Quantum Dot Transfer from the Organic Phase to Acrylic Monomers for the Controlled Integration of Single-Photon Sources by Photopolymerization.

This paper reports on a new strategy for obtaining homogeneous dispersion of grafted quantum dots (QDs) in a photopolymer matrix and their use for the integration of single-photon sources by two-photon polymerization (TPP) with nanoscale precision. The method is based on phase transfer of QDs from organic solvents to an acrylic matrix. The detailed protocol is described, and the corresponding mechanism is investigated and revealed. The phase transfer is done by ligand exchange through the introduction of mono-2-(methacryloyloxy) ethyl succinate (MES) that replaces oleic acid (OA). Infrared (IR) measurements show the replacement of OA on the QD surface by MES after ligand exchange. This allows QDs to move from the hexane phase to the pentaerythritol triacrylate (PETA) phase. The QDs that are homogeneously dispersed in the photopolymer without any clusterization do not show any significant broadening in their photoluminescence spectra even after more than 3 years. The ability of the hybrid photopolymer to create micro- and nanostructures by two-photon polymerization is demonstrated. The homogeneity of emission from 2D and 3D microstructures is confirmed by confocal photoluminescence microscopy. The fabrication and integration of a single-photon source in a spatially controlled manner by TPP is achieved and confirmed by auto-correlation measurements.

[1]  R. Bachelot,et al.  Advanced hybrid plasmonic nano-emitters using smart photopolymer , 2022, Photonics Research.

[2]  Sadahiro Masuo,et al.  Enhanced Single-Photon Emission from Single Quantum Dots Interacting with a One-Dimensional Plasmonic Chip , 2022, The Journal of Physical Chemistry C.

[3]  Robin L. Williams,et al.  Unity yield of deterministically positioned quantum dot single photon sources , 2021, Scientific Reports.

[4]  Gilma Granados-Oliveros,et al.  CdSe/ZnS quantum dots capped with oleic acid and L-glutathione: structural properties and application in detection of Hg2+ , 2021, Journal of Molecular Structure.

[5]  R. Bachelot,et al.  One Strategy for Nanoparticle Assembly onto 1D, 2D, and 3D Polymer Micro and Nanostructures. , 2021, ACS applied materials & interfaces.

[6]  R. Bachelot,et al.  Three-Dimensional Photoluminescent Crypto-Images Doped with (CdSe)ZnS Quantum Dots by One-Photon and Two-Photon Polymerization , 2021, ACS Applied Nano Materials.

[7]  A. De Luca,et al.  Leveraging on ENZ Metamaterials to Achieve 2D and 3D Hyper‐Resolution in Two‐Photon Direct Laser Writing , 2021, Advanced materials.

[8]  R. Bachelot,et al.  Hybrid plasmonic nano-emitters with controlled single quantum emitter positioning on the local excitation field , 2020, Nature Communications.

[9]  Andrew C. Lamont,et al.  A facile multi-material direct laser writing strategy. , 2019, Lab on a chip.

[10]  Marcelo Davanco,et al.  Indistinguishable photons from deterministically integrated single quantum dots in heterogeneous GaAs/ Si3N4 quantum photonic circuits. , 2019, Nano letters.

[11]  R. Caputo,et al.  Integration of Nanoemitters onto Photonic Structures by Guided Evanescent-Wave Nano-Photopolymerization , 2019, The Journal of Physical Chemistry C.

[12]  R. Bachelot,et al.  Hybrid plasmonic nanosystem with controlled position of nanoemitters , 2019, Applied Physics Letters.

[13]  Hongyi Zhang,et al.  Characterization of the Ligand Exchange Reactions on CdSe/ZnS QDs by Capillary Electrophoresis. , 2019, Langmuir : the ACS journal of surfaces and colloids.

[14]  Xiao Wei Sun,et al.  3D Photoluminescent Nanostructures Containing Quantum Dots Fabricated by Two‐Photon Polymerization: Influence of Quantum Dots on the Spatial Resolution of Laser Writing , 2018, Advanced Materials Technologies.

[15]  Harald Giessen,et al.  Single Quantum Dot with Microlens and 3D-Printed Micro-objective as Integrated Bright Single-Photon Source , 2017, ACS photonics.

[16]  N. Spooner,et al.  Versatile PbS Quantum Dot Ligand Exchange Systems in the Presence of Pb-Thiolates. , 2017, Small.

[17]  Igor L. Medintz,et al.  Energy Transfer with Semiconductor Quantum Dot Bioconjugates: A Versatile Platform for Biosensing, Energy Harvesting, and Other Developing Applications. , 2017, Chemical reviews.

[18]  H. Giessen,et al.  Combining in-situ lithography with 3D printed solid immersion lenses for single quantum dot spectroscopy , 2017, Scientific Reports.

