Silver‐Based Nanoparticles for Surface Plasmon Resonance in Organic Optoelectronics

Organic optoelectronic devices including organic light‐emitting diodes (OLEDs) and polymer solar cells (PSCs) have many advantages, including low‐cost, mechanical flexibility, and amenability to large‐area fabrication based on printing techniques, and have therefore attracted attention as next‐generation flexible optoelectronic devices. Although almost 100% internal quantum efficiency of OLEDs has been achieved by using phosphorescent emitters and optimizing device structures, the external quantum efficiency (EQE) of OLEDs is still limited due to poor light extraction. Also, although intensive efforts to develop new conjugated polymers and device architectures have improved power conversion efficiency (PCE) up to 8%–9%, device efficiency must be improved to >10% for commercialization of PSCs. The surface plasmon resonance (SPR) effect of metal nanoparticles (NPs) can be an effective way to improve the extraction of light produced by decay of excitons in the emission layer and by absorption of incident light energy within the active layer. Silver (Ag) NPs are promising plasmonic materials due to a strong SPR peak and light‐scattering effect. In this review, different SPR properties of Ag NPs are introduced as a function of size, shape, and surrounding matrix, and review recent progress on application of the SPR effect of AgNPs to OLEDs and PSCs.     

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.     

Enhanced efficiency and stability of polymer solar cells using solution-processed nickel oxide as hole transport material

Solution-processed nickel oxide (s-NiO_x) was synthesized for use as hole-transport layers (HTLs) in the fabrication of polymer solar cell (PSC) devices. The s-NiO_x thin-films were deposited using spin-coating and post-annealed at 300 °C, 400 °C, or 500 °C. With increased annealing temperature, the nickel acetate precursor decomposes more fully and forms s-NiO_x films that show larger crystalline grain sizes with lower root mean square surface roughness. Bulk heterojunction solar cells fabricated with the new random polymer RP(BDT-PDBT) and [6,6]-phenyl-C₇₀-butyric acid methyl ester (PC₇₀BM) using s-NiO_x as HTLs exhibit a 4.46% enhancement in power conversion efficiency and better stability compared to conventional PSCs using poly (3,4-ethylenedioxythiophene):poly(styrene sulfonate) as HTLs. We believe that the solution-processable and highly stable s-NiO_x could be a potential alternative for functional interface materials in optoelectronic devices.     

溶剂预处理结合热退火提升聚噻吩结晶度及其光伏性能

活性层的微观形貌在很大程度上决定了聚合物光伏器件的性能表现并依赖于制备工艺条件。为了改善薄膜内部分子排布结构并追求较高的器件光电转化效率,采用溶液法制备了基于P3HT：PCBM的聚合物太阳能电池（器件结构:ITO/PEDOT：PSS/P3HT：PCBM/Al）,通过改变器件制备流程中活性层退火处理工艺,研究了热退火、溶剂退火以及溶剂预处理结合热处理的双重退火对聚合物太阳电池性能的影响。研究发现:双重退火的光伏器件的各项性能参数均优于单一退火处理器件,获得了3.25%的光电转化效率。原子力显微镜及X射线衍射仪的表征结果进一步证明:双重退火处理能够在促进聚合物给体良好有序结晶的同时保证共混组分适度地相分离,从而有利于光生激子的解离以及载流子的传输。     

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.     

Bathocuproine/Ag复合电极对于聚合物光伏器件效率和稳定性的影响

采用Bathocuproine/Ag (BCP/Ag)复合电极代替Ca/Al复合电极, 制备PTB7:PC71BM 作为光敏层的聚合物光伏器件, 并通过改变BCP薄膜厚度来研究BCP/Ag复合电极对于器件光电转换器和稳定性的影响. 研究发现: 在光敏层和金属电极之间插入BCP修饰层后, 器件性能得到了显著的改善, 在BCP厚度为5 nm时, 器件的效率达到了6.82%, 且略高于Ca/Al复合电极的器件效率; 相比于采用Ca/Al复合电极的器件, BCP/Ag复合电极增大了器件的短路电流和外量子效率, 使器件效率得到提高; 同时器件的稳定性得到了显著的改善, BCP/Ag 复合电极器件的衰减速率几乎和未插入BCP的器件衰减速率相同, 相对于Ca/Al复合电极器件大幅提高.     

