Vacuum-deposited interconnection layers for tandem solar cells

Two different types of vacuum-deposited interconnection layers (ICLs) were investigated for tandem solar cells: (1) a pure metal oxide and (2) an organic matrix doped with conductive dopants. The optical and electrical properties of these ICLs were systematically studied and compared. Taking the characteristics of ICLs into consideration, optical design methodology for balancing the photocurrent of each sub-cell in the tandem cell is presented. According to the design, highly efficient small-molecule tandem solar cells with power conversion efficiencies up to 7.3%–7.4% were experimentally demonstrated in both devices utilizing pure metal oxide and organic matrix ICLs.     

Cathodic multilayer transparent electrodes for ITO-free inverted organic solar cells

We demonstrate cathodic multilayer transparent electrodes based on a ZnS/Ag/TiO_x (ZAT) structure for ITO-free inverted organic solar cells. A quality solution-based TiO_x layer is adopted as an inner dielectric layer to modify the effective work function of Ag, ensuring the ZAT electrode works as a cathode. The effect of the TiO_x layer is seen on the open-circuit voltage of a solar cell incorporating this layer, increasing to 900 mV from 600 mV in the case of a cell with a bare Ag layer for a bulk-heterojunction of poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C₇₀-butyric acid methyl ester (PCBM70). The results of a joint theoretical and experimental study indicate that the photocurrent of a ZAT-based solar cell can be significantly enhanced by carefully balancing the optical-spacer and cavity-resonance effects, both of which are modulated by the thickness of the WO₃ layer used as a hole-collection layer at the top anode side. ZAT-based inverted solar cells with an optimized structure exhibit a power conversion efficiency as high as 5.1%, which is comparable to that of the ITO-based equivalent.     

Spontaneous growth by sol-gel process of low temperature ZnO as cathode buffer layer in flexible inverted organic solar cells

In this study, the sol–gel method was employed to prepare zinc oxide (ZnO) thin films as cathode buffer layers for inverted organic solar cells (IOSCs). We used a low temperature sol-gel process for the synthesis of ZnO thin films, in which the molar ratio of zinc acetate dihydrate (ZAD) to ethanolamine (MEA) was varied; subsequently, using the thin films, we successfully fabricated inverted solar cells on flexible plastic substrates. A ZnO sol–gel was first prepared by dissolving ZAD and MEA in ethylene glycol monomethyl ether (EGME). The molar ratios of ZAD to MEA were set as 1:1.2, 1:1, and 1:0.8, and we investigated the characteristics of the resulting ZnO thin films. We investigated the optical transmittance, surface roughness, and surface morphology of the films. Then, we discussed the reasons about the improvement of the device efficiency. The devices were fabricated using the ZnO thin films as cathode buffer layers. The results indicated that the morphology of the thin films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 changed to a rippled nanostructure after two-step annealing. The PCE was enhanced because of the higher light absorption in the active layer caused by the nanostructure. The structure of the inverted device was ITO/ZnO/P3HT:PC₆₁BM/MoO₃/Ag. The short-circuit current densities (8.59 mA/cm² and 8.34 mA/cm²) of the devices with films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 ratios, respectively, and annealed at 125 °C were higher than that of the device containing the ZnO thin film that was annealed at 150 °C. Inverted solar cells with ZnO films that were prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 and annealed at 125 °C exhibited PCEs of 3.38% and 3.30%, respectively. More than that, PCEs of the flexible device can reach up to 1.53%.     

Highly conductive Zinc-Tin-Oxide buffer layer for inverted polymer solar cells

Thin-films of Zinc Tin Oxide (ZTO) with an extremely high charge carrier mobility and superior optical transmittance are synthesized using a simple solution method. These ZTO films have been systematically studied for the application in inverted polymer solar cells (PSCs). The Hall effects measurements show that the charge mobility of the ZTO semiconductor is over 16.5 cm².V⁻¹.S⁻¹, which is the highest mobility value ever reported for oxide buffer made by using solution process. By applying the ZTO buffer layer in the inverted PSCs of P3HT:PC₆₁BM, the power conversion efficiency of the device is 30% higher than that of the devices made with other common buffer layers such as ZnO and TiO₂. Light intensity-dependent JV studies and PL measurements also indicate that ZTO buffer layer reduces surface recombination. This work demonstrates that the solution-synthesized ZTO is a promising new buffer layer with superior electron extraction capability for the solar cells.     

