Type II hybrid structures of TiO2 nanorods conjugated with CdS quantum dots: assembly and optical properties

We developed a novel method to assemble TiO₂ nanorods conjugated with CdS quantum dots by L-cysteine molecular linker for type II semiconducting hybrid structure. The XRD patterns indicate that the CdS quantum dots perform the cubic phase structure, and TEM images show that CdS quantum dots are well dispersed on the surfaces of anatase TiO₂ nanorods with little agglomeration. The UV-vis absorption spectra reveal the bandgap alignment in type II configuration between CdS QDs and TiO₂ nanorods.     

Two-step annealed CdS/CdSe co-sensitizers for quantum dot-sensitized solar cells

CdS/CdSe co-sensitizers on TiO₂ films were annealed using a two-step procedure; high temperature (300 °C) annealing of TiO₂/CdS quantum dots (QDs), followed by low temperature (150 °C) annealing after the deposition of CdSe QDs on the TiO₂/CdS. For comparison, two types of films were prepared; CdS/CdSe-assembled TiO₂ films conventionally annealed at a single temperature (150 or 300 °C) and non-annealed films. The 300 °C-annealed TiO₂/CdS/CdSe showed severe coalescence of CdSe QDs, leading to the blocked pores and hindered ion transport. The QD-sensitized solar cell (QD-SSC) with the 150 °C-annealed TiO₂/CdS/CdSe exhibited better overall energy conversion efficiency than that with the non-annealed TiO₂/CdS/CdSe because the CdSe QDs annealed at a suitable temperature (150 °C) provided better light absorption over long wavelengths without the hindered ion transport. The QD-SSC using the two-step annealed TiO₂/CdS/CdSe increased the cell efficiency further, compared to the QD-SSC with the 150 °C-annealed TiO₂/CdS/CdSe. This is because the 300 °C-annealed, highly crystalline CdS in the two-step annealed TiO₂/CdS/CdSe improved electron transport through CdS, leading to a significantly hindered recombination rate.     

ZnS overlayer on in situ chemical bath deposited CdS quantum dot-assembled TiO2 films for quantum dot-sensitized solar cells

ZnS overlayers were deposited on the CdS quantum dot (QD)-assembled TiO₂ films, where the CdS QDs were grown on the TiO₂ by repeated cycles of the in situ chemical bath deposition (CBD). With increasing the CdS CBD cycles, the CdS QD-assembled TiO₂ films were transformed from the TiO₂ film partially covered by small CdS QDs (Type I) to that fully covered by large CdS QDs (Type II). The ZnS overlayers significantly improved the overall energy conversion efficiency of both Types I and II. The ZnS overlayers can act as the intermediate layer and energy barrier at the interfaces. However, the dominant effects of the ZnS overlayers were different for the Types I and II. For Type I, ZnS overlayer dominantly acted as the intermediate layer between the exposed TiO₂ surface and the electrolyte, leading to the suppressed recombination rate for the TiO₂/electrolyte and the significantly enhanced charge-collection efficiency. On the contrary, for Type II, it dominantly acted as the efficient energy barrier at the interface between the CdS QDs and the electrolyte, leading to the hindered recombination rate from the large CdS QDs to the electrolyte and thus enhanced electron injection efficiency.     

Effect of CdS modification on photoelectric properties of TiO2/PbS quantum dots bulk heterojunction

TiO₂/PbS(CdS) quantum dots (QDs) bulk heterojunction has been fabricated by successive ionic layer adsorption and reaction method via alternate deposition of PbS and CdS QDs. In comparison with TiO₂/PbS heterojunction, the incident photon to current conversion efficiency was increased almost 50% in the visible region. Meantime, the short-circuit current and open-circuit voltage were enhanced 200% and 35% respectively. The influence mechanism of CdS is related to reduction of trap state density at TiO₂/PbS interface and PbS QDs surface by the discussion of the dark current density–voltage curves, the transient photocurrent response curves and the electrochemical impedance spectra spectroscopy (EIS).     

A comparative study on the performance of hybrid solar cells containing ZnSTe QDs in hole transporting layer and photoactive layer

In this paper, ZnSTe quantum dots-based hybrid solar cells (HSC) with two different device architectures have been investigated. The improved performance of the poly(3-hexylthiophene) (P3HT) and [6,6]phenyl C₇₁ butyric acid methyl ester (PC₇₁BM)-based bulk heterojunction (BHJ) solar cells by the incorporation of ZnSTe quantum dots (QDs) with an average size of 2.96 nm in PEDOT:PSS layer and active layer that have been demonstrated. Although the efficiency of both types of devices is almost the same, a close comparison reveals different reasons behind their improved performance. The device prepared with QDs in the HTL has shown reduced series resistance, increased shunt resistance, and improved mobility. On the other hand, QDs in the photoactive layer demonstrates increased photo-generation leading to improved efficiency.     

