High Performance Roll‐to‐Roll Produced Fullerene‐Free Organic Photovoltaic Devices via Temperature‐Controlled Slot Die Coating

Solution‐processed organic photovoltaics (OPVs) have continued to show their potential as a low‐cost power generation technology; however, there has been a significant gap between device efficiencies fabricated with lab‐scale techniques—i.e., spin coating—and scalable deposition methods. Herein, temperature‐controlled slot die deposition is developed for the photoactive layer of OPVs. The influence of solution and substrate temperatures on photoactive films and their effects on power conversion efficiency (PCE) in slot die coated OPVs using a 3D printer‐based slot die coater are studied on the basis of device performance, molecular structure, film morphology, and carrier transport behavior. These studies clearly demonstrate that both substrate and solution temperatures during slot die coating can influence device performance, and the combination of hot substrate (120 °C) and hot solution (90 °C) conditions result in mechanically robust films with PCE values up to 10.0% using this scalable deposition method in air. The efficiency is close to that of state‐of‐the‐art devices fabricated by spin coating. The deposition condition is translated to roll‐to‐roll processing without further modification and results in flexible OPVs with PCE values above 7%. The results underscore the promising potential of temperature‐controlled slot die coating for roll‐to‐roll manufacturing of high performance OPVs.     

High Efficiency Planar p‐i‐n Perovskite Solar Cells Using Low‐Cost Fluorene‐Based Hole Transporting Material

For commercial applications, it is a challenge to find suitable and low‐cost hole‐transporting material (HTM) in perovskite solar cells (PSCs), where high efficiency spiro‐OMeTAD and PTAA are expensive. A HTM based on 9,9‐dihexyl‐9H‐fluorene and N,N‐di‐p‐methylthiophenylamine (denoted as FMT) is designed and synthesized. High‐yield FMT with a linear structure is synthesized in two steps. The dopant‐free FMT‐based planar p‐i‐n perovskite solar cells (pp‐PSCs) exhibit a high power conversion efficiency (PCE) of 19.06%, which is among the highest PCEs reported for the pp‐PSCs based on organic HTM. For comparison, a PEDOT:PSS HTM‐based pp‐PSC is fabricated under the same conditions, and its PCE is found to be 13.9%.     

All‐Carbon‐Electrode‐Based Endurable Flexible Perovskite Solar Cells

Endured, low‐cost, and high‐performance flexible perovskite solar cells (PSCs) featuring lightweight and mechanical flexibility have attracted tremendous attention for portable power source applications. However, flexible PSCs typically use expensive and fragile indium–tin oxide as transparent anode and high‐vacuum processed noble metal as cathode, resulting in dramatic performance degradation after continuous bending or thermal stress. Here, all‐carbon‐electrode‐based flexible PSCs are fabricated employing graphene as transparent anode and carbon nanotubes as cathode. All‐carbon‐electrode‐based flexible devices with and without spiro‐OMeTAD (2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene) hole conductor achieve power conversion efficiencies (PCEs) of 11.9% and 8.4%, respectively. The flexible carbon‐electrode‐based solar cells demonstrate superior robustness against mechanical deformation in comparison with their counterparts fabricated on flexible indium–tin oxide substrates. Moreover, all carbon‐electrode‐based flexible PSCs also show significantly enhanced stability compared to the flexible devices with gold and silver cathodes under continuous light soaking or 60 °C thermal stress in air, retaining over 90% of their original PCEs after 1000 h. The promising durability and stability highlight that flexible PSCs are fully compatible with carbon materials and pave the way toward the realization of rollable and low‐cost flexible perovskite photovoltaic devices.     

