Highly conductive Zinc-Tin-Oxide buffer layer for inverted polymer solar cells

Thin-films of Zinc Tin Oxide (ZTO) with an extremely high charge carrier mobility and superior optical transmittance are synthesized using a simple solution method. These ZTO films have been systematically studied for the application in inverted polymer solar cells (PSCs). The Hall effects measurements show that the charge mobility of the ZTO semiconductor is over 16.5 cm².V⁻¹.S⁻¹, which is the highest mobility value ever reported for oxide buffer made by using solution process. By applying the ZTO buffer layer in the inverted PSCs of P3HT:PC₆₁BM, the power conversion efficiency of the device is 30% higher than that of the devices made with other common buffer layers such as ZnO and TiO₂. Light intensity-dependent JV studies and PL measurements also indicate that ZTO buffer layer reduces surface recombination. This work demonstrates that the solution-synthesized ZTO is a promising new buffer layer with superior electron extraction capability for the solar cells.     

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.     

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.     

Properties of inverted polymer solar cells based on novel small molecular electrolytes as the cathode buffer layer

Novel small-molecule electrolytes were designed and synthesized for use in the cathode interlayer in bulk-heterojunction polymer solar cells (PSCs). The synthesized materials consist of polar quaternary ammonium bromide with the addition of multiple hydroxyl groups, which are N,N,N,N,N,N-hexakis(2-hydroxyethyl)butane-1,4-diaminium bromide (C4) and N,N,N,N,N,N-hexakis(2-hydroxyethyl)hexane-1,6-diaminium bromide (C6). The materials generate a favorable interface dipole through the quaternary ammonium bromide. In addition, the multiple polar hydroxyl groups increased the interface dipole magnitude. The power conversion efficiency of the devices with the interlayer was up to 9.20% with a J_sc of 17.22 mA/cm², a V_oc of 0.75 V, and an FF of 71.3%. The PCE of devices with an interlayer show better long-term stability than a device without an interlayer. Our strategy shows that it is possible to enhance the efficiency of PSCs by simple approaches without complicated syntheses.     

Solution-processed annealing-free ZnO nanoparticles for stable inverted organic solar cells

We report the development and application of high-quality zinc oxide nanoparticles (ZnO NPs) processed in air for stable inverted bulk heterojunction solar cells as an electron extraction layer (EEL). The ZnO NPs (average size ∼11 nm) were dispersed in chloroform and stabilized by propylamine (PA). We demonstrated that the ZnO NP dispersion with 4 vol.% of PA as stabilizer can be used in air directly and remains clear up to one month after preparation. Our inverted solar cells consisted of a blade-coated poly(N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole (PCDTBT) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) (1: 4 by weight) active layer sandwiched between a ZnO electron extraction layer and a MoO₃/Ag anode. All solar cells with ZnO films fabricated in air using PA-stabilized ZnO dispersions prepared within a time window of one month exhibited power conversion efficiencies (PCE) above 4%. In contrast, if the ZnO film was prepared in air using regular un-stabilized ZnO NP dispersion, the PCE would drop to 0.2% due to poor film quality. More interestingly, X-ray photoelectron spectroscopy and nuclear magnetic resonance measurements indicated that the PA ligands were not covalently bonded to ZnO NPs and did not exist in the deposited ZnO films. The spin-cast ZnO thin films (without any thermal treatment) are insoluble in organic solvents and can be directly used as an EEL in solar cells. This feature is beneficial for fabricating organic solar cells on flexible polymer substrates. More importantly, our non-encapsulated inverted solar cells are highly stable with their PCEs remaining unchanged after being stored in air for 50 days.     

Enhanced photovoltaic performance in inverted polymer solar cells using Li ion doped ZnO cathode buffer layer

We have proposed an approach to improve the photovoltaic performance of inverted polymer solar cells (i-PSC) using lithium ion doped ZnO (LiZnO) as cathode buffer layer (CBL). The LiZnO CBL was prepared using the diffusion technique, performed by inducing the Li ion of 8-hydroxyquinolatolithium (Liq) to diffuse into ZnO film through annealing the bi-layer ZnO/Liq film. Doping concentration of Li ion was controlled by using various thickness of Liq film and annealing temperature. Based on LiZnO CBL, the poly (3-hexylthiophene) [6,6]:-phenyl C61-butyric acid methyl ester (P3HT:PCBM) i-PSC device possessed a optimal power conversion efficiency (PCE) of 4.07%, which was 30% improved than that of the device with neat ZnO as CBL. The enhancement of the device performance could be attributed to the enhanced electron mobility and better band matching of the LiZnO CBL. Our finding indicates that the LiZnO film fabricated with relatively low temperature treatment has great potential for high-performance i-PSCs.     

