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1.
Solar cells based on kesterite‐type Cu2ZnSnS4 (CZTS) were fabricated on molybdenum coated soda lime glass by evaporation using ZnS, Sn, Cu, and S sources. The coevaporation process was performed at a nominal substrate temperature of 550°C and at a sulfur partial pressure of 2–3 × 10−3 Pa leading to polycrystalline CZTS thin films with promising electronic properties. The CZTS absorber layers were grown copper‐rich, requiring a KCN etch step to remove excess copper sulfide. The compositional ratios as determined by energy‐dispersive X‐ray spectroscopy (EDX) after the KCN etch are Cu/(Zn + Sn): 1.0 and Zn/Sn: 1.0. A solar cell with an efficiency of 4.1% and an open‐circuit voltage of 541 mV was obtained. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

2.
To improve the photovoltaic properties of Cu2ZnSnS4 (CZTS) cells, we investigated the effect of both the thickness of the deposited CdS layers and the post‐annealing temperature following CdS deposition on the photovoltaic properties of CZTS cells using a two‐layer CZTS structure. By depositing a thin CdS layer (40 nm) followed by high temperature annealing (603 K), we observed a remarkable increase in the short‐circuit current density because of the enhancement of the external quantum efficiency in the wavelength range of 400–800 nm. The best CZTS cell exhibited a conversion efficiency of 9.4% in the active area (9.1% in the designated area). In addition, we also fabricated a CZTS cell with open‐circuit voltage of 0.80 V by appropriately tuning the composition of the CZTS layers. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

3.
Improving the efficiency of kesterite (Cu2ZnSn(S,Se)4; CZTSSe) solar cells requires understanding the effects of Na doping. This paper investigates these effects by applying a NaF layer at various positions within precursors. The NaF position is important because Na produces Na-related defects in the absorber and suppresses the formation of intrinsic defects. By investigating precursors with various NaF positions, the sulfo-selenization mechanism and the characteristics of defect formation are confirmed. Applying a NaF layer onto a Zn layer in a CZTSSe precursor limits Zn diffusion and suppresses Cu-Zn alloy formation, thus changing the sulfo-selenization mechanism. In addition, the surface NaF layer provides reactive Se and S to the absorber layer by generating Na2Sex and Na2Sx liquid phases during sulfo-selenization, thus limiting the incorporation of Na into the absorber and reducing the Na effects. Efficiency values of 11.16% and 11.19% are obtained for a flexible CZTSSe solar cell by applying NaF between the Zn layer and back contact and between the Cu and Sn layers, respectively. This study presents methods for doping with alkali metals and improving the efficiency of photovoltaics.  相似文献   

4.
A method for fabricating high‐efficiency Cu2ZnSn(S,Se)4 (CZTSSe) solar cells is presented, and it is based on a non‐explosive, low‐cost, and simple solution process followed by a two‐step heat treatment. 2‐Methoxyethanol was used as a solvent, and Cu, Zn, Sn, chloride salts, and thiourea were used as solutes. A CZTSSe absorber was prepared by sulfurising and then selenising an as‐coated Cu2ZnSnS4 (CZTS) film. Sulfurisation in a sulfur vapour filled furnace for a long time (2 h) enhanced the crystallisation of the as‐coated CZTS film and improved the stability of the CZTS precursor, and selenisation promoted further grain growth to yield a void‐free CZTSSe film. Segregation of Cu and S at the grain boundaries, the absence of a fine‐grain bottom layer, and the large grain size of the CZTSSe absorber were the main factors that enhanced the grain‐to‐grain transport of carriers and consequently the short‐circuit current (Jsc ) and efficiency. The efficiency of the CZTS solar cell was 5.0%, which increased to 10.1% after selenisation. For the 10.1% CZTSSe solar cell, the external quantum efficiency was approximately 80%, the open‐circuit voltage was 450 mV, the short‐circuit current was 36.5 mA/cm2, and the fill factor was 61.9%. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

5.
Cu2ZnSnS4 (CZTS)‐based materials have a useful band gap and a high absorption coefficient; however, their power conversion efficiency is low compared with that of CdTe and Cu(In,Ga)Se2‐based solar cells. Two of the factors that strongly affect CZTS solar cell characteristics are the MoS2 layer and the presence of defects. In this study, Mo back‐contact layers were annealed to control MoS2 layer formation and the Na content in the Mo layer before the absorber precursor layer was deposited. The increase in oxygen content in the Mo layer suppressed MoS2 layer formation. In addition, the increase in Na diffusion during the initial stage of the absorber precursor deposition decreased the defect density in the absorber layer and in the absorber–buffer interface. These results were verified through measurements of the external quantum efficiency, the temperature dependence of the open‐circuit voltage (VOC), and admittance spectra. The current densities (JSC) and VOC, as well as the power conversion efficiencies, improved as the annealing temperature of the Mo layer increased, which suggests that CZTS solar cell characteristics can be improved by suppressing MoS2 layer formation and increasing Na content in the Mo layer before deposition of the absorber precursor layer. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