High Performance PbS Colloidal Quantum Dot Solar Cells by Employing Solution‐Processed CdS Thin Films from a Single‐Source Precursor as the Electron Transport Layer

CdS thin films are a promising electron transport layer in PbS colloidal quantum dot (CQD) photovoltaic devices. Some traditional deposition techniques, such as chemical bath deposition and RF (radio frequency) magnetron sputtering, have been employed to fabricate CdS films and CdS/PbS CQD heterojunction photovoltaic devices. However, their power conversion efficiencies (PCEs) are moderate compared with ZnO/PbS and TiO₂/PbS heterojunction CQD solar cells. Here, efficiencies have been improved substantially by employing solution‐processed CdS thin films from a single‐source precursor. The CdS film is deposited by a straightforward spin‐coating and annealing process, which is a simple, low‐cost, and high‐material‐usage fabrication process compared to chemical bath deposition and RF magnetron sputtering. The best CdS/PbS CQD heterojunction solar cell is fabricated using an optimized deposition and air‐annealing process achieved over 8% PCE, demonstrating the great potential of CdS thin films fabricated by the single‐source precursor for PbS CQDs solar cells.     

A universal roll‐to‐roll slot‐die coating approach towards high‐efficiency organic photovoltaics

This work develops a combinational use of solvent additive and in‐line drying oven on the flexible organic photovoltaics to improve large‐area roll‐to‐roll (R2R) slot‐die coating process. Herein, addition of 1,8‐diiodooctane (DIO) in the photoactive layer is conducted to yield a performance of 3.05% based on the blending of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PC₆₁BM), and a very promising device performance of 7.32% based on the blending of poly[[4,8‐bis[(2‐ethylhexyl)oxy] benzo[1,2‐b:4,5‐b’] dithiophene‐2,6‐diyl] [3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]] (PTB7) and [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM). Based on this R2R slot‐die coating approach for various polymers, we demonstrate the high‐performance result with respect to the up‐scaling from small high‐PCE cell to large‐area module. This present study provides a route for fabricating a low‐cost, large‐area, and environmental‐friendly flexible organic photovoltaics.     

Ambient Layer‐by‐Layer ZnO Assembly for Highly Efficient Polymer Bulk Heterojunction Solar Cells

The use of metal oxide interlayers in polymer solar cells has great potential because metal oxides are abundant, thermally stable, and can be used in flexible devices. Here, a layer‐by‐layer (LbL) protocol is reported as a facile, room‐temperature, solution‐processed method to prepare electron transport layers from commercial ZnO nanoparticles and polyacrylic acid (PAA) with a controlled and tunable porous structure, which provides large interfacial contacts with the active layer. Applying the LbL approach to bulk heterojunction polymer solar cells with an optimized ZnO layer thickness of ≈25 nm yields solar cell power‐conversion efficiencies (PCEs) of ≈6%, exceeding the efficiency of amorphous ZnO interlayers formed by conventional sputtering methods. Interestingly, annealing the ZnO/PAA interlayers in nitrogen and air environments in the range of 60–300 °C reduces the device PCEs by almost 20% to 50%, indicating the importance of conformational changes inherent to the PAA polymer in the LbL‐deposited films to solar cell performance. This protocol suggests a new fabrication method for solution‐processed polymer solar cell devices that does not require postprocessing thermal annealing treatments and that is applicable to flexible devices printed on plastic substrates.     

Roll‐to‐Roll Printed Silver Nanowire Semitransparent Electrodes for Fully Ambient Solution‐Processed Tandem Polymer Solar Cells

Silver nanowires (AgNWs) and zinc oxide (ZnO) are deposited on flexible substrates using fast roll‐to‐roll (R2R) processing. The AgNW film on polyethylene terephthalate (PET) shows >80% uniform optical transmission in the range of 550–900 nm. This electrode is compared to the previously reported and currently widely produced indium‐tin‐oxide (ITO) replacement comprising polyethylene terephthalate (PET)|silver grid|poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)|ZnO known as Flextrode. The AgNW/ZnO electrode shows higher transmission than Flextrode above 490 nm in the electromagnetic spectrum reaching up to 40% increased transmission at 750 nm in comparison to Flextrode. The functionality of AgNW electrodes is demonstrated in single and tandem polymer solar cells and compared with parallel devices on traditional Flextrode. All layers, apart from the semitransparent electrodes which are large‐scale R2R produced, are fabricated in ambient conditions on a laboratory roll‐coater using printing and coating methods which are directly transferrable to large‐scale R2R processing upon availability of materials. In a single cell structure, Flextrode is preferable with active layers based on poly‐3‐hexylthiophene(P3HT):phenyl‐C61‐butyric acid methylester (PCBM) and donor polymers of similar absorption characteristics while AgNW/ZnO electrodes are more compatible with low band gap polymer‐based single cells. In tandem devices, AgNW/ZnO is more preferable resulting in up to 80% improvement in PCE compared to parallel devices on Flextrode.     

