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1.
Organic–inorganic hybrid perovskite solar cells (PSCs) are a promising photovoltaic technology that has rapidly developed in recent years. Nevertheless, a large number of ionic defects within perovskite absorber can serve as non‐radiative recombination center to limit the performance of PSCs. Here, organic donor‐π‐acceptor (D‐π‐A) molecules with different electron density distributions are employed to efficiently passivate the defects in the perovskite films. The X‐ray photoelectron spectroscopy (XPS) analysis shows that the strong electron donating N,N‐dibutylaminophenyl unit in a molecule causes an increase in the electron density of the passivation site that is a carboxylate group, resulting in better binding with the defects of under‐coordinated Pb2+ cations. Carrier lifetime in the perovskite films measured by the time‐resolved photoluminescence spectrum is also prolonged by an increase in donation ability of the D‐π‐A molecules. As a consequence, these benefits contribute to an increase of 80 mV in the open circuit voltage of the devices, enabling a maximum power conversion efficiency (PCE) of 20.43%, in comparison with PCE of 18.52% for the control device. The authors' findings provide a novel strategy for efficient defect passivation in the perovskite solar cells based on controlling the electronic configuration of passivation molecules.  相似文献   

2.
The refunctionalization of a series of four well‐known industrial laser dyes, based on benzophenoxazine, is explored with the prospect of molecularly engineering new chromophores for dye‐sensitized solar cell (DSC) applications. Such engineering is important since a lack of suitable dyes is stifling the progress of DSC technology. The conceptual idea involves making laser dyes DSC‐active by chemical modification, while maintaining their key property attributes that are attractive to DSC applications. This molecular engineering follows a stepwise approach. First, molecular structures and optical absorption properties are determined for the parent laser dyes: Cresyl Violet ( 1 ), Oxazine 170 ( 2 ), Nile Blue A ( 3 ), Oxazine 750 ( 4 ). These reveal structure‐property relationships which define the prerequisites for computational molecular design of DSC dyes; the nature of their molecular architecture (D‐π‐A) and intramolecular charge transfer. Second, new DSC dyes are computationally designed by the in silico addition of a carboxylic acid anchor at various chemical substitution points in the parent laser dyes. A comparison of the resulting frontier molecular orbital energy levels with the conduction band edge of a TiO2 DSC photoanode and the redox potential of two electrolyte options I?/I3? and Co(II/III)tris(bipyridyl) suggests promise for these computationally designed dyes as co‐sensitizers for DSC applications.  相似文献   

3.
A new series of 4‐hexyl‐4H‐thieno[3,2‐b]indole (HxTI) based organic chromophores is developed by structural engineering of the electron donor (D) group in the D–HxTI–benzothiadiazole‐phenyl‐acceptor platform with different fluorenyl moieties, such as unsubstituted fluorenyl (SGT‐146) and hexyloxy (SGT‐147), decyloxy (SGT‐148) and hexyloxy‐phenyl substituted (SGT‐149) fluorenyl moieties. In comparison to a reference dye SGT‐137 with a biphenyl‐based donor, the effects of the donating ability and bulkiness of the fluorenyl based donor in this D–π–A‐structured platform on molecular properties and photovoltaic performance are investigated to establish the structure–property relationship. The photovoltaic performance of dye‐sensitized solar cells (DSSCs) is improved according to the bulkiness of the donor groups. As a result, the DSSCs based on SGT‐149 show high power conversion efficiencies (PCEs) of 11.7% and 10.0% with a [Co(bpy)3]2+/3+ (bpy = 2,2′‐bipyridine) and an I?/I3? redox electrolyte, respectively. Notably, the co‐sensitization of SGT‐149 with a SGT‐021 porphyrin dye by utilizing a simple “cocktail” method, exhibit state‐of‐the‐art PCEs of 14.2% and 11.6% with a [Co(bpy)3]2+/3+ and an I?/I3? redox electrolyte, respectively.  相似文献   

