Hole‐extraction layer dependence of defect formation and operation of planar CH3NH3PbI3 perovskite solar cells

Three planar CH₃NH₃PbI₃ (MAPbI₃) solar cells having the same structure except a hole‐extraction layer (HEL) showed distinctive difference in operation characteristics. Analysis of frequency‐dependent capacitance and dielectric‐loss spectra of the three MAPbI₃ devices showed two types of recombination‐loss channels with different time constants that we attributed respectively to interface and bulk defects. Discrepancy in defect formation among the three devices with a HEL of PEDOT:PSS, NiO_x, or Cu‐doped NiO_x was not surprising because grain‐size distribution and crystalline quality of MAPbI₃ can be affected by surface energy and morphology of underlying HELs. We were able to quantify interface and bulk defects in these MAPbI₃solar cells based on systematic and simultaneous simulations of capacitance and dielectric‐loss spectra, and current–voltage characteristics by using the device simulator SCAPS.

     

Anionic nonconjugated polyelectrolyte as an anode interfacial layer for polymer solar cells

Since the most high-performing donor polymers in polymer solar cells (PSCs) possessed the deep highest occupied molecular orbital (HOMO) level, interfacial engineering on anode contact is becoming increasingly important. Herein, we demonstrated efficient PSCs using an anionic poly(styrene sulfonate) (PSS) as an anode interfacial layer (AIL). With the formation of the dipole layer, the effective work function (WF) of indium tin oxide (ITO) electrode is significantly increased from 4.8 to 5.3 eV, providing favorable energetic alignment to the quasi-Fermi level of various donor polymers. Moreover, by incorporating cationic polyelectrolytes as a cathode interfacial layer, a pair of electric dipole layers induces a strong built-in electric field across the photoactive layer to drive efficient sweep-out of photogenerated charges. Consequently, the device with PSS AIL exhibited high power conversion efficiencies of 9.2 and 14.8% in PTB7-Th:PC₇₁BM- and PM6:Y6-based PSCs, respectively, both of which are higher than those of the devices with PEDOT:PSS.     

Improving the performance of perovskite solar cells with glycerol-doped PEDOT:PSS buffer layer

In this paper, we investigate the effects of glycerol doping on transmittance, conductivity and surface morphology of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate))(PEDOT:PSS) and its influence on the performance of perovskite solar cells.. The conductivity of PEDOT:PSS is improved obviously by doping glycerol. The maximum of the conductivity is 0.89 S/cm when the doping concentration reaches 6 wt%, which increases about 127 times compared with undoped. The perovskite solar cells are fabricated with a configuration of indium tin oxide(ITO)/PEDOT:PSS/CH_3NH_3PbI_3/PC_(61)BM/Al, where PEDOT:PSS and PC_(61)BM are used as hole and electron transport layers, respectively. The results show an improvement of hole charge transport as well as an increase of short-circuit current density and a reduction of series resistance, owing to the higher conductivity of the doped PEDOT:PSS. Consequently, it improves the whole performance of perovskite solar cell. The power conversion efficiency(PCE) of the device is improved from 8.57% to 11.03% under AM 1.5 G(100 mW/cm~2 illumination) after the buffer layer has been modified.     

有机阳离子对卤素钙钛矿太阳能电池性能的影响

采用第一性原理计算了CH_3NH_3PbI_3中有机部分CH_3NH_3~+和CH_3NH_3的静电特性.结果表明:CH_3NH_3~+具有强的亲电特性,CH_3NH_3的CH_3~-端具有弱亲电性,而NH_3~-端具有弱亲核性.发现在CH_3NH_3PbI_3中CH_3NH_3~+之间强静电排斥作用在相变中起着重要的作用,且在室温条件下CH_3NH_3~+在无机笼中具备活性和无序的特性,使得TiO_2/CH_3NH_3PbI_3异质结中n型TiO_2的电子通过界面扩散到CH_3NH_3PbI_3材料,并与CH_3NH_3~+结合形成CH_3NH_3,CH_3NH_3的静电特性导致在内建电场作用下更容易取向,取向的CH_3NH_3周围形成的静电场会变得更弱和更加均匀.这对无机框架上载流子的产生和传输更加有利,这样的异质结比传统的pn结具有更大优势.这是CH_3NH_3PbI_3太阳能电池高的光电转换效率的重要原因.     