Non‐destructive lateral mapping of the thickness of the photoactive layer in polymer‐based solar cells

Non‐destructive lateral mapping of the thickness of the photoactive layer in poly(3‐hexyl‐thiophene) : 1‐(3‐methoxy‐carbonyl)propyl‐1‐phenyl‐(6,6)C₆₁ (P3HT : PCBM) solar cells is demonstrated. The method employs a spatially resolved (XY) recording of ultraviolet‐visible spectra in reflection geometry at normal incidence, using a dense raster defined by a circular probe spot of 800‐µm diameter. The evaluation of the thickness of the photoactive layer at each raster point employs an algorithm‐driven comparison of the measured absorption spectrum with spectral features, as compiled from the corresponding simulated spectrum. For the robustness of the applied algorithm toward noise in the recorded absorption data to be increased, a new minimum finder algorithm is described and implemented. The thickness evaluation relies on the correct assignment of extrema in the experimental absorption spectra to the corresponding extrema in the simulated absorption spectra, and a new algorithm for this is also implemented and described. For a level of confidence for the method to be established, first thickness mapping is performed for a set of reference samples consisting of P3HT : PCBM spin‐coated on indium tin oxide‐coated float glass substrates. After this, two application examples for solar cells processed either by spin coating or slot die coating of the P3HT : PCBM layer follow. The spin‐coated solar cells have glass as the substrate with the P3HT : PCBM spun at different spinning speeds. The slot die‐coated solar cells were processed on polyethylene terephthalate foil in a roll‐to‐roll experiment involving a continuously changing P3HT : PCBM concentration along the printing direction. Copyright © 2011 John Wiley & Sons, Ltd.     

2D/3D Heterostructure for Semitransparent Perovskite Solar Cells with Engineered Bandgap Enables Efficiencies Exceeding 25% in Four‐Terminal Tandems with Silicon and CIGS

Wide‐bandgap perovskite solar cells (PSCs) with optimal bandgap (E_g) and high power conversion efficiency (PCE) are key to high‐performance perovskite‐based tandem photovoltaics. A 2D/3D perovskite heterostructure passivation is employed for double‐cation wide‐bandgap PSCs with engineered bandgap (1.65 eV ≤ E_g ≤ 1.85 eV), which results in improved stabilized PCEs and a strong enhancement in open‐circuit voltages of around 45 mV compared to reference devices for all investigated bandgaps. Making use of this strategy, semitransparent PSCs with engineered bandgap are developed, which show stabilized PCEs of up to 25.7% and 25.0% in four‐terminal perovskite/c‐Si and perovskite/CIGS tandem solar cells, respectively. Moreover, comparable tandem PCEs are observed for a broad range of perovskite bandgaps. For the first time, the robustness of the four‐terminal tandem configuration with respect to variations in the perovskite bandgap for two state‐of‐the‐art bottom solar cells is experimentally validated.     

Control of Crystal Growth toward Scalable Fabrication of Perovskite Solar Cells

With the impressive record power conversion efficiency (PCE) of perovskite solar cells exceeding 23%, research focus now shifts onto issues closely related to commercialization. One of the critical hurdles is to minimize the cell‐to‐module PCE loss while the device is being developed on a large scale. Since a solution‐based spin‐coating process is limited to scalability, establishment of a scalable deposition process of perovskite layers is a prerequisite for large‐area perovskite solar modules. Herein, this paper reports on the recent progress of large‐area perovskite solar cells. A deeper understanding of the crystallization of perovskite films is indeed essential for large‐area perovskite film formation. Various large‐area coating methods are proposed including blade, slot‐die, evaporation, and post‐treatment, where blade‐coating and gas post‐treatment have so far demonstrated better PCEs for an area larger than 10 cm². However, PCE loss rate is estimated to be 1.4 × 10^?2% cm^?2, which is 82 and 3.5 times higher than crystalline Si (1.7 × 10^?4% cm^?2) and thin film technologies (≈4 × 10^?3% cm^?2) respectively. Therefore, minimizing PCE loss upon scaling‐up is expected to lead to PCE over 20% in case of cell efficiency of >23%.     

