Electroluminescence from light-emitting diodes by using water-dispersed ZnSe nanocrystals and polymer

Electroluminescence was obtained from an indium-tin-oxide/poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV): ZnSe/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/ 8-tris-hydroxyquinoline (Alq3)/LiF/Al structured device, in which ZnSe nanocrystals were synthesized in aqueous solution by using mercapto-acetate acid as stabilizer. The mechanical, electrical, and optical properties of the device were established. The photoluminescence and electroluminescence spectra changed with the mass ratio of ZnSe to MEH-PPV in the composite. Comparison between the absorption spectra and photoluminescence spectra of the ZnSe nanocrystals and the MEH-PPV thin film exhibited an effective energy transfer from ZnSe nanocrystals to MEH-PPV, which was one reason for the difference between the photoluminescence and electroluminescence spectra of the MEH-PPV: ZnSe composite film. The recombination mechanism of ZnSe nanocrystals under photo excitation and electric injection was investigated with the help of a single layer device structure of indium-tin-oxide/ZnSe/LiF/Al.     

Hybrid nanocrystal/polymer solar cells based on tetrapod-shaped CdSe(x)Te(1-x) nanocrystals

A series of ternary tetrapodal nanocrystals of CdSe(x)Te(1-x) with x = 0?(CdTe), 0.23, 0.53, 0.78, 1 (CdSe) were synthesized and used to fabricate hybrid nanocrystal/polymer solar cells. Herein, the nanocrystals acted as electron acceptors, and poly(2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV) was used as an electron donor. It was found that the open circuit voltage (V(oc)), short-circuit current (J(sc)) and power conversion efficiency (η) of the devices all increased with increasing Se content in the CdSe(x)Te(1-x) nanocrystals under identical experimental conditions. The solar cell based on the blend of tetrapodal CdSe nanocrystals and MEH-PPV (9:1?w/w) showed the highest power conversion efficiency of 1.13% under AM 1.5, 80?mW?cm(-2), and the maximum incident photon to converted current efficiency (IPCE) of the device reached 47% at 510?nm. The influence of nanocrystal composition on the photovoltaic properties of the hybrid solar cells was explained by the difference of the band level positions between MEH-PPV and the nanocrystals.     

Aqueous synthesis and bio-imaging application of highly luminescent and low cytotoxicity Mn-doped ZnSe nanocrystals

In this paper, Mn²⁺-doped ZnSe quantum dots (Mn:ZnSe d-dots) are synthesized successfully by a nucleation-doping method in aqueous solution with 3-Mercaptopropionic acid as the stabilizer and sodium selenite as the Se source for the first time in contrast to the use of oxygen-sensitive NaHSe or H₂Se as Se source. The obtained quantum dots performed strong band-edge luminescence, narrow size distribution and weak trap emission without post-treatments. The results of transmission electron microscopy and X-ray diffraction demonstrated the small particle size (3-4 nm), good monodispersity and ZnSe(S) alloyed structure of as-prepared quantum dots. Finally, the biological application of luminescent Mn²⁺-doped ZnSe nanocrystals to PK 15 cell imaging was also illustrated, which showed excellent biocompatibility and low cytotoxicity, implying their potential as a new generation of fluorescent labels for biological assays, tissues, and even in vivo investigations.     

Traps and performance of MEH-PPV/CdSe(ZnS) nanocomposite-based organic light-emitting diodes

We report the fabrication and investigations of organic light-emitting diodes (OLEDs) using a composite made by mixing poly[2-methoxy-5(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) with CdSe/ZnS core/shell quantum dots (QDs). The electroluminescence efficiency of the studied devices was found to be improved as compared to devices using MEH-PPV. Moreover, the current density decreased with increasing QD concentration. We checked the effects of QDs on the electrical transport by determining the trap states, making use of the charge-based deep level transient spectroscopy (Q-DLTS) technique. The most striking result obtained is the decrease in trap density when adding QDs to the MEH-PPV polymer film. These results suggest that QDs would heal defects in nanocomposite-based devices and that CdSe/ZnS QDs prevent the trap center formation.     

