Quantum-dot-sensitized solar cells fabricated by the combined process of the direct attachment of colloidal CdSe quantum dots having a ZnS glue layer and spray pyrolysis deposition

We were able to attach CdSe quantum dots (QDs) having a ZnS inorganic glue layer directly to a mesoporous TiO(2) (mp-TiO(2)) surface by spray coating and thermal annealing. Quantum-dot-sensitized solar cells based on CdSe QDs having ZnS as the inorganic glue layer could easily transport generated charge carriers because of the intimate bonding between CdSe and mp-TiO(2). The application of spray pyrolysis deposition (SPD) to obtain additional CdSe layers improved the performance characteristics to V(oc) = 0.45 V, J(sc) = 10.7 mA/cm(2), fill factor = 35.8%, and power conversion efficiency = 1.7%. Furthermore, ZnS post-treatment improved the device performance to V(oc) = 0.57 V, J(sc) = 11.2 mA/cm(2), fill factor = 35.4%, and power conversion efficiency = 2.2%.     

A solid-state CdSe quantum dot sensitized solar cell based on a quaterthiophene as a hole transporting material

A hybrid quantum dot sensitized solar cell (QDSC) composed of CdSe quantum dots (QDs) as light harvesters and TiO(2) and 3,3'-didodecyl-quaterthiophene (QT12) as electron and hole conductors, respectively, has been fully processed in air. The sensitizer has been introduced into the TiO(2) nanoporous layer either by the successive ionic layer adsorption and reaction method or by attaching colloidal QDs either directly or through molecular cables (linkers). As previously observed for QDSCs based on liquid electrolytes, the efficiency depends on the way of QD attachment, the direct adsorption of QDs being the procedure yielding the best results. Thermal annealing was applied in order to enhance the device response under illumination. Remarkable open circuit potentials are attained (close to 1 V), leading to an efficiency of 0.34% (AM 1.5G) in initial tests. Although low, it ranks as one of the highest values reported for solid state QDSCs based on titanium dioxide and colloidal quantum dots.     

Enhancing the device performance of a blue light‐emitting copolymer using CdSe/ZnS quantum dots

An alternating triarylamine‐functionalized fluorene‐based copolymer synthesized using a Suzuki–Miyaura cross‐coupling procedure is used as blue emitting layer in polymer light‐emitting diodes (PLEDs). Subsequently, the effects of CdSe/ZnS quantum dots (QDs) on the optoelectronic properties of the copolymer are investigated. Therefore, CdSe/ZnS QDs are embedded into the copolymer matrix and hybrid PLEDs are fabricated. The devices comprised of CdSe/ZnS QDs reveal enhanced performances, yielding about 3.4 times more luminous efficiency than that of the device without QDs. Further enhancement is achieved by using electron transport layer; the luminous efficiency rose from 0.065 to 1.740 cd A^?1 for the hybrid PLEDs, corresponding to a superb 27‐fold intensification of the efficiency. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 147–156     

Synthesis of Mn-doped zinc blende CdSe nanocrystals for quantum dot-sensitized solar cells

Mn-doped CdSe quantum dots (QDs) with a zinc blende structure were synthesized via a phosphine-free method in octadecene (ODE) and oleic acid. The structure, size, morphology, and optical property of the QDs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–visible absorption spectra (UV–Vis), respectively. The QDs were assembled onto a microporous TiO₂ photoanode by an ex situ ligand exchange route. Quantum dot-sensitized solar cells (QDSCs) based on the above-synthesized QDs and polysulfide electrolytes were fabricated. The photovoltaic performance and impedance of the CdSe and Mn-doped CdSe QDSCs were further investigated. An improvement in efficiency to 1.84 % was achieved as compared with 0.94 % for the QDSCs based on the pure CdSe QDs. The improvement was ascribed to the existence of long-lived high-energy doping levels on the large-sized Mn-doped CdSe QDs, which provides a significant driving force for faster charge separation and electron transfer.     

Energy Relay from an Unconventional Yellow Dye to CdS/CdSe Quantum Dots for Enhanced Solar Cell Performance

A new design for a quasi‐solid‐state Forster resonance energy transfer (FRET) enabled solar cell with unattached Lucifer yellow (LY) dye molecules as donors and CdS/CdSe quantum dots (QDs) tethered to titania (TiO₂) as acceptors is presented. The Forster radius is experimentally determined to be 5.29 nm. Sequential energy transfer from the LY dye to the QDs and electron transfer from the QDs to TiO₂ is followed by fluorescence quenching and electron lifetime studies. Cells with a donor–acceptor architecture (TiO₂/CdS/CdSe/ZnS‐LY/S^2?‐multi‐walled carbon nanotubes) show a maximum incident photon‐to‐current conversion efficiency of 53 % at 530 nm. This is the highest efficiency among Ru‐dye free FRET‐enabled quantum dot solar cells (QDSCs), and is much higher than the donor or acceptor‐only cells. The FRET‐enhanced solar cell performance over the majority of the visible spectrum paves the way to harnessing the untapped potential of the LY dye as an energy relay fluorophore for the entire gamut of dye sensitized, organic, or hybrid solar cells.     

