Nanoscale Wet Chemical Engineering of III-V Quantum Dots for Emerging Solar Applications
Authors: Bouttemy Muriel , Aureau Damien , Frégnaux Mathieu , Shoji Yasushi , Jehl Zacharie , Suchet Daniel , Guillemoles Jean François , Etcheberry Arnaud , Okada Yoshitaka 
Published: February 2020

III-V materials have yet proved to be promising candidates for photovoltaic applications. Solar cell technologies based on III-V semiconductors are competitive in term of fabrication cost but also have the potential to reach the highest photovoltaic efficiencies. To overcome the 30% conversion limitation established for a single junction, the Shockley Queisser limit [1], due to different losses that cannot be avoided (transmission, thermalization, emission…), different solar cell architectures have been proposed. One of them, multi-junctions, are using a stack of absorbing materials enabling to cover a wider part of the solar spectrum with high efficiency due to their optimized bang-gaps. Among other recent concepts, intermediate band solar cells have gained interest with predicted efficiency greater than 60% (under maximum concentration) and almost 48.2% under one sun [2], similar to the efficiency potential of a 3 material stack, but with a single material. By implementing quantum dots at the surface of a III-V single layer, an intermediate band can be generated [3, 4] and tuned by changing the quantum dots nature, size and shape. More complex structures with multi-stacked quantum dots have also been studied [5].
The present work focuses on the preparation of III-V quantum dots surfaces using wet chemistry. Not only dots evolution but also the development of a specific soaking to eliminate the wetting layer, detrimental for optoelectronic properties, will be shown. Numerous studies and formulation have been reported for chemical etching of III-V semiconductors [6]. Nevertheless, the remaining challenge concerns the implementation of this chemical engineering at nanometric scale [7], in consistency with the miniaturization trend and requirements of the materials, structures and devices. The study is carried out on InAs and InGaAs quantum dots grown by MBE on GaAs substrates. They present different surface densities. The structure of the samples is presented figure 1 where the wetting layer, essential for the quantum dots epitaxial growth, is illustrated. A multi-technique methodology combining XPS, AFM and nano-Auger is employed to precisely determine the surface chemical and morphologic modifications from micrometric to nanometric scale. Thanks to XPS, the evolutions of the fine chemistries of quantum dots and their surface are accessible, giving crucial information about the dissolution processes and enabling to re-adjust the experimental conditions. In Figure 1 b, the In3d photopeak evolution with the chemical treatment employed on a sample presenting only the wetting layer is shown. Indium atoms are only present in the wetting layer in this case. Thus it represents the tracking element indicative of the maintenance, thinning or elimination of this layer. The complementary use of AFM brings the evidence of the dots conservation or disappearance as illustrated Figure 1c. Nano-Auger provides additional information on local chemistry. Various formulations, in acidic or base media, are developed to enable a differential dissolution between the wetting layer and the quantum dots. Both oxidation-deoxidation cycling and direct dipping procedures were experimented and optimized taking account the differences in oxides solubility. The various scenarios likely to occur during deoxidation are presented Figure 1a, the elimination of QD being also possible by the dissolution of the wetting layer below. Finally, a comparison of capabilities for nano-etching and possible selectivity of the different solutions considered here will be presented.

References
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Figure 1