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1.
Very high lateral ionic conductivities in epitaxial cubic yttria‐stabilized zirconia (YSZ) synthesized on single‐crystal SrTiO3 and MgO substrates by reactive direct current magnetron sputtering are reported. Superionic conductivities (i.e., ionic conductivities of the order ~1 Ω?1cm?1) are observed at 500 °C for 58‐nm‐thick films on MgO. The results indicate a superposition of two parallel contributions – one due to bulk conductivity and one attributable to conduction along the film–substrate interface. Interfacial effects dominate the conductivity at low temperatures (<350 °C), showing more than three orders of magnitude enhancement compared to bulk YSZ. At higher temperatures, a more bulk‐like conductivity is observed. The films have a negligible grain‐boundary network, thus ruling out grain boundaries as a pathway for ionic conduction. The observed enhancement in lateral ionic conductivity is caused by a combination of misfit dislocation density and elastic strain in the interface. These very high ionic conductivities in the temperature range 150–500 °C are of great fundamental importance but may also be technologically relevant for low‐temperature applications.  相似文献   

2.
Coupling between colloidal semiconductor nanocrystals (NCs) with long‐range order is critical for designing advanced nanostructures with controlled energy flow and charge carrier transport. Herein, under the premise of keeping long‐range order in 2D NC monolayer, its native organic ligands are exchanged with halogen ions in situ at the liquid–air interface to enhance the coupling between NCs. Further treatments on the films with dimethyl sulfoxide, methanol, or their mixture effectively improve carrier mobility of the devices. The devices show repeatable enhanced p‐type transport behavior with hole mobility of up to 0.224 ± 0.069 cm2 V?1 s?1, the highest value reported for lead sulfide NC solids without annealing treatment. Thanks to accurate control over the surface of NCs as well as the structure of NC film, the ordered NC monolayer film of high hole mobility suggests great potentials for making reliable high performance devices.  相似文献   

3.
Here, the surface functionalization of CdSe and CdSe/CdS core/shell nanocrystals (NCs) with compact chloride and indium‐chloride‐complex ligands is reported. The ligands provide not only short interparticle distances but additionally control doping and passivation of surface trap states, leading to enhanced electronic coupling in NC‐based arrays. The solids based on these NCs show an excellent electronic transport behavior after heat treatment at the relatively low temperature of 190 °C. Indeed, the indium‐chlorido‐capped 4.5 nm CdSe NC based thin‐film field‐effect transistor reaches a saturation mobility of μ = 4.1 cm2 (V s)?1 accompanied by a low hysteresis, while retaining the typical features of strongly quantum confined semiconductor NCs. The capping with chloride ions preserves the high photoluminescence quantum yield ( ≈ 66%) of CdSe/CdS core/shell NCs even when the CdS shell is relatively thin (six monolayers). The simplicity of the chemical incorporation of chlorine and indium species via solution ligand exchange, the efficient electronic passivation of the NC surface, as well as their high stability as dispersions make these materials especially attractive for wide‐area solution‐processable fabrication of NC‐based devices.  相似文献   

4.
Ultrafast time‐domain thermoreflectance (TDTR) is utilized to extract the through‐plane thermal conductivity (Λ LSCO) of epitaxial La0.5Sr0.5CoO3?δ (LSCO) of varying thickness (<20 nm) on LaAlO3 and SrTiO3 substrates. These LSCO films possess ordered oxygen vacancies as the primary means of lattice mismatch accommodation with the substrate, which induces compressive/tensile strain and thus controls the orientation of the oxygen vacancy ordering (OVO). TDTR results demonstrate that the room‐temperature Λ LSCO of LSCO on both substrates (1.7 W m?1 K?1) are nearly a factor of four lower than that of bulk single‐crystal LSCO (6.2 W m?1 K?1). Remarkably, this approaches the lower limit of amorphous oxides (e.g., 1.3 W m?1 K?1 for glass), with no dependence on the OVO orientation. Through theoretical simulations, origins of the glass‐like thermal conductivity of LSCO are revealed as a combined effect resulting from oxygen vacancies (the dominant factor), Sr substitution, size effects, and the weak electron/phonon coupling within the LSCO film. The absence of OVO dependence in the measured Λ LSCO is rationalized by two main effects: (1) the nearly isotropic phononic thermal conductivity resulting from the imperfect OVO planes when δ is small; (2) the missing electronic contribution to Λ LSCO along the through‐plane direction for these ultrathin LSCO films on insulating substrates.  相似文献   