Enhanced performance in inverted polymer solar cells employing microwave-annealed sol-gel ZnO as electron transport layers

In this work, we propose a facile microwave-assisted approach for annealing sol-gel derived ZnO films to serve as electron transport layers (ETLs) for inverted bulk heterojunction polymer solar cells. We have demonstrated an impressive enhancement in performance for devices based on a poly (3-hexylthiophene) (P3HT): (6,6)-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) system employing the microwave-annealed ZnO (ZnO (MW)) ETLs in comparison to the cases using the conventional hotplate-annealed ZnO (ZnO (HP)) ones. The better electron transport in the device with the ZnO (MW) ETL is mainly ascribed to the preferable interfacial contact as evidenced by the morphology characteristics. Furthermore, the comprehensive analyses conducted from the light intensity dependent photocurrent and photovoltage measurements, the capacitance-voltage characteristics, and the alternating current impedance spectra suggest that the utilization of the ZnO (MW) ETLs can effectively suppress trap-assisted recombination as well as charge accumulation at the interface between P3HT: PC₆₁BM layers and ZnO layers, which is responsible for the enhanced device performance.     

A new alcohol-soluble electron-transporting molecule for efficient inverted polymer solar cells

A new electron-transporting material 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid (DPPA) was synthesized by modifying a n-type small molecule bathocuproine (BCP). The introduced carboxyl groups make DPPA soluble in polar solvent and compatible with large-scale solution-processing techniques. The anchoring of carboxyl on ZnO (or ITO) substrates helps to form a DPPA electron transporting layer, building an improved interfacial contact between the substrate and active layer. Furthermore, the highest occupied molecular orbital level of DPPA shifts to ?6.45 eV, which is 0.38 eV deeper than that of BCP, suggesting enhanced hole-blocking. Inverted polymer solar cells using P3HT:PCBM blend as the active layer and DPPA modified ZnO as the electron transporting layer were fabricated. A power conversion efficiency (PCE) of 3.55% was obtained, which is about 10% higher than that of the conventional ZnO buffered devices (3.25%). The DPPA was also used to replace ZnO as the sole electron-extracting layer, resulting in an improved PCE of 3.46%, which indicates that DPPA-ETL/ITO forms a better cathode than conventional ZnO/ITO.     

Polyacetylene-based polyelectrolyte as a universal interfacial layer for efficient inverted polymer solar cells

Here we report that poly(N-dodecyl-2-ethynylpyridiniumbromide) (PDEPB) interlayers between electron-collecting zinc oxide (ZnO) layers and bulk heterojunction (BHJ) layers act as a universal interfacial layer for improving the performances of inverted-type polymer:fullerene solar cells. Three different BHJ layers, poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), poly[(4,8-bis(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(N-2-ethylhexylthieno[3,4-c]pyrrole-4,6-dione)-2,6-diyl]] (PBDTTPD):PC₆₁BM, and 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) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), were employed so as to prove the role of the PDEPB interlayers. Results showed that the power conversion efficiency (PCE) of polymer:fullerene solar cells with the three different BHJ layers increased in the presence of the PDEPB interlayers prepared from 0.5 mg/ml solutions. The improved PCE was attributed to the conformal coating of the PDEPB layers on the ZnO layers (by atomic force microscopy measurement), lowered work functions of ZnO induced by the PDEPB layers (by Kelvin probe measurement), and reduced interface resistance (by impedance spectroscopy measurement), as supported by the noticeable change in the atom environments of both the ZnO and PDEPB layers (by X-ray photoelectron spectroscopy measurement).     

Large area roll-to-roll sputtering of transparent ITO/Ag/ITO cathodes for flexible inverted organic solar cell modules

We fabricated solution-processed flexible inverted organic solar cell (IOSC) modules (10 cm × 10 cm) on roll-to-roll (RTR) sputtered ITO/Ag/ITO multilayer cathodes. By using a pilot-scale RTR sputtering system equipped with mid-range frequency power for dual ITO targets and direct current power for the Ag target, we were able to continuously deposit a high-quality ITO/Ag/ITO multilayer on PET substrate with a width of 700 mm and length of 20,000 mm as a function of Ag thickness. At the Ag thickness of 12 nm, the ITO/Ag/ITO multilayer had a very low sheet resistance of 3.03 Ohm/square and high transmittance of 88.17%, which are better values than those of amorphous ITO film. A strip-type ITO/Ag/ITO cathode was successfully patterned using a RTR wet etching process. Successful operation of flexible IOSC modules on RTR sputtered ITO/Ag/ITO cathodes indicate that the RTR sputtering technique is a promising coating process for fabrication of high-quality transparent and flexible cathodes and can advance the commercialization of cost-efficient flexible IOSCs.     

