Browsing by Subject "Colloidal nanocrystals"

Now showing 1 - 16 of 16

Embargo
Bright-dark exciton interplay evidenced by spin polarization in cdse/cdmns nanoplatelets for spin-optronics
(American Chemical Society, 2025-01-08) Shornikova, Elena V.; Yakovlev, Dmitri R.; Tolmachev, Danil O.; Prosnikov, Mikhail A.; Christianen, Peter C. M.; Shendre, Sushant; Işık, Furkan; Delikanlı, Savaş; Demir, Hilmi Volkan; Bayer, Manfred
Diluted magnetic semiconductor (DMS) colloidal nanocrystals demonstrate remarkable magneto-optical properties. The ability to control their magnetization and, consequently, the circular polarization of exciton emission holds significant potential for spintronic applications. However, the interplay between bright and dark exciton recombination and its impact on the polarization of emission are not yet fully understood. We measure the magneto-optical properties of colloidal CdSe/CdMnS nanoplatelets at cryogenic temperatures in high magnetic fields up to 30 T. The degree of circular polarization of photoluminescence demonstrates nonmonotonous behavior in a magnetic field. In low magnetic fields, the polarization degree is positive due to an exchange interaction of excitons with localized spins of magnetic Mn2+ ions. After reaching a maximum, the polarization degree starts to decrease and reverses the sign to negative in high magnetic fields, which is unusual in DMSs. The critical magnetic field, in which the sign is reversed, increases when the temperature is elevated. We develop a model that explains this behavior by an interplay of bright and dark exciton recombination. In high magnetic fields, the dark exciton radiative recombination rate accelerates due to mixing with the bright state, and the intrinsic Zeeman splitting of dark exciton overcomes the exchange with Mn2+ ions. As a result, the lowest |-2 > exciton energy level dominates in emission, providing negatively polarized photoluminescence.
Open Access
Colloidal nanocrystals embedded in macrocrystals: methods and applications
(American Chemical Society, 2016) Adam, M.; Gaponik N.; Eychmüller A.; Erdem, T.; Soran-Erdem, Z.; Demir, Hilmi Volkan
Colloidal semiconductor nanocrystals have gained substantial interest as spectrally tunable and bright fluorophores for color conversion and enrichment solids. However, they suffer from limitations in processing their solutions as well as efficiency degradation in solid films. As a remedy, embedding them into crystalline host matrixes has stepped forward for superior photostability, thermal stability, and chemical durability while simultaneously sustaining high quantum yields. Here, we review three basic methods for loading the macrocrystals with nanocrystals, namely relatively slow direct embedding, as well as accelerated methods of vacuum-assisted and liquid-liquid diffusion-assisted crystallization. We discuss photophysical properties of the resulting composites and present their application in light-emitting diodes as well as their utilization for plasmonics and excitonics. Finally, we present a future outlook for the science and technology of these materials.
Open Access
Colloidal semiconductor nanocrystals
(Springer Singapore, 2022-10-28) Erdem, Onur; Demir, Hilmi Volkan
In this chapter, we review colloidal semiconductor nanocrystals (NCs) and their remarkable size-dependent properties. We emphasize on colloidal nanoplatelets and explain how they differ from NCs of other classes.
