Tailoring the interfacial structure of colloidal "giant" quantum dots for optoelectronic applications

Colloidal semiconductor quantum dots (QDs) are promising building blocks for the realization of future optoelectronic technologies, thanks to their size-tunable electronic and optical properties. Among various types of QDs, colloidal "giant" QDs (g-QDs, core/thick-shell) have been widely used in different applications, such as solar cells, light emitting devices, luminescent solar concentrators and photoelectrochemical (PEC) hydrogen production. However, g-QDs have a thick-shell which serves as a physical barrier for electron and hole transfer, leading to a slow charge transfer rate. In this work, we synthesized CdSe/CdSexS1-x/CdS core/shell/shell g-QDs with an intermediate CdSexS1-x alloyed layer. The presence of this interfacial layer largely improves the absorption of CdSe/CdS QDs, particularly in the 300-650 nm range. By engineering the interfacial layer, the holes can leak more into the CdS shell region compared to that of CdSe/CdS QDs. PEC devices based on alloyed g-QDs exhibit a 20% higher saturated photocurrent density (11 ± 0.5 mA cm-2) compared to CdSe/CdS QDs. In addition, after one-hour illumination (100 mW cm-2), the PEC cell based on alloyed g-QDs still exhibits a photocurrent density of 7.5 mA cm-2, maintaining 70% of its initial value. Such alloyed g-QDs are very promising for several emerging optoelectronic applications, where charge separation, transfer and transport play a critical role for the realization of high performance devices.Colloidal semiconductor quantum dots (QDs) are promising building blocks for the realization of future optoelectronic technologies, thanks to their size-tunable electronic and optical properties. Among various types of QDs, colloidal "giant" QDs (g-QDs, core/thick-shell) have been widely used in different applications, such as solar cells, light emitting devices, luminescent solar concentrators and photoelectrochemical (PEC) hydrogen production. However, g-QDs have a thick-shell which serves as a physical barrier for electron and hole transfer, leading to a slow charge transfer rate. In this work, we synthesized CdSe/CdSexS1-x/CdS core/shell/shell g-QDs with an intermediate CdSexS1-x alloyed layer. The presence of this interfacial layer largely improves the absorption of CdSe/CdS QDs, particularly in the 300-650 nm range. By engineering the interfacial layer, the holes can leak more into the CdS shell region compared to that of CdSe/CdS QDs. PEC devices based on alloyed g-QDs exhibit a 20% higher saturated photocurrent density (11 +/- 0.5 mA cm(-2)) compared to CdSe/CdS QDs. In addition, after one-hour illumination (100 mW cm(-2)), the PEC cell based on alloyed g-QDs still exhibits a photocurrent density of 7.5 mA cm(-2), maintaining 70% of its initial value. Such alloyed g-QDs are very promising for several emerging optoelectronic applications, where charge separation, transfer and transport play a critical role for the realization of high performance devices