6.
A new atomic layer deposition process was developed for deposition of Zn–Sn–O buffer layers for Cu(In,Ga)Se2 solar cells with tetrakis(dimethylamino) tin, Sn(N(CH3)2)4, diethyl zinc, Zn(C2H5)2, and water, H2O. The new process gives good control of thickness and [Sn]/([Sn] + [Zn]) content of the films. The Zn–Sn–O films are amorphous as found by grazing incidence X‐ray diffraction, have a high resistivity, show a lower density compared with ZnO and SnOx, and have a transmittance loss that is smeared out over a wide wavelength interval. Good solar cell performance was achieved for a [Sn]/([Sn] + [Zn]) content determined to be 0.15–0.21 by Rutherford backscattering. The champion solar cell with a Zn–Sn–O buffer layer had an efficiency of 15.3% (Voc = 653 mV, Jsc(QE) = 31.8 mA/cm2, and FF = 73.8%) compared with 15.1% (Voc = 663 mV, Jsc(QE) = 30.1 mA/cm2, and FF = 75.8%) of the best reference solar cell with a CdS buffer layer. There is a strong light‐soaking effect that saturates after a few minutes for solar cells with Zn–Sn–O buffer layers after storage in the dark. Stability was tested by 1000 h of dry heat storage in darkness at 85 °C, where Zn–Sn–O buffer layers with a thickness of 76 nm retained their initial value after a few minutes of light soaking. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

7.
The thin‐film photovoltaic material Cu2ZnSnS4 (CZTS) has drawn worldwide attention in recent years due to its earth‐abundant, nontoxic element constitution, and remarkable photovoltaic performance. Although state‐of‐the‐art power conversion efficiency is achieved by hydrazine‐based methods, effort to fabricate such devices in a high throughput, environmental‐friendly way is still highlydesired. Here a hydrazine‐free all‐solution‐processed CZTS solar cell with Na2S self‐depleted back contact modification layer for the first time is demonstrated, using a ball‐milled CZTS as light absorber, low‐temperature solution‐processed ZnO electron‐transport layer as well as silver‐nanowire transparent electrode. The inserting of Na2S self‐depleted layer is proven to effectively stabilize the CZTS/Mo interface by eliminating a detrimental phase segregation reaction between CZTS and Mo‐coated soda lime glass, thus leading to a better crystallinity of CZTS light absorbing layer, enhanced carrier transportation at CZTS/Mo interface as well as a smaller series resistance. Furthermore, the self‐depletion feature of the Na2S modification layer also averts hole‐transportation barrier within the devices. The results show the vital importance of interfacial engineering for these CZST devices and the Na2S interface layer can be extended to other optoelectronic devices using Mo contact.  相似文献   

8.
The impacts of preheating of an electrodeposited Cu/Sn/Zn (CTZ) stack precursor on structural changes of the CTZ precursor and the impact on structural and electric properties of the finally obtained Cu2ZnSnS4 (CZTS) films are discussed in detail. We found that preheating for relatively long durations improved the qualities of CZTS films: these films were composed of large grains and had compact and flat surface morphologies. The best solar cell with efficiency of 8.1% was obtained on the basis of a CZTS film derived from the CTZ precursor preheated for 200 min. The external quantum efficiency response of the cell indicated efficient utilization of photons with relatively long wavelength regions because of its good structural and electronic properties. On the other hand, a short circuit current density–temperature property of one of the best cells in this study suggested that the CZTS film had deep acceptor levels and/or an appreciable energy barrier to the Mo back contact. Moreover, an open circuit voltage–temperature property of the corresponding device showed activation energy of 1.18 eV, indicating preferential occurrence of CdS–CZTS interface recombination. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

9.
In this study, the impacts of different precursors on Cu2ZnSnS4 thin film solar cells were investigated. The two kinds of precursors of (Cu+Sn)/Zn and (Cu+Sn)/ZnS were deposited on Mo-coated soda lime glasses by magnetron sputtering. Cu2ZnSnS4 (CZTS) films based on different precursors were fabricated by soft annealing and following two-step sulfurization in sulphur vapour. The crystal structure, phase purity, surface morphology, composition and optical properties of CZTS films from different precursors were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), energy dispersive spectrometry (EDS) and UV–vis–NIR spectroscopy, respectively. As a result, the CZTS thin films with smooth surface and uniform compositional ratio distribution were obtained from the precursors of (Cu+Sn)/ZnS. The best conversion efficiency of the fabricated CZTS film solar cell based on (Cu+Sn)/ZnS precursors was 3.36%.  相似文献   

