Non-peripherally octaalkyl-substituted nickel phthalocyanines used as non-dopant hole transport materials in perovskite solar cells

This report presents two non-perihperally octaalkyl-substituted nickel phthalocyanines (NiPcs), namely, NiEt₂Pc and NiPr₂Pc, for use as dopant-free hole transport materials in perovskite solar cells (PSCs). The length extension of the alkyl chains from ethyl to propyl significantly tunes the NiPcs' energy levels, thus reducing charge carrier recombination at the perovskite/hole transport layer (HTL) interface and leading to higher open-circuit voltage (V_OC) and short-circuit current density (J_SC) observed for the NiPr₂Pc-based PSC. And higher charge carrier mobility, higher thin film crystallinity, and lower surface roughness of the NiPr₂Pc HTL compared with that of the NiEt₂Pc one also lead to higher J_SC and fill factor (FF) observed for the NiPr₂Pc-based device. Consequently, the NiPr₂Pc-based PSC exhibits a higher power conversion efficiency (PCE) of 14.07% than that of the NiEt₂Pc-based device (8.63%).     

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.     

Theoretical design of azaacene-based non-fullerene electron transport material used in inverted perovskite solar cells

ABSTRACT

Inverted perovskite solar cells (PSCs) have attracted much attention due to their low-temperature and solution-based process. Electron transport layers are important components in inverted PSCs. Non-fullerene n-type organic small molecules seem to be more attractive as electron transport layers, because their structures are easy to be synthesised and modified. In this paper, density functional theory and semi-classical Marcus electron transfer theory were used to explore the electron transport properties in three azaacene derivatives, including one experimentally reported molecule, 1,4,9,16-tetrakis((triisopropylsilyl)ethynyl)quinoxalino[2^?,3^?:4^″,5^″]cyclopenta[1^″,2^″,3^″:5^′,6^′]acenaphtho[1^′,2^′:5,6]pyrazino[2,3-b]phenazine (1), and two theoretically designed molecules (2 and 3). Compound 2 is formed by substituting i-Pr groups in compound 1 with H atoms, which is designed to evaluate the effect of i-Pr groups on the electron transport properties. Compound 3 is designed by adding one more benzopyrazine group to the conjugation structure of compound 1. It shows that i-Pr group can increase HOMO and LUMO energy levels and improve solubility in organic solvent and hydrophobicity. Enlarging conjugation can not only decrease LUMO energy level and electron reorganisation energy, but also can increase solubility and electron mobility. So our designed compound 3 is expected to be a potential electron transport material in inverted PSCs.     

Mg2C高压性质的从头计算法研究

运用基于密度泛函理论的平面波赝势方法,结合广义梯度近似,系统地研究了Mg2C在高压下的结构相变、电子结构和光学性质。计算结果表明Mg2C在高压下将发生两次相变,一次是从反萤石到反氯化铅结构的一阶相变在30.09 GPa,另一次是从反氯化铅结构到Ni2In型结构的二阶相变在260 GPa。此外,对压力下电子结构和光学性质的分析表明,Mg2C的带隙宽度随着压力增加而增加,与Mg2Si在压力下表现出金属性有很大不同。     

Sputtered SnO2 as an interlayer for efficient semitransparent perovskite solar cells

SnO₂ is widely used as the electron transport layer (ETL) in perovskite solar cells (PSCs) due to its excellent electron mobility, low processing temperature, and low cost. And the most common way of preparing the SnO₂ ETL is spin-coating using the corresponding colloid solution. However, the spin-coated SnO₂ layer is sometimes not so compact and contains pinholes, weakening the hole blocking capability. Here, a SnO₂ thin film prepared through magnetron-sputtering was inserted between ITO and the spin-coated SnO₂ acted as an interlayer. This strategy can combine the advantages of efficient electron extraction and hole blocking due to the high compactness of the sputtered film and the excellent electronic property of the spin-coated SnO₂. Therefore, the recombination of photo-generated carriers at the interface is significantly reduced. As a result, the semitransparent perovskite solar cells (with a bandgap of 1.73 eV) based on this double-layered SnO₂ demonstrate a maximum efficiency of 17.7% (stabilized at 17.04%) with negligible hysteresis. Moreover, the shelf stability of the device is also significantly improved, maintaining 95% of the initial efficiency after 800-hours of aging.     

