title: A single-source solid-precursor method for making eco-friendly doped semiconductor nanoparticles emitting multi-color luminescence.
abstract: A novel synthesis method is presented for the preparation of eco-friendly, doped semiconductor nanocrystals encapsulated within oxide-shells, both formed sequentially from a single-source solid-precursor. Highly luminescent ZnS nanoparticles, in situ doped with Cu(+)-Al3+ pairs and encapsulated with ZnO shells are prepared by the thermal decomposition of a solid-precursor compound, zinc sulfato-thiourea-oxyhydroxide, showing layered crystal structure. The precursor compound is prepared by an aqueous wet-chemical reaction involving necessary chemical reagents required for the precipitation, doping and inorganic surface capping of the nanoparticles. The elemental analysis (C, H, N, S, O, Zn), quantitative estimation of different chemical groups (SO4(2-) and NH4(-)) and infrared studies suggested that the precursor compound is formed by the intercalation of thiourea, and/or its derivatives thiocarbamate (CSNH2(-)), dithiocarbamate (CS2NH2(-)), etc., and ammonia into the gallery space of zinc-sulfato-oxyhydroxide corbel where the Zn(II) ions are both in the octahedral as well as tetrahedral coordination in the ratio 3 : 2 and the dopant ions are incorporated within octahedral voids. The powder X-ray diffraction of precursor compound shows high intensity basal reflection corresponding to the large lattice-plane spacing of d = 11.23 angstroms and the Rietveld analysis suggested orthorhombic structure with a = 9.71 angstroms, b = 12.48 angstroms, c = 26.43 angstroms, and beta = 90 degrees. Transmission electron microscopy studies show the presence of micrometer sized acicular monocrystallites with prismatic platy morphology. Controlled thermolysis of the solid-precursor at 70-110 degrees C leads to the collapse of layered structure due to the hydrolysis of interlayer thiourea molecules or its derivatives and the S2- ions liberated thereby reacts with the tetrahedral Zn(II) atoms leading to the precipitation of ZnS nanoparticles at the gallery space. During this process, the dopant ions situated at octahedral voids gets incorporated into the nano-ZnS lattice and results in bright photoluminescence. On further heat treatment above 1100 degrees C, the corbel zinc-oxyhydroxide sheets undergo dehydroxylation to form ZnO which eventually encapsulates the ZnS nanoparticles at the gallery leading to significant enhancement in the luminescence quantum efficiency, up to approximately 22%. The emission color of thus formed nano-ZnS/micro-ZnO composites could be tuned over wide spectral ranges from 480 to 618 nm and the spectral changes are attributed to a number of factors including lattice defects, Cu(+)-Al3+ dopant-pairs and iso-electronic oxygen in nano-ZnS and oxygen-vacancy or -interstitial centers in non-stoichiometric ZnO.
authors: Materials Development Group, Defence Laboratory, Jodhpur 342 011, Rajasthan, India.
authors: K
authors: K
authors: Manzoor
authors: V
authors: V
authors: Aditya
authors: S R
authors: SR
authors: Vadera
authors: N
authors: N
authors: Kumar
authors: T R N
authors: TR
authors: Kutty
mesh_terms: D000535:Aluminum / Q000737:chemistry; D000641:Ammonia / Q000737:chemistry; D003116:Color; D003300:Copper / Q000737:chemistry; D003460:Crystallization; D006358:Hot Temperature; D008027:Light; D049449:Luminescence; D049408:Luminescent Agents / Q000032:analysis / Q000737:chemistry* / Q000528:radiation effects; D008422:Materials Testing; D046529:Microscopy, Electron, Transmission; D008956:Models, Chemical; D053758:Nanoparticles / Q000032:analysis / Q000737:chemistry* / Q000528:radiation effects / Q000648:ultrastructure; D036103:Nanotechnology / Q000379:methods*; D010316:Particle Size; D012666:Semiconductors; D017550:Spectroscopy, Fourier Transform Infrared; D013440:Sulfides / Q000032:analysis / Q000737:chemistry / Q000528:radiation effects; D013859:Thiocarbamates / Q000737:chemistry; D013890:Thiourea / Q000737:chemistry; D014867:Water / Q000737:chemistry; D014961:X-Ray Diffraction; D017967:Zinc Compounds / Q000032:analysis / Q000737:chemistry / Q000528:radiation effects; D015034:Zinc Oxide / Q000737:chemistry
chemical_list: D049408:Luminescent Agents; D013440:Sulfides; D013859:Thiocarbamates; D017967:Zinc Compounds; D014867:Water; D000641:Ammonia; D003300:Copper; D000535:Aluminum; D013890:Thiourea; C031238:zinc sulfide; D015034:Zinc Oxide