Easily manufactured TiO2 hollow fibers for quantum dot sensitized solar cells

TiO(2) hollow fibers with high surface area were manufactured by a simple synthesis method, using natural cellulose fibers as template. The effective light scattering properties of the hollow fibers, originating from their micron size, were observed by diffuse reflectance spectroscopy. In spite of the micrometric length of the TiO(2) hollow fibers, the walls were highly porous and high surface area (78.2 m(2) g(-1)) was obtained by the BET method. TiO(2) hollow fibers alone and mixed with other TiO(2) pastes were sensitized with CdSe quantum dots (QDs) by Successive Ionic Layer Adsorption and Reaction (SILAR) and integrated as a photoanode in quantum dot sensitized solar cells (QDSCs). High power conversion efficiency was obtained, 3.24% (V(oc) = 503 mV, J(sc) = 11.92 mA cm(-2), FF = 0.54), and a clear correspondence of the cell performance with the photoanode structure was observed. The unique properties of these fibers: high surface area, effective light scattering, hollow structure to facile electrolyte diffusion and the rather high efficiencies obtained here suggest that hollow fibers can be introduced as promising nanostructures to make highly efficient quantum dot sensitized solar cells.     

3-巯基丙酸修饰的CdSe/ZnS量子点的合成及测定牛血清白蛋白的研究

以3-巯基丙酸作为修饰剂,在水溶液中合成了稳定的CdSe/ZnS量子点(QDs),透射电镜观察所合成量子点的形貌近似球形,粒径约为25 nm.吸收光谱与荧光光谱的研究表明,CdSe QDs在410 nm处有最大吸收峰,而CdSe/ZnS QDs的最大吸收峰在470 nm处,CdSe/ZnS QDs的荧光强度是CdSe QDs的11倍.考察了缓冲溶液的体积、pH值、反应温度、反应时间对体系荧光的影响.在最佳实验条件下,体系的荧光强度与BSA的浓度呈线性关系,线性响应范围为0.746×10-7～4.48×10-7 mol/L,检出限为3.846×10-10 mol/L.并且CdSe/ZnS QDs荧光强度基本保持稳定,可达两个多月.该方法应用于合成样品的测定,结果满意.     

Toward highly efficient CdS/CdSe quantum dots-sensitized solar cells incorporating ordered photoanodes on transparent conductive substrates

A series of ordered photoanodic architectures (including ordered TiO(2) nanotube arrays (TNT), ZnO nanorods, ZnO/TiO(2) core/shell nanostructures) for CdS/CdSe sensitized solar cells (QDSCs), were fabricated directly on transparent conductive oxide glasses by a facile sol-gel assisted template process. The morphologies, optical and electrical properties of TNTs and CdS/CdSe co-sensitized TNTs have been demonstrated. The effect of CdSe deposition time on the cell performance was clarified, and the growth mechanism of the CdSe quantum dots on the surface of the TNTs has been proposed as well. Furthermore, the evolution of open-circuit photovoltage (V(oc)) towards CdSe deposition time has been investigated by electrochemical impedance spectroscopy (EIS). A promising light-to-electricity conversion efficiency of up to 4.61% has been achieved with 3 μm long TNT arrays, which is the best record for sandwich-type ordered TNT-based QDSCs.     

Preparation and characterization of thiacalix[4]arene coated water-soluble CdSe/ZnS quantum dots as a fluorescent probe for Cu2+ ions

