Solid Additive-Assisted Layer-by-Layer Processing for 19%Efficiency Binary Organic Solar Cells

Morphology is of great significance to the performance of organic solar cells(OSCs),since appropriate morphology could not only promote the exciton dissociation,but also reduce the charge recombination.In this work,we have developed a solid additive-assisted layer-by-layer(SAA-LBL)processing to fabricate high-efficiency OSCs.By adding the solid additive of fatty acid(FA)into polymer donor PM6 solution,controllable pre-phase separation forms between PM6 and FA.This intermixed morphology facilitates the diffusion of acceptor Y6 into the donor PM6 during the LBL processing,due to the good miscibility and fast-solvation of the FA with chloroform solution dripping.Interestingly,this results in the desired morphology with refined phase-separated domain and vertical phase-separation structure to better balance the charge transport/collection and exciton dissociation.Consequently,the binary single junction OSCs based on PM6:Y6 blend reach champion power conversion efficiency(PCE)of 18.16%with SAA-LBL processing,which can be generally applicable to diverse systems,e.g.,the PM6:L8-BO-based devices and thick-film devices.The efficacy of SAA-LBL is confirmed in binary OSCs based on PM6:L8-BO,where record PCEs of 19.02%and 16.44%are realized for devices with 100 and 250 nm active layers,respectively.The work provides a simple but effective way to control the morphology for high-efficiency OSCs and demonstrates the SAA-LBL processing a promising methodology for boosting the industrial manufacturing of OSCs.

Optimization of solvent swelling for efficient organic solar cells via sequential deposition

Compared to bulk heterojunction(BHJ)organic solar cells(OSCs)prepared by the blend casting in“one step process”,sequential deposition(SD)processed OSCs can realize an ideal profile of vertical component distribution due to the swelling of polymer films.Herein,we did trials on several kinds of second solvents for swelling the polymer layer,and investigated the packing structure and morphology of the swollen films and the performance of the resulting devices.We found that an optimized morphology can be achieved by solvent swelling while using orthodichlorobenzene(o-DCB)as the second layer processing-solvent,with polymer donor PffBT-3 as bottom layer,PC71BM as top layer and bicontinuous networks in the middle.Such solvent swelling process also makes the SD method exempt from thermal annealing treatment.The device based on SD yields a power conversion effi-ciency(PCE)up to 8.7%without any post-treatment,outperforming those from the devices based on SD using other solvents and that(7.06%)from BHJ device,respectively.We also extended the use of this approach to allpolymer blend system,and successfully improved the efficiency from 4.72%(chloroform)to 9.35%(o-DCB),which is among the highest PCEs in all-polymer-based OSCs fabricated with SD method.The results demonstrate that the swelling of the polymer by the second layer solvent is a necessity for SD,paving the way towards additivefree high-performance OSCs.

GaInP/GaInAs/GaInNAs/Ge Four-Junction Solar Cell Grown by Metal Organic Chemical Vapor Deposition with High Efficiency

We directly grow a lattice matched GalnP/GalnAs/GalnNAs/Ge （1.88 eVil .42 eVil .05 eV/0.67eV） four-junction （4J） solar cell on a Ge substrate by the metal organic chemical vapor deposition technology. To solve the current limit of the GalnNAs sub cell, we design three kinds of anti-reflection coatings and adjust the base region thickness of the GalnNAs sub cell. Developed by a series of experiments, the external quantum efficiency of the GalnNAs sub cell exceeds 80%, and its current density reaches 11.24 mA/cm2. Therefore the current limit of the 4J solar cell is significantly improved. Moreover, we discuss the difference of test results between 4J and GalnP/GalnAs/Ge solar cells under the 1 sun AMO spectrum.

Layer-by-layer slot-die coated high-efficiency organic solar cells processed using twin boiling point solvents under ambient condition

Layer-by-layer (LbL) strategy has been developed to form bulk heterojunction (BHJ) structure for processing efficient organic solar cells (OSCs). Herein, LbL slot-die coating with twin boiling point solvents (TBPS) strategy was developed to fabricate highly efficient OSCs, which matches with large-scale, high throughput roll-to-roll (R2R) industrialized mass process. The TBPS strategy could produce high-quality thin film without any additive, leading to the optimized vertical phase separation with interpenetrating nanostructures, as well as the enhanced charge transport and extraction. Thus, the power conversion efficiency up to 14.42% was achieved for [(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo [1,2-b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′-c′]dithiophene-4,8-dione)]:2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4″,5″]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene)) bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (PM6:Y6) OSCs fabricated via sequentially LbL slot-die coating using the TBPS strategy under ambient condition. The research provides a potential route for industrialized production of high-efficiency and large-area OSC devices.

