Cosensitized Quantum Dot Solar Cells with Conversion Efficiency over 12%

The improvement of sunlight utilization is a fundamental approach for the construction of high‐efficiency quantum‐dot‐based solar cells (QDSCs). To boost light harvesting, cosensitized photoanodes are fabricated in this work by a sequential deposition of presynthesized Zn–Cu–In–Se (ZCISe) and CdSe quantum dots (QDs) on mesoporous TiO₂ films via the control of the interactions between QDs and TiO₂ films using 3‐mercaptopropionic acid bifunctional linkers. By the synergistic effect of ZCISe‐alloyed QDs with a wide light absorption range and CdSe QDs with a high extinction coefficient, the incident photon‐to‐electron conversion efficiency is significantly improved over single QD‐based QDSCs. It is found that the performance of cosensitized photoanodes can be optimized by adjusting the size of CdSe QDs introduced. In combination with titanium mesh supported mesoporous carbon as a counterelectrode and a modified polysulfide solution as an electrolyte, a champion power conversion efficiency up to 12.75% (V_oc = 0.752 V, J_sc = 27.39 mA cm^?2, FF = 0.619) is achieved, which is, as far as it is known, the highest efficiency for liquid‐junction QD‐based solar cells reported.     

Enhanced photovoltaic performance of solar cell based on front-side illuminated CdSe/CdS double-sensitized TiO2 nanotube arrays electrode

Free-standing TiO₂ nanotube (NT) arrays have been prepared by a two-step anodization method. These translucent TiO₂ NT arrays can be transferred to the fluorine-doped tin oxide glass substrates to form front-side illuminated TiO₂ NT electrodes. The TiO₂ NT electrodes were double-sensitized by CdSe/CdS quantum dots (QDs) through successive ionic layer adsorption and reaction (SILAR) process. The absorption range of the TiO₂ NT electrode was extended from ~380 to 700 nm after sensitization with CdSe/CdS QDs. The SILAR cycles were investigated to find out the best combination of CdS and CdSe QDs for photovoltaic performance. The power conversion efficiency of 2.42 % was achieved by the CdSe(10)/CdS(8)/TiO₂ NT solar cell. A further improved efficiency of 2.57 % was obtained with two cycles of ZnS overlayer on the CdSe(10)/CdS(8)/TiO₂ NT electrode, which is 45.19 % higher than that of back-side illuminated solar cell. Furthermore, the ZnS(2)/CdSe(10)/CdS(8)/TiO₂ NT solar cell possesses a higher stability than CdSe(10)/CdS(8)/TiO₂ NT solar cell during the same period. The better photovoltaic performance of the ZnS(2)/CdSe(10)/CdS(8)/TiO₂ NT solar cell has demonstrated the promising value to design quantum dots-sensitized solar cells with double-sensitized front-side illuminated TiO₂ NT arrays strategy.     

Growth and photovoltaic performance of SnS quantum dots

Tin sulphide (SnS) quantum dots of size ranging from 2.4 to 14.4 nm are prepared by chemical precipitation method in aqueous media. Growth of the SnS particles is monitored by controlling the deposition time. Both XRD and SAED patterns confirm that the particles possess orthorhombic structure. The uncapped SnS particles showed secondary phases like Sn₂S₃ and SnS₂ which is visible in the SAED pattern. From the electrochemical characterization, HOMO–LUMO levels of both TiO₂ and SnS are determined and the band alignment is found to be favorable for electron transfer from SnS to TiO₂. Moreover, the HOMO–LUMO levels varied for different particle sizes. Solar cell is fabricated by sensitizing porous TiO₂ thin film with SnS QDs. Cell structure is characterized with and without buffer layer between FTO and TiO₂. Without the buffer layer, cell showed an open circuit voltage (V_oc) of 504 mV and short circuit current density (J_sc) of 2.3 mA/cm² under AM1.5 condition. The low fill factor of this structure (15%) is seen to be increased drastically to 51%, on the incorporation of the buffer layer. The cell characteristics are analyzed using two different size quantum dots.     

