Chen Weijie

Publication date: 15 January 2020

Source: Joule, Volume 4, Issue 1

Author(s): Wenchao Huang, Zhi Jiang, Kenjiro Fukuda, Xuechen Jiao, Christopher R. McNeill, Tomoyuki Yokota, Takao Someya

Four low‐cost copolymer donors of poly(thiophene‐quinoxaline) (PTQ) derivatives are developed to investigate the effect of their fluorination forms on charge‐separation and voltage loss (V _loss) of their polymer solar cells. The device based on the PTQ derivative with a bifluorine substituent on its quinoxaline A‐unit demonstrates a high power conversion efficiency of 16.21%, benefitting from the efficient charge separation and low V _loss.

Abstract

Four low‐cost copolymer donors of poly(thiophene‐quinoxaline) (PTQ) derivatives are demonstrated with different fluorine substitution forms to investigate the effect of fluorination forms on charge separation and voltage loss (V _loss) of the polymer solar cells (PSCs) with the PTQ derivatives as donor and a A–DA'D–A‐structured molecule Y6 as acceptor. The four PTQ derivatives are PTQ7 without fluorination, PTQ8 with bifluorine substituents on its thiophene D‐unit, PTQ9, and PTQ10 with monofluorine and bifluorine substituents on their quinoxaline A‐unit respectively. The PTQ8‐ based PSC demonstrates a low power conversion efficiency (PCE) of 0.90% due to the mismatch in the highest occupied molecular orbital (HOMO) energy levels alignment between the donor and acceptor. In contrast, the devices based on PTQ9 and PTQ10 show enhanced charge‐separation behavior and gradually reduced V _loss, due to the gradually reduced nonradiative recombination loss in comparison with the PTQ7‐based device. As a result, the PTQ10‐based PSC demonstrates an impressive PCE of 16.21% with high open‐circuit voltage and large short‐circuit current density simultaneously, and its V _loss is reduced to 0.549 V. The results indicate that rational fluorination of the polymer donors is a feasible method to achieve fast charge separation and low V _loss simultaneously in the PSCs.

Nature Communications, Published online: 14 November 2019; doi:10.1038/s41467-019-12951-7

Quantum dots are regarded as neutralized charged intermedia to transfer ligands for interfacial modification, which can significantly adjust surface electric properties to reduce V _OC loss and improve device performance. A stable V _OC enhancement with excellent reproducibility is fulfilled by simple solution‐processed QDs modification, achieving 20.6% power conversion efficiency (PCE) and enhanced stability.

The tremendous passion for inverted planar heterojunction perovskite solar cells (PSCs) is originated from their great tendency in the roll‐to‐roll process‐compatible fabrication and huge potential for integration into tandem solar cells. But the device efficiency is still lower than regular structured PSCs. Engineering of the cathode interface to efficiently control and reduce V _OC loss lights a lamp for increasing electrochemical properties and boosting overall performance. Herein, a simple interfacial modification strategy is developed by introducing a hybrid ligand interfacial layer to reduce V _OC loss in PSCs with inverted planar structure. Heavily washed QDs are used as neutral charged intermedia to enable alloying reaction to transfer ligands without damage to perovskite (PVK). A band bending is immediately generated on the top surface of PVK film after QDs modification, which is directly confirmed by ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe force microscopy (KPFM). This contributes to ≈50 mV reduced V _OC loss, leading to a V _OC of 1.15 V and a power conversion efficiency (PCE) of 20.6% in inverted PSCs. Meanwhile, enhanced stability is achieved for these devices after QDs modification, in which PCE is maintained at >90% of initial value after 1000 h storage.

A new small molecule IBC‐F as the third component to improve efficiency and stability of ternary polymer solar cells is developed. The ternary device with 20% IBC‐F exhibits a higher efficiency of 15.06% compared with the host binary PBDB‐T:IE4F‐S‐based device with an efficiency of 13.70%. Furthermore, the ternary devices show better thermal and photoinduced stability compared the binary devices.

