Influence of flexible substrates on inverted organic solar cells using sputtered ZnO as cathode interfacial layer

Zinc oxide (ZnO) has recently shown to be of considerable interest for the development of interfacial buffer layers in inverted organic solar cells (OSCs). High quality ZnO thin films can indeed be prepared on large-area ITO-coated flexible substrates, using low temperature deposition techniques such as sputtering, a compatible technique with roll-to-roll process. However, further studies are still needed for a better understanding of the influence of the flexible substrate properties on the photovoltaic performances of those devices. In this work, ZnO films have been sputtered on ITO-coated flexible (PEN) substrates and annealed at different temperatures. The role of the surface morphology and the crystalline quality of ZnO films has been investigated. In the window of flexible compatible process, we found that moderate annealing temperatures of ZnO (?180 °C) lead to improved structural properties and performances. Interestingly, we achieve optimal performances for an annealing temperature of 160 °C, resulting in power conversion efficiency (PCE) equivalent to the highest performances usually achieved on rigid cells.     

Spontaneous growth by sol-gel process of low temperature ZnO as cathode buffer layer in flexible inverted organic solar cells

In this study, the sol–gel method was employed to prepare zinc oxide (ZnO) thin films as cathode buffer layers for inverted organic solar cells (IOSCs). We used a low temperature sol-gel process for the synthesis of ZnO thin films, in which the molar ratio of zinc acetate dihydrate (ZAD) to ethanolamine (MEA) was varied; subsequently, using the thin films, we successfully fabricated inverted solar cells on flexible plastic substrates. A ZnO sol–gel was first prepared by dissolving ZAD and MEA in ethylene glycol monomethyl ether (EGME). The molar ratios of ZAD to MEA were set as 1:1.2, 1:1, and 1:0.8, and we investigated the characteristics of the resulting ZnO thin films. We investigated the optical transmittance, surface roughness, and surface morphology of the films. Then, we discussed the reasons about the improvement of the device efficiency. The devices were fabricated using the ZnO thin films as cathode buffer layers. The results indicated that the morphology of the thin films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 changed to a rippled nanostructure after two-step annealing. The PCE was enhanced because of the higher light absorption in the active layer caused by the nanostructure. The structure of the inverted device was ITO/ZnO/P3HT:PC₆₁BM/MoO₃/Ag. The short-circuit current densities (8.59 mA/cm² and 8.34 mA/cm²) of the devices with films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 ratios, respectively, and annealed at 125 °C were higher than that of the device containing the ZnO thin film that was annealed at 150 °C. Inverted solar cells with ZnO films that were prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 and annealed at 125 °C exhibited PCEs of 3.38% and 3.30%, respectively. More than that, PCEs of the flexible device can reach up to 1.53%.     

Sputtered ZnO seed layer enhances photovoltaic behavior in hybrid ZnO/P3HT solar cells

We investigated the characteristics of inverted solar cells comprising bulk-heterojunction active layers of ZnO nanowire arrays and poly(3-hexylthiophene), P3HT. By utilizing a sputtered ZnO seed layer, we are able to grow vertically oriented ZnO nanowire arrays homoepitaxially. Unlike the ZnO nanowires that are grown on sol–gel derived seed layers, our nanowires are more uniform in their dimensions and spatial distribution. This sputtered seed layer also acts as the hole-blocking layer when these nanowire arrays are incorporated in solar cells; hybrid solar cells comprising these nanowires and P3HT exhibit power conversion efficiencies of 1.6%. To date, this is the highest efficiency observed for ZnO nanowire arrays:P3HT hybrid solar cells.     

Amphiphilic fullerene derivative as effective interfacial layer for inverted polymer solar cells

Amphiphilic fullerene derivative with poly(ethylene glycol) chain (C60-PEG) was applied as effective interfacial layer to improve the performance of inverted polymer solar cells. C60-PEG could not only be used as cathode buffer layer alone by replacing ZnO, but also be used as a self-assembled monolayer to modify ZnO. C60-PEG can tune energy level alignment and improve the interfacial compatibility between active layer and ITO or ZnO. Moreover, due to the strong interaction between ZnO nanoparticles and PEG chain, C60-PEG can passivate the surface defects and traps of ZnO, and facilitate the charge selective and dissociation. Consequently, inverted polymer solar cells based on thieno[3,4-b]thiophene/benzodithiophene (PTB7):[6,6]- phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) present a PCE of 6.6% by incorporating C60-PEG into as cathode buffer layer. Moreover, an improved PCE of 7.4% with good long-term stability in air were further achieved by using C60-PEG/ZnO interlayer. In this work, C60-PEG could be prepared by solution process at room temperature without additional annealing, which shows the potential in large-scale printed polymer solar cells.     

