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The development of high-performance organic photovoltaic materials is of crucial importance for the commercialization of organic solar cells (OSCs). Herein, two structurally simple donor-π-conjugated linker-acceptor (D-π-A)-configured small-molecule donors with methyl-substituted triphenylamine as D unit, 1,1-dicyanomethylene-3-indanone as A unit, and thiophene or furan as π-conjugated linker, named DTICPT and DTICPF, are developed. DTICPT and DTICPF are facilely prepared via a two-step synthetic process with simple procedures. DTICPF with a furan π-conjugated linker exhibits stronger and broader optical absorption, deeper highest occupied molecular orbital (HOMO) energy levels, and better charge transport, compared to its thiophene analog DTICPT. As a result, vacuum-deposited OSCs based on DTICPF: C70 show an impressive power conversion efficiency (PCE) of 9.36% (certified 9.15%) with short-circuit current density (Jsc) up to 17.49 mA cm-2 (certified 17.56 mA cm-2), which is the highest Jsc reported so far for vacuum-deposited OSCs. Besides, devices based on DTICPT: C70 and DTICPF: C70 exhibit excellent long-term stability under different aging conditions. This work offers important insights into the rational design of D-π-A configured small-molecule donors for high efficient and stable vacuum-deposited OSCs.
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The fabrication of perovskite light-emitting diodes (PeLEDs) with vacuum deposition shows great potential and commercial value in realizing large-area display panel manufacturing. However, the electroluminescence (EL) performance of vacuum-deposited PeLEDs still lags behind the counterparts fabricated by solution process, especially in the field of blue PeLEDs. Here, the fabrication of high-quality CsPbBr3- x Clx film through tri-source co-evaporation is reported to achieve high photoluminescence quantum yield (PLQY). Compared with the conventional traditional dual-source co-evaporation, the tri-source co-evaporation method allows for freely adjustable elemental ratios, enabling the introduction of the lattice-matched Cs4 Pb(Br/Cl)6 phase with the quantum-limited effect into the inorganic CsPb(Br/Cl)3 emitter. By adjusting the phase distribution, the surface defects of the emitter can be effectively reduced, leading to better blue emission and film quality. Further, the effects of Cs/Pb ratio and Br/Cl ratio on the PLQY and carrier recombination dynamics of perovskite films are investigated. By optimizing the deposition rate of each precursor source, spectrally stable blue PeLEDs are achieved with tunable emission ranging from 468 to 488 nm. Particularly, the PeLEDs with an EL peak at 488 nm show an external quantum efficiency (EQE) of 4.56%, which is the highest EQE value for mixed-halide PeLEDs fabricated by vacuum deposition.
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Since the discovery of ionic liquids (ILs) as a new class of liquid that can survive in a vacuum at room temperature, they have been aimed at being characterized with vacuum analysis techniques and used in vacuum processes for the last two decades. In this review, our state-of-the-art of the vacuum engineering of ILs will be introduced. Beginning with nanoscale vacuum deposition of IL films and their thickness-dependent ionic conductivity, there are presented some new applications of the ellipsometry to in situ monitoring of the thickness of IL films and their glass transitions, and of the surface thermal fluctuation spectroscopy to investigation of the rheological properties of IL films. Furthermore, IL-VLS (vapor-liquid-solid) growth, a vacuum deposition via IL, has been found successful, enhancing the crystallinity of vacuum-deposited crystals and films, and sometimes controlling their surface morphology and polymorphs. Among recent applications of ILs are the use of metal ions-containing IL and thin film nano IL gel. The former is proposed as a low temperature evaporation source of metals, such as Ta, in vacuum deposition, while the latter is demonstrated to work as a gate electrolyte in an electric double layer organic transistor.
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Líquidos Iónicos , Líquidos Iónicos/química , Vacio , Análisis Espectral , Metales , GasesRESUMEN
Staphylococcus aureus is a bacterium which people have been in contact with for thousands of years. Its presence often leads to severe disorders of the respiratory and circulatory systems. The authors of this article present a prototype of a textronic sensor enabling the detection of this bacterium. This sensor was created using a process of physical vacuum deposition on a flexible textile substrate which can be implemented on clothing. With increasing numbers of bacterial colonies, changes in the sensor's electrical parameters were observed. The sensor's resistance reduced by 50% and the capacitance more than doubled within the first two days of starting bacterial cultures. Extensive changes in electrical parameters were observed at 100 Hz and 120 Hz of the measurement signal.
