退火温度对电子束蒸发沉积Cu_2O薄膜性能的影响

近年来,钙钛矿太阳电池(PSCs)得到了迅猛发展,而无机空穴传输材料(IHTMs)的使用可进一步降低电池的成本,提高电池的稳定性.本文通过电子束蒸发制备了Cu_2O薄膜,研究了空气中退火温度及时间对薄膜组成、结构及光电性能的影响,并构筑了p-i-n反型平面异质结钙钛矿太阳电池.研究发现:由于热解作用,直接通过电子束蒸发制备的薄膜为Cu_2O和Cu的混合物;而在空气中经过退火后,由于氧化作用,随着退火温度的升高,薄膜的组分由混合物转变为纯的Cu_2O,再转变成纯的CuO.通过控制退火温度制备的Cu_2O薄膜的光学带隙约为2.5 eV,载流子迁移率约为30 cm~2·V~(-1)·s~(-1).应用于PSCs,薄膜的最佳厚度为40 nm,但电池性能低于PEDOT:PSS基的PSCs.这主要是由于钙钛矿前驱液在Cu_2O薄膜的润湿性较差,吸收层中有大量微孔洞存在,致使漏电流增强,电池的性能降低.然而,当采用Cu_2O/PEDOT:PSS双HTMs设计时,由于PEDOT:PSS对Cu_2O具有较强的腐蚀作用,使电池性能恶化.     

十二烷二酸修饰TiO_2电子传输层改善钙钛矿太阳电池的电流特性

在经典的平面异质结钙钛矿太阳电池中,TiO_2致密层的电子传输性能一直是获得优异光伏性能的决定性因素之一.相较于spriro-OMe TAD等常见的空穴传输材料优异的空穴传输能力,作为电子传输材料的TiO_2的导电性较弱,无法形成良好的电荷匹配.为了解决这个问题,我们使用自组装的十二烷二酸(DDDA)单分子层来修饰TiO_2致密层的表面,TiO_2致密层的导电性能得到大幅提升,并且其能带结构得到优化,促进了电子传输,降低了电子积聚和载流子复合,使得电池的短路电流密度(JSC)从修饰前的20.34 mA·cm~(-2)提升至修饰后的23.28 mA·cm~(-2),进而使得电池在标准测量条件下的光电能量转换效率从14.17%提升至15.92%.同时还发现,通过DDDA修饰TiO_2致密层,所制备的器件的光稳定性显著提升,器件未封装暴露在AM 1.5光强100 mW·cm~(-2)的模拟太阳光下超过720 min,保持初始效率的71%以上且趋于稳定.     

Theoretical insight into the carrier mobility anisotropy of hole transport material Spiro-OMeTAD

All-solid-state organic-inorganic halide perovskite solar cells (PSCs) have attracted wide attention due to the rapid progress of power conversion efficiency in recent years. Hole transport material (HTM) in PSCs plays the role of extracting and transporting photo-excited holes. Anisotropy of carrier mobility is one important property for semiconductors, however, which still remains unclear for the dominant HTM spiro-OMeTAD used in PSCs. Based on Density Functional Theory (DFT) and Marcus theory, we for the first time conducted investigations on the anisotropy of carrier mobility along representative crystal planes of spiro-OMeTAD by recombination energy λ and electronic coupling integral V. Results indicate that the holes and electrons show transport orientations consistency parallel to the (010), (101) and (111) crystal planes while inconsistency was found parallel to (100), (110), (011) and (001) crystal planes (with an angle ranged from 40° to 70° between the hole and electron transport directions). Our work embodies the theoretical significance of controllable and oriented fabrication of HTM in PSCs.     

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.     

Correlation of band electronic structure with efficiency in perovskite solar cells with vanadium (Ⅳ) oxide thin film buffers

Perovskite solar cells have been studied extensively in the area of perovskite solar cells because they have a comparatively free hysteresis. Through fabrication of a perovskite solar cell based on a vanadium oxide buffer, this study clarified the mechanism of electron and hole transport in the laminated layer upon irradiation with light. The power conversion efficiency (PCE) of the Vanadium (Ⅳ) oxide (VO₂) sputtering process device was approximately 13% and with the spin-coating process was 8.5%. To investigate the physicochemical origin of such PCE differences depending on the process type, comprehensive band alignment and band structure analyses of the actual cell stacks were performed using X-ray photoelectron spectroscopy depth measurements. Accordingly, it was found that the inconsistent valence band offset between the perovskite absorption layer and V₂O₅ layer as a function of the VO₂ process type caused a difference in the hole transport, resulting in the difference in the efficiency.     