An air-stable inverted photovoltaic device using ZnO as the electron selective layer and MoO3 as the blocking layer

An air-stable photovoltaic device based on znic oxide nanoparticles (ZNP) in an inverted structure of indium tin oxide (ITO)/ZnO/poly (3-hexylthiophene) (P3HT): [6,6]-phenyl C61-butyric acid methyl ester (PCBM)/MoO3/Ag is studied. We find that the optimum thickness of the MoO3 layer is 2 nm. When the MoO3 blocking layer is introduced, the fill factor of the devices is increased from 29% to 40%, the power conversion efficiency is directly promoted from 0.35% to 1.27%.The stability under ambient conditions of this inverted structure device much is better due to the improved stability at the polymer/Ag interface. The enhancement is attributed to the high carriers mobility and suitable band gap of MoO3 layer.     

Enhanced performance in inverted polymer solar cells employing microwave-annealed sol-gel ZnO as electron transport layers

In this work, we propose a facile microwave-assisted approach for annealing sol-gel derived ZnO films to serve as electron transport layers (ETLs) for inverted bulk heterojunction polymer solar cells. We have demonstrated an impressive enhancement in performance for devices based on a poly (3-hexylthiophene) (P3HT): (6,6)-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) system employing the microwave-annealed ZnO (ZnO (MW)) ETLs in comparison to the cases using the conventional hotplate-annealed ZnO (ZnO (HP)) ones. The better electron transport in the device with the ZnO (MW) ETL is mainly ascribed to the preferable interfacial contact as evidenced by the morphology characteristics. Furthermore, the comprehensive analyses conducted from the light intensity dependent photocurrent and photovoltage measurements, the capacitance-voltage characteristics, and the alternating current impedance spectra suggest that the utilization of the ZnO (MW) ETLs can effectively suppress trap-assisted recombination as well as charge accumulation at the interface between P3HT: PC₆₁BM layers and ZnO layers, which is responsible for the enhanced device performance.     

Interfacial engineering of ZnO nanoarrays as electron transport layer for polymer solar cells

Highly uniform one-dimensional ZnO nanoarrays (ZnO NAs) fabricated by hydrothermal process were successfully explored as electron transport layer (ETL) for offering a direct and efficient path for electron transport in inverted polymer solar cells (PSCs). The inorganic CdS shell layer by in situ growth on the ZnO NAs surface was used to passivate and repair the surface defects of ZnO NAs. To further engineer the ZnO surface and improve the compatibility between ETL of inorganic ZnO/CdS core/shell and polymer blend contact junction, those organic molecules of 3,6,7,10,11-pentakis-(hexyloxy)-2-hydroxytriphenylene (TP-OH), 1-pyrenol (Py-OH) and 4′-(7-hydroxy-heptanoyl)-biphenyl-4-carbonitrile (BP-OH) were respectively spin-coated on the ZnO NAs/CdS surface to fabricate ETL based on ZnO/CdS/TP-OH NAs, ZnO/CdS/Py-OH NAs, ZnO/CdS/BP-OH NAs. The π–π interactions between the organic molecules and fullerene acceptors could lead to the well-organized distribution of active layer materials, which is in favor of the enhancement of electron selectivity and the reduction of recombination probability of electrons and holes. The incorporation of ZnO/CdS/Py-OH NAs as ETL into the inverted PSCs based on P3HT:PC₆₁BM resulted in a superior power conversion efficiency (PCE) of 4.2% with enhanced short circuit current (J_sc) and fill factor (FF), compared to 3.1% for bare ZnO NAs, due to the intermolecular close-stacking and relative stronger π–π interaction energy between Py-OH and fullerenes. In addition, the sensitized ZnO surface led to intimate interface between ETL and active layer, which would be in favor of increasing the stability of the device.     