Preparation of organic/inorganic hybrid nanocomposites by ultraviolet irradiation and their packaging applications for organic optoelectronic devices

By ultraviolet (UV)-assisted synthetic procedure, we have successfully prepared several UV curable organic/inorganic hybrid nanocomposites with excellent gas barrier capabilities, moderate hardness, and good adhesive strength. The experimental results reveal that the physical properties of nanocomposites depend on their chemical structures. Therefore, introduction of silicone and polyurethane (PU) into the Acrylics backbone dramatically raises the adhesive strength as well as refractive index and lowers the gas penetration. Furthermore, we have also applied lab-made nanocomposite g for the encapsulation of organic optoelectronic devices such as OLEDs, flexible OLEDs, and organic solar cells. With the package of lab-made nanocomposite g, the organic optoelectronic devices effectively resist the entry of moisture and oxygen in the air, extending the lifetimes.     

Recent advances of interface engineering in inverted perovskite solar cells

Perovskite solar cells (PSCs) have witnessed great achievement in the past decade. Most of previous researches focus on the n—i—p structure of PSCs with ultra-high efficiency. While the n—i—p devices usually used the unstable charge transport layers, such as the hygroscopic doped spiro-OMeTAD, which affect the long-term stability. The inverted device with the p—i—n structure owns better stability when using stable undoped organic molecular or metal oxide materials. There are significant progresses in inverted PSCs, most of them related to charge transport or interface engineering. In this review, we will mainly summarize the inverted PSCs progresses related to the interface engineering. After that, we prospect the future direction on inverted PSCs.     

Below-gap excitation of pi-conjugated polymer-Fullerene blends: implications for bulk organic heterojunction solar cells

We used a variety of optoelectronic techniques such as broadband fs transient and cw photomodulation spectroscopies, electroabsorption, and short-circuit photocurrent in bulk heterojunctions organic solar cells for studying the photophysics in pi-conjugated polymer-fullerene blends with below-gap excitation. In contrast to the traditional view, we found that below-gap excitation, which is incapable of generating intrachain excitons, nevertheless efficiently generates polarons on the polymer chains and fullerene molecules. The polaron action spectrum extends deep inside the gap as a result of a charge-transfer complex state formed between the polymer chain and fullerene molecule. With appropriate design engineering the long-lived polarons might be harvested in solar cell devices.     

Performance improvement of MEH-PPV:PCBM solar cells using bathocuproine and bathophenanthroline as the buffer layers

In this work, bathocuproine (BCP) and bathophenanthroline (Bphen), commonly used in small-molecule organic solar cells (OSCs), are adopted as the buffer layers to improve the performance of the polymer solar cells (PSCs) based on poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV): [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojunction. By inserting BCP or Bphen between the active layer and the top cathode, all the performance parameters are dramatically improved. The power conversion efficiency is increased by about 70% and 120% with 5-nm BCP and 12-nm Bphen layers, respectively, when compared with that of the devices without any buffer layer. The performance enhancement is attributed to BCP or Bphen (i) increasing the optical field, and hence the absorption in the active layer, (ii) effectively blocking the excitons generated in MEH-PPV from quenching at organic/aluminum (Al) interface due to the large band-gap of BCP or Bphen, which results in a significant reduction in series resistance (Rs), and (iii) preventing damage to the active layer during the metal deposition. Compared with the traditional device using LiF as the buffer layer, the BCP-based devices show a comparable efficiency, while the Bphen-based devices show a much larger efficiency. This is due to the higher electron mobility in Bphen than that in BCP, which facilitates the electron transport and extraction through the buffer layer to the cathode.     

