Exciton Dynamics of Colloidal Semiconductor Quantum Well Stacks

Colloidal semiconductor nanoplatelets (NPLs) have recently emerged as a new class of colloidal nanocrystals. NPLs are quasi two-dimensional nanocrystals having atomically flat surfaces and have unique properties such as narrow photoluminescence (PL) emission (similar to 10 nm) and giant oscillator strength. NPLs can be self-assembled into stacks. These are one-dimensional superstructures that can contain tens or hundreds of NPLs in one chain

Nonradiative energy transfer in colloidal CdSe nanoplatelet films

Nonradiative energy transfer (NRET) has been extensively studied in colloidal nanocrystal (quantum dots) and nanorod (quantum wires) assemblies. In this work, we present the first account of spectroscopic evidence of NRET in solid thin films of CdSe based colloidal nanoplatelets (NPLs), also known as colloidal quantum wells. The NRET was investigated as a function of the concentration of two NPL populations with different vertical thicknesses via steady state and time resolved spectroscopy. NRET takes place from the NPLs with smaller vertical thickness (i.e., larger band gap) to the ones with a larger vertical thickness (i.e., smaller band gap) with efficiency up to similar to 60%. Here, we reveal that the NRET efficiency is limited in these NPL solid film assemblies due to the self-stacking of NPLs within their own population causing an increased distance between the donor-acceptor pairs, which is significantly different to previously studied colloidal quantum dot based architectures for nonradiative energy transfer

CdSe/CdSe1-xTex Core/Crown Heteronanoplatelets: Tuning the Excitonic Properties without Changing the Thickness

Here we designed and synthesized CdSe/CdSe1-xTex core/crown nanoplatelets (NPLs) with controlled crown compositions by using the core-seeded-growth approach. We confirmed the uniform growth of the crown regions with well-defined shape and compositions by employing transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. By precisely tuning the composition of the CdSe1-xTex crown region from pure CdTe (x = 1.00) to almost pure CdSe doped with several Te atoms (x = 0.02), we achieved tunable excitonic properties without changing the thickness of the NPLs and demonstrated the evolution of type-II electronic structure. Upon increasing the Te concentration in the crown region, we obtained continuously tunable photoluminescence peaks within the range of similar to 570 nm (for CdSe1-xTex crown with x = 0.02) and similar to 660 nm (for CdSe1-xTex crown with x = 1.00). Furthermore, with the formation of the CdSe1-xTex crown region, we observed substantially improved photoluminescence quantum yields (up to similar to 95%) owing to the suppression of nonradiative hole trap sites. Also, we found significantly increased fluorescence lifetimes from similar to 49 up to similar to 326 ns with increasing Te content in the crown, suggesting the transition from quasi-type-II to type-II electronic structure. With their tunable excitonic properties, this novel material presented here will find ubiquitous use in various efficient light-emitting and-harvesting applications

Understanding the Journey of Dopant Copper Ions in Atomically Flat Colloidal Nanocrystals of CdSe Nanoplatelets Using Partial Cation Exchange Reactions

Unique electronic and optical properties of doped semiconductor nanocrystals (NCs) have widely stimulated a great deal of interest to explore new effective synthesis routes to achieve controlled doping for highly efficient materials. In this work, we show copper doping via postsynthesis partial cation exchange (CE) in atomically flat colloidal semiconductor nanoplatelets (NPLs). Here chemical reactivity of different dopant precursors, reaction kinetics, and shape of seed NPLs were extensively elaborated for successful doping and efficient emission. Dopant-induced Stokes shifted and tunable photoluminescence emission (640 to 830 nm) was observed in these Cu-doped CdSe NPLs using different thicknesses and heterostructures. High quantum yields (reaching 63%) accompanied by high absorption cross sections (>2.5 times) were obtained in such NPLs compared to those of Cu-doped CdSe colloidal quantum dots (CQDs). Systematic tuning of the doping level in these two-dimensional NPLs provides an insightful understanding of the chemical dopant based orbital hybridization in NCs. The unique combination of doping via the partial CE method and precise control of quantum confinement in such atomically flat NPLs originating from their magic-sized vertical thickness exhibits an excellent model platform for studying photophysics of doped quantum confined systems