A low-cost and low-temperature processable zinc oxide-polyethylenimine (ZnO:PEI) nano-composite as cathode buffer layer for organic and perovskite solar cells

Nanocomposite buffer layer based on metal oxide and polymer is merging as a novel buffer layer for organic solar cells, which combines the high charge carrier mobility of metal oxide and good film formation properties of polymer. In this work, a nanocomposite of zinc oxide and a commercialized available polyethylenimine (PEI) was developed and used as the cathode buffer layer (CBL) for the inverted organic solar cells and p-i-n heterojunction perovskite solar cells. The cooperation of PEI in nano ZnO offers a good film forming ability of the composite material, which is an advantage in device fabrication. In addition, power conversion efficiency (PCE) of the ZnO:PEI CBL based device was also improved when compared to that of ZnO-only and PEI-only devices. The highest PCE of P3HT:PC₆₁BM and PTB7-Th:PC₆₁BM devices reached to 3.57% and 8.16%, respectively. More importantly, there is no obvious device performance loss with the increase of the layer thickness of ZnO:PEI CBL to 60 nm in organic solar cells, which is in contrast to the PEI based devices, whose device performance decreases dramatically when the PEI layer thickness is higher than 6 nm. Such a nano composite material is also applicable in inverted heterojunction perovskite solar cells. A PCE of 11.76% was achieved for the perovskite solar cell with a thick ZnO:PEI CBL (150 nm) CBL, which is around 1.71% higher than that of the reference cell without CBL, or with ZnO CBL. In addition, stability of the organic and perovskite solar cells having ZnO:PEI CBL was also found to be improved in comparison with that of PEI based device.     

Improvement of ITO-free inverted polymer-based solar cells by using colloidal zinc oxide nanocrystals as electron-selective buffer layer

In this study, we report on the improvement of ITO-free inverted polymer/fullerene solar cells by introducing a zinc oxide (ZnO) layer between the active layer and the cathode. The ZnO layers are deposited from solution, using colloidal ZnO nanocrystals with a rodlike shape, which are obtained using a wet-chemical synthesis route at low temperature. The nanocrystals are widely characterized with respect to their structural, optical, and electronic properties. In particular, simulations of powder X-ray diffraction data based on Rietveld refinement are shown to be a suitable method to characterize the average crystallite shape and particle size. Cyclic voltammetry reveals that nanocrystalline ZnO is an appropriate choice as electron-selective buffer layer in organic solar cells based on a bulk heterojunction of poly (3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM). Using ITO-free inverted solar cells in substrate configuration with an opaque Cr/Al/Cr bottom electrode, we demonstrate that introducing a cathodic interlayer of ZnO nanocrystals leads to a notable enhancement in photovoltaic performance. The magnitude of the effect is found to depend on the solvents used to process the active layer. In case of absorber blends processed from o-dichlorobenzene, we show an almost threefold increase in efficiency from 0.8 to 2.2% at an active area of 1 cm².     

Effects of the Morphology of a ZnO Buffer Layer on the Photovoltaic Performance of Inverted Polymer Solar Cells

The influences of morphology and thickness of zinc oxide (ZnO) buffer layers on the performance of inverted polymer solar cells are investigated. ZnO buffer layers with different morphology and thickness varying from several nanometers to ≈55 nm are fabricated by adjusting the concentration of the precursor sol. The ZnO buffer layers with nearly same surface quality but with thickness varying from ≈7 to ≈65 nm are also fabricated by spinning coating for comparison. The photovoltaic performance is found to be strongly dependent on ZnO surface quality and less dependent on the thickness. The use of dense and homogenous ZnO buffer layers enhances the fill factor and short‐circuit current of inverted solar cell without sacrificing the open‐circuit voltage of device due to an improvement in the contact between the ZnO buffer layer and the photoactive layer. Inverted devices with a dense and homogenous ZnO buffer layer derived from 0.1 M sol exhibit an overall conversion efficiency of 3.3% which is a 32% increase compared to devices with a rough ZnO buffer layer made from 1 M sol, which exhibited a power conversion efficiency of 2.5%. The results indicate that the efficiency of inverted polymer solar cells can be significantly influenced by the morphology of the buffer layer.     