Enhanced performance in inverted polymer solar cells via solution process: Morphology controlling of PEDOT:PSS as anode buffer layer by adding surfactants

Inverted polymer solar cells were fabricated by adding the amphiphilic surfactant ‘Surfynol 104 series’ to Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a anode buffer layer by solution process. With the introduction of Surfynol 104 series-added PEDOT:PSS, it was able to form a homogeneous film by adjusting the wettability of a hydrophobic poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) film. With decrease in series resistance (R_S) and increase in shunt resistance (R_SH), as a result, the short circuit current density (J_SC), open circuit voltage (V_OC) and fill factor (FF) of the optimized device were 10.2 mA/cm², 0.63 V and 61.3%, respectively, calculated the power conversion efficiency (PCE) was 4.0%. In addition, the air stability of the fabricated device was improved.     

Polyacetylene-based polyelectrolyte as a universal interfacial layer for efficient inverted polymer solar cells

Here we report that poly(N-dodecyl-2-ethynylpyridiniumbromide) (PDEPB) interlayers between electron-collecting zinc oxide (ZnO) layers and bulk heterojunction (BHJ) layers act as a universal interfacial layer for improving the performances of inverted-type polymer:fullerene solar cells. Three different BHJ layers, poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), poly[(4,8-bis(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(N-2-ethylhexylthieno[3,4-c]pyrrole-4,6-dione)-2,6-diyl]] (PBDTTPD):PC₆₁BM, and 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), were employed so as to prove the role of the PDEPB interlayers. Results showed that the power conversion efficiency (PCE) of polymer:fullerene solar cells with the three different BHJ layers increased in the presence of the PDEPB interlayers prepared from 0.5 mg/ml solutions. The improved PCE was attributed to the conformal coating of the PDEPB layers on the ZnO layers (by atomic force microscopy measurement), lowered work functions of ZnO induced by the PDEPB layers (by Kelvin probe measurement), and reduced interface resistance (by impedance spectroscopy measurement), as supported by the noticeable change in the atom environments of both the ZnO and PDEPB layers (by X-ray photoelectron spectroscopy measurement).     

Improved performance of inverted polymer solar cells by utilizing alcohol-soluble oligofluorenes as efficient cathode interlayers

Two star-shaped oligofluorenes with hexakis(fluoren-2-yl)benzene as core are designed and synthesized, namely Tn0 and Tn1. Diethylamino groups are attached to the side chain of fluorene units of Tn0 and Tn1 and enable them alcohol solubility, additional hydrophobic nhexyl chains are grafted on the π-extended fluorene arms of Tn1. Power conversion efficiency (PCE) as high as 8.62% and 8.80% are achieved when utilizing Tn0 and Tn1 as cathode interlayers in inverted polymer solar cells, respectively. The work function of ITO effectively decreased by introducing interlayer, resulting in high Voc of the device, besides, the wetting properties of the interlayers can be tuned by modifying the oligofluorenes with π-extended structure, and the more hydrophobic interlayer will benefit the device performance with enhanced Jsc and FF.     

Acid-functionalized fullerenes used as interfacial layer materials in inverted polymer solar cells

