Low-temperature-processed ZnO thin films as electron transporting layer to achieve stable perovskite solar cells

Morphology and surface property of ZnO thin films as electron transporting layer in perovskite solar cells are crucial for obtaining high-efficient and stable perovskite solar cells. In this work, two different preparation methods of ZnO thin films were carried out and the photovoltaic performances of the subsequent perovskite solar cells were investigated. ZnO thin film prepared by sol–gel method was homogenous but provided high series resistance in solar cells, leading to low short circuit current density. Lower series resistance of solar cell was obtained from homogeneous ZnO thin film from spin-coating of colloidal ZnO nanoparticles (synthesized by hydrolysis–condensation) in a mixture of 1-butanol, chloroform and methanol. The perovskite solar cells using this film achieved the highest power conversion efficiency (PCE) of 4.79% when poly(3-hexylthiophene) was used as a hole transporting layer. In addition, the stability of perovskite solar cells was also examined by measuring the photovoltaic characteristic for six consecutive weeks with the interval of 2 weeks. It was found that using double layers of the sol–gel ZnO and ZnO nanoparticles provided better stability with no degradation of PCE in 10 weeks. Therefore, this work provides a simple method for preparing homogeneous ZnO thin films in order to achieve stable perovskite solar cells, also for controlling their surface properties which help better understand the characteristics of perovskite solar cells.     

Interfacial engineering of CuO nanorod/ZnO nanowire hybrid nanostructure photoanode in dye-sensitized solar cell

Developing efficient and cost-effective photoanode plays a vital role determining the photocurrent and photovoltage in dye-sensitized solar cells (DSSCs). Here, we demonstrate DSSCs that achieve relatively high power conversion efficiencies (PCEs) by using one-dimensional (1D) zinc oxide (ZnO) nanowires and copper (II) oxide (CuO) nanorods hybrid nanostructures. CuO nanorod-based thin films were prepared by hydrothermal method and used as a blocking layer on top of the ZnO nanowires’ layer. The use of 1D ZnO nanowire/CuO nanorod hybrid nanostructures led to an exceptionally high photovoltaic performance of DSSCs with a remarkably high open-circuit voltage (0.764 V), short current density (14.76 mA/cm² under AM1.5G conditions), and relatively high solar to power conversion efficiency (6.18%) . The enhancement of the solar to power conversion efficiency can be explained in terms of the lag effect of the interfacial recombination dynamics of CuO nanorod-blocking layer on ZnO nanowires. This work shows more economically feasible method to bring down the cost of the nano-hybrid cells and promises for the growth of other important materials to further enhance the solar to power conversion efficiency.     

Influence of H2O/DEZ ratio on LPCVD ZnO:B films for application in a-Si:H/μc-Si:H tandem solar cells

In this study, boron doped zinc oxide (ZnO:B) films were prepared at different water to diethyl zinc (H₂O/DEZ) flow ratios from 0.6 to 1.4 by a low pressure chemical vapor deposition (LPCVD) technique. It is found that the morphology of ZnO:B films varies from small leaf-like to pyramidal surface structures with the increasing H₂O/DEZ flow ratio. The rough ZnO:B films deposited at a relatively H₂O/DEZ flow ratio such as 1.2 or 1.4 show a high haze value of up to 28 % at 600 nm and $\mathrm{a} (11\overline{2}0)$ preferential crystallographic orientation. All ZnO:B films were applied in hydrogenated amorphous silicon/microcrystalline silicon tandem solar cells (a-Si:H/μc-Si:H) as front electrodes. The efficiency of the solar cells increases with the increasing H₂O/DEZ flow ratio, which is attributed to a high spectral response mainly in the long-wavelength range and the consequent enhancement of short-circuit current. A high-efficiency a-Si:H/μc-Si:H tandem solar cell of 10 % was achieved. The H₂O/DEZ ratio is an important process parameter to tune the material properties of LPCVD ZnO:B films and the performances of corresponding silicon thin film solar cells.     

