Chen Weijie

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.

Solar cells employing light‐harvesting alloyed Sb_0.67Bi_0.33SI (ASBSI) are demonstrated, which exhibit a power conversion efficiency of 4.07%. After incorporating Bi into Sb₂S₃, the bandgap decreases from 1.73 eV (Sb₂S₃) to 1.62 eV (ASBSI). This work paves the way for the application of alloy metal chalcohalogens in solar cells and provides intermediates for synthesizing new perovskite materials.

Abstract

Sb_{1− x} Bi _x SI, an isostructural material with the well‐known quasi‐1D SbSI, possesses good semiconductive and ferroelectric properties but is not applied in solar cells. Herein, solar cells based on alloyed Sb_0.67Bi_0.33SI (ASBSI) as a light harvester are fabricated. ASBSI is prepared through the reaction of bismuth triiodide in N,N‐dimethylformamide solution with an antimony trisulfide film deposited on a mesoporous (mp)‐TiO₂ electrode via chemical bath deposition at 250 °C under an argon or nitrogen atmosphere; the alloy exhibits a promising bandgap (1.62 eV). The best performing cell fabricated with poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)] as the hole‐transporting layer shows 4.07% in a power conversion efficiency (PCE) under the standard illumination conditions of 100 mW cm⁻². The unencapsulated cells exhibit good comprehensive stability with retention of 92% of zjr initial PCE under ambient conditions of 60% relative humidity over 360 h, 93% after 1 sun illumination for 1254 min, and 92% after storage at 85 °C in air for 360 h.

Two solid additives are proven to improve the molecular packing of acceptors, while devices processed with different additives exhibit different photovoltaic performances due to the different volatilities. The working mechanism and basic design rules of solid additives are revealed, and a feasible method for achieving high‐efficiency polymer solar cells is established.

Abstract

Fine‐tuning of the nanoscale morphologies of the active layers in polymer solar cells (PSCs) through various techniques plays a vital role in improving the photovoltaic performance. However, for emerging nonfullerene (NF) PSCs, the morphology optimization of the active‐layer films empirically follows the methods originally developed in fullerene‐based blends and lacks systematic studies. In this work, two solid additives with different volatilities, SA‐4 and SA‐7, are applied to investigate their influence on the morphologies and photovoltaic performances of NF‐PSCs. Although both solid additives effectively promote the molecular packing of the NF acceptors, due to the higher volatility of SA‐4, the devices processed with SA‐4 exhibit a power conversion efficiency of 13.5%, higher than that of the control devices, and the devices processed with SA‐7 exhibit poor performances. Through a series of detailed morphological analyses, it is found that the volatilization of SA‐4 after thermal annealing is beneficial for the self‐assembly packing of acceptors, while the residuals due to the incomplete volatilization of SA‐7 have a negative effect on the film morphology. The results delineate the feasibility of applying volatilizable solid additives and provide deeper insights into the working mechanism, establishing guidelines for further material design of solid additives.

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.

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.

Fluorinated perylenediimide (F‐PDI) is first introduced to optimize photovoltaic performance and stability of perovskite solar cells. Conductive F‐PDI effectively passivates defects and promotes charge transfer. The hydrophobicity of F‐PDI preventing moisture penetration as well as the strong hydrogen bonding immobilizing methylamine ions, thereby, endow excellent moisture and thermal stability with nearly 70% efficiency retention after thermal treatment at 100 °C.

Abstract

The notoriously poor stability of perovskite solar cells is a crucial issue restricting commercial applications. Here, a fluorinated perylenediimide (F‐PDI) is first introduced into perovskite film to enhance the device's photovoltaic performance, as well as thermal and moisture stability simultaneously. The conductive F‐PDI molecules filling at grain boundaries (GBs) and surface of perovskite film can passivate defects and promote charge transport through GBs due to the chelation between carbonyl of F‐PDI and noncoordinating lead. Furthermore, an effective multiple hydrophobic structure is formed to protect perovskite film from moisture erosion. As a result, the F‐PDI‐incorporated devices based on MAPbI₃ and Cs_0.05 (FA_0.83MA_0.17)_0.95 Pb (Br_0.17I_0.83)₃ absorber achieve champion efficiencies of 18.28% and 19.26%, respectively. Over 80% of the initial efficiency is maintained after exposure in air for 30 days with a relative humidity (RH) of 50%. In addition, the strong hydrogen bonding of F···H‐N can immobilize methylamine ion (MA⁺) and thus enhances the thermal stability of device, remaining nearly 70% of the initial value after thermal treatment (100 °C) for 24 h at 50% RH condition.