新型空穴传输材料在钙钛矿太阳能电池中的研究进展

钙钛矿太阳能电池是一种全新的全固态薄膜电池. 报道的能量转换效率已提高到19.3%, 成为可再生能源领域的热点研究方向. 空穴传输材料是构成高效钙钛矿太阳能电池的重要组分之一. 本文介绍了钙钛矿太阳能电池的基本结构, 对空穴传输材料的分子结构、能级水平和迁移率等对电池性能的影响进行了详细的总结和评述.     

TiO2/SnO2 electron transport double layers with ultrathin SnO2 for efficient planar perovskite solar cells

The electron transport layer (ETL) plays an important role on the performance and stability of perovskite solar cells (PSCs). Developing double ETL is a promising strategy to take the advantages of different ETL materials and avoid their drawbacks. Here, an ultrathin SnO₂ layer of ～ 5 nm deposited by atomic layer deposit (ALD) was used to construct a TiO₂/SnO₂ double ETL, improving the power conversion efficiency (PCE) from 18.02% to 21.13%. The ultrathin SnO₂ layer enhances the electrical conductivity of the double layer ETLs and improves band alignment at the ETL/perovskite interface, promoting charge extraction and transfer. The ultrathin SnO₂ layer also passivates the ETL/perovskite interface, suppressing nonradiative recombination. The double ETL achieves outstanding stability compared with PSCs with TiO₂ only ETL. The PSCs with double ETL retains 85% of its initial PCE after 900 hours illumination. Our work demonstrates the prospects of using ultrathin metal oxide to construct double ETL for high-performance PSCs.     

Electron transport layer engineering with rubidium chloride alkali halide to boost the performance of perovskite absorber layer

The mesoscopic perovskite solar cells (PSCs) based on titanium oxide (TiO₂) with a certified 25.2% efficiency are the forefront devices in the PSCs field. Hence, it can conclude the mesoporous titanium oxide (mp-TiO₂) is one of the most promising candidates to use as an electron transport layer (ETL) in PSCs. Improving the conductivity of mp-TiO₂ can consider as a simple route to motivate the electron extraction ability of this layer and increase the efficiency of PSCs. Herein, rubidium chloride (RbCl) was introduced as an additive source to boost the optoelectronic properties of mp-TiO₂ ETL. It was observed through ETL modification with RbCl, the optical transmittance of mp-TiO₂ remains constant but increases its electro-conductivity. Results showed that the morphology and crystalline properties of the perovskite layer with a modified ETL substrate is improved. It indicates a perovskite layer with enlarger grains and lower lead iodide (PbI₂) surplus. Altogether, ETL modification brings a champion efficiency of 11.10% for hole transport layer (HTL)-free PSCs higher than that of 8.65% for the HTL-free PSCs based on pristine ETL. Besides, Modified PSCs compared to pristine PSCs showed higher stability response as a result of lower grain boundaries in the modified perovskite layer.     

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.     

高效平面异质结有机-无机杂化钙钛矿太阳电池的质量管理

基于有机-无机杂化钙钛矿材料的太阳电池具有能量转换效率高和制备工艺简单等优点,引起了学术界的高度关注.其中平面异质结结构太阳电池具有结构简单,可与其他类型电池相兼容以构筑叠层电池设计,以及可低温制备等诸多优点,成为当前的一个重要研究方向.然而,电池性能的优劣与钙钛矿薄膜质量的高低有着直接的联系.本文对钙钛矿材料的特性、一步溶液法制备薄膜的成核-生长机理、电池结构的演变等进行了概述,其中重点介绍了高质量钙钛矿薄膜溶液法制备过程的一些最新的质量控制方法;最后对钙钛矿太阳电池的发展及存在问题进行了总结和展望,为今后的研究提供参考.     