Correlation between crystal growth and photosensitization of nanostructured TiO2 electrodes using supporting Ti substrates by self-assembled CdSe quantum dots

Crystal growth of semiconductor quantum dots (QDs) adsorbed on nanostructured TiO₂ electrodes is important not only for crystallographic studies but also for improving the photovoltaic efficiency of semiconductor-sensitized solar cells. In this study, nanostructured TiO₂ electrodes using supporting Ti substrates were prepared. These electrodes are then adsorbed with self-assembled CdSe QDs as photosensitizers to investigate the crystal growth and photoelectrochemical current properties. Average diameters of the CdSe QDs can be estimated from optical absorption spectra by using photoacoustic (PA) technique. PA technique is a powerful tool for evaluating the optical absorption of opaque and scattered samples because of the detection by photothermal phenomenon. When the adsorption time increases, the CdSe QDs diameter increases and then shows saturation for all the cases. Normal solution growth plus suppression (negative growth) contributions can be derived by PA spectroscopic analysis. Both of them depend on adsorption temperatures for CdSe QDs formation. Photosensitization of the nanostructured TiO₂ electrodes in the visible region resulting from CdSe QDs deposition can be clearly observed. Incident photon to current conversion efficiency (IPCE) of CdSe QDs adsorbed at high temperature formation is smaller than that adsorbed at low temperature one, indicating the increase of recombination centers with increasing adsorption temperature. This implies that negative growth, or dissolving effect, produces much more recombination centers inside of CdSe QDs and/or interface between the QDs and TiO₂.     

Size dependent electron transfer from CdTe quantum dots linked to TiO2 thin films in quantum dot sensitized solar cells

In this present study, we demonstrate the size dependent charge transfer from CdTe quantum dots (QDs) into TiO₂ substrate and relate this charge transfer to the actual behavior of a CdTe sensitized solar cell. CdTe QDs was synthesized using mercaptopropionic acid as the capping agent. The conduction band offset for TiO₂ and CdTe QDs indicates thermodynamically favorable band edge positions for smaller QDs for the electron-transfer at the QD–TiO₂ interface. Time-resolved emission studies were carried out for CdTe QD on glass and CdTe QD on TiO₂ substrates. Results on the quenching of QD luminescence, which relates to the transfer kinetics of electrons from the QD to the TiO₂ film, showed that at the smaller QD sizes the transfer kinetics are much more rapid than at the larger sizes. I–V characteristics of quantum dot sensitized solar cells (QDSSC) with different sized QDs were also investigated indicating higher current densities at smaller QD sizes consistent with the charge transfer results. The maximum injection rate constant and photocurrent were obtained for 2.5 nm CdTe QDs. We have been able to construct a solar cell with reasonable characteristics (V_oc = 0.8 V, J_sc = 1 mA cm⁻², FF = 60%, η = 0.5%).     

Fabrication of nanocomposite particles with superparamagnetic and luminescent functionalities

A new kind of superparamagnetic luminescent nanocomposite particles has been synthesized using a modified Stöber method combined with an electrostatic assembly process. Fe₃O₄ superparamagnetic nanoparticles were coated with uniform silica shell, and then 3-aminopropyltrimethoxysilane was used to terminate the silica surface with amino groups. Finally, negatively charged CdSe quantum dots (QDs) were assembled onto the surface of the amino-terminated SiO₂/Fe₃O₄ nanoparticles through electrostatic interactions. X-ray diffraction (XRD), transmission electron microscopy (TEM), microelectrophoresis, UV-vis absorption and emission spectroscopy and magnetometry were applied to characterize the nanocomposite particles. Dense CdSe QDs were immobilized on the silica surface. The thickness of silica shell was about 35 nm and the particle size of the final products was about 100 nm. The particles exhibited favorable superparamagnetic and photoluminescent properties.     

Bifacial illuminated PbS quantum dot-sensitized solar cells with translucent CuS counter electrodes

This paper reports the optimization of the TiO₂ photoanode and the fabrication of bifacial illuminated PbS quantum dot-sensitized solar cells (QDSSCs) with translucent CuS counter electrodes. TiO₂ photoanode is prepared by introducing a compact TiO₂ layer between FTO substrate and TiO₂ film with titanium diisopropoxide bis(acetylacetonate) in 1-butanol and post-treatment with TiCl₄ aqueous solution; then, PbS quantum dots (QDs) are deposited on the surface of TiO₂ film by successive ionic layer adsorption and reaction method; also, by means of control of the TiO₂ surface charge, QD density of TiO₂ film is improved by adding triethanolamine into the cationic precursor solution. Using this optimized TiO₂ photoanode and a translucent CuS counter electrode, a bifacial illuminated PbS QDSSC is fabricated. The preparation conditions are optimized and the surface morphology and electrochemical properties of TiO₂ photoanodes are characterized. The bifacial illuminated PbS QDSSC achieves a power conversion efficiency of 2.16 %, which is increased by 48.97 % compared with the single illuminated QDSSC.     