Layer-by-layered organic solar cells:Morphology optimizing strategies and processing techniques

The last decades have witnessed the rapid development and the gradually improved efficiencies of organic solar cells(OSCs),which show great potentials in the fabrication of eco-friendly and flexible photovoltaic panels.Layer-by-layered(LBL)structure via sequential processing of the donor and acceptor layers becomes an advisable option to construct pseudo-bilayer configurations in OSC active layer.Favorable vertical phase separation and sufficient exciton dissociation interfaces can be simultaneously realized in such aggregation morphology via different processing technologies and strategies.High efficiencies of over 18%in ternary LBL device and 11.9%in LBL-processed module(11.52 cm2)have been successfully achieved in recent works.Moreover,the unique merits of LBL structure in individual layer processing enable it a promising candidate for large-scale printing and further industrialization of OSCs.This perspective provides the recent advance of LBL OSCs with the focus on fabrication technologies and strategies for morphology control and also proposes the current thinking and perspective on LBL structures for future development.

Enhanced performance of InGaN/GaN multiple quantum well solar cells with double indium content

The performance of a multiple quantum well （MQW） InGaN solar cell with double indium content is investigated. It is found that the adoption of a double indium structure can effectively broaden the spectral response of the external quantum efficiencies and optimize the overall performance of the solar cell. Under AM1.5G illumination, the short-circuit current density （Jsc） and conversion efficiency of the solar cell are enhanced by 65% and 13% compared with those of a normal single-indium-content MQW solar cell. These improvements are mainly attributed to the expansion of the absorption spectrum and better extraction efficiency of the photon-generated carriers induced by higher polarization.

Performance enhancement in organic solar cells and photodetectors enabled by donor phase optimization at the surface of hole transport layer

The domain purity,material crystallinity and distribution at the interface between the active layer and the transport layer have an important impact on the performance of organic solar cells(OSCs)and organic photodetectors(OPDs),while this focal issue has received less attention in previous studies.From this perspective,a new method to simultaneously enhance the performance of OSC and OPD is proposed,namely,using a sequential deposition method to first construct a compact stacking structure of dualdonor(D18-Cl:PTO2)eutectic in the donor layer,and then induce the ordered deposition of the acceptor(Y6).Compared with the conventional bulk heterojunction(BHJ),the active layer realized by this method not only improves the crystallinity and stacking order of the constituent material on the surface of the transport layer,but also regulates a good vertical distribution,which is conducive to improving the charge transport and extraction efficiency,reducing the leakage current,and enhancing the stability of the device.As a result,the OSC device based on the D18-Cl:PTO2/Y6 structure achieves a power conversion efficiency of up to 17.65%and good light-degradation stability,which is much better than that of BHJbased OSC(PCE of 16.37%).For the OPD,the dark current at reverse bias is reduced by more than an order of magnitude,and the maximum responsivity is improved to 0.52 A/W through the optimization of the donor phase at the interface.Moreover,the strategy does not require additional post-processing compared to the BHJ preparation,which reduces the device construction cost and process complexity,providing an effective way for developing high-performance organic optoelectronic devices.

Advantages of InGaN/GaN multiple quantum well solar cells with stepped-thickness quantum wells

InGaN/GaN multiple quantum well （MQW） solar cells with stepped-thickness quantum wells （SQW） are designed and grown by metal-organic chemical vapor deposition. The stepped-thickness quantum wells structure, in which the well thickness becomes smaller and smaller along the growth direction, reveals better crystalline quality and better spectral overlap with the solar spectrum. Consequently, the short-circuit current density （Jsc） and conversion efficiency of the solar cell are enhanced by 27.12% and 56.41% compared with the conventional structure under illumination of AM1.5G （100 mW/cm2）. In addition, approaches to further promote the performance of InGaN/GaN multiple quantum well solar cells are discussed and presented.

