Recent progress of colloidal quantum dot based solar cells

Colloidal quantum dot （CQD） solar cells have attracted great interest due to their low cost and superior photo-electric properties. Remarkable improvements in cell performances of both quantum dot sensitized solar cells （QDSCs） and FbX （X = S, Se） based CQD solar cells have been achieved in recent years, and the power conversion efficiencies （PCEs） ex- ceeding 12% were reported so far. In this review, we will focus on the recent progress in CQD solar cells. We firstly summarize the advance of CQD sensitizer materials and the strategies for enhancing carrier collection efficiency in QD- SCs, including developing multi-component alloyed CQDs and core-shell structured CQDs, as well as various methods to suppress interfacial carrier recombination. Then, we discuss the device architecture development of PbX CQD based solar cells and surface/interface passivation methods to increase light absorption and carrier extraction efficiencies. Finally, a short summary, challenge, and perspective are given.

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.

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）.

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.

Higher open-circuit voltage set by cobalt redox shuttle in SnO_2 nanofibers-sensitized CdTe quantum dot solar cells

In this study, we report an efficient CdTe-SnOquantum dot（QD） solar cell fabricated by heat-assisted drop-casting of hydrothermally synthesized CdTe QDs on electrospun SnOnanofibers. The as-prepared QDs and SnOnanofibers were characterized by dynamic light scattering（DLS）, UV–Vis spectroscopy,photoluminescence（PL） spectra, X-ray diffraction（XRD） and transmission electron microscopy（TEM）. The SnOnanofibers deposited on fluorine-doped tin oxide（SnO） and sensitized with the CdTe QDs were assembled into a solar cell by sandwiching against a platinum（Pt） counter electrode in presence of cobalt electrolyte. The efficiency of cells was investigated by anchoring QDs of varying sizes on SnO. The best photovoltaic performance of an overall power conversion efficiency of 1.10%, an open-circuit voltage（Voc）of 0.80 V, and a photocurrent density（JSC） of 3.70 m A/cmwere obtained for cells with SnOthickness of5–6 μm and cell area of 0.25 cmunder standard 1 Sun illumination（100 m W/cm）. The efficiency was investigated for the same systems under polysulfide electrolyte as well for a comparison.

Composite Semiconductor Quantum Dots CdSe/CdS Co-sensitized TiO_2 Nanorod Array Solar Cells

CdSe/CdS semiconductor quantum dots co-sensitized TiO2 nanorod array was fabricated on the transparent conductive fluorine-doped tin oxide （FTO） substrate using the hydrothermal and successive ionic layer adsorption and reaction （SILAR） process. The structural and morphological properties of the samples were characterized by X-ray diffraction （XRD）, field-emission scanning electron microscopy （FESEM）, and transmission electron microscopy （TEM）. The results indicate that CdSe/CdS QDs are uniformly coated on the surface of the TiO2 nanorods. The shift of light absorption edge was monitored by taking UV-visible absorption spectra. Compared with the absorption spectra of the TiO2 nanorod array, deposition of CdSe/CdS QDs shifts the absorption edge to the higher wavelength. The enhanced light absorption in the visible-light region of CdSe/CdS/TiO2 nanorod array indicates that CdSe/CdS layers can act as co-sensitizers in quantum dots sensitized solar cells （QDSSCs）. By optimizing the CdSe layer deposition cycles, a photocurrent of 5.78 mA/cm2, an open circuit photovoltage of 0.469 V and a conversion efficiency of 1.34 % were obtained under an illumination of 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.

A series of conducting gel electrolytes for quasi-solid-state quantum dot-sensitized solar cells with boosted electron transfer processes

To pursue electron-generation stability with no sacrifice of photovoltaic performance has been a persistent objective for all kinds of solar cells. Here, we demonstrate the experimental realization of this objective by quasi-solid-state quantum dot-sensitized solar cells from a series of conducting gel electrolytes composed of polyacrylamide（PAAm） matrix and conductive polymers [polyaniline（PANi）, polypyrrole（PPy） or polythiophene（PT）]. The reduction of Sx2- occurred in both interface and three dimensional framework of conducting gel electrolyte as a result of the electrical conduction of PANi, PPy and PT toward refluxed electrons from external circuit to Pt electrode. The resulting solar cells can yield the solarto-electrical conversion efficiency of 2.33%, 2.25% and 1.80% for PANi, PPy and PT based gel electrolytes,respectively. Those solar cells possessed much higher efficiency than that of 1.74% based on pure PAAm gel electrolyte owing to the enhanced kinetics for Sx2- ？ S2- conversion. More importantly, the stability of quasi-solid-state solar cell is significantly advanced, arising from the localization of liquid electrolyte into the three dimensional framework and therefore reduced leakage and volatilization.

