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.     

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.     

Electro‐Optics of Colloidal Quantum Dot Solids for Thin‐Film Solar Cells

The electro‐optics of thin‐film stacks within photovoltaic devices plays a critical role for the exciton and charge generation and therefore the photovoltaic performance. The complex refractive indexes of each layer in heterojunction colloidal quantum dot (CQD) solar cells are measured and the optical electric field is simulated using the transfer matrix formalism. The exciton generation rate and the photocurrent density as a function of the quantum dot solid thickness are calculated and the results from the simulations are found to agree well with the experimentally determined results. It can therefore be concluded that a quantum dot solid may be modeled with this approach, which is of general interest for this type of materials. Optimization of the CQD solar cell is performed by using the optical simulations and a maximum solar energy conversion efficiency of 6.5% is reached for a CQD solid thickness of 300 nm.     

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.     

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.     

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.     

Highly efficient bifacial transparent organic solar cells with power conversion efficiency greater than 3% and transparency of 50%

In this work, we present vacuum-deposited bifacial transparent organic solar cells on indium-tin-oxide-coated glass substrates. Good performances and high transparencies are achieved simultaneously by employing the planar-mixed heterojunction of the organic donor 2-{[7-(5-N,N-ditolylaminothiophen-2-yl)-2,1,3-benzothiadiazol-4-yl]methylene}malononitrile (DTDCTB) and fullerenes with carefully designed resonance top electrodes. Comprehensive optical simulation is exploited to investigate the effect of the top-electrode configuration on the cell transparency and efficiency. Cells with structures designed for high transparencies were fabricated and tested. The DTDCTB:C₆₀ device yields a high transmission of up to 66.4% at 530 nm and a power conversion efficiency (PCE) of 2.11%. Moreover, the DTDCTB:C₇₀ device demonstrates an exceptional PCE as high as 3.24% with a balanced transmission of ≈50% in the visible spectrum. Enhanced PCE values of transparent solar cells are also revealed with the use of external reflectors. Efficiency enhancements of ≈15% and ≈65% are achieved by simply attaching a reflection mirror at the cathode or anode side, respectively.     

Highly efficient ITO-free polymer solar cells based on metal resonant microcavity using WO3/Au/WO3 as transparent electrodes

Indium tin oxide (ITO)-free polymer solar cells (PSCs) with the structure of Glass/tungsten trioxide (WO₃)/Au/WO₃/PCDTBT: PC₇₀BM/LiF/Al was fabricated and studied. The multilayer structure of WO₃/Au/WO₃ is used as the potential transparent electrode to replace ITO. Metal resonant microcavity, which can enhance light harvesting of active layers, was constructed between Au and Al electrodes. According to the J–V and IPCE characterization with 70 nm active layer, power conversion efficiency (PCE) of the ITO-free microcavity device is approaching 4.55%, which is higher than that of the ITO-based device. However, PCE of the ITO-free device is much lower than that of the ITO-based device when the thickness of active layer increases to 130 nm. The opposite experimental tendency leads to theoretical research toward the simulation of light absorption and optical electric field and the calculation of maximum short circuit current density (J_{sc max}) as a function of active layer thickness based on ITO-free and ITO-based devices. The research results show that microcavity effect is closely linked to intrinsic absorption of active layers.     

Visualization of Current and Mapping of Elements in Quantum Dot Solar Cells

The delicate influence of properties such as high surface state density and organic–inorganic boundaries on the individual quantum dot electronic structure complicates pursuits toward forming quantitative models of quantum dot thin films ab initio. This report describes the application of electron beam‐induced current (EBIC) microscopy to depleted‐heterojunction colloidal quantum dot photovoltaics (DH‐CQD PVs), a technique which affords one a “map” of current production within the active layer of a PV device. The effects of QD sample size polydispersity as well as layer thickness in CQD active layers as they pertain to current production within these PVs are imaged and explained. The results from these experiments compare well with previous estimations, and confirm the ability of EBIC to function as a valuable empirical tool for the design and betterment of DH‐CQD PVs. Lastly, extensive and unexpected PbS QD penetration into the mesoporous TiO₂ layer is observed through imaging of device cross sections by energy‐dispersive X‐ray spectroscopy combined with scanning transmission electron microscopy. The possible effects of this finding are discussed and corroborated with the EBIC studies on similar devices.     