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.     

Mixed-cation perovskite solar cells in space

<正>The metal halide perovskite materials demonstrate outstanding performance in photovoltaics because of their excellent optoelectronic properties [1-7]. The perovskite solar cells (PSCs) exhibiting outstanding efficiency [8,9], high power-per-weight [10], and excellent radiation resistance[11-13] are considered to be promising for developing the new-generation energy technology for space application.However, the extreme space environment would impose     

First-principles study of defect control in thin-film solar cell materials

A solar cell is a photovoltaic device that converts solar radiation energy to electrical energy, which plays a leading role in alleviating global energy shortages and decreasing air pollution levels typical of conventional fossil fuels. To render solar cells more efficient, high visible-light absorption rates and excellent carrier transport properties are required to generate high carrier levels and high output voltage. Hence, the core material, i.e., the absorption layer, should have an appropriate direct band gap and be effectively doped by both p-and n-types with minimal carrier traps and recombination centers. Consequently, defect properties of absorbers are critical in determining solar cell efficiency. In this work, we review recent first-principles studies of defect properties and engineering in four representative thin-film solar cells, namely CdTe, Cu(In,Ga)Se_2, Cu_2ZnSnS_4, and halide perovskites. The focal points include basic electronic and defect properties, existing problems, and possible solutions in engineering defect properties of those materials to optimize solar cell efficiency.     

A facile and low-cost fabrication of TiO2 compact layer for efficient perovskite solar cells

A uniform and compact hole blocking layer is necessary for high efficient perovskite-based thin film solar cell. In this study, we fabricated TiO₂ compact layers by using a simple dip-coating method in contrast to the widely used techniques such as spin coating and spray pyrolysis. In this study, we optimized the surface morphologies of dip-coating based TiO₂ compact layers by controlling the concentration of Ti precursor solution diluted in ethanol. The analyses of devices performance characteristics showed that thickness and surface morphologies of different TiO₂ compact layers played a critical role in affecting the efficiencies. The dip-coating route to prepare TiO₂ compact layers employed in this study is more amenable to fabricate the large area device and less expensive.     

Novel hole transport layer of nickel oxide composite with carbon for high-performance perovskite solar cells

A depth behavioral understanding for each layer in perovskite solar cells(PSCs)and their interfacial interactions as a whole has been emerged for further enhancement in power conversion efficiency(PCE).Herein,NiO@Carbon was not only simulated as a hole transport layer but also as a counter electrode at the same time in the planar heterojunction based PSCs with the program wx AMPS(analysis of microelectronic and photonic structures)-1D.Simulation results revealed a high dependence of PCE on the effect of band offset between hole transport material(HTM)and perovskite layers.Meanwhile,the valence band offset(?E_v)of NiO-HTM was optimized to be -0.1 to -0.3 eV lower than that of the perovskite layer.Additionally,a barrier cliff was identified to significantly influence the hole extraction at the HTM/absorber interface.Conversely,the ?E_v between the active material and NiO@Carbon-HTM was derived to be -0.15 to 0.15 eV with an enhanced efficiency from 15% to 16%.     

Efficient design of perovskite solar cell using mixed halide and copper oxide

Solar cells based on perovskites have emerged as a transpiring technology in the field of photovoltaic. These cells exhibit high power conversion efficiency. The perovskite material is observed to have good absorption in the entire visible spectrum which can be well illustrated by the quantum efficiency curve. In this paper, theoretical analysis has been done through device simulation for designing solar cell based on mixed halide perovskite. Various parameters have efficacy on the solar cell efficiency such as defect density, layer thickness, doping concentration, band offsets, etc. The use of copper oxide as the hole transport material has been analyzed. The analysis divulges that due to its mobility of charge carriers, it can be used as an alternative to spiro-OMeTAD. With the help of simulations, reasonable materials have been employed for the optimal design of solar cell based on perovskite material. With the integration of copper oxide into the solar cell structure, the results obtained are competent enough. The simulations have shown that with the use of copper oxide as hole transport material with mixed halide perovskite as absorber, the power conversion efficiency has improved by 6%.The open circuit voltage has shown an increase of 0.09 V, short circuit current density has increased by 2.32 m A/cm~2, and improvement in fill factor is 8.75%.     