The Dynamic Resistance of CdS/CdSe/ZnS Co-Sensitized TiO2 Solar Cells

Quantum dots' sensitized solar cells (QDSSCs) can create the high-performance and low-cost photovoltaic in the future. In this study, we synthesized the film of TiO₂/CdS/CdSe/ZnS photoanodes by successive ionic layer adsorption reaction (SILAR) method. The absorption spectra, photoluminescent spectra and electrochemical impedance spectra (EIS) of the film TiO₂/CdS/CdSe/ZnS photoanodes show that the structure of energy levels in the conduction band (CB) of photoanode materials CdS, CdSe, and ZnS quantum dots (QDs) can absorb a great number of photons in each region and inject stimulated electrons quickly into the conduction band (CB) of TiO₂. Furthermore, we also studied the influence of the SILAR cycles on the dynamic resistance, the lifetime of electrons in QDSSCs through Nyquist and Bode.     

Investigation of Interfacial Charge Separation at PbS QDs/(001) TiO2 Nanosheets Heterojunction Solar Cell

In the recent years, the heterojunction solar cells based on quantum dots (QDs) have attracted attention due to strong light absorbing characteristics and the size effect on the bandgap tuning. This paper reports on the kinetics of interfacial charge separation of PbS QDs/(001) TiO₂ nanosheets heterojunction solar cells. PbS QDs are deposited using a bifunctional linker molecule on two different TiO₂ films, i.e., TiO₂ nanosheets (with 001 dominant exposed facet) and TiO₂ nanoparticles (with 101 dominant exposed facet). Upon bandgap excitation, electrons are transferred from the PbS QDs conduction band to the lower lying conduction band of TiO₂. Based on the ultrafast pump‐probe laser spectroscopy technique, the kinetics of charge separation is scrutinized at the PbS/TiO₂ interface. The interfacial charge separation at PbS/TiO₂ nanosheets films made of (001) dominant exposed facets is five times faster than that on (101) dominant exposed facets TiO₂ nanoparticles. The quantum yields for charge injection are higher for the (001) TiO₂ nanosheets than the (101) TiO₂ nanoparticles due to enhanced interfacial interaction with (001) surface compared to the (101) nanoparticles. The superior interfacial charge separation at PbS/(001) nanosheets respect to PbS/(101) nanoparticles is consistent with the higher photocurrent and enhanced power conversion efficiency in the PbS QDs/(001) TiO₂ heterojunction solar cell. The use of (001) TiO₂ nanosheets can be a better alternative to conventional mesoporous TiO₂ films in QD heterojunction solar cells and perovskites‐based heterojunction solar cells.     

Assembly,characterization, and photocatalytic activities of TiO<Subscript>2</Subscript> nanotubes/CdS quantum dots nanocomposites

The semiconductor quantum dots (QDs) can be very efficient to tune the response of photocatalyst of TiO₂ to visible light. In this study, CdS QDs formed in situ with about 8 nm have been successfully deposited onto the surfaces of TiO₂ nanotubes (TNTs) to form TNTs/CdS QDs nanocomposites by use of a simple bifunctional organic linker, thiolactic acid. The diffuse reflectance spectroscopy (DRS) spectra of as prepared samples showed that the absorption edge of the TNTs/CdS composite is extended to visible range, with absorption edge at 530 nm. The photocatalytic activity and stability of TNTs/CdS were also evaluated for the photodegradation of rhodamine B. The results showed that when TNTs/CdS QDs was used, photocatalytic degradation of RhB under visible light irradiation reached 91.6%, higher than 45.4 and 30.5% for P25 and TNTs, respectively. This study indicated that the TNTs/CdS QDs nanocomposites were superior catalysts for photodegradation under visible light irradiation compared with TNTs and P25 samples, which may find wide application as a powerful photocatalyst in environmental field.     

