Self‐Compensated Insulating ZnO‐Based Piezoelectric Nanogenerators

Remarkable enhancement of piezoelectric power output from a nanogenerator (NG) based on a zinc oxide (ZnO) thin film is achieved via native defect control. A large number of unintentionally induced point defects that act as n‐type carriers in ZnO have a strong influence on screening the piezoelectric potential into a piezoelectric NG. Here, additional oxygen molecules bombarded into ZnO lead to oxygen‐rich conditions, and the n‐type conductivity of ZnO is decreased dramatically. The acceptor‐type point defects such as zinc vacancies created during the deposition process trap n‐type carriers occurring from donor‐type point defects through a self‐compensation mechanism. This unique insulating‐type ZnO thin film‐based NGs (IZ‐NGs) generates output voltage around 1.5 V that is over ten times higher than that of an n‐type ZnO thin film‐based NG (around 0.1 V). In addition, it is found that the power output performance of the IZ‐NG can be further increased by hybridizing with a p‐type polymer (poly(3‐hexylthiophene‐2,5‐diyl):phenyl‐C₆₁‐butyric acid methyl ester) via surface free carrier neutralization.     

Effects of ZnO fabricating process on the performance of inverted organic solar cells

The effects of zinc oxide (ZnO) fabricating process on the performance of the inverted bulk heterojunction (BHJ) solar cells were explored in this study. The ZnO layers were prepared by either sputtering or solution-processed method. These ZnO films on the indium tin oxide (ITO) substrates were used as the cathode of the inverted solar cells. It was found that the topography of the ZnO films played a leading role on the device performance. The devices based on solution-processed ZnO films displayed better electric output compared with that of sputtered ones. The measurement of capacitance against bias voltage indicated that ZnO film with certain degree of roughness exhibited high charge extraction efficiency, which resulted in improved device performance. The measurement of ultraviolet photoelectron spectroscopy revealed that a shift of work function was observed due to the fabricating process of ZnO films.     

Enhancement of Light Extraction Through the Wave‐Guiding Effect of ZnO Sub‐microrods in InGaN Blue Light‐Emitting Diodes

The improvement of the light extraction efficiency (LEE) of a conventional InGaN blue light‐emitting diode (LED) by the incorporation of one‐dimensional ZnO sub‐microrods is reported. The LEE is improved by 31% through the wave‐guiding effect of ZnO sub‐microrods compared to LEDs without the sub‐microrods. Different types of ZnO microrods/sub‐microrods are produced using a simple non‐catalytic wet chemical growth method at a low temperature (90 °C) on an indium‐tin‐oxide (ITO) top contact layer with no seed layer. The crystal morphologies of needle‐like or flat‐top hexagonal structures, and the ZnO microrods/sub‐microrod density and size are easily modified by controlling the pH value and growth time. The wave‐guiding phenomenon within the ZnO rods is observed using confocal scanning electroluminescence microscopy and micro‐electroluminescence spectra.     

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.     

DC‐sputtered ZnO:Al as transparent conductive oxide for silicon heterojunction solar cells with µc‐Si:H emitter

Silicon heterojunction (SHJ) solar cells are highly interesting, because of their high efficiency and low cost fabrication. So far, the most applied transparent conductive oxide (TCO) is indium tin oxide (ITO). The replacement of ITO with cheaper, more abundant and environmental friendly material with texturing capability is a promising way to reduce the production cost of the future SHJ solar cells. Here, we report on the fabrication of the SHJ solar cells with direct current‐sputtered aluminum‐doped zinc oxide (ZnO:Al) as an alternative TCO. Furthermore, we address several important differences between ITO and the ZnO:Al layers including a high Schottky barrier at the emitter/ZnO:Al interface and a high intrinsic resistivity of the ZnO:Al layers. To overcome the high Schottky barrier, we suggest employing micro‐crystalline silicon (µc‐Si:H) emitter, which also improves temperature threshold and passivation of the solar cell precursor. In addition, we report on the extensive studies of the effect of the ZnO:Al deposition parameters including layer thickness, oxygen flow, power density and temperature on the electrical properties of the fabricated SHJ solar cells. Finally, the results of our study indicate that the ZnO:Al deposition parameters significantly affect the electrical properties of the obtained solar cell. By understanding and fine‐tuning all these parameters, a high conversion efficiency of 19.2% on flat wafer (small area (5 × 5 mm²) and without any front metal grid) is achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