Anti-reflection layer formed by monolayer of microspheres

In this study, we demonstrate a cost-effective method to deposit an anti-reflection coating on glass. Hexagonally arranged layers are formed by a monolayer of microspheres deposited by a dip-coating method. After the deposition of the microspheres with diameter of 200 nm, the forward transmission of the glass substrate is enhanced from 88.8% to 97.2% at an incident wavelength of 600 nm, demonstrating that the nano-scale monolayer coating of microspheres can be used as an anti-reflection layer. This method can be applied to organic light emitting diodes and solar cells in order to enhance the forward transmission of the light at the interface of the optoelectronic devices.     

Theoretical Study of the Electronic and Optical Properties to Design Dye-Sensitivity for Using in Solar Cell Device

In this work, the structural and optoelectronic properties of phenanthrene-1,3,4-thaidiazoles oligomers were calculated using density functional theory (DFT) at B3LYP/6-31G(d) basis set level, to evaluate their possible application as organic semiconductor materials in photovoltaic and solar cell devices. For this reason, the energy gaps, frontier orbital (HOMO, and LUMO) distributions, total energies, Fermi level energies, work functions and maximum wavelength absorption, vertical absorption energies, and oscillator strengths have been investigated and discussed. The structures of phenanthrene-1,3,4-thiadiazoles oligomers are expanded from 1 to 10 thiadiazole monomeric units, to examine the increase of thiadiazole monomeric units on the optoelectronic properties. We observed that increased the number of monomeric units lead to significantly enhance the optoelectronic properties, which caused to decrease the gap energy from 3.69 eV in the structure with one thiadiazole ring just to 2.36 eV with 10 units. These changes give the shift of maximum absorption wavelengths from 376 to 578 nm. Consequently, these molecules have main absorption bands within the solar spectrum, to give the best performance for photovoltaic and organic solar cells devices.     

应用于钙钛矿太阳能电池中金属氧化物电子传输材料的研究进展

基于有机金属卤化铅钙钛矿材料作为光活性层的太阳能电池(PSCs)已经获得了25.2%的认证效率,是除硅基太阳能电池外被认为最有可能实现商业化的太阳能电池之一。电子传输层是PSCs器件结构的最基本组成之一,其构成材料与光活性层的成膜质量、界面电荷的快速提取以及能级匹配等密切相关。因而,电子传输材料在PSCs的光伏性能及稳定性调控方面发挥着重要作用。本文对应用在PSCs中的金属氧化物电子传输材料进行了回顾与总结,着重强调了材料的纳米结构与制备工艺、半导体特性与分类以及掺杂与界面修饰等方面的研究进展,并对其今后的发展进行了展望。     

复合阴极Ag/LiF/Al对P3HT:PCBM太阳能电池性能的影响

在P3HT∶PCBM聚合物太阳能电池的阴极LiF/Al中引入纳米结构的银膜组成Ag/LiF/Al复合阴极,太阳能电池的光电流能显著提高。在AM1.5G和100mW.cm-2的模拟太阳光照射下,当银膜厚度为4纳米时,优化的太阳能电池的光电流要比只有LiF/Al的参比太阳能电池高20%以上。研究表明,纳米银膜产生的表面等离子体效应是增强聚合物太阳能电池光电池的主要原因。不过,银膜修饰的太阳能电池填充因子和开路电压要比参考电池低,最终使该类型电池效率降低。在银膜处增加的载流子复合可能是导致电池填充因子、开路电压和能量转化效率降低的重要原因。     

Improved performance of polymer solar cells by using inorganic,organic, and doped cathode buffer layers