Temperature-dependent photovoltaic behavior of CdSe quantum dots/P3HT hybrid thinfilm

An organic–inorganic hybrid solar cell based on CdSe quantum dots (QDs) and poly(3-hexylthiophene) (P3HT) was fabricated. Its temperature-dependent photovoltaic behaviors, such as I–V characteristic curves and open circuit voltage (V_oc) transient response, were measured. The photovoltaic behavior of this hybrid thin film device was similar with that of organic thin film solar cells, according to analysis results based on the equivalent circuit method. The exact carrier lifetime was remarkably different between under low-temperature region and under temperature above 197 K.     

Effect of ZnS layers on optical properties of prepared CdS/TiO<Subscript>2</Subscript> nanotube arrays for photocatalyst

The TiO₂ nanotube arrays (TiO₂ NTAs) prepared by re-oxidation were chosen as basement. The NTAs prepared through re-oxidation show smoother surface and more uniform tube mouth on large scale compared with the first as-grown one. We use successive ionic layer adsorption and reaction method to deposit quantum dots (ZnS and CdS) onto the sample successively. The findings reveal that two kinds of quantum dots (～10 nm) distribute regularly and the nanotube mouth is open. From the UV–Vis absorption spectrum of samples, the red shift occurs after the sedimentation of the two quantum dots, which proves that the double modification can expand the absorption to 650 nm. Among all specimens, the sample produced by co-deposition has the highest speed of catalytic efficiency of 90.7% compared with bare TiO₂ NTAs (52.9%) and just CdS QDs sensitized sample (65.8%). In the test of photocatalysis durability, the decay percentages of CdS/TiO₂ NTAs and ZnS/CdS/TiO₂ NTAs were 35.8 and 48.4%, respectively, which means that the ZnS passivation layer plays a crucial role in enhancing photocatalytic activities.     

Synthesis of hybrid organic–inorganic nanocomposite materials based on CdS nanocrystals for energy conversion applications

Efficient solar energy conversion is strongly related to the development of new materials with enhanced functional properties. In this context, a wide variety of inorganic, organic, or hybrid nanostructured materials have been investigated. In particular, in hybrid organic–inorganic nanocomposites are combined the convenient properties of organic polymers, such as easy manipulation and mechanical flexibility, and the unique size-dependent properties of nanocrystals (NCs). However, applications of hybrid nanocomposites in photovoltaic devices require a homogeneous and highly dense dispersion of NCs in polymer in order to guarantee not only an efficient charge separation, but also an efficient transport of the carriers to the electrodes without recombination. In previous works, we demonstrated that cadmium thiolate complexes are suitable precursors for the in situ synthesis of nanocrystalline CdS. Here, we show that the soluble [Cd(SBz)₂]₂·(1-methyl imidazole) complex can be efficiently annealed in a conjugated polymer obtaining a nanocomposite with a regular and compact network of NCs. The proposed synthetic strategies require annealing temperatures well below 200 °C and short time for the thermal treatment, i.e., less than 30 min. We also show that the same complex can be used to synthesize CdS NCs in mesoporous TiO₂. The adsorption of cadmium thiolate molecule in TiO₂ matrix can be obtained by using chemical bath deposition technique and subsequent thermal annealing. The use of NCs, quantum dots, as sensitizers of TiO₂ matrices represents a very promising alternative to common dye-sensitized solar cells and an interesting solution for heterogeneous photocatalysis.     

Electrostatic assembly of CdTe quantum dots with different charged ligands into TiO2 porous film for solar cells

We have demonstrated an approach for the electrostatic assembly of CdTe quantum dots (QDs) with different charged ligands as sensitizers, achieving high coverage and good dispersion in TiO₂ porous films. The CdTe QD-sensitized TiO₂ porous films were subjected to thermal annealing in a high vacuum chamber to remove the ligand linker, resulting in the formation of direct heterojunctions between the bare CdTe QDs and TiO₂ for a favorable charge transfer. The as-received CdTe QD-sensitized TiO₂ porous films were employed as photoanodes for quantum dot-sensitized solar cells (QSSCs), and the photocurrent density reached as high as 4.69 mA/cm² under a standard illumination condition of simulated AM 1.5G (100 mW/cm²).     