Abstract

The use of a ternary active layer offers a promising approach to enhance the power conversion efficiency (PCE) of polymer solar cells (PSCs) via simply incorporating a third component. Here, a ternary PSC with improved efficiency and stability facilitated by a new small molecule IBC‐F is demonstrated. Even though the PBDB‐T:IBC‐F‐based device gives an extremely low PCE of only 0.21%, a remarkable PCE of 15.06% can be realized in the ternary device based on PBDB‐T:IE4F‐S:IBC‐F with 20% IBC‐F, which is ≈10% greater than that (PCE = 13.70%) of the control binary device based on PBDB‐T:IE4F‐S. The improvement in the device performance of the ternary PSC is mainly attributed to the enhancement of fill factor, which is due to the improved charge dissociation and extraction, suppressed bimolecular and trap‐assisted recombination, longer charge‐carrier lifetime, and enhanced intermolecular interactions for preferential face‐on orientation. Additionally, the ternary device with 20% IBC‐F shows better thermal and photoinduced stability over the control binary device. This work provides a new angle to develop the third components for building ternary PSCs with enhanced photovoltaic performance and stability for practical applications.

A carrier‐resolved photo‐Hall characterization technique is employed to simultaneously access majority/minority carrier properties as a function of light intensity for CH₃NH₃PbI₃ perovskite films processed without and with photovoltaic performance‐enhancing additives. Measurements on films with variable grain size reveal the passivation of bulk defects and n‐doping effect with PbI₂ excess and relative insensitivity to grain boundary density and thiocyanate additive concentration.

Abstract

With power conversion efficiencies now exceeding 25%, hybrid perovskite solar cells require deeper understanding of defects and processing to further approach the Shockley‐Queisser limit. One approach for processing enhancement and defect reduction involves additive engineering—, e.g., addition of MASCN (MA = methylammonium) and excess PbI₂ have been shown to modify film grain structure and improve performance. However, the underlying impact of these additives on transport and recombination properties remains to be fully elucidated. In this study, a newly developed carrier‐resolved photo‐Hall (CRPH) characterization technique is used that gives access to both majority and minority carrier properties within the same sample and over a wide range of illumination conditions. CRPH measurements on n‐type MAPbI₃ films reveal an order of magnitude increase in carrier recombination lifetime and electron density for 5% excess PbI₂ added to the precursor solution, with little change noted in electron and hole mobility values. Grain size variation (120–2100 nm) and MASCN addition induce no significant change in carrier‐related parameters considered, highlighting the benign nature of the grain boundaries and that excess PbI₂ must predominantly passivate bulk defects rather than defects situated at grain boundaries. This study offers a unique picture of additive impact on MAPbI₃ optoelectronic properties as elucidated by the new CRPH approach.

In this work, a “perovskite” template‐assisted structure is developed to fabricate high‐quality α‐FAPbI₃. The δ‐FAPbI₃ phases are avoided. Defects are substantially reduced with an excellent light harvesting. A power conversion efficiency of 21.24% (the highest efficiency reported for pure α‐FAPbI₃) is achieved. It also realizes a great stability in 800 h thermal ageing and 500 h light soaking.

Abstract

Formamidinium (FA) lead halide (α‐FAPbI₃) perovskites are promising materials for photovoltaic applications because of their excellent light harvesting capability (absorption edge 840 nm) and long carrier diffusion length. However, it is extremely difficult to prepare a pure α‐FAPbI₃ phase because of its easy transformation into a nondesirable δ‐FAPbI₃ phase. In the present study, a “perovskite” template (MAPbI₃‐FAI‐PbI₂‐DMSO) structure is used to avoid and suppress the formation of δ‐FAPbI₃ phases. The perovskite structure is formed via postdeposition involving the treatment of colloidal MAI‐PbI₂‐DMSO film with FAI before annealing. In situ X‐ray diffraction in vacuum shows no detectable δ‐FAPbI₃ phase during the whole synthesis process when the sample is annealed from 100 to 180 °C. This method is found to reduce defects at grain boundaries and enhance the film quality as determined by means of photoluminescence mapping and Kelvin probe force microscopy. The perovskite solar cells (PSCs) fabricated by this method demonstrate a much‐enhanced short‐circuit current density (  J _sc) of 24.99 mA cm⁻² and a power conversion efficiency (PCE) of 21.24%, which is the highest efficiency reported for pure FAPbI₃, with great stability under 800 h of thermal ageing and 500 h of light soaking in nitrogen.