4.
A series of four new dyes, based on the D35 type donor moiety with varied linker units, is synthesized using a facile convergent/divergent method, enabled by an improved synthesis of the D35 donor. The dyes are evaluated in dye sensitized solar cells with Co(II/III)(bpy)3‐based electrolytes. By extending the linker fragment, higher photocurrents and solar energy conversion efficiencies are achieved. It is also found that the linker unit plays a crucial role in maintaining a high open‐circuit photovoltage. Based on the photovoltaic performance it is concluded that the hexylthiophene unit is the most suitable for this purpose, as it allows further enhancement of the already high open‐circuit voltage of D35 to 0.92 V. The best dye in this series reaches an efficiency of 6.8%.  相似文献   

5.
For a sensitizer with a strong π‐conjugation system, a coadsorbent is needed to hinder dye aggregation. However, coadsorption always brings a decrease in dye coverage on the TiO2 surface. Organic ‘‘D–A–π–A’’ dyes, WS‐6 and WS‐11, are designed and synthesized based on the known WS‐2 material for coadsorbent‐free, dye‐sensitized solar cells (DSSCs). Compared with the traditional D–π–A structure, these D–A–π–A indoline dyes, with the additional incorporated acceptor unit of benzothiadiazole in the π‐conjugation, exhibit a broad photoresponse, high redox stability, and convenient energy‐level tuning. The attached n‐hexyl chains in both dyes are effective to suppress charge recombination, resulting in a decreased dark current and enhanced open‐circuit voltage. Electrochemical impedance spectroscopy studies indicate that both the resistance for charge recombination and the electron lifetime are increased after the introduction of alkyl chains to the dye molecules. Without deoxycholic acid coadsorption, the power‐conversion efficiency of WS‐6 (7.76%) on a 16 μm‐thick TiO2 film device is 45% higher than that of WS‐2 (5.31%) under the same conditions. The additional n‐hexylthiophene in WS‐11 extends the photoresponse to a panchromatic spectrum but causes a low incident photon‐to‐current conversion efficiency.  相似文献   

6.
The elongation of π‐conjugated bridges between the donor (D) and the acceptor (A) represents a feasible strategy towards enhancement of light‐harvesting in both breadth and depth of organic D‐π‐A dyes suitable for nanocrystalline TiO2‐based dye‐sensitized solar cells (DSSCs). Here, a series of organic dyes with elongating conjugated bridges is synthesized and characterized. DSSC devices employing a cobalt (II/III) redox electrolyte are fabricated using these dyes as light‐harvesting sensitizers. Compared to a dye with the 3,4‐ethylenedioxythiophene (EDOT) linker ( G188 ), the three counterparts with further extended π‐bridges present gradually red‐shifted electronic absorption spectra and a persistent decrease in oxidation potential. The photocurrent action spectra show that the extension of π‐conjugated bridges decreases the open‐circuit photovoltage. The best performance is shown in G268 with a short‐circuit photocurrent density (Jsc) of 16.27 mA cm2, an open‐circuit photovoltage (Voc) of 0.83 V, and a fill factor (FF) of 0.67, corresponding to an overall conversion efficiency of 9.24%. Unexpectedly, G270, which has with the longest π‐bridge , showed the lowest Jsc, Voc, and efficiency.  相似文献   

7.
Next‐generation organic solar cells such as dye‐sensitized solar cells (DSSCs) and perovskite solar cells (PSCs) are studied at the National Institute of Advanced Industrial Science and Technology (AIST), and their materials, electronic properties, and fabrication processes are investigated. To enhance the performance of DSSCs, the basic structure of an electron donor, π‐electron linker, and electron acceptor, i.e., D–π–A, is suggested. In addition, special organic dyes containing coumarin, carbazole, and triphenylamine electron donor groups are synthesized to find an effective dye structure that avoids charge recombination at electrode surfaces. Meanwhile, PSCs are manufactured using both a coating method and a laser deposition technique. The results of interfacial studies demonstrate that the level of the conduction band edge (CBE) of a compact TiO2 layer is shifted after TiCl4 treatment, which strongly affects the solar cell performance. Furthermore, a special laser deposition system is developed for the fabrication of the perovskite layers of PSCs, which facilitates the control over the deposition rate of methyl ammonium iodide used as their precursor.  相似文献   

