Quantum confinement effect of CdSe induced by nanoscale solvothermal reaction

We report a novel method, nanoscale solvothermal reaction (NSR), to induce the quantum confinement effect of CdSe on nanostructured TiO2 by solvothermal route. The time-dependent growth of CdSe is observed in solution at room temperature, which is found to be accomplished instantly by heat-treatment in the presence of solvent at 1 atm. However, no crystal growth occurs upon heat-treatment in the absence of solvent. The nanoscale solvothermal growth of CdSe quantum dot is realized on the nanocrystalline oxide surface, where Cd(NO3)(2)center dot 4H(2)O and Na2SeSO3 solutions are sequentially spun on nanostructured TiO2, followed by heat-treatment at temperatures ranging from 100 degrees C to 250 degrees C. Size of CdSe increases from 4.4 nm to 5.3 nm, 8.7 nm and 14.8 nm, which results in decrease in optical band gap from 2.19 eV to, 1.95 eV, 1.74 eV and 1.75 eV with increasing the NSR temperature from 100 degrees C to 150 degrees C, 200 degrees C and 250 degrees C, respectively, which is indicative of the quantum confinement effect. Thermodynamic studies reveal that increase in the size of CdSe is related to increase in enthalpy, for instance, from 3.77 J mg(-1) for 100 degrees C to 8.66 J mg(-1) for 200 degrees C. Quantum confinement effect is further confirmed from the CdSe-sensitized solar cell, where onset wavelength in external quantum efficiency spectra is progressively shifted from 600 nm to 800 nm as the NSR temperature increases, which leads to a significant improvement of power conversion efficiency by a factor of more than four. A high photocurrent density of 13.7 mA cm(-2) is obtained based on CdSe quantum dot grown by NSR at 200 degrees C.