Open Access
Color-enrichment semiconductor nanocrystals for biorhythm-friendly backlighting
(De Gruyter, 2018) Erdem, T.; Demir, Hilmi Volkan
Nanocrystals (NCs) offer great opportunities for developing novel light-emitting devices possessing superior properties such as high quality indoor lighting, efficient outdoor lighting, and display backlighting with increased color definition. The narrow-band emission spectra of these materials also offer opportunities to protect the human daily biological rhythm against the adverse effects of display backlighting. For this purpose, here we address this problem using color converting NCs and analyzed the effect of the NC integrated color converting light-emitting diode (NC LED) backlight spectra on the human circadian rhythm. We employed the three existing models including the circadian light, the melanopic sensitivity function, and the circadian effect factor by simultaneously satisfying the National Television Standards Committee (NTSC) requirements. The results show that NC LED backlighting exhibits (i) 33% less disruption on the circadian cycle if the same color gamut of the commercially available YAG:Ce LED is targeted and (ii) 34% wider color gamut while causing 4.1% weaker disruption on the circadian rhythm compared to YAG:Ce LED backlight if the NTSC color gamut is fully reproduced. Furthermore, we found out that blue and green emission peaks have to be located at 465 with 30 nm bandwidth and at 535 nm with 20 nm bandwidth, respectively, for a circadian rhythm friendly design while the red component offers flexibility around the peak emission wavelength at 636 nm as opposed to the requirements of quality indoor lighting. These design considerations introduced as a new design perspective for the displays of future will help avoiding the disruption of the human circadian rhythm.
Open Access
Efficient generation of emissive many-body correlations in copper-doped colloidal quantum wells
(Cell Press, 2022-09-21) Yu, Junhong; Sharma, Manoj; Li, Mingjie; Liu, Baiquan; Hernández-Martínez, Pedro Ludwig; Delikanli, Savaş; Sharma, Ashma; Altintas, Yemliha; Hettiarachchi, Chathuranga; Sum, Tze Chien; Demir, Hilmi Volkan; Dang, Cuong
Colloidal quantum wells (CQWs) provide an appealing platform to achieve emissive many-body correlations for novel optoelectronic devices, given that they act as hosts for strong carrier Coulomb interactions and present suppressed Auger recombination. However, the demonstrated high-order excitonic emission in CQWs requires ultrafast pumping with high excitation levels and can only be spectrally resolved at the single-particle level under cryogenic conditions. Here, through systematic investigation using static power-dependent emission spectroscopy and transient carrier dynamics, we show that Cu-doped CdSe CQWs exhibit continuous-wave-pumped high-order excitonic emission at room temperature with a large binding energy of ∼64 meV. We attribute this unique behavior to dopant excitons in which the ultralong lifetime and the highly localized wavefunction facilitate the formation of many-body correlations. The spectrally resolved high-order excitonic emission generated at power levels compatible with solar irradiation and electrical injection might pave the way for novel solution-processed solid-state devices. © 2022 The Authors
Open Access
Excitonic improvement of colloidal nanocrystals in salt powder matrix for quality lighting and color enrichment
(OSA - The Optical Society, 2016) Erdem, T.; Soran-Erdem, Z.; Kelestemur, Y.; Gaponik, N.; Demir, Hilmi Volkan
Here we report excitonic improvement in color-converting colloidal nanocrystal powders enabled by co-integrating nonpolar greenand red-emitting nanocrystal energy transfer pairs into a single LiCl salt matrix. This leads to nonradiative energy transfer (NRET) between the cointegrated nanocrystals in the host matrix. Here we systematically studied the resulting NRET process by varying donor and acceptor concentrations in the powders. We observed that NRET is a strong function of both of the nanocrystal concentrations and that NRET efficiency increases with increasing acceptor concentration. Nevertheless, with increasing donor concentration in the powders, NRET efficiency was found to first increase (up to a maximum level of 53.9%) but then to decrease. As a device demonstrator, we employed these NRET-improved nanocrystal powders as color-converters on blue light-emitting diodes (LEDs), with the resulting hybrid LED exhibiting a luminous efficiency >70 lm/Welect . The proposed excitonic nanocrystal powders potentially hold great promise for quality lighting and color enrichment applications.