8.
To overcome the low energy density bottleneck of graphene‐based supercapacitors and to organically endow them with high‐power density, ultralong‐life cycles, etc., one rational strategy that couple graphene sheets with multielectron, redox‐reversible, and structurally‐stable organic compounds. Herein, a graphene‐indanthrone (IDT) donor–π–acceptor heterojunction is conceptualized for efficient and smooth 6H+/6e? transfers from pseudocapacitive IDT molecules to electrochemical double‐layer capacitive graphene scaffolds. To construct this, water‐processable graphene oxide (GO) is employed as a graphene precursor, and to in situ exfoliate IDT industrial dyestuff, followed by a hydrothermally‐induced reduction toward GO and self‐assembly between reduced GO (rGO) donors (D) and IDT acceptors (A), affording rGO‐π‐IDT D–A heterojunctions. Electrochemical tests indicate that rGO‐π‐IDT heterojunctions deliver a gravimetric capacitance of 535.5 F g?1 and an amplified volumetric capacitance of 685.4 F cm?3. The assembled flexible all‐solid‐state supercapacitor yields impressive volumetric energy densities of 31.3 and 25.1 W h L?1, respectively, at low and high power densities of 767 and 38 554 W L?1, while exhibiting an exceptional rate capability, cycling stability, and enduring mechanically‐challenging bending and distortions. The concept and methodology may open up opportunities for other two‐dimensional materials and other energy‐related devices.  相似文献   

9.
Organic solar cells are promising in terms of full‐solution‐processing which enables low‐cost and large‐scale fabrication. While single‐junction solar cells have seen a boost in power conversion efficiency (PCE), multi‐junction solar cells are promising to further enhance the PCE. In all‐solution‐processed multi‐junction solar cells, interfacial losses are often encountered between hole‐transporting layer (HTL) and the active layers and therefore greatly limit the application of newly developed high‐performance donor and acceptor materials in multi‐junction solar cells. Here, the authors report on a systematic study of interface losses in both single‐junction and multi‐junction solar cells based on representative polymer donors and HTLs using electron spectroscopy and time‐of‐flight secondary ion mass spectrometry. It is found that a facile mixed HTL containing poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and MoO x nanoparticles successfully overcomes the interfacial losses in both single‐ and multi‐junction solar cells based on various active layers by reducing interface protonation, promoting better energy‐level alignment, and forming a dense and smooth layer. Solution‐processed single‐junction solar cells are demonstrated to reach the same performance as with evaporated MoO x (over 7%). Multi‐junction solar cells with polymers containing nitrogen atoms as the first layer and the mixed PEDOT:PSS and MoO x nanoparticles as hole extraction layer reach fill factor (FF) of over 60%, and PCE of over 8%, while the identical stack with pristine PEDOT:PSS or MoO x nanoparticles show FF smaller than 50% and PCE less than 5%.  相似文献   

10.
High‐output triboelectric nanogenerators (TENGs) are demonstrated based on polyimide (PI)‐based polymers by introducing functionalities (e.g., electron‐withdrawing and electron‐donating groups) into the backbone. The TENG based on 6FDA‐APS PI, possessing the most negative electrostatic potential and the low‐lying lowest unoccupied molecular orbital level, produces the highest effective charge density of about 860 µC m?2 in practical working conditions with the ion injection process. This may be ascribed to the excellent charge‐retention characteristics as well as the enhanced charge transfer capability, which increases the output power by 7 times compared to the commercially available Kapton film‐based TENG. Finally, a 6FDA‐APS‐driven sensor network system is demonstrated, providing the identity of three gases (H2, CO, and NO2) by illuminating the light‐emitting diodes within several seconds.  相似文献   

