We introduce a modified method of powder-diffraction data analysis to obtain precise structural information on freestanding ZnS and CdS nanoparticles with diameters well below 5 nm, i.e., in a range where common bulk-derived approaches fail. The method is based on the Debye equation and allows us to access the crystal structure and the size of the particles with high precision. Detailed information on strain, relaxation effects, stacking faults, and the shape of the particles becomes available. We find significant size differences between our new results and those obtained by established methods, and conclude that a mixed zinc-blende/wurtzite stacking and significant lattice distortions occur in our CdS nanoparticles. Our approach should have direct impact on the understanding and modeling of quantum size effects in nanoparticles.

Using high‐energy synchrotron radiation, powder diffraction experiments were carried out on CdS nanocrystals stabilized with glutathione. The radial distribution function was calculated from the data and analysed. The nanoparticle core, of diameter estimated as 15–20 Å, consists of Cd and S atoms in the proportion 1:1. Inside the core, both Cd and S atoms coordinate each other approximately tetrahedrally. The surface S atoms are connected to just two or three Cd atoms of the core and belong to the glutathione molecules of the particle shell. These S atoms are also a part of the core structure and contribute about one half of the total number of S atoms per particle. First‐neighbour Cd—S distances are 2.523 Å with a narrow distance distribution. No difference is observed between the lengths of Cd—S bonds involving the sulfur of the glutathione molecules and the sulfur atoms which are solely bound to Cd. The bond angle Cd—S—Cd at the surface bridging S atoms of glutathione is ca 99.5°, i.e. significantly smaller than an average one of 109.5° characteristic of the Cd and S atom packing inside the core. Beyond the range of the near interatomic distances, the influence of the surface and the defects cause a significant distinction of the particle core structure from those of zincblende and wurtzite, characteristic of bulk CdS.

The colloidal synthesis of CdS nanoparticles with the biostabilizers cysteine and glutathione, respectively, at pH values ranging from 4 to 10 is described. For the adjustment of their UV/Vis absorption properties and hence their band gap energies, the Statistical Design of Experiments (DoE) was used. This method allows the simultaneous variation of the synthesis parameters in a systematic manner, and thereby synergistic interaction effects can be obtained. The band gap energies of the quantum dots can be tuned from 3.32 to 4.26 eV by varying kind and concentration of stabilizer, pH value, and concentration of sulfide source. The energy position is significantly dependent on the interaction between the pH value and the concentration of the stabilizer, and the effect of high glutathione concentration is opposite at acidic and alkaline conditions thus leading to band gaps of 4.10 eV at pH = 6 and of 3.64 eV at pH = 10. Examples for the synthesis of semiconductor nanoparticles with predefined spectroscopic properties and preset preparation conditions, e.g., alkaline conditions for the implementation of acid-sensitive dopants, are given.

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