Efficient quantum dot sensitized solar cells via improved loading amount management

High light-harvesting efficiency and low interfacial charge transfer loss are essential for the fabrication of high-efficiency quantum dot-based solar cells(QDSCs). Increasing the thickness of mesoporous TiO2films can improve the loading of pre-synthesized QDs on the film and enhance the absorbance of photoanode, but commonly accompanied by the increase in the unfavorable charge recombination due to prolonged electron transmission paths. Herein, we systematically studied the influence of the balance between QD loading and TiO2film thickness on the performance of QDSCs. It is found that the relative thin photoanode prepared by the cationic surfactant-assisted multiple deposition procedure has achieved a high QD loading which is comparable to that of the thick photoanode commonly used. Under AM 1.5G illumination, Zn–Cu–In–Se and Zn–Cu–In–S based QDSCs with optimized 11.8 μm photoanodes show the PCE of 10.03% and 8.53%, respectively, which are comparable to the corresponding highest PCE of Zn–Cu–In–Se and Zn–Cu–In–S QDSCs(9.74% and 8.75%) with over 25.0 μm photoanodes. Similarly, an impressive PCE of 6.14% was obtained for the CdSe based QDSCs with a 4.1 μm photoanode, which is slightly lower than the best PCE(7.05%)of reference CdSe QDSCs with 18.1 μm photoanode.

Titania Nanostructures for Dye-sensitized Solar Cells

Titania is one kind of important materials, which has been extensively investigated because of its unique electronic and optical properties. Research efforts have largely focused on the optimization of the dye,but recently the titania nanostructures electrode itself has attracted more attention. It has been shown that particle size, shape, crystallinity, surface morphology, and chemistry of the TiO_2 material are key parameters which should be controlled for optimized performance of the solar cell. Titania can be found in different shape of nanostructures including mesoporous, nanotube, nanowire, and nanorod structures. The present article reviews the structural, synthesis, electronic, and optical properties of TiO_2 nanostructures for dye sensitized solar cells.

200-nm long TiO_2 nanorod arrays for efficient solid-state Pb S quantum dot-sensitized solar cellsR

To ensure the infiltration of spiro-OMeTAD into the quantum dot-sensitized photoanode and to consider the limit of the hole diffusion length in the spiro-OMeTAD layer, a rutile TiO2 nanorod array with a length of 200 nm, a diameter of 20 nm and an areal density of 720 ram 2 was successfully prepared using a hydrothermal method with an aqueous-grown solution of 38 mM titanium isopropoxide and 6 M hydrochloric acid at 170 ℃ for 75 min. PbS quantum dots were deposited by a spin coating-assisted successive ionic layer adsorption and reaction （spin-SILAR）, and all solid-state PbS quantum dot-sensitized TiO2 nanorod array solar cells were fabricated using spiro-OMeTAD as electrolytes. The results revealed that the average crystal size of PbS quantum dots was -78 nm using Pb（NO3）2 as the lead source and remain unchanged with the increase of the number of spin-SILAR cycles. The all solid-state PbS quantum dot-sensitized TiO2 nanorod array solar cells with spin-SILAR cycle numbers of 20, 30 and 40 achieved the photoelectric conversion efficiencies of 3.74%, 4.12% and 3.11%, respectively, under AM 1.5 G illumination （100 mW/cm2）.

Decrease of back recombination rate in CdS quantum dots sensitized solar cells using reduced graphene oxide

The photovoltaic performance of CdS quantum dots sensitized solar cells （QDSSCs） using the 0.2 wt% of reduced graphene oxide and TiO2 nanoparticles （RGO＋TiO2 nanocomposite） photoanode is investigated. CdS QDs are adsorbed onto RGO＋TiO2 nanocomposite films by the successive ionic layer adsorption and reaction （SILAR） technique for several cycles. The current density-voltage （J-V） characteristic curves of the assembled QDSSCs are measured at AM1.5 simulated sunlight. The optimal photovoltaic performance for CdS QDSSC was achieved for six SILAR cycles. Solar cells based on the RGO＋TiO2 nanocomposite photoanode achieve a 33% increase in conversion efficiency （η） compared with those based on plain TiO2 nanoparticle （NP） photoanodes. The electron back recombination rates decrease significantly for CdS QDSSCs based on RGO＋TiO2 nanocomposite photoanodes. The lifetime constant （τ） for CdS QDSSC based on the RGO＋TiO2 nanocomposite photoanode is at least one order of magnitude larger than that based on the bare TiO2NPs photoanode.