Luminescent Properties of Hybrid Nanostructures Based on Quantum Dots of CdS,Europium 1,3-Diketonate,and Methylene Blue Molecules

The luminescent properties of hybrid nanostructures constructed from colloidal quantum dots (QDs) of CdS passivated with thioglycolic acid, europium(III) tris(tenoyltrifluoroacetonate), and methylene blue dye molecules are studied. Spectral features typical for the formation of core/shell QDs of the CdS/CdS:Eu³⁺ type are found. It is noted that the adsorption of the europium complex at the QD interfaces and the formation of QDs of the CdS/TGA/Eu³⁺ are probable. Spectral patterns that reveal nonradiative energy transfer from the recombination luminescence centers of CdS QDs to the Eu³⁺ ions in the CdS/CdS:Eu³⁺ and CdS/TGA/Eu³⁺ structures are obtained. This is manifested in quenching the recombination luminescence of QDs and in the ignition of the intracentric luminescence of Eu³⁺, which enhance with an increase in the concentration of the europium complex. When such structures are combined with methylene blue molecules, the half-width of the absorption spectra is found to increase by 10–15% with an unchanged position of the absorption band maximum. With an increase in the concentration of methylene blue molecules, decreases in the intensity of the recombination luminescence band of CdS QDs at a wavelength of 530 nm and in the luminescence intensity of Eu³⁺ ions and simultaneously the rise up of the fluorescence of methylene blue at a wavelength of about 675 nm are observed. At the same time, a decrease in the luminescence lifetime of the bands of QDs and europium ions are observed. It is concluded that the nonradiative excitation energy transfer from both the recombination luminescence centers and Eu³⁺ ions to methylene blue molecules takes place.     

TiO<Subscript>2</Subscript> Nanorod Arrays Sensitized with CdS Quantum Dots for Solar Cell Applications: Effects of Rod Geometry on Photoelectrochemical Performance

CdS quantum dot (QD) sensitized TiO₂ nanorod array (NRA) film electrodes with different rod geometries were fabricated via a solvothermal route followed by a sequentialchemical bath deposition (S-CBD) process. By controlling the solution growth conditions, the rod geometries, especially the tip structures, of the TiO₂ NRAs were tuned. The results indicated that the vertically aligned hierarchical NRAs possessed conically shaped tip geometry, which was favorable for film electrodes due to the reduced reflectance, enhanced light harvesting, fast charge-carrier separation and transfer, suppression of carrier recombination, sufficient electrolyte penetration and subsequent efficient QD assembly. CdS QD sensitized TiO₂ NRA film electrodes with tapered tips exhibited an enhanced photoelectrochemical (PEC) performance, a photocurrent intensity of 5.13 mA/cm² at a potential of 0 V vs. saturated calomel electrode, an open-circuit potential of −0.68 V vs. saturated calomel electrode and an incident photon to current conversion efficiency (IPCE) of 22% in the visible-light region from 400 to 500 nm. The effects of rod geometry on the optical absorption, reflectance, hydrophilic properties and PEC performance of bare TiO₂ and CdS QD sensitized TiO₂ NRA film electrodes were investigated. The mechanism of charge-carrier generation and transfer in these CdS QD sensitized solar cells based on vertically aligned TiO₂ nanorods is discussed.     

Co-sensitized quantum dot solar cell based on ZnO nanowire

An efficient photoelectrode is fabricated by sequentially assembled CdS and CdSe quantum dots (QDs) onto a ZnO-nanowire film. As revealed by UV-vis absorption spectrum and scanning electron microscopy (SEM), CdS and CdSe QDs can be effectively adsorbed on ZnO-nanowire array. Electrochemical impedance spectroscopy (EIS) measured demonstrates that the electron lifetime for ZnO/CdS/CdSe (13.8 ms) is calculated longer than that of ZnO/CdS device (6.2 ms), which indicates that interface charge recombination rate is reduced by sensitizing CdSe QDs. With broader light absorption range and longer electron lifetime, a power conversion efficiency of 1.42% is achieved for ZnO based CdS/CdSe co-sensitized solar cell under the illumination of one Sun (AM 1.5G, 100 mW cm⁻²).     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO2 Interface in Quantum Dot‐Sensitized Solar Cells

Quantum dot‐sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next‐generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO₂ acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. To understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO₂ substrate are simulated using a rigorous ab initio density functional method. This method capitalizes on localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO₂ occurring via the strong bonding between the conduction bands of QDs and TiO₂ is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO₂ acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO₂ systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO₂ acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.     