Improved efficiency and stability in polymer solar cells using a Tetra-nuclear Zinc(II) complex interfacial layer

Tetra-nuclear Zinc(II) complex Zn₄O(AID)₆ [AID = 7-azaindolate] is a wide band gap luminescent material that exhibits efficient emission matching the absorption spectra of organic donor materials such as polythiophene (P3HT). This work demonstrates polymer solar cells (PSC) based on P3HT:PCBM (phenyl-C₆₁-butyric acid methyl ester) blend active layer with a Zn₄O(AID)₆ cathode interfacial layer achieving a power conversion efficiency (PCE) significantly higher than that of the reference devices. The energy level and impedance spectroscopy analysis show that the Zn₄O(AID)₆ cathode interfacial layer acts as an efficient exciton/hole blocking layer, and reduces charge recombination rate with more efficient electron extraction. The Zn₄O(AID)₆ interfacial layer also helps achieve longer lifetime of PSC devices. The improved efficiency and stability combined with low cost and nontoxicity of Zn₄O(AID)₆ make it a promising cathode interfacial material for high-performance and stable PSC devices.     

Performance improvement mechanisms of P3HT:PCBM inverted polymer solar cells using extra PCBM and extra P3HT interfacial layers

A novel P3HT:PCBM inverted polymer solar cell (IPSC) was fabricated and investigated. An extra PCBM and an extra P3HT interfacial layers were inserted into the bottom side and the top side of the P3HT:PCBM absorption layer of the IPSCs to respectively enhance electron transport and hole transport to the corresponding electrodes. According to the surface energy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurement results, the extra PCBM interfacial layer could let more P3HT to form on the top side of the P3HT:PCBM blends. It revealed that the non-continuous pathways of P3HT in the P3HT:PCBM absorption layer could be reduced. Consequently, the carrier recombination centers were reduced in the absorption layer of IPSCs. The power conversion efficiency (PCE) of the P3HT:PCBM IPSCs with an extra PCBM interfacial layer greatly increased from 3.39% to 4.50% in comparison to the P3HT:PCBM IPSCs without an extra PCBM interfacial layer. Moreover, the performance of the P3HT:PCBM IPSCs with an extra PCBM interfacial layer could be improved by inserting an extra P3HT interfacial layer between the absorption layer and the MoO₃ layer. The PCE of the resulting IPSCs increased from 4.50% to 4.97%.     

An efficient inverted organic solar cell with improved ZnO and gold contact layers

This paper presents a high efficiency (～3.8%) inverted organic photovoltaic devices based on a P3HT:PCBM bulk heterojunction (BHJ) blend with improved electron- and hole-selective contact layers. Zinc oxide (ZnO) nanoparticle films with different thicknesses are deposited on the transparent electrodes as a nano-porous electron-selective contact layer. A thin gold film is used between the BHJ photoactive layer and the poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), which improves the wettability and significantly enhances the stability of the device (>50 days of air exposure). Photovoltaic device parameters such as power conversion efficiency (PCE) and external quantum efficiency (EQE) are systematically examined for inverted devices with different thicknesses of ZnO and gold layers in comparison to the non-inverted and reference inverted devices with no contact layers. The optimized organic devices with ZnO and Au contact layers show exceptional short circuit currents (in excess of 13 mA/cm²), in comparison to the reference devices, which is related to increased quantum efficiency of the device observed in measured EQE experiments. These results are important for development of high efficiency and stable all-printed organic solar cells and point out the role of contact layers, in particular, ZnO conductivity and morphology in the device performance.     

Performance improvement of conventional and inverted polymer solar cells with hydrophobic fluoropolymer as nonvolatile processing additive

The morphology of the photoactive layer critically affects the performance of the bulk heterojunction polymer solar cells (PSCs). To control the morphology, we introduced a hydrophobic fluoropolymer polyvinylidene fluoride (PVDF) as nonvolatile additive into the P3HT:PCBM active layer. The effect of PVDF on the surface and the bulk morphology were investigated by atomic force microscope and transmission electron microscopy, respectively. Through the repulsive interactions between the hydrophilic PCBM and the hydrophobic PVDF, much more uniform phase separation with good P3HT crystallinity is formed within the active layer, resulting enhanced light harvesting and improved photovoltaic performance in conventional devices. The PCE of the conventional device can improve from 2.40% to 3.07% with PVDF additive. The PVDF distribution within the active layer was investigated by secondary ion mass spectroscopy, confirming a bottom distribution of PVDF. Therefore, inverted device structure was designed, and the PCE can improve from 2.81% to 3.45% with PVDF additive. Our findings suggest that PVDF is a promising nonvolatile processing additive for high performance polymer solar cells.     