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Staphylococcus aureus , Textiles , Vacio , Humanos , Dispositivos Electrónicos VestiblesRESUMEN
This paper compares methods for measuring selected morphological features on the surface of thin metallic layers applied to flexible textile substrates. The methods were tested on a silver layer with a thickness of several hundred nanometers, which was applied to a textile composite with the trade name Cordura. Measurements were carried out at the micro scale using both optical coherent tomography (OCT) and the traditional contact method of using a profilometer. Measurements at the micro-scale proved the superiority of the OCT method over the contact method. The method of contactless measurement employs a dedicated algorithm for three-dimensional surface image analysis and does not affect the delicate surface structure of the measured layer in any way. Assessment of the surface profile of textile substrates and the thin films created on them, is important when estimating the contact angle, wetting behavior, or mechanical durability of the created metallic structure that can be used as the electrodes or elements of wearable electronics or textronics systems.
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Flexible perovskite solar cells have attracted widespread research effort because of their potential in portable electronics. The efficiency has exceeded 18 % owing to the high-quality perovskite film achieved by various low-temperature fabrication methods and matching of the interface and electrode materials. This Review focuses on recent progress in flexible perovskite solar cells concerning low-temperature fabrication methods to improve the properties of perovskite films, such as full coverage, uniform morphology, and good crystallinity; demonstrated interface layers used in flexible perovskite solar cells, considering key figures-of-merit such as high transmittance, high carrier mobility, suitable band gap, and easy fabrication via low-temperature methods; flexible transparent electrode materials developed to enhance the mechanical stability of the devices; mechanical and long-term environmental stability; an outlook of flexible perovskite solar cells in portable electronic devices; and perspectives of commercialization for flexible perovskite solar cells based on cost.
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The hydroxyapatite and copper-doped hydroxyapatite coatings (Ca10-xCux(PO4)6(OH)2; xCu = 0, 0.03; HAp and 3CuHAp) were obtained by the vacuum deposition technique. Then, both coatings were analyzed by the X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and water contact angle techniques. Information regarding the in vitro antibacterial activity and biological evaluation were obtained. The XRD studies confirmed that the obtained thin films consist of a single phase associated with hydroxyapatite (HAp). The obtained 2D and 3D SEM images did not show cracks or other types of surface defects. The FTIR studies' results proved the presence of vibrational bands characteristic of the hydroxyapatite structure in the studied coating. Moreover, information regarding the HAp and 3CuHAp surface wettability was obtained by water contact angle measurements. The biocompatibility of the HAp and 3CuHAp coatings was evaluated using the HeLa and MG63 cell lines. The cytotoxicity evaluation of the coatings was performed by assessing the cell viability through the MTT assay after incubation with the HAp and 3CuHAp coatings for 24, 48, and 72 h. The results proved that the 3CuHAp coatings exhibited good biocompatible activity for all the tested intervals. The ability of Pseudomonas aeruginosa 27853 ATCC (P. aeruginosa) cells to adhere to and develop on the surface of the HAp and 3CuHAp coatings was investigated using AFM studies. The AFM studies revealed that the 3CuHAp coatings inhibited the formation of P. aeruginosa biofilms. The AFM data indicated that P. aeruginosa's attachment and development on the 3CuHAp coatings were significantly inhibited within the first 24 h. Both the 2D and 3D topographies showed a rapid decrease in attached bacterial cells over time, with a significant reduction observed after 72 h of exposure. Our studies suggest that 3CuHAp coatings could be suitable candidates for biomedical uses such as the development of new antimicrobial agents.
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At present, the power conversion efficiency of single-junction perovskite-based solar cells reaches over 26%. The further efficiency increase of perovskite-based optoelectronic devices is limited mainly by defects, causing the nonradiative recombination of charge carriers. To improve efficiency and ensure reproducible fabrication of high-quality layers, it is crucial to understand the perovskite nucleation and growth mechanism along with associated process control to reduce the defect density. In this study, we investigate the growth kinetics of a promising narrow bandgap perovskite, formamidinium methylammonium lead iodide (FAMAPbI3), for high-performance single-junction solar cells. The temporal evolution of structural and optoelectronic properties during FAMAPbI3 vacuum codeposition was inspected in real time by grazing-incidence wide-angle X-ray scattering and photoluminescence. Such a combination of analytical techniques unravels the evolution of intrinsic defect density and layer morphology correlated with lattice strain from the early stages of the perovskite deposition.