Continuously Tunable Emission in Inverted Type-I CdS/CdSe Core/Crown Semiconductor Nanoplatelets

The synthesis and unique tunable optical properties of core/crown nanoplatelets having an inverted Type-I heterostructure are presented. Here, colloidal 2D CdS/CdSe heteronanoplatelets are grown with thickness of four monolayers using seed-mediated method. In this work, it is shown that the emission peak of the resulting CdS/CdSe heteronanoplatelets can be continuously spectrally tuned between the peak emission wavelengths of the core only CdS nanoplatelets (421 nm) and CdSe nanoplatelets (515 nm) having the same vertical thickness. In these inverted Type-I nanoplatelets, the unique continuous tunable emission is enabled by adjusting the lateral width of the CdSe crown, having a narrower bandgap, around the core CdS nanoplatelet, having a wider bandgap, as a result of the controlled lateral quantum confinement in the crown region additional to the pure vertical confinement. As a proof-of-concept demonstration, a white light generation is shown by using color conversion with these CdS/CdSe heteronanoplatelets having finely tuned thin crowns, resulting in a color rendering index of 80. The robust control of the electronic structure in such inverted Type-I heteronanoplatelets achieved by tailoring the lateral extent of the crown coating around the core template presents a new enabling pathway for bandgap engineering in solution-processed quantum wells

Type-II Colloidal Quantum Wells: CdSe/CdTe Core/Crown Heteronanoplatelets

Solution-processed quantum wells, also known as colloidal nanoplatelets (NPLs), are emerging as promising materials for colloidal optoelectronics. In this work, we report the synthesis and characterization of CdSe/CdTe core/crown NPLs exhibiting a Type-II electronic structure and Type-II specific optical properties. Here, based on a core-seeded approach, the CdSe/CdTe core/crown NPLs were synthesized with well-controlled CdTe crown coatings. Uniform and epitaxial growth of CdTe crown region was verified by using structural characterization techniques including transmission electron microscopy (TEM) with quantitative EDX analysis and X-ray diffraction (XRD). Also the optical properties were systematically studied in these Type-II NPLs that reveal strongly red-shifted photoluminescence (up to similar to 150 nm) along with 2 orders of magnitude longer fluorescence lifetimes (up to 190 ns) compared to the Type-I NPLs owing to spatially indirect excitons at the Type-II interface between the CdSe core and the CdTe crown regions. Photoluminescence excitation spectroscopy confirms that this strongly red-shifted emission actually arises from the CdSe/CdTe NPLs. In addition, temperature-dependent time-resolved fluorescence spectroscopy was performed to reveal the temperature-dependent fluorescence decay kinetics of the Type-II NPLs exhibiting interesting behavior. Also, water-soluble Type-II NPLs were achieved via ligand exchange of the CdSe/CdTe core/crown NPLs by using 3-mercaptopropionic acid (MPA), which allows for enhanced charge extraction efficiency owing to their shorter chain length and enables high quality film formation by layer-by-layer (LBL) assembly. With all of these appealing properties, the CdSe/CdTe core/crown heterostructures having Type-II electronic structure presented here are highly promising for light-harvesting applications

Giant modal gain coefficients in colloidal II-VI nanoplatelets

Modal gain coefficient is a key figure of merit for a laser material. Previously, net modal gain coefficients larger than a few thousand cm-1 were achieved in II-VI and III-V semiconductor gain media, but this required operation at cryogenic temperatures. In this work, using pump-fluence-dependent variable-stripe-length measurements, we show that colloidal CdSe nanoplatelets enable giant modal gain coefficients at room temperature up to 6600 cm-1 under pulsed optical excitation. Furthermore, we show that exceptional gain performance is common to the family of CdSe nanoplatelets, as shown by examining samples having different vertical thicknesses and lateral areas. Overall, colloidal II-VI nanoplatelets with superior optical gain properties are promising for a broad range of applications, including high-speed light amplification and loss compensation in plasmonic photonic circuits.Accepted versio