfactant-free nanomaterials with high purity.
However, due to the difficulty in the control of the particle synthesis
process, the as-prepared nanomaterials always have a broad size distribution
with a large polydispersity (σ). Surfactant-free properties
can also cause problems with particle growth, which further increases
the difficulty in size control of the colloids. Therefore, searching
for strategies to simultaneously unify the sizes of colloids and inhibit
particle growth has become significantly important for LAL-synthesized
nanomaterials to be extensively used for biological, catalytic, and
optical applications, in which fields particle size plays an important
role. In this work, we present a facile way to simultaneously realize
these two goals by ex situ SU-8 photoresist functionalization. Ag
nanoparticles (NPs) synthesized by femtosecond laser ablation of silver
in acetone at laser powers of 300 and 600 mW were used as starting
materials. The synthesized Ag NPs have a broad size distribution between
1 and 200 nm with an average size of ca. 5.9 nm and σ of 127–207%.
After ex situ SU-8 functionalization and 6 months storage, most particles
larger than 10 nm become aggregates and precipitate, which makes the
size distribution narrow with an average diameter of 4–5 nm
and σ of 48–78%. The precipitation process is accompanied
by the decrease in colloid mass from the initial ∼0.2 to 0.10–0.11
mg after ex situ SU-8 functionalization and 6 months colloid storage.
Morphology analysis indicates that ex situ SU-8 functionalization
inhibits the particle growth into polygonal nanocrystals. Radical
polymerization of SU-8 on Ag NPs is considered to be the reason for
both spontaneous size separation and growth inhibition phenomena.
Benefiting from Ag NPs embedment and acetone dissolution, the glass-transition
temperature of SU-8 photoresist increased from 314 to 331 °C
according to thermogravimetric analysis. The universality of ex situ
SU-8 functionalization-induced growth inhibition and size separation
behaviors is further proved using the Au colloids generated by LAL
in acetone. This work is expected to provide a new route for better
size control of LAL-synthesized colloids via ex situ photoresist functionalization,
although a half of colloidal mass is wasted due to radical polymerization-induced
colloidal precipitation.
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