Effect of the surface chemical modification on the optical properties of polymer-stabilized PbS nanoparticles

PbS Nanoparticles in the range 3.8–4.5 nm have been prepared in solution by H2S treatment of a Pb2+- containing copolymer (P-Pb). The variations of the P-Pb molecular weight before and after reacting with H2S implied that there existed some chemical bonds between the surface of the PbS nanoparticles and the copolymer. IR results proved that the chemical bond was Pb—OOC. When the molar ratio (the ratio H2S:Pb2+) was ⩽ 1, there existed Pb—OOC bonds on the particle surface, while most of the Pb—OOC bonds were broken when the molar ratio increased to 2.5:1. Different surface bonding situations are represented by different absorption spectra, the higher the molar ratio, the larger the absorption coefficient. These effects prove that the surface defects relative to the Pb—OOC bonds on the particle surface, can trap the electron–hole pairs effectively and cause a decrease in the absorption coefficient. On the other hand, excess H2S removed the Pb—OOC bonds and saturated the sulfur vacancies on the particle surface, where the radiation combination of the charge carriers occurred. As a result, the laser-induced luminescence bands appearing for the 0.75:1 and 1:1 colloids disappeared completely for the 2.5:1 colloid.

[1]  V. Vasić,et al.  Transient bleaching of small lead sulfide colloids: influence of surface properties , 1990 .

[2]  Horst Weller,et al.  Photochemistry of colloidal semiconductors. 20. Surface modification and stability of strong luminescing CdS particles , 1987 .

[3]  H. Yoneyama,et al.  Photochemical properties of PbS microcrystallites prepared in Nafion , 1990 .

[4]  Louis E. Brus,et al.  Luminescence and photophysics of cadmium sulfide semiconductor clusters: the nature of the emitting electronic state , 1986 .

[5]  A. Eychmüller,et al.  Detection of shallow electron traps in quantum sized CdS by fluorescence quenching experiments , 1993 .

[6]  Ying Wang,et al.  PbS in polymers. From molecules to bulk solids , 1987 .

[7]  Ying Wang,et al.  Optical transient bleaching of quantum‐confined CdS clusters: The effects of surface‐trapped electron–hole pairs , 1990 .

[8]  R. Eichberger,et al.  Chemistry and photophysics of mixed cadmium sulfide/mercury sulfide colloids , 1993 .

[9]  N. Herron,et al.  Chemical effects on the optical properties of semiconductor particles , 1987 .

[10]  Louis E. Brus,et al.  Higher excited electronic states in clusters of ZnSe, CdSe, and ZnS: Spin‐orbit, vibronic, and relaxation phenomena , 1986 .

[11]  Y. Wang Nonlinear optical properties of nanometer-sized semiconductor clusters , 1991 .

[12]  Louis E. Brus,et al.  Electronic wave functions in semiconductor clusters: experiment and theory , 1986 .

[13]  A. Henglein,et al.  Small-particle research: physicochemical properties of extremely small colloidal metal and semiconductor particles , 1989 .