Influence of P<Superscript>+</Superscript>-ZnTe back surface contact on photovoltaic performance of ZnTe based solar cells

In order to improve photovoltaic performance of solar cells based on ZnTe thin films two device structures have been proposed and its photovoltaic parameters have been numerically simulated using Solar Cell Capacitance Simulator software. The first one is the ZnO/CdS/ZnTe conventional structure and the second one is the ZnO/CdS/ZnTe/P⁺-ZnTe structure with a P⁺-ZnTe layer inserted at the back surface of ZnTe active layer to produce a back surface field effect which could reduce back carrier recombination and thus increase the photovoltaic conversion efficiency of cells. The effect of ZnO, CdS and ZnTe layer thicknesses and the P⁺-ZnTe added layer and its thickness have been optimized for producing maximum working parameters such as: open-circuit voltage V_oc, short-circuit current density J_sc, fill factor FF, photovoltaic conversion efficiency η. The solar cell with ZnTe/P⁺-ZnTe junction showed remarkably higher conversion efficiency over the conventional solar cell based on ZnTe layer and the conversion efficiency of the ZnO/CdS/ZnTe/P⁺-ZnTe solar cell was found to be dependent on ZnTe and P⁺-ZnTe layer thicknesses. The optimization of ZnTe, CdS and ZnTe layers and the inserting of P⁺-ZnTe back surface layer results in an enhancement of the energy conversion efficiency since its maximum has increased from 10% for ZnO, CdS and ZnTe layer thicknesses of 0.05, 0.08 and 2 µm, respectively to 13.37% when ZnO, CdS, ZnTe and P⁺-ZnTe layer thicknesses are closed to 0.03, 0.03, 0.5 and 0.1 µm, respectively. Furthermore, the highest calculated output parameters have been J_sc?=?9.35 mA/cm², V_oc?=?1.81 V, η?=?13.37% and FF?=?79.05% achieved with ZnO, CdS, ZnTe, and P⁺-ZnTe layer thicknesses about 0.03, 0.03, 0.5 and 0.1 µm, respectively. Finally, the spectral response in the long-wavelength region for ZnO/CdS/ZnTe solar cells has decreased at the increase of back surface recombination velocity. However, it has exhibited a red shift and showed no dependence of back surface recombination velocity for ZnO/CdS/ZnTe/P?+?-ZnTe solar cells.     

Short-circuit current improvement in CdTe solar cells by combining a ZnO buffer layer and a solution back contact

Conventional CdTe solar cells have a CdS window layer, in which an absorption loss of photons with more than 2.4 eV occurs through the CdS layer. A thinner CdS layer was applied to enhance light transmission and a ZnO buffer layer with a band gap of 3.3 eV was introduced to suppress shunting through the thinner CdS window layer. A 100-nm thick ZnO layer sputter-deposited at 300 °C had uniform coverage on a transparent conductive oxide (TCO) after a subsequent high-temperature process. The ZnO layer was effective in preventing shunting through the CdS window layer so that the open-circuit voltage and fill factor of the CdTe solar cells were recovered and the short-circuit current was enhanced over that of the conventional CdTe solar cell. In the ZnO/CdS/CdTe configuration, the short-circuit current was further improved throughout the visible wavelength region by replacing the Cu-metal contact with a Cu solution contact. As a result the short-circuit current from 21.7 to 26.1 mA/cm² and the conversion efficiency of the CdTe solar cell increased from 12 to 15% without antireflective coating. Our result indicates that the Cu solution back contact is a critical factor for achieving a higher cell efficiency in addition to ZnO buffer layer.     