Searching of new,cheap, air- and thermally stable hole transporting materials for perovskite solar cells

In this work, two thermal- and air-stable, hole transporting materials (HTM) in perovskite solar cells are analyzed. Those obtained and investigated materials were two polyazomethines: the first one with three thiophene rings and 3,3′-dimethoxybenzidine moieties (S9) and the second one with three thiophene rings and fluorene moieties (S7). Furthermore, presented polyazomethines were characterized by Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy, atomic force microscopy (AFM) and thermogravimetric analysis (TGA) experiments. Both polyazomethines (S7 and S9) possessed good thermal stability with a 5% weight loss at 406 and 377 °C, respectively. The conductivity of S7 was two orders of magnitude higher than for S9 polymer (2.7 × 10^?8 S/cm, and 2.6 × 10^?10 S/cm, respectively). Moreover, polyazomethine S9 exhibited 31 nm bathochromic shift of the absorption band maximum compared to S7.Obtained perovskite was investigated by UV–vis and XRD. Electrical parameters of perovskite solar cells (PSC) were investigated at Standard Test Conditions (STC). It was found that both polyazomethines protect perovskite which is confirmed by ageing test where V_oc did not decrease significantly for solar cells with HTM in contrast to solar cell without hole conductor, where V_oc decrease was substantial. The best photoconversion efficiency (PCE = 6.9%), among two investigated in this work polyazomethines, was obtained for device with the following architectures FTO/TiO₂/TiO₂ + perovskite/S7/Au. Stability test proved the procreative effects of polyazomethines on perovskite absorber.     

Charge transfer modification of inverted planar perovskite solar cells by NiOx/Sr:NiOx bilayer hole transport layer

Perovskite solar cells (PSCs) are the most promising commercial photoelectric conversion technology in the future. The planar p-i-n structure cells have advantages in negligible hysteresis, low temperature preparation and excellent stability. However, for inverted planar PSCs, the non-radiative recombination at the interface is an important reason that impedes the charge transfer and improvement of power conversion efficiency. Having a homogeneous, compact, and energy-level-matched charge transport layer is the key to reducing non-radiative recombination. In our study, NiO$_{x}$/Sr:NiO$_{x}$ bilayer hole transport layer (HTL) improves the holes transmission of NiO$_{x}$ based HTL, reduces the recombination in the interface between perovskite and HTL layer and improves the device performance. The bilayer HTL enhances the hole transfer by forming a driving force of an electric field and further improves $J_{\rm sc}$. As a result, the device has a power conversion efficiency of 18.44%, a short circuit current density of 22.81 mA$\cdot$cm$^{-2}$ and a fill factor of 0.80. Compared to the pristine PSCs, there are certain improvements of optical parameters. This method provides a new idea for the future design of novel hole transport layers and the development of high-performance solar cells.     

Pentacene as a hole transport material for high performance planar perovskite solar cells

A cost-effective and efficient organic semiconductor pentacene was developed as a hole transport layer (HTL) material to replace classical PEDOT:PSS for planar perovskite solar cells (PSCs). As expected, the pentacene based device exhibits power conversion efficiency (PCE) of 15.90% (J_sc of 19.44 mA/cm², V_oc of 1.07 V, and FF of 77%), comparable to the PEDOT:PSS based device (PCE of 15.65%, J_sc of 18.78 mA/cm², V_oc of 1.07 V, and FF of 77%) under the same experimental conditions. The excellent performance of vacuum deposited pentacene is mainly attributed to the high efficient charge extraction and transfer in device due to the high-quality perovskite film grown on the top of pentacene substrate and a favorable energy-level alignment together with a desired downward band bending formed at the perovskite/pentacene interface. Our research has confirmed that pentacene could be served as a promising HTL material to achieve effective and potentially economical planar type PSCs.     