Composite Electrode SnO_2/TiO_2 for Dye-Sensitized Solar Cells

Composite nanoporous electrode SnO2/TiO2 was fabricated for the dye sensitized solar cell (DSSC) with N3 (Cis-Ru). After introducing of TiO2, the open-circuit photovoltage (Voc) was higher than that of the pure SnO2 electrode, while short-circuit photocurrent (Isc) was varied with the ratio of the TiO2. Appropriate content of the TiO2 can be beneficial to the efficiency of the solar cell, and it gives negative impact on the composite electrode when the content of TiO2 is higher.

New tetrazole-based organic dyes for dye-sensitized solar cells

A series of new metal-free organic dyes that contain donors with triphenylamine or its derivatives and tetrazole-based acceptors were synthesized and characterized by photophysical, electrochemical, and the- oretical computational methods. They were applied in nanocrystalline TiO2 solar cells （DSSCs）. It is found that the introduction of diphenylamine units as antennas in the as-synthesized dyes could improve photo- voltaic performance compared with phenothiazine and carbazole units as antennas in DSSCs. The dye with （2H-tetrazol-5-yl） acrylonitrile electron acceptor also displayed the highest solar-to-electrical energy conver- sion efficiency.

Double-layered TiO_(2) cavity/nanoparticle photoelectrodes for efficient dye-sensitized solar cells

TiO_(2) nanoparticles(NPs)in the size of-25 nm,namely P25,are very common material as the electron collecting layer in dye-sensitized solar cells(DSsCs).However,the light-scattering improvement of TiO2 NP photoelectrodes is stll a challenge.Here,we built TiO2 cavities on the top of the TiO2 NP layer by using carbonaceous microspheres as the template,forming the TiO_(2) cavity/nanoparticle(C/NP)photoelectrode for the application in DSSCs.The cavity amount in the TiO_(2) C/NP photoelectrode was controlled by adjusting the weight ratio of carbonaceous microspheres.SEM results confirm the successful formation of the double-layered TiO_(2) C/NP electrode.J-V tests show that the optimized TiO_(2) C/NP electrode prepared with 25 wt.%carbonaceous microspheres contributes to remarkable improvement of the short-circuit current density(Jsc)and the power conversion efficiency(PcE).The best photovoltaic performance solar cell with the PCE of 9.08%is achieved with the optimized TiO_(2) C/NP photoelectrode,which is over 98% higher than that of the TiO_(2) NP photoelectrode.Further investigations of UV-vis DRS,IPCE,OCVD,and EIS demonstrate that the competition between light scattering effect and charges recombination in this TiO_(2) C/NP photoelectrode is responsiblefor the PCE enhancement.

Boosting the efficiency of quantum dot–sensitized solar cells over 15%through light-harvesting enhancement

How to improve the capacity of light-harvesting is still an important point and essential strategy for the assembling of high-efficiency quantum dot–sensitized solar cells(QDSCs).A believable approach is to implant new light absorption materials into QDSCs to stimulate the charge transfer.Herein,the few-layer black phosphorus quantum dots(BPQDs)are synthesized by electrochemical intercalation technology using bulk BP as source.Then the obtained BPQDs are deposited onto the surface of Zn–Cu–In–S–Se(ZCISSe)QD-sensitized TiO2 substrate to serve as another light-harvesting material for the first time.The experimental results have shown that BPQDs can not only increase the absorption intensity by photoanode but also reduce unnecessary charge recombination processes at the interface of photoanode/electrolyte.Through optimizing the size and deposition process of BPQDs,the champion power conversion efficiency of ZCISSe QDSCs is increased to 15.66%(26.88 mA/cm2,Voc=0.816 V,fill factor[FF]=0.714)when compared with the original value of 14.11%(Jsc=25.41 mA/cm^(2),Voc=0.779 V,FF=0.713).