A highly transparent nickel oxide hole transport layer prepared by oxygen‐assisted electron beam evaporation for perovskite‐based photovoltaics is reported. Using these layers in perovskite solar cells, efficient devices with stable power conversion efficiencies up to 18.5% for inkjet‐printed absorbers and 15.4% for co‐evaporated absorbers are demonstrated. In addition, good stability at elevated temperature and under ultraviolet radiation is shown.

Abstract

High‐quality charge carrier transport materials are of key importance for stable and efficient perovskite‐based photovoltaics. This work reports on electron‐beam‐evaporated nickel oxide (NiO _x ) layers, resulting in stable power conversion efficiencies (PCEs) of up to 18.5% when integrated into solar cells employing inkjet‐printed perovskite absorbers. By adding oxygen as a process gas and optimizing the layer thickness, transparent and efficient NiO _x hole transport layers (HTLs) are fabricated, exhibiting an average absorptance of only 1%. The versatility of the material is demonstrated for different absorber compositions and deposition techniques. As another highlight of this work, all‐evaporated perovskite solar cells employing an inorganic NiO _x HTL are presented, achieving stable PCEs of up to 15.4%. Along with good PCEs, devices with electron‐beam‐evaporated NiO _x show improved stability under realistic operating conditions with negligible degradation after 40 h of maximum power point tracking at 75 °C. Additionally, a strong improvement in device stability under ultraviolet radiation is found if compared to conventional perovskite solar cell architectures employing other metal oxide charge transport layers (e.g., titanium dioxide). Finally, an all‐evaporated perovskite solar mini‐module with a NiO _x HTL is presented, reaching a PCE of 12.4% on an active device area of 2.3 cm².

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.

By using the new electron‐rich heptacyclic anthracene(cyclopentadithiophene) (AT) core, together with energy level modulations by end‐group optimizations enabling the match with polymer donors, two new nonfullerene small molecule acceptors AT‐NC and AT‐4Cl are synthesized. With both halogenated donor and acceptor, the organic photovoltaics device based on AT‐4Cl achieves a high power conversion efficiency of 13.27% with simultaneously improved J _sc and fill factor.

Abstract

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 V _oc 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 V _oc of 0.901 V, significantly enhanced J _sc 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.

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.

By using the new electron‐rich heptacyclic anthracene(cyclopentadithiophene) (AT) core, together with energy level modulations by end‐group optimizations enabling the match with polymer donors, two new nonfullerene small molecule acceptors AT‐NC and AT‐4Cl are synthesized. With both halogenated donor and acceptor, the organic photovoltaics device based on AT‐4Cl achieves a high power conversion efficiency of 13.27% with simultaneously improved J _sc and fill factor.

Abstract

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 V _oc 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 V _oc of 0.901 V, significantly enhanced J _sc 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.

The photophysics and nature of localized traps and their role on the optical properties of lead bromide perovskite films are investigated using optical spectroscopy and theoretical modeling. A clear understanding of the origin and nature of localized traps has important ramifications for perovskite light harvesting and emitting applications, as well as the design of new perovskites.

Abstract

Traps exert an omnipotent influence over the performance of halide perovskite optoelectronic devices. A clear understanding of the origin and nature of the traps in halide perovskites is the key to controlling them and realizing optimal devices. Herein, the role of localized traps on the optical properties of lead bromide perovskite films is investigated. In the low‐temperature orthorhombic phase of CH₃NH₃PbBr₃ perovskite, band‐edge carrier dynamics exhibit a power‐law decay due to the presence of structural‐disorder‐induced localized traps, which has a depth of ≈40 meV. The continuous distribution of these localized traps gives rise to a broad sub‐band‐gap emission that becomes more prominent in thicker films with a larger trap density. The presence of this emission only from the hybrid organic–inorganic perovskites points to the vital role of organic dipoles in localized trap states formation. This study explicates the nature of these localized traps as well as their nontrivial role in carrier recombination kinetics, which is of fundamental importance in perovskites optoelectronics.