Rubrene-based interfacial engineering toward enhanced performance in inverted polymer solar cells

Rubrene, an organic semiconductor having stable fused-ring molecular structure was used as a double interfacial layer in inverted organic solar cells. When a thin, 3 nm-thick layer of rubrene was introduced between a MoO₃-based hole-collecting layer and a bulk-heterojunction (BHJ) photo-active layer consisting of poly{4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl} (PTB7) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM), the power conversion efficiency was improved over 12% (from 7.2% to 8.1%). It was demonstrated that the insertion of thin rubrene layer showed suppressed exciton quenching and improved exciton dissociation, resulting in more efficient charge carrier collection and weaker charge recombination, thus improving the device performance.     

Efficient and ultraviolet durable inverted polymer solar cells using thermal stable GZO-AgTi-GZO multilayers as a transparent electrode

The optical and electrical properties of GZO/AgTi/AZO (GATG) multilayer transparent conducting films fabricated by magnetron sputtering method were investigated. The sheet resistance and maximum optical transmittance of GATG films are 5 Ω/sq and 86%, respectively. The sheet resistance of GATG still retains stable under annealing at 400 °C, which shows better thermal stability compared to GZO/Ag/AZO (GAG) film. The enhanced thermal stability of GATG is attributed to the formation of TiO_X in Ti doped Ag nanostructure film, which can inhibit Ag atom diffusion and aggregation. PTB7-TH:PC₇₁BM based inverted polymer solar cells (PSCs) with GATG electrode gave PCE of 9.20%, which is comparable to PCE (9.23%) of the control PSCs with ITO electrode. The PCE of PSCs with GATG and ITO electrodes respectively remain 59% and 23% of the original PCE values after UV exposure for 20 min with relativize humidity of 68% in air, indicating that PSCs with GATG show better UV durability. Our results suggest that GATG as an alternative to ITO electrode can obtain efficient inverted PSCs and have stronger anti-UV ability due to its low UV transparency.     

Effect of PEI cathode interlayer on work function and interface resistance of ITO electrode in the inverted polymer solar cells

In this paper, we investigated the effect of PEI cathode interlayer on the work function and the interface resistance of ITO electrode in the inverted polymer solar cells (PSCs) based on PBDTTT-C-T:PC₇₀BM. It is found that a very thin layer of PEI (⩽5.5 nm), either linear PEI (l-PEI) or branched PEI (b-PEI) with different molecular weights, is enough to lower the work function of the ITO electrode and to enhance the photovoltaic performance of the devices. The champion power conversion efficiency (PCE) of the devices with the PEI cathode interlayer is 7.84%, more than doubled of that without the interlayer. However, a thicker PEI interlayer (⩾10 nm) results in abrupt decrease of the PCEs due to the increase of the resistance. Interestingly, for the thicker interlayers, the l-PEI shows high photovoltaic performance than that of b-PEI, which can also be explained by their difference in the resistances. This work supplies an insight into the function of PEI cathode interlayer on improving the work function and resistance of ITO electrode in the inverted PSCs, and provides some instructions on the future design of interlayer materials in PSCs.     

大面积、高性能柔性 GaInP/GaAs/InGaAs叠层太阳电池的制备

柔性高效Ⅲ-Ⅴ族多结太阳电池正在被开发、应用于无人机、可穿戴设备和空间能源等领域.采用MOCVD技术在Ga As衬底上制备太阳电池外延层, 之后通过低温键合和外延层剥离方法将外延层转移到柔性衬底上.通过外延层剥离设备设计和大量参数优化实验, 实现了GaAs太阳电池结构从四英寸砷化镓晶圆上的有效分离, 且不产生缺陷并保持原有的性能.近期, 在50μm聚酰亚胺薄膜上制备的30 cm2大面积柔性GaInP/Ga As/InGaAs三结太阳电池实现了31. 5%的转换效率 (AM0光谱) , 其中开路电压3. 01 V, 短路电流密度16. 8 mA/cm2, 填充因子0. 845.由于采用了轻质的聚酰亚胺材料, 所得到的柔性太阳电池面密度仅为168. 5 g/m2, 比功率高达2 530 W/kg.     

Indium tin oxide-free semi-transparent inverted polymer solar cells using conducting polymer as both bottom and top electrodes

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is investigated as a transparent cathode to replace indium tin oxide (ITO) in inverted polymer solar cells. Increasing the thickness of the PEDOT:PSS electrode leads to a reduction in transparency and sheet resistance which lowers the photocurrent but increases the fill factor of the solar cells. The offset of photocurrent and fill factor as the thickness is increased leads to a saturation of the power conversion efficiency to 3%. These electrodes were applied to flexible substrates showing similar device performance to glass based devices. Cyclic bending test of these flexible polymer electrodes show improved conversion efficiency retention (92%) when compared to flexible ITO based electrodes (50%) after 300 bend cycles. In addition to using PEDOT:PSS as a cathode replacement for ITO in inverted solar cells, its use as a semi-transparent anode replacement to Ag is also examined. Semi-transparent inverted solar cells fabricated with ITO as the cathode and PEDOT:PSS as the top anode electrode were demonstrated showing efficiencies of 2.51% while replacement of both ITO and Ag with PEDOT:PSS as both the cathode and anode show efficiencies of 0.47%.     