Tunable and High Photoluminescence Quantum Yield from Self‐Decorated TiO2 Quantum Dots on Fluorine Doped Mesoporous TiO2 Flowers by Rapid Thermal Annealing

Herein a novel approach is reported to achieve tunable and high photoluminescence (PL) quantum yield (QY) from the self‐grown spherical TiO₂ quantum dots (QDs) on fluorine doped TiO₂ (F‐TiO₂) flowers, mesoporous in nature, synthesized by a simple solvothermal process. The strong PL emission from F‐TiO₂ QDs centered at ≈485 nm is associated with shallow and deep traps, and a record high PL QY of ≈5.76% is measured at room temperature. Size distribution and doping of F‐TiO₂ nanocrystals (NCs) are successfully tuned by simply varying the HF concentration during synthesis. During the post‐growth rapid thermal annealing (RTA) under vacuum, the arbitrary shaped F‐TiO₂ NCs transform into spherical QDs with smaller sizes and it shows dramatic enhancement (≈163 times) in the PL intensity. Electron spin resonance (ESR) and X‐ray photoelectron spectroscopy (XPS) confirm the high density of oxygen vacancy defects on the surface of TiO₂ NCs. Confocal fluorescence microscopy imaging shows bright whitish emission from the F‐TiO₂ QDs. Low temperature and time resolved PL studies reveal that the ultrafast radiative recombination in the TiO₂ QDs results in highly efficient PL emission. A highly stable, biologically inert, and highly fluorescent TiO₂ QDs/flowers without any capping agent demonstrated here is significant for emerging applications in bioimaging, energy, and environmental cleaning.     

非晶/结晶共混对聚合物光伏电池性能的影响

以局域规整聚（3-己基噻吩） （P3HT）制备了TiO₂/聚合物型双层结构光伏电池.利用稳态电流-电压测试和动态强度调制光电压谱,结合差热分析、吸收光谱和荧光光谱, 研究了非晶支化聚亚乙基亚胺（BPEI）作为P3HT膜层的添加成分对TiO₂/P3HT双层电池性能的影响.由于P3HT链的高结晶性,使得TiO₂/P3HT界面接触不好,导致电池性能差.当在P3HT中共混重量比W_BPEI/P3HT=1％—5％的BPEI时,电池性能得到显著改善;尤其是当W_BPEI/P3HT= 1％时,电池表现出近0.8V的开路电压和20μA/cm²的短路电流.结果表明BPEI对电池性能的影响不是源于P3HT-BPEI共混体系光学性能的变化,而主要是由于其改变了TiO₂/P3HT界面接触性能.BPEI对TiO₂/P3HT界面接触有两个相互竞争的影响,这取决于P3HT-BPEI共混体系的组成.一方面,通过降低P3HT的结晶度和增强与TiO₂表面的相互作用,改善P3HT链在TiO₂ 表面的附着;另一方面,当BPEI含量过高时,BPEI在TiO₂表面的附着量将增加,反而会阻碍P3HT与TiO₂表面的接触.良好的TiO₂/P3HT界面接触有利于提高激子的界面分离效率、光生电子的寿命和电池效率.本文结果有望为聚合物光伏电池性能的改善提供新的认识和方法. 关键词： 聚（3-己基噻吩） 二氧化钛 共轭聚合物 光伏电池     

Synthesis,biocompatibility and luminescence properties of quantum dots conjugated with amino acid-functionalized β-cyclodextrin

A series of CdSe and CdSe/CdS quantum dots (QDs) labeled with amino acid-modified β-cyclodextrin (β-CD) was prepared by a simple ultrasonic method. These amino acid-modified β-CD-coated QDs are very soluble and stable in biological buffer. They also have high colloidal stability and strong optical emission properties that are similar to those of untreated tri-n-octylphosphine oxide (TOPO)-coated QDs. The quantum yields (QYs) of these amino acid-modified β-CD-coated CdSe and CdSe/CdS QDs in biological buffer were found to be very high. In particular, the QYs of the positively charged l-His-β-CD-coated CdSe/CdS QDs were as high as 33.5±1.8%. In addition, the fluorescence lifetime of these QDs was also very long in PBS solutions as determined by frequency domain spectroscopy. For example, the lifetime of l-His-β-CD-coated CdSe/CdS QDs was 8.6 ns. The in vitro cytotoxicity of these QDs in ECV-304, SH-SY5Y and HeLa cells was found to be lower. l-His-β-CD-coated CdSe/CdS QDs were the least cytotoxic (IC₅₀ 95.6±3.2 mg mL^?1 in ECV-304 cells after 48 h). The flow cytometry results show that the positively charged amino acid led to a considerable increase in biocompatibility of QDs. This may be attributed to the presence of an amino acid-modified β-CD outer layer, which enhanced the biocompatibility.