When light interacts with metallic nanostructures, it instantaneously generates plasmonic hot carriers, which serve as key intermediates for converting optical energy into high-value energy sources such as electricity and chemical energy. Among these, hot holes play a crucial role in enhancing photoelectrochemical reactions. However, they thermally dissipate within picoseconds (trillionths of a second), making practical applications challenging. Now, a Korean research team has successfully developed a method for sustaining hot holes longer and amplifying their flow, accelerating the commercialization of next-generation, high-efficiency, light-to-energy conversion technologies.
< (From left) Professor Jeong Young Park of KAIST Department of Chemistry, Professor Moonsang Lee of Inha University, Dr. Hyunhwa Lee of KAIST Department of Chemistry, and Dr. Yujin Park of the University of Texas-Austin >
KAIST (represented by President Kwang Hyung Lee) announced on the 12th of March that a research team led by Distinguished Professor Jeong Young Park from the Department of Chemistry, in collaboration with Professor Moonsang Lee from the Department of Materials Science and Engineering at Inha University, has successfully amplified the flow of hot holes and mapped local current distribution in real time, thereby elucidating the mechanism of photocurrent enhancement.
The team designed a nanodiode structure by placing a metallic nanomesh on a specialized semiconductor substrate (p-type gallium nitride) to facilitate hot hole extraction at the surface. As a result, in gallium nitride substrates aligned with the hot hole extraction direction, the flow of hot holes was amplified by approximately two times compared to substrates aligned in other directions.
< Figure 1. A) Fabrication process of Au nanomesh, B) Microscopic image of Au nanomesh, C) Optical absorption spectrum of Au nanomesh-p-type GaN substrate. >
To fabricate the Au nanomesh, a polystyrene nano-bead monolayer assembly was first placed on a gallium nitride (p-GaN) substrate, and then the polystyrene nano-beads were etched to form a nanomesh template (Figure 1A). Then, a 20 nm thick gold nano-film was deposited, and the etched polystyrene nano-beads were removed to realize the gold nano-mesh structure on the GaN substrate (Figure 1B). The fabricated Au nanomesh exhibited strong light absorption in the visible range due to the plasmonic resonance effect (Figure 1C).
Furthermore, using a photoconductive atomic force microscopy (pc-AFM)-based photocurrent mapping system, the researchers analyzed the flow of hot holes in real time at the nanometer scale (one hundred-thousandth the thickness of a human hair). They observed that hot hole activation was strongest at "hot spots," where light was locally concentrated on the gold nanomesh. However, by modifying the growth direction of the gallium nitride substrate, hot hole activation extended beyond the hot spots to other areas as well.
Through this research, the team discovered an efficient method for converting light into electrical and chemical energy. This breakthrough is expected to significantly advance next-generation solar cells, photocatalysts, and hydrogen production technologies.
< Figure 2. A) Schematic diagram of real-time hot-hole flux observation via atomic force microscopy. B) Real-time images (left column) of the Au nanomesh on non-polarized gallium nitride (GaN) (upper row) and polarized GaN (lower row) substrates, and mapping of hot-hole flux detected in real time (middle and right columns). An atomic force microscope was used to detect the hot-hole flux occurring in the Au nanomesh in real time (Figure 2A). When irradiated with light, the hot-hole flow was activated only in the hot-spot region of the Au nanomesh on the non-polarized GaN substrate, whereas the hot-hole flow was activated even in the non-hot-spot region on the polarized GaN substrate. >
Professor Jeong Young Park stated, "For the first time, we have successfully controlled the flow of hot holes using a nanodiode technique. This innovation holds great potential for various optoelectronic devices and photocatalytic applications. For example, it could lead to groundbreaking advancements in solar energy conversion technologies, such as solar cells and hydrogen production. Additionally, the real-time analysis technology we developed can be applied to the development of ultra-miniaturized optoelectronic devices, including optical sensors and nanoscale semiconductor components."
< Figure 3. Conceptual diagram of controlling hot-hole using Au nanomesh >
The study was led by Hyunhwa Lee (PhD., KAIST Department of Chemistry) and Yujin Park (Postdoc Researcher, University of Texas at Austin Department of Chemical Engineering) as co-first authors and Professors Moonsang Lee (Inha University, Department of Materials Science and Engineering) and Jeong Young Park (KAIST, Department of Chemistry) serving as corresponding authors. The research findings were published online in Science Advances on March 7.
(Paper Title: "Reconfiguring hot-hole flux via polarity modulation of p-GaN in plasmonic Schottky architectures", DOI: https://www.science.org/doi/10.1126/sciadv.adu0086)
This research was supported by the National Research Foundation of Korea (NRF).