[19]  Sae Woo Nam,et al.  Heterogeneous integration for on-chip quantum photonic circuits with single quantum dot devices , 2016, Nature Communications.

[20]  Roberto Caputo,et al.  Two-Color Single Hybrid Plasmonic Nanoemitters with Real Time Switchable Dominant Emission Wavelength. , 2015, Nano letters.

[21]  O. Park,et al.  Effects of ligand exchanged CdSe quantum dot interlayer for inverted organic solar cells , 2015 .

[22]  W. Tremel,et al.  Morphology control in biphasic hybrid systems of semiconducting materials. , 2015, Macromolecular rapid communications.

[23]  Martin Wegener,et al.  Polymerization Kinetics in Three‐Dimensional Direct Laser Writing , 2014, Advanced materials.

[24]  S. Achilefu,et al.  Broad spectrum photoluminescent quaternary quantum dots for cell and animal imaging. , 2013, Chemical communications.

[25]  M. Delcea,et al.  Fabrication of quantum dot microarrays using electron beam lithography for applications in analyte sensing and cellular dynamics. , 2013, ACS nano.

[26]  S. Reitzenstein,et al.  In situ electron-beam lithography of deterministic single-quantum-dot mesa-structures using low-temperature cathodoluminescence spectroscopy , 2013, 1304.3631.

[27]  Igor L. Medintz,et al.  Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology. , 2013, Chemical reviews.

[28]  Dae-Young Chung,et al.  Nanoscale patterning of colloidal quantum dots on transparent and metallic planar surfaces , 2012, Nanotechnology.

[29]  W. Chin,et al.  Aggregation, dissolution, and stability of quantum dots in marine environments: importance of extracellular polymeric substances. , 2012, Environmental science & technology.

[30]  S. Karan,et al.  Controlled surface trap state photoluminescence from CdS QDs impregnated in poly(methyl methacrylate) , 2012, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[31]  D. Y. Yoon,et al.  Bright and efficient full-color colloidal quantum dot light-emitting diodes using an inverted device structure. , 2012, Nano letters.

[32]  R. Gadonas,et al.  Nanophotonic lithography: a versatile tool for manufacturing functional three-dimensional micro-/nano-objects , 2012 .

[33]  K. Gupta,et al.  Optical and electrical properties of polyaniline-cadmium sulfide nanocomposite , 2011 .

[34]  J. Martínez‐Pastor,et al.  Photoluminescence waveguiding in CdSe and CdTe QDs–PMMA nanocomposite films , 2011, Nanotechnology.

[35]  Chinho Park,et al.  Photoluminescence Blue-Shift of CdSe Nanoparticles Caused by Exchange of Surface Capping Layer , 2011 .

[36]  Igor L. Medintz,et al.  Semiconductor quantum dots in bioanalysis: crossing the valley of death. , 2011, Analytical chemistry.

[37]  Costas Fotakis,et al.  3D conducting nanostructures fabricated using direct laser writing , 2011 .

[38]  Siglinda Perathoner,et al.  Creating and mastering nano-objects to design advanced catalytic materials , 2011 .

[39]  Stavros Pissadakis,et al.  Direct laser writing of microoptical structures using a Ge-containing hybrid material , 2011 .

[40]  Christian Schneider,et al.  Lithographic alignment to site-controlled quantum dots for device integration , 2008 .

[41]  W. Tremel,et al.  Liquid Crystalline Phases from Polymer‐Functionalized TiO2 Nanorods , 2007 .

[42]  Moungi G Bawendi,et al.  In-situ encapsulation of quantum dots into polymer microspheres. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[43]  W. Tan,et al.  Multifunctional Quantum‐Dot‐Based Magnetic Chitosan Nanobeads , 2005 .

[44]  Yeshaiahu Fainman,et al.  PMMA quantum dots composites fabricated via use of pre-polymerization. , 2005, Optics express.

[45]  D. A. Long Infrared and Raman characteristic group frequencies. Tables and charts George Socrates John Wiley and Sons, Ltd, Chichester, Third Edition, 2001. Price £135 , 2004 .

[46]  Hong‐Bo Sun,et al.  Experimental investigation of single voxels for laser nanofabrication via two-photon photopolymerization , 2003 .

[47]  Satoshi Kawata,et al.  Two-photon photopolymerization and diagnosis of three-dimensional microstructures containing fluorescent dyes , 2001 .

[48]  Paul Mulvaney,et al.  Silica encapsulation of quantum dots and metal clusters , 2000 .

[49]  Stephan W Koch,et al.  Quantum theory of the optical and electronic properties of semiconductors, fifth edition , 2009 .

[50]  D. Walls,et al.  Proposal for the measurement of the resonant Stark effect by photon correlation techniques , 1976 .