11.
While the demonstrated power conversion efficiency of organic photovoltaics (OPVs) now exceeds 10%, new design rules are required to tailor interfaces at the molecular level for optimal exciton dissociation and charge transport in higher efficiency devices. We show that molecular shape‐complementarity between donors and acceptors can drive performance in OPV devices. Using core hole clock (CHC) X‐ray spectroscopy and density functional theory (DFT), we compare the electronic coupling, assembly, and charge transfer rates at the interface between C60 acceptors and flat‐ or contorted‐hexabenzocorone (HBC) donors. The HBC donors have similar optoelectronic properties but differ in molecular contortion and shape matching to the fullerene acceptors. We show that shape‐complementarity drives self‐assembly of an intermixed morphology with a donor/acceptor (D/A) ball‐and‐socket interface, which enables faster electron transfer from HBC to C60. The supramolecular assembly and faster electron transfer rates in the shape complementary heterojunction lead to a larger active volume and enhanced exciton dissociation rate. This work provides fundamental mechanistic insights on the improved efficiency of organic photovoltaic devices that incorporate these concave/convex D/A materials.  相似文献   

12.
A novel approach for enhancing the performance of dye‐sensitized solar cells is presented. It is based on the analysis of five sensitizers by utilizing triarylamine as donor, thiophene benzothiadiazole as chromophore and substituted thienyl linked with cyanoacrylic acid as the anchoring group (LI‐80‐LI‐84). Accompanied with the increasing steric hindrance of the substituents on the thienyl isolation group, the conformation of the dyes, in particular the angle between the chromophore and the anchoring group, becomes more and more twisted. Surprisingly, sensitizers with poorer conjugation effects (the higher twisted conformation) achieve better photovoltaic performances, showing a contrary trend to the traditional donor‐(π‐spacer)‐acceptor dyes with a better co‐planarity. On the basis of the preceding fundamental comprehensions, an empirical method is successfully applied to a new phenyl‐based system (LI‐85 and LI‐86) to improve their performances. The systematical investigation indicates that the twisted structures can contribute to the ECB of the TiO2 film, electron lifetime and resistance at the TiO2/dye/electrolyte interface. Thereby, the efficiency of the initial LI‐80‐based cell has been dramatically improved to 2.45 times higher for LI‐86‐based cell, paving a new way for the design of better sensitizers with higher device performances.  相似文献   

13.
Two new nonfullerene small molecule acceptors (NF‐SMAs) AT‐NC and AT‐4Cl based on heptacyclic anthracene(cyclopentadithiophene) (AT) core and different electron‐withdrawing end groups are designed and synthesized. Although the two new acceptor molecules use two different end groups, naphthyl‐fused indanone (NINCN) and chlorinated INCN (INCN‐2Cl) demonstrate similar light absorption. AT‐4Cl with chlorinated INCN as end groups are shifted significantly due to the strong electron‐withdrawing ability of chlorine atoms. Thus, desirable Voc and photovoltaic performance are expected to be achieved when polymer PBDB‐T is used as the electron donor with AT‐NC as the acceptor, and fluorinated analog PBDB‐TF with down‐shifted energy levels is selected to blend with AT‐4Cl. Consequently, the device based on PBDB‐TF:AT‐4Cl yields a high power conversion efficiency of 13.27% with a slightly lower Voc of 0.901 V, significantly enhanced Jsc of 19.52 mA cm?2 and fill factor of 75.5% relative to the values based on PBDB‐T:AT‐NC. These results demonstrate that the use of a new electron‐rich AT core, together with energy levels modulations by end‐group optimizations enabling the match with polymer donors, is a successful strategy to construct high‐performance NF‐SMAs.  相似文献   