10.
Cu2ZnSnS4 (CZTS) is a promising thin‐film absorber material that presents some interesting challenges in fabrication when compared with Cu(In,Ga)Se2. We introduce a two‐step process for fabrication of CZTS films, involving reactive sputtering of a Cu‐Zn‐Sn‐S precursor followed by rapid annealing. X‐ray diffraction and Raman measurements of the sputtered precursor suggest that it is in a disordered, metastable CZTS phase, similar to the high‐temperature cubic modification reported for CZTS. A few minutes of annealing at 550 °C are sufficient to produce crystalline CZTS films with grain sizes in the micrometer range. The first reported device using this approach has an AM1.5 efficiency of 4.6%, with Jsc and Voc both appearing to be limited by interface recombination. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

11.
Cu2ZnSnS4 (CZTS) is made of earth abundant elements and also have suitable optical properties for solar cell applications. But, in phase diagram, CZTS exists in a narrow range of temperature and composition. Therefore, optimizing the elemental composition and annealing time is very important for obtaining phase pure CZTS. In this study, the effects of elemental composition and short annealing time on the structural and optical properties of reactively sputtered CZTS thin films are reported. Thin films were deposited by reactive sputtering of Cu: Sn (60:40 wt%), Sn and Zn targets sequentially in the presence of H2S at room temperature. Amount of Zn precursor was varied by changing the sputter time for Zn. The films were rapidly annealed in inert atmosphere for varying time. The band gap of sample changed with change in the composition as well as annealing time. Sample with higher Zn content showed better crystallinity. With increase in the annealing time the crystallinity of samples improved. Sample annealed for 12 min at 550 °C was phase pure. Obtaining good quality film even for very short anneal time is the novelty of reactive sputtering method as all the elements are already mixed and short annealing is required only for crystal growth. Through detailed experiments, the optimum composition and annealing time required for the growth of phase pure CZTS has been established.  相似文献   

12.
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   

13.
We investigate the effects of interfacial dielectric layers (IDLs) on the electrical properties of top‐gate In‐Ga‐Zn‐oxide (IGZO) thin film transistors (TFTs) fabricated at low temperatures below 200°C, using a target composition of In:Ga:Zn = 2:1:2 (atomic ratio). Using four types of TFT structures combined with such dielectric materials as Si3N4 and Al2O3, the electrical properties are analyzed. After post‐annealing at 200°C for 1 hour in an O2 ambient, the sub‐threshold swing is improved in all TFT types, which indicates a reduction of the interfacial trap sites. During negative‐bias stress tests on TFTs with a Si3N4 IDL, the degradation sources are closely related to unstable bond states, such as Si‐based broken bonds and hydrogen‐based bonds. From constant‐current stress tests of Id = 3 µA, an IGZO‐TFT with heat‐treated Si3N4 IDL shows a good stability performance, which is attributed to the compensation effect of the original charge‐injection and electron‐trapping behavior.  相似文献   

14.
Control of localized metal–organic framework (MOF) thin film formation is a challenge. Zeolitic imidazolate frameworks (ZIFs) are an important sub‐class of MOFs based on transition metals and imidazolate linkers. Continuous coatings of intergrown ZIF crystals require high rates of heterogeneous nucleation. In this work, substrates coated with zinc oxide layers are used, obtained by atomic layer deposition (ALD) or by magnetron sputtering, to provide the Zn2+ ions required for nucleation and localized growth of ZIF‐8 films ([Zn(mim)2]; Hmim = 2‐methylimidazolate). The obtained ZIF‐8 films reveal the expected microporosity, as deduced from methanol adsorption studies using an environmentally controlled quartz crystal microbalance (QCM) and comparison with bulk ZIF‐8 reference data. The concept is transferable to other MOFs, and is applied to the formation of [Al(OH)(1,4‐ndc)]n (ndc = naphtalenedicarboxylate) thin films derived from Al2O3 nanolayers.  相似文献   

15.
Core–shell‐structured, ultrafine SnOx/carbon nanofiber (CNF)/carbon nanotube composite films are in situ synthesized by electrospinning through a dual nozzle. The carbon shell layer functions as a buffer to prevent the separation of SnOx particles from the CNF core, allowing full utilization of high‐capacity SnOx in both Li‐ion and Na‐ion batteries. The composite electrodes reveal an anomalous Li‐ and Na‐ion storage mechanism where all the intermediate phases, like LixSn and NaxSn alloys, maintain amorphous states during the entire charge/discharge process. The uniform dispersion on an atomic scale and the amorphous state of the SnOx particles remain intact in the carbon matrix without growth or crystallization even after 300 cycles, which is responsible for sustaining excellent capacity retention of the electrodes. These discoveries not only shed new insights into fundamental understanding of the electrochemical behavior of SnOx electrodes but also offer a potential strategy to improve the cyclic stability of other types of alloy anodes that suffer from rapid capacity decays due to large volume changes.  相似文献   