Influence of annealing temperature of ZnO film as the electron transport layer on the performance of polymer solar cells

The surface morphology of ZnO films at different annealing temperatures and the performance of polymer solar cells (PSCs) with ZnO as the electron transport layer are studied. The low temperature sol-gel processed ZnO film has smoother surface than that in higher temperature, which results in the best photovoltaic performance with a power conversion efficiency (PCE) of 3.66% for P3HT:PC61BM based solar cell. With increasing annealing temperature, the photovoltaic performance first deceases and then increases. It could be ascribed to the synergy effects of interface area, the conductivity and surface energy of ZnO film and series resistance of devices.     

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.     

Device stability of inverted and conventional bulk heterojunction solar cells with MoO3 and ZnO nanoparticles as charge transport layers

The performance and stability of both inverted and conventional organic photovoltaic devices were examined with low temperature chemically synthesized ZnO nanoparticles as electron transporting layer and MoO₃ as hole transporting layer. The device efficiency and energy conversion efficiency in inverted devices were found to be 3.48% and 68%, respectively, whereas, in conventional devices these were 2.86% and 55%, respectively. This change of efficiency in inverted and conventional devices relates with the change of flatband voltage extracted from Mott-Schottky capacitance study. The inverted device shows excellent efficiency even after 250 h in unencapsulated condition. However, the conventional device efficiency degrades very quickly compared with the inverted one. Thus, the films deposition order plays a pivotal role for fabricating a stable and high performance organic photovoltaic device.     

Incorporation of SiO2 dielectric nanoparticles for performance enhancement in P3HT:PCBM inverted organic solar cells

It is well known that organic solar cells (OSCs) with inverted geometry have not only demonstrated a better stability and longer device life time but also have shown improved power conversion efficiency (PCE). Recent studies exhibit that incorporation of metal and/or semiconducting nanoparticles (NPs) can further increase the PCE for OSCs. In this present work, we have synthesized SiO₂ NPs of various sizes (25, 50, 75 and 100 nm) using the modified Stober method and incorporated them into P3HT:PCBM photoactive layer and ZnO based electron transport layer (ETL) in order to investigate the light trapping effects in an OSC. Absorption studies have shown a considerable increase in photo absorption in both cases. The fabricated devices demonstrated 13% increase in the PCE when SiO₂ NPs are incorporated in P3HT:PCBM photoactive layer, whereas PCE was increased by 20% when SiO₂ NPs are incorporated in ZnO based ETL. Mott–Schottky analysis and impedance spectroscopy measurements have been carried out to determine the depletion width and global mobility for both the devices. The possible reason for PCE enhancement and the role of SiO₂ NPs in active layer and ZnO ETL are explained on the basis of the results obtained from Mott–Schottky analysis and impedance spectroscopy measurements.     

In-situ investigation of interfacial effects on charge accumulation and extraction in organic solar cells based on transient photocurrent studies

In organic solar cells, the interfacial and bulk photovoltaic processes are typically coupled based on charge transport and accumulation. In this article, we demonstrated that the in situ transient photocurrent measurements can be a powerful approach to separately investigate the interfacial effects on interfacial and bulk photovoltaic process. Based on this method, the effects of interfacial dipoles on charge extraction, accumulation, and recombination are solely studied by comparing Ca and Al devices with standard architecture of ITO/PEDOT/P3HT:PCBM/cathode. We observe that stronger interfacial dipoles can significantly decrease the charge extraction time and consequently increase the charge extraction efficiency. More importantly, stronger interfacial dipoles can also decrease the charge accumulation within the bulk photovoltaic layer. Furthermore, our experimental results indicate that the bulk-accumulated charges can act as recombination centers under device-operating condition, resulting in the recombination loss in photogenerated carriers. Clearly, our studies of transient photocurrents elucidated the charge extraction, accumulation, and recombination in OSCs.