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.     

ZnO电子传输层对于反型结构聚合物太阳电池光浴效应的影响

采用金属氧化物电子传输层(ETL)的聚合物光伏器件在制备完成之初通常性能表现低下, J-V曲线呈异常“S”形. 当器件受白光持续照射后, 该不良状况会逐渐好转, 此过程称为光浴(light-soaking). 光浴现象普遍被认为是ETL界面问题所致. 从器件结构着手, 研究了ZnO 纳米颗粒ETL相邻的两个界面在光浴问题上的作用. 制备了功能层相同的(电极除外)正型、反型器件及复合ETL结构器件, 发现光浴现象仅出现于包含ZnO/ITO界面的反型器件中, 证明该界面是导致光浴现象的主要原因. 分析认为: ZnO颗粒表面O₂吸附形成的电子陷阱增加了ITO/ZnO势垒厚度, 使得光生电子无法逾越而成为空间电荷积累, 从而导致器件初始性能不佳. 器件经光照后, ETL内部受激而生的空穴电子对填补了ZnO缺陷, 提升了ETL的电荷选择性并减小了界面势垒厚度, 被束缚的光生电子得以隧穿至ITO电极, 反型器件性能最终得以改善.     

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.     

Mg-doped ZnO layer to enhance electron transporting for PbS quantum dot solar cells

In this work, the effect of Mg doping on the performance of PbS quantum dot (QD) solar cells (QDSCs) is investigated. To elucidate that, PbS QDSCs with pristine ZnO and Mg-doped ZnO (ZMO) as electron transporting layers (ETLs) are fabricated, respectively. The current density-voltage (J-V) measurements are performed. The results show that the cell efficiency of the device with ZMO as an ETL is 9.46%, which increases about 75% compared to that of the pristine ZnO based device (5.41%). Enhanced short current density (J_sc) and fill factor (FF) are observed. It is demonstrated that Mg doping could passivate the surface defects and suppress the carrier recombination in ZnO ETL, thus resulting in larger bandgap and higher Fermi level (E_F). The strategy of Mg-doped ZnO ETL provides a promising way for pushing solar cell performance to a high level.     

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.     

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.     

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.     

Modulation of light absorption by optical spacer in perovskite solar cells

Lead halide perovskite solar cells with planar heterojunction configuration have recently attracted tremendous attention because of their excellent power conversion efficiencies. The modulation of optical absorption by using an optical spacer layer is a unique method to enhance the device efficiency. Here, we demonstrate the application of thin ZnO layer that act as an optical spacer that enhance the power conversion efficiency perovskite devices from 8.92% to 10.7%, which is mainly due to increment in short‐circuit current density by 16% compared to the reference solar cell. The simulation data revealed that ZnO acts as an optical spacer layer that shifts length (average) of electric field |E|² distribution from 500 nm to 750 nm wavelength is 25 nm in the perovskite layer. Which represents that exciton generation region is moved to near the hole transport layer that enhances the exciton dissociation efficiency and device efficiency.     

有机/无机复合双层电子传输层的量子点发光二极管

采用有机/无机复合双层电子传输层（ETL）研制绿色QLEDs,其中有机ETL采用OLED中常见的ETL材料,无机ETL采用ZnO纳米颗粒,并通过调控有机ETL厚度改变电子注入,使电子/空穴达到平衡。制备的器件结构为:ITO/PEDOT:PSS/TFB/QDs/ZnO NPs/TPBI:Liq/Al,其中有机电子传输层TPBI:Liq采用真空蒸镀沉积。与仅采用ZnO电子传输层的器件相比,可以使器件性能得到大幅提升:器件的最大电流效率从11.53 cd/A提升到22.77 cd/A,同时器件的启亮电压、电致发光光谱无明显变化。判断有机ETL的主要作用是抑制了过量电子的注入和传输,在发光亮度变化不大的情况下,降低了器件的无效复合（例如俄歇复合）电流,从而使电流效率明显提升。     

Improved blue quantum dot light-emitting diodes via chlorine passivated ZnO nanoparticle layer

In blue quantum dot light emitting diodes (QLEDs), electron injection is insufficient, which would degrade device efficiency and stability. Herein, we employ chlorine passivated ZnO nanoparticles as electron transport layer to facilitate electron injection into QDs effectively. Moreover, it suppresses exciton quenching at the QD/ZnO interface by blocking charge transfer channel. As a result, the maximum external quantum efficiency of blue QLED was increased from 2.55% to 4.60%, and the operation lifetime of blue QLED was nearly 4 times longer than that of the control device. Our work indicates that election injection plays an important role in blue QLED efficiency and stability.     

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.     

Growth of Fe-doped ZnO nanorods using aerosol-assisted chemical vapour deposition via in situ doping

In situ Fe doping of ZnO nanorods (NRs) was performed using aerosol assisted chemical vapour deposition (AA-CVD) technique. As the aerosol generator is located outside the reactor, AA-CVD provides the flexibility to control doping parameters, such as doping timing, doping duration and a wider choice of dopant precursors. The Fe dopant aerosol was flowed into the reactor during the growth of ZnO NRs to achieve in situ doping. The X-ray diffraction analysis indicates that the Fe dopants were introduced into the ZnO lattice and present mainly in the form of Fe²⁺. This result is supported by the X-ray photoelectron spectroscopy analysis as the doublet separation is 13.6 eV, although there is a shift of Fe_1/2 and Fe_3/2 peaks to a lower binding energy levels. A strong green emission of PL of Fe-doped ZnO NRs shows that the NRs have poor crystal quality attributed to the Fe-induced defects (recombination centres). The poor photocatalytic performance in degrading Rhodamine B solution of Fe-doped ZnO NRs further proves that the Fe-induced defects were recombination centres rather than traps. Lastly, the growth mechanism of in situ Fe doping of ZnO NRs was discussed.     