Mesoporous boron‐doped TiO₂ (B‐TiO₂) is demonstrated as an improved electron transport layer (ETL) for perovskite solar cells for the reduction of hysteresis. The incorporation of boron dopant in TiO₂ ETL not only reduces the hysteresis but also improves device performance. Consequently, a methylammonium lead iodide photovoltaic device based on B‐TiO₂ ETL achieves a promising efficiency of 20.51% with negligible hysteresis.

Abstract

Perovskite solar cells (PSCs) have witnessed astonishing improvement in power conversion efficiency (PCE), more recently, with advances in long‐term stability and scalable fabrication. However, the presence of an anomalous hysteresis behavior in the current density–voltage characteristic of these devices remains a key obstacle on the road to commercialization. Herein, sol–gel‐processed mesoporous boron‐doped TiO₂ (B‐TiO₂) is demonstrated as an improved electron transport layer (ETL) for PSCs for the reduction of hysteresis. The incorporation of boron dopant in TiO₂ ETL not only reduces the hysteresis behavior but also improves PCE of the perovskite device. The simultaneous improvements are mainly ascribed to the following two reasons. First, the substitution of under‐coordinated titanium atom by boron species effectively passivates oxygen vacancy defects in the TiO₂ ETL, leading to increased electron mobility and conductivity, thereby greatly facilitating electron transport. Second, the boron dopant upshifts the conduction band edge of TiO₂, resulting in more efficient electron extraction with suppressed charge recombination. Consequently, a methylammonium lead iodide (MAPbI₃) photovoltaic device based on B‐TiO₂ ETL achieves a higher efficiency of 20.51% than the 19.06% of the pure TiO₂ ETL based device, and the hysteresis is reduced from 0.13% to 0.01% with the B‐TiO₂ based device showing negligible hysteresis behavior.

A low bandgap nonfullerene acceptor (NFA) is incorporated into fullerene electron‐transporting layer (ETL) of an inverted perovskite solar cell aiming to intercept the NIR light passing through the device. However, it cannot enhance the device's NIR photoresponse. Further adding a p‐type polymer effectively enhances the device's NIR photoresponse due to better cascade energy‐level alignment and increased hole mobility.

Abstract

How to extend the photoresponse of perovskite solar cells (PVSCs) to the region of near‐infrared (NIR)/infrared light has become an appealing research subject in this field since it can better harness the solar irradiation. Herein, the typical fullerene electron‐transporting layer (ETL) of an inverted PVSC is systematically engineered to enhance device's NIR photoresponse. A low bandgap nonfullerene acceptor (NFA) is incorporated into the fullerene ETL aiming to intercept the NIR light passing through the device. However, despite forming type II charge transfer with fullerene, the blended NFA cannot enhance the device's NIR photoresponse, as limited by the poor dissociation of photoexciton induced by NIR light. Fortunately, it can be addressed by adding a p‐type polymer. The ternary bulk‐heterojunction (BHJ) ETL is demonstrated to effectively enhance the device's NIR photoresponse due to the better cascade‐energy‐level alignment and increased hole mobility. By further optimizing the morphology of such a BHJ ETL, the derived PVSC is finally demonstrated to possess a 40% external quantum efficiency at 800 nm with photoresponse extended to the NIR region (to 950 nm), contributing ≈9% of the overall photocurrent. This study unveils an effective and simple approach for enhancing the NIR photoresponse of inverted PVSCs.

A donor derivative is incorporated in benzodithiophene terthiophene rhodanine (BTR)‐based thick‐film all‐small‐molecule (ASM) organic solar cells (OSC), which achieves power conversion efficiency of 10.14% and fill factor of 74.2%, outperforms its binary counterparts, and stands the record value for thick‐film dual‐donor ternary ASM OSCs. The results demonstrate that the donor derivative is a promising third component to boost the performance of ASM OSCs.