Metal chalcogenide complex-mediated fabrication of Cu_2S film as counter electrode in quantum dot sensitized solar cells

Cu2S film onto FTO glass substrate was obtained to function as counter electrode for polysulfide redox reactions in CdS/CdSe co-sensitized solar cells by sintering after spraying a metal chalcogenide complex, N4H9Cu7S4 solution. Relative to Pt counter electrode, the Cu2S counter electrode provides greater electrocatalytic activity and lower charge transfer resistance. The pre- pared CuzS counter electrode represented nanoflower-like porous film which was composed of Cu2S nanosheets on FTO and had a higher surface area and lower sheet resistance than that of sulfided brass Cu2S counter electrode. An energy conversion efficiency of 3.62% was achieved using the metal chalcogenide complex-mediated fabricated Cu2S counter electrode for CdS/CdSe co-sensitized solar cells under 1 sun, AM 1.5 illumination.

Analysis on dye-sensitized solar cells based on Fe-doped TiO_2 by intensity-modulated photocurrent spectroscopy and Mott-Schottky

The pure TiO2 and Fe salts [Fe（C2O4）3,5H2O]-doped TiO2 electrodes were prepared by the hydrothermal method. The pure TiO2 or Fe-doped TiO2 slurry was coated onto the fluorine-doped tin oxide glass substrate by the Doctor Blade method and then sintered at 450 ℃. The Mott-Schottks, plot indicates that the fiat band potential of TiO2 was shifted positively after Fe-doped TiO2. The positive shift of the fiat band potential improves the driving force of injected electrons from the LUMO of the dye to the conduction band of TiO2. This study shows that photovoltaic efficiency increased by 22.9% from 6.07% to 7.46% compared to pure TiO2, and the fill factors increased from 0.53 to 0.63.

Efficient dye-sensitized solar cells based on concerted companion dyes:Systematic optimization of thiophene units in the organic dye components

To develop efficient concerted companion(CC)dyes for fabricating high-performance DSSCs,three organic dyes XL1-XL3 have been designed by varying the position and number of theβ-hexylthiophene(HT)bridges,and these organic dye units are covalently linked with our previously reported porphyrin dye XW10 to construct the corresponding CC dyes XW74-XW76.Among the organic dyes,XL3 contains twoβ-hexylthiophene units at both the donor and acceptor parts and thus possesses stronger light-harvesting capability in the green light region.Because of the most complementary absorption between XL3 and XW10 as well as the excellent photovoltaic behavior of the individual XL3 dye,the corresponding CC dye XW76 affords the best PCE(10.78%)among all the CC dyes.Upon coadsorption with CDCA,XW76 affords a highest PCE of 11.35%,which outperforms the previous cosensitization system of XW10+WS-5.This work provides an approach for developing efficient DSSCs based on CC dyes composed of an organic dye unit with suitableπspacers inserted at appropriate positions.

Preparation of hierarchical TiO_2 microspheres for enhancing photocurrent of dye sensitized solar cells

Hierarchically structured TiO2 microspheres were prepared at a low temperature by combining a sol-gel process with a solvothermal route and characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction analysis. Results indicate that the phase structure of the as-prepared TiO2 products undergoes a transformation, which changes from amorphous microspheres with a smooth surface in the sol-gel process to hierarchical anatase ones consisting of nanocrystallines after the solvothermal treatment. The hierarchical anatase TiO2 microsphere shows large surface areas and good light scattering effects as the photoelectrodes for dye sensitized solar cells (DSSCs). DSSCs based on TiO2 microspheres exhibit an improvement power conversion efficiency of 6.58% and a high short current density of 13.83 mA/cm2 as compared to the commercial P25 based DSSCs with a power conversion efficiency of 4.94% and a high short current density of 10.28 mA/cm2.

CdS Quantum Dots-sensitized TiO_2 Nanotube Arrays for Solar Cells

CdS quantum dots（QDs） sensitized TiO2 nanotube arrays photoelectrodes were investigated for their photovoltaic performance of quantum dots-sensitized solar cells. The highly ordered TiO2 nanotube arrays（TNAs） were synthesized on Ti foils by anodic oxidation method. Then CdS quantum dots were deposited onto the TiO2 nanotube arrays by successive ionic layer absorption and reaction（SILAR） method to serve as the sensitizers. Cd（NO3）2 and Na2S were used as the precursor materials of Cd＋ and S2- ions, respectively. It is found that the CdS QDs sensitizer may significantly increase the light response of TiO2 nanotube arrays. With increasing CdS QDs deposition cycles, the visible light response increases. Maximum photocurrent was obtained for the QDs that have an absorption peak at about 500 nm. Under AM 1.5 G illuminations（100 mW cm^-2）, a 4.85 mA/cm^2 short circuit current density was achieved, and the maximium energy conversion efficiency of the asprepared CdS QDs-sensitized TNAs solar cells was obtained as high as 0.81% at five SILAR cycles.