14.
The structure evolution of oligomer fused‐ring electron acceptors (FREAs) toward high efficiency of as‐cast polymer solar cells (PSCs) is reported. First, a series of FREAs (IC‐(1‐3)IDT‐IC) based on indacenodithiophene (IDT) oligomers as cores are designed and synthesized, effects of IDT number (1–3) on their basic optical and electronic properties are investigated, and more importantly, the relationship between device performance of as‐cast PSCs and donor(D)/acceptor(A) matching (absorption, energy level, morphology, and charge transport) of IC‐(1‐3)IDT‐IC acceptors and two representative polymer donors, PTB7‐Th and PDBT‐T1 is surveyed. Then, the most promising D/A system (PDBT‐T1/IC‐1IDT‐IC) with the best D/A harmony among the six D/A combinations, which yields a power conversion efficiency (PCE) of 7.39%, is found. Finally, changing the side‐chains in IC‐1IDT‐IC from alkylphenyl to alkyl enhances the PCE from 7.39% to 9.20%.  相似文献   

15.
In this paper, two novel D‐π‐D hole‐transporting materials (HTM) are reported, abbreviated as BDT‐PTZ and BDT‐POZ , which consist of 4,8‐di(hexylthio)‐benzo[1,2‐b:4,5‐b′]dithiophene (BDT) as π‐conjugated linker, and N‐(6‐bromohexyl) phenothiazine (PTZ)/N‐(6‐bromohexyl) phenoxazine (POZ) as donor units. The above two HTMs are deployed in p‐i‐n perovskite solar cells (PSCs) as dopant‐free HT layers, exhibiting excellent power conversion efficiencies of 18.26% and 19.16%, respectively. Particularly, BDT‐POZ demonstrates a superior fill factor of 81.7%, which is consistent with its more efficient hole extraction and transport verified via steady‐state/transient fluorescence spectra and space‐charge‐limited current technique. Single‐crystal X‐ray diffraction characterization implies these two molecules present diverse packing tendencies, which may account for various interfacial hole‐transport ability in PSCs.  相似文献   

16.
All‐polymer solar cells (all‐PSCs) utilizing p‐type polymers as electron‐donors and n ‐typepolymers as electron‐acceptors have attracted a great deal of attention, and their efficiencies have been improved considerably. Here, five polymer donors with different molecular orientations are synthesized by random copolymerization of 5‐fluoro‐2,1,3‐benzothiadiazole with different relative amounts of 2,2′‐bithiophene (2T) and dithieno[3,2‐b;2′,3′‐d]thiophene (DTT). Solar cells are prepared by blending the polymer donors with a naphthalene diimide‐based polymer acceptor (PNDI) or a [6,6]‐phenyl C71‐butyric acid methyl ester (PC71BM) acceptor and their morphologies and crystallinity as well as optoelectronic, charge‐transport and photovoltaic properties are studied. Interestingly, charge generation in the solar cells is found to show higher dependence on the crystal orientation of the donor polymer for the PNDI‐based all‐PSCs than for the conventional PC71BM‐based PSCs. As the population of face‐on‐oriented crystallites of the donor increased in PNDI‐based PSC, the short‐circuit current density (JSC) and external quantum efficiency of the devices are found to significantly improve. Consequently, device efficiency was enhanced of all‐PSC from 3.11% to 6.01%. The study reveals that producing the same crystal orientation between the polymer donor and acceptor (face‐on/face‐on) is important in all‐PSCs because they provide efficient charge transfer at the donor/acceptor interface.  相似文献   

17.
Three new thieno[3,2‐b][1]benzothiophene ( TBT )‐based donor–π–acceptor (D–π–A) sensitizers, coded as SGT ‐ 121 , SGT ‐ 129 , and SGT ‐ 130 , have been designed and synthesized for dye‐sensitized solar cells (DSSCs), for the first time. The TBT , prepared by fusing thiophene unit with the phenyl unit of triphenylamine donor, is utilized as the π‐bridge for all sensitizers with good planarity. They have been molecularly engineered to regulate the highest occupied molecular orbital (HOMO)‐lowest unoccupied molecular orbital (LUMO) energy levels and extend absorption range as well as to control the electron‐transfer process that can ensure efficient dye regeneration and prevent undesired electron recombination. The photovoltaic performance of SGT‐sensitizer‐based DSSCs employing Co(bpy)32+/3+ (bpy = 2,2′‐bipyridine) redox couple is systematically evaluated in a thorough comparison with Y123 as a reference sensitizer. Among them, SGT ‐ 130 with benzothiadiazole‐phenyl ( BTD ‐ P ) unit as an auxiliary acceptor exhibits the highest power‐conversion efficiency (PCE) of 10.47% with Jsc = 16.77 mA cm?2, Voc = 851 mV, and FF = 73.34%, whose PCE is much higher than that of Y123 (9.5%). It is demonstrated that the molecular combination of each fragment in D–π–A organic sensitizers can be a pivotal factor for achieving the higher PCEs and an innovative strategy for strengthening the drawbacks of the π‐bridge.  相似文献   