Open Access
High-efficiency optical gain in type-II semiconductor nanocrystals of alloyed colloidal quantum wells
(American Chemical Society, 2017) Guzelturk, B.; Kelestemur Y.; Olutas M.; Li, Q.; Lian, T.; Demir, Hilmi Volkan
Colloidal nanocrystals having controlled size, tailored shape, and tuned composition have been explored for optical gain and lasing. Among these, nanocrystals having Type-II electronic structure have been introduced toward low-threshold gain. However, to date, their performance has remained severely limited due to diminishing oscillator strength and modest absorption cross-section. Overcoming these problems, here we realize highly efficient optical gain in Type-II nanocrystals by using alloyed colloidal quantum wells. With composition-tuned core/alloyed-crown CdSe/CdSexTe1-x quantum wells, we achieved amplified spontaneous emission thresholds as low as 26 μJ/cm2, long optical gain lifetimes (τgain ≈ 400 ps), and high modal gain coefficients (gmodal ≈ 930 cm-1). We uncover that the optical gain in these Type-II quantum wells arises from the excitations localized to the alloyed-crown region that are electronically coupled to the charge-transfer state. These alloyed heteronanostructures exhibiting remarkable optical gain performance are expected to be highly appealing for future display and lighting technologies.
Open Access
High-frequency EPR and ENDOR spectroscopy of Mn2+ ions in CdSe/CdMnS nanoplatelets
(American Chemical Society, 2023-02-20) Babunts, Roman A.; Uspenskaya, Yulia A.; Romanov, Nikolai G.; Orlinskii, Sergei B.; Mamin, Georgy V.; Shornikova, Elena V.; Yakovlev, Dmitri R.; Bayer, M.; Işık, Furkan; Shendre, S.; Delikanlı, Savaş; Demir, Hilmi Volkan
Semiconductor colloidal nanoplatelets based of CdSe have excellent optical properties. Their magneto-optical and spin-dependent properties can be greatly modified by implementing magnetic Mn2+ ions, using concepts well established for diluted magnetic semiconductors. A variety of magnetic resonance techniques based on high-frequency (94 GHz) electron paramagnetic resonance in continuous wave and pulsed mode were used to get detailed information on the spin structure and spin dynamics of Mn2+ ions in core/shell CdSe/(Cd,Mn)S nanoplatelets. We observed two sets of resonances assigned to the Mn2+ ions inside the shell and at the nanoplatelet surface. The surface Mn demonstrates a considerably longer spin dynamics than the inner Mn due to lower amount of surrounding Mn2+ ions. The interaction between surface Mn2+ ions and 1H nuclei belonging to oleic acid ligands is measured by means of electron nuclear double resonance. This allowed us to estimate the distances between the Mn2+ ions and 1H nuclei, which equal to 0.31 ± 0.04, 0.44 ± 0.09, and more than 0.53 nm. This study shows that the Mn2+ ions can serve as atomic-size probes for studying the ligand attachment to the nanoplatelet surface.
Open Access
Implementation of high-quality warm-white light-emitting diodes by a model-experimental feedback approach using quantum dot-salt mixed crystals
(American Chemical Society, 2015) Adam, M.; Erdem, T.; Stachowski, G.M.; Soran-Erdem Z.; Lox, J. F. L.; Bauer, C.; Poppe, J.; Demir, Hilmi Volkan; Gaponik N.; Eychmüller A.
In this work, a model-experimental feedback approach is developed and applied to fabricate high-quality, warm-white light-emitting diodes based on quantum dots (QDs) as color-conversion materials. Owing to their unique chemical and physical properties, QDs offer huge potential for lighting applications. Nevertheless, both emission stability and processability of the QDs are limited upon usage from solution. Incorporating them into a solid ionic matrix overcomes both of these drawbacks, while preserving the initial optical properties. Here borax (Na2B4O7·10H2O) is used as a host matrix because of its lower solubility and thereby reduced ionic strength in water in comparison with NaCl. This guarantees the stability of high-quality CdSe/ZnS QDs in the aqueous phase during crystallization and results in a 3.4 times higher loading amount of QDs within the borax crystals compared to NaCl. All steps from the synthesis via mixed crystal preparation to the warm-white LED preparation are verified by applying the model-experimental feedback, in which experimental data and numerical results provide feedback to each other recursively. These measures are taken to ensure a high luminous efficacy of optical radiation (LER) and a high color rendering index (CRI) of the final device as well as a correlated color temperature (CCT) comparable to an incandescent bulb. By doing so, a warm-white LED with a LER of 341 lm/Wopt, a CCT of 2720 K and a CRI of 91.1 is produced. Finally, we show that the emission stability of the QDs within the borax crystals on LEDs driven at high currents is significantly improved. These findings indicate that the proposed warm-white light-emitting diodes based on QDs-in-borax hold great promise for quality lighting. © 2015 American Chemical Society.