Enhanced light harvesting and electron collection in quantum dot sensitized solar cells by TiO_2 passivation on ZnO nanorod arrays

Light capture and electron recombination are the essential processes that determine power conversion efficiency （PCE） in quantum dot sensitized solar cells （QD- SCs）. It is well known that charges are easily transported in well-built QDSCs based on nauorod arrays. However, this advantage can be drastically weakened by defects located at the zinc oxide （ZnO） array surface which permit faster electron recombination. Hence, we developed a composite nanostructure consisting of ZnO nanorods coated with orthorhombic configuration titanium dioxide （TiO2） nanopartides, which were synthesized using a solution of H3BO3 and （NH4）2TiF6. This composite nanostructure was designed to take the advantage of the enlarged surface area provided by the nanoparticles and improved electron transport along the nanorods, in order to yield good charge transport and light harvesting. At the same time, the TiO2/ZnO nanorod arrays have fewer recombination centers （hydroxyl groups） after TiO2 modification, which results in fewer electron trapping events at the ZnO nanorod surface; thereby, a reduced charge recombination and longer electron lifetime can be achieved. As a result, the PCE of the QDSCs with TiO2-nanopartides-decorated ZnO nanorod arrays photoelectrode reaches 4.8%, which is ～78% higher efficiency compared to 2.7% for solar cells without modification.

Dye-sensitized solar cells based on functionalized truxene structure

Three new metal-free organic dyes （TX1, TX2 and TX3） based on truxene core structure, with triphenylamine as the electron donor, thiophene as the n spacers, and cyanoacetic acid or rhodanine-3- acetic acid as the electron acceptor are designed and synthesized. Their UV-vis absorption spectra, electrochemical and photovoltaic properties were investigated. The cyanoacrylic acid is verified to be a better acceptor unit （meanwhile the anchoring group） compared to the rhodanine-3-acetic acid. And also, two anchoring groups in TX2 could provide stronger adsorption ability on the TiO2 surface. In addition, the EIS results indicate a slower charge recombination processes for TX2. As a result, dye TX2 bearing two cyanoacetic acid outperforms the other two dyes, exhibiting the photo-conversion efficiency of 2.64%, with Jsc = 5.09 mAcm^-2, Voc = 729 mV, FF = 71.1.

Improving photoelectrochemical activity of dye sensitized solar cell by a bilayered electrode with an overlayer of mesoporous anatase TiO_2

For better performance of dye sensitized solar cells （DSSCs）, a bilayer structured electrode was constructed by employing a mesoporous anatase TiO2 overlayer above a commercial P25 TiO2 nanoparticles underlayer. The mesoporous anatase TiO2, prepared through a facile surfactant-assisted sol-gel process, possessed large pore size and well inter-connected network structure, both beneficial for dye adsorption and electron transfer. The dye adsorption capability of the mesoporous TiO2 was nearly twice that of the P25 counterpart. In the electrode, the mesoporous TiO2 film enhanced both dye adsorption and lightharvest, to increase photocurrent （Jsc） from 12.32 to 14.78 mA/cm^2. Compared to the single P25 TiO2 film, the synergy of the mesoporous TiO2 and the P25 TiO2 nanoparticle films in the electrode resulted in a 24% improvement in light-to-electricity conversion efficiency （η）. This bilayered electrode provides an alternative approach for further developing a photovoltaic device with better cell performance.