Combustion Synthesized Zinc Oxide Electron‐Transport Layers for Efficient and Stable Perovskite Solar Cells

Perovskite solar cells (PSCs) have advanced rapidly with power conversion efficiencies (PCEs) now exceeding 22%. Due to the long diffusion lengths of charge carriers in the photoactive layer, a PSC device architecture comprising an electron‐ transporting layer (ETL) is essential to optimize charge flow and collection for maximum performance. Here, a novel approach is reported to low temperature, solution‐processed ZnO ETLs for PSCs using combustion synthesis. Due to the intrinsic passivation effects, high crystallinity, matched energy levels, ideal surface topography, and good chemical compatibility with the perovskite layer, this combustion‐derived ZnO enables PCEs approaching 17–20% for three types of perovskite materials systems with no need for ETL doping or surface functionalization.     

Synergistic Roll‐to‐Roll Transfer and Doping of CVD‐Graphene Using Parylene for Ambient‐Stable and Ultra‐Lightweight Photovoltaics

A roll‐to‐roll (R2R) transfer technique is employed to improve the electrical properties of transferred graphene on flexible substrates using parylene as an interfacial layer. A layer of parylene is deposited on graphene/copper (Cu) foils grown by chemical vapor deposition and are laminated onto ethylene vinyl acetate (EVA)/poly(ethylene terephthalate). Then, the samples are delaminated from the Cu using an electrochemical transfer process, resulting in flexible and conductive substrates with sheet resistances of below 300 Ω sq^?1, which is significantly better (fourfold) than the sample transferred by R2R without parylene (1200 Ω sq^?1). The characterization results indicate that parylene C and D dope graphene due to the presence of chlorine atoms in their structure, resulting in higher carrier density and thus lower sheet resistance. Density functional theory calculations reveal that the binding energy between parylene and graphene is stronger than that of EVA and graphene, which may lead to less tear in graphene during the R2R transfer. Finally, organic solar cells are fabricated on the ultrathin and flexible parylene/graphene substrates and an ultra‐lightweight device is achieved with a power conversion efficiency of 5.86%. Additionally, the device shows a high power per weight of 6.46 W g^?1 with superior air stability.     

Roll‐to‐roll gravure printing of organic photovoltaic modules—insulation of processing defects by an interfacial layer

Gravure printing as direct patterning roll‐to‐roll (R2R) production technology can revolutionize the design of thin‐film organic photovoltaic (OPV) devices by allowing feasible manufacturing of arbitrary‐shaped modules. This makes a distinction to coating methods, such as slot die coating, in which the pattern is limited to continuous stripes. Here, we analyze the thin‐film formation and its influence on OPV module performance as the gravure printing of hole transport and photoactive layers are transferred from laboratory to R2R pilot production environment. Insertion of a 0.8‐nm layer of lithium fluoride (LiF) as an interfacial layer between the active layer and the electron contact provided insulation against the detrimental pinholes formed in the R2R printing process. Using this device configuration, we produced well‐performing R2R‐printed monolithic modules with a mean efficiency of 1.7%. In comparison, reference modules with an efficiency of 2.2% were fabricated using laboratory‐scale bench top sheet‐level process. Surface energy and tension measurements together with optical microscopy were used to analyze the printability of the materials. The pinhole insulation was investigated in detail by processing R2R‐printed OPV modules with different interfacial layer materials and performing electrical measurements under dark and AM1.5 illumination conditions. Furthermore, we analyzed the LiF distribution using X‐ray photoelectron spectroscopy. The insulating nature of the LiF layer to improve module performance was confirmed by manufacturing lithographically artificial pinholes in device structures. The results show the possibility to loosen the production environment constraints and the feasibility of fabricating well‐performing thin‐film devices by R2R gravure printing. Copyright © 2014 John Wiley & Sons, Ltd.     