The efficiency limits in non‐fullerene organic solar cells are examined using a numerical simulator. Power conversion efficiency (PCE) of over 18% using recently reported carrier mobility values and voltage losses, are predicted. Increasing the mobility to >10⁻³ cm² V⁻¹ s⁻¹ and decreasing the recombination constant to <10⁻¹² cm³ s⁻¹ is shown to yield a single‐junction and 2T‐tandem cell with PCEs of >20% and >25%, respectively.

Abstract

The reported power conversion efficiencies (PCEs) of nonfullerene acceptor (NFA) based organic photovoltaics (OPVs) now exceed 14% and 17% for single‐junction and two‐terminal tandem cells, respectively. However, increasing the PCE further requires an improved understanding of the factors limiting the device efficiency. Here, the efficiency limits of single‐junction and two‐terminal tandem NFA‐based OPV cells are examined with the aid of a numerical device simulator that takes into account the optical properties of the active material(s), charge recombination effects, and the hole and electron mobilities in the active layer of the device. The simulations reveal that single‐junction NFA OPVs can potentially reach PCE values in excess of 18% with mobility values readily achievable in existing material systems. Furthermore, it is found that balanced electron and hole mobilities of >10⁻³ cm² V⁻¹ s⁻¹ in combination with low nongeminate recombination rate constants of 10⁻¹² cm³ s⁻¹ could lead to PCE values in excess of 20% and 25% for single‐junction and two‐terminal tandem OPV cells, respectively. This analysis provides the first tangible description of the practical performance targets and useful design rules for single‐junction and tandem OPVs based on NFA materials, emphasizing the need for developing new material systems that combine these desired characteristics.

Suppression of the interfacial recombination are achieved by facile alkali chloride modification of the nickel oxide in inverted perovskite solar cells. It is demonstrated that the interface modification induces the ordering of the perovskite crystal at the interfaces, which in turn reduces defect/trap density, causing reduced interfacial recombination. This results in dramatically improvement of the open circuit voltage and power conversion efficiency.

Abstract

In this work, significant suppression of the interfacial recombination by facile alkali chloride interface modification of the NiOx hole transport layer in inverted planar perovskite solar cells is achieved. Experimental and theoretical results reveal that the alkali chloride interface modification results in improved ordering of the perovskite films, which in turn reduces defect/trap density, causing reduced interfacial recombination. This leads to a significant improvement in the open‐circuit voltage from 1.07 eV for pristine NiOx to 1.15 eV for KCl‐treated NiOx, resulting in a power conversion efficiency approaching 21%. Furthermore, the suppression of the ion diffusion in the devices is observed, as evidenced by stable photoluminescence (PL) under illumination and high PL quantum efficiency with alkali chloride treatment, as opposed to the luminescence enhancement and low PL quantum efficiency observed for perovskite on pristine NiOx. The suppressed ion diffusion is also consistent with improved stability of the devices with KCl‐treated NiOx. Thus, it is demonstrated that a simple interfacial modification is an effective method to not only suppress interfacial recombination but also to suppress ion migration in the layers deposited on the modified interface due to improved interface ordering and reduced defect density.

Solar cells employing light‐harvesting alloyed Sb_0.67Bi_0.33SI (ASBSI) are demonstrated, which exhibit a power conversion efficiency of 4.07%. After incorporating Bi into Sb₂S₃, the bandgap decreases from 1.73 eV (Sb₂S₃) to 1.62 eV (ASBSI). This work paves the way for the application of alloy metal chalcohalogens in solar cells and provides intermediates for synthesizing new perovskite materials.