Microwave-reduced graphene oxide for efficient and stable hole extraction layers of polymer solar cells

Microwave-assisted reduced graphene oxide (MR-GO) layer was applied to hole extraction layer (HEL) of polymer solar cells (PSCs) and was compared with the widely used poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) in bulk hetero-junction (BHJ) solar cells. The power conversion efficiency (PCE) of 3.57% was achieved with the MR-GO layer, which is 21% higher than that of PSCs with the conventional PEDOT:PSS HEL material. This enhancement of PCE is mainly attributed to the increase of short-circuit current density originated from the hydrophobic surface of the MR-GO layer. The hydrophobic graphene oxide surface is believed to improve wetting property and physical contact of active blends. In addition, the MR-GO interfacial layer is found to show the excellent device stability in atmospheric condition. The PCE of conventional PEDOT:PSS based PSCs showed total degradation when the device was exposed to atmospheric condition for 1000 h without any encapsulation, while that of MR-GO based PSC showed over 85% of PCE.     

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%).     

Device simulation of lead-free CH_3NH_3SnI_3 perovskite solar cells with high efficiency

The lead-free perovskite solar cells(PSCs) have drawn a great deal of research interest due to the Pb toxicity of the lead halide perovskite.CH_3NH_3SnI_3 is a viable alternative to CH_3NH_3PbX_3,because it has a narrower band gap of 1.3 eV and a wider visible absorption spectrum than the lead halide perovskite.The progress of fabricating tin iodide PSCs with good stability has stimulated the studies of these CH_3NH_3SnI_3 based cells greatly.In the paper,we study the influences of various parameters on the solar cell performance through theoretical analysis and device simulation.It is found in the simulation that the solar cell performance can be improved to some extent by adjusting the doping concentration of the perovskite absorption layer and the electron affinity of the buffer and HTM,while the reduction of the defect density of the perovskite absorption layer significantly improves the cell performance.By further optimizing the parameters of the doping concentration(1.3 × 10~(16) cm~3) and the defect density(1 × 10~(15) cm~3) of perovskite absorption layer,and the electron affinity of buffer(4.0 eV) and HTM(2.6 eV),we finally obtain some encouraging results of the J_(sc) of 31.59 mA/cm~2,V_(oc) of 0.92 V,FF of 79.99%,and PCE of 23.36%.The results show that the lead-free CH_3NH_3SnI_3 PSC is a potential environmentally friendly solar cell with high efficiency.Improving the Sn~(2+) stability and reducing the defect density of CH_3NH_3SnI_3 are key issues for the future research,which can be solved by improving the fabrication and encapsulation process of the cell.     

Reveal the large open-circuit voltage deficit of all-inorganicCsPbIBr2 perovskite solar cells

Due to excellent thermal stability and optoelectronic properties, all-inorganic perovskite is one of the promising candidates to solve the thermal decomposition problem of conventional organic—inorganic hybrid perovskite solar cells (PSCs), but the larger voltage loss (V_loss) cannot be ignored, especially CsPbIBr₂, which limits the improvement of efficiency. To reduce V_loss, one promising solution is the modification of the energy level alignment between the perovskite layer and adjacent charge transport layer (CTL), which can facilitate charge extraction and reduce carrier recombination rate at the perovskite/CTL interface. Therefore, the key issues of minimum V_loss and high efficiency of CsPbIBr₂-based PSCs were studied in terms of the perovskite layer thickness, the effects of band offset of the CTL/perovskite layer, the doping concentration of the CTL, and the electrode work function in this study based on device simulations. The open-circuit voltage (V_oc) is increased from 1.37 V to 1.52 V by replacing SnO₂ with ZnO as the electron transport layer (ETL) due to more matching conduction band with the CsPbIBr₂ layer.     

