Simple and greener synthesis of highly photoluminescence Mn2+-doped ZnS quantum dots and its surface passivation mechanism

Abstract In this paper, we reported a simple synthetic method of highly photoluminescent (PL) and stable Mn2+-doped ZnS quantum dots (QDs) with glutathione (GSH) as the capping molecule and focused on mechanism of the surface passivation of QDs. The Mn2+-doped ZnS QDs that was synthesized in basic solution (pH 10) at 120 °C for 5 h exhibited blue trap-state emission around 418 nm and a strong orange-red emission at about 580 nm with an excitation wavelength of 330 nm. The optimum doping concentration is determined to be 1.5 at.%, and the present Mn2+-doped ZnS QDs synthesized under the optimal reaction condition exhibited a quantum yield of 48%. High resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) indicated that the Mn2+-doped ZnS QDs were 3–5 nm in size with a zinc blend structure. More importantly, the PL intensity and chemical stability can be improved using organic ligand modification strategies, it was found that GSH could passivate surface defects very efficiently by comparing and analyzing the results of the different organic ligands modification. The cadmium-free Mn2+-doped ZnS QDs well-passivated with GSH as capping molecule acquired the advantages of strong PL and excellent chemical stability, which are important to QD applications.

[1]  Roberto Cingolani,et al.  Temperature dependence of the photoluminescence properties of colloidal Cd Se ∕ Zn S core/shell quantum dots embedded in a polystyrene matrix , 2005 .

[2]  Catherine J. Murphy,et al.  Photophysical Properties of ZnS Nanoclusters with Spatially Localized Mn2 , 1996 .

[3]  N. Jana,et al.  Highly Luminescent Mn-Doped ZnS Nanocrystals: Gram-Scale Synthesis , 2010 .

[4]  Xiaoji Ye,et al.  The evolution of optical properties during hydrothermal coarsening of ZnS nanoparticles , 2008 .

[5]  W. Shih,et al.  Non-heavy-metal ZnS quantum dots with bright blue photoluminescence by a one-step aqueous synthesis , 2007 .

[6]  Gallagher,et al.  Optical properties of manganese-doped nanocrystals of ZnS. , 1994, Physical review letters.

[7]  P. Alivisatos.  The use of nanocrystals in biological detection , 2004, Nature Biotechnology.

[8]  Developments in Luminescence and Display Materials Over the Last 100 Years as Reflected in Electrochemical Society Publications , 2002 .

[9]  W. Webb,et al.  Water-Soluble Quantum Dots for Multiphoton Fluorescence Imaging in Vivo , 2003, Science.

[10]  S. Bhatia,et al.  Probing the Cytotoxicity Of Semiconductor Quantum Dots. , 2004, Nano letters.

[11]  Chuanwei Cheng,et al.  Low-temperature synthesis and optical properties of wurtzite ZnS nanowires , 2006 .

[12]  K. Okuyama,et al.  Photoluminescence characteristics of YAG:Tb phosphor particles with spherical morphology and non-aggregation , 1999 .

[13]  T. Uyar,et al.  Sensitive Surface States and their Passivation Mechanism in CdS Quantum Dots , 2013 .

[14]  J. D. Levine,et al.  Theory and Observation of Intrinsic Surface States on Ionic Crystals , 1966 .

[15]  K. Senthilkumar,et al.  RETRACTED: Low temperature method for synthesis of ZnS quantum dots and its luminescence characterization studies , 2013 .

[16]  Hao Zhang,et al.  Simple Synthesis of Highly Luminescent Water-Soluble CdTe Quantum Dots with Controllable Surface Functionality , 2011 .

[17]  J. M. Costa-Fernández,et al.  Optical sensors based on luminescent quantum dots , 2006, Analytical and bioanalytical chemistry.

[18]  Xianwen Kan,et al.  Fluorescence for the determination of protein with functionalized nano-ZnS. , 2002, The Analyst.

[19]  S. K. Mishra,et al.  Photoconductivity and photoluminescence of ZnO nanoparticles synthesized via co-precipitation method. , 2011, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[20]  Anders Hagfeldt,et al.  Light-Induced Redox Reactions in Nanocrystalline Systems , 1995 .