Construction of TiO<Subscript>2</Subscript> NP@TiO<Subscript>2</Subscript> NT double-layered structural photoanode to enhance photovoltaic performance of CdSe/CdS quantum dots sensitized solar cells

TiO₂ nanoparticles (NP) at top of TiO₂ nanotube (TiO₂ NP@TiO₂NT) double-layered architecture is constructed to combine the advantages of TiO₂ NP and TiO₂ NT together. This composite TiO₂ NP@TiO₂NT architecture as photoanode possesses a larger surface area for more QDs loading, and highly tubular structure for electron swift transport. Based on this architecture, CdSe/CdS quantum dots (QDs) have been successfully synthesized by successive ionic layer adsorption reaction (SILAR) method for quantum dots-sensitized solar cell application. The photovoltaic performance of QDSSCs based on TiO₂ NP@TiO₂ NT have been investigated in contrast with bare TiO₂ NP and bare TiO₂ NT architectures with almost the same thickness. The results show that the power conversion efficiency (PCE) of QDSSCs could be enhanced using TiO₂ NP@TiO₂ NT and improved to 3.26%, which is 80% and 38% higher than QDSSCs based on bare TiO₂ NT and bare TiO₂ NP, respectively. The BET surface area, UV–vis absorption spectra, and incident photon to current conversion efficiency (IPCE) measurements results show the evidence that the TiO₂ NP@TiO₂ NT can combine advantages of TiO₂ NP and TiO₂ NT structures together and lead to a higher light harvesting efficiency, electron collecting efficiency, and efficient electron transport.     

Hybrid photovoltaic cells with II–VI quantum dot sensitizers fabricated by layer-by-layer deposition of water-soluble components

We present the fabrication of all solid state heterojunction photovoltaic devices consisting of TiO₂ films sensitized by colloidal CdSe and CdTe quantum dots (QDs) and a hole transport layer of the conjugated polymer poly(9,9-dioctyl-fluorene-co-N-(4-butylenphenyl)diphenylamine). The sensitized films were prepared by alternating the layer-by-layer deposition of TiO₂ nanoparticles, water-soluble semiconductor QDs and polycations. Photovoltaic devices sandwiched between fluorinated tin oxide and gold electrodes showed a high rectification ratio and photovoltages of up to 1.15 V. Effective sensitization was observed for CdSe QDs, while incorporated CdTe QDs apparently had no such effect. These findings are explained by confinement effects in QDs.     

CdSe/Cd1−x Zn x S core/shell quantum dots with tunable emission: growth and morphology evolution

We demonstrate an organic synthesis to fabricate hydrophobic core/shell CdSe/Cd_1?x Zn _x S quantum dots (QDs) with tunable photoluminescence (PL) between green and red at relatively low temperature using trioctylphosphine S reacted directly with cadmium and zinc acetate. A seeded growth strategy was used for preparing large CdSe cores. Large CdSe cores revealed a rod-like morphology while small one exhibited a spherical shape. Being coated with a Cd_1?x Zn _x S shell on spherical CdSe cores with an average size of 3.9 nm in diameter, core/shell QDs exhibited a cubic morphology (a length of 5 nm). In contrast, the core/shell QDs created using a small core (3.3 nm in diameter) show a spherical morphology. Namely, the anisotropic aggregation behavior of CdS monomers on CdSe cores occurs when the rod-like core is coated with a Cd_1?x Zn _x S shell. CdS interlayer plays an important role for such morphology evolution because all CdSe cores with a pure ZnS shell exhibited a spherical morphology. The PL properties of CdSe/Cd_1?x Zn _x S core/shell QDs depended strongly on the size and morphology of the cores. The QDs revealed a narrow and tunable PL spectrum. It is believed that this facile strategy can be extended to synthesize other core–shell QDs at low temperature.     