An Indium‐Free Anode for Large‐Area Flexible OLEDs: Defect‐Free Transparent Conductive Zinc Tin Oxide

Flexible large‐area organic light‐emitting diodes (OLEDs) require highly conductive and transparent anodes for efficient and uniform light emission. Tin‐doped indium oxide (ITO) is the standard anode in industry. However, due to the scarcity of indium, alternative anodes that eliminate its use are highly desired. Here an indium‐free anode is developed by a combinatorial study of zinc oxide (ZnO) and tin oxide (SnO₂), both composed of earth‐abundant elements. The optimized Zn–Sn–O (ZTO) films have electron mobilities of up to 21 cm² V^?1 s^?1, a conductivity of 245 S cm^?1, and <5% absorptance in the visible range of the spectrum. The high electron mobilities and low surface roughness (<0.2 nm) are achieved by producing dense and void‐free amorphous layers as confirmed by transmission electron microscopy. These ZTO layers are evaluated for OLEDs in two anode configurations: i) 10 cm² devices with ZTO/Ag/ZTO and ii) 41 cm² devices with ZTO plus a metal grid. The ZTO layers are compatible with OLED processing steps and large‐area white OLEDs fabricated with the ZTO/grid anode show better performance than those with ITO/grid anodes. These results confirm that ZTO has the potential as an In‐free and Earth‐abundant alternative to ITO for large‐area flexible OLEDs.     

Poly(3‐hexylthiophene) Nanorods with Aligned Chain Orientation for Organic Photovoltaics

A structured polymer solar cell architecture featuring a large interface between donor and acceptor with connecting paths to the respective electrodes is explored. To this end, poly‐(3‐hexylthiophene) (P3HT) nanorods oriented perpendicularly to indium tin oxide (ITO) glass are fabricated using an anodic aluminum oxide template. It is found that the P3HT chains in bulk films or nanorods are oriented differently; perpendicular or parallel to the ITO substrate, respectively. Such chain alignment of the P3HT nanorods enhanced the electrical conductivity up to tenfold compared with planar P3HT films. Furthermore, the donor/acceptor contact area could be maximised using P3HT nanorods as donor and C60 as acceptor. In a photovoltaic device employing this structure, remarkable photoluminescence quenching (88%) and a seven‐fold efficiency increase (relative to a device with a planar bilayer) are achieved.     

Enhanced output power of (indium) gallium nitride light emitting diodes by a transparent current spreading-film composed of a disordered network of indium tin oxide nanorods

A thin film consisting of a disordered nanorod network of indium tin oxide (ITO) and conventional ITO films are fabricated on gallium nitride (GaN) based-light emitting diodes (LEDs) by electron beam evaporation. The surface morphologies are observed by scanning electron microscopy (SEM). The disordered nanorod network of ITO is grown in vacuum without oxygen. It can be applied directly on the LED as the current spreading film unlike other nanorods which require growth on a conductive layer. The transmittance, current–voltage characteristic, and the dependence of light output power on current are measured for disordered nanorod network ITO LEDs and conventional ITO LEDs, respectively. The measurement results indicate that the nanorod network provides a significant improvement in the light output power of GaN-based LEDs. The influence of the structure of ITO films on the light output power of GaN-based LEDs is discussed.     

Unidirectional High‐Power Generation via Stress‐Induced Dipole Alignment from ZnSnO3 Nanocubes/Polymer Hybrid Piezoelectric Nanogenerator

The extremely stable high‐power generation from hybrid piezoelectric nanogenerator (HP‐NG) based on a composite of single‐crystalline piezoelectric perovskite zinc stannate (ZnSnO₃) nanocubes and polydimethylsiloxane without any electrical poling treatment is reported. The HP‐NG generates large power output under only vertical compression, while there is negligible power generation with other configurations of applied strain, such as bending and folding. This unique high unidirectionality of power generation behavior of the HP‐NG provides desirable features for large‐area piezoelectric power generation based on vertical mechanical compression such as moving vehicles, railway transport, and human walking. The HP‐NGs of ZnSnO₃ nanocubes exhibit high mechanical durability, excellent robustness, and high power‐generation performance. A large recordable output voltage of about 20 V and an output current density value of about 1 μA cm^?2 are successfully achived, using a single cell of HP‐NG obtained under rolling of a vehicle tire.     

