Control of photoluminescence of carbon nanodots via surface functionalization using para-substituted anilines

Carbon nanodots (C-dots) are a kind of fluorescent carbon nanomaterials, composed of polyaromatic carbon domains surrounded by amorphous carbon frames, and have attracted a great deal of attention because of their interesting properties. There are still, however, challenges ahead such as blue-biased photoluminescence, spectral broadness, undefined energy gaps and etc. In this report, we chemically modify the surface of C-dots with a series of para-substituted anilines to control their photoluminescence. Our surface functionalization endows our C-dots with new energy levels, exhibiting long-wavelength (up to 650 nm) photoluminescence of very narrow spectral widths. The roles of para-substituted anilines and their substituents in developing such energy levels are thoroughly studied by using transient absorption spectroscopy. We finally demonstrate light-emitting devices exploiting our C-dots as a phosphor, converting UV light to a variety of colors with internal quantum yields of ca. 20%.open116665Ysciescopu

Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size.

Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter DB (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nanocrystals (NCs) in a dimension > DB (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than DB show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and perfluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (∼60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs

Formation of highly luminescent nearly monodisperse carbon quantum dots via emulsion-templated carbonization of carbohydrates

Highly luminescent nearly monodisperse carbon quantum dots (CQDs) are synthesized by facile emulsion-templated carbonization of low cost and non toxic carbohydrates excluding the size selection procedure. The present method is further combined with in situ nitric acid treatment to offer high quantum yields up to 53% which, to our best knowledge, is unprecedented in the past.open113131sciescopu

Carbon Quantum Dot-Based Field-Effect Transistors and Their Ligand Length-Dependent Carrier Mobility

We report electrical measurements of films of carbon quantum dots (CQDs) that serve as the channels of field-effects transistors (FETs). To investigate the dependence of the field-effect mobility on ligand length, colloidal CQDs are synthesized and ligand-exchanged with several primary amines of different ligand lengths. We measure current as a function of gate voltage and find that the devices show ambipolar conductivity, with electron and hole mobilities as high as 8.49 X 10(-5) and 3.88 X 10(-5) cm(2) V-1 s(-1) respectively. The electron mobilities are consistently 2-4 times larger than the hole mobilities. Furthermore, the mobilities decrease exponentially with the increase of the ligand length, which is well-described by the Miller-Abrahams model for nearest-neighbor hopping. Our results provide a theoretical basis to examine charge transport in CQD films and offer new prospects for the fabrication of high-mobility CQD-based optoelectronic devices, including solar cells, light-emitting devices, and optical sensors.X112224sciescopu

Size-Controlled Soft-Template Synthesis of Carbon Nanodots toward Versatile Photoactive Materials

Size-controlled soft-template synthesis of carbon nanodots (CNDs) as novel photoactive materials is reported. The size of the CNDs can be controlled by regulating the amount of an emulsifier. As the size increases, the CNDs exhibit blue-shifted photoluminescence (PL) or so-called an inverse PL shift. Using time-correlated single photon counting, ultraviolet photoelectron spectroscopy, and low-temperature PL measurements, it is revealed that the CNDs are composed of sp(2) clusters with certain energy gaps and their oleylamine ligands act as auxochromes to reduce the energy gaps. This insight can provide a plausible explanation on the origin of the inverse PL shift which has been debatable over a past decade. To explore the potential of the CNDs as photoactive materials, several prototypes of CND-based optoelectronic devices, including multicolored light-emitting diodes and air-stable organic solar cells, are demonstrated. This study could shed light on future applications of the CNDs and further expedite the development of other related fields.X1111093sciescopu

Freestanding Luminescent Films of Nitrogen-Rich Carbon Nanodots toward Large-Scale Phosphor-Based White-Light-Emitting Devices

In this work, nitrogen-rich carbon nanodots (CNDs) are prepared by the emulsion-templated carbonization of polyacrylamide. The formation mechanism and chemical structure are investigated by infrared, nuclear magnetic resonance, and X-ray photoelectron spectroscopies. Transmission electron microscopy also reveals that the obtained CNDs have well-developed graphitic structure and narrow size distribution without any size selection procedure. We vary the molecular weight of the polymer to control the size of the CNDs and finally obtain the CNDs rendering bright visible light under UV illumination with a high quantum yield of 40%. Given that the CNDs are worth utilizing in phosphor applications, we fabricate large-scale (20 X 20 cm) freestanding luminescent films of the CNDs based on a poly(methyl methacrylate) matrix. The polymer matrix can not only provide mechanical support but also disperse the CNDs to prevent solid-state quenching. For practical application, we demonstrate white LEDs consisting of the films as color converting phosphors and InGaN blue LEDs as illuminators. Such white LEDs exhibit no temporal degradation in the emission spectrum under practical operation conditions. This study would suggest a promising way to exploit the luminescence from solid-state CNDs and offer strong potential for future CND based solid-state lighting systems.X11128118sciescopu

Corrigendum: High Color-Purity Green, Orange, and Red Light-Emitting Diodes Based on Chemically Functionalized Graphene Quantum Dots (vol 6, 24205, 2016)

Y

High color-purity green, orange, and red light-emitting didoes based on chemically functionalized graphene quantum dots

Chemically derived graphene quantum dots (GQDs) to date have showed very broad emission linewidth due to many kinds of chemical bondings with different energy levels, which significantly degrades the color purity and color tunability. Here, we show that use of aniline derivatives to chemically functionalize GQDs generates new extrinsic energy levels that lead to photoluminescence of very narrow linewidths. We use transient absorption and time-resolved photoluminescence spectroscopies to study the electronic structures and related electronic transitions of our GQDs, which reveals that their underlying carrier dynamics is strongly related to the chemical properties of aniline derivatives. Using these functionalized GQDs as lumophores, we fabricate light-emitting didoes (LEDs) that exhibit green, orange, and red electroluminescence that has high color purity. The maximum current efficiency of 3.47 cd A(-1) and external quantum efficiency of 1.28% are recorded with our LEDs; these are the highest values ever reported for LEDs based on carbon-nanoparticle phosphors. This functionalization of GQDs with aniline derivatives represents a new method to fabricate LEDs that produce natural color.Y

Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size

Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter D-B (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nano crystals (NCs) in a dimension > D-B (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than D-B show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and per fluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (similar to 60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs.1158sciescopu