Investigation on photoconductive properties of MEH-PPV/CdSe-nanocrystal nanocomposites

The photoconductive properties of photodiodes based on nanocomposites of water-soluble CdSe nanocrystals and poly[2-methoxy-5-(2-ethylhexyloxy-p-phenylenevinylen)] (MEH-PPV) were investigated. The photoluminescence intensity of the nanocomposites decreased with the increasing weight ratios of CdSe nanocrystals to MEH-PPV. By comparing the photocurrent action spectra of the nanocomposite device and the pristine MEH-PPV device, it was found that the nanocomposite device exhibited a wider photocurrent action range. In addition, the nanocomposite device displayed an obvious photovoltaic effect upon illumination. The process of exciton dissociation and charge transfer between the interface of CdSe nanocrystals and MEH-PPV was discussed.     

'Giant' CdSe/CdS core/shell nanocrystal quantum dots as efficient electroluminescent materials: strong influence of shell thickness on light-emitting diode performance

We use a simple device architecture based on a poly(3,4-ethylendioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-coated indium tin oxide anode and a LiF/Al cathode to assess the effects of shell thickness on the properties of light-emitting diodes (LEDs) comprising CdSe/CdS core/shell nanocrystal quantum dots (NQDs) as the emitting layer. Specifically, we are interested in determining whether LEDs based on thick-shell nanocrystals, so-called "giant" NQDs, afford enhanced performance compared to their counterparts incorporating thin-shell systems. We observe significant improvements in device performance as a function of increasing shell thickness. While the turn-on voltage remains approximately constant for all shell thicknesses (from 4 to 16 CdS monolayers), external quantum efficiency and maximum luminance are found to be about one order of magnitude higher for thicker shell nanocrystals (≥13 CdS monolayers) compared to thinner shell structures (<9 CdS monolayers). The thickest-shell nanocrystals (16 monolayers of CdS) afforded an external quantum efficiency and luminance of 0.17% and 2000 Cd/m(2), respectively, with a remarkably low turn-on voltage of ~3.0 V.     

Shape control of doped semiconductor nanocrystals (d-dots)

Formation of Mn²⁺-doped ZnSe quantum dots (Mn:ZnSe d-dots) with both branched and nearly spherical shapes has been studied. Structure analysis indicates that the Mn²⁺ dopants were localized in the core of a branched nanocrystal. The growth of branched d-dots, rather than spherical ones, was achieved by simply varying the concentration of two organic additives, fatty acids, and fatty amines. The photoluminescence properties of the branched nanocrystals were explored and compared with those of the nearly spherical particles. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Solution-processed PbS quantum dot infrared photodetectors and photovoltaics

In contrast to traditional semiconductors, conjugated polymers provide ease of processing, low cost, physical flexibility and large area coverage. These active optoelectronic materials produce and harvest light efficiently in the visible spectrum. The same functions are required in the infrared for telecommunications (1,300-1,600 nm), thermal imaging (1,500 nm and beyond), biological imaging (transparent tissue windows at 800 nm and 1,100 nm), thermal photovoltaics (>1,900 nm), and solar cells (800-2,000 nm). Photoconductive polymer devices have yet to demonstrate sensitivity beyond approximately 800 nm (refs 2,3). Sensitizing conjugated polymers with infrared-active nanocrystal quantum dots provides a spectrally tunable means of accessing the infrared while maintaining the advantageous properties of polymers. Here we use such a nanocomposite approach in which PbS nanocrystals tuned by the quantum size effect sensitize the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) into the infrared. We achieve, in a solution-processed device and with sensitivity far beyond 800 nm, harvesting of infrared-photogenerated carriers and the demonstration of an infrared photovoltaic effect. We also make use of the wavelength tunability afforded by the nanocrystals to show photocurrent spectra tailored to three different regions of the infrared spectrum.     