CaCO_3/TiO_2 Nanoparticles Based Dye Sensitized Solar Cell

In this communication, the synthesis and structural, morphological, optical, and photo-electrochemical properties of TiO2 and CaCO3/TiO2 nanoparticles as well as their applications in dye sensitized solar cells （DSSCs）, have been reported. In an X-ray diffraction pattern of CaCO3/TiO2 nanoparticles, the peak at 29.41 ° of CaCO3 has been detected, demonstrating its coating on the surface of TiO2, which is further verified using high resolution-transmission electron microscopy, energy dispersive X-ray spectroscopy and Fourier transform infrared spectroscopy. The strong quenching in photoluminescence emission, in the case of CaCO3/TiO2 nanoparticles, has been attributed to the decrease in recombination rate of photo-generated electron-hole pairs. In the case of UV-visible reflectance spectra, the absorption edge for CaCO3/TiO2 nanoparticles has slightly been found to be blue-shifted as compared to bare TiO2 nanoparticles, which corresponds to an increase in energy band gap of the former. The dye desorption studies reveal that CaCO3/TiO2 electrodes adsorbed more dye than the bare TiO2 electrode. CaCO3/TiO2 based DSSC show improved photo- electrochemical properties compared to the bare TiO2 based DSSC as CaCO3 coating on mi02 forms an energy barrier, and, consequently suppressing the charge recombination, and, thus, improving the overall energy conversion efficiency （η） from 0.46% to 1.44% under the illumination of simulated light of 100 mW/cm2.

Hierarchical TiO2 Flower-spheres with Large Surface Area and High Scattering Ability： an Excellent Candidate for High Efficiency Dye Sensitized Solar Cells

Hierarchical TiO2 flower-spheres assembled from porous nanosheets-stacked of nanoparticles were synthesized by a simple hydrothermal method with one-step. The as-prepared TiO2 flower-spheres showed a diameter range from 200 nm to 550 nm and a large surface area of 188 m^2/g. A double layer photoanode made of P25 nano- particles and as-prepared TiO2 flower-spheres was fabricated for the dye sensitized solar cells（DSSCs）. The efficient light scattering and dye absorption of the photoanode can be attributed to the top-layer of hierarchical TiO2 flower-spheres. DSSCs based on the double layers photoanode exhibit a higher energy conversion efficiency of 8.11% with a short-circuit photocurrent density of 17.87 mA/cm^2, indicating that there is an increase of 38% in the conversion efficiency compared to those based on electrode P25（5.91%, 14.09 mA/cm^2）.

Solution-Processed Graphene Composite Films as Freestanding Platinum-Free Counter Electrodes for Bendable Dye Sensitized Solar Cells

Sulfuric acid-treated poly（3,4-ethylenedioxythiophene）：poly（styrenesulfonate）/less-defective reduced graphene oxide （ST-PEDOT：PSS/L-rGO） composite films were prepared via a solution-processing route and used as the counter electrodes of dye sensitized solar cells （DSSCs）. These platinum （Pt）- and transparent conductive oxide （TCO）-free counter electrodes exhibited strong catalytic activity and excellent flexibility, showing no obvious change in their sheet resistances after 10000 cycles of bending. The integrated quasi-solid-state DSSC device with a TiO2 nanotube/Ti mesh photoanode and a ST-PEDOT：PSS/L-rGO counter electrode exhibited an energy conversion efficiency （~/） of about 1.8%. It also displayed an excellent mechanical stability and durability after bending for 1000 cycles at a small curvature radius of 10 mm. The high flexibility, low cost and efficient catalytic activity make ST-PEDOT：PSS/L-rGO composite films promising counter electrodes for flexible DSSCs.

Molecular engineering of dithiafulvene organic sensitizers with pyridine acceptor for high efficiency dye-sensitized solar cells

Donor-π-acceptor(D-π-A) organic compounds have drawn keen interests as photosensitizers in dye sensitized solar cells(DSSCs). Recent studies showed that pyridine ring as an electron-withdrawing anchoring group could lead to efficient electron injection. To improve the performance of pyridine containing sensitizers based DSSCs, the electron donor, π-bridge and the whole structure should be well engineered at molecular level. In this work, we prepared two monomer type dithiafulvene based sensitizers both with a pyridine acceptor but differing in the phenyl-thienyl(DTFPy3) and thienyl-phenyl π-bridges(DTFPy4), and two corresponding dimeric congeners D-DTFPy3 and D-DTFPy4, and tested them in DSSCs. It was found that the arrangement of the electron-rich thienyl group adjacent to the electron donor moiety in the π-bridge red-shifted in the absorption, and the dimeric sensitizers exhibited significantly enhanced absorption. Among them, D-DTFPy4 garnered the highest light harvesting efficiency, yielding an overall power conversion efficiency up to 5.26%.