Highly fluorescent water-soluble CdSe/ZnS (core/shell) quantum dots (QDs) as a fluorescent Cu2+ ion probe were synthesized using thiacalix[4]arene carboxylic acid (TCC) as a surface coating agent. Hydrophobic trioctylphosphine oxide (TOPO) capped CdSe/ZnS QDs were overcoated with TCC in tetrahydrofuran at room temperature, and deprotonation of the carboxyl groups of TCC resulted in the formation of water-soluble QDs. The surface structure of the QDs was characterized by using transmission electron microscopy (TEM) and fluorescence correlation spectroscopy (FCS). TEM images showed that TCC-coated QDs were monodispersed with the particle size (core-shell moiety) of approximately 5 nm. Hydrodynamic diameter of the TCC-coated QDs was determined to be 8.9 nm by FCS, showing that the thickness of the surface organic layer of the QDs was approximately 2 nm. These results indicate that the surface layer of TCC-coated QDs forms a bilayer structure consisting of TOPO and TCC molecules. TCC-coated CdSe/ZnS QDs were highly fluorescent (quantum yield, 0.21) compared to the QDs surface-modified with mercaptoacetic acid and mercaptoundecanoic acid. Fluorescence of the TCC-coated QDs was effectively quenched by Cu2+ ions even in the presence of other transition metal ions such as Cd2+, Zn2+, Co2+, Fe2+, and Fe3+ ions in the same solution. The Stern-Volmer plot for the fluorescence quenching by Cu2+ ions showed a linear relationship up to 30 microM of Cu2+ ions. The ion selectivity of TCC-coated QDs was determined by measurements of fluorescence responses towards biologically important transition metal ions (50 microM) including Fe2+, Fe3+, Co2+>Zn2+, Cd2+. The fluorescence of TCC-coated QDs was almost insensitive to other biologically important ions such as Na+, K+, Mg2+, and Ca2+, suggesting that TCC-coated QDs can be used as a fluorescent Cu2+ ion probe for biological samples. A possible quenching mechanism by Cu2+ ions was also discussed on the basis of a Langmuir-type adsorption isotherm.     

Forming water-soluble CdSe/ZnS QDs using amphiphilic polymers, stearyl methacrylate/methylacrylate copolymers with different hydrophobic moiety ratios and their optical properties and stability

The amphiphilic stearyl methacrylate/methylacrylic acid copolymers (PSMs) were used as phase transfer reagents to convert CdSe/ZnS core-shell quantum dots (QDs) in chloroform to water-soluble PSMs-coated quantum dots (PSM-QDs). The optical properties and stability of PSM-QDs were influenced by the hydrophobic moiety ratios of PSMs, the PSM/QDs mass/volume ratio and the reaction time. The resulting PSM-QDs on optimum reaction conditions retained 60% of the photoluminescence value of the original CdSe/ZnS QDs in chloroform. The carboxylate-based PSM-QDs survived UV irradiation in air for at least 15 days. Upon UV irradiation, the PSM-QDs became about 2 times brighter than the original CdSe/ZnS QDs in chloroform, and the UV-brightened PL can retain the brightness for at least several months. Experimental results further confirmed the stability of PSM-QDs against strong acid, photochemical and thermal treatments. In addition to good performance of PSM-QDs, the synthesis of PSM and the corresponding water-soluble QDs is relatively simple.     

基于量子点涂料的柔性光阳极及碳基对电极的制备和优化

首先制备出量子点(QDs)/TiO_2涂料,分别采用丝网印刷法与刀刮法将涂料涂覆于ITO/PET柔性基底上,结果表明刀刮法制备量子点敏化太阳电池(QDSCs)效果更佳,且具有普适性。基于铜片对电极所组装的ZnCuInSe,CdSe和CdSeTe量子点半柔性QDSCs最高效率分别达2.83%,2.46%和1.99%。另外,我们对石墨纸进行表面化学修饰以提高亲水性,再通过简单的连续离子交换吸附法(SILAR)在石墨纸上负载Cu_xS纳米粒子,制备出Cu_xS/GP柔性对电极,进一步组装成全柔性QDSCs,获得了2.13%光电转化效率。     

基于量子点涂料的柔性光阳极及碳基对电极的制备和优化

首先制备出量子点（QDs）/TiO₂涂料,分别采用丝网印刷法与刀刮法将涂料涂覆于ITO/PET柔性基底上,结果表明刀刮法制备量子点敏化太阳电池（QDSCs）效果更佳,且具有普适性。基于铜片对电极所组装的ZnCuInSe,CdSe和CdSeTe量子点半柔性QDSCs最高效率分别达2.83%,2.46%和1.99%。另外,我们对石墨纸进行表面化学修饰以提高亲水性,再通过简单的连续离子交换吸附法（SILAR）在石墨纸上负载Cu_xS纳米粒子,制备出Cu_xS/GP柔性对电极,进一步组装成全柔性QDSCs,获得了2.13%光电转化效率。     

Nanoscale connectivity in a TiO2/CdSe quantum dots/functionalized graphene oxide nanosheets/Au nanoparticles composite for enhanced photoelectrochemical solar cell performance