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In this study, we present a novel method for controlling the growth of perovskite crystals in the vacuum thermal evaporation process by utilizing a vacuum-processable additive, propylene urea (PU). By coevaporation of perovskite precursors with PU to form the perovskite layer, PU, acting as a Lewis base additive, retards the direct reaction between the perovskite precursors. This facilitates a larger domain size and reduced defect density. Following the removal of the residual additive, the perovskite layer, exhibiting improved crystallinity, demonstrates reduced charge recombination, as confirmed by a time-resolved microwave conductivity analysis. Consequently, there is a notable enhancement in open-circuit voltage and power conversion efficiency, increasing from 1.05 to 1.15 V and from 17.17 to 18.31%, respectively. The incorporation of a vacuum-processable and removable Lewis base additive into the fabrication of vacuum-processed perovskite solar cells offers new avenues for optimizing these devices.
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Although vacuum-deposited metal halide perovskite light-emitting diodes (PeLEDs) have great promise for use in large-area high-color-gamut displays, the efficiency of vacuum-sublimed PeLEDs currently lags that of solution-processed counterparts. In this study, highly efficient vacuum-deposited PeLEDs are prepared through a process of optimizing the stoichiometric ratio of the sublimed precursors under high vacuum and incorporating ultrathin under- and upper-layers for the perovskite emission layer (EML). In contrast to the situation in most vacuum-deposited organic light-emitting devices, the properties of these perovskite EMLs are highly influenced by the presence and nature of the upper- and presublimed materials, thereby allowing us to enhance the performance of the resulting devices. By eliminating Pb° formation and passivating defects in the perovskite EMLs, the PeLEDs achieve an outstanding external quantum efficiency (EQE) of 10.9% when applying a very smooth and flat geometry; it reaches an extraordinarily high value of 21.1% when integrating a light out-coupling structure, breaking through the 10% EQE milestone of vacuum-deposited PeLEDs.
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Understanding the formation process of organic-inorganic halide perovskite (OIHP) thin films is important for the fabrication of high-quality thin films, which, in turn, are crucial for achieving high-performance devices. To address this challenge, we developed an in situ system of infrared multiple-angle incidence-resolved spectroscopy (IR-MAIRS) combined with a vacuum deposition system. "Orientation-free" isotropic spectra constructed from IR-MAIRS spectra enable us to perform quantitative analysis of the formation process of C(NH2)3SnI3 (GASnI3) thin films from unreacted C(NH2)3I (guanidine hydroiodide (GAI))/SnI2 bilayer structures predeposited in a vacuum. The analysis of the dependence of the GASnI3 formation rate on the reaction temperature using the Avrami model has revealed that a diffusion-controlled reaction process of GAI and SnI2 governs the formation kinetics. The present study points to the usefulness of in situ IR-MAIRS analysis in understanding the growth mechanisms of vacuum-deposited OIHP thin films and hence the potential to accelerate the development of vacuum processes for the fabrication of high-quality OIHP thin films.
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Using solution-coating methods for the fabrication of organic light-emitting devices (OLEDs) offers a tremendous opportunity for enabling low-cost products and new applications. The electroluminescence (EL) stability of solution-coated (SOL) OLEDs, however, is significantly lower than that of vacuum-deposited (VAC) OLEDs, causing their operational lifetimes to be much shorter-an issue that continues to hamper their commercialization. The root causes of the lower EL stability of these devices remain unclear. This article briefly reviews and summarizes some of the work that has been done to-date for elucidating the root cause of the lower EL stability of SOL OLEDs, giving special attention to studies where side-by-side comparisons of SOL and VAC devices of the same materials have been conducted. Such comparisons allow for more-reliable conclusions about the specific effects of the solution-coating process on device stability to be made. The mini-review is intended to introduce the work done to-date on the causes of lower stability in SOL OLEDs and to stimulate further work for the purpose of closing the existing knowledge gap in this area and surmounting this long-standing challenge in the SOL OLED technology.