Triboelectric and Piezoelectric Effects in a Combined Tribo‐Piezoelectric Nanogenerator Based on an Interfacial ZnO Nanostructure

In this contribution, combined triboelectric and piezoelectric generators (TPEG) with a sandwich structure of aluminum‐polydimethylsiloxane/polyvinylidene fluoride composite‐carbon (Al‐PPCF‐Carbon) are fabricated for the purpose of mechanical energy harvesting. Improved by the surface modification of PPCF with zinc oxide (ZnO) nanorods through a hydrothermal method, the TPEG generates an open‐circuit voltage (V_oc) of ≈40 V, a short‐circuit current (I_sc) of 0.28 μA with maximum power density of ≈70 mWm^?2_, and maximum conversion efficiency of 34.56%. Subsequently, in order to understand the transduction mechanism of the triboelectric and piezoelectric effects, analyses focusing on the potential composition ratio in the final output and the impact of ZnO interfacial nanostructure are carried out. The observed potential ratio between triboelectric and piezoelectric effects is 12.75:1 and the highest potential improvement by ZnO nanorods of 21.8 V is achieved by the TPEG fabricated with spacer. Finally, the relationships between the voltage, power density, conversion efficiency, and the external load resistances are also discussed. Overall, the fabricated TPEG is proved to be a simple and effective nanogenerator in mechanical energy conversion with enhanced output potential and conversion efficiency.     

Bendable Solar Cells from Stable,Flexible, and Transparent Conducting Electrodes Fabricated Using a Nitrogen‐Doped Ultrathin Copper Film

Copper has attracted significant interests as an abundant and low‐cost alternative material for flexible transparent conducting electrodes (FTCEs). However, Cu‐based FTCEs still present unsolved technical issues, such as their inferior light transmittance and oxidation durability compared to conventional indium tin oxide (ITO) and silver metal electrodes. This study reports a novel technique for fabricating highly efficient FTCEs composed of a copper ultrathin film sandwiched between zinc oxides, with enhanced transparency and antioxidation performances. A completely continuous and smooth copper ultrathin film is fabricated by a simple room‐temperature reactive sputtering process involving controlled nitrogen doping (<1%) due to a dramatic improvement in the wettability of copper on zinc oxide surfaces. The electrode based on the nitrogen‐doped copper film exhibits an optimized average transmittance of 84% over a spectral range of 380 ?1000 nm and a sheet resistance lower than 20 Ω sq^?1, with no electrical degradation after exposure to strong oxidation conditions for 760 h. Remarkably, a flexible organic solar cell based on the present Cu‐based FTCE achieves a power conversion efficiency of 7.1%, clearly exceeding that (6.6%) of solar cells utilizing the conventional ITO film, and this excellent performance is maintained even in almost completely bent configurations.     

Realizing the Potential of ZnO with Alternative Non‐Metallic Co‐Dopants as Electrode Materials for Small Molecule Optoelectronic Devices

High performance indium tin oxide (ITO)‐free small molecule organic solar cells and organic light‐emitting diodes (OLEDs) are demonstrated using optimized ZnO electrodes with alternative non‐metallic co‐dopants. The co‐doping of hydrogen and fluorine reduces the metal content of ZnO thin films, resulting in a low absorption coefficient, a high transmittance, and a low refractive index as well as the high conductivity, which are needed for the application in organic solar cells and OLEDs. While the established metal‐doped ZnO films have good electrical and optical properties, their application in organic devices is not as efficient as other alternative electrode approaches. The optimized ZnO electrodes presented here are employed in organic solar cells as well as OLEDs and allow not only the replacement of ITO, but also significantly improve the efficiency compared to lab‐standard ITO. The enhanced performance is attributed to outstanding optical properties and spontaneously nanostructured surfaces of the ZnO films with non‐metallic co‐dopants and their straightforward integration with molecular doping technology, which avoids several common drawbacks of ZnO electrodes. The observations show that optimized ZnO films with non‐metallic co‐dopants are a promising and competitive electrode for low‐cost and high performance organic solar cells and OLEDs.     