CdHgTe Quantum Dots Sensitized Solar Cell with Using of Titanium Dioxide Nanotubes

The sensitization of TiO2 nanotubes with CdHgTe quantum dots (QDs) was applied by using the direct dispersion technique. The CdHgTe-QDs were fabricated with different Hg% ratio in organic medium for controlling their particle size. While TiO2 nanotubes (NTs) were fabricated by anodization technique. The QDs and NTs were characterized using SEM, TEM and UV-VIS spectrophotometer. In this work, the photovoltaic parameters of the quantum dots sensitized solar cell (QDSSC) depend mainly on the Hg% ratio in the QDs. The most efficient QDSSC was obtained at 25% of Hg ratio with Jsc of 4 mA/cm2, Voc of 0.63 V, FF of 0.32 and efficiency of 0.81%.

TiO_2 hierarchical pores/nanorod arrays composite film as photoanode for quantum dot-sensitized solar cells

Power conversion efficiency(PCE) of quantum dot-sensitized solar cells(QDSSCs) was boosted in a TiO_2 composite film(TCSF) with delicate design in structure where TiO_2 hierarchical porous film(THPF) situated on the top of TiO_2 nanorod arrays film(TNAF). In this case, TNAF could supply efficient scattering centers for high light harvesting and direct electrical pathways for fast electron transfer while the THPF could offer porous channels for loading high quantity of previously synthetized quantum dots(QDs) and facilitate the penetration of electrolyte. Meanwhile, in this specific configuration, the presence of anatase–rutile heterojunction at the interface could help the rutile TNAF layer to efficiently collect photo-injected electrons from the anatase THPF layer thus suppressing the recombination of electrons and holes in electrolyte. The results showed that the PCE of QDSSC based on the TNAF photoanode was about 1.4-fold higher(η = 3.05%, J_(sc)= 15.86 m A cm^(-2), V_(oc)= 0.602 V, FF = 0.319) than that of device based on pure THPF(η = 2.20%, J_(sc)= 13.82 m A cm^(-2), V_(oc)= 0.572 V, FF = 0.278).

Selenium cooperated polysulfide electrolyte for efficiency enhancement of quantum dot-sensitized solar cells

The modification of polysulfide electrolyte with additives has been demonstrated as an effective way to improve the photovoltaic performance of quantum dot-sensitized solar cells(QDSCs). Most of these additives can inhibit the charge recombination processes at photoanode/electrolyte interface and favor the improvement of V oc of cell devices. Herein, we showed that the incorporation of elemental selenium(Se) in polysulfide electrolyte to form polyselenosulfide species can notably improve the performance of QDSCs. Unlike previous reports, we present here an integrated investigation of the effects of polyselenosulfide species in polysulfide electrolyte on the photovoltaic performance of QDSCs from both of the photoanode and counter electrode(CE) aspects. Electrochemical impedance spectroscopy(IS) and opencircuit voltage-decay(OCVD) measurements demonstrated that the introduction of Se into polysulfide electrolyte can not only retard charge recombination at photoanode/electrolyte interface, but also reduce the charge transfer resistance at CE/electrolyte interface, resulting in the improvement of J sc and FF values. Consequently, the average efficiency of Zn-Cu-In-Se QDSCs was improved from 9.26% to 9.78% under AM 1.5 G full one sun illumination.

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).