Graphene Doping Improved Device Performance of ZnMgO/PbS Colloidal Quantum Dot Photovoltaics

Lead sulfide (PbS) colloidal quantum dots (CQDs) solar cells possess the advantages of absorption into the infrared, solution processing, and multiple exciton generation, making them very competitive as a low‐cost photovoltaic alternative. Employing an n‐i‐p ZnO/tetrabutylammonium (TBAI)–PbS/ethanedithiol (EDT)–PbS device configuration, the present study reports a 9.0% photovoltaic device through ZnMgO electrode engineering and graphene doping. Sol–gel‐derived Zn_0.9Mg_0.1O buffer layer shows better transparency and higher conduction band maximum than ZnO, and incorporation of graphene and chlorinated graphene oxide into the TBAI–PbS and EDT–PbS layer respectively boosts carrier collection, leading to device with significantly enhanced open circuit voltage and short‐circuit current density. It is believed that incorporation of graphene into PbS CQD film as proposed here, and more generally nanosheets of other materials, would potentially open a simple and powerful avenue to overcome the carrier transport bottleneck of CQD optoelectronic device, thus pushing device performance to a new level.     

Ligand‐Free Synthesis of Aluminum‐Doped Zinc Oxide Nanocrystals and their Use as Optical Spacers in Color‐Tuned Highly Efficient Organic Solar Cells

The color of polymer solar cells using an opaque electrode is given by the reflected light, which depends on the composition and thickness of each layer of the device. Metal‐oxide‐based optical spacers are intensively studied in polymer solar cells aiming to optimize the light absorption. However, the low conductivity of materials such as ZnO and TiO₂ limits the thickness of such optical spacers to tenths of nanometers. A novel synthesis route of cluster‐free Al‐doped ZnO (AZO) nanocrystals (NCs) is presented for solution processing of highly conductive layers without the need of temperature annealing, including thick optical spacers on top of polymer blends. The processing of 80 nm thick optical spacers based on AZO nanocrystal solutions on top of 200 nm thick polymer blend layer is demonstrated leading to improved photocurrent density of 17% compared to solar cells using standard active layers of 90 nm in combination with thin ZnO‐based optical spacers. These AZO NCs also open new opportunities for the processing of high‐efficiency color tuned solar cells. For the first time, it is shown that applying solution‐processed thick optical spacer with polymer blends of different thicknesses can process solar cells of similar efficiency over 7% but of different colors.     

Role of the CdS buffer layer as an active optical element in Cu(In,Ga)Se2 thin‐film solar cells

ZnO/CdS/Cu(In,Ga)Se₂ (CIGS) thin‐film heterojunction solar cells with CdS buffer layers of thicknesses between 0 and 85 nm are characterized by current–voltage, quantum efficiency, and optical reflection measurements. We investigate the correlation between the short‐circuit current density and the CdS layer thickness, focusing on the counteracting effects of light absorption and reduced optical reflection induced by the CdS layer. Both effects almost compensate each other for CdS layer thicknesses between 0 and 40 nm. Thus, an optimization of the short‐circuit current density is not achieved by omitting the CdS layer, but rather by replacing the CdS buffer with an alternative buffer material with higher bandgap energy and optical constants similar to those of CdS. Copyright © 2002 John Wiley & Sons, Ltd.     

