Rear‐Passivated Ultrathin Cu(In,Ga)Se2 Films by Al2O3 Nanostructures Using Glancing Angle Deposition Toward Photovoltaic Devices with Enhanced Efficiency

In this work, for the first time, the addition of aluminum oxide nanostructures (Al₂O₃ NSs) grown by glancing angle deposition (GLAD) is investigated on an ultrathin Cu(In,Ga)Se₂ device (400 nm) fabricated using a sequential process, i.e., post‐selenization of the metallic precursor layer. The most striking observation to emerge from this study is the alleviation of phase separation after adding the Al₂O₃ NSs with improved Se diffusion into the non‐uniformed metallic precursor due to the surface roughness resulting from the Al₂O₃ NSs. In addition, the raised Na concentration at the rear surface can be attributed to the increased diffusion of Na ion facilitated by Al₂O₃ NSs. The coverage and thickness of the Al₂O₃ NSs significantly affects the cell performance because of an increase in shunt resistance associated with the formation of Na₂Se_X and phase separation. The passivation effect attributed to the Al₂O₃ NSs is well studied using the bias‐EQE measurement and J–V characteristics under dark and illuminated conditions. With the optimization of the Al₂O₃ NSs, the remarkable enhancement in the cell performance occurs, exhibiting a power conversion efficiency increase from 2.83% to 5.33%, demonstrating a promising method for improving ultrathin Cu(In,Ga)Se₂ devices, and providing significant opportunities for further applications.     

Novel Atmospheric Growth Technique to Improve Both Light Absorption and Charge Collection in ZnO/Cu2O Thin Film Solar Cells

In low temperature grown ZnO/Cu₂O solar cells, there is a discrepancy between collection length and depletion width in the Cu₂O which makes the simultaneous achievement of efficient charge collection and high open‐circuit voltage problematic. This is addressed in this study by fabricating ZnO/Cu₂O/Cu₂O⁺ back surface field devices using an atmospheric atomic layer deposition (AALD) printing method to grow a sub‐200‐nm Cu₂O⁺ film on top of electrodeposited ZnO and Cu₂O layers. The AALD Cu₂O⁺ has a carrier concentration around 2 orders of magnitude higher than the electrodeposited Cu₂O, allowing the electrodeposited Cu₂O layer thickness in a back surface field cell to be reduced from 3 μm to the approximate charge collection length, 1 μm, while still allowing a high potential to be built into the cell. The dense conformal nature of the AALD layer also blocks shunt pathways allowing the voltage enhancement to be maintained. The thinner cell design reduces recombination losses and increases charge collection from both incident light and light reflected off the back electrode. Using this design, a short circuit current density of 6.32 mA cm^?2 is achieved–the highest reported J_SC for an atmospherically deposited ZnO/Cu₂O device to date.     

Spatially separated atomic layer deposition of Al2O3, a new option for high‐throughput Si solar cell passivation

A next generation material for surface passivation of crystalline Si is Al₂O₃. It has been shown that both thermal and plasma‐assisted (PA) atomic layer deposition (ALD) Al₂O₃ provide an adequate level of surface passivation for both p‐ and n‐type Si substrates. However, conventional time‐resolved ALD is limited by its low deposition rate. Therefore, an experimental high‐deposition‐rate prototype ALD reactor based on the spatially separated ALD principle has been developed and Al₂O₃ deposition rates up to 1.2 nm/s have been demonstrated. In this work, the passivation quality and uniformity of the experimental spatially separated ALD Al₂O₃ films are evaluated and compared to conventional temporal ALD Al₂O₃, by use of quasi‐steady‐state photo‐conductance (QSSPC) and carrier density imaging (CDI). It is shown that spatially separated Al₂O₃ films of increasing thickness provide an increasing surface passivation level. Moreover, on p‐type CZ Si, 10 and 30 nm spatial ALD Al₂O₃ layers can achieve the same level of surface passivation as equivalent temporal ALD Al₂O₃ layers. In contrast, on n‐type FZ Si, spatially separated ALD Al₂O₃ samples generally do not reach the same optimal passivation quality as equivalent conventional temporal ALD Al₂O₃ samples. Nevertheless, after “firing”, 30 nm of spatially separated ALD Al₂O₃ on 250 µm thick n‐type (2.4 Ω cm) FZ Si wafers can lead to effective surface recombination velocities as low as 2.9 cm/s, compared to 1.9 cm/s in the case of 30 nm of temporal ALD Al₂O₃. Copyright © 2011 John Wiley & Sons, Ltd.     

Vertically Well‐Aligned ZnO Nanowires on c‐Al2O3 and GaN Substrates by Au Catalyst

In this letter, we report that vertically well‐aligned ZnO nanowires were grown on GaN epilayers and c‐plane sapphire via a vapor‐liquid‐solid process by introducing a 3 nm Au thin film as a catalyst. In our experiments, epitaxially grown ZnO nanowires on Au‐coated GaN were vertically well‐aligned, while nanowires normally tilted from the surface when grown on Au‐coated c‐Al₂O₃ substrates. However, pre‐growth annealing of the Au thin layer on c‐Al₂O₃ resulted in the growth of well‐aligned nanowires in a normal surface direction. High‐resolution transmission electron microscopy measurements showed that the grown nanowires have a hexagonal c‐axis orientation with a single‐crystalline structure.     

