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%.     

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.     

Rubrene作电子传输层的异质结有机太阳能电池

以Rubrene为电子传输层(ETL),制备了结构为ITO/MoO3(5nm)/Rubrene(50nm)/C60(45nm)/Rubrene(0,3,5.5,9.5nm)/Al(130nm)的有机太阳能电池.与没有ETL的器件相比,含5.5nmRubrene的电池的开路电压、填充因子、功率转换效率分别从0.68V,0.488,0.315%增加到0.86V,0.574,0.490%.实验结果分析表明:热的Al原子直接沉积在C60上,破坏了C60层,形成高功函数的C60/Al阴极,弱化内建电场,降低电池性能;当插入ETL后,C60层得到保护,热的Al原子沉积破坏了Rubrene层,形成了缺陷态能级,提高电池的内建电场,促进了电子的传输.进一步的单电子电池实验表明,缺陷态能级低于C60的最低未占据分子轨道.     

Inverted organic solar cells with solvothermal synthesized vanadium-doped TiO_2 thin films as efficient electron transport layer

We investigated the effects of using different thicknesses of pure and vanadium-doped thin films of TiO_2 as the electron transport layer in the inverted configuration of organic photovoltaic cells based on poly(3-hexylthiophene) P3HT:[6-6] phenyl-(6) butyric acid methyl ester(PCBM). 1% vanadium-doped TiO_2nanoparticles were synthesized via the solvothermal method. Crystalline structure, morphology, and optical properties of pure and vanadium-doped TiO_2 thin films were studied by different techniques such as x-ray diffraction, scanning electron microscopy, transmittance electron microscopy, and UV–visible transmission spectrum. The doctor blade method which is compatible with roll-2-roll printing was used for deposition of pure and vanadium-doped TiO_2 thin films with thicknesses of 30 nm and 60 nm. The final results revealed that the best thickness of TiO_2 thin films for our fabricated cells was 30 nm. The cell with vanadium-doped TiO_2 thin film showed slightly higher power conversion efficiency and great J_(sc) of 10.7 mA/cm~2 compared with its pure counterpart. In the cells using 60 nm pure and vanadium-doped TiO_2 layers, the cell using the doped layer showed much higher efficiency. It is remarkable that the external quantum efficiency of vanadium-doped TiO_2 thin film was better in all wavelengths.     

Bicontinuous network of electron donor-acceptor composites achieved by additive-free sequential deposition for efficient polymer solar cells

We report that sequential deposition of a highly crystalline polymer donor and a soluble fullerene acceptor leads to a well-defined interpenetrating network and enhanced power conversion efficiencies in bilayer polymer solar cells. Even without the use of solvent additives, layered thin films of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di(2-octyldodecyl)-2,2’; 5′,2’’; 5″,2‴-quaterthiophen-5,5‴-diyl)] (PffBT4T-2OD) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM), as electron donor and acceptor materials, respectively, showed bicontinuous networks similar to those of a PffBT4T-2OD:PC₇₁BM bulk-heterojunction (BHJ) thin film processed with 1,8-diiodooctane (DIO) as a solvent additive. Transmission electron microscopy results confirmed the BHJ-like morphology of the bilayered PffBT4T-2OD/PC₇₁BM thin films. Bilayer solar cells fabricated without the DIO additive produced a power conversion efficiency of η ≈ 7.65%, which is even higher than that of a BHJ solar cell fabricated with the DIO additive (η ≈ 7.04%). These results demonstrate that a highly crystalline polymer donor and an electron-accepting small molecule can be a good combination for efficient bilayer polymer solar cells.     

Highly efficient inverted polymer solar cells using aqueous ammonia processed ZnO as an electron selective layer

The authors demonstrate a simple method to deposit solution-processable ZnO thin film by directly dissolving the ZnO powder into aqueous ammonia. ZnO film casting from its aqueous ammonia solution (a-ZnO) is used successfully as an electron selective layer in poly(3-hexylthiophene) and indene-C₆₀ bisadduct (IC₆₀BA) based heterojunction solar cells with improved power conversion efficiency (PCE) compared with that using conventional sol–gel based ZnO (c-ZnO). The improved PCE is mainly attributed to an increase of short-circuit current density owing to the better transmittance of a-ZnO than that of c-ZnO in the absorption range of IC₆₀BA, and efficient electron extraction at cathode. In addition, no additional by-products originated from the organic solvents are introduced as like in sol–gel based ZnO films.     