Abstract

Thick‐film all‐small‐molecule (ASM) organic solar cells (OSCs) are preferred for large‐scale fabrication with printing techniques due to the distinct advantages of monodispersion, easy purification, and negligible batch‐to‐batch variation. However, ASM OSCs are typically constrained by the morphology aspect to achieve high efficiency and maintain thick film simultaneously. Specifically, synchronously manipulating crystallinity, domain size, and phase segregation to a suitable level are extremely challenging. Herein, a derivative of benzodithiophene terthiophene rhodanine (BTR) (a successful small molecule donor for thick‐film OSCs), namely, BTR‐OH, is synthesized with similar chemical structure and absorption but less crystallinity relative to BTR, and is employed as a third component to construct BTR:BTR‐OH:PC₇₁BM ternary devices. The power conversion efficiency (PCE) of 10.14% and fill factor (FF) of 74.2% are successfully obtained in ≈300 nm OSC, which outperforms BTR:PC₇₁BM (9.05% and 69.6%) and BTR‐OH:PC₇₁BM (8.00% and 65.3%) counterparts, and stands among the top values for thick‐film ASM OSCs. The performance enhancement results from the enhanced absorption, suppressed bimolecular/trap–assisted recombination, improved charge extraction, optimized domain size, and suitable crystallinity. These findings demonstrate that the donor derivative featuring similar chemical structure but different crystallinity provides a promising third component guideline for high‐performance ternary ASM OSCs.

High performance flexible organic solar cells with efficiency above 12% for 1 cm² cells are fabricated using a Ag/Cu composite grid electrode. The excellent optical and electrical properties of the Ag/Cu electrode contribute to the high performance and good mechanical resistance of the flexible organic solar cell.

Abstract

With the rapid progress of organic solar cells (OSCs), improvement in the efficiency of large‐area flexible OSCs (>1 cm²) is crucial for real applications. However, the development of the large‐area flexible OSCs severely lags behind the growth of the small‐area OSCs, with the electrical loss due to the large sheet resistance of the electrode being a main reason. Herein, a high conductive and high transparent Ag/Cu composite grid with sheet resistance <1 Ω sq⁻¹ and an average visible light transparency of 84% is produced as the transparent conducting electrode of flexible OSCs. Based on this Ag/Cu composite grid electrode, a high efficiency of 12.26% for 1 cm² flexible OSCs is achieved. The performances of large‐area flexible OSCs also reach 7.79% (4 cm²) and 7.35% (9 cm²), respectively, which are much higher than those of the control devices with conventional flexible indium tin oxide electrodes. Surface planarization using highly conductive PEDOT:PSS and modification of the ZnO buffer layer by zirconium acetylacetonate (ZrAcac) are two necessary steps to achieve high performance. The flexible OSCs employing Ag/Cu grid have excellent mechanical bending resistance, maintaining high performance after bending at a radius of 2 mm.

The efficiency and stability of 2D perovskite solar cells are synergistically improved through metal ion doping. The hole extraction and transport abilities are significantly enhanced by Cu ion doping in the NiO _x layers, while the optoelectronic properties of the BA₂MA₃Pb₄I₁₃ (BA = butylamine; MA = methylammonium) layers are effectively improved with Cs ion doping.

Abstract

2D perovskites hold a great prospective to create highly efficient and stable solar cell devices. In order to explore their full potential, every component of 2D perovskite solar cells (PSCs) has to be carefully designed and engineered. Herein, the metal ion doping strategy is taken to optimize both the hole transport layers (HTLs) and the light absorbing layers of the BA₂MA₃Pb₄I₁₃ (BA = butylamine; MA = methylammonium) based 2D PSC devices. The hole extraction and transport abilities are significantly enhanced by Cu ion doping in the nickel oxide layers, while the optoelectronic properties of the BA₂MA₃Pb₄I₁₃ layers are effectively improved with Cs ion doping. The synergistic incorporations of Cu and Cs ions have boosted the device power conversion efficiency to 13.92%, the highest for 2D PSCs based on inorganic HTLs. In addition, the inorganic nature of the Cu doped nickel oxide film and the high quality of the Cs doped 2D perovskite film also endow the PSC device with extraordinary humidity and thermal stabilities.