Solution sequential deposited organic photovoltaics:From morphology control to large-area modules

Organic optoelectronic materials enable cutting-edge,low-cost organic photodiodes,including organic solar cells(OSCs)for energy conversion and organic photodetectors(OPDs)for image sensors.The bulk heterojunction(BHJ)structure,derived by blending donor and acceptor materials in a single solution,has dominated in the construction of active layer,but its morphological evolution during film formation poses a great challenge for obtaining an ideal nanoscale morphology to maximize exciton dissociation and minimize nongeminate recom-bination.Solution sequential deposition(SSD)can deliver favorable p–i–n vertical component distribution with abundant donor/acceptor interfaces and relatively neat donor and acceptor phases near electrodes,making it highly promising for excellent device performance and long-term stability.Focusing on the p–i–n structure,this review provides a systematic retrospect on regulating this morphology in SSD by summarizing solvent selection and additive strategies.These methods have been successfully implemented to achieve well-defined morphology in ternary OSCs,all-polymer solar cells,and OPDs.To provide a practical perspective,comparative studies of device stability with BHJ and SSD film are also discussed,and we review influential progress in blade-coating techniques and large-area modules to shed light on industrial production.Finally,challenging issues are out-lined for further research toward eventual commercialization.

Control of vertical phase separation in high performance non-fullerene organic solar cell by introducing oscillating stratification preprocessing

Non-fullerene organic solar cell(NFOSC)has attracted tremendous attention due to their great potential for commercial applications.To improve its power conversion efficiency(PCE),generally,sequential solution deposition(SSD)methods have been employed to construct the graded vertical phase separation(VPS)of the bulk-heterojunction(BHJ)active layer for efficient exciton separation and charge transition.However,a variety of orthogonal solvents used in the SSD may lead to the unpredicted change in the BHJ morphology and introduce additional defects inside the BHJ bulk thus complicate the fabrication process.Here,a simple oscillating stratification preprocessing(OSP)is developed to facilitate the formation of graded VPS among the BHJ layer.As a result,a significant improvement is obtained in PCE from 10.96%to 12.03%,which is the highest value reported among PBDB-T:ITIC based NFOSC.

Interfacial engineering of printable bottom back metal electrodes for full-solution processed flexible organic solar cells

Printing of metal bottom back electrodes of flexible organic solar cells（FOSCs） at low temperature is of great significance to realize the full-solution fabrication technology. However, this has been difficult to achieve because often the interfacial properties of those printed electrodes, including conductivity, roughness, work function,optical and mechanical flexibility, cannot meet the device requirement at the same time. In this work, we fabricate printed Ag and Cu bottom back cathodes by a low-temperature solution technique named polymer-assisted metal deposition（PAMD） on flexible PET substrates. Branched polyethylenimine（PEI） and ZnO thin films are used as the interface modification layers（IMLs） of these cathodes. Detailed experimental studies on the electrical, mechanical, and morphological properties, and simulation study on the optical properties of these IMLs are carried out to understand and optimize the interface of printed cathodes. We demonstrate that the highest power conversion efficiency over 3.0% can be achieved from a full-solution processed OFSC with the device structure being PAMDAg/PEI/P3 HT：PC61BM/PH1000. This device also acquires remarkable stability upon repeating bending tests.

逐层沉积型有机太阳能电池的研究进展

近30年来,基于给/受体材料的本体异质结被认为是有机光伏器件最理想的器件结构.优化有源层中给/受体互穿网络结构,提高激子解离和载流子传输效率是提高本体异质结有机光伏器件性能的有效途径.近年来,给/受体逐层沉积的分层异质结有机光伏器件得到了快速发展,其光电转化效率可与本体异质结有机光伏器件的效率相媲美,这说明有机光伏器件领域诸多科学问题还有待深入研究.本文从工作机理、优化策略以及大面积制作潜力等方面,综合评述分层异质结有机光伏器件的代表性成果,重点阐述掺入添加剂、热处理及多元策略等在提高器件性能方面发挥的关键作用,讨论分层异质结有机光伏器件的现存问题,并展望了其发展趋势.