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。     

A silazane additive for CsPbI2Br perovskite solar cells

Adding additives into peroskite precursor solution has been proven as a simple and efficient strategy to improve the quality of peroskite films. In this work, we demonstrate an effective additive strategy to improve the quality of all-inorganic perovskite films by adding a novel silazane additive heptamethyldisilazane (HDMS). The power conversion efficiency (PCE) of the optimized devices is enhanced from 14.55% to 15.31% with an open-circuit voltage over 1.26 V due to the higher quality perovskite films with lower trap density after the incorporation of HDMS. More interestingly, the HDMS devices exhibit superior humidity and thermal stability compared with the control ones. This work provides a simple and efficient strategy to enhance the device performance and stability of all-inorganic perovskite solar cells, which could facilitate its commercialization.     

Theoretical study on the electronic structures and properties of diindolocarbazole isomers

The objective of this work is to provide an in‐depth interpretation of the electronic structures and optical properties of diindolocarbazole isomers. A systematic study of these different structures caused by the linkage pattern was performed via theoretical calculations. The optimized geometries, electronic properties, frontier molecular orbitals, ionization potentials, electron affinities, reorganization energies, and absorption and emission spectra of these isomers have been calculated and analyzed. Based on the detailed comparisons, the diindolocarbazoles act as candidates of different functional materials for optoelectronic application was predicted and the theoretical reference for the synthesis efforts and experimental investigation was provided. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface modulation of halide perovskite films for efficient and stable solar cells

As the main distribution place of deep-level defects and the entrance of water, the interface is critical to determining both the power conversion efficiency (PCE) and the stability of perovskite solar cells (PSCs). Suitable interface design can dramatically passivate interface defects and optimize energy level alignment for suppressing the nonradiative recombination and effectively extracting the photogenerated carriers towards higher PCE. Meanwhile, a proper interface design can also block the interface diffusion of ions for high operational stability. Therefore, interface modification is of great significance to make the PSCs more efficient and stable. Upon optimized material choices, the three-dimensional halide perovskite graded junction layer, low-dimensional halide perovskite interface layer and organic salt passivation layer have been constructed on perovskite films for superior PSCs, yet a systematic review of them is missing. Thus, a guide and summary of recent advances in modulating the perovskite films interface is necessary for the further development of more efficient interface modification.     

Ab initio calculations of electronic and optical properties in O-doped LiF crystal

We present a first-principle study of electronic and optical properties in pure LiF and O-doped LiF crystals. The pure LiF crystal exhibits a wide band gap while the O-doped LiF crystal shows the less band gap due to the contribution of O 2p. Some optical constants, such as dielectric functions, reflectivity and the refractive index, have been performed. The calculated reflectivity and refractive index from the pure LiF crystal agree with the experimental and recently calculated results in the low-energy range. Meanwhile, the optical properties have also been predicted from the O-doped LiF crystal. The absorption band in 200 nm has been observed, which is relatively close to the experimental result.      

四种耐热含能化合物电子结构的第一性原理研究

本文模拟计算了2,2’,4,4’,6,6’-六硝基联苯(HNBP)、2,2’,4,4’,6,6’-六硝基二苯乙烯(HNS)、2,5-二苦基-1,3,4-噁二唑(DPO)和5,5''-双(2,4,6-三硝基苯基)-2,2''-双(1,3,4-噁二唑)(TKX-55)四种耐热含能化合物的分子结构、Mulliken电荷布居、分子静电势(MEP)和Hirshfeld表面, 通过研究其分子特性、电子特性以及分子间相互作用, 以了解高耐热性含能化合物的耐热机理. 结果表明, 桥连接结构的复杂性以及分子间强氢键相互作用会增强含能化合物的稳定性. 此外, 本研究还发现中间基团的加入会对四种含能化合物分子两侧芳香环上碳原子的电荷分布以及分子表面正负静电势区域面积产生一定的影响.     