Controlled synthesis and characterization of ZnSe quantum dots

Adopting improved metal-organic "Green method," Colloidal ZnSe quantum dots were synthesized by using cheap and low toxic zinc oxide (ZnO) in an organic solvent system of 1-hexadecylamine (HDA), lauric acid (LA) and tri-n-octylphosphine (TOP). The effects of HDA dosage, injection temperature, growth temperature and time on the microstructure and optical properties of ZnSe were studied by means of X-Ray diffraction(XRD), transmission electron microscopy (TEM), spectrofluorometers and ultraviolet spectrophotometer, respectively. The results showed that ZnSe quantum dots with the best range of the size evolution were obtained under the condition of injection at 280 degrees C and growth at 240 degrees C by choosing the optimal parameters of ZnO:HDA:LA= 1:2.1:5.2 and TOPSe = 1 mol/L. Its size became larger and the emission peak shifted obviously to red with increasing the growth time. Meanwhile, the obtained ZnSe was of the wurtzite structure, had good uniformity and fluorescent characteristics.     

On the absence of detectable carrier multiplication in a transient absorption study of InAs/CdSe/ZnSe core/Shell1/Shell2 quantum dots

Tunable femtosecond pump-near IR probe measurements on InAs/CdSe/ZnSe core/shell1/shell2 nanocrystal quantum dots were conducted to quantify spontaneous carrier multiplication previously reported in this system. Experimental conditions were chosen to eliminate the need for determining absolute wavelength dependent cross sections of the nanocrystals and allow direct comparison of band edge absorption bleach kinetics for different excitation energies up to 3.7 times the band gap. Results for two sample sizes show no signs of carrier multiplication within that range. This result is discussed in light of reports describing occurrence of this novel phenomenon in quantum dots based on this as well as numerous other semiconductor materials.     

One-step and rapid synthesis of high quality alloyed quantum dots (CdSe-CdS) in aqueous phase by microwave irradiation with controllable temperature

In this paper, we presented a seed-mediated approach for rapid synthesis of high quality alloyed quantum dots (CdSe-CdS) in aqueous phase by microwave irradiation with controllable temperature in 1 h. In the synthesis, CdSe seeds were first formed by the reaction of NaHSe and Cd²⁺, and then alloyed quantum dots (CdSe-CdS) were rapidly produced by releasing of sulfide ions from 3-mercaptopropionic acid as sulfide source with microwave irradiation. The alloyed quantum dots synthesized had good optical properties, the quantum yield was up to 25%, and the full width at half maximum of the emission spectrum peak was about 28 nm. The as-prepared alloyed CdSe-CdS QDs were characterized by XRD, XPS and ICP-AES in order to explore the structure and component of the alloyed nanocrystals and the reaction mechanism. We speculate that the alloyed CdSe-CdS quantum dots may exist a gradient internal structure according to our preliminary results.     

Photoelectronic behaviors of self-assembled ZnSe/ZnS/L-Cys quantum dots synthesized at low temperature

The photogenerated carriers’ transport and microstructure of self-assembled core–shell ZnSe/ZnS/L-Cys quantum dots (QDs), which was synthesized at room temperature, are studied via the surface photovoltaic and transient photovoltaic techniques, X-ray diffraction, high-resolution transmission electron microscopy, Fourier transform infrared spectroscopy and ultraviolet–visible absorption spectra. The results suggest that the ZnSe nanocrystals prepared at room temperature prefer to nucleate at (111) and (220) faces, and grow a shell–ZnS at (220) face rather than at (311) face. The quantum well depth in some interface space charge region (SCR) of the QDs prepared at room temperature is smaller than that prepared at 90 °C. The evolution of the band bending from a depletion layer to an accumulation layer may occur in the graded-band-gap and at the side of the interface SCR, as compared the QDs with p-type photovoltaic characteristic synthesized at room temperature to that at 90 °C. This electron structural shift may be ascribed to the reduced quantum well depth and then an obvious resonance quantum tunneling of the QDs synthesized at room temperature.     