5.
Two blue‐emitting cationic iridium complexes with 2‐(1H‐pyrazol‐1‐yl)pyridine (pzpy) as the ancillary ligands, namely, [Ir(ppy)2(pzpy)]PF6 and [Ir(dfppy)2(pzpy)]PF6 (ppy is 2‐phenylpyridine, dfppy is 2‐(2,4‐difluorophenyl) pyridine, and PF6? is hexafluorophosphate), have been prepared, and their photophysical and electrochemical properties have been investigated. In CH3CN solutions, [Ir(ppy)2(pzpy)]PF6 emits blue‐green light (475 nm), which is blue‐shifted by more than 100 nm with respect to the typical cationic iridium complex [Ir(ppy)2(dtb‐bpy)]PF6 (dtb‐bpy is 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine); [Ir(dfppy)2(pzpy)]PF6 with fluorine‐substituted cyclometalated ligands shows further blue‐shifted light emission (451 nm). Quantum chemical calculations reveal that the emissions are mainly from the ligand‐centered 3ππ* states of the cyclometalated ligands (ppy or dfppy). Light‐emitting electrochemical cells (LECs) based on [Ir(ppy)2(pzpy)]PF6 gave green‐blue electroluminescence (486 nm) and had a relatively high efficiency of 4.3 cd A?1 when an ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate was added into the light‐emitting layer. LECs based on [Ir(dfppy)2(pzpy)]PF6 gave blue electroluminescence (460 nm) with CIE (Commission Internationale de L'Eclairage) coordinates of (0.20, 0.28), which is the bluest light emission for iTMCs‐based LECs reported so far. Our work suggests that using diimine ancillary ligands involving electron‐donating nitrogen atoms (like pzpy) is an efficient strategy to turn the light emission of cationic iridium complexes to the blue region.  相似文献   

6.
Recent progress in fabricating Cd‐ and Se‐free wide‐gap chalcopyrite thin‐film solar devices with Zn(S,O) buffer layers prepared by an alternative chemical bath process (CBD) using thiourea as complexing agent is discussed. Zn(S,O) has a larger band gap (Eg = 3·6–3·8 eV) than the conventional buffer material CdS (Eg = 2·4 eV) currently used in chalcopyrite‐based thin films solar cells. Thus, Zn(S,O) is a potential alternative buffer material, which already results in Cd‐free solar cell devices with increased spectral response in the blue wavelength region if low‐gap chalcopyrites are used. Suitable conditions for reproducible deposition of good‐quality Zn(S,O) thin films on wide‐gap CuInS2 (‘CIS’) absorbers have been identified for an alternative, low‐temperature chemical route. The thickness of the different Zn(S,O) buffers and the coverage of the CIS absorber by those layers as well as their surface composition were controlled by scanning electron microscopy, X‐ray photoelectron spectroscopy, and X‐ray excited Auger electron spectroscopy. The minimum thickness required for a complete coverage of the rough CIS absorber by a Zn(S,O) layer deposited by this CBD process was estimated to ∼15 nm. The high transparency of this Zn(S,O) buffer layer in the short‐wavelength region leads to an increase of ∼1 mA/cm2 in the short‐circuit current density of corresponding CIS‐based solar cells. Active area efficiencies exceeding 11·0% (total area: 10·4%) have been achieved for the first time, with an open circuit voltage of 700·4 mV, a fill factor of 65·8% and a short‐circuit current density of 24·5 mA/cm2 (total area: 22·5 mA/cm2). These results are comparable to the performance of CdS buffered reference cells. First integrated series interconnected mini‐modules on 5 × 5 cm2 substrates have been prepared and already reach an efficiency (active area: 17·2 cm2) of above 8%. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