III‐Vs at scale: a PV manufacturing cost analysis of the thin film vapor–liquid–solid growth mode

The authors present a manufacturing cost analysis for producing thin‐film indium phosphide modules by combining a novel thin‐film vapor–liquid–solid (TF‐VLS) growth process with a standard monolithic module platform. The example cell structure is ITO/n‐TiO₂/p‐InP/Mo. For a benchmark scenario of 12% efficient modules, the module cost is estimated to be $0.66/W(DC) and the module cost is calculated to be around $0.36/W(DC) at a long‐term potential efficiency of 24%. The manufacturing cost for the TF‐VLS growth portion is estimated to be ~$23/m², a significant reduction compared with traditional metalorganic chemical vapor deposition. The analysis here suggests the TF‐VLS growth mode could enable lower‐cost, high‐efficiency III‐V photovoltaics compared with manufacturing methods used today and open up possibilities for other optoelectronic applications as well. Copyright © 2016 John Wiley & Sons, Ltd.     

Growth of Transparent and Conductive Polycrystalline (0001)‐ZnO Films on Glass Substrates Under Low‐Temperature Hydrothermal Conditions

Flat panel display technology seems to be an ever‐expanding field developing into a multibillion dollar market. A set of technical solutions involve a transparent conducting film (TCF) that is today still dominated by indium‐tin‐oxide (ITO). In a race to find alternatives that would avoid the indium pitfalls, mainly due to its increasing price and limited natural availablity, replacement materials have been extensively investigated. This work demonstrates that by exploiting basic principles of crystal growth in geometrically constrained conditions, zinc oxide (ZnO) could easily be utilized for this purpose. ZnO layers were grown on inexpensive glass substrates via low‐temperature citrate‐assisted hydrothermal (HT) method. It was shown that in the nucleation stage the crystal growth can be efficiently controlled by spatially confined oriented growth (SCOG) mechanism to produce smooth and dense (0001) oriented polycrystalline ZnO films with superb optical properties. Our products show optical transparency of 82% and surprisingly low sheet resistance for undoped ZnO, only in the order of few 100 Ω sq^?1. We believe that a very high degree of self‐organization between the ZnO crystals in our polycrystalline films grown under controlled SCOG conditions is main reason for the highest so far reported transparency to conductivity ratio for undoped ZnO thin film ceramics.     

生长时间对氧化锌纳米杆形貌的影响

采用旋涂法在洗净的玻璃衬底上制备了醋酸锌薄膜,并进一步在空气中退火获得了氧化锌(ZnO)薄膜,X射线衍射分析显示退火后获得的ZnO薄膜具有c轴(002)择优取向生长特性.通过水热法以ZnO薄膜为种子层,生长了ZnO纳米杆阵列.研究了在相同的ZnO种子层、前驱液浓度和生长温度条件下,不同生长时间对ZnO纳米杆形貌的影响.扫描电子显微镜照片显示,随着生长时间的增加,ZnO纳米杆阵列的生长具有阶段性规律,并且在经过52h生长后得到了顶端中心被溶解的ZnO纳米管.分析认为该现象和前驱液中Zn2+离子和OH-离子的浓度变化有关,同时也和ZnO的非极性结构有关.     

A stacked chalcopyrite thin‐film tandem solar cell with 1.2 V open‐circuit voltage

CuGaSe₂ (CGS) thin films were prepared on tin‐doped indium oxide (ITO) coated soda‐lime glass substrates by thermal co‐evaporation to fabricate transparent solar cells. The films consisted of columnar grains with a diameter of approximately 1 μm. Some deterioration of the transparency of the ITO was observed after deposition of the CGS film. The CGS solar cells were electrically connected in series with Cu(In,Ga)Se₂ (CIGS) solar cells and mechanically stacked on the CIGS cells to construct tandem cells. The tandem solar cell with the CGS cell as the top cell showed an efficiency of 7.4% and an open‐circuit voltage of 1.18 V (AM 1.5, total area). Copyright © 2003 John Wiley & Sons, Ltd.     