Aqueous synthesis of CdSe and CdSe/CdS quantum dots with controllable introduction of Se and S sources

A new and convenient route is developed to synthesize CdSe and core–shell CdSe/CdS quantum dots (QDs) in aqueous solution. CdSe QDs are prepared by introducing H₂Se gas into the aqueous medium containing Cd²⁺ ions. The synthesized CdSe QDs are further capped with CdS to form core–shell CdSe/CdS QDs by reacting with H₂S gas. The gaseous precursors, H₂Se and H₂S, are generated on-line by reducing SeO₃ ^2? with NaBH₄ and the reaction between Na₂S and H₂SO₄, and introduced sequentially into the solution to form CdSe and CdSe/CdS QDs, respectively. The synthesized water-soluble CdSe and CdSe/CdS QDs possess high quantum yield (3 and 20 %) and narrow full-width-at-half-maximum (43 and 38 nm). The synthesis process is easily reproducible with simple apparatus and low-toxic chemicals. The relatively standard deviation of maxima fluorescence intensity is only 2.1 % (n = 7) for CdSe and 3.6 % (n = 7) for CdSe/CdS QDs. This developed route is simple, environmentally friendly and can be readily extended to the large-scale aqueous synthesis of QDs.     

Hydrothermal growth of double-layer TiO2 nanostructure film for quantum dot sensitized solar cells

A double-layer (DL) film with a TiO₂ nanosheet-layer on a layer of TiO₂ nanorod-array, was synthesized on a transparent conductive fluorine-doped tin oxide substrate by a two-step hydrothermal method. Starting from the precursors of NaSeSO₃, CdSO₄ and the complex of N(CH₂COOK)₃, CdSe quantum dots (QDs) were grown on the DL-TiO₂ substrate by chemical bath deposition method. The samples were characterized by X-ray diffraction, Scanning electron microscopy, Energy dispersion spectroscopy, and their optical scattering property was measured by light reflection spectrometry. Some CdSe QDs sensitized DL-TiO₂ films serve as the photoanodes, were assembled into solar cell devices and their photovoltaic performance were also characterized. The short circuit current and open-circuit voltage of the solar cells range from 0.75 to 4.05 mA/cm² and 0.20 − 0.42 V under the illumination of one sun (AM1.5, 100 mW/cm²), respectively. The photocurrent density of the DL-TiO₂ film is five times higher than that of a bare TiO₂ nanorod array photoelectrode cell.     

A three-dimensional electrode for photoelectrochemical cell: TiO2 coated ITO mesoporous film

In this letter, TiO₂ coated ITO mesoporous film was prepared by dipping doctor-blade ITO mesoporous film in TiO₂ sol, followed by sintering at 500 °C for 30 min. The CdS quantum dots (QDs) were deposited on TiO₂ coated ITO mesoporous film using sequential chemical bath deposition (S-CBD) method to form a three-dimensional (3D) electrode. The photo-activity of ITO mesoporous film/TiO₂/CdS electrode was investigated by forming a photoelectrochemical cell, which indicated that the ITO mesoporous film/TiO₂/CdS electrode was efficient in photoelectrochemical cell as a working electrode. The 3D electrode showed lower performance than the conventional electrode of TiO₂ mesoporous film/CdS, and more works are needed to improve the performance of 3D electrode.     

Synthesis and size dependent optical studies in CdSe quantum dots via inverse micelle technique

Cadmium selenide quantum dots (CdSe QDs) were successfully synthesized without using trioctylphosphine (TOP). The XRD pattern showed zinc-blend phase of the CdSe QDs. The absorption and PL spectra exhibit a strong blue shift as the QDs size decreases due to the quantum confinement effect. In addition, the quantum efficiency of CdSe QDs with TOP capping is higher than CdSe QDs with oleic acid capping. TEM image shows a spherical shape, compact and dense structure of CdSe QDs. A good agreement between the Tauc's model and experimentally measured absorption spectra of CdSe QDs is achieved. The FTIR peak at ～1712 cm^?1 spectra confirms the influence of oleic acid as a capping agent.     

Giant Zeeman Effects and Spin Dynamics of Excitons in Dense Self-Organized Quantum Dots of CdSe and Cd1?xMnxSe

Giant Zeeman effects and spin dynamics of excitons are studied in dense self-organized quantum dots (QDs) of CdSe and Cd_1–xMn_xSe. Microphotoluminescence (PL) measurements for each individual dot reveal the typical dot diameter of 3.5 ± 0.2 nm and the density of 5000 m^–2 in the CdSe QDs. The exciton lifetime is shorter in smaller dots with higher energies, indicating energy transfer and tunneling processes among the dots. Circular polarization of excitonic PL is observed at 0 T with an opposite sign to that of the excited light and with the rise time of 50 ps. The CdSe QDs coupled with a Zn_1–xMn_xSe layer show the giant Zeeman shift of exciton, arising from overlapping of exciton wavefunctions in the dots with Mn ions. Spin polarization dynamics in the coupled QDs is also studied.     