Open Access
Introduction
(Springer Singapore, 2022-10-28) Erdem, Onur; Demir, Hilmi Volkan
We begin by giving a short overview of colloidal nanoplatelets, and we explain why their orientation-controlled assemblies are of particular interest. We finalize the chapter by giving an outline of our brief.
Open Access
Liquid-liquid diffusion ‐ assisted crystallization: a fast and versatile approach toward high quality mixed quantum dot ‐ salt crystals
(Wiley-VCH Verlag, 2015) Adam, M.; Wang, Z.; Dubavik, A.; Stachowski, G. M.; Meerbach, C.; Soran-Erdem, Z.; Rengers, C.; Demir, Hilmi Volkan; Gaponik N.; Eychmuller, A.
Here, a new, fast, and versatile method for the incorporation of colloidal quantum dots (QDs) into ionic matrices enabled by liquid-liquid diffusion is demonstrated. QDs bear a huge potential for numerous applications thanks to their unique chemical and physical properties. However, stability and processability are essential for their successful use in these applications. Incorporating QDs into a tight and chemically robust ionic matrix is one possible approach to increase both their stability and processability. With the proposed liquid-liquid diffusion-assisted crystallization (LLDC), substantially accelerated ionic crystallization of the QDs is shown, reducing the crystallization time needed by one order of magnitude. This fast process allows to incorporate even the less stable colloids including initially oil-based ligand-exchanged QDs into salt matrices. Furthermore, in a modified two-step approach, the seed-mediated LLDC provides the ability to incorporate oil-based QDs directly into ionic matrices without a prior phase transfer. Finally, making use of their processability, a proof-of-concept white light emitting diode with LLDC-based mixed QD-salt films as an excellent color-conversion layer is demonstrated. These findings suggest that the LLDC offers a robust, adaptable, and rapid technique for obtaining high quality QD-salts.
Open Access
Magneto-optics of excitons interacting with magnetic ions in CdSe/CdMnS colloidal nanoplatelets
(American Chemical Society, 2020-06) Shornikova, E. V.; Yakovlev, D. R.; Tolmachev, D. O.; Ivanov, V. Y.; Kalitukha, I. V.; Sapega, V. F.; Kudlacik, D.; Kusrayev, Y. G.; Golovatenko, A. A.; Shendre, S.; Delikanlı, Savaş; Demir, Hilmi Volkan; Bayer, M.
Excitons in diluted magnetic semiconductors represent excellent probes for studying the magnetic properties of these materials. Various magneto-optical effects, which depend sensitively on the exchange interaction of the excitons with the localized spins of the magnetic ions can be used for probing. Here, we study core/shell CdSe/(Cd,Mn)S colloidal nanoplatelets hosting diluted magnetic semiconductor layers. The inclusion of the magnetic Mn2+ ions is evidenced by three magneto-optical techniques using high magnetic fields up to 15 T: polarized photoluminescence, optically detected magnetic resonance, and spin-flip Raman scattering. We show that the holes in the excitons play the dominant role in exchange interaction with magnetic ions. We suggest and test an approach for evaluation of the Mn2+ concentration based on the spin− lattice relaxation dynamics of the Mn2+ spin system.
