Highly conductive ZnO films with high near infrared transparency

We present an approach for deposition of highly conductive nominally undoped ZnO films that are suitable for the n‐type window of low band gap solar cells. We demonstrate that low‐voltage radio frequency (RF) biasing of growing ZnO films during their deposition by non‐reactive sputtering makes them as conductive as when doped by aluminium (ρ≤1·10⁻³Ω cm). The films prepared with additional RF biasing possess lower free‐carrier concentration and higher free‐carrier mobility than Al‐doped ZnO (AZO) films of the same resistivity, which results in a substantially higher transparency in the near infrared region (NIR). Furthermore, these films exhibit good ambient stability and lower high‐temperature stability than the AZO films of the same thickness. We also present the characteristics of Cu(InGa)Se₂, CuInSe₂ and Cu₂ZnSnSe₄‐based solar cells prepared with the transparent window bilayer formed of the isolating and conductive ZnO films and compare them to their counterparts with a standard ZnO/AZO bilayer. We show that the solar cells with nominally undoped ZnO as their transparent conductive oxide layer exhibit an improved quantum efficiency for λ > 900 nm, which leads to a higher short circuit current density J_SC. This aspect is specifically beneficial in preparation of the Cu₂ZnSnSe₄ solar cells with band gap down to 0.85 eV; our champion device reached a J_SC of nearly 39 mAcm⁻², an open circuit voltage of 378mV, and a power conversion efficiency of 8.4 %. Copyright © 2015 John Wiley & Sons, Ltd.     

Development of Nano‐TiO2 dye sensitised solar cells on high mobility transparent conducting oxide thin films

The optical transmission of dye‐sensitised solar cells (DSCs) can be tuned by altering the dye and/or particle size of the mesoporous TiO₂ layers, to allow their application as the top device in tandem solar cells. To benefit from this semi‐transparency, parasitic optical losses by the transparent electrodes must be minimised. This work investigates the influence of using two different transparent conductors, namely, the high mobility material titanium doped indium oxide (ITiO) and fluorine doped tin oxide (FTO) as electrodes for semi‐transparent DSCs. The overall NIR transparency through the DSCs increased significantly as each FTO electrode was replaced by an ITiO electrode. This increase was from 20–45% in the 1300–700 nm wavelength range for fully FTO‐based cells, to about 60% for fully ITiO‐based cells, across the same spectrum. DSCs prepared on these electrodes exhibited short circuit currents ranging from 14·0–14·9 mA/cm². The conversion efficiency of the cell with ITiO as both the front and rear electrodes was 5·8%, which though significant, was lower than the 8·2% attained by the cell using FTO electrodes, as a result of a lower fill factor. Improvements in the ITiO thermal stability and in the processing of the TiO₂ interfacial layer are expected to improve the cell efficiency of such single DSC devices. The high current density and optical transparency of ITiO‐based DSCs make them an interesting option for tandem solar cells. Copyright © 2008 John Wiley & Sons, Ltd.     

绒面AZO最新研究进展及应用

掺铝氧化锌(AZO)透明导电膜作为一种光电性能优异的透明导电膜(TCO)受到研究人员的广泛关注,并被认为是当前大规模使用的传统铟锡氧化物(ITO)的替换材料。绒面AZO薄膜因其电阻率低、高透过率且具有良好的陷光效果,可以提高太阳能电池的光电转换效率,而被认为是太阳能电池前电极的理想材料。综述了绒面AZO透明导电膜的制备方法和性能研究现状,并针对AZO的国内外研究状况提出了今后的发展趋势和研究方向。     

All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

Revisiting Metal Sulfide Semiconductors: A Solution‐Based General Protocol for Thin Film Formation,Hall Effect Measurement,and Application Prospects

Nanostructured thin films of metal sulfides (MS) are highly desirable materials for various optoelectronic device applications. However, a general low‐temperature protocol that describes deposition of varieties of MS structures, especially in their film form is still not available in literatures. Here, a simple and highly effective general solution‐based deposition protocol for highly crystalline and well‐defined nanostructured MS thin films from ethanol on variety of conducting and non‐conducting substrates is presented. The films display remarkable electronic properties such as high carrier mobility and high conductivity. When NiS thin film deposited on a flexible polyethylene terephthalate (PET) substrate is used as a fluorine doped tin oxide (FTO)‐free counter electrode in dye‐sensitized solar cells, it exhibits a solar‐to‐electric power conversion efficiency of 9.27 ± 0.26% with the highest conversion efficiency as high as 9.50% (vs 8.97 ± 0.07% exhibited by Pt‐electrode). In addition, the NiS film deposited on a Ti‐foil has demonstrated an outstanding catalytic activity for the hydrogen and oxygen evolution reactions from water.     