Low-temperature photo-activated inorganic electron transport layers for flexible inverted polymer solar cells

A simple and versatile route of forming sol–gel-derived metal oxide n-type electron transport layers (ETLs) for flexible inverted polymer solar cells (PSCs) is proposed using low-temperature photochemical activation process. The photochemical activation, which is induced by deep ultraviolet irradiation on sol–gel films, allows formation of metal oxide n-type ETLs such as zinc oxide (ZnO) and indium gallium zinc oxide films at a low temperature. Compared to poly(3-hexylthiophene)/phenyl-C₆₁-butyric acid methyl ester inverted PSCs with thermally annealed ZnO ETLs (optimized efficiency of 3.26 ± 0.03 %), the inverted PSCs with photo-activated ZnO ETLs showed an improved efficiency of 3.60 ± 0.02 %. The enhanced photovoltaic property is attributed to efficient charge collection from low overall series resistance and high surface area-to-geometric area ratio by the photo-activated ZnO ETLs.     

Sputter-deposited ZnO thin films consisting of nano-networks for binder-free dye-sensitized solar cells

ZnO nano-network structures with high porosity were prepared for use in the photoelectrodes of binder-free dye-sensitized solar cells (DSSCs) by DC sputtering and subsequent thermal oxidation. Zn thin films prepared at 100 °C showed nano-network structures with high porosity, while those prepared at 25 °C did not. This was partially attributed to the high mobility of sputter-deposited particles that arrived at the surface of the substrate and partially to a supersaturation mechanism. The prepared nano-network Zn was successfully transformed to ZnO without a morphological change via subsequent annealing in air. The power conversion efficiency of DSSCs based on the ZnO nano-network structures exhibited 10 times higher efficiency than those based on ZnO film prepared at 25 °C because of its large surface area for adsorption of dye molecules. The thickness of the ZnO nano-network structures increased linearly at 10 μm h^?1 as a function of sputter time. As the film thickness increased, the power conversion efficiency of DSSCs increased from 1.09% to 1.82%.     

In_2O_3:Sn中间层改善B掺杂ZnO薄膜的性能及其应用研究

金属有机化学气相沉积(MOCVD)法生长的掺硼氧化锌(BZO)薄膜,具有天然的"类金字塔"绒面结构,作为硅基薄膜太阳电池的前电极具有良好的陷光效果.但直接获得的BZO薄膜表面形貌过于尖锐,影响后续硅基薄膜材料生长质量及太阳电池的光电转换效率.本文设计了以一层超薄In2O3:Sn(ITO)薄膜(～4 nm厚度)作为中间层的多层膜,并通过对顶层BZO薄膜的厚度调制,改善BZO薄膜的表面特性,薄膜结构为:glass/底层BZO/ITO/顶层BZO.合适厚度的顶层BZO薄膜有助于获得类似"菜花状"形貌特征,尖锐的表面趋于"柔和",而较厚的顶层BZO薄膜仍然保持"类金字塔状"结构."柔和"的BZO薄膜表面结构有助于提高后续生长薄膜电池的结晶质量.将获得的新型"三明治"结构多层膜应用于p-i-n型氢化微晶硅(μc-Si:H)薄膜太阳电池,相比传统的BZO薄膜,电池的量子效率QE在500—800 nm波长范围提高了～10%,并且电池的Jsc和Voc均有所提高.     

Heterojunction solar cells produced by porous silicon layer transfer technology

In this paper, we present the result of heterojunction solar cells based on porous silicon layer transfer technology. a-Si/c-Si structured solar cells were prepared in which the c-Si was deposited on annealed double-layer porous silicon by low-pressure chemical vapor deposition. The structural properties and the evolvement of the double-layer porous silicon before and after thermal annealing were investigated by scanning electron microscopy. X-ray diffraction, Raman spectroscopy and a microwave photoconductive decay method were used to investigate the properties of the epitaxial silicon thin films deposited at different pressures. And, the influence of the deposition pressure on the properties of the c-silicon thin films was investigated. The spectral responses of the cells were studied by a quantum efficiency test. The results show that the epitaxial silicon thin film deposited at 100 Pa has better carrier lifetime and better spectral response. Furthermore, the Raman peak intensity of the silicon film prepared at 100 Pa is much closer to that of a monocrystalline silicon wafer. A simple solar cell structure without any light-trapping features showed an efficiency of up to 10.1 %.     