Giant Zeeman Effects and Spin Dynamics of Excitons in Dense Self-Organized Quantum Dots of CdSe and Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se

Giant Zeeman effects and spin dynamics of excitons are studied in dense self-organized quantum dots (QDs) of CdSe and Cd_1–xMn_xSe. Microphotoluminescence (PL) measurements for each individual dot reveal the typical dot diameter of 3.5 ± 0.2 nm and the density of 5000 m^–2 in the CdSe QDs. The exciton lifetime is shorter in smaller dots with higher energies, indicating energy transfer and tunneling processes among the dots. Circular polarization of excitonic PL is observed at 0 T with an opposite sign to that of the excited light and with the rise time of 50 ps. The CdSe QDs coupled with a Zn_1–xMn_xSe layer show the giant Zeeman shift of exciton, arising from overlapping of exciton wavefunctions in the dots with Mn ions. Spin polarization dynamics in the coupled QDs is also studied.     

Indium phthalocyanine–CdSe/ZnS quantum dots nanocomposites showing size dependent and near ideal optical limiting behaviour

Indium phthalocyanine–CdSe/ZnS quantum dots (QDs) nanocomposites (InPc–CdSe/ZnS) of three sizes (5.57, 8.12 and 8.75 nm) were synthesized according to known procedures. The particle size of the CdSe/ZnS QDs alone are 3.95, 6.02, and 6.66 nm, and are denoted as QD1, QD2 and QD3 respectively. The nonlinear absorption (NLA) properties of the nanoconjugates (InPc–CdSe/ZnS) were investigated with nanosecond laser radiation at 532 nm wavelength. Enhanced NLA properties compared to the InPc alone were observed in the conjugates. The NLA was found to increase with the size of the CdSe/ZnS particles attached to the phthalocyanine. The observed increase was due to the availability of more free-carrier ions in the larger QDs, thus giving rise to the enhanced free-carrier absorption. The measured free-carrier absorption cross-sections (σ_FCA) are 1.10, 1.65 and 1.95 (×10⁻¹⁹ cm²) for InPc-QD1, InPc-QD2 and InPc-QD3 respectively. The nanoconjugates (InPc–CdSe/ZnS) showed a much lower threshold for optical limiting together with a much lower transmission at high fluences, than the previously reported nanocomposite limiters.     

CdSe胶质量子点的电致发光特性研究

采用胶体化学法合成硒化镉(CdSe)胶质量子点, 在此基础上制成了以CdSe胶质量子点为有源层, 结构为ITO/ZnS/CdSe/ZnS/Al的电致发光(EL)器件. 透射电镜测量表明量子点的尺寸为4.3 nm, 扫描电子显微镜测量ZnS薄膜和Al薄膜结果显示表面均较为平整, 由器件结构的X射线衍射分析观察到了CdSe(111)、ZnS(111)等晶面的衍射, 表明器件中包含了CdSe量子点和ZnS绝缘层材料. 光致发光谱表征胶质量子点的室温发光峰位于614 nm, 电致发光测量得到器件在室温下的发光波长位于450 ~ 850 nm, 峰值在800 nm附近. 本文对电致发光机制及其与光致发光谱的区别进行了讨论.     

Photoluminescent, transparent and flexible di-ureasil hybrids containing CdSe/ZnS quantum dots

We describe, in this paper, the sol-gel synthesis of di-ureasil based nanocomposites prepared in situ in the presence of organically capped CdSe quantum dots (QDs) or CdSe QDs which have been coated with a ZnS shell. For the latter a new chemical route to coat the CdSe QDs with ZnS shells was investigated and is now reported. The QDs became well dispersed in the final nanocomposites, whose microstructural homogeneity was evaluated by atomic force microscopy (AFM) and transmission electron microscopy (TEM) analyses. In order to understand the optical behaviour of di-ureasil containing QDs, a detailed photoluminescent study was undertaken for a selected particle size distribution of ZnS coated CdSe QDs (d～4.5?nm). Emission quantum yields up to 0.11 were measured in the final nanocomposites that present a huge (between 3 and 6 orders of magnitude) increase in the lifetime of the QDs (relative to that of isolated ones), as a result of energy transfer occurring between the intimately mixed di-ureasil host and the QDs.