Improving efficiency of inverted perovskite solar cells via ethanolamine-doped PEDOT:PSS as hole transport layer

In order to fabricate high-performance inverted perovskite solar cells (PeSCs), an appropriate hole transport layer (HTL) is essential since it will affect the hole extraction at perovskite/HTL interface and determine the crystallization quality of the subsequent perovskite films. Herein, a facile and simple method is developed by adding ethanolamine (ETA) into poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as HTL. The doping of a low-concentration ETA can efficiently modify the electrical properties of the PEDOT:PSS film and lower the highest occupied molecular orbital (HOMO) level, which is more suitable for the hole extraction from the perovskite to HTL. Besides, ETA-doped PEDOT:PSS will create a perovskite film with larger grain size and higher crystallinity. Hence, the results show that the open-circuit voltage of the device increases from 0.99 V to 1.06 V, and the corresponding power conversion efficiency (PCE) increases from 14.68% to 19.16%. The alkaline nature of ethanolamine greatly neutralizes the acidity of PEDOT:PSS, and plays a role in protecting the anode, leading the stability of the devices to be improved significantly. After being stored for 2000 h, the PCE of ETA-doped PEDOT:PSS devices can maintain 84.2% of the initial value, which is much higher than 67.1% of undoped devices.     

Activated carbon as back contact for HTM-free mixed cation perovskite solar cell

Carbon materials have potential applications in perovskite solar cell because of their excellent electronic properties and low cost. In this paper, we report, for the first time, activated carbon as a back contact for hole transport layer-free mixed halide perovskite solar cells. The ability of activated carbon to form conducting chain-like structure when dispersed in a polymeric solution makes it a possible candidate for back contact. A composite of activated carbon and PEMA was optimized with varying concentration. Mixed cation was used as a perovskite absorber and was analysed for its structural and optical properties. The fabricated devices were studied for their electrical performance. They were also subjected to stability study and showed promising results.     

Enhanced stability of low temperature processed perovskite solar cells via augmented polaronic intensity of hole transporting layer

The commercial mass production of perovskite solar cells requires full compatibility with roll‐to‐roll processing with enhanced device stability. In line with this, the present work addresses following issues simultaneously from multiple fronts: (i) low temperature processed (140 °C) ZnO is used as electron transport layer (ETL) for fabricating the mixed organic cation based perovskite solar cells, (ii) the expensive hole transporting layer (HTL) spiro‐OMeTAD is replaced with F4TCNQ doped P3HT and (iii) the fabrication method does not incorporate the dopant TBP which is known to induce degradation processes in perovskite layer. All the devices under study were fabricated in ambient conditions. The F4TCNQ doped P3HT (HTL) based devices exhibits 14 times higher device stability compared to the conventional Li‐TFSI/TBP doped P3HT devices. The underlying mechanism behind the enhanced device lifetime in F4TCNQ doped P3HT (HTL) based devices was investigated via in‐depth electronic, ionic and polaronic characterization. The enhanced polaronic property in F4TCNQ doped P3HT HTL device ascertains its superior hole extraction and electron blocking capability; and consequently higher stability retained even after a month of ageing.

     

Wannier-based definition of layer polarizations in perovskite superlattices

In insulators, the method of Marzari and Vanderbilt [Phys. Rev. B 56, 12 847 (1997)] can be used to generate maximally localized Wannier functions whose centers are related to the electronic polarization. In the case of layered insulators, this approach can be adapted to provide a natural definition of the local polarization associated with each layer, based on the locations of the nuclear charges and one-dimensional Wannier centers comprising each layer. Here, we use this approach to compute and analyze layer polarizations of ferroelectric perovskite superlattices, including changes in layer polarizations induced by sublattice displacements (i.e., layer-decomposed Born effective charges) and local symmetry breaking at the interfaces. The method provides a powerful tool for analyzing the polarization-related properties of complex layered oxide systems.     