用平衡相容性和相分离的新策略提高有机太阳电池效率

选择了两种具有不同末端基的非富勒烯受体分子3,9-双-[2-甲烯基-(3-1,1-甲烯丙二腈茚酮)-5,5,11,11-四-(4-己基苯基)]-噻吩[3,2-b]并噻吩引达省二噻吩(ITIC)和3,9-双-[2-甲烯基-(3-1,1-甲烯丙二腈-6,7-一氟茚酮)-5,5,11,11-四-(4-己基苯基)]-噻吩[3,2-b]并噻吩引达省二噻吩(IT-2F)作为第三组分,通过一步沉积(O-SD)和分步顺序沉积(T-SD)两种活性层构筑工艺,分别制备了常规的本体异质结(BHJ)和优化的准平面异质结(PPHJ)三元器件.研究发现,本体异质结薄膜中第三组分相容性的差异可以用来调控薄膜相分离形貌;其中,基于IT-2F的三元薄膜活性层相分离明显增大,器件效率由二元器件的12.02%下降至9.25%;而ITIC的三元薄膜相分离形貌无明显改变,器件效率略有提升.值得注意的是,通过T-SD方法均可以获得垂直梯度分布的异质结活性层薄膜,避免了相容性差异对薄膜形貌的影响,相应的准平面异质结器件获得了超过了13%的光电效率.本文工作表明,利用相容性差异以及顺序沉积工艺来调控活性层的相分离形貌是制备高性能有机太阳电池有效策略.

AlGaN双势垒结构对高In组分InGaN/GaN MQWs太阳能电池材料晶体质量和发光性能的影响

本文利用金属有机化合物化学气相沉积(MOCVD)技术在(001)面图形化蓝宝石衬底(PSS)上生长了一种含有AlGaN-InGaN/GaN MQWs(multiple quantum wells)-AlGaN双势垒结构的高In组分太阳能电池外延材料。高分辨率X射线衍射(HRXRD)和光致发光(PL)谱分析表明,与含有AlGaN电子阻挡层的低In组分的量子阱结构太阳能电池外延材料相比,该结构材料具有较小的半峰全宽(FWHM),计算表明:此结构材料的位错密度降低了一个数量级,达到10^(7)cm^(-2);同时,有源区中的应变弛豫降低了51%;此外,此结构材料的发光强度增强了35%。研究结果表明含有AlGaN双势垒结构的外延材料可以减小有源区的位错密度,降低非辐射复合中心的数目,增大有源区有效光生载流子的数目,为制备高质量太阳能电池提供实验依据。

高分子涂层制备技术研究进展

高分子涂层具有阻隔、耐腐蚀、耐摩擦、防潮湿和绝缘等优点,广泛应用于航空航天、机械等领域。本文综述了高分子涂层的制备,发现其制备方法具有多样性,但多在大气环境中进行,存在高温分解、涂层内应力大和衬底结合力差等问题。对聚酰亚胺薄膜制备研究表明,溶胶-凝胶薄膜存在大量微孔,干燥过程中逸出气体及有机物易产生收缩效应,降低涂层与基底的结合强度;气相沉积聚合法所制薄膜均匀性不易控制,易受挥发溶剂影响;缩聚法对设备要求较高,适于实验室研究。真空喷射法作为一种新方法,可弥补上述不足,具有良好的应用前景,有待进一步研究。

钙钛矿太阳电池吸收层制备工艺

有机/无机杂化钙钛矿太阳电池因具有高光吸收系数、高转换效率以及低制备成本等优点引起了科学界的广泛关注。综述了近年来有机/无机杂化钙钛矿吸收层几种制备工艺的研究进展,重点分析了目前应用较为广泛且制备工艺相对简单的一步溶液法和两步连续沉积法的工艺条件对钙钛矿薄膜质量及太阳电池光伏性能的影响,并详细介绍了几种制备工艺存在的主要问题及其调控的研究现状。此外,对后续工艺中的有机空穴传输材料及其溶剂、添加剂对钙钛矿太阳电池稳定性的影响及其调控的研究现状进行了简要阐述。为更好地提高钙钛矿太阳电池的效率和长期稳定性,制备工艺的优化和创新是未来钙钛矿太阳电池发展的趋势。

