shuhui

Publication date: June 2019

Source: Nano Energy, Volume 60

Author(s): Mriganka Singh, Annie Ng, Zhiwei Ren, Hanlin Hu, Hong-Cheu Lin, Chih-Wei Chu, Gang Li

Graphical abstract

A facile new solid-state synthesis of composite Tin-oxide electron transport layer (ETL) leads to power conversion efficiency up to 21.09% for mixed-cation lead mixed-halide perovskite solar cells.

Fluorinated aromatic cations (FPEAI) can react with the excess PbI₂ in a 3D perovskite film to form a capping 2D perovskite layer. Compared to the control device, the resulting multidimensional perovskite shows enhanced environmental stability with equally superior device performances. Judicious optimization of the perovskite precursor recipe realizes a power conversion efficiency of 20.54% for mesoporous perovskite solar cells.

Abstract

Supported by the density functional theory (DFT) calculations, for the first time, a fluorinated aromatic cation, 2‐(4‐fluorophenyl)ethyl ammonium iodide (FPEAI), is introduced to grow in situ a low dimensional perovskite layer atop 3D perovskite film with excess PbI₂. The resulted (p‐FC₆H₄C₂H₄NH₃)₂[PbI₄] perovskite functions as a protective capping layer to protect the 3D perovskite from moisture. In the meantime, the thin layer facilitates charge transfer at the interfaces, thereby reducing the nonradiative recombination pathways. Laser scanning confocal microscopy unveils visually the distribution of the 2D perovskite layer on top of the 3D perovskite. When employing the 3D–2D perovskite as the absorbing layer in the photovoltaic cells, a high power conversion efficiency of 20.54% is realized. Superior device performance and moisture stability are observed with the modified perovskite over the whole stability test period.

A novel wide‐bandgap nonfullerene acceptor TfIF‐4FIC is synthesized. PBDB‐T‐2F:TfIF‐4FIC‐based organic solar cell acquires a power conversion efficiency (PCE) of 13.1%, a high open‐circuit voltage of 0.98 V, which is the best performed device with bandgap larger than 1.60 eV. When using PBDB‐T‐2F:TfIF‐4FIC as front cell and PTB7‐Th:PCDTBT:IEICO‐4F as back cell to construct tandem device, PCE of 15% is achieved.

Abstract

A tandem organic solar cell (OSC) is a valid structure to widen the photon response range and suppress the transmission loss and thermalization loss. In the past few years, the development of low‐bandgap materials with broad absorption in long‐wavelength region for back subcells has attracted considerable attention. However, wide‐bandgap materials for front cells that have both high short‐circuit current density (J _SC) and open‐circuit voltage (V _OC) are scarce. In this work, a new fluorine‐substituted wide‐bandgap small molecule nonfullerene acceptor TfIF‐4FIC is reported, which has an optical bandgap of 1.61 eV. When PBDB‐T‐2F is selected as the donor, the device offers an extremely high V _OC of 0.98 V, a high J _SC of 17.6 mA cm⁻², and a power conversion efficiency of 13.1%. This is the best performing acceptor with such a wide bandgap. More importantly, the energy loss in this combination is 0.63 eV. These properties ensure that PBDB‐T‐2F:TfIF‐4FIC is an ideal candidate for the fabrication of tandem OSCs. When PBDB‐T‐2F:TfIF‐4FIC and PTB7‐Th:PCDTBT:IEICO‐4F are used as the front cell and the back cell to construct tandem solar cells, a PCE of 15% is obtained, which is one of best results reported to date in the field of organic solar cells.

The ITC‐2Cl‐based device yields an excellent power conversion efficiency of 13.6% with a low E _loss of 0.67 eV, which is superior to those of the devices based on ITCPTC, IT‐4F, and IT‐4Cl.

Abstract

Generally, highly efficient organic solar cells require both a high open‐circuit voltage (V _OC) and a high short‐circuit current density (J _SC). Reducing the energy loss (E _loss) is an effective way to achieve a high V _OC without compromising the photocurrent, which is ideal for enhancing the power conversion efficiencies (PCEs). Herein, a new chlorinated nonfullerene acceptor (ITC‐2Cl) with chlorinated thiophene‐fused end groups is developed. In comparison with the unchlorinated counterpart (ITCPTC), the introduction of Cl improves not only the electronic properties by redshifting the absorption spectra and deepening the lowest unoccupied molecular orbital energy levels, but also the molecular packing and thus thin‐film morphology. The PM6:ITC‐2Cl‐based device yields a significantly higher PCE (13.6%) with a lower E _loss (0.67 eV) than the ITCPTC‐based device (PCE of 12.3% with E _loss of 0.70 eV). More importantly, compared to the archetypal nonfullerene acceptors such as IT‐4F (PCE of 12.9% with E _loss of 0.73 eV) and IT‐4Cl (PCE of 12.7% with E _loss of 0.76 eV), the ITC‐2Cl‐based device shows a higher PCE and a lower E _loss. These results demonstrate that the chlorinated thiophene‐fused end group is a promising candidate for a high‐performance nonfullerene acceptors with low energy loss.