Photovoltaic Properties of CdSe Quantum Dot Sensitized Inverse Opal TiO₂Solar Cells: The Effect of TiCl₄Post Treatment

Recently, semiconductor quantum dot (QD) sensitized solar cells (QDSSCs) are expected to achieve higher conversion efficiency because of the large light absorption coefficient and multiple exciton generation in QDs. The morphology of TiO2 electrode is one of the most important factors in QDSSCs. Inverse opal (IO) TiO2 electrode, which has periodic mesoporous structure, is useful for QDSSCs because of better penetration of electrolyte than conventional nanoparticulate TiO2 electrode. In addition, the ordered three dimensional structure of IO-TiO2 would be better for electron transport. We have found that open circuit voltage Voc of QDSSCs with IO-TiO2 electrodes was much higher (0.2 V) than that with nanoparticulate TiO2 electrodes. But short circuit current density Jsc was lower in the case of IO-TiO2 electrodes because of the smaller surface area of IO-TiO2. In this study, for increasing surface area of IO-TiO2, we applied TiCl4 post treatment on IO-TiO2 and investigated the effect of the post treatment on photovoltaic properties of CdSe QD sensitized IO-TiO2 solar cells. It was found that Jsc could be enhanced due to TiCl4 post treatment, but decreased again for more than one cycle treatment, which indicates excess post treatment may lead to worse penetration of electrolyte. Our results indicate that the appropriate post treatment can improve the energy conversion efficiency of the QDSSCs.

Optical properties and dynamic process in metal ions doped on CdSe quantum dots sensitized solar cells

In recent years, the nanostructure for solar cells have attracted considerable attention from scientists as a result of a promising candidate for low cost devices. In this work, quantum dots sensitized solar cells with effective performance based on a co-sensitized Cd S∕Cd Se：Mn2＋（or Cu2＋） nanocrystal, which was made by successive ionic layer absorption and reaction, are discussed. The optical, physical, chemical, and photovoltaic properties of quantum dots sensitized solar cells were sensitized to Mn2＋and Cu2＋dopants. Therefore, the short current（JSC）of the quantum dot sensitized solar cells is boosted dramatically from 12.351 mA∕cm2 for pure Cd Se nanoparticles to 18.990 mA∕cm2 for Mn2＋ions and 19.915 mA∕cm2 for Cu2＋ions. Actually, metal dopant extended the band gap of pure Cd Se nanoparticles, reduced recombination, enhanced the efficiency of devices, and improved the charge transfer and collection. In addition, Mn2＋and Cu2＋dopants rose to the level of the conduction band of pure Cd Se nanoparticles, which leads to the reduction of the charge recombination, enhances the lightharvesting efficiency, and improves the charge diffusion and collection. The results also were confirmed by the obtained experimental data of photoluminescence decay and electrochemical impedance spectroscopy.

Optimization of CdSe Quantum Dots Sensitized TiO_2 Photo Anodes in Fabrication of Quantum Dots Sensitized Solar Cells

As one of the most promising candidates for the third generation solar cells,quantum dots sensitized solar cells(QDSCs) have been comprehensively studied.In this work,we synthesize the CdSe QDs with the absorption range from 450-550 nm,which are suitable to be applied in the QDSCs.Then,we found that the self-assembly(SA) deposition method is superior to the successive ionic layer adsorption and reaction(SILAR) deposition method in the fabrication of the photo anodes.Furthermore,the influence of TiO_2's thickness of the photo anodes to the QDSCs' efficiency has been studied.With the optimized CdSe QDs sensitized photo anodes,the efficiency of the QDSCs can reach 3.38%in this work.

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.

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.

Reduced interface energy loss in non-fullerene organic solar cells using room temperature-synthesized SnO2 quantum dots

We herein report the room temperature synthesis of colloidal SnO2 quantum dots and their application in non-fullerene organic solar cells as an excellent electron transport layer.The thiourea-assisted hydrolysis at room temperature affords the nanocrystalline SnO2 quantum dots with a diameter of 3-4 nm.The utilization of the SnO2 quantum dots as an electron transporting layer effectively reduces the interfacial trap density and charge recombination in the solar cell devices,leading to not only the reduced energy loss but also excellent photocurrent generation.The optimized organic solar cells employing SnO2 quantum dots with polyethylenimine ethoxylated achieves power conversion efficiencies up to 12.023%with a VOC,a JSC,and a FF of 0.89 V,18.89 mA cm^–2,and 0.72.This work suggest that the SnO2 quantum dot is a promising electron transporting material to construct efficient organic solar cells for practical applications.This work also demonstrates the key strategy for thiourea-assisted hydrolysis to synthesize fine and nanocrystalline SnO2 quantum dots.