Ultrathin Highly Luminescent Two‐Monolayer Colloidal CdSe Nanoplatelets

Surface effects in atomically flat colloidal CdSe nanoplatelets (NLPs) are significantly and increasingly important with their thickness being reduced to subnanometer level, generating strong surface related deep trap photoluminescence emission alongside the bandedge emission. Herein, colloidal synthesis of highly luminescent two-monolayer (2ML) CdSe NPLs and a systematic investigation of carrier dynamics in these NPLs exhibiting broad photoluminescence emission covering the visible region with quantum yields reaching 90% in solution and 85% in a polymer matrix is shown. The astonishingly efficient Stokes-shifted broadband photoluminescence (PL) emission with a lifetime of ≈100 ns and the extremely short PL lifetime of around 0.16 ns at the bandedge signify the participation of radiative midgap surface centers in the recombination process associated with the underpassivated Se sites. Also, a proof-of-concept hybrid LED employing 2ML CdSe NPLs is developed as color converters, which exhibits luminous efficacy reaching 300 lm Wopt. The intrinsic absorption of the 2ML CdSe NPLs (≈2.15 × 106 cm−1) reported in this study is significantly larger than that of CdSe quantum dots (≈2.8 × 105 cm−1) at their first exciton signifying the presence of giant oscillator strength and hence making them favorable candidates for next-generation light-emitting and light-harvesting applications.

[1]  G. Galli,et al.  Direct Synthesis of Six-Monolayer (1.9 nm) Thick Zinc-Blende CdSe Nanoplatelets Emitting at 585 nm , 2018, Chemistry of Materials.

[2]  Alexander N. Cartwright,et al.  Time-resolved photoluminescence study of CdSe/CdMnS/CdS core/multi-shell nanoplatelets , 2016 .

[3]  Masayuki Kanehara,et al.  Origin of surface trap states in CdS quantum dots: relationship between size dependent photoluminescence and sulfur vacancy trap states. , 2015, Physical chemistry chemical physics : PCCP.

[4]  M. Castro,et al.  Optical Investigation of Broadband White-Light Emission in Self-Assembled Organic–Inorganic Perovskite (C6H11NH3)2PbBr4 , 2015 .

[5]  K. Ramasamy,et al.  Low-Temperature Synthesis of Magic-Sized CdSe Nanoclusters: Influence of Ligands on Nanocluster Growth and Photophysical Properties , 2012 .

[6]  S. Erwin,et al.  An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets , 2016, Nature materials.

[7]  Vincent Loriette,et al.  Spectroscopy of single CdSe nanoplatelets. , 2012, ACS nano.

[8]  Piernicola Spinicelli,et al.  Efficient exciton concentrators built from colloidal core/crown CdSe/CdS semiconductor nanoplatelets. , 2014, Nano letters.

[9]  Jiayu Zhang,et al.  Surface-Related Emission in Highly Luminescent CdSe Quantum Dots , 2003 .

[10]  Ulrike Woggon,et al.  Linear Absorption in CdSe Nanoplates: Thickness and Lateral Size Dependency of the Intrinsic Absorption , 2015 .

[11]  X. Zhu,et al.  Mechanism for Broadband White-Light Emission from Two-Dimensional (110) Hybrid Perovskites. , 2016, The journal of physical chemistry letters.

[12]  Savas Delikanli,et al.  Amplified spontaneous emission and lasing in colloidal nanoplatelets. , 2014, ACS nano.

[13]  R. R. Cooney,et al.  State-resolved studies of biexcitons and surface trapping dynamics in semiconductor quantum dots. , 2008, The Journal of chemical physics.

[14]  K. B. Whaley,et al.  A theoretical study of the influence of the surface on the electronic structure of CdSe nanoclusters , 1994 .

[15]  S. Tretiak,et al.  Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites , 2017, Science.

[16]  H. Demir,et al.  Stable and efficient colour enrichment powders of nonpolar nanocrystals in LiCl. , 2015, Nanoscale.

[17]  J. I. Climente,et al.  Directed emission of CdSe nanoplatelets originating from strongly anisotropic 2D electronic structure. , 2017, Nature nanotechnology.

[18]  Benoit Dubertret,et al.  Quasi 2D colloidal CdSe platelets with thicknesses controlled at the atomic level. , 2008, Journal of the American Chemical Society.

[19]  Oleksandr Voznyy,et al.  Colloidal CdSe(1-x)S(x) Nanoplatelets with Narrow and Continuously-Tunable Electroluminescence. , 2015, Nano letters.

[20]  Theo Siegrist,et al.  One-dimensional organic lead halide perovskites with efficient bluish white-light emission , 2017, Nature Communications.

[21]  Shuming Nie,et al.  Semiconductor nanocrystals: structure, properties, and band gap engineering. , 2010, Accounts of chemical research.