7.
Here, cation exchange (CE) reactions are exploited to radiolabel ZnSe, ZnS, and CuFeS2 metal chalcogenide nanocrystals (NCs) with 64Cu. The CE protocol requires one simple step, to mix the water‐soluble NCs with a 64Cu solution, in the presence of vitamin C used to reduce Cu(II) to Cu(I). Given the quantitative cation replacement on the NCs, a high radiochemical yield, up to 99%, is reached. Also, provided that there is no free 64Cu, no purification step is needed, making the protocol easily translatable to the clinic. A unique aspect of the approach is the achievement of an unprecedentedly high specific activity: by exploiting a volumetric CE, the strategy enables to concentrate a large dose of 64Cu (18.5 MBq) in a small NC dose (0.18 µg), reaching a specific activity of 103 TBq g?1. Finally, the characteristic dielectric resonance peak, still present for the radiolabeled 64Cu:CuFeS2 NCs after the partial‐CE reaction, enables the generation of heat under clinical laser exposure (1 W cm?2). The synergic toxicity of photo‐ablation and 64Cu ionization is here proven on glioblastoma and epidermoid carcinoma tumor cells, while no intrinsic cytotoxicity is seen from the NC dose employed for these dual experiments.  相似文献   

8.
CuIn1‐xGaxSe2 (CIGS) thin films were grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker was used to deliver reactive Se molecules. The Cu0·6 Ga0·4 and Cu0·4In0·6 targets were simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on CIGS film deposition were investigated. The CIGS film growth rate decreased, and the surface roughness of a film increased as the Se flux increased. The [112] crystal orientation was dominant, and metallic crystal phases such as Cu9Ga4 and Cu16In9 in a film were disappearing with increasing Se flux. A solar cell fabricated using a 900‐nm CIGS film showed the power conversion efficiency of 8·6%, the highest value found in a sub‐micron thick CIGS solar cell related to a reactive sputtering process with metallic targets. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

9.
Recently, a new seeding growth approach for perovskite thin films is reported to significantly enhance the device performance of perovskite solar cells. This work unveils the intermediate structures and the corresponding growth kinetics during conversion to perovskite crystal thin films assisted by seeding PbS nanocrystals (NCs), using time‐resolved grazing‐incidence X‐ray scattering. Through analyses of time‐resolved crystal formation kinetics obtained from synchrotron X‐rays with a fast subsecond probing time resolution, an important “catalytic” role of the seed‐like PbS NCs is clearly elucidated. The perovskite precursor‐capped PbS NCs are found to not only accelerate the nucleation of a highly oriented intermediate phase, but also catalyze the conversion of the intermediate phase into perovskite crystals with a reduced activation energy Ea = 47 (±5) kJ mol?1, compared to 145 (±38) kJ mol?1 for the pristine perovskite thin film. The reduced Ea is attributed to a designated crystal lattice alignment of the perovskite nanocrystals with perovskite cubic crystals; the pivotal heterointerface alignment of the perovskite crystals coordinated by the Pb NCs leads to an improved film surface morphology with less pinholes and enhanced crystal texture and thermal stability. These together contribute to the significantly improved photovoltaic performance of the corresponding devices.  相似文献   

10.
Thin films of Ce0.8Gd0.2O1.9‐δ (CGO) are deposited by flame spray deposition with a deposition rate of about 30 nm min?1. The films (deposited at 200 °C) are dense, smooth, and particle‐free and show a biphasic amorphous/nanocrystalline microstructure. Isothermal grain growth and microstrain are determined as a function of dwell time and temperature and correlated to the electrical conductivity. CGO films annealed for 10 h at 600 °C present the best electrical conductivity of 0.46 S m?1 measured at 550 °C. Reasons for the superior performance of films annealed at low temperature over higher‐temperature‐treated samples are discussed and include grain‐size evolution, microstrain relaxation, and chemical decomposition. Nanoindentation measurements are conducted on the CGO thin films as a function of annealing temperature to determine the hardness and elastic modulus of the films for potential application as free‐standing electrolyte membranes in low‐temperature micro‐SOFCs (solid oxide fuel cells).  相似文献   

11.
Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10−3 Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al2O3 barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al2O3 films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

12.
A 3D solar‐blind photodetector array is realized from amorphous Ga2O3 films grown on polyethylene terephthalate substrates via an origami route. The photodetector cells exhibit a dark current of 0.17 nA, and the peak responsivity is about 8.9 A W?1 at 250 nm with a quantum efficiency of 4450%. The photodetector shows a distinct cut‐off wavelength at 268 nm with a solar‐blind ratio of more than two orders of magnitude (photocurrent ratio between 250 nm/300 nm). The photodetector cells reveal excellent electrical stability after thousands of bending cycles. All the photodetector cells of the 3D photodetector array have a highly consistent performance. In addition, the device can execute the functions of capturing a real‐time light trajectory and identifying multipoint light spatial distribution, which cannot be achieved in all the previously reported 2D solar‐blind photodetectors. The results suggest new pathways to fabricate 3D photodetectors from conventional semiconductor films, which may find potential applications in optical positioning, tracking, imaging and communications, etc.  相似文献   