Enhanced Performance of I2‐Free Solid‐State Dye‐Sensitized Solar Cells with Conductive Polymer up to 6.8%

An iodine‐free solid‐state dye‐sensitized solar cell (ssDSSC) is reported here, with 6.8% energy conversion efficiency—one of the highest yet reported for N719 dye—as a result of enhanced light harvesting from the increased transmittance of an organized mesoporous TiO₂ interfacial layer and the good hole conductivity of the solid‐state‐polymerized material. The organized mesoporous TiO₂ (OM‐TiO₂) interfacial layer is prepared on large‐area substrates by a sol‐gel process, and is confirmed by scanning electron microscopy (SEM) and grazing incidence small‐angle X‐ray scattering (GISAXS). A 550‐nm‐thick OM‐TiO₂ film coated on fluorine‐doped tin oxide (FTO) glass is highly transparent, resulting in transmittance increases of 8 and 4% compared to those of the bare FTO and conventional compact TiO₂ film on FTO, respectively. The high cell performance is achieved through careful control of the electrode/hole transport material (HTM) and nanocrystalline TiO₂/conductive glass interfaces, which affect the interfacial resistance of the cell. Furthermore, the transparent OM‐TiO₂ film, with its high porosity and good connectivity, exhibits improved cell performance due to increased transmittance in the visible light region, decreased interfacial resistance ( Ω ), and enhanced electron lifetime ( τ ). The cell performance also depends on the conductivity of HTMs, which indicates that both highly conductive HTM and the transparent OM‐TiO₂ film interface are crucial for obtaining high‐energy conversion efficiencies in I₂‐free ssDSSCs.     

绒面掺铝氧化锌透明导电薄膜研究进展

绒面掺铝氧化锌(AZO)透明导电薄膜由于电阻率低、在可见光区域透过率高、绒面结构能有效散射入射光,提高太阳电池光电转换效率,被广泛应用于太阳电池前电极。概述了绒面AZO薄膜的制备方法,重点介绍了磁控溅射技术沉积AZO薄膜后再进行湿法刻蚀制绒面方法,制备的样品呈现"坑状"或"类月球地貌"的绒面,并讨论了工艺对薄膜结构、光电性能和刻蚀行为的影响,最后介绍了绒面AZO薄膜在硅薄膜太阳电池中的应用,进一步降低生产成本和实现大规模产业化生产是绒面AZO薄膜的发展趋势。     

Coral‐shaped ZnO nanostructures for dye‐sensitized solar cell photoanodes

A highly efficient ZnO photoanode for dye‐sensitized solar cells was successfully grown by a simple, low cost, and scalable method. A nanostructured coral‐shaped Zn layer was deposited by sputtering onto fluorine‐doped tin oxide/glass slices at room temperature and then thermally oxidized in ambient atmosphere. Stoichiometry, crystalline phase, quality, and morphology of the film were investigated, evidencing the formation of a highly porous branched nanostructure, with a pure wurtzite crystalline structure. ZnO‐based dye‐sensitized solar cells were fabricated with customized microfluidic architecture. Dye loading on the oxide surface was analyzed with ultraviolet‐visible spectroscopy, and the dependence of the cell efficiency on sensitizer incubation time and film thickness was studied by current‐voltage electrical characterization, incident photon‐to‐electron conversion efficiency, and impedance spectroscopy measurements, showing the promising properties of this material for the fabrication of dye‐sensitized solar cell photoanodes with a solar conversion efficiency up to 4.58%. Copyright © 2012 John Wiley & Sons, Ltd.     

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

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

Transparent Flexible Substrates Based on Polyimides with Aluminum Doped Zinc Oxide (AZO) Thin Films

In this paper, transparent flexible substrates based on polyimides (PIs) with aluminum doped zinc oxide (AZO) thin films for organic electroluminescent devices have been prepared. PI film based on 2,2'-bis-(3,4-dicarboxyphenyl) hexafluoropropanedianhydride (6FDA) and 2,2'-bis-(trifluoromethyl)-4,4'-diaminobiphenyl (TFDB) were used for transparent flexible substrates. AZO thin films were prepared at two substrate deposition temperatures of 100/spl deg/C and 200/spl deg/C with a typical radio-frequency (r.f.) planar magnetron sputtering system. The sheet resistance and the optical transmission properties for AZO films on the fluorinated PI substrate were comparable with those for the AZO films on a glass substrate. The substrate properties were better when the deposition temperature was higher.     