Synthesis of self-light-scattering wrinkle structured ZnO photoanode by sol–gel method for dye-sensitized solar cells

A special morphological zinc oxide (ZnO) photoanode for dye-sensitized solar cell was fabricated by simple sol–gel drop casting technique. This film shows a wrinkled structure resembling the roots of banyan tree, which acts as an effective self scattering layer for harvesting more visible light and offers an easy transport path for photo-injected electrons. These ZnO electrode of low thickness (~5 μm) gained an enhanced short-circuit current density of 6.15 mA/cm², open-circuit voltage of 0.67 V, fill factor of 0.47 and overall conversion efficiency of 1.97 % under 1 sun illumination. This shows a high conversion efficiency and a superior performance than that of ZnO nanoparticle-based photoanode (η ~ 1.13 %) of high thickness (~8 μm).     

连续离子层吸附反应沉积后硫化法制备柔性铜锌锡硫薄膜太阳电池

在柔性钼箔衬底上采用连续离子层吸附反应法(successive ionic layer absorption and reaction)制备ZnS/Cu2SnSx叠层结构的预制层薄膜,预制层薄膜在蒸发硫气氛、550 C温度条件下进行退火得到Cu2ZnSnS4吸收层.分别采用EDS,XRD,Raman,SEM表征吸收层薄膜的成分、物相和表面形貌.结果表明,退火后薄膜结晶质量良好,表面形貌致密.用在普通钠钙玻璃上采用相同工艺制备的CZTS薄膜表征薄膜的光学和电学性能,表明退火后薄膜带隙宽度为1.49 eV,在可见光区光吸收系数大于104cm 1,载流子浓度与电阻率均满足薄膜太阳电池器件对吸收层的要求.用上述柔性衬底上的吸收层制备Mo foil/CZTS/CdS/i-ZnO/ZnO:Al/Ag结构的薄膜太阳电池得到2.42%的效率,是目前报道柔性CZTS太阳电池最高效率.     

Structural, optical and electrical properties of ZnO:Al thin films for optoelectronic applications

Undoped and aluminum-doped ZnO thin films are prepared by the sol–gel spin-coating process. Zinc acetate dihydrate, ethanol and mono-ethanolamine are used as precursor, solvent and stabilizer, respectively. The atomic percentage of dopant in solution were [Al/Zn] = 1 %, 2 % and 3 %. The effect of Al doping on the optical and electrical properties of ZnO films was investigated by X-ray diffraction (XRD), Four-Point probe technique and UV–visible spectrophotometery. The results from the X-ray diffraction show that the pure ZnO thin films had a polycrystalline structure of the hexagonal Wurtzite Type. A minimum resistivity of $3.3 \times 10^{-3} \Omega \cdot \mathrm{cm}$ was obtained for the film doped with 2 mol % Al. Optical transmissions reveal a good transmittance within the visible wavelength spectrum region for all of the films. The value of the band gap is enhanced from 3.21 eV (undoped ZnO) to 3.273 eV (Al/Zn = 3 %), the increase in the band gap can be explained by the Burstein–Moss effect.     

Double-layer indium doped zinc oxide for silicon thin-film solar cell prepared by ultrasonic spray pyrolysis

Indium doped zinc oxide(ZnO:In) thin films were prepared by ultrasonic spray pyrolysis on corning eagle 2000 glass substrate.1 and 2 at.% indium doped single-layer ZnO:In thin films with different amounts of acetic acid added in the initial solution were fabricated.The 1 at.% indium doped single-layers have triangle grains.The 2 at.% indium doped single-layer with 0.18 acetic acid adding has the resistivity of 6.82×10-3Ω·cm and particle grains.The doublelayers structure is designed to fabricate the ZnO:In thin film with low resistivity(2.58×10-3Ω·cm) and good surface morphology.It is found that the surface morphology of the double-layer ZnO:In film strongly depends on the substratelayer,and the second-layer plays a large part in the resistivity of the double-layer ZnO:In thin film.Both total and direct transmittances of the double-layer ZnO:In film are above 80% in the visible light region.Single junction a-Si:H solar cell based on the double-layer ZnO:In as front electrode is also investigated.     