13.
The off‐stoichiometry effects and gram‐scale production of luminescent CuInS2‐based semiconductor nanocrystals, as well as their application in electroluminescence devices are reported. The crystal structures and optical properties of CuInS2 nanocrystals can be significantly influenced by controlling their [Cu]/[In] molar ratio. A simple model adapted from the bulk materials is proposed to explain their off‐stoichiometry effects. Highly emissive and color‐tunable CuInS2‐based NCs are prepared by a combination of [Cu]/[In] molar ratio optimization, ZnS shell coating, and CuInS2–ZnS alloying. The method is simple, hassle‐free, and easily scalable to fabricate tens of grams of nanocrystal powders with photoluminescence quantum yields up to around 65%. Furthermore, the performance of high‐quality CuInS2‐based NCs in electroluminescence devices is examined. These devices have lower turn‐on voltages of around 5 V, brighter luminance up to approximately 2100 cd m?2 and improved injection efficiency of around 0.3 lm W?1 (at 100 cd m?2) in comparison to recent reports.  相似文献   

14.
Parasitic absorption in transparent electrodes is one of the main roadblocks to enabling power conversion efficiencies (PCEs) for perovskite‐based tandem solar cells beyond 30%. To reduce such losses and maximize light coupling, the broadband transparency of such electrodes should be improved, especially at the front of the device. Here, the excellent properties of Zr‐doped indium oxide (IZRO) transparent electrodes for such applications, with improved near‐infrared (NIR) response, compared to conventional tin‐doped indium oxide (ITO) electrodes, are shown. Optimized IZRO films feature a very high electron mobility (up to ≈77 cm2 V?1 s?1), enabling highly infrared transparent films with a very low sheet resistance (≈18 Ω □?1 for annealed 100 nm films). For devices, this translates in a parasitic absorption of only ≈5% for IZRO within the solar spectrum (250–2500 nm range), to be compared with ≈10% for commercial ITO. Fundamentally, it is found that the high conductivity of annealed IZRO films is directly linked to promoted crystallinity of the indium oxide (In2O3) films due to Zr‐doping. Overall, on a four‐terminal perovskite/silicon tandem device level, an absolute 3.5 mA cm?2 short‐circuit current improvement in silicon bottom cells is obtained by replacing commercial ITO electrodes with IZRO, resulting in improving the PCE from 23.3% to 26.2%.  相似文献   

15.
Metal–organic framework (MOF) films have recently emerged as highly permselective membranes yielding orders of magnitude higher gas permeance than that from the conventional membranes. However, synthesis of highly intergrown, ultrathin MOF films on porous supports without complex support‐modification has proven to be a challenge. Moreover, there is an urgent need of a generic crystallization route capable of synthesizing a wide range of MOF structures in an intergrown, thin‐film morphology. Herein, a novel electrophoretic nuclei assembly for crystallization of highly intergrown thin‐films (ENACT) approach, that allows synthesis of ultrathin, defect‐free ZIF‐8 on a wide range of unmodified supports (porous polyacrylonitrile, anodized aluminum oxide, metal foil, porous carbon and graphene), is reported. As a result, a remarkably high H2 permeance of 8.3 × 10?6 mol m?2 s?1 Pa?1 and ideal gas selectivities of 7.3, 15.5, 16.2, and 2655 for H2/CO2, H2/N2, H2/CH4, and H2/C3H8, respectively, are achieved from an ultrathin (500 nm thick) ZIF‐8 membrane. A high C3H6 permeance of 9.9 × 10?8 mol m?2 s?1 Pa?1 and an attractive C3H6/C3H8 selectivity of 31.6 are obtained. The ENACT approach is straightforward, reproducible and can be extended to a wide range of nanoporous crystals, and its application in the fabrication of intergrown ZIF‐7 films is demonstrated.  相似文献   