Electron transfer dynamics in a photoactive coating made of CdSe quantum dots (QDs) and Au nanoparticles (NPs) tethered to a framework of ionic liquid functionalized graphene oxide (FGO) nanosheets and mesoporous titania (TiO(2)) was studied. High resolution transmission electron microscopy analyses on TiO(2)/CdSe/FGO/Au not only revealed the linker mediated binding of CdSe QDs with TiO(2) but also, surprisingly, revealed a nanoscale connectivity between CdSe QDs, Au NPs and TiO(2) with FGO nanosheets, achieved by a simple solution processing method. Time resolved fluorescence decay experiments coupled with the systematic quenching of CdSe emission by Au NPs or FGO nanosheets or by a combination of the latter two provide concrete evidences favoring the most likely pathway of ultrafast decay of excited CdSe in the composite to be a relay mechanism. A balance between energetics and kinetics of the system is realized by alignment of conduction band edges, whereby, CdSe QDs inject photogenerated electrons into the conduction band of TiO(2), from where, electrons are promptly transferred to FGO nanosheets and then through Au NPs to the current collector. Conductive-atomic force microscopy also provided a direct correlation between the local nanostructure and the enhanced ability of composite to conduct electrons. Point contact I-V measurements and average photoconductivity results demonstrated the current distribution as well as the population of conducting domains to be uniform across the TiO(2)/CdSe/FGO/Au composite, thus validating the higher photocurrent generation. A six-fold enhancement in photocurrent and a 100 mV increment in photovoltage combined with an incident photon to current conversion efficiency of 27%, achieved in the composite, compared to the inferior performance of the TiO(2)/CdSe/Au composite imply that FGO nanosheets and Au NPs work in tandem to promote charge separation and furnish less impeded pathways for electron transfer and transport. Such a hierarchical rapid electron transfer model can be adapted to other nanostructures as well, as they can favorably impact photoelectrochemical performance.     

Identification of cadmium containing metabolites in HepG2 cells after treatment with cadmium-selenium quantum dots

The transformation of quantum dots (QDs) by organisms has attracted broad attention but remains unclear. Understanding of the metabolites helps to reveal the transformation pathway of QDs. Cd containing-metallothionein (MT) are the main species formed by Cd released from CdSe QDs in HepG2 cells, while speciation analysis of Cd containing MTs remains a challenge because MTs has several subisoforms and can bind with several metals. Herein, we built a hyphenated platform for speciation analysis of QDs in HepG2 cells after treatment with CdSe/ZnS QDs. The Cd-containing MTs were separated in reversed phase high performance liquid chromatography (RP-HPLC) and subsequently online detected by inductively coupled plasma mass spectrometry (ICP-MS) and electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Q-TOF-MS) parallelly. Four groups of Cd-containing metabolites were found by detecting Cd in ICP-MS. Their structures were identified in ESI-Q-TOF-MS and further confirmed with standards of four subisoforms of MT, including N-terminal acetylation MT2a, N-terminal acetylation MT1e, N-terminal acetylation MT1g and MT1m. Each group of them contains various stoichiometry of Cd/Zn. The metabolites of QDs remain same while the concentrations of each metabolite and its stoichiometry of Cd/Zn vary for different incubation concentration/time. This work provides a new parallel hyphenation technique of HPLC-ICP-MS/ESI-MS with high separation resolution and powerful detection ability, and the obtained results provide detailed metabolism information of QDs in HepG2 cells after treatment of CdSe/ZnS QDs, contributing to deep exploration of the functional mechanisms of QDs in organisms.     

Optical properties of CdSe and CdSe/ZnS quantum dots dispersed in solvents of different polarity

Original organic capping TOPO/TOP groups of CdSe and CdSe/ZnS quantum dots (QDs), from mother solution were replaced with 2_mercaptoethanol, which was chosen as model compound, in order to achieve water solubility. Obtained water dispersions of CdSe and CdSe/ZnS QDs were characterized by UV/VIS absorption and luminescence techniques. Luminescence measurements revealed that bare cores are very sensitive to surface capping, transfer into water diminished emission intensity. Core/shell, CdSe/ZnS, QDs are much more resistant to changes of the capping and solvent, and significant part of emission intensity was preserved in water. The article is published in the original.     