18.
Significant development has been achieved in nonfullerene organic solar cells. However, most of the high‐efficiency nonfullerene systems are composed of polymer donors and fused‐ring acceptors, and only a few small molecule donors can work well. Herein, a new A–D–A small molecule donor named NDTSR with naphtho[1,2‐b:5,6‐b′]dithiophene (NDT) as building blocks is synthesized. Two energy levels well‐matched fused‐ring acceptors ITIC and IDIC are chosen to construct all‐small‐molecule solar cells with NDTSR, respectively. When mixed with IDIC, a high power conversion efficiency (PCE) of 8.05% is achieved, which is the highest efficiency for NDT‐based small molecule donor. However, the NDTSR:ITIC system only exhibits a low PCE of 1.77%. The big difference in the performance of these two systems should be attributed to the different morphology and phase separation resulting from the crystallinity and aggregation ability of the acceptors. The results demonstrate that NDT‐based small molecule is a promising candidate donor for all‐small‐molecule systems, while the crystallinity of fused‐ring acceptors is a critical factor for optimizing the phase separation in the active layer.  相似文献   

19.
Two narrow bandgap non‐fullerene acceptors (NBG‐NFAs), namely, COTIC‐4F and SiOTIC‐4F, are designed and synthesized for the fabrication of efficient near‐infrared organic solar cells (OSCs). The chemical structures of the NBG‐NFAs contain a D′‐D‐D′ electron‐rich internal core based on a cyclopentadithiophene (or dithienosilole) (D) and alkoxythienyl (D′) core, end‐capped with the highly electron‐deficient unit 2‐(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (A), ultimately providing a A‐D′‐D‐D′‐A molecular configuration that enhances the intramolecular charge transfer characteristics of the excited states. One can thereby reduce the optical bandgap (Egopt) to as low as ≈1.10 eV, one of the smallest values for NFAs reported to date. In bulk‐heterojunction (BHJ) OSCs, NBG‐NFA blends with the polymer donor PTB7‐Th yield power conversion efficiencies (PCE) of up to 9.0%, which is particularly high when compared against a range of NBG BHJ blends. Most significantly, it is found that, despite the small energy loss (Egopt ? eVOC) of 0.52 eV, the PTB7‐Th/NBG‐NFA bulk heterojunction blends can yield short‐circuit current densities of up to 22.8 mA cm?2, suggesting that the design and application of NBG‐NFA materials have substantial potential to further improve the PCE of OSCs.  相似文献   

20.
A 3D polymer‐network‐membrane (3D‐PNM) electrolyte is described for highly stable, solid‐state dye‐sensitized solar cells (DSCs) with excellent power‐conversion efficiency (PCE). The 3D‐PNM electrolyte is prepared by using one‐pot in situ cross‐linking polymerization on the surface of dye‐sensitized TiO2 particles in the presence of redox species. This method allows the direct connection of the 3D‐PNM to the surface of the TiO2 particles as well as the in situ preparation of the electrolyte gel during device assembly. There are two junction areas (liquid and solid‐state junctions) in the DSCs that employ conventional polymer electrolytes, and the major interface is at the liquid‐state junction. The solid‐state junction is dominant in the DSCs that employ the 3D‐PNM electrolyte, which exhibit almost constant performance during aging at 65 °C for over 700 h (17.0 to 17.2 mA cm–2). The best cell performance gives a PCE of 9.1%; this is slightly better than the performance of a DSC that employs a liquid electrolyte.  相似文献   

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