Two types of carboxylic acid functionalized fullerence derivatives, 4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (p-EHO-PCBA) and bis-4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (bis-p-EHO-PCBA), were synthesized and investigated as an interfacial layer for inverted polymer solar cells (iPSCs). The –COOH groups on the PCBAs chemisorb to inorganic metal oxide (TiO_X), generating fullerene-based self-assembled monolayers (FSAMs). The devices with the mono- and bis-FSAMs exhibited substantially lower series resistance (R_S) values of 2.10 Ω cm² and 1.46 Ω cm², compared to that (4.15 Ω cm²) of the unmodified device. The TiO_X films modified with mono- and bis-FSAMs showed higher contact angles of 50° and 91°, respectively, than that of the pristine TiO_X film (33°). The increased contact angles were attributed to the enhanced hydrophobicity, improving the wetting properties with the organic photoactive layer. In addition, a comparison of device characteristics with electroactive FSAMs and non-electroactive benzoic acid SAMs clearly indicates that the FSAMs may suggest an additional pathway for photo-induced charge transfer and charge collection to ITO. After surface modification with FSAMs, the short-circuit current density (J_SC) and fill factor (FF) values increased substantially. The iPSCs based on poly(5,6-bis(octyloxy)-4-(thiophen-2-l)benzo[c][1,2,5]thiadiazole) (PTBT) and [6,6]phenyl-C₆₁-butyric acid methyl ester (PCBM) as an active layer showed remarkably improved power conversion efficiency up to 5.13% through incorporation of the FSAMs-based interfacial layer.     

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.     

High-resistivity sol-gel ITO thin film as an interfacial buffer layer for bulk heterojunction organic solar cells

Bulk heterojunction organic solar cells have been fabricated by inserting a high-resistivity sol-gel ITO buffer layer between an ITO anode and a PEDOT:PSS hole injection layer. The performance of the devices with the sol-gel ITO atop the ITO anodes treated by conventional annealing at 500 °C for 1 h and rapid thermal process (RTP) at 800 °C for 20 and 30 s was compared. The best power conversion efficiency of 3.5% was achieved for the device with the 15-nm-thick sol-gel ITO treated with RTP at 800 °C for 30 s, as compared with 2.7% of the standard device under an illumination of AM 1.5. In addition, the short circuit current of the device was significantly increased by 42.7%. The observed enhancement of the short circuit current can be attributed an interfacial energy step created by the high-resistivity sol-gel ITO between the ITO anode and the PEDOT:PSS.     

基于CuBB为阴极缓冲层有机太阳能电池性能的研究

通过定向合成Cu(I)配合物,首次将 其作为阴极缓冲层引入到有机太阳能电池(OSCs)中。实验分析发现,OSCs的光电能量转换效 率(PCE)与CuBB层厚度紧密相关,在标准太阳 光照条件下,结构为ITO/CuPc (20nm)/C60(40nm)/CuBB (x m m)/Al (100nm)的器件PCE随着CuBB厚度的增加 先增大后变小,当厚为8nm 时PCE达到0.94%。器件性能提高的原因主要是CuBB具有良好 的电子迁移率,但厚度过大时则由于串联电阻增加及电子不能经阴极缓冲层传输而使性能降 低。     

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.     

Atomic layer deposition of ZnO electron transporting layers directly onto the active layer of organic solar cells

Interlayers in organic solar cells (OSCs) are used to reduce energy barriers for charge injection/extraction, act as optical spacers, introduce carrier selectivity and increase organic/contact compatibility. To date, the most widely used inorganic interlayers are metal oxides such as TiO₂ and ZnO. However, these materials require harsh deposition conditions that could damage the organic active layers, and hence are generally used in inverted devices. Here we show, for the first time, that judicious selection of materials and processing conditions allow the use of an atomic layer deposition (ALD) system to deposit thin conformal ZnO interlayers on bulk heterojunctions (BHJs). ALD-ZnO interlayers were utilized as electron transporting layers (ETLs) in OSCs and compared to similar devices with solution deposited ZnO nanoparticle (np) ETLs. OSCs with ALD-ZnO ETLs exhibited higher photocurrent densities, J_sc, but lower open circuit voltages, V_oc. The low V_oc is associated with the presence of pinholes and an offset between the ALD-ZnO and PC₇₀BM electron conducting states. This offset results from traps and acceptor sites generated during the low temperature ALD process. To recover the V_oc we introduced a fluorinated phosphonic acid (PA) additive to the blend. We suggest that the additive migrates to the film surface, interacts with the ZnO to produce a denser layer and to passivate traps, effectively improving the device shunt resistance and energy level alignment and increasing V_oc. Overall, the devices with PA and ALD-ZnO ETLs possess significantly higher power conversion efficiencies (PCEs) than those with np-ZnO ETLs. For example, the champion ALD-ZnO device PCE is 3.5%, while that with np-ZnO is 2.75%.     

