Photoluminescence Property of Cu(In,Ga)S2 Quantum Dots Depending on Their Composition and Nanostructure
Authors: Torimoto Tsukasa , Jiang Chang , Kameyama Tatsuya , Uematsu Taro , Kuwabata Susumu 
Published: September 2023

Multinary quantum dots (QDs) composed of less toxic elements, such as CuInS2 and AgInS2, have been intensively investigated for the application to highly efficient solar energy conversion systems and novel luminescent devices, because their electronic energy structure and optical properties can be controlled by the size and chemical composition of QDs. Recently we have successfully prepared alloy QDs composed of Ag–In–Ga–S and Ag–In–Ga–Se semiconductors, the Eg of which was tunable in the visible and near-IR wavelength regions, respectively [1, 2]. These QDs exhibited a narrow PL peak assignable to the band-edge emission and their peak wavelengths were widely tunable by changing their Eg. However, there have been few investigations to prepare Cu-based multinary QDs with a narrow PL peak. Thus, in this study, we prepare spherical QDs composed of less-toxic Cu–In–Ga–S (CIGS) alloy semiconductor and investigate their composition-dependent optical properties.

The synthesis of CIGS QDs was carried out by our previous heating-up method with a slight modification [1]. Powders of Cu(OAc)2, In(acac)3, Ga(acac)3, elemental sulfur were dispersed in a mixture solution of oleylamine and dodecanethiol, followed by the heat treatment at 300 oC. The resulting solution was subjected to centrifugation to remove large precipitates, and QDs were isolated from the supernatant by adding methanol as a non-solvent. Thus-obtained QDs were used as a core to prepare cores-shell-structured particles, in which the surface of CIGS core was coated by thin shell composed of ZnS or GaSx.

The chemical composition of obtained QDs was controlled by the fractions of individual metal salts used as precursors. The Cu/(In+Ga) and In/(In+Ga) of obtained QDs roughly agreed with those used in preparation. The obtained QDs were spherical and their average diameter decreased from 5.4 nm to 3.4 nm with an increase in the In fraction. The absorption spectra of CIGS QDs were varied depending on both the fractions of Cu and In. The onset wavelength of QDs was blue-shifted from 840 nm to 540 nm with a decrease in the Cu/(In+Ga) in preparation from 0.7 to 0.1 when the QDs were prepared with the fixed ratio of In/(In+Ga)= 0.7. On the other hand, the QDs exhibited a blue shift of absorption onset from ca. 750 nm to 480 nm with a decrease in In/(In+Ga) ratio from 1.0 to 0 under the fixed Cu fraction in preparation, Cu/(In+Ga)= 0.3. The obtained Eg monotonously decreased from 2.77 eV to 1.74 eV with an increase in In/(In+Ga) ratio from 0 to 1.0, and these values were larger than those of corresponding bulk semiconductors due to the quantum size effect. From the ionization energy of the QDs evaluated from the onset energy of the photoelectron yield spectra in air, we determined the electronic energy structure of CIGS QDs. With a decrease in the Eg of QDs, the conduction band minimum level shifted to a lower level from ca. –2.3 eV to –3.4 eV, while the valence band maximum level was almost constant to ca. 5.1–5.2 eV.

Surface coating of CIGS QDs with other semiconductor shells increased the photoluminescence (PL) intensity. The ZnS shell coating to form CIGS@ZnS core-shell QDs produced a PL peak at 649 nm (FWHM: 0.47 eV), being much broader than that of CIGS cores (FWHM: 0.23 eV) because of alloying at the interface between ZnS shell and CIGS core, though the PL quantum yield (QY) increased to 30% from 8%. In contrast, the GaSx coating on CIGS QD surface enlarged the intensity of PL peak without changing its peak width: CIGS@GaSx QDs exhibited a narrow PL peak (FWHM: 0.20 eV) at 671 nm, being comparable to the PL peak of CIGS QDs (the peak wavelength of 675 nm and the FWHM of 0.23 eV). The PL QY was also increased to 27% from 8% by the GaSx coating on CIGS QDs. The tunabilities of electronic energy structure and PL property of CIGS QDs are useful for constructing efficient light energy conversion systems and luminescent devices.

[1] T. Kameyama, et al., ACS Applied. Mater. Interfaces
2018, 10, 42844-42855.

[2] T. Kameyama, et al., ACS Appl. Nano Mater.
2020, 3, 3275-3287.