The efficiencies of semitransparent perovskite device and four‐terminal perovskite/silicon multijunction/tandem solar cells rise to 18.3% and 27.0%, respectively. This is the highest recorded efficiency for semitransparent perovskite solar cells thus far. The high efficiencies originate from good transparency and high conductivity of the nanomesh‐structured gold top electrode.

Abstract

Multijunction/tandem solar cells have naturally attracted great attention because they are not subject to the Shockley–Queisser limit. Perovskite solar cells are ideal candidates for the top cell in multijunction/tandem devices due to the high power conversion efficiency (PCE) and relatively low voltage loss. Herein, sandwiched gold nanomesh between MoO₃ layers is designed as a transparent electrode. The large surface tension of MoO₃ effectively improves wettability for gold, resulting in Frank–van der Merwe growth to produce an ultrathin gold nanomesh layer, which guarantees not only excellent conductivity but also great optical transparency, which is particularly important for a multijunction/tandem solar cell. The top MoO₃ layer reduces the reflection at the gold layer to further increase light transmission. As a result, the semitransparent perovskite cell shows an 18.3% efficiency, the highest reported for this type of device. When the semitransparent perovskite device is mechanically stacked with a heterojunction silicon solar cell of 23.3% PCE, it yields a combined efficiency of 27.0%, higher than those of both the sub‐cells. This breakthrough in elevating the efficiency of semitransparent and multijunction/tandem devices can help to break the Shockley–Queisser limit.

Laminated perovskite layers with different crystal sizes and optical and electrical characteristics are achieved by using aniline as the solvent in the perovskite precursor solution. Inverted planar perovskite solar cells with the laminated films as active layers achieve an average power conversion efficiency of 20.65%, originating from the high V _OC 1.112 V and fill factor of 80.8%.

Abstract

Laminated multilayers of perovskite films with different optical and electronic characteristics will easily realize high‐performance optoelectronic devices because it is widely demonstrated that differential distribution of film properties in the vertical direction of devices plays particularly important roles in device performance. However, the existing laminated perovskite films are hardly prepared by a solution process because there is no solvent with sufficient selectivity of solubility for different perovskite materials. Here, it is demonstrated that aniline (AN) has a largely different solubility toward the perovskite MAPbI₃ and the MAPbI₃ blend with an additive of hydrochloride diethylammonium chloride. By using AN as the solvent in the perovskite precursor solution, two laminated perovskite layers with different crystal size and optical and electrical characteristics are achieved. Inverted perovskite solar cells with the laminated films as active layers achieve an averaged power conversion efficiency of 20.65% originating from the high V _OC 1.112 V and fill factor of 80.8%. The devices maintain 98% efficiency after 400 h under 65% RH. This work provides a very simple and feasible method for production of laminated perovskite films to achieve high‐performance perovskite solar cells.

Low‐cost and efficient organic small molecules are desired as hole transporting materials for high‐performance perovskite solar cells. Two new molecules containing a benzodithiophene core and triphenylamine side chains are synthesized from cheap starting materials by a simple and low‐cost method. Lead‐free, tin‐based perovskite solar cells employing these new benzodithiophene‐based hole transporting materials achieve good efficiencies.

Abstract

Developing efficient interfacial hole transporting materials (HTMs) is crucial for achieving high‐performance Pb‐free Sn‐based halide perovskite solar cells (PSCs). Here, a new series of benzodithiophene (BDT)‐based organic small molecules containing tetra‐ and di‐triphenyl amine donors prepared via a straightforward and scalable synthetic route is reported. The thermal, optical, and electrochemical properties of two BDT‐based molecules are shown to be structurally and energetically suitable to serve as HTMs for Sn‐based PSCs. It is reported here that ethylenediammonium/formamidinium tin iodide solar cells using BDT‐based HTMs deliver a champion power conversion efficiency up to 7.59%, outperforming analogous reference solar cells using traditional and expensive HTMs. Thus, these BDT‐based molecules are promising candidates as HTMs for the fabrication of high‐performance Sn‐based PSCs.