Performance enhancement in inverted polymer solar cells incorporating ultrathin Au and LiF modified ZnO electron transporting interlayer

The performance enhancement of inverted polymer solar cells (PSCs), based on the blend system of regioregular poly(3-hexylthiophene) and [6,6]-phenyl C₆₁-butyric acid methylester, due to incorporating ultrathin Au and LiF interlayer between the front transparent indium tin oxide and a ZnO electron transporting layer was analyzed. The results reveal that a 40% increase in PCE, e.g., from 2.62% to 3.67%, was observed for PSCs made with an optimal Au/LiF interlayer as compared to the one having a bare ZnO electron transporting layer. The presence of Au/LiF-modified ZnO interlayer between ITO and the organic layer helps to improve the charge collection. The absorption enhancement arising from the plasmon resonance of Au nanostructures also contributed to the improvement in PCE. It is shown that PSCs with LiF incorporated ZnO electron transporting layer allow improving cell lifetime, demonstrating <50% decrease in PCE compared to that of the ones with a bare ZnO interlayer after 240 day aging test for cells without encapsulation in air.     

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.     

High-performance inverted polymer solar cells with lead monoxide-modified indium tin oxides as the cathode

The photovoltaic stability of polymer solar cells (PSCs) can be greatly improved by adopting an inverted device structure. This paper reports high-performance inverted PSCs with lead monoxide (PbO)-modified indium tin oxide (ITO) as the cathodes. A thin PbO layer can effectively lower the work function of ITO from 4.5 to 3.8 eV. The optimal inverted PSCs with poly(3-hexylthiophene) (P3HT) as the donor and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as the acceptor exhibited high photovoltaic performance: open-circuit voltage of 0.59 V, short-circuit current density of 10.8 mA cm⁻², fill factor of 0.632, and power conversion efficiency of 4.00% under simulated AM1.5G illumination (100 mW cm⁻²). The photovoltaic efficiency is significantly higher than that of the control inverted PSCs with unmodified ITO as the cathode. It is even better than that of the control PSCs with normal architecture, which have an optimal efficiency of 3.5%. The lowering in the work function by the PbO modification is attributed to the charge transfer between PbO and ITO, as evidenced by the X-ray photoelectron spectra.     

Enhanced performance of inverted perovskite solar cells using solution-processed carboxylic potassium salt as cathode buffer layer

Using a novel solution-processed carboxylic potassium salt (F-R-COOK) as cathode buffer layer (CBL), a power conversion efficiency (PCE) of 14.37% is obtained, which is more than 51% increase compared with that of the Ag-only device under similar fabrication conditions. The test result of single electron devices and Electrochemical impedance spectroscopy (EIS) measurements demonstrate that the interlayer decreases charge transport resistance. Ultraviolet photoelectron spectroscopy (UPS) measurements are used to study the interfacial effects induced by the new CBL. It is found that F-R-COOK can reduce the work function of the Ag electrode by forming desired interfacial dipoles. Our work indicates the promising applications of F-R-COOK based CBL in perovskite solar cells and may provide some insights into the design and synthesis of new interfacial materials to further improve the device performance.     

Effect of PEI cathode interlayer on work function and interface resistance of ITO electrode in the inverted polymer solar cells

In this paper, we investigated the effect of PEI cathode interlayer on the work function and the interface resistance of ITO electrode in the inverted polymer solar cells (PSCs) based on PBDTTT-C-T:PC₇₀BM. It is found that a very thin layer of PEI (⩽5.5 nm), either linear PEI (l-PEI) or branched PEI (b-PEI) with different molecular weights, is enough to lower the work function of the ITO electrode and to enhance the photovoltaic performance of the devices. The champion power conversion efficiency (PCE) of the devices with the PEI cathode interlayer is 7.84%, more than doubled of that without the interlayer. However, a thicker PEI interlayer (⩾10 nm) results in abrupt decrease of the PCEs due to the increase of the resistance. Interestingly, for the thicker interlayers, the l-PEI shows high photovoltaic performance than that of b-PEI, which can also be explained by their difference in the resistances. This work supplies an insight into the function of PEI cathode interlayer on improving the work function and resistance of ITO electrode in the inverted PSCs, and provides some instructions on the future design of interlayer materials in PSCs.