气相沉积法制备有机—无机杂化钙钛矿研究进展

有机—无机杂化钙钛矿材料(简称钙钛矿)因其具有光吸收系数高,电荷扩散长度大,吸收光谱较宽等特点而成为极具潜力的太阳能电池吸光层材料,引起了科学界的广泛关注。2009年至今,基于钙钛矿的太阳能电池的转换效率已经从3.8%提高至20.2%,效率的快速提升得益于钙钛矿薄膜制备方法的不断改进和创新。本文评述了气相沉积法制备钙钛矿薄膜的研究进展,重点分析了溶液—气相沉积法和化学气相沉积法对薄膜物性的调控及其所制备出的薄膜在电池应用中效率,并对比分析了几种气相沉积方法各自的优缺点,提出了未来在钙钛矿薄膜制备方面应当关注的主要问题。

钝化剂乙酰水杨酸对钙钛矿太阳能电池性能影响的研究

有机-无机杂化钙钛矿太阳能电池因其优异的光电性能和低廉的制备成本,成为目前光伏领域内的研究热点。然而,钙钛矿薄膜表面和晶界处存在大量缺陷,这易于导致载流子非辐射复合,并进而影响太阳能电池的光电转换效率。本工作通过在两步法制备钙钛矿的铅盐前驱液中引入钝化剂乙酰水杨酸(acetylsalicylic acid,ASA),利用吸收/光致发光光谱、扫描电镜和电学测试等技术手段研究了ASA分子对钙钛矿薄膜质量与器件性能的影响。结果表明:适量的ASA分子可以通过路易斯酸碱相互作用增大钙钛矿晶粒尺寸,并有效降低钙钛矿薄膜的缺陷密度;当ASA的浓度为2.5 mmol/L时,所制得的钙钛矿电池取得了19.83%的最高光电转换效率,明显高于对照器件的转换效率(17.47%)。本工作首次报道了ASA对钙钛矿薄膜缺陷的良好钝化效果,并为提高钙钛矿太阳能电池性能提供了一种简单有效的制备方法。

由电泳沉积ZIF-67薄膜制备高效染料敏化太阳能电池对电极

为了提高碳化ZIF-67薄膜制备的染料敏化太阳能对电极的光电性能,本研究通过碳化电泳沉积ZIF-67薄膜得到多孔碳电极,并进一步在多孔碳电极热分解氯铂酸得到负载铂的多孔碳复合电极。通过光电流-电压曲线、电化学阻抗谱和强度调制光电流谱等的测试,对比单独在FTO导电玻璃基底热分解氯铂酸得到的铂电极和单独碳化电泳沉积ZIF-67薄膜得到的多孔碳电极,研究了负载铂的多孔碳复合电极作为染料敏化太阳能电池对电极的光电性能。与其它两种对电极相比,以负载铂的多孔碳复合电极为对电极的染料敏化太阳能电池光电转换效率最高,因碳化ZIF-67薄膜的多孔电极具有较大的比表面积,能负载足够量的铂,从而提供更多的催化位点,具有更好的催化性能,从而使染料敏化太阳能电池的光电转换效率得到显著提升。

非晶硅太阳电池背反射电极ZnO∶B薄膜研究

摘要：采用金属有机物化学气相沉积（MOCVD）生长技术，以H：O和二乙基锌（Zn（CH2）2）为反应源，硼烷（B2H6，氢气稀释为1％）为掺杂气体，在面积为23cm×23em的普通玻璃衬底上生长ZnO：B薄膜，分析各工艺参数对薄膜光电特性的影响。结果表明：衬底温度对ZnO：B薄膜的透过率影响显著，其次是反应压力，B：H。掺杂量对透过率影响较小，但是对电阻率影响十分明显。通过优化工艺条件，在衬底温度为185℃，反应压力为0．5torr（1torr=133．3Pa），B，H。流量为4cm3／min下获得了厚度为580nm、在400～800nm光谱范围内透过率大于85％、电阻率为2．78×1013Q·cm的ZnO：B薄膜。将该ZnO：B薄膜作为背反射电极应用于大面积（23（31／1×23cm）非晶硅及硅锗太阳电池后，可使电池短路电流密度分别增加2．82和1．5mA／em。．