Investigation of the crystallinity,structural, and optical properties in hydrotreating of Li–W co-doped ZnO thin films

The hydrotreated Li–W co-doped ZnO (LWZO:H) thin films was prepared on quartz glass substrates by RF magnetron sputtering at substrate temperature 100 °C with varied hydrogen flow ratios. The X-ray diffraction spectra indicated that the hydrotreating Li–W co-doped ZnO films showed a preferred orientation toward the c-axis. The chemical compositions of all samples were confirmed by X-ray photoelectron spectroscopy, which clearly showed the existence of W as a doping element into ZnO crystal lattice. The surface morphology of LWZO:H thin films changed with the increasing R value can clearly be seen. The average transmittance of the films was found to be almost 85 % for the wavelength range of 400–1,200 nm. Meanwhile, the optical band gap increase of the films may be attributed to the band Burstein–Moss effect.     

Effects of deposition temperature and hydrogen flow rate on the properties of the Al-doped ZnO thin films and amorphous silicon thin-film solar cells

A compound of 98 mol% ZnO and 1 mol% Al₂O₃ (AZO, Al:Zn = 98:2) was sintered at 1350 °C as a target and the AZO thin films were deposited on glass using a radio frequency magnetron sputtering system. The effects of deposition temperature (from room temperature to ～300 °C) on the optical transmission spectrum of the AZO thin films were studied. The Burstein–Moss shift was observed and used to prove that defects in the AZO thin films decreased with increasing deposition temperature. The variations in the optical band gap (E _g) values of the AZO thin films were evaluated from plots of (αhv)²=c(hν?E _g), revealing that the measured E _g values increased with increasing deposition temperature. The effects of the H₂ flow rate during deposition (0 %～11.76 %, deposition temperature of 200 °C) on the crystallization, morphology, resistivity, carrier concentration, carrier mobility, and optical transmission spectrum of the AZO thin films were measured. The chemical structures of the Ar-deposited and 2 % H₂-flow rate-deposited AZO thin films (both were deposited at 200 °C) were investigated by XPS to clarify the mechanism of improvement in resistivity. The prepared AZO thin films were also used as transparent electrodes to fabricate amorphous silicon thin-film solar cells, and their properties were also measured.     

Superstrate p-i-n a-Si:H solar cells on textured ZnO:Al front transparent conduction oxide

Superstrate p-i-n amorphous silicon thin-film (a-Si:H) solar cells are prepared on SnO₂:F and ZnO:Al transparent conducting oxides (TCOs) in order to see the effect of TCO/p-layers on a-Si:H solar cell operation. The solar cells prepared on textured ZnO:Al have higher open circuit voltage V_oc than cells prepared on SnO₂:F. The presence of a thin microcrystalline p-type silicon layer (μc-Si:H) between ZnO:Al and p a-SiC:H plays a major role by causing an improvement in the fill factor as well as in V_oc of a-Si:H solar cells prepared on ZnO:Al TCO. Without any treatment of the p-i interface, we could obtain a high V_oc of 994 mV while keeping the fill factor (72.7%) and short circuit current density J_sc at the same level as for the cells on SnO₂:F TCO. This high V_oc value can be attributed to modification in the current transport in this region due to creation of a potential barrier.     

