Study of surface and bulk electronic structure of II-VI semiconductor nanocrystals using Cu as a nanosensor.
Efficiency of the quantum dots based solar cells relies on charge transfer at the interface and hence on the relative alignment of the energy levels between materials. Despite a high demand to obtain size specific band offsets, very few studies exist where meticulous methods like photoelectron spectroscopy are used. However, semiconductor charging during measurements could result in indirect and possibly inaccurate measurements due to shift in valence and conduction band position. Here, in this report, we devise a novel method to study the band offsets by associating an atomic like state with the conduction band and hence obtaining an internal standard. This is achieved by doping copper in semiconductor nanocrystals, leading to the development of a characteristic intragap Cu-related emission feature assigned to the transition from the conduction band to the atomic-like Cu d state. Using this transition we determine the relative band alignment of II-VI semiconductor nanocrystals as a function of size in the below 10 nm size regime. The results are in excellent agreement with the available photoelectron spectroscopy data as well as the theoretical data. We further use this technique to study the excitonic band edge variation as a function of temperature in CdSe nanocrystals. Additionally, surface electronic structure of CdSe nanocrystals have been studied using quantitative measurements of absolute quantum yield and PL decay studies of the Cu related emission and the excitonic emission. The role of TOP and oleic acid as surface passivating ligand molecules has been studied for the first time.
New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, P.O., Jakkur, Bangalore 560064, India.
G Krishnamurthy
GK
Grandhi
Renu
R
Tomar
Ranjani
R
Viswanatha
D003217:Conductometry / Q000295:instrumentation*; D003300:Copper / Q000737:chemistry*; D004553:Electric Conductivity; D004579:Electron Transport; D004867:Equipment Design; D019544:Equipment Failure Analysis; D008422:Materials Testing / Q000295:instrumentation*; D049329:Nanostructures / Q000737:chemistry* / Q000648:ultrastructure; D036103:Nanotechnology / Q000295:instrumentation*; D010316:Particle Size; D012666:Semiconductors
D003300:Copper