[21]  A. Malko,et al.  Optical gain and stimulated emission in nanocrystal quantum dots. , 2000, Science.

[22]  J. Demas,et al.  Synthesis, luminescence, and excited-state complexes of the tris(1,10-phenanthroline)- and bis(terpyridine)iridium(III) cations , 1990 .

[23]  Yining Huang,et al.  Pressure dependence of Mn2+ fluorescence in ZnS : Mn2+ nanoparticles , 2000 .

[24]  Jinju Zheng,et al.  Efficient Photoluminescence of Mn2+ Ions in MnS/ZnS Core/Shell Quantum Dots , 2009 .

[25]  M. Lü,et al.  Solution-phase synthesis of spherical zinc sulfide nanostructures. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[26]  Chong Xiao,et al.  Synthesis and photoluminescence of water-soluble Mn2+-doped ZnS quantum dots , 2008 .

[27]  P. Sagayaraj,et al.  Investigation on one-pot hydrothermal synthesis, structural and optical properties of ZnS quantum dots , 2013 .

[28]  D. Meisel,et al.  Thiol surface complexation on growing CdS clusters , 1990 .

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

[30]  D. J. Lockwood,et al.  Developments in Luminescence and Display Materials Over the Last 100 Years as Reflected in Electrochemical Society Publications , 2002 .

[31]  N. Pradhan,et al.  An alternative of CdSe nanocrystal emitters: pure and tunable impurity emissions in ZnSe nanocrystals. , 2005, Journal of the American Chemical Society.

[32]  Yun Chan Kang,et al.  Gd2O3:Eu phosphor particles with sphericity, submicron size and non-aggregation characteristics , 1999 .

[33]  Xun Wang,et al.  Synthesis and characterization of sulfide and selenide colloidal semiconductor nanocrystals. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[34]  S. K. Mishra,et al.  Photoluminescence and photoconductivity of ZnS:Mn(2+) nanoparticles synthesized via co-precipitation method. , 2010, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[35]  Nikodem Tomczak,et al.  Designer polymer–quantum dot architectures , 2009 .

[36]  W. Shih,et al.  Highly Photoluminescent and Stable Aqueous ZnS Quantum Dots. , 2010, Industrial & engineering chemistry research.

[37]  Liping Wang,et al.  Low-temperature synthesis of hexagonal transition metal ion doped ZnS nanoparticles by a simple colloidal method , 2013 .

[38]  C. Tiwary,et al.  Room temperature synthesis of Mn2+ doped ZnS d-dots and observation of tunable dual emission: Effects of doping concentration, temperature, and ultraviolet light illumination , 2013 .

[39]  R. Nitschke,et al.  Quantum dots versus organic dyes as fluorescent labels , 2008, Nature Methods.

[40]  S. Masten,et al.  Mesoporous Microsphere of ZnS Photocatalysts Loaded with CuO or Mn3O4 for the Visible-Light-Assisted Photocatalytic Degradation of Orange II Dye , 2013 .

[41]  Samuel Woojoo Jun,et al.  Efficient Photoluminescence of Mn2+-Doped ZnS Quantum Dots Excited by Two-Photon Absorption in Near-Infrared Window II , 2013 .

[42]  D. Su,et al.  Colloidal Synthesis and Electroluminescence Properties of Nanoporous MnIIZnS Films , 1999 .

[43]  J. F. Suyver,et al.  Synthesis and Photoluminescence of Nanocrystalline ZnS:Mn^(2+) , 2001 .

[44]  V. Ramasamy,et al.  Synthesis, characterization and optical properties of water-soluble ZnS:Mn2+ nanoparticles , 2010 .

[45]  A. R. Williams,et al.  Relative fluorescence quantum yields using a computer-controlled luminescence spectrometer , 1983 .

[46]  K. G. Gopchandran,et al.  Studies on optical absorption and photoluminescence of thioglycerol-stabilized ZnS nanoparticles , 2009 .