TiO2微球的合成及其作为散射层在量子点敏化太阳能电池中的应用

以十六烷基三甲基溴化铵（CTAB）为模板剂,通过TiCl₄在乙醇水溶液中的直接水解,制备了介孔TiO₂微球. X射线衍射（XRD）结果表明所制备的微球晶型为金红石,扫描电镜（SEM）结果显示微球的直径大约为700 nm,由粒径约为16 nm的小颗粒堆积而成. 通过刮涂法制备了在TiO₂小颗粒层上涂覆有作为散射层的TiO₂微球和未涂覆微球的薄膜. 并通过化学浴沉积（CBD）的方法在膜上生长CdS/CdSe量子点,得到了量子点敏化太阳能电池（QDSCs）. 紫外吸收和漫反射结果表明,这种微球结构有利于量子点的沉积,具有较强的光散射作用,有效地增加了光线的收集,从而提高了电池的光电流,最终得到了4.5%的光电转换效率,比不加散射层的电池的效率高27.7%,也比利用传统散射层（由20 nm TiO₂ 小颗粒和400 nm TiO₂ 固体颗粒组成）的电池效率高10.2%. 我们把电池效率的提升归因于较强的光散射作用和较长的电子寿命.     

Quantum dot solar cells. harvesting light energy with CdSe nanocrystals molecularly linked to mesoscopic TiO2 films

By using bifunctional surface modifiers (SH-R-COOH), CdSe quantum dots (QDs) have been assembled onto mesoscopic TiO(2) films. Upon visible light excitation, CdSe QDs inject electrons into TiO(2) nanocrystallites. Femtosecond transient absorption as well as emission quenching experiments confirm the injection from the excited state of CdSe QDs into TiO(2) nanoparticles. Electron transfer from the thermally relaxed s-state occurs over a wide range of rate constant values between 7.3 x 10(9) and 1.95 x 10(11) s(-1). The injected charge carriers in a CdSe-modified TiO(2) film can be collected at a conducting electrode to generate a photocurrent. The TiO(2)-CdSe composite, when employed as a photoanode in a photoelectrochemical cell, exhibits a photon-to-charge carrier generation efficiency of 12%. Significant loss of electrons occurs due to scattering as well as charge recombination at TiO(2)/CdSe interfaces and internal TiO(2) grain boundaries.     

Graphene quantum dots assisted photovoltage and efficiency enhancement in CdSe quantum dot sensitized solar cells

CdSe quantum dot sensitized solar cells(QDSCs) modified with graphene quantum dots(GQDs) have been successfully achieved in this work for the first time. Satisfactorily, the optimized photovoltage(Voc) of the modified QDSCs was approximately 0.04 V higher than that of plain CdSe QDSCs, consequently improving the photovoltaic performance of the resulting QDSCs. Served as a novel coating on the CdSe QD sensitized photoanode, GQDs played a vital role in improving Vocdue to the suppressed charge recombination which has been confirmed by electron impedance spectroscopy as well as transient photovoltage decay measurements. Moreover, different adsorption sequences, concentration and deposition time of GQDs have also been systematically investigated to boost the power conversion efficiency(PCE) of CdSe QDSCs. After the coating of CdSe with GQDs, the resulting champion CdSe QDSCs exhibited an improved PCE of 6.59% under AM 1.5G full one sun illumination.     

Employing Core‐Shell Quantum Dots as Triplet Sensitizers for Photon Upconversion

A new family of surface‐functionalized CdSe/ZnS core‐shell quantum dots (csQD) has been developed, which work as triplet sensitizers for triplet‐triplet annihilation‐based photon upconversion (TTA‐UC). The surface modification of csQD with acceptor molecules plays a key role in the efficient relay of the excited energy of csQD to emitter molecules in the bulk solution, where the generated emitter triplets undergo triplet‐triplet annihilation that leads to photon upconversion. Interestingly, improved UC properties were achieved with the core‐shell QDs compared with core‐only CdSe QDs (cQD). The threshold excitation intensity, which is defined as the necessary irradiance to achieve efficient TTA process, decreases by more than a factor of four. Furthermore, the total UC quantum yield is enhanced more than 50‐fold. These enhancements should be derived from better optical properties of csQD, in which the non‐radiative surface recombination sites are passivated by the shell layer with wider bandgap.     

Probing biocatalytic transformations with CdSe-ZnS QDs

CdSe/ZnS QDs enable the optical probing of the biocatalytic oxidation of tyrosine derivatives and of the scission of peptides by thrombin. CdSe/ZnS QDs were modified with tyrosine methyl ester or with a tyrosine-containing peptide. The tyrosine units were reacted with tyrosinase/O2 to yield the respective l-DOPA and quinone derivatives. The luminescence of QDs modified by the enzyme-generated quinone units is quenched. The quinone-functionalized peptide associated with the QDs was cleaved by thrombin, a process that restored the luminescence of the QDs.