Modified spontaneous emissions of europium complex in weak PMMA opals.

Engineering spontaneous emission by means of photonic crystals (PHC) is under extensive study. However PHC modification of line emissions of rare earth (RE) ions has not been thoroughly understood, especially in cases of weak opal PHCs and while emitters are well dispersed into dielectric media. In this study, poly-methyl methacrylate (PMMA) opal PHCs containing uniformly dispersed europium chelate were fabricated with finely controlled photonic stop band (PSB) positions. Measurements of luminescent dynamics and angle resolved/integrated emission spectra as well as numerical calculations of total densities of states (DOS) were performed. We determined that in weak opals, the total spontaneous emission rate (SER) of Σ(5)D(0)-(7)F(J) for Eu(3+) was independent of PSB positions but was higher than that of the disordered powder sample, which was attributed to higher effective refractive indices in the PHC rather than PSB effect. Branch SER of (5)D(0)-(7)F(2) for Eu(3+) in the PHCs, on the other hand, was spatially redistributed, suppressed or enhanced in directions of elevated or reduced optical modes, keeping the angle-integrated total unchanged. All the results are in agreement with total DOS approximation. Our paper addressed two unstudied issues regarding modified narrow line emission in weak opal PHCs: firstly whether PSB could change the SER of emitters and whether there exist, apart from PSB, other reasons to change SERs; secondly, while directional enhancement and suppression by PSB has been confirmed, whether the angle-integrated overall effect is enhancing or suppressing.

[1]  J. C. Caris,et al.  Synthesis and Fluorescence of Some Trivalent Lanthanide Complexes , 1964 .

[2]  I. Krieger,et al.  Diffraction of light by ordered suspensions , 1969 .

[3]  D. L. Dexter Two ideas on energy transfer phenomena: Ion-pair effects involving the OH stretching mode, and sensitization of photovoltaic cells , 1979 .

[4]  S. K. Wong,et al.  Fluorescence-lifetime measurements in monodispersed suspensions of polystyrene particles , 1993 .

[5]  Steven G. Johnson,et al.  Photonic Crystals: Molding the Flow of Light , 1995 .

[6]  Rudolf Sprik,et al.  Optical emission in periodic dielectrics , 1996 .

[7]  Willem L. Vos,et al.  Fluorescence lifetimes and linewidths of dye in photonic crystals , 1999 .

[8]  Sergey V. Gaponenko,et al.  Spontaneous emission of dye molecules, semiconductor nanocrystals, and rare-earth ions in opal-based photonic crystals , 1999 .

[9]  E. Petrov,et al.  Petrov et al. Reply , 1999 .

[10]  Andreas Stein,et al.  Synthesis of highly ordered, three-dimensional, macroporous structures of amorphous or crystalline inorganic oxides, phosphates, and hybrid composites , 1999 .

[11]  Jane F. Bertone,et al.  Single-Crystal Colloidal Multilayers of Controlled Thickness , 1999 .

[12]  Z. Vardeny,et al.  Emission spectrum of a dipole in a semi-infinite periodic dielectric structure: Effect of the boundary , 2000, cond-mat/0004456.

[13]  Richard M. De La Rue,et al.  Eu3+ emission in an anisotropic photonic band gap environment , 2000 .

[14]  B. Gu,et al.  Decay distribution of spontaneous emission from an assembly of atoms in photonic crystals with pseudogaps. , 2002, Physical review letters.

[15]  Yi-quan Wang,et al.  Probing method for the density of states in a photonic crystal with luminescent molecules , 2003 .

[16]  Hongwei Song,et al.  Temperature dependence of luminescent spectra and dynamics in nanocrystalline Y2O3:Eu3+ , 2003 .

[17]  L. E. Scriven,et al.  Opaline Photonic Crystals: How Does Self‐Assembly Work? , 2004 .

[18]  Willem L. Vos,et al.  Controlling the dynamics of spontaneous emission from quantum dots by photonic crystals , 2004, Nature.

[19]  Willem L Vos,et al.  Directional fluorescence spectra of laser dye in opal and inverse opal photonic crystals. , 2005, The journal of physical chemistry. B.

[20]  Youyi Sun,et al.  Effects of synergetic ligands on the thermal and radiative properties of Eu(TTA)3nL-doped poly(methyl methacrylate) , 2005 .

[21]  Hongwei Song,et al.  Fabrication and photoluminescent characteristics of La2O3:Eu3+ nanowires. , 2006, Physical chemistry chemical physics : PCCP.

[22]  T. Asano,et al.  Spontaneous-emission control by photonic crystals and nanocavities , 2007 .

[23]  Suwen Li,et al.  Electrospinning Preparation and Photoluminescence Properties of Rare-Earth Complex/Polymer Composite Fibers , 2007 .

[24]  Weidong Zhou,et al.  Optical add-drop filters based on photonic crystal ring resonators. , 2007, Optics express.

[25]  Min Gu,et al.  Spectral Redistribution in Spontaneous Emission from Quantum‐Dot‐Infiltrated 3D Woodpile Photonic Crystals for Telecommunications , 2007 .

[26]  F. V. Veggel,et al.  Significant Suppression of Spontaneous Emission in SiO2 Photonic Crystals Made with Tb3+-Doped LaF3 Nanoparticles , 2007 .

[27]  F. V. van Veggel,et al.  Wavelength redistribution and color purification action of a photonic crystal. , 2008, Journal of the American Chemical Society.

[28]  W. Vos,et al.  Fluorescence Lifetime of Emitters with Broad Homogeneous Linewidths Modified in Opal Photonic Crystals , 2008 .

[29]  Christian Schneider,et al.  Scalable fabrication of optical resonators with embedded site-controlled quantum dots. , 2008, Optics letters.

[30]  O. Marty,et al.  Critical dimension where the macroscopic definition of refractive index can be applied at a nanometric scale , 2008 .

[31]  D. Jeon,et al.  Self-assembled SiO2 photonic crystal infiltrated by Ormosil:Eu(DBM)(3)phen phosphor and its enhanced photoluminescence. , 2009, Optics express.

[32]  K. Yano,et al.  A novel route to luminescent opals for controlling spontaneous emission , 2009 .

[33]  R. Colombelli,et al.  Electrically pumped photonic-crystal terahertz lasers controlled by boundary conditions , 2009, Nature.

[34]  Frank Marlow,et al.  Opals: status and prospects. , 2009, Angewandte Chemie.

[35]  A. Fujishima,et al.  Anisotropic Accelerated Emission of the Chromophores in Photonic Crystals Consisting of a Polystyrene Opal Structure , 2009 .

[36]  Chun-Hua Yan,et al.  Colour modification action of an upconversion photonic crystal. , 2009, Chemical communications.

[37]  Hongwei Song,et al.  Three-Dimensionally Ordered Macroporous ZrO2:Eu3+: Photonic Band Effect and Local Environments , 2009 .

[38]  Hongwei Song,et al.  Modified optical properties in a samarium doped titania inverse opal. , 2010, Optics letters.

[39]  Serge Ravaine,et al.  Fine tuning of emission through the engineering of colloidal crystals. , 2010, Physical chemistry chemical physics : PCCP.

[40]  Yong‐Ill Lee,et al.  Fluorescence Spectroscopy of Polymer Systems Doped with Rare-Earth Metal Ions and Their Complexes , 2010 .

[41]  K. Yano,et al.  Directional study of the optical properties of Tb3+- and Eu3+-doped nanoparticles embedded in silica photonic crystals. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[42]  J. Galisteo‐López,et al.  Self‐Assembled Photonic Structures , 2011, Advanced materials.