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Highly sensitive X-ray detection is crucial in, for example, medical imaging and secure inspection. Halide perovskite X-ray detectors are promising candidates for detecting highly energetic radiation. In this report, we describe vacuum-deposited Cs-based perovskite X-ray detectors possessing a p-i-n architecture. Because of the built-in potential of the p-i-n structure, these perovskite X-ray detectors were capable of efficient charge collection and displayed an exceptionally high X-ray sensitivity (1.2 C Gyair-1 cm-3) under self-powered, zero-bias conditions. We ascribe the outstanding X-ray sensitivity of the vacuum-deposited CsPbI2Br devices to their prominent charge carrier mobility. Moreover, these devices functioned with a lowest detection limit of 25.69 nGyair s-1 and possessed excellent stability after exposure to over 3000 times the total dose of a chest X-ray image. For comparison, we also prepared traditional spin-coated CH3NH3-based perovskite devices having a similar device architecture. Their volume sensitivity was only one-fifth of that of the vacuum-deposited CsPbI2Br devices. Thus, all-vacuum deposition appears to be a new strategy for developing perovskite X-ray detectors; with a high practical deposition rate, a balance can be reached between the thickness of the absorbing layer and the fabrication time.
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Harnessing solar energy by employing concentrated solar power (CSP) systems requires materials with high electrical conductivity and optical reflectivity. Silver, with its excellent optical reflectance, is traditionally used as a reflective layer in solar mirrors for CSP technologies. However, silver is soft and expensive, quickly tarnishes, and requires a protective layer of glass for practical applications. Moreover, supply-side constraints and high-temperature instability of silver have led to the search for alternative materials that exhibit high solar and infrared reflectance. Transition metal nitrides, such as titanium nitride, have emerged as alternative plasmonic materials to gold starting from a spectral range of â¼500 nm. However, to achieve high solar reflection (â¼320-2500 nm), materials with epsilon-near-zero starting from the near-ultraviolet (UV) spectral region are required. Here, we show the development of refractory epitaxial hafnium nitride (HfN) and zirconium nitride (ZrN) thin films as excellent mirrors with a solar reflectivity of â¼90.3% and an infrared reflectivity of â¼95%. Low-loss and high-quality epsilon-near-zero resonance at near-UV (â¼340-380 nm) spectral regions are achieved in HfN and ZrN by carefully controlling the stoichiometry, leading to a sharp increase in the reflection edge that is on par with silver. Temperature-dependent reflectivity and dielectric constants are further measured to demonstrate their high-temperature suitability. The development of refractory epitaxial HfN and ZrN thin films with high solar and infrared reflectance makes them excellent alternative plasmonic materials to silver and would pave their applications in CSP, daytime radiative cooling, and others.
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A comprehensive study of the optical properties of CsPbBr3 perovskite multiple quantum wells (MQW) with organic barrier layers is presented. Quantum confinement is observed by a blue-shift in absorption and emission spectra with decreasing well width and agrees well with simulations of the confinement energies. A large increase of emission intensity with thinner layers is observed, with a photoluminescence quantum yield up to 32 times higher than that of bulk layers. Amplified spontaneous emission (ASE) measurements show very low thresholds down to 7.3 µJ cm-2 for a perovskite thickness of 8.7 nm, significantly lower than previously observed for CsPbBr3 thin-films. With their increased photoluminescence efficiency and low ASE thresholds, MQW structures with CsPbBr3 are excellent candidates for high-efficiency perovskite-based LEDs and lasers.
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The process dynamics for the vacuum deposition of methylammonium lead iodide (MAPbI3) perovskite was analyzed by in situ X-ray diffraction using synchrotron radiation. MAPbI3 was fabricated by alternatingly supplying PbI2 and methylammonium iodide via a laser deposition system installed at the synchrotron beamline BL46XU at SPring-8, and in situ crystallization analysis was conducted. Microscopic insights into the crystallization were obtained, including observation of Laue oscillation during the PbI2 growth and octahedral unit (PbI6) rotation during the transformation into perovskite. On the basis of this analysis, conditions that favor the construction of atomically flat MAPbI3 perovskite films were deduced.