The interface between the active layer and the electrode is one of the most critical factors that could affect the device performance of polymer solar cells. In this work, based on the typical poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester(P3HT:PCBM) polymer solar cell, we studied the effect of the cathode buffer layer(CBL) between the top metal electrode and the active layer on the device performance. Several inorganic and organic materials commonly used as the electron injection layer in an organic light-emitting diode(OLED) were employed as the CBL in the P3HT:PCBM polymer solar cells. Our results demonstrate that the inorganic and organic materials like Cs_2CO_3, bathophenanthroline(Bphen), and 8-hydroxyquinolatolithium(Liq) can be used as CBL to efficiently improve the device performance of the P3HT:PCBM polymer solar cells. The P3HT:PCBM devices employed various CBLs possess power conversion efficiencies(PCEs) of 3.0%–3.3%, which are ca. 50% improved compared to that of the device without CBL. Furthermore, by using the doped organic materials Bphen:Cs_2CO_3 and Bphen:Liq as the CBL, the PCE of the P3HT:PCBM device will be further improved to 3.5%, which is ca. 70% higher than that of the device without a CBL and ca. 10% increased compared with that of the devices with a neat inorganic or organic CBL.     

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.     

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.     

Dual plasmonic‐enhanced bulk‐heterojunction solar cell incorporating gold nanoparticles into solution‐processed anode buffer layer and active layer

A dual plasmonic resonance effect on the performance of poly(3‐hexylthiophene) (P3HT):phenyl C61‐butyricacid methyl ester (PC61BM) based polymer solar cells (PSCs) has been demonstrated by selectively incorporating 25 nm colloidal gold nanoparticles (Au NPs) in a solution‐processed molybdenum oxide (MoO₃) anode buffer layer and 5 nm colloidal Au NPs in the active P3HT:PCBM layer. The devices exhibit up to ～20% improvement in power conversion efficiency which is attributed to the dual effect of localized surface plasmon resonance (LSPR) of Au NPs with enhanced light absorption and exciton generation. Our report shows a guideline on the usage of dual LSPR effect for the solution‐processed polymer solar cells to achieve high efficiencies. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Improved efficiency of ternary the blend polymer solar cells by doping a narrow band gap polymer material

A series of P3HT:PC71BM polymer solar cells(PSCs)with different PIDTDTQx doping concentrations were fabricated to investigate the effect of the PIDTDTQx as a complementary electron donor on the performance of PSCs.The power conversion efficiency(PCE)of the optimized ternary blend PSCs(with 2 wt%PIDTDTQx)reached 3.87%,which is 28%higher than that of the PSCs based on P3HT:PC71BM(control cells).The short-circuit current density(Jsc)was increased to 10.20 m A/cm2compared with the control cells.The PCE improvement could be attributed to more photon harvest and charge carrier transport by appropriate doping PIDTDTQx.The energy transfer from P3HT to PIDTDTQx was demonstrated from the 650 nm emission intensity decrease and the red-shifted emission peaks from 725 nm to 737 nm along with the increase of PIDTDTQx doping concentrations.     

界面修饰对有机-无机杂化钙钛矿太阳能电池性能的影响

作为近些年来最耀眼的明星材料之一,钙钛矿以其优异独特的光电特性成功吸引研究人员的广泛关注.自2009年报道了第一篇光电转换效率为3.8%的钙钛矿电池,到现在短短10年期间效率已经突破25.2%,几乎可以与商用多晶硅电池媲美.尽管其制备过程简单,但在薄膜的形成过程中很容易引入大量的缺陷.缺陷的存在会加速载流子的复合,阻碍载流子传输通道,不利于制备高效率的钙钛矿太阳能电池;同时也会影响钙钛矿电池工作的长期稳定性,加速材料的降解,阻碍了钙钛矿太阳能电池进一步商业化发展.因此,理解缺陷的存在机制并有效地抑制缺陷产生,对制备高性能长寿命器件至关重要.而界面修饰作为一种有效的钝化缺陷方法之一,已经被广泛使用.本文讨论了不同结构电池器件的缺陷产生位置及对器件性能的影响.分别从载流子传输层钝化策略和钙钛矿界面修饰策略入手,分析了常用的传输层/钙钛矿界面钝化缺陷的机制,指出了钝化策略发展的巨大优势,并对合适的钝化材料进行分类,希望能够对高重复性、高光电转换效率、长期工作稳定的钙钛矿太阳能电池发展提供有益的指导.