[22]  M. El-Sayed,et al.  On the Nanoparticle to Molecular Size Transition: Fluorescence Quenching Studies , 2001 .

[23]  Sandrine Ithurria,et al.  Colloidal atomic layer deposition (c-ALD) using self-limiting reactions at nanocrystal surface coupled to phase transfer between polar and nonpolar media. , 2012, Journal of the American Chemical Society.

[24]  S. Rosenthal,et al.  Ultrafast Carrier Dynamics in CdSe Nanocrystals Determined by Femtosecond Fluorescence Upconversion Spectroscopy , 2001 .

[25]  James R. McBride,et al.  Near‐Unity Emitting Copper‐Doped Colloidal Semiconductor Quantum Wells for Luminescent Solar Concentrators , 2017, Advanced materials.

[26]  B. Dubertret,et al.  Colloidal nanoplatelets with two-dimensional electronic structure. , 2011, Nature materials.

[27]  Adam Jaffe,et al.  Intrinsic white-light emission from layered hybrid perovskites. , 2014, Journal of the American Chemical Society.

[28]  Savas Delikanli,et al.  Type-II Colloidal Quantum Wells: CdSe/CdTe Core/Crown Heteronanoplatelets , 2015 .

[29]  Hilmi Volkan Demir,et al.  CdSe/CdSe1–xTex Core/Crown Heteronanoplatelets: Tuning the Excitonic Properties without Changing the Thickness , 2017 .

[30]  Richard H. Friend,et al.  An improved experimental determination of external photoluminescence quantum efficiency , 1997 .

[31]  Sharon M. Weiss,et al.  Encapsulated white-light CdSe nanocrystals as nanophosphors for solid-state lighting , 2008 .

[32]  Savas Delikanli,et al.  sp-d Exchange Interactions in Wave Function Engineered Colloidal CdSe/Mn:CdS Hetero-Nanoplatelets. , 2018, Nano letters.

[33]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[34]  Peter D Dahlberg,et al.  Red, Yellow, Green, and Blue Amplified Spontaneous Emission and Lasing Using Colloidal CdSe Nanoplatelets. , 2015, ACS nano.

[35]  Amanda P. Siegel,et al.  Pure white-light emitting ultrasmall organic-inorganic hybrid perovskite nanoclusters. , 2016, Nanoscale.

[36]  Savas Delikanli,et al.  Lateral Size-Dependent Spontaneous and Stimulated Emission Properties in Colloidal CdSe Nanoplatelets. , 2015, ACS nano.

[37]  Savas Delikanli,et al.  Experimental Determination of the Absorption Cross-Section and Molar Extinction Coefficient of Colloidal CdSe Nanoplatelets , 2015 .

[38]  S. M. Claiborne,et al.  Bright white light emission from ultrasmall cadmium selenide nanocrystals. , 2012, Journal of the American Chemical Society.

[39]  S. Weiss,et al.  White Light Emission Characteristics of Polymer-Encapsulated CdSe Nanocrystal Films , 2010, IEEE Photonics Technology Letters.

[40]  Chem. , 2020, Catalysis from A to Z.

[41]  Hilmi Volkan Demir,et al.  Platelet‐in‐Box Colloidal Quantum Wells: CdSe/CdS@CdS Core/Crown@Shell Heteronanoplatelets , 2016 .

[42]  A. C. Carter,et al.  Surface structure of cadmium selenide nanocrystallites , 1997 .

[43]  M. Nasilowski,et al.  Two-Dimensional Colloidal Nanocrystals. , 2016, Chemical reviews.

[44]  J. Schins,et al.  Nature and decay pathways of photoexcited states in CdSe and CdSe/CdS nanoplatelets. , 2014, Nano letters.

[45]  James R McBride,et al.  White-light emission from magic-sized cadmium selenide nanocrystals. , 2005, Journal of the American Chemical Society.

[46]  Xiaogang Peng,et al.  Size/shape-controlled synthesis of colloidal CdSe quantum disks: ligand and temperature effects. , 2011, Journal of the American Chemical Society.

[47]  Peiyao Zhang,et al.  Mn(2+)-Doped CdSe/CdS Core/Multishell Colloidal Quantum Wells Enabling Tunable Carrier-Dopant Exchange Interactions. , 2015, ACS nano.

[48]  Savas Delikanli,et al.  Continuously Tunable Emission in Inverted Type‐I CdS/CdSe Core/Crown Semiconductor Nanoplatelets , 2015 .

[49]  Jung Ho Yu,et al.  Low-temperature solution-phase synthesis of quantum well structured CdSe nanoribbons. , 2006, Journal of the American Chemical Society.

[50]  Savas Delikanli,et al.  Nanocrystal light-emitting diodes based on type II nanoplatelets , 2018 .

[51]  Andreas Kornowski,et al.  Ultrathin PbS Sheets by Two-Dimensional Oriented Attachment , 2010, Science.