双电子传输层结构硫硒化锑太阳电池的界面特性优化

硫硒化锑薄膜太阳电池因其制备方法简单、原材料丰富无毒、光电性质稳定等优点,成为了光伏领域的研究热点.经过近几年的发展,硫硒化锑太阳电池的光电转换效率已经突破10%,极具发展潜力.本文针对硫硒化锑太阳电池中n/i界面引起的载流子复合进行了深入研究.发现硫硒化锑太阳电池的界面特性会受到界面电子迁移能力和能带结构两方面的影响.界面电子迁移率的提高能使电子更有效地传输至电子传输层,实现器件短路电流密度和填充因子的有效提升.在此基础上,引入ZnO/Zn_1-xMg_xO双电子传输层结构能够进一步优化硫硒化锑太阳电池性能.其中,Zn_1-xMg_xO能级位置的改变可以同时调节界面和吸光层的能级分布,在Zn_1-xMg_xO导带能级为-4.2 eV,对应Mg含量为20%时,抑制载流子复合的效果最为明显,硫硒化锑太阳电池也获得了最佳的器件性能.在去除缺陷态的理想情况下,双电子传输层结构硫硒化锑太阳电池在600 nm厚时获得了20.77%的理论光电转换效率,该研究结果为硫硒化锑太阳电池...     

Dark currents in bulk heterojunction devices for imaging applications: The effect of a cathode interfacial layer

While sol–gel-processed metal oxides are widely used as an electron transport layer to enhance photovoltaic performances, their effect on photodetector application was not studied. We found sol–gel-processed titanium oxide deteriorated dark current characteristics in reverse biases by almost two orders of magnitude, whereas bare Al cathodes exhibited ideal dark current characteristics. Increased dark current came from space charge limited currents in microscopic p-i-p metal-semiconductor-metal configurations. The spatial variation of workfunction values was believed to form local leakage paths by partial filling of traps on the surface of sol–gel titanium oxide.     

蒸汽辅助溶液过程制备钙钛矿材料及钙钛矿太阳能电池

有机无机杂化钙钛矿材料被广泛应用于光电器件领域,特别是其作为太阳能电池的吸光材料,受到学术界和工业界越来越多的关注。钙钛矿太阳能电池的产业化进程正在进行中,而在进一步降低制备成本、提高电池转换效率的同时,研究出一种操作简单且可重复性高的制备钙钛矿薄膜的技术具有十分重要的意义。与其他传统的溶液处理方法不同,蒸汽辅助溶液过程(VASP)处理法避免了薄膜在生长过程中溶解以及溶剂化作用,抑制了晶核的形成,使薄膜快速重组,获得致密的高质量钙钛矿薄膜。目前报道,基于此薄膜制备的平面结构钙钛矿太阳能电池转换效率高达16.8%。本文综述了低温(150℃)VASP法制备的钙钛矿薄膜及光伏器件的相关研究进展,并对该技术的产业化前景做了展望。VASP制备过程简单、薄膜性能优异且可重复性高,为进一步制备大面积、高质量薄膜提供了可能。     

准二维钙钛矿太阳能电池的研究进展

目前,钙钛矿太阳能电池的光电转换效率已超过25％,飞速提升的效率使得人们越来越期待商业化的应用,但钙钛矿材料的稳定性问题却是其商业化所面临的最大挑战,准二维钙钛矿有望解决这一问题.利用大的有机间隔阳离子的疏水性和热稳定性,以及更高的晶体形成能和更加稳固的结构,准二维钙钛矿能够有效提高钙钛矿的稳定性.此外,准二维钙钛矿对...     

Advances in stable and flexible perovskite solar cells

Roll-to-roll (R2R) production is an innovative approach and is fast becoming a very popular industrial method for high throughput and mass production of solar cells. Replacement of costly indium tin oxide (ITO), which conventionally has served as the transparent electrode would be a great approach for roll to roll production of flexible cost effective solar cells. Indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) are brittle and ultimately limit the device flexibility. Perovskite solar cells (PSCs) have been the centre of photovoltaic research community during the recent years owing to its exceptional performance and economical prices. The best reported PSCs fabricated by employing mesoporous TiO₂ layers require elevated temperatures in the range of 400–500 °C which limits its applications to solely glass substrates. In such a scenario developing flexible PSCs technology can be considered a suitable and exciting arena from the application point of view, them being flexible, lightweight, portable, and easy to integrate over both small, large and curved surfaces.