ZnO和Al2O3缓冲层对AZO透明导电膜薄膜性能的影响

采用射频磁控溅射法,以纯度为99.9%,质量分数98%ZnO、2%Al2O3陶瓷靶为溅射靶材,在预先沉积了ZnO和Al2O3的玻璃衬底上制备了Al2O3掺杂的ZnO薄膜。研究并对比了两种不同的缓冲层对ZnO∶Al(AZO)薄膜的微观结构和光电性能的影响。并借助X线衍射(XRD)仪、扫描电子显微镜(SEM)、紫外可见光谱仪(UV-Vis)等方法测试和分析了不同缓冲层,对AZO薄膜的形貌结构、光电学性能的影响。结果表明:加入缓冲层后,在衬底温度为200℃时,溅射30min,负偏压为60V、在氮气气氛下经300℃退火处理后,制得薄膜的可见光透过率为83%～87%,AZO薄膜的最低电阻率,从9.2×10-4Ω.cm(玻璃)分别下降到8.0×10-4Ω.cm(ZnO)和5.4×10-4Ω.cm(Al2O3)。     

绒面ZnO薄膜的生长及其在太阳电池前电极的应用

研究了MOCVD技术制备的不同B2H6掺杂流量下ZnO薄膜的微观结构和光电性能变化.XRD和SEM的研究结果表明,ZnO薄膜具有(110)峰择优取向的绒面结构特征.当B2H6流量为10sccm时,在6cm×6cm面积玻璃衬底上生长出厚度为1000nm,方块电阻为～12Ω/□,平均透过率大于80%,迁移率为30.5cm2/(V·s)的绒面结构ZnO薄膜.PL谱测试表明B掺杂提高了ZnO薄膜的晶体质量,有力地说明了B掺杂ZnO薄膜具有更好的电学稳定性;低压H2氛围中退火可以有效提高ZnO薄膜的电子迁移率.将其用作Si薄膜太阳电池的前电极,电池性能与日本Asahi-U type SnO2作前电极的电池具有同等效果.     

绒面ZnO薄膜的生长及其在太阳电池前电极的应用

研究了MOCVD技术制备的不同B2H6掺杂流量下ZnO薄膜的微观结构和光电性能变化.XRD和SEM的研究结果表明,ZnO薄膜具有(110)峰择优取向的绒面结构特征.当B2H6流量为10sccm时,在6cm×6cm面积玻璃衬底上生长出厚度为1000nm,方块电阻为～12Ω/□,平均透过率大于80%,迁移率为30.5cm2/(V·s)的绒面结构ZnO薄膜.PL谱测试表明B掺杂提高了ZnO薄膜的晶体质量,有力地说明了B掺杂ZnO薄膜具有更好的电学稳定性;低压H2氛围中退火可以有效提高ZnO薄膜的电子迁移率.将其用作Si薄膜太阳电池的前电极,电池性能与日本Asahi-U type SnO2作前电极的电池具有同等效果.     

PbTiO3 as Electron‐Selective Layer for High‐Efficiency Perovskite Solar Cells: Enhanced Electron Extraction via Tunable Ferroelectric Polarization

PbTiO₃ (PTO) is explored as a versatile and tunable electron‐selective layer (ESL) for perovskite solar cells. To demonstrate effectiveness of PTO for electron–hole separation and charge transfer, perovskite solar cells are designed and fabricated in the laboratory with the PTO as the ESL. The cells achieve a power conversion efficiency (PCE) of ≈12.28% upon preliminary optimization. It is found that the PTO ferroelectric layer can not only increase the PCE, but also tune the photocurrent via tuning PTO's ferroelectric polarization. Moreover, to understand the physical mechanism underlying the carrier transport by the ferroelectric polarization, the electronic structure of PTO/CH₃NH₃PbI₃ heterostructure is computed using the first‐principles methods, for which the triplet state is used to simulate charge transfer in the heterostructure. It is shown that the synergistic effect of type II band alignment and the specific ferroelectric polarization direction provide the effective extraction of electrons from the light absorber, while minimize recombination of photogenerated electron–hole pairs. Overall, the ferroelectric PTO is a promising and tunable ESL for optimizing electron transport in the perovskite solar cells. The design offers a different strategy for altering direction of carrier transport in solar cells.     

Eclipse Pulsed Laser Deposition for Damage‐Free Preparation of Transparent ZnO Electrodes on Top of Organic Solar Cells

Pulsed laser deposited gallium doped zinc oxide (ZnO:Ga) is reported as transparent top electrode for organic solar cells. In contrast to standard coating techniques, prone to harm organic sublayers and leading to strongly reduced device efficiencies, eclipse pulsed laser deposition (PLD) in argon atmosphere is identified as compatible, nonharmful deposition method for ZnO:Ga, even on top of sensitive organic material. Although PLD is not yet ready for mass production, the experiments reveal and solve crucial process limitations, e.g., droplet impacts, which might be useful also for high yield deposition methods. Optimized ZnO:Ga top electrodes achieve a high mean transparency in the visible spectral range of T_vis = 82.7% and a reasonable sheet resistance of R_S = 83 Ω sq^?1. The organic photovoltaic devices prepared with this electrode obtained an efficiency of η = 2.9%, almost equal to the efficiency of reference samples using a state‐of‐the‐art metal top contact (η = 3.0%). The investigations here demonstrate the successful deposition of transparent conductive oxides as top electrode for organic devices and open a new path towards the combination of metal oxides and organic semiconductors.     

Room‐Temperature Tailoring of Vertical ZnO Nanoarchitecture Morphology for Efficient Hybrid Polymer Solar Cells

A ZnO nanoarchitecture, i.e., ZnO nanosheet (NS) framework, is demonstrated to be a promising electron acceptor and direct electron transport matrix for polymer‐inorganic hybrid solar cells. The ZnO NS framework is constructed on nanoneedles/indium tin oxide substrate via a room‐temperature chemical bath deposition (RT CBD). The framework morphology can be simply tailored by varying the concentration of precursor solution in the RT CBD. The ZnO nