Modulation doping of absorbent cotton derived carbon dots for quantum dot-sensitized solar cells

In order to improve the power conversion efficiency (PCE) of quantum dot-sensitized solar cells (QDSC), a series of absorbent cotton derived carbon quantum dots (CQDs) with different dopants (namely carbamide, thiourea, and 1,3-diaminopropane) have been successfully synthesized by a one-pot hydrothermal method. The average particle sizes of the three doped CQDs are 1.7 nm, 5.6 nm, and 1.4 nm respectively, smaller than that of the undoped ones (24.2 nm). The morphological and structural characteristics of the four CQDs have been studied in detail. In addition, the three doped CQDs exhibit better optical properties compared with the undoped ones in the UV-vis and PL spectra. Then CQD-based QDSC are experimentally fabricated, showing that the short current density (Jsc) and open circuit voltage (Voc) of the QDSC are distinctly improved owing to the dopants. Especially the QDSC with the 1,3-diaminopropane doped CQD achieves the highest PCE (0.527%), 299% larger than that without dopant (0.176%). In order to highlight a reasonable mechanism, the UV-vis diffuse reflectance spectrum of CQD sensitized TiO2 and the calculated energy band structures of various CQDs are investigated. It's found from the above analysis that the addition of carbamide, thiourea, and 1,3-diaminopropane is beneficial to obtain CQDs of smaller size, and with a smaller band gap and more nitrogenous or sulphureous functional groups, which enhance the light absorption performance and photo-excitation properties. The above factors are helpful to improve the Jsc of QDSC. Nitrogen, acting as a donor to the CQDs, will assist the sensitized photoanode with a higher Fermi level, resulting in a larger Voc of the QSDC. Finally this study builds the relation among the microstructure of the CQDs, three characteristics of the CQDs (namely the spectra, energy band structure and functional groups) and the photoelectric properties of the QDSC, which will provide guidance for the modulation doping of CQDs to improve the PCE of QDSC.