Effects of Piezoelectric Potential of ZnO on Resistive Switching Characteristics of Flexible ZnO/TiO<Subscript>2</Subscript> Heterojunction Cells

Flexible resistance random access memory (ReRAM) devices with a heterojunction structure of PET/ITO/ZnO/TiO₂/Au were fabricated on polyethylene terephthalate/indium tin oxide (PET/ITO) substrates by different physical and chemical preparation methods. X-ray diffraction, scanning electron microscopy and atomic force microscopy were carried out to investigate the crystal structure, surface topography and cross-sectional structure of the prepared films. X-ray photoelectron spectroscopy was also used to identify the chemical state of Ti, O and Zn elements. Theoretical and experimental analyses were conducted to identify the effect of piezoelectric potential of ZnO on resistive switching characteristics of flexible ZnO/TiO₂ heterojunction cells. The results showed a pathway to enhance the performance of ReRAM devices by engineering the interface barrier, which is also feasible for other electronics, optoelectronics and photovoltaic devices.     

Plasmonic Au/TiO2‐Dumbbell‐On‐Film Nanocavities for High‐Efficiency Hot‐Carrier Generation and Extraction

Plasmon‐induced hot carriers have vast potential for light‐triggered high‐efficiency carrier generation and extraction, which can overcome the optical band gap limit of conventional semiconductor‐based optoelectronic devices. Here, it is demonstrated that Au/TiO₂ dumbbell nanostructures assembled on a thin Au film serve as an efficient optical absorber and a hot‐carrier generator in the visible region. Upon excitation of localized surface plasmons in such coupled particle‐on‐film nanocavities, the energetic conduction electrons in Au can be injected over the Au/TiO₂ Schottky barrier and migrated to TiO₂, participating in the chemical reaction occurring at the TiO₂ surface. Compared with the same dumbbell nanostructures on an indium tin oxide (ITO) film, such nanocavities exhibit remarkable enhancement in both photocurrent amplitude and reaction rate that arise from increased light absorption and near‐field amplification in the presence of the Au film. The incident‐wavelength‐dependent photocurrent and reaction rate measurements jointly reveal that Au‐film‐mediated near‐field localization facilitates more efficient electron–hole separation and transport in the dumbbells and also promotes strong d‐band optical transitions in the Au film for generation of extra hot electrons. Such nanocavities provide a new plasmonic platform for effective photoexcitation and extraction of hot carriers and also better understanding of their fundamental science and technological implications in solar energy harvesting.     

A Transparent,Flexible, Low‐Temperature,and Solution‐Processible Graphene Composite Electrode

The synthesis and preparation of a new type of graphene composite material suitable for spin‐coating into conductive, transparent, and flexible thin film electrodes in ambient conditions is reported here for the first time. Solution‐processible graphene with diameter up to 50 μm is synthesized by surfactant‐assisted exfoliation of graphite oxide and in situ chemical reduction in a large quantity. Spin‐coating the mixing solution of surfactant‐functionalized graphene and PEDOT:PSS yields the graphene composite electrode (GCE) without the need for high temperature annealing, chemical vapor deposition, or any additional transfer‐printing process. The conductivity and transparency of GCE are at the same level as those of an indium tin oxide (ITO) electrode. Importantly, it exhibits high stability (both mechanical and electrical) in bending tests of at least 1000 cycles. The performance of organic light‐emitting diodes based on a GCE anode is comparable, if not superior, to that of OLEDs made with an ITO anode.     

Smooth indium zinc oxide film prepared by sputtering a In2O3:ZnO=95:5 target

Indium zinc oxide (IZO) films with surface roughness Ra<0.3 nm have been prepared by radio frequency sputtering. The IZO film is the possible candidate for replacing the indium tin oxide (ITO) film in pattern precision or low processing temperature concern. Instead of commonly used In₂O₃:ZnO=90:10 in weight percentage (wt%) target, a target doped with 5 wt% impurities was used in this study. It was found that the electrical resistivity of the IZO film increases rapidly if oxygen gas was introduced during the sputtering process. This increase tendency in electrical resistivity is much more significant than the IZO film prepared with a 10 wt% doped ZnO target. The electrical resistivity increased rapidly as soon as the IZO film became crystallized in heat treatment. Optical properties of the IZO film do not change significantly with varying process parameters. The appropriate processing condition for the prepared IZO film is no oxygen feeding and no heat treatment.