16.
A ZnS/Zn1‐xMgxO buffer combination was developed to replace the CdS/i‐ZnO layers in in‐line co‐evaporated Cu(In,Ga)Se2(CIGS)‐based solar cells. The ZnS was deposited by the chemical bath deposition (CBD) technique and the Zn1‐xMgxO layer by RF magnetron sputtering from ceramic targets. The [Mg]/([Mg] + [Zn]) ratio in the target was varied between x = 0·0 and 0·4. The composition, the crystal structure, and the optical properties of the resulting layers were analyzed. Small laboratory cells and 10 × 10 cm2 modules were realized with high reproducibility and enhanced stability. The transmission is improved in the wavelength region between 330 and 550 nm for the ZnS/Zn1‐xMgxO layers. Therefore, a large gain in the short‐circuit current density up to 12% was obtained, which resulted in higher conversion efficiencies up to 9% relative as compared to cells with the CdS/i‐ZnO buffer system. Peak efficiencies of 18% with small laboratory cells and 15·2% with 10 × 10 cm2 mini‐modules were demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

17.
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.  相似文献   

18.
Thin Zn Sn O films are evaluated as new buffer layer material for Cu(In,Ga)Se2‐based solar cell devices. A maximum conversion efficiency of 13.8% (Voc = 691 mV, Jsc(QE) = 27.9 mA/cm2, and FF = 71.6%) is reached for a solar cell using the Zn Sn O buffer layer which is comparable to the efficiency of 13.5% (Voc = 706 mV, Jsc(QE) = 26.3 mA/cm2, and FF = 72.9%) for a cell using the standard reference CdS buffer layer. The open circuit voltage (Voc) and the fill factor (FF) are found to increase with increasing tin content until an optimum in both parameters is reached for Sn/(Zn + Sn) values around 0.3–0.4. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

19.
We determined the electrical junction (EJ) locations in Cu(In,Ga)Se2 (CIGS) and Cu2ZnSnSe4 (CZTS) solar cells with ~20‐nm accuracy by developing scanning capacitance spectroscopy (SCS) applicable to the thin‐film devices. Cross‐sectional sample preparation for the SCS measurement was developed by high‐energy ion milling at room temperature for polishing the cross section to make it flat, followed by low‐energy ion milling at liquid nitrogen temperature for removing the damaged layer and subsequent annealing for growing a native oxide layer. The SCS shows distinct p‐type, transitional, and n‐type spectra across the devices, and the spectral features change rapidly with location in the depletion region, which results in determining the EJ with ~20‐nm resolution. We found an n‐type CIGS in the region next to the CIGS/CdS interface; thus, the cell is a homojunction. The EJ is ~40 nm from the interface on the CIGS side. In contrast, such an n‐type CZTS was not found in the CZTS/CdS cells. The EJ is ~20 nm from the CZTS/CdS interface, which is consistent with asymmetrical carrier concentrations of the p‐CZTS and n‐CdS in a heterojunction cell. Our results of unambiguously determination of the junction locations contribute significantly to understanding the large open‐circuit voltage difference between CIGS and CZTS. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

20.
High efficiency dye‐sensitized solar cells (DSSCs) are fabricated with a heterostructured photoanode that consists of a 500‐nm‐thick organized mesoporous TiO2 (om‐TiO2) interfacial layer (IF layer), a 7 or 10‐μm thick nanocrystalline TiO2 layer (NC layer), and a 2‐μm‐thick mesoporous Bragg stack (meso‐BS layer) as the bottom, middle and top layers, respectively. An om‐TiO2 layer with a high porosity, transmittance, and interconnectivity is prepared via a sol‐gel process, in which a poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer is used as a structure‐directing agent. The meso‐BS layer with large pores is prepared via alternating deposition of om‐TiO2 and colloidal SiO2 (col‐SiO2) layers. Structure and optical properties (refractive index) of the om‐TiO2 and meso‐BS layers are studied and the morphology of the heterostructured photoanode is characterized. DSSCs fabricated with the heterostructured IF/NC/BS photoanode and combined with a polymerized ionic liquid (PIL) exhibit an energy conversion efficiencies of 6.6% at 100 mW/cm2, one of the highest reported for solid‐state DSSCs and much larger than cells prepared with only a IF/NC layer (6.0%) or a NC layer (4.5%). Improvements in energy conversion efficiency are attributed to the combination of improved light harvesting, decreased resistance at the electrode/electrolyte interface, and excellent electrolyte infiltration.  相似文献   

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