Publication date: 11 April 2019

Source: Chem, Volume 5, Issue 4

Author(s): Lingfeng Chao, Yingdong Xia, Bixin Li, Guichuan Xing, Yonghua Chen, Wei Huang

The Bigger Picture

Summary

Graphical Abstract

A controllable ultraviolet/ozone (UVO) treatment is employed to prepare a high‐quality electrochemically deposited NiO_x hole transport layer (HTL). Under optimal conditions of UVO treatment, the increased hole conductivity in the HTL reduces defects at the HTL/perovskite interface, and a narrowed offset of the valence band between the HTL and perovskite film are obtained, which results in high‐performance perovskite solar cells with an efficiency of 19.67%.

Nickel oxide (NiO_x) has exhibited great potential as a hole transport layer (HTL) for fabricating efficient and stable perovskite solar cells (PSCs). However, it has been greatly limited by its fabrication and manipulation process. In this work, a simple processing method on an ultrathin electrochemical mesoporous NiO_x film manipulated by controllable ultraviolet/ozone (UVO) treatmentis employed; the duration of UVO treatment on the NiO_x film significantly affects the photovoltaic properties of the PSCs. When the exposure duration increases, the wettability, electrical conductivity, nonstoichiometry, and valence band energy of the NiO_x film are improved with varying degrees. Besides, the perovskite grain size, recombination resistance at the perovskite/NiO_x interface, and build‐in potential of the device also increase, resulting in higher short‐circuit current density (J _SC) and open‐circuit voltage (V _OC). Combining these factors together, an optimal exposure time of UVO treatment on the NiO_x film has been achieved at 5 min, which results in a significantly high performance with an efficiency of 19.67%, large V _OC (>1.1 V), and J _SC (>23 mA cm⁻²). Furthermore, the experimental results are coincide well with simulation results on the different corresponding subjects. Hopefully, this work could facilitate material manipulation toward scalable, high efficiency, and stable solar cells.

Methoxy‐functionalized triphenylamine‐imidazole derivatives, simultaneously working as hole transport materials and bifacial interface‐modifiers passivating defects in the perovskite and NiO _x layers, are developed for high‐performance and stable perovskite solar cell. They are advantageous to improve charge‐extraction kinetics of devices and significantly enhance the stability of devices under constant UV illumination in air.

Abstract

Methoxy‐functionalized triphenylamine‐imidazole derivatives that can simultaneously work as hole transport materials (HTMs) and interface‐modifiers are designed for high‐performance and stable perovskite solar cells (PSCs). Satisfying the fundamental electrical and optical properties as HTMs of p‐i‐n planar PSCs, their energy levels can be further tuned by the number of methoxy units for better alignment with those of perovskite, leading to efficient hole extraction. Moreover, when they are introduced between perovskite photoabsorber and low‐temperature solution‐processed NiO _x interlayer, widely featured as an inorganic HTM but known to be vulnerable to interfacial defect generation and poor contact formation with perovskite, nitrogen and oxygen atoms in those organic molecules are found to work as Lewis bases that can passivate undercoordinated ion‐induced defects in the perovskite and NiO _x layers inducing carrier recombination, and the improved interfaces are also beneficial to enhance the crystallinity of perovskite. The formation of Lewis adducts is directly observed by IR, Raman, and X‐ray photoelectron spectroscopy, and improved charge extraction and reduced recombination kinetics are confirmed by time‐resolved photoluminescence and transient photovoltage experiments. Moreover, UV‐blocking ability of the organic HTMs, the ameliorated interfacial property, and the improved crystallinity of perovskite significantly enhance the stability of PSCs under constant UV illumination in air without encapsulation.

Phenylethylamine bromide is demonstrated to be capable of improving the ordering extent of alternatively arranged [AgX₆]⁵⁻ and [BiX₆]³⁻ octahedra in a Cs₂AgBiBr₆ single crystal, and thereby tuning the band gap and suppressing self‐trapped exciton formation, which consequently promotes its application in an X‐ray detector with faster current response and higher sensitivity, which largely outperforms the devices based on lower‐ordering single crystals.