Study of thermal stability of ZnO:B films grown by LPCVD technique

Zinc oxide thin films with different boron doping levels (ZnO:B) are prepared by low pressure chemical vapor deposition (LPCVD) technique. All films here exhibit a pyramid-like surface texture. Stability of the ZnO:B films is systematically investigated through a post heat treatment at ambient temperatures of 300 °C and 250 °C for different durations. It is found that total transmission (TT) of these films at near infrared (NIR) wavelength range increases with the enhanced thermal treating intensity, which could be attributed to decrease of free carrier concentration inside the films. Moreover, light absorption in NIR wavelength range decreases profoundly with the increasing carrier concentration after a post thermal treatment in particular for highly doped ZnO:B films. However, morphology of these ZnO:B films does not vary after the thermal treatment and thus the corresponding light scattering properties do not change as well. Therefore, the thermally treated ZnO:B films may lead to an increase in light-generated current and resulting a higher cell efficiency due to the enhancement of TT when they work as front contact in silicon thin film solar cells.     

Light trapping for a‐Si:H/µc‐Si:H tandem solar cells using direct pulsed laser interference texturing

We present a‐Si:H/µc‐Si:H tandem solar cells on laser textured ZnO:Al front contact layers. Direct pulsed laser interference patterning (DLIP) was used for writing arrays of one‐dimensional micro gratings of submicron period into ZnO:Al films. The laser texture provides good light trapping which is indicated by an increase in short‐circuit current density of 20% of the bottom cell limited device compared to cells on planar ZnO:Al. The open‐circuit voltage of the cells on laser textured ZnO:Al is almost the same as for cells on planar substrates, indicating excellent growth conditions for amorphous and microcrystalline silicon on the U‐shaped grating grooves. DLIP is a simple, single step and industrially applicable method for large area periodic texturing of ZnO:Al thin films. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

In-process ZnO thin films alloying during pulsed laser deposition

Alloyed ZnO:Al thin films were prepared by a pulsed laser deposition by the altering of two pure targets (ZnO and Al) during the deposition process. Two deposition temperatures (?197 °C and 400 °C) were applied and differences of diffusion dynamics were compared. As-grown layered films were annealed and aluminium distribution was homogenized. The results revealed that the amorphous structure (samples grown at ?197 °C) of ZnO provide more positive conditions for efficient Al diffusion in comparison with crystalline structure (samples grown at 400 °C). A detailed investigation by SIMS depth profiling confirmed a homogeneous chemical composition of annealed and recrystallized films which exhibited a porous nature and wurtzite crystalline structure.     

Interaction of ultra-short laser pulses with CIGS and CZTSe thin films

The thin-film solar cell technologies based on complex quaternary chalcopyrite and kesterite materials are becoming more attractive due to their potential for low production costs and optimal spectral performance. As in all thin-film technologies, high efficiency of small cells might be maintained with the transition to larger areas when small segments are interconnected in series to reduce photocurrent and related ohmic losses in thin films. Interconnect formation is based on the three scribing steps, and the use of a laser is here crucial for performance of the device. We present our simulation and experimental results on the ablation process investigations in complex CuIn_1?x Ga _x Se₂ (CIGS) and Cu₂ZnSn(S,Se)₄ (CZTSe) cell’s films using ultra-short pulsed infrared (~1 μm) lasers which can be applied to the damage-free front-side scribing processes. Two types of processes were investigated—direct laser ablation of ZnO:Al/CIGS films with a variable pulse duration of a femtosecond laser and the laser-induced material removal with a picosecond laser in the ZnO:Al/CZTSe structure. It has been found that the pulse energy and the number of laser pulses have a significantly stronger effect on the ablation quality in ZnO:Al/CIGS thin films rather than the laser pulse duration. For the thin-film scribing applications, it is very important to carefully select the processing parameters and use of ultra-short femtosecond pulses does not have a significant advantage compared to picosecond laser pulses. Investigations with the ZnO:Al/CZTSe thin films showed that process of the absorber layer removal was triggered by a micro-explosive effect induced by high pressure of sublimated material due to a rapid temperature increase at the molybdenum-CZTSe interface.