Efficient and stable inverted polymer solar cells using TiO2 nanoparticles and analysized by Mott-Schottky capacitance

The performance of both inverted and conventional polymer solar cells (PSCs) were examined with a low-temperature, solution-processed synthesized TiO₂ nanoparticles (TiO₂ NPs) as the electron extraction layer. The performance of inverted PSCs based on P3HT:PCBM bulk-heterojunction with a TiO₂ NPs layer was dramatically improved and the highest power conversion efficiency (PCE) of 4.56% was achieved via 24 h exposure in air, which is one of the highest PCEs for P3HT:PCBM bulk-heterojunction PSCs using TiO₂ as electron extraction layer. Meanwhile, the performance of inverted PSCs was superior to regular PSCs. Mott-Schottky capacitance analysis was carried out for both inverted and regular PSCs to obtain the built-in potential, the depletion width, as well as the doping level of the active layer, which all support the performance improvement of PSCs devices with inverted structure. In addition, inverted PSCs show excellent stability in air without encapsulation. The PCE can retain 87% of its original values after 400 h exposure in air, which is much better than that of regular PSCs. The results indicate that solution-processed TiO₂ NPs shows great potential applications in the fabrication of highly efficient and stable inverted PSCs as well as large-area, flexible printed PSCs.     

Acid-functionalized fullerenes used as interfacial layer materials in inverted polymer solar cells

Two types of carboxylic acid functionalized fullerence derivatives, 4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (p-EHO-PCBA) and bis-4-(2-ethylhexyloxy)-[6,6]-phenyl C₆₁-butyric acid (bis-p-EHO-PCBA), were synthesized and investigated as an interfacial layer for inverted polymer solar cells (iPSCs). The –COOH groups on the PCBAs chemisorb to inorganic metal oxide (TiO_X), generating fullerene-based self-assembled monolayers (FSAMs). The devices with the mono- and bis-FSAMs exhibited substantially lower series resistance (R_S) values of 2.10 Ω cm² and 1.46 Ω cm², compared to that (4.15 Ω cm²) of the unmodified device. The TiO_X films modified with mono- and bis-FSAMs showed higher contact angles of 50° and 91°, respectively, than that of the pristine TiO_X film (33°). The increased contact angles were attributed to the enhanced hydrophobicity, improving the wetting properties with the organic photoactive layer. In addition, a comparison of device characteristics with electroactive FSAMs and non-electroactive benzoic acid SAMs clearly indicates that the FSAMs may suggest an additional pathway for photo-induced charge transfer and charge collection to ITO. After surface modification with FSAMs, the short-circuit current density (J_SC) and fill factor (FF) values increased substantially. The iPSCs based on poly(5,6-bis(octyloxy)-4-(thiophen-2-l)benzo[c][1,2,5]thiadiazole) (PTBT) and [6,6]phenyl-C₆₁-butyric acid methyl ester (PCBM) as an active layer showed remarkably improved power conversion efficiency up to 5.13% through incorporation of the FSAMs-based interfacial layer.     

Flexible organic solar cells using an oxide/metal/oxide trilayer as transparent electrode

Organic solar cells (OSCs) have attracted much attention as a clean and renewable energy convention system, owning to the low-cost and easy-processing nature of organic semiconductors. While indium tin oxide (ITO) is commonly used in OSCs as the transparent conductive electrode, the rising cost of indium, the high temperature process and the poor flexibility of ITO, make it incompatible with large-scale roll-to-roll manufacture of OSCs. In this paper, the MoO₃/thin metal/MoO₃ trilayer structure was used to replace the ITO electrode in OSCs. The optical and electrical properties of the trilayer were shown to depend on the material and thickness of the intermediate metal layer. The maximum power conversion efficiency of up to 2.5% under simulated 1 sun AM 1.5 solar illumination was achieved for OSCs based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), compared to a maximum efficiency of 3.1% for the ITO-based devices. Moreover, due to the flexible nature of the trilayer structure, the OSCs with the trilayer electrode exhibited good mechanical flexibility. The efficiency of the flexible device was only reduced by ∼6% from its original performance after 500 bending cycles with a bending radius of 1.3 cm. Therefore, the performance of the ITO-free devices on rigid/flexible substrates suggests that this oxide/metal/oxide trilayer electrode is a promising ITO replacement in OSCs.     