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.     

Composition and Energy Band–Modified Commercial FTO Substrate for In Situ Formed Highly Efficient Electron Transport Layer in Planar Perovskite Solar Cells

Perovskite solar cells (PSCs) have received much attention and with them a power conversion efficiency (PCE) of over 22% has been achieved. Electron transport layers (ETLs) based on metal oxide materials play an important role in transferring electrons and reducing back recombination. However, existing fabrication approaches are generally waste too many materials and consume too much energy for commercial application. Here, a brand new plasma preannealing procedure is proposed that can replace the traditional ETL preparation process and alleviate the above‐mentioned problems. A pure SnO₂ phase in situ formed on the fluorine‐doped tin oxide (FTO) surface can be obtained at room temperature by only 15 min oxygen plasma assisted reaction without postheating treatment. It enables the precise control of compositions, defects, and energy levels of band at the surface of FTO substrate, resulting in a prominent PCE of 20.39% with excellent stability and reproducibility. This simple and efficient source‐free fabrication technology provides a versatile platform for the manufacture of PSCs in the future.     

射频磁控溅射法制备AZO/p-Si异质结及其性能研究

利用射频磁控溅射法,在p-Si衬底上生长了Al掺杂的ZnO(AZO)薄膜,并进而制备了AZO/p-Si异质结。X射线衍射仪、紫外-可见光分光光度计、四探针测试仪和霍尔效应测试仪测量表明,AZO薄膜具有良好的结晶质量、光学和电学特性。暗态下的I-V测试表明,AZO/p-Si异质结具有较好的整流特性,反向饱和电流为1.29×10-6A,±2V处的正向和反向电流之比为229.41,计算得出异质结的理想因子为2.28。在标准光照下AZO/p-Si异质结呈现出明显的光生伏特效应,这种异质结太阳电池具有2.51%的光电转换效率。     

Improved conversion efficiency of a‐Si:H/µc‐Si:H thin‐film solar cells by using annealed Al‐doped zinc oxide as front electrode material

In recent years, zinc oxide has been investigated as a front electrode material in hydrogenated amorphous silicon/hydrogenated microcrystalline silicon (a‐Si:H/µc‐Si:H) tandem solar cells. Such as for other transparent conducting oxide materials and applications, a proper balancing of transparency and conductivity is necessary. The latter is directly related to the density and the mobility of charge carriers. A high density of charge carriers increases conductivity but leads to a higher absorption of light in the near‐infrared part of the spectrum due to increased free‐carrier absorption. Hence, the only way to achieve high conductivity while keeping the transparency as high as possible relies on an increase of carrier mobility. The carrier density and the mobility of sputtered Al‐doped zinc oxide (ZnO:Al) can be tailored by a sequence of different annealing steps. In this work, we implemented such annealed ZnO:Al films as a front electrode in a‐Si:H/µc‐Si:H tandem solar cells and compared the results with those of reference cells grown on as‐deposited ZnO:Al. We observed an improvement of short‐circuit current density as well as open‐circuit voltage and fill factor. The gain in current density could be attributed to a reduction of both sub‐band‐gap absorption and free‐carrier absorption in the ZnO:Al. The higher open‐circuit voltage and fill factor are indicators of a better device quality of the silicon for cells grown on annealed ZnO:Al. Altogether, the annealing led to an improved initial conversion efficiency of 12.1%, which was a gain of +0.7% in absolute terms. Copyright © 2013 John Wiley & Sons, Ltd.     

磁控溅射AlN∶Mg/ZnO∶Al异质结二极管及其光电特性的研究

利用磁控溅射方法,在ITO玻璃基底上分别溅射镁掺杂的氮化铝(AlN∶Mg)薄膜、铝掺杂的氧化锌(ZnO∶Al或AZO)薄膜,成功制备AlN∶Mg/ZnO∶Al透明异质结二极管.实验结果表明:AlN∶Mg/ZnO∶Al异质结具有明显的Ⅰ-Ⅴ整流特性,正向开启电压1V左右,在氙灯光照下,二极管的反向电流在5V偏置时达到3m...     