Cu掺杂ZnSe高效量子点的合成及其光学特性研究

采用生长掺杂方式制备了Cu掺杂ZnSe高效量子点, 探索了不同Zn、Se前驱体配比对ZnSe晶核以及ZnSe:Cu量子点质量的影响, 并研究了Cu离子掺杂过程中的光谱特征。研究表明, 进一步通过在表面掺杂的ZnSe:Cu量子点上同质包覆ZnSe壳层, 能够实现其发光效率和稳定性的有效提高; 采用配体交换能够实现ZnSe:Cu量子点由油溶性到水溶性的转变。这种新型的掺杂量子点有望替代传统含Cd量子点应用于环境友好型固体发光器件和生物标记。     

Luminescent properties and excitation mechanism of ZnSe quantum dots embedded in ZnS Matrix

In this paper, we report alternative-current thin film electroluminescence structure with ZnSe quantum dots embedded in ZnS matrix as light-emitting center, i.e., ITO/SiO_x (100 nm)/[ZnS (10 nm)/ZnSe (1 nm)]₃₀/SiO_x (100 nm)/Al. Blue emissions at 390 and 477 nm are obtained in its alternative-current electroluminescent spectra. By studying its luminescent spectroscopy and brightness oscillogram of the device, we found that blue emission came from defect states at ZnSe/ZnS interface and the excitation mechanism was hot-electron impact.     

CdSe/ZnSe量子点的制备及电化学发光性能

利用ZnSe半导体纳米材料晶体结构与CdSe相似、带隙更宽的特点,采用水热法合成了核-壳型CdSe/ZnSe量子点。结果表明：温度在70~160℃时,ZnSe壳逐渐包裹在CdSe核上,反应时间在0~4 h时,内壳在核上是均匀包裹的,当核壳摩尔比为1∶3时,CdSe/ZnSe QDs的电化学发光性能最强,其电化学发光强度是CdSe量子点的6倍,且发光信号稳定。     

Photo- and electro-luminescent properties of 5,10,15,20-tetra-p-tolyl-21H,23H-porphine doped poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] films

In this work we studied both photoluminescence (PL) and electroluminescence (EL) properties of 5, 10, 15, 20-tetra-p-tolyl-21H, 23H-porphine (TTP) doped poly[2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylenevinylene] (MEH-PPV) with the weight percentages of 0, 0.5, 1, 3, 5, 8 and 12, respectively. In the process of PL the significant energy transfer occurs from MEH-PPV to TTP, even though there is a small spectral overlap between the absorption of TTP and the emission of MEH-PPV. For investigation of the process of EL a series of organic light-emitting diodes were fabricated with the device structure of ITO/PEDOT:PSS/TTP-doped polymer layer/Al (ITO = Indium Tin Oxides; PEDOT:PSS = poly (3,4-oxyethyleneoxythiophene): poly-(styrene sulfonate)). In devices in which the TTP was present at 5% the emission of EL was dominated by TTP; at lower doping levels MEH-PPV emission dominated. Moreover, multi-color emission was observed at the doping level below 5%. On the other hand, the mechanism for the EL process was reported.     

Investigation of photophysical, morphological and photovoltaic behavior of poly(p-phenylene vinylene) based polymer/oligomer blends

Two cyano oligo-phenylene-vinylenes [α-CNOPV and β-CNOPV] distinguished by the position of cyano (CN) group at the vinylic double bond were synthesized. The acceptor oligomer CNOPVs were blended with poly(2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene) MEH-PPV to achieve α and β blends. The pronounced influence of cyano position on the photophysical and morphological properties of blends was observed through UV-vis absorption, photoluminescence and atomic force microscopy. The optical characterization suggests wider spectral photon harvesting in α blends and more planar conformation of molecules in β blends. The steady-state and time-resolved photoluminescence study provides evidence for efficient energy transfer from α-CNOPV to MEH-PPV. On the other hand, the 3:1 β blend exhibits quenching of PL intensity indicative of charge transfer. In addition, the feasibility of MEH-PPV:CNOPV blends in organic photovoltaic devices have been investigated. The initial device parameters show that power conversion efficiency is as high as 0.05% in β 1:1 devices. The photovoltaic efficiencies were limited by weak exciton dissociation in α blends while poor morphology restricted the efficiency in β blends.     

Poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene)(MEH-PPV) /Nitrogen Containing Derivatives of Fullerene Composites: Optical Characterization and Application in Flexible Polymer Solar Cells

New soluble organofullerenes were synthesized by the reaction of organic amines and azides with the [60]fullerene. The comparative investigations of the IR- and optical absorption spectra of blends MEH-PPV/fullerene derivative in solutions and in films showed no ground-state interaction between the components. Photoluminescence (PL) experiments, and photocurrent-voltage measurements were performed on model photovoltaic (PV) cells. We found that PL of MEH-PPV is completely quenched by a small admixture of fullerene derivative which assumes a high efficiency of charge separation in the composite material. The photocurrent in the PV device containing fullerene derivative is two orders of magnitude higher than that in pure MEH-PPV. An attempt to observe the magnetic field spin effect (MFSE) on the photocurrent in MEH-PPV/fullerene composites was made.     

Phosphine-free synthesis of high-quality reverse type-I ZnSe/CdSe core with CdS/Cd(x)Zn(1 - x)S/ZnS multishell nanocrystals and their application for detection of human hepatitis B surface antigen

Highly photoluminescent (PL) reverse type-I ZnSe/CdSe nanocrystals (NCs) and ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs were successfully synthesized by a phosphine-free method. By this low-cost, 'green' synthesis route, more than 10 g of high-quality ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS NCs were synthesized in a large scale synthesis. After the overgrowth of a CdS/Cd(x)Zn(1 - x)S/ZnS multishell on ZnSe/CdSe cores, the PL quantum yields (QYs) increased from 28% to 75% along with the stability improvement. An amphiphilic oligomer was used as a surface coating agent to conduct a phase transfer experiment, core/multishell NCs were dissolved in water by such surface modification and the QYs were still kept above 70%. The as-prepared water dispersible ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs not only have high fluorescence QYs but also are extremely stable in various physiological conditions. Furthermore, a biosensor system (lateral flow immunoassay system, LFIA) for the detection of human hepatitis B surface antigen (HBsAg) was developed by using this water-soluble core/multishell NCs as a fluorescent label and a nitrocellulose filter membrane for lateral flow. The result showed that such ZnSe/CdSe/CdS/Cd(x)Zn(1 - x)S/ZnS core/multishell NCs were excellent fluorescent labels to detect HBsAg. The sensitivity of HBsAg detection could reach as high as 0.05 ng ml( - 1).     

Effect of shell layers on luminescence of colloidal CdSe/Zn(0.5)Cd(0.5)Se/ZnSe/ZnS core/multishell quantum dots

Colloidal CdSe/Zn(0.5)Cd(0.5)Se/ZnSe/ZnS core/multishell quantum dots (QDs) were synthesized by using the well developed successive ion layer adsorption and reaction (SILAR) technique. The UV-vis and PL spectra, TEM, X-ray diffraction and Raman measurement were performed to investigate the structure and optical properties of prepared QDs during the growth of shell layers, which indicated that the stress in CdSe core became stronger with the increasing shell thickness. Due to the gradual adjustment of the lattice parameters in the radial direction and the radial increase of the respective valence- and conduction-band offsets, the optical measurements show a significant enhancement in the photoluminescence quantum yield (QY) and an expedited radiative decay in QDs overcoated with thicker shell. The temperature-dependent optical spectra were measured, and the relation between the microstructure and the optical properties of these core/multishell quantum dots was discussed.