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.

     

Study of Au/ZnO nanorods Schottky light-emitting diodes grown by low-temperature aqueous chemical method

High quality vertically aligned ZnO nanorods (NRs) were grown by low-temperature aqueous chemical technique on 4H-n-SiC substrates. Schottky light-emitting diodes (LEDs) were fabricated. The current-voltage (I–V) characteristics of Schottky diodes reveal good rectifying behavior. Optical properties of the ZnO nanorods (NRs) were probed by cathodoluminescence (CL) measurements at room temperature complemented with electroluminescence (EL). The room-temperature CL spectra of the ZnO NRs exhibit near band edge (NBE) emission as well as strong deep level emission (DLE) centered at 690 nm. At room temperature the CL spectra intensity of the DLE was enhanced with the increase of the electron beam penetration depth due to the increase of defect concentration at the interface and due to the conversion of self-absorbed UV emission. We observed a variation in the DLE along the nanorod depth. This indicates a relatively lower structural quality near the interface between ZnO NRs and n-SiC substrate. The room-temperature CL spectra of SiC show very weak emission, which confirms that most of the DLE is originating from the ZnO NRs, and SiC has a minute contribution to the emission.     

Effect of an Al-doped ZnO electron transport layer on the efficiency of inverted bulk heterojunction solar cells

Doping is a widely-implemented strategy for enhancing the inherent electrical properties of metal oxide charge transport layers in photovoltaic devices because higher conductivity of electron transport layer (ETL) can increment the photocurrent by reducing the series resistance. To improve the conductivity of ETL, in this study we doped the ZnO layer with aluminum (Al), then investigated the influence of AZO on the performance of inverted bulk heterojunction (BHJ) polymer solar cells based on poly [[4,8-bis [(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b’]dithiophene-2,6-diyl]-[3-fluoro-2[(2-ethylhexyl)-carbonyl]-thieno-[3,4-b]thiophenediyl ]] (PTB7):[6,6]-phenyl C71 butyric acid methyl ester (PC₇₁BM). The measured conductivity of AZO was ~10⁻³ S/cm, which was two orders of magnitude higher than that of intrinsic ZnO (~10⁻⁵ S/cm). By decreasing the series resistance (R_s) in a device with an AZO layer, the short circuit current (J_sc) increased significantly from 15.663 mA/cm² to 17.040 mA/cm². As a result, the device with AZO exhibited an enhanced power conversion efficiency (PCE) of 8.984%.     

Improvement of ZnO nanorod based quantum Dot (cadmium sulfide) sensitized solar cell efficiency by aluminum doping

This study investigates the performance of quantum dot sensitized solar cells (QDSSCs) based on aluminum (Al)-doped and undoped ZnO nanorods. Current density–voltage (J–V) characterization shows that Al doping into ZnO nanorods (AZO NRs) can improve short circuit current density (J_sc) and the energy conversion efficiency (η) of QDSSCs. The maximum η=1.15% is achieved in QDSSCs when Al concentration is 0.5 wt%, as compared to undoped state where η=0.57%. These current densities and the energy conversion efficiency improvement are studied using the electrochemical impedance spectroscopy (EIS). EIS results indicate that the electron transport resistance in the photoanode of QDSCs is reduced with introduction of Al into ZnO structure, which leads to increasing J_sc. It is also found that recombination resistance reduces with introduction of Al into ZnO because of the upward displacement of Fermi level with respect to AZO conduction band (CB) and increasing electron density in the ZnO CB. This reduction of recombination resistance causes higher recombination rate in QDSCs based AZO NRs.     

Highly efficient and low turn-on voltage quantum-dot light-emitting diodes using a ZnMgO/ZnO double electron transport layer

A ZnMgO and ZnO double-layered structure was prepared to create a stepwise interfacial electronic structure to improve the electron-injection and electron-transport behaviors in quantum-dot light-emitting diodes (QLEDs). The current density of the electron-only device (EOD) with ZnMgO/ZnO was higher than that of the EOD with only ZnMgO. The detailed QLED interfacial electronic structure was measured using X-ray and ultraviolet photoelectron spectroscopy. A stepwise interfacial electronic structure for electron injection and electron transport was observed connecting the aluminum cathode to the ZnMgO conduction band minimum (CBM) via the ZnO CBM. The QLEDs with the ZnMgO/ZnO double electron transport layer showed an improved performance, with a maximum luminance and current efficiency of 90,892 cd m⁻² and 19.2 cd A⁻¹, respectively. Moreover, the turn-on voltage of the device was significantly reduced to 2.6 V due to the stepwise interfacial electronic structure between the aluminum cathode and ZnMgO CBM. This research provides a useful method for developing highly efficient and low turn-on voltage QLEDs using a ZnMgO/ZnO double ETL for next-generation display.     

混合界面对溶液制备的磷光OLED器件性能的影响

利用混蒸的方法、将空穴阻挡材料2,9-Dimethyl-4,7-diphenyl-1,10-phenanhroline及电子传输材料Tris(8-hydroxy-quinolinato)aluminium混合,在电子传输层及空穴阻挡层之间制备了薄层的混合界面.在相同驱动电压下,采用混合界面的器件比常规器件的电流密度和亮...     

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.     

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.