基于PTB7,Bis-PC_(70)BM,PC_(70)BM的高效率有机三元太阳能电池

我们将Bis-PC_(70)BM作为第二种电子受体混入基于PTB7:PC_(70)BM的聚合物太阳能电池中,制备了三元混合聚合物太阳能电池.相比于PC_(70)BM,Bis-PC_(70)BM的最低未占分子轨道(lowest unoccupied molecular orbital,LUMO)能级更高,所以掺入Bis-PC_(70)BM后器件的开路电压(V_(oc))得到了提升.Bis-PC_(70)BM在PTB7和PC_(70)BM之间起到桥梁的作用,因此在给体/受体界面创造了更多的电荷传递通道.而且从原子力显微镜中得到的结果来看,当混入质量比为3%的Bis-PC_(70)BM后薄膜的表面形貌更为平整,平均粗糙度从原来的1.87 nm降到了1.80 nm.能量转换效率(power conversion efficiency,PCE)达到7.00%,其中器件的V_(OC)为0.77 V,短路电流(J_(SC))为13.92 mA·cm~(-2),比PTB7:PC_(70)BM的器件效率6.07%提高了15%.     

Importance of ligands on TiO_2 nanocrystals for perovskite solar cells

The fabrication of high-quality electron-selective layers at low temperature is a prerequisite to realizing efficient flexible and tandem perovskite solar cells(PSCs). A colloidal-quantum-dot ink that contains TiO_2 nanocrystals enables the deposition of a flat film with matched energy level for PSCs; however, the selection of ligands on the TiO_2 surface is still unexplored. Here, we systematically studied the effect of the titanium diisopropoxide bis(acetylacetonate)(TiAc_2)ligand on the performance of PSCs with a planar n-i-p architecture. We prepared TiO_2 nanocrystals from TiCl4 and ethyl alcohol with Cl~- ligands attached on its surface and we found that a tiny amount of TiAc_2 treatment of as-prepared TiO_2 nanocrystals in a mixed solution of chloroform and methyl alcohol can enhance PSC power conversion efficiency(PCE)from 14.7% to 18.3%. To investigate the effect of TiAc_2 ligand on PSCs, TiO_2 samples with different TiAc_2 content were prepared by adding TiAc_2 into the as-obtained TiO_2 nanocrystal solution. We use x-ray photoelectron spectroscopy to identify the content of Cl so as to reveal that Cl ligands can be substituted by TiAc_2. We speculate that the improvement in PCE originates from amorphous TiO_2 formation on the TiO_2 nanocrystal surface, whereby a single-molecule layer of amorphous TiO_2 facilitates charge transfer between the perovskite film and the TiO_2 electronic transport layer, but excessive TiAc_2 lowers the PSC performance dramatically. We further prove our hypothesis by x-ray diffraction measurements. We believe the PCE of PSCs can be further improved by carefully choosing the type and changing the content of surface ligands on TiO_2 nanocrystal.     

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.     

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.     

Ferroelectric Ba0.75Sr0.25TiO3 tunable charge transfer in perovskite devices

Interfacial charge recombination is a main issue causing the efficiency loss of the perovskite solar cells (PSCs). Here, ferroelectric Ba_0.75Sr_0.25TiO₃ (BST) is introduced as a polarization tunable layer to promote the interfacial charge transfer of the PSCs. The coexistence of ferroelectric polarization and charge carriers in BST is confirmed by density functional theory (DFT) calculations. Experimental characterization demonstrates the polarization reversal and the existence of domain in BST film. The BST film conductivity is tested as 2.98×10^-4 S/cm, which is comparable to the TiO₂ being used as the electron transporting layer (ETL) in PSCs. The calculations results prove that BST can be introduced into the PSCs and the interfacial charge transfer can be tuned by ferroelectric polarization. Thus, we fabricated the BST-based PSCs with a champion power conversion efficiency (PCE) of 19.05% after poling.     

二硫化钨纳米片制备及其钙钛矿太阳能电池空穴传输层应用

开发新型无机空穴传输层材料是钙钛矿电池实现商业应用的重要挑战之一。本文开展了二硫化钨纳米片制备及其钙钛矿太阳能电池空穴传输层应用研究。采用液相超声剥离法成功制备了WS 2纳米片,并将其引入钙钛矿太阳能电池中用作空穴传输层。结果表明,当WS 2纳米片溶液浓度为1 mg/mL时,制备的WS 2纳米片空穴传输层具有较合适的厚度,并且后续在其上生长的钙钛矿活性层成膜质量高、结晶性能好,电池取得6.3%的光电转换效率。结果证实WS 2纳米片可作为新型无机空穴传输层材料用于钙钛矿太阳能电池。