Molecular Intercalation and Cohesion of Organic Bulk Heterojunction Photovoltaic Devices

The phase separated bulk heterojunction (BHJ) layer in BHJ polymer:fullerene organic photovoltaic devices (OPV) are mechanically weak with low values of cohesion. Improved cohesion is important for OPV device thermomechanical reliability. BHJ devices are investigated and how fullerene intercalation within the active layer affects cohesive properties in the BHJ is shown. The intercalation of fullerenes between the side chains of the polymers poly(3,3″′‐didocecyl quaterthiophene) (PQT‐12) and poly(2,5‐bis(3‐hexadecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (pBTTT) is shown to enhance BHJ layer cohesion. Cohesion values range from ≈1 to 5 J m^?2, depending on the polymer:fullerene blend, processing conditions, and composition. Devices with non‐intercalated BHJ layers are found to have significantly reduced values of cohesion. The resulting device power conversion efficiencies (PCE) are also investigated and correlated with the device cohesion.     

Sulfurized Colloidal Quantum Dot/Tungsten Disulfide Multi-Dimensional Heterojunction for an Efficient Self-Powered Visible-to-SWIR Photodetector

Emerging semiconducting materials show considerable promise for application in the development of next-generation optoelectronic devices. In particular, broadband light detection is crucial in various applications, including multispectral imaging and cognition. Therefore, tuning the physical properties of semiconductors and thereby building an efficient heterojunction are important for achieving a high-performance photodetection device. In this study, a heavy p-type colloidal quantum dot (CQD) is synthesized through solution-based sulfurization. The resulting cubic-shaped CQD exhibits broadband and strong absorption, which enable its broadband absorption. Further, a multidimensional 0D-2D heterojunction is developed using p-type CQD and n-type tungsten disulfide (WS₂). This efficient p-n junction is operated as a fully self-powered optical sensor and phototransistor under various light illumination conditions. Under the self-powered condition, the CQD/WS₂ heterojunction device exhibits 440- and 200-fold-higher responsivity and detectivity, respectively, than pristine WS₂.     

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.     

A–D–A type organic donors employing coplanar heterocyclic cores for efficient small molecule organic solar cells

Two linear organic A–D–A molecules (DTPT and DTPTT) comprised of electron-donating (D) coplanar heteroacenes as core end-capping with electron-accepting (A) dicyanovinylene were investigated as electron donor materials in organic photovoltaic (OPV) applications. The photophysical and electrochemical properties of these two dyes were examined. The A–D–A configuration renders these two molecules to have intense and red-shifted absorption characteristics for better light-harvesting (higher photocurrent density), while retaining relatively low HOMO energy levels for keeping sufficiently high open circuit voltage (V_oc) in OPV. The optical constants and molecular orientation of thin films were acquired with variable-angle spectroscopic ellipsometry (VASE). Due to the anisotropic behavior observed in thin film, these two organic donors were firstly adopted to combine with electron acceptor C₆₀ in a vacuum-processed planar heterojunction (PHJ) solar cells. The optimized DTPT-based PHJ device yielded a PCE of 3.01%, whereas the PHJ device based on DTPTT, delivered an inferior PCE of 1.70%. The exciton diffusion length extracted from spectrum-response modeling of PHJ devices is ∼5 nm and ∼4 nm for DTPT and DTPTT, respectively. Replacement of C₆₀ with C₇₀ for a better spectral response in 400–500 nm, planar-mixed heterojunction (PMHJ) SMOSCs without a thin donor layer in between the active layer and MoO₃ was found to produce optimum device results. The optimized DTPTT-based device showed a PCE of 3.02%, while the shorter counterpart DTPT delivered a PCE up to 5.64%.     

Modulation‐Doped Multiple Quantum Wells of Aligned Single‐Wall Carbon Nanotubes

Heterojunctions, quantum wells, and superlattices with precise doping profiles are behind today's electronic and photonic devices based on III–V compound semiconductors such as GaAs. Currently, there is considerable interest in constructing similar artificial 3D architectures with tailored electrical and optical properties by using van der Waals junctions of low‐dimensional materials. In this study, the authors have fabricated a novel structure consisting of multiple thin (≈20 nm) layers of aligned single‐wall carbon nanotubes with dopants inserted between the layers. This “modulation‐doped” multiple‐quantum‐well structure acts as a terahertz polarizer with an ultra‐broadband working frequency range (from ≈0.2 to ≈200 THz), a high extinction ratio (20 dB from ≈0.2 to 1 THz), and a low insertion loss (<2.5 dB from ≈0.2 to 200 THz). The individual carbon nanotube films—highly aligned, densely packed, and large (2 in. in diameter)—were produced using vacuum filtration and then stacked together in the presence of dopants. This simple, robust, and cost‐effective method is applicable to the fabrication of a variety of devices relying on macroscopically 1D properties of aligned carbon nanotube assemblies.     