Open Access
Nonradiative energy transfer in colloidal CdSe nanoplatelet films
(Royal Society of Chemistry, 2015) Güzeltürk, B.; Olutas M.; Delikanlı, S.; Keleştemur, Y.; Erdem, O.; Demir, Hilmi Volkan
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 ∼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. © The Royal Society of Chemistry 2015.
Open Access
Organic-inorganic composites of semiconductor nanocrystals for efficient excitonics
(American Chemical Society, 2015) Güzeltürk, B.; Demir, Hilmi Volkan
Nanocomposites of colloidal semiconductor nanocrystals integrated into conjugated polymers are the key to soft-material hybrid optoelectronics, combining advantages of both plastics and particles. Synergic combination of the favorable properties in the hybrids of colloidal nanocrystals and conjugated polymers offers enhanced performance and new functionalities in light-generation and light-harvesting applications, where controlling and mastering the excitonic interactions at the nanoscale are essential. In this Perspective, we highlight and critically consider the excitonic interactions in the organic inorganic nanocomposites to achieve highly efficient exciton transfer through rational design of the nanocomposites. The use of strong excitonic interactions in optoelectronic devices can trigger efficiency breakthroughs in hybrid optoelectronics.
Embargo
Orientation-dependent photoconductivity of quasi-2D nanocrystal self-assemblies: face-down, edge-up versus randomly oriented quantum wells
(Wiley-VCH Verlag GmbH & Co. KGaA, 2024-07-25) Ibrahem, Mohammed A.; Waris, Mohsin; Miah, Md Rumon; Shabani, Farzan; Canımkurbey, Betül; Ünal, Emre; Delikanlı, Savaş; Demir, Hilmi Volkan
Here, strongly orientation-dependent lateral photoconductivity of a CdSe monolayer colloidal quantum wells (CQWs) possessing short-chain ligands is reported. A controlled liquid-air self-assembly technique is utilized to deliberately engineer the alignments of CQWs into either face-down (FO) or edge-up (EO) orientation on the substrate as opposed to randomly oriented (RO) CQWs prepared by spin-coating. Adapting planar configuration metal-semiconductor-metal (MSM) photodetectors, it is found that lateral conductivity spans ≈2 orders of magnitude depending on the orientation of CQWs in the film in the case of utilizing short ligands. The long native ligands of oleic acid (OA) are exchanged with short-chain ligands of 2-ethylhexane-1-thiol (EHT) to reduce the inter-platelet distance, which significantly improved the photoresponsivity from 4.16, 0.58, and 4.79 mA W−1 to 528.7, 6.17, and 94.2 mA W−1, for the MSM devices prepared with RO, FO, and EO, before and after ligands exchange, respectively. Such CQW orientation control profoundly impacts the photodetector performance also in terms of the detection speed (0.061 s/0.074 s for the FO, 0.048 s/0.060 s for the EO compared to 0.10 s/0.16 s for the RO, for the rise and decay time constants, respectively) and the detectivity (1.7 × 1010, 2.3 × 1011, and 7.5 × 1011 Jones for the FO, EO, and RO devices, respectively) which can be further tailored for the desired optoelectronic device applications. Attributed to charge transportation in colloidal films being proportional to the number of hopping steps, these findings indicate that the solution-processed orientation of CQWs provides the ability to tune the photoconductivity of CQWs with short ligands as another degree of freedom to exploit and engineer their absorptive devices.
Open Access
White light generating nonradiative energy transfer directly from epitaxial quantum wells to colloidal nanocrystal quantum dots
(Optical Society of America, 2009) Nizamoğlu, Sedat; Sarı, Emre; Baek J.-H.; Lee I.-H.; Demir, Hilmi Volkan
We present white light generating nonradiative Förster resonance energy transfer at a rate of (2ns)-1 directly from epitaxial InGaN/GaN quantum wells to CdSe/ZnS heteronanocrystals in their close proximity at chromaticity-coordinates (x,y)=(0.42,0.39) and correlated-color-temperature CCT=3135K. ©2009 Optical Society of America.