Evolution of ZnO architecture on a nanoporous TiO2 film by a hydrothermal method and the photoelectrochemical performance

The synthesis of ZnO architecture on a fluorine-doped SnO2 (FTO) conducting glass pre-coated with nanoporous TiO2 film has been achieved by a one-step hydrothermal method at a temperature of 70 ℃.The effect of the reaction time on the morphology of the ZnO architecture has been investigated,and a possible growth mechanism for the formation of the ZnO architecture is discussed in detail.The morphology and phase structures of the as-obtained composite films have been investigated by field-emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD).The results show that the growth time greatly affects the morphology of the obtained ZnO architecture.The photoelectrochemical performances of as-prepared composite films are measured by assembling them into dye sensitized solar cells (DSSCs).The DSSC based on the as-prepared composite film (2 h) has obtained the best power conversion efficiency of 1.845％.     

引入微晶硅底电池的PIN型三结Si基薄膜太阳电池的制备

为充分利用太阳光谱能量,在玻璃衬底的PIN型a-Si/a-SiGe电池中直接引入了微晶硅(μc-Si:H)底电池.从透明导电氧化物(TCO)衬底的光透过率估算了PIN型a-Si:H/a-SiGe:H/μc-Si:H三结电池实现高转化效率的可行性.通过调整μc-Si:H底电池厚度考察三结电池的性能变化,结果发现,受中间电...     

Silicon thin‐film solar cells with rectangular‐shaped grating couplers

As an alternative to randomly textured transparent conductive oxides as front contact for thin‐film silicon solar cells the application of transparent grating couplers was studied. The grating couplers were prepared by sputtering of aluminium‐doped zinc oxide (ZnO) on glass substrate, a photolithography and a lift‐off process and were used as periodically textured substrates. The period size and groove depth of these transparent gratings were tuned independently from each other and varied between 1 and 4 μm and 100–600 nm. The optical properties of rectangular‐shaped gratings and the opto‐electronic behaviour of amorphous and microcrystalline silicon solar cells with integrated grating couplers as a function of the grating parameters (period size P and groove depth h_g) are presented. The optical properties of the gratings are discussed with respect to randomly textured substrates and the achieved solar cell results are compared with the opto‐electronic properties of solar cells deposited on untextured (flat) and randomly textured substrates. Copyright © 2005 John Wiley & Sons, Ltd.     

High rate (~7 nm/s), atmospheric pressure deposition of ZnO front electrode for Cu(In,Ga)Se2 thin‐film solar cells with efficiency beyond 15%

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.     

A path towards a better characterisation of silicon thin‐film solar cells: depth profile analysis by pulsed radiofrequency glow discharge optical emission spectrometry

The analytical potential of radiofrequency pulsed glow discharge optical emission spectrometry (rf‐PGD‐OES) is investigated for quantitative depth profiling analysis of thin‐film solar cells (TFSC) based on hydrogenated amorphous silicon (a‐Si:H). This method does not require sampling at ultra‐high‐vacuum conditions, and so it facilitates higher sample throughput than do reference techniques. In this paper, the determination of compositional depth profiles of a‐Si:H TFSC was performed by resorting to a multi‐matrix calibration procedure. For this purpose, certified reference materials, as well as laboratory standards based on individual layers of doped a‐Si:H, were simultaneously employed to build the analytical calibration curves. Results show that rf‐PGD‐OES allows us to discriminate the different layers of photovoltaic devices: the front contact composed by ZnO:Al₂O₃ (AZO), the a‐Si:H layer (the B‐doped, intrinsic a‐Si:H and P‐doped films), the AZO/Al back contact and substrate. A good agreement with the nominal values for element concentrations (e.g. 0.4% of H, 1.5% of B and 3.7% of P) and layer thicknesses (in the range of 950 nm for the front contact and 13 nm for the P‐doped a‐Si:H layer) was obtained, demonstrating the ability of rf‐PGD‐OES for a direct, sensitive and high‐depth‐resolution analysis of photovoltaic devices. Moreover, diffusion processes between the coating layers, which could have an important influence on the final efficiency of TFSC, can be identified as well. Hence, the findings support the use of rf‐PGD‐OES as an analysis method in the development of photovoltaic thin films. Copyright © 2013 John Wiley & Sons, Ltd.