Self‐Powered Flexible TiO2 Fibrous Photodetectors: Heterojunction with P3HT and Boosted Responsivity and Selectivity by Au Nanoparticles

A novel inorganic–organic heterojunction (TiO₂/P3HT (poly(3‐hexylthiophene)) is easily prepared by a combination of anodization and vacuumed dip‐coating methods, and the constructed flexible fibrous photodetector (FPD) exhibits high‐performance self‐powered UV–visible broadband photoresponse with fast speed, high responsivity, and good stability, as well as highly stable performance at bending states, showing great potential for wearable electronic devices. Moreover, Au nanoparticles are deposited to further boost the responsivity and selectivity by regulating the sputtering intervals. The optimal Au/TiO₂/P3HT FPD yields an ≈700% responsivity enhancement at 0 V under 350 nm illumination. The sharp cut‐off edge and high UV–visible rejection ratio (≈17 times higher) indicate a self‐powered flexible UV photodetector. This work provides an effective and versatile route to modulate the photoelectric performance of flexible electronic devices.     

Transparent Ultrathin Oxygen‐Doped Silver Electrodes for Flexible Organic Solar Cells

An effective method for depositing highly transparent and conductive ultrathin silver (Ag) electrodes using minimal oxidation is reported. The minimal oxidation of Ag layers significantly improves the intrinsic optical and structural properties of Ag without any degradation of its electrical conductivity. Oxygen‐doped Ag (AgO_x) layers of thicknesses as low as 6 nm exhibit completely 2D and continuous morphologies on ZnO films, smaller optical reflections and absorbances, and smaller sheet resistances compared with those of discontinuous and granular‐type Ag layers of the same thickness. A ZnO/AgO_x/ZnO (ZAOZ) electrode using an AgO_x (O/Ag = 3.4 at%) layer deposited on polyethylene terephthalate substrates at room temperature shows an average transmittance of 91%, with a maximum transmittance of 95%, over spectral range 400?1000 nm and a sheet resistance of 20 Ω sq^?1. The average transmittance value is increased by about 18% on replacing a conventional ZnO/Ag/ZnO (ZAZ) electrode with the ZAOZ electrode. The ZAOZ electrode is a promising bottom transparent conducting electrode for highly flexible inverted organic solar cells (IOSCs), and it achieves a power conversion efficiency (PCE) of 6.34%, whereas an IOSC using the ZAZ electrode exhibits a much lower PCE of 5.65%.     

Self‐Organized Nanoporous Anodic Titania Films and Ordered Titania Nanodots/Nanorods on Glass

We report a new method to fabricate self‐organized nanoporous titania films (pore diameter ≈ 30 nm; ≈ 1100 nm thick) and ordered titania nanorod arrays (rod diameter ≈ 30–60 nm; 70–260 nm high) by combined anodizing of superimposed Al/Ti layers sputter‐deposited on glass substrates. The titania nanostructures mimic the ordered nanoporous anodic alumina films via a through‐mask anodization. We propose a new anodizing electrolyte, i.e., a diluted nitric acid solution, for fabricating uniform, self‐organized, ordered nanoporous titania films with parallel cylindrical pores and without any thickness limit. More significantly, the nanoporous titania films contain a small amount of titanium nitride and dissociated nitrogen, and exhibit a moderate transparency and an enhanced absorption throughout the UV and visible light regions of the electromagnetic spectrum. After heating at 600 °C for 2 h, the nanoporous titania films develop a small absorption red‐shift and exhibit high photocatalytic activity under UV illumination.