Abstract

The double perovskite Cs₂AgBiBr₆ single crystal holds great potential for detecting applications because of its low minimum detectable dose rate and toxic‐free merit. Nevertheless, the disordered arrangement of Ag⁺/Bi³⁺ usually gives rise to unexpected structural distortion and thereafter heavily influences the photoelectric properties of the Cs₂AgBiBr₆ single crystal. Herein, phenylethylamine bromide is demonstrated to be capable of in situ regulation of the order–disorder phase transition in the Cs₂AgBiBr₆ single crystal. The improved ordering extent of alternatively arranged [AgX₆]⁵⁻ and [BiX₆]³⁻ octahedra is theoretically and experimentally proven to decrease the defect density and suppress self‐trapped exciton formation, and thereby tune the band gap and enhance the carrier mobility, which consequently promotes its application in an X‐ray detector. The performance of a corresponding detector based on PEA‐Cs₂AgBiBr₆ single crystal displays superior performances, e.g., longer carrier drift distance, higher photoconductive gain, and faster current response (13 vs 3190 µs). Prominently, the as‐fabricated PEA‐Cs₂AgBiBr₆ single‐crystal X‐ray detector has an extremely high sensitivity with a value of 288.8 µC Gy_air ⁻¹ cm⁻² under a bias of 50 V (22.7 V mm⁻¹), which largely outperforms those of their counterparts with lower ordering structure.

The [7]helicenes with stable partial open‐shell biradical ground states are demonstrated as effective surface modifiers of the inorganic NiO _x hole‐transporting layer in p–i–n perovskite solar cells. Their nonpolar feature improves the crystallinity of the perovskite films grown on them. Meanwhile, their biradical character provides a certain defect passivation function to facilitate charge transfer/extraction across the perovskite interface.

Abstract

Organic–inorganic hybrid perovskites have realized a high power conversion efficiency (PCE) in both n–i–p and p–i–n device configurations. However, since the p–i–n structure exempts the sophisticated processing of charge‐transporting layers, it seems to possess better potential for practical applications than the n–i–p one. Currently, the inorganic NiO _x is the most prevailing hole‐transporting layer (HTL) used in p–i–n perovskite solar cells. Nevertheless, defects might exist on its surface to influence the charge transfer/extraction across the interface with perovskite and to affect the quality of the perovskite film grown on it. Herein, two novel [7]helicenes with stable open‐shell singlet biradical ground states at room temperature are demonstrated as an effective surface modifier of the NiO _x HTL. Their nonpolar feature effectively promotes the crystallinity of the perovskite film grown on them; meanwhile, their unique partial biradical character seems to provide a certain degree of defect passivation function at the perovskite interface to facilitate interfacial charge transfer/extraction. As a result, both 1ab‐ and 1bb‐modifed devices yield a PCE of >18%, exceeding the value (15.6%) of the control device using a sole NiO _x HTL, and the maximum PCE can reach 19%. Detailed characterizations are carefully conducted to understand the underlying reasons behind such enhancement.

A 1D closely packed and high aspect ratio metal oxide nanowire‐based thin film is demonstrated to achieve favorable bifacial contact junction engineering for large‐area perovskite solar cells with efficiency exceeding 21% owing to the facilitated electron extraction, effective hole blocking, and suppressed charge recombination.

Abstract

Ordered 1D metal oxide structure is desirable in thin film solar cells owing to its excellent charge collection capability. However, the electron transfer in 1D electron transporting layer (ETL)‐based devices is still limited to a submicrometer‐long pathway that is vertical to the substrate. Here, an innovative closely packed rutile TiO₂ nanowire (CRTNW) network parallel to the facet of fluorine‐doped tin oxide (FTO) substrate is reported, which can serve as a 1D nanoscale electron transport pathway for efficient perovskite solar cells (PSCs). The PSC constructed using newly prepared CRTNW ETL achieves an impressive power conversion efficiency of 21.10%, which can be attributed to the facilitated electron extraction induced by the favorable junctions formed at FTO/ETL and ETL/perovskite interfaces and also the suppressed charge recombination originating from improved perovskite morphology with large grains, flat surface, and good surface coverage. The bifacial contact junctions engineering also enables large‐area device fabrication. The PSC with 1 cm² aperture yields an efficiency of 19.50% under one sun illumination. This work highlights the significance of controlling the orientation and packing density of the ordered 1D oxide nanostructured thin films for highly efficient optoelectronic devices in a large‐scale manner.

Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene)

Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene), Published online: 27 March 2019; doi:10.1038/s41586-019-1036-3

Surface passivation of perovskite film for efficient solar cells

Surface passivation of perovskite film for efficient solar cells, Published online: 01 April 2019; doi:10.1038/s41566-019-0398-2

High‐performance and stable perovskite solar cells with a power conversion efficiency exceeding 20% are achieved based on a low‐temperature solution‐processed ZnO electron transport layer. Dual passivation layers with TiO _x and phenyl‐C61‐butyric acid methyl ester (PCBM) enable the devices to exhibit good stability under an ambient air condition.

ZnO is considered as a potential electron transport layer (ETL) in solar cells due to its high charge carrier mobility and low‐temperature processability. However, it is challenging to obtain highly efficient and stable perovskite solar cells (PSCs) using low‐temperature ZnO ETL due to the poor chemical compatibility between ZnO and perovskite films. Hence, proper surface passivation strategies of ZnO ETL are developed to enhance the ZnO/perovskite interface stability for highly efficient PSCs. In this study, low‐temperature TiO _x post‐treatment is performed to passivate the ZnO surface, suppress the interface charge recombination, and stabilize the ZnO/perovskite interface. The fullerene treatment is further applied to enhance the electron transfer from perovskite to ZnO and reduce the hysteresis behavior. Finally, high‐performance PSCs with an efficiency of over 20% and improved stability are achieved.

Lead‐free double perovskite of Cs₂AgBiBr₆ was utilized as photocatalyst in a novel alcohol‐based photocatalytic system. Stable and highly efficient photocatlaytic degradation of dyes has been demonstrated.

Abstract

Composition engineering of halide perovskite allows the tunability of the band gap over a wide range so that photons can be effectively harvested, an aspect that is of critical importance for increasing the efficiency of photocatalysis under sunlight. However, the poor stability and the low photocatalytic activity of halide perovskites prevent use of these defect‐tolerant materials in wide applications involving photocatalysis. Here, an alcohol‐based photocatalytic system for dye degradation demonstrated high stability through the use of double perovskite of Cs₂AgBiBr₆. The reaction rate on Cs₂AgBiBr₆ is comparable to that on CdS, a model inorganic semiconductor photocatalyst. The fact of fast reaction between free radicals and dye molecules indicates the unique catalytic properties of the Cs₂AgBiBr₆ surface. Deposition of metal clusters onto Cs₂AgBiBr₆ effectively enhances the photocatalytic activity. Although the stability (five consecutive photocatalytic cycles without obvious decrease of efficiency) requires further improvements, the results indicate the significant potential of Cs₂AgBiBr₆‐based photocatalysis.

Retaining a stable and high built‐in potential across bulk heterojunction through interfacial modification and device engineering is a prerequisite for efficient and stable operation of nonfullerene organic solar cells.

Abstract

Remarkable progress has been made in the development of high‐efficiency solution‐processable nonfullerene organic solar cells (OSCs). However, the effect of the vertical stratification of bulk heterojunction (BHJ) on the efficiency and stability of nonfullerene OSCs is not fully understood yet. In this work, we report our effort to understand the stability of nonfullerene OSCs, made with the binary blend poly[(2,6‐(4, 8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′] dithiophene‐4,8‐dione)] (PBDB‐T):3,9‐ bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(4‐hexylphenyl)‐ dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′] dithiophene (ITIC) system. It shows that a continuous vertical phase separation process occurs, forming a PBDB‐T‐rich top surface and an ITIC‐rich bottom surface in PBDB‐T:ITIC BHJ during the aging period. A gradual decrease in the built‐in potential (V ₀) in the regular configuration PBDB‐T:ITIC OSCs, due to the interfacial reaction between the poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS) hole transporting layer and ITIC acceptor, is one of the reasons responsible for the performance deterioration. The reduction in V ₀, caused by an inevitable reaction at the ITIC/PEDOT:PSS interface in the OSCs, can be suppressed by introducing a MoO₃ interfacial passivation layer. Retaining a stable and high V ₀ across the BHJ through interfacial modification and device engineering, e.g., as seen in the inverted PBDB‐T:ITIC OSCs, is a prerequisite for efficient and stable operation of nonfullerene OSCs.

Schematic of the influence of light and thermal fluctuations on the PCBM:dimer population dynamics of a polymer:fullerene active layer. It is shown that a minimal rate model, parameterized by data from a facile UV–vis assay, can be employed to forecast the evolution and asymptotic behavior of this population, impacting the morphological and performance stability of solar cells.