Two‐Step Sequential Deposition of Organometal Halide Perovskite for Photovoltaic Application

Organometal halide perovskite materials have become a superstar in the photovoltaic (PV) field because of their advantageous properties, which boost the power conversion efficiency (PCE) of perovskite solar cells (PSCs) from about 3.8% to above 22% in just seven years. Most importantly, such promising achievement is mainly based on its low‐cost and solution‐processed fabrication technique. One of the most promising and famous approaches to fabricating perovskite is a two‐step sequential deposition method because precursor (e.g., PbI₂) deposition is controllable, versatile, and flexible. Due to tremendous efforts, great progress has been achieved on the two‐step sequential deposition method, which helps to promote the development of PSCs. Herein, the progresses on the two‐step sequential deposition method of perovskite layers is reviewed thoroughly. At first, the reaction process and principle is introduced and discussed. Then, the research on the deposition techniques, structures, and compositions of precursors (the first step) is presented. Subsequently, the developments on the conversion techniques, conversion solutions, and growth of large crystals at the second step are introduced. Finally, four important issues on the two‐step sequential deposition method will be stated, accompanied with proposed solutions.     

Organometal Halide Perovskite Solar Cells with Improved Thermal Stability via Grain Boundary Passivation Using a Molecular Additive

Organometal halide perovskite solar cells (PeSCs) are regarded as promising photovoltaics due to their outstanding power conversion efficiencies (PCEs). However, even though their PCEs are achieved over 20%, their intrinsically poor stability is a big bottleneck for their practical uses. Here, a simple method is reported using phenyl‐C₆₁‐butyric acid methyl ester as a molecular additive to improve thermal stability of organometal halide perovskite crystals, which also improves the PCEs of the associated PeSCs. Moreover, by varying the grain size of perovskite crystals up to ≈150 µm, it is demonstrated that grain boundary plays a significant role in their thermal stability. Cells with smaller grain interface area (i.e., larger grain size) have higher thermal stability. The additive is located at grain boundaries and found to induce electron transfer reactions with halogens in the perovskite. The reaction products chemically passivate perovskite crystals and strongly bind halogen atoms at grain boundaries to their crystal lattice, preventing them from exiting from the crystal lattice, which improves thermal stability of perovskite crystals. This study offers a simple method for improving thermal stability of perovskite without any loss and opens up the possibility of the use of various molecular additives to achieve highly stable PeSCs.     

Solution‐Processable Perovskite Solar Cells toward Commercialization: Progress and Challenges

In the last few years, organometal halide perovskites (OHPs) have emerged as a promising candidate for photovoltaic (PV) applications. A certified efficiency as high as 23.7% has been achieved, which is comparable with most of the well‐established PV technologies. Their good solubility due to the ionic nature enables versatile low‐temperature solution processes, including blade coating, slot‐die coating, etc., most of which are scalable and compatible with roll‐to‐roll large‐scale manufacturing processes. The low cost, high efficiency, and facile processable features make perovskite solar cells (PSCs) a very competitive PV technology. Despite the great progress, long‐term durability concerns, toxicity issues of both materials and manufacturing process, and lack of robust high‐throughput production technology for fabricating efficient large‐area modules are major obstacles toward commercialization. In this review, the recent progress of commercially available process of PSCs is surveyed, the underlying determinants for upscaling high‐quality PSCs from hydrodynamic characteristics and crystallization thermodynamic mechanism are identified, the influence of external stress factors on stability of PSCs and intrinsic instability mechanism in OHPs themselves is revealed, and the environmental impact and sustainable development of PSC technology are analyzed. Strategies and opportunities for large‐scale production of PSCs are suggested to promote the development of PSCs toward commercialization.     