Abstract

Sb_{1− x} Bi _x SI, an isostructural material with the well‐known quasi‐1D SbSI, possesses good semiconductive and ferroelectric properties but is not applied in solar cells. Herein, solar cells based on alloyed Sb_0.67Bi_0.33SI (ASBSI) as a light harvester are fabricated. ASBSI is prepared through the reaction of bismuth triiodide in N,N‐dimethylformamide solution with an antimony trisulfide film deposited on a mesoporous (mp)‐TiO₂ electrode via chemical bath deposition at 250 °C under an argon or nitrogen atmosphere; the alloy exhibits a promising bandgap (1.62 eV). The best performing cell fabricated with poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)] as the hole‐transporting layer shows 4.07% in a power conversion efficiency (PCE) under the standard illumination conditions of 100 mW cm⁻². The unencapsulated cells exhibit good comprehensive stability with retention of 92% of zjr initial PCE under ambient conditions of 60% relative humidity over 360 h, 93% after 1 sun illumination for 1254 min, and 92% after storage at 85 °C in air for 360 h.

Two solid additives are proven to improve the molecular packing of acceptors, while devices processed with different additives exhibit different photovoltaic performances due to the different volatilities. The working mechanism and basic design rules of solid additives are revealed, and a feasible method for achieving high‐efficiency polymer solar cells is established.

Abstract

Fine‐tuning of the nanoscale morphologies of the active layers in polymer solar cells (PSCs) through various techniques plays a vital role in improving the photovoltaic performance. However, for emerging nonfullerene (NF) PSCs, the morphology optimization of the active‐layer films empirically follows the methods originally developed in fullerene‐based blends and lacks systematic studies. In this work, two solid additives with different volatilities, SA‐4 and SA‐7, are applied to investigate their influence on the morphologies and photovoltaic performances of NF‐PSCs. Although both solid additives effectively promote the molecular packing of the NF acceptors, due to the higher volatility of SA‐4, the devices processed with SA‐4 exhibit a power conversion efficiency of 13.5%, higher than that of the control devices, and the devices processed with SA‐7 exhibit poor performances. Through a series of detailed morphological analyses, it is found that the volatilization of SA‐4 after thermal annealing is beneficial for the self‐assembly packing of acceptors, while the residuals due to the incomplete volatilization of SA‐7 have a negative effect on the film morphology. The results delineate the feasibility of applying volatilizable solid additives and provide deeper insights into the working mechanism, establishing guidelines for further material design of solid additives.

The device with binary additive of octance‐1,8‐dithiol:1,8‐diiodooctane (ODT:DIO) (0.375%:0.125%) based on FTAZ:ITIC‐Th blends exhibits a higher power conversion efficiency of 10.93% than the devices processed with only 0.5% ODT, 0.5% DIO, or excess binary additive of ODT:DIO (0.5%:0.5%). The reason is that additives with different boiling point work in different stages during the whole filming process as in situ grazing incidence wide‐angle X‐ray scattering characterization indicates.

Abstract

The power conversion efficiency of polymer solar cells (PSCs) is strongly affected by active layer morphology. Here, two solvent additives (ODT: octance‐1,8‐dithiol; DIO: 1,8‐diiodooctane) are used to optimize the bulk heterojunction morphology of FTAZ:ITIC‐Th based PSCs and ≈11% efficiency is obtained, which is 10% higher than the untreated device. Based on the morphological characterizations, the influence of binary solvent additives on manipulating molecular packing and phase separation of blend films is successfully revealed. More importantly, in situ grazing incidence wide‐angle X‐ray scattering characterization is adopted to explore the crucial role played by these two solvent additives at different stages of the film‐forming process, that is, ODT influences the initial stage of the film‐forming process, while DIO later establishes the ultimate photoactive film formation. Due to the impacts of two additives at different film processing stages, an optimal ratio of ODT:DIO (0.375%:0.125%) is obtained, which helps in realizing the optimized morphology.

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.