Abstract

Photoinduced dimerization of phenyl‐C61‐butyric acid methyl ester (PCBM) has a significant impact on the stability of polymer:PCBM organic solar cells (OSCs). This reaction is reversible, as dimers can be thermally decomposed at sufficiently elevated temperatures and both photodimerization and decomposition are temperature dependent. In operando conditions of OSCs evidently involve exposure to both light and heat, following periodic diurnal and seasonal profiles. In this work, the kinetics of dimer formation and decomposition are examined and quantified as a function of temperature, light intensity, blend composition, and time. The activation energy for photodimerization is estimated to be 0.021(3) eV, considerably smaller than that for decomposition (0.96 eV). The findings are benchmarked with a variety of conjugated polymer matrices to propose a descriptive dynamic model of PCBM:dimer population in OSCs, and a framework is proposed to rationalize its interplay with morphology evolution and charge quenching. The model and parameters enable the prediction of the dynamic and long‐term PCBM:dimer populations, under variable temperature and light conditions, which impact the morphological stability of OSCs.

This paper presents aqueous, ultrasonically sprayed NiO_x hole transport layers (HTLs) with large‐area scalability and high photovoltaic performance in double cation perovskite solar cells, outperforming spin‐coated NiO_x from organic precursors and dramatically improving the fracture energy, a key metric of thermomechanical reliability. This robust and scalable HTL technology therefore has the potential to become a platform for scaling perovskite modules.

Abstract

Organometal halide perovskites have powerful intrinsic potential to drive next‐generation solar technology, but their insufficient thermomechanical reliability and unproven large‐area manufacturability limit competition with incumbent silicon photovoltaics. This work addresses these limitations by leveraging large‐area processing and robust inorganic hole transport layers (HTLs). Inverted perovskite solar cells utilizing NiO_x HTLs deposited by rapid aqueous spray‐coating that outperform spin‐coated NiO_x and lead to a 5× improvement in the fracture energy (G _c), a primary metric of thermomechanical stability, are presented. The morphology, chemical composition, and optoelectronic properties of the NiO_x films are characterized to understand and optimize compatibility with an archetypal double cation perovskite, Cs_.17FA_.83Pb(Br_.17I_.83)₃. Perovskite solar cells with sprayed NiO_x show higher photovoltaic performance, exhibiting up to 82% fill factor and 17.7% power conversion efficiency (PCE)—the highest PCE reported for inverted cell with scalable charge transport layers—as well as excellent stability under full illumination and after 4000 h aging in inert conditions at room temperature. By utilizing open‐air techniques and aqueous precursors, this combination of robust materials and low‐cost processing provides a platform for scaling perovskite modules with long‐term reliability.

High‐quality inorganic charge extraction layers are of key importance for efficient and stable perovskite‐based photovoltaics. In article number 1802995, Tobias Abzieher, Ulrich W. Paetzold, and co‐workers introduce oxygen‐assisted electron beam evaporation of NiO _x as a promising approach for the fabrication of highly transparent hole transport layers. By integrating these layers in inkjet‐printed and all‐evaporated perovskite solar cells, record PCEs are achieved.

Halide double perovskites represent a promising direction to fabricate lead‐free optoelectronic devices. The current progress and setbacks in crystal structures, materials preparation, optoelectronic properties, stability, challenge, and photovoltaic applications of lead‐free halide double perovskite compounds are reviewed in detail.

Abstract

The field of halide metal perovskite photovoltaics has caught widespread interest in the last decade. This is seen in the rapid rise of power conversion efficiency, which is currently over 23%. It has also stimulated a widespread application of halide metal perovskites in other fields, such as light‐emitting diodes, field‐effect transistors, detectors, and lasers. Despite the fascinating characteristics of the halide metal perovskites, the presence of toxic lead (Pb) in their chemical composition is regarded as one of the major limiting factors preventing their commercialization. Addressing the toxicity issues in these compounds by a careful and strategic replacement of Pb²⁺ with other nontoxic candidate elements represents a promising direction to fabricate lead‐free optoelectronic devices. Such attempts yield a halide double perovskite structure which allows flexibility for various compositional adjustments. Here, the authors present the current progress and setbacks in crystal structures, materials preparation, optoelectronic properties, stability, and photovoltaic applications of lead‐free halide double perovskite compounds. Prospective research directions to improve the optoelectronic properties of existing materials are given that may help in the discovery of new lead‐free halide double perovskites.