Sequential Deposition of High‐Quality Photovoltaic Perovskite Layers via Scalable Printing Methods

Sequential deposition is demonstrated as an effective technology for preparation of high‐performance perovskite solar cells based on lab‐scale spin coating. However, devices fabricated by scalable methods are lagging far behind their state‐of‐the‐art spin‐coated counterparts, largely due to the difficulty in obtaining high‐quality thin films of perovskites crystallized from printed precursors. Here, a generic strategy that allows sequential deposition of dense and uniform perovskite films via two‐step blade coating is reported. The rational selection of solvent combined with a mild vacuum extraction process enables us to produce uniform lead iodide (PbI₂) films over large areas. Significantly, the resulting PbI₂ films possess a mesoporous structure that is highly beneficial for the insertion reaction with methylammonium iodide (MAI). It is further identified that the deposition temperature of MAI plays an important role in determining the morphology and crystallinity of the perovskite films. Solar cells using these sequentially bladed perovskite layers yield efficiencies over 16% with high fill factors up to 78%. These results represent important progress toward the large‐scale deposition of perovskite thin films for practical applications.     

High‐speed atmospheric atomic layer deposition of ultra thin amorphous TiO2 blocking layers at 100 °C for inverted bulk heterojunction solar cells

Ultrafast, spatial atmospheric atomic layer deposition, which does not involve vacuum steps and is compatible with roll‐to‐roll processing, is used to grow high quality TiO₂ blocking layers for organic solar cells. Dense, uniform thin TiO₂ films are grown at temperatures as low as 100 °C in only 37 s (~20 nm/min growth rate). Incorporation of these films in P3HT‐PCBM‐based solar cells shows performances comparable with cells made using TiO₂ films deposited with much longer processing times and/or higher temperatures. Copyright © 2013 John Wiley & Sons, Ltd.     

Octadecylamine‐Functionalized Single‐Walled Carbon Nanotubes for Facilitating the Formation of a Monolithic Perovskite Layer and Stable Solar Cells

Organic–inorganic lead halide perovskites have shown great future for application in solar cells owing to their exceptional optical and electronic properties. To achieve high‐performance perovskite solar cells, a perovskite light absorbing layer with large grains is desirable in order to minimize grain boundaries and recombination during the operation of the device. Herein, a simple yet efficient approach is developed to synthesize perovskite films consisting of monolithic‐like grains with micrometer size through in situ deposition of octadecylamine functionalized single‐walled carbon nanotubes (ODA‐SWCNTs) onto the surface of the perovskite layer. The ODA‐SWCNTs form a capping layer that controls the evaporation rate of organic solvents in the perovskite film during the postthermal treatment. This favorable morphology in turn dramatically enhances the short‐circuit current density of the perovskite solar cells and almost completely eliminates the hysteresis. A maximum power conversion efficiency of 16.1% is achieved with an ODA‐SWCNT incorporated planar solar cell using (FA_0.83MA_0.17)_0.95Cs_0.05Pb(I_0.83Br_0.17)₃ as light absorber. Furthermore, the perovskite solar cells with ODA‐SWCNT demonstrate extraordinary stability with performance retention of 80% after 45 d stability testing under high humidity (60–90%) environment. This work opens up a new avenue for morphology manipulation of perovskite films and enhances the device stability using carbon material.     

Dithieno[3,2‐b:2′,3′‐d]pyrrol‐Cored Hole Transport Material Enabling Over 21% Efficiency Dopant‐Free Perovskite Solar Cells

Dopant‐free hole transport materials (HTMs) are essential for commercialization of perovskite solar cells (PSCs). However, power conversion efficiencies (PCEs) of the state‐of‐the‐art PSCs with small molecule dopant‐free HTMs are below 20%. Herein, a simple dithieno[3,2‐b:2′,3′‐d]pyrrol‐cored small molecule, DTP‐C6Th, is reported as a promising dopant‐free HTM. Compared with commonly used spiro‐OMeTAD, DTP‐C6Th exhibits a similar energy level, a better hole mobility of 4.18 × 10^?4 cm² V^?1 s^?1, and more efficient hole extraction, enabling efficient and stable PSCs with a dopant‐free HTM. With the addition of an ultrathin poly(methyl methacrylate) passivation layer and properly tuning the composition of the perovskite absorber layer, a champion PCE of 21.04% is achieved, which is the highest value for small molecule dopant‐free HTM based PSCs to date. Additionally, PSCs using the DTP‐C6Th HTM exhibit significantly improved long‐term stability compared with the conventional cells with the metal additive doped spiro‐OMeTAD HTM. Therefore, this work provides a new candidate and effective device engineering strategy for achieving high PCEs with dopant‐free HTMs.