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.     

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.     

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.     

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.     

Metal oxide buffer layer for improving performance of polymer solar cells

We report the application of aluminum doped ZnO (ZnO:Al) layer as a buffer on ITO glass for fabrication of non-inverted polymer solar cells. The ZnO:Al thin film was deposited using DC magnetron sputtering, with the thickness being varied from 23 to 100 nm. The devices showed most discernible improvements in their efficiencies when a thin layer of ZnO:Al film of thickness ∼40 nm was introduced. The observed enhancement in short circuit current density and open circuit voltage is likely attributed to the role of the ZnO:Al film as an optical tuner and an interfacial diffusion barrier. The result suggests that a metal oxide layer inserted between ITO and polymer layers can be a route for improving both efficiency and stability of polymer solar cells.     

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.     

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...     

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.     

Simultaneous reduction and sulfonation of graphene oxide for efficient hole selectivity in polymer solar cells

We developed sulfonated, reduced graphene oxide (S-RGO) through fuming/concentrated sulfuric acid treatment of graphene oxide (GO) in ambient conditions. It was demonstrated that the optical band gap and electrical conductivity of S-RGO are easily tunable, and depend on the level of reduction and sulfonation of GO. Whereas, reduction and sulfonation were found dependent on SO₃ content, acid strength, and gas tightness of the reaction mixture. It's actually the water content of oleum that determines the nature of the final product. The easily adjustable band gap and electrical conductivity suggest that S-RGO can be employed as a potential hole extraction layer (HEL) material for several donor-acceptor systems. For P3HT:PC₆₁BM based inverted polymer solar cells, it was observed that the shape of the J–V curve is tailorable with the choice of HEL. Compared to a 2.75% power conversion efficiency (PCE) attained with PEDOT:PSS, a PCE of 2.80% was achieved with tuned S-RGO. Our results imply that an S-RGO of sufficiently high band gap and conductivity can replace some of the state of the art HEL materials for a host of device applications.     

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.     

MoO3/Ag/AI/ZnO intermediate layer for inverted tandem polymer solar cells

We report an MoO3/Ag/Al/ZnO intermediate layer connecting two identical bulk heterojunction subcells with a poly（3-hexylthiophene） and [6,6]-phenyl-C61-butyric acid methyl ester （P3HT and PCBM） active layer for inverted tan- dem polymer solar cells. The highly transparent intermediate layer with an optimized thickness realizes an Ohmic contact between the two subcells for effective charge extraction and recombination. A maximum power conversion efficiency of 3.76% is obtained for the tandem cell under 100 mW/cm2 illumination, which is larger than that of a single cell （3.15%）. The open-circuit voltage of the tandem cell （1.18 V） approaches double that of the single cell （0.61 V）.     

MoO_3/Ag/Al/ZnO intermediate layer for inverted tandem polymer solar cells

We report an MoO3/Ag/Al/ZnO intermediate layer connecting two identical bulk heterojunction subcells with a poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester(P3HT and PCBM) active layer for inverted tandem polymer solar cells. The highly transparent intermediate layer with an optimized thickness realizes an Ohmic contact between the two subcells for effective charge extraction and recombination. A maximum power conversion efficiency of 3.76% is obtained for the tandem cell under 100 mW/cm2 illumination, which is larger than that of a single cell(3.15%).The open-circuit voltage of the tandem cell(1.18 V) approaches double that of the single cell(0.61 V).     

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.     

Thickness study of Al:ZnO film for application as a window layer in Cu(In1−xGax)Se2 thin film solar cell

Structural, electrical and optical properties of Al doped ZnO (Al:ZnO) thin film of various thicknesses, grown by radio-frequency magnetron sputtering system were studied in relation to the application as a window layer in Cu(In_1−xGa_x)Se₂ (CIGS) thin film solar cell. It was found that the electrical and structural properties of Al:ZnO film improved with increasing its thickness, however, the optical properties degraded. The short circuit current density, J_sc of the fabricated CIGS based solar cells was significantly influenced by the variation of the Al:ZnO window layer thickness. Best efficiency was obtained when CIGS solar cell was fabricated with electrically and optically optimized Al:ZnO window layer.