An ultrathin functional polymer layer is used to enhance the nucleation of atomic layer deposited (ALD) SnO₂ contacts in metal‐halide perovskite solar cells. These nucleation‐enhanced ALD layers act as “built‐in” barriers to both internal and external degradation pathways, significantly improving the long‐term operational stability of high efficiency unencapsulated devices (>18%) in air.

Abstract

Metal‐halide perovskites show promise as highly efficient solar cells, light‐emitting diodes, and other optoelectronic devices. Ensuring long‐term stability is now a major priority. In this study, an ultrathin (2 nm) layer of polyethylenimine ethoxylated (PEIE) is used to functionalize the surface of C₆₀ for the subsequent deposition of atomic layer deposition (ALD) SnO₂, a commonly used electron contact bilayer for p–i–n devices. The enhanced nucleation results in a more continuous initial ALD SnO₂ layer that exhibits superior barrier properties, protecting Cs_0.25FA_0.75Pb(Br_0.20I_0.80)₃ films upon direct exposure to high temperatures (200 °C) and water. This surface modification with PEIE translates to more stable solar cells under aggressive testing conditions in air at 60 °C under illumination. This type of “built‐in” barrier layer mitigates degradation pathways not addressed by external encapsulation, such as internal halide or metal diffusion, while maintaining high device efficiency up to 18.5%. This nucleation strategy is also extended to ALD VO _x films, demonstrating its potential to be broadly applied to other metal oxide contacts and device architectures.

Various definitions of band gaps are used in the perovskite solar cell community as a reference to analyze losses in open‐circuit voltage. This essay proposes a band‐gap independent method to reference voltages that is easy to implement and a meta‐analysis of literature data to illustrate the state of the art and development of voltage losses in perovskite solar cells.

Abstract

Open‐circuit voltages of lead‐halide perovskite solar cells are improving rapidly and are approaching the thermodynamic limit. Since many different perovskite compositions with different bandgap energies are actively being investigated, it is not straightforward to compare the open‐circuit voltages between these devices as long as a consistent method of referencing is missing. For the purpose of comparing open‐circuit voltages and identifying outstanding values, it is imperative to use a unique, generally accepted way of calculating the thermodynamic limit, which is currently not the case. Here a meta‐analysis of methods to determine the bandgap and a radiative limit for open‐circuit voltage is presented. The differences between the methods are analyzed and an easily applicable approach based on the solar cell quantum efficiency as a general reference is proposed.

Lead–tin‐based perovskites represent a promising route for achieving low‐gap perovskite solar absorbers and light‐emitters. Films composed of heterostructures of 2D and 3D lead–tin perovskite domains are fabricated with distinctively unique optoelectronic properties. These tunable structures enhance the understanding of the growth and optoelectronic properties of 2D/3D perovskite heterojunctions, and will see use in energy funneling and passivating structures.

Abstract

Halide perovskites are emerging as valid alternatives to conventional photovoltaic active materials owing to their low cost and high device performances. This material family also shows exceptional tunability of properties by varying chemical components, crystal structure, and dimensionality, providing a unique set of building blocks for new structures. Here, highly stable self‐assembled lead–tin perovskite heterostructures formed between low‐bandgap 3D and higher‐bandgap 2D components are demonstrated. A combination of surface‐sensitive X‐ray diffraction, spatially resolved photoluminescence, and electron microscopy measurements is used to reveal that microstructural heterojunctions form between high‐bandgap 2D surface crystallites and lower‐bandgap 3D domains. Furthermore, in situ X‐ray diffraction measurements are used during film formation to show that an ammonium thiocyanate additive delays formation of the 3D component and thus provides a tunable lever to substantially increase the fraction of 2D surface crystallites. These novel heterostructures will find use in bottom cells for stable tandem photovoltaics with a surface 2D layer passivating the 3D material, or in energy‐transfer devices requiring controlled energy flow from localized surface crystallites to the bulk.

Nature Energy, Published online: 11 November 2019; doi:10.1038/s41560-019-0492-1