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Highly efficient vacuum-deposited CsPbBr3 perovskite light-emitting diodes (PeLEDs) are demonstrated by introducing a separate polyethylene oxide (PEO) passivation layer. A CsPbBr3 film deposited on the PEO layer via thermal co-evaporation of CsBr and PbBr2 exhibits an almost 50-fold increase in photoluminescence quantum yield intensity compared to a reference sample without PEO. This enhancement is attributed to the passivation of interfacial defects of the perovskite, as evidenced by temperature-dependent photoluminescence measurements. However, direct application of PEO to an LED device is challenging because of the electrically insulating nature of PEO. This issue is solved by doping PEO layers with MgCl2. This strategy results in an enhanced luminance and external quantum efficiency (EQE) of up to 6887 cd m-2 and 7.6%, respectively. To the best of our knowledge, this is the highest EQE reported to date among vacuum-deposited PeLEDs.
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The spectral properties of new boron-containing dyes were studied. One-component (pure dyes) and composite "Alq3+dye" thin films were fabricated using the thermal vacuum deposition method. The positions of the transmission spectra maxima in a one-component film are different for different film thicknesses. The best correlation of the maxima positions of the dye transmission spectra in solid and liquid solutions was observed for thicknesses of films close to a few (up to 10) monolayers. On the other hand, the absorption spectra maxima positions of one-component dye films (upper 10 nm) and composite films with high concentration, did not match the corresponding positions of absorption spectra maxima recorded in solutions. Comparison of the absorption spectra in one-component dye films and in solutions indicates the presence of both monomers and their aggregates in one-component films (contrary to solutions where such processes of aggregation do not take place, even at very high concentrations). Simultaneously with aggregation manifestation in the absorption spectra, the intensity of fluorescence of one-component dye films dramatically decreases. A quantum chemical simulation of the possible relative arrangement of two dye molecules indicates that the most possible of the simplest types of aggregates are physical dimers. Films of practical importance (due to efficient energy transfer from host to guest molecules when all singlet excitons are captured) possess a high quantum yield of fluorescence when reaching an impurity concentration of a few percent (aggregation does not take place yet).
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Electronic devices relying on the combination of different conjugated organic materials are considerably appealing for their potential use in many applications such as photovoltaics, light emission, and digital/analog circuitry. In this study, the electrical response of field-effect transistors achieved through the evaporation of picene and PDIF-CN2 molecules, two well-known organic semiconductors with remarkable charge transport properties, was investigated. With the main goal to get a balanced ambipolar response, various device configurations bearing double-layer, triple-layer, and codeposited active channels were analyzed. The most suitable choices for the layer deposition processes, the related characteristic parameters, and the electrode position were identified to this purpose. In this way, ambipolar organic field-effect transistors exhibiting balanced mobility values exceeding 0.1 cm2 V-1 s-1 for both electrons and holes were obtained. These experimental results highlight also how the combination between picene and PDIF-CN2 layers allows tuning the threshold voltages of the p-type response. Scanning Kelvin probe microscopy (SKPM) images acquired on picene/PDIF-CN2 heterojunctions suggest the presence of an interface dipole between the two organic layers. This feature is related to the partial accumulation of space charge at the interface being enhanced when the electrons are depleted in the underlayer.
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III-nitride resonant cavity-enhanced Schottky barrier photodetectors were fabricated on 2 µm thick GaN templates by radio frequency plasma-assisted molecular beam epitaxy. The optical cavity was formed by a bottom distributed Bragg reflector based on 10 periods of Al0.3Ga0.7N/GaN, an Au-based Schottky contact as top mirror, and an active zone of 40 nm-thick GaN layer. The devices were fabricated with planar geometry. To evaluate the main benefits allowed by the optical cavity, conventional Schottky photodetectors were also processed. The results revealed a planar spectral response for the conventional photodetector, unlike the resonant devices that showed two raised peaks at 330 and 358 nm with responsivities of 0.34 and 0.39 mA/W, respectively. Both values were 80 times higher than the planar response of the conventional device. These results demonstrate the strong effect of the optical cavity to achieve the desired wavelength selectivity and to enhance the optical field thanks to the light resonance into the optical cavity. The research of such a combination of nitride-based Bragg mirror and thin active layer is the kernel of the present paper.