16.
CuIn1‐xGaxSe2 (CIGS) thin films are grown on Mo/soda lime glass using a reactive sputtering process in which a Se cracker is used to deliver reactive Se molecules. The Cu and (In0.7Ga0.3)2Se3 targets are simultaneously sputtered under the delivery of reactive Se. The effects of Se flux on film composition are investigated. The Cu/(In+Ga) composition ratio increases as the Se flux increases at a plasma power of less than 30 W for the Cu target. The (112) crystal orientation becomes dominant, and crystal grain size is larger with Se flux. The power conversion efficiency of a solar cell fabricated using an 800‐nm CIGS film is 8.5%.  相似文献   

17.
n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]2. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]2, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]2‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.  相似文献   

18.
Nanoelectronics is in urgent demand of exceptional device architecture with ultrathin thickness below 10 nm and dangling‐bond‐free surface to break through current physical bottleneck and achieve new record of integration level. The advance in 2D van der Waals materials endows scientists with new accessibility. This study reports an all‐layered 2D Bi2Te3‐SnSe‐Bi2Te3 photodetector, and the broadband photoresponse of the device from ultraviolet (370 nm) to near‐infrared (808 nm) is demonstrated. In addition, the optimized responsivity reaches 5.5 A W?1, with the corresponding eternal quantum efficiency of 1833% and detectivity of 6 × 1010 cm Hz1/2 W?1. These figures‐of‐merits are among the best values of the reported all‐layered 2D photodetectors, which are several orders of magnitude higher than those of the previous SnSe photodetectors. The superior device performance is attributed to the synergy of highly conductive surface state of Bi2Te3 topological insulator, perfect band alignment between Bi2Te3 and SnSe as well as small interface potential fluctuation. Meanwhile, the all‐layered 2D device is further constructed onto flexible mica substrate and its photoresponse is maintained roughly unchanged upon 60 bending cycles. The findings represent a fundamental scenario for advancement of the next generation high performance and high integration level flexible optoelectronics.  相似文献   

19.
Transparent p‐type semiconductors with wide‐range tunability of the hole density are rare. Developing such materials is a challenge in the field of transparent electronics that utilize invisible electric circuits. In this paper, a CuI–CuBr alloy (CuI1?xBrx) is proposed as a hole‐density‐tunable p‐type transparent semiconductor that can be fabricated at room temperature. First‐principles calculations predict that the acceptor state originating from copper vacancies in CuBr is deeper than that in CuI, leading to the hypothesis that the hole density in CuI1?xBrx can be tuned over a wide range by varying x between 0 and 1. The experimental results support this hypothesis. The hole density in CuI1?xBrx polycrystalline alloy layers can be tuned by over three orders of magnitude (1017–1020 cm?3) by varying x. In other words, the p‐type conductivity of the CuI1?xBrx alloy shows metallic and semiconducting properties. Such alloy layers can be prepared at room temperature without sacrificing transparency. Furthermore, CuI1?xBrx forms transparent p–n diodes with n‐type amorphous In–Ga–Zn–O layers, and these diodes have satisfactory rectification performance. Therefore, CuI1?xBrx alloy is an excellent p‐type transparent semiconductor for which the p‐type conductivity can be tailored in a wide range.  相似文献   

20.
Thin films of samarium‐oxide‐doped (20 mol%) ceria (SDC) are grown by pulsed‐laser deposition (PLD) on (001) MgO single‐crystal substrates. SrTiO3 (STO) prepared by PLD is used as a buffer layer on the MgO substrates to enable epitaxial growth of the fluorite‐structured SDC film; the STO layer provides a proper crystalline match between SDC and MgO, resulting in highly crystalline, epitaxial SDC films grown in the (001) orientation. Film conductivity is evaluated by electrochemical impedance spectroscopy measurements, which are performed at various temperatures (400–775 °C) in a wide range of oxygen partial pressure (pO2) values (10?25?1 atm) in order to separate ionic and electronic conductivity contributions. At 700 °C, SDC/STO films on (100) MgO exhibit a dominant ionic conductivity of about 7 × 10?2 S cm?1, down to pO2 values of about 10?15 atm. The absence of grain boundaries make the SDC/STO/MgO heterostructures stable to oxidation‐reduction cycles at high temperatures, in contrast to that observed for the more disordered SDC/STO films, which degraded after hydrogen exposure.  相似文献   

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