Enhanced efficiency in GaInP/GaAs tandem solar cells using carbon doped GaAs in tunnel junction

Carbon doping of GaAs using CBr₄ (carbon tetrabromide) in metal-organic chemical vapor deposition (MOCVD) was investigated to obtain very high and sharp doping profiles required for tunnel junction in tandem solar cells. It was found that the hole concentration increased with decreasing growth temperature and V/III ratio. Hole doping profiles versus distance from the sample surface showed that the hole concentration near the surface was very low in comparison with that far below the surface. As a post-growth treatment, CBr₄ was supplied during the cool down process and produced almost constant hole concentration of 1 × 10²⁰ cm⁻³ regardless of the depth, when CBr₄ flow rate was 9.53 μmol/min. Based on these results, solar cells were fabricated using both carbon (C) and zinc (Zn) as a p-type dopant. It was shown that C doping exhibits higher efficiency and lower series resistance than those of Zn doping in GaInP/GaAs tandem solar cells.     

High-performance inverted polymer solar cells with lead monoxide-modified indium tin oxides as the cathode

The photovoltaic stability of polymer solar cells (PSCs) can be greatly improved by adopting an inverted device structure. This paper reports high-performance inverted PSCs with lead monoxide (PbO)-modified indium tin oxide (ITO) as the cathodes. A thin PbO layer can effectively lower the work function of ITO from 4.5 to 3.8 eV. The optimal inverted PSCs with poly(3-hexylthiophene) (P3HT) as the donor and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as the acceptor exhibited high photovoltaic performance: open-circuit voltage of 0.59 V, short-circuit current density of 10.8 mA cm⁻², fill factor of 0.632, and power conversion efficiency of 4.00% under simulated AM1.5G illumination (100 mW cm⁻²). The photovoltaic efficiency is significantly higher than that of the control inverted PSCs with unmodified ITO as the cathode. It is even better than that of the control PSCs with normal architecture, which have an optimal efficiency of 3.5%. The lowering in the work function by the PbO modification is attributed to the charge transfer between PbO and ITO, as evidenced by the X-ray photoelectron spectra.     

Performance improvement mechanisms of P3HT:PCBM inverted polymer solar cells using extra PCBM and extra P3HT interfacial layers

A novel P3HT:PCBM inverted polymer solar cell (IPSC) was fabricated and investigated. An extra PCBM and an extra P3HT interfacial layers were inserted into the bottom side and the top side of the P3HT:PCBM absorption layer of the IPSCs to respectively enhance electron transport and hole transport to the corresponding electrodes. According to the surface energy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurement results, the extra PCBM interfacial layer could let more P3HT to form on the top side of the P3HT:PCBM blends. It revealed that the non-continuous pathways of P3HT in the P3HT:PCBM absorption layer could be reduced. Consequently, the carrier recombination centers were reduced in the absorption layer of IPSCs. The power conversion efficiency (PCE) of the P3HT:PCBM IPSCs with an extra PCBM interfacial layer greatly increased from 3.39% to 4.50% in comparison to the P3HT:PCBM IPSCs without an extra PCBM interfacial layer. Moreover, the performance of the P3HT:PCBM IPSCs with an extra PCBM interfacial layer could be improved by inserting an extra P3HT interfacial layer between the absorption layer and the MoO₃ layer. The PCE of the resulting IPSCs increased from 4.50% to 4.97%.     

Semiconducting single-walled carbon nanotubes as interfacial modification layers for organic-Si solar cells

A semiconducting single-walled carbon nanotubes (s-SWCNTs) interlayer between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and n-Si was used for high performance organic-Si hybrid photovoltaic (PV) devices. The s-SWCNTs films with different thickness were utilized to investigate the PV effect on PEDOT:PSS/Si device performance. The surface potential of Si substrate with s-SWCNTs was dramatically reduced, which increased the compatibility between Si and PEDOT:PSS. In addition, s-SWCNTs with good semiconducting properties, guaranteed the charge transfer between Si and PEDOT:PSS. Therein, the electrical contact was dramatically improved with addition of s-SWCNTs interlayer, which led to increased fill factor. A power conversion efficiency (PCE) of 12.14% was achieved with an optimized thickness of s-SWCNTs layer. The s-SWCNTs interface layer was fabricated by a simple solution processed method, which was easily coupled with organic-Si solar cells to enhance the PCE.