钙钛矿薄膜气相制备的晶粒尺寸优化及高效光伏转换

钙钛矿薄膜的气相制备是一种极具潜力的工业化生产工艺,但薄膜的质量控制目前远落后于溶液制备法.本文通过建立PbI_2薄膜向钙钛矿薄膜完全转化过程中反应时间、晶粒尺寸与温度的关系,实现了薄膜的质量优化及大面积钙钛矿薄膜的制备,将薄膜的平均晶粒粒径从0.42μm优化到0.81μm.基于空间电荷限制电流模型对缺陷密度的研究显示,钙钛矿薄膜的缺陷密度由5.90×10~(16)cm~(–3)降低到2.66×10~(16)cm~(–3).光伏器件(FTO/TiO_2/C_(60)/MAPbI_3/spiro-OMeTAD/Au结构)测试显示,面积为0.045cm~2器件的平均光电转换效率从14.00%提升到17.42%,最佳光电转换效率达到17.80%,迟滞因子减小至4.04%.同时,基于180℃制备的1cm~2器件的光电转换效率达到13.17%.     

Cd、Sr掺杂Mg2Ge电子结构和光学性质的第一性原理研究

此文用基于密度泛函理论(DFT)的第一性原理计算方法,分别研究了本征、掺Cd、掺Sr的Mg₂Ge的能带结构、电子态密度和光学性质.研究结果表明,本征Mg₂Ge是一种间接带隙半导体,带隙值为0.228eV.Sr的掺入使其变成带隙为0.591 eV的直接带隙半导体,Cd掺杂Mg₂Ge后表现出半金属性质.掺杂后的主要吸收峰减小,吸收谱范围增加.在可见光能量范围内,掺杂的Mg₂Ge有更低的反射率,对可见光的利用率增强.此外,掺杂还提高了高能区的光电导率.     

Benzotriazole-based dyes containing a low band gap for dye-sensitised solar cells: a theoretical study

In this study, we investigated a series of metal-free benzotriazole-based organic dyes. The geometries, electronic properties, light harvesting efficiency, and electronic absorption spectra of these dyes were studied using the density functional theory and time-dependent density functional theory. The optimised geometries indicate that these dyes are non-planar and thereby effectively inhibit close intermolecular π–π aggregation. The band gap of these dyes ensures a positive effect on the process of electron injection and dye regeneration. The band gap trend corroborates well with the predicted spectra data. Our theoretical calculations reveal that the designed metal-free organic dyes can be used as potential sensitisers for solar cells compared to the best known organic sensitiser (Y123) to date.     

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...     

从头计算对GanNm团簇的结构与稳定性的研究

用B3LYP-DFT方法对GanN2(n=1~7)和GanN(n=2~8)团簇的结构与稳定性进行了研究.在6-31G*水平上进行了结构优化和频率分析,得到了GanN2(n=1~7)和GanN(n=2~8)团簇的基态结构.在GanN(n=2~8)团簇的基态几何结构中,N原子处在分子结构的中心;在GanN2(n=1~3)团簇中,N—N键比Ga—N键强;在GanN2(n=4~7)团簇中存在Ga3N单元和Ga4N单元.在GanN2(n=1~7)和GanN(n=2~8)团簇中,Ga4N2,Ga6P2,Ga3N,Ga5N和Ga7N较其它团簇稳定.     

First-principles study of the electronic structure and optical properties of cubic Perovskite NaMgF_3

The structural, electronic, and optical properties of cubic perovskite NaMgF3 are calculated by plane-wave pseudopo- tential density functional theory. The calculated lattice constant a0, bulk modulus B0, and the derivative of bulk modulus B~ are 3.872/~, 78.2 GPa, and 3.97, respectively. The results are in good agreement with the available experimental and theo- retical values. The electronic structure shows that cubic NaMgF3 is an indirect insulator with a wide forbidden band gap of Eg = 5.90 eV. The contribution of the different bands is analyzed by total and partial density of states curves. Population analysis of NaMgF3 indicates that there is strong ionic bonding in the MgF2 unit, and a mixture of ionic and weak covalent bonding in the NaF unit. Calculations of dielectric function, absorption coefficient, refractive index, electronic energy loss spectroscopy, optical reflectivity, and conductivity are also performed in the energy range 0 to 70 eV.