Publication date: June 2019

Source: Nano Energy, Volume 60

Author(s): Fengyou Wang, Yuhong Zhang, Meifang Yang, Lin Fan, Lili Yang, Yingrui Sui, Jinghai Yang, Xiaodan Zhang

Graphical abstract

Publication date: June 2019

Source: Nano Energy, Volume 60

Author(s): Chan Ul Kim, Jae Choul Yu, Eui Dae Jung, In Young Choi, Wonjin Park, Hyungmin Lee, Inho Kim, Dok-Kwon Lee, Kuen Kee Hong, Myoung Hoon Song, Kyoung Jin Choi

Graphical abstract

A low‐temperature solution‐processed TFB is demonstrated as an ideal hole‐transporting layer to push the PCE of the inverted perovskite solar cells (PVSCs) up to 20.2%. Moreover, this TFB‐based inverted PVSC exhibits good stability, retaining 90% of its original efficiency after storage for 30 days in ambient air.

Abstract

Low‐temperature‐processed inverted perovskite solar cells (PVSCs) attract increasing attention because they can be fabricated on both rigid and flexible substrates. For these devices, hole‐transporting layers (HTLs) play an important role in achieving efficient and stable inverted PVSCs by adjusting the anodic work function, hole extraction, and interfacial charge recombination. Here, the use of a low‐temperature (≤150 °C) solution‐processed ultrathin film of poly[(9,9‐dioctyl‐fluorenyl‐2,7‐diyl)‐co‐(4,4′‐(N‐(4‐secbutylphenyl) diphenylamine)] (TFB) is reported as an HTL in one‐step‐processed CH₃NH₃PbI₃ (MAPbI₃)‐based inverted PVSCs. The fabricated device exhibits power conversion efficiency (PCE) as high as 20.2% when measured under AM 1.5 G illumination. This PCE makes them one of the MAPbI₃‐based inverted PVSCs that have the highest efficiency reported to date. Moreover, this inverted PVSC also shows good stability, which can retain 90% of its original efficiency after 30 days of storage in ambient air.

A new asymmetric, terminally tetrafluorinated nonfullerene acceptor, namely ITIF, was prepared for ternary solar cells based on PBDB‐T:ITIF:ITIC blends. Owing to the unique structure, ITIF is promised to work efficiently in ternary blends, simultaneously boosting the devices performance parameters. Therefore, the power conversion efficiencies of the ternary solar cells are boosted from 9.2% to 10.5%.

Abstract

Fabricating ternary solar cells is a pivotal strategy to improve the power conversion efficiencies (PCEs) of organic photovoltaic devices. However, it is still a challenge to simultaneously improve the performance parameters of ternary devices. Therefore, the third ingredient in ternary blends should be precisely designed or selected. Herein, a new medium‐bandgap small‐molecule acceptor, namely, 3,9‐bis(2‐methylene‐(3‐(1‐(3,5‐dimethylphenyl)‐1cyanomethylene)indanone))‐5,5,11,11‐tetrakis‐(4‐hexylphenyl)dithieno[2,3‐d:2′,3′‐d′]‐sindaceno[1,2‐b:5,6‐b′]dithiophene (ITIF), is synthesized by end‐capping with a new fluorinated, asymmetric terminal group, (Z)‐2‐(3,5‐difluorophenyl)‐2‐(3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene) acetonitrile. Replacing the CN substituent with the asymmetric 3,5‐difluorophenyl substituent obviously up‐shifts the lowest unoccupied molecular orbital (LUMO) level of ITIF to −3.78 eV, enlarges the bandgap to 1.82 eV, and improves the absorption coefficient to ≈50% higher than that of 3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)indanone))‐5,5,11,11‐tetrakis‐(4‐hexylphenyl)dithieno[2,3‐d:2′,3′‐d′]‐sindaceno[1,2‐b:5,6‐b′]dithiophene (ITIC). Due to the similar structures, ITIF and ITIC can combine as an alloyed acceptor, which makes it convenient to tune the morphology and optical and electrochemical properties of ternary blends. The enhanced absorption coefficient of ITIF and the rapid fluorescence resonance energy transfer from ITIF to ITIC remarkably improve the absorption of the ternary blend film, hence compensating for the external quantum efficiency (EQE) curves. When ITIF is introduced into ternary solar cells based on 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):ITIF:ITIC blends, the PCEs of the ternary devices are increased from 9.2% to 10.5%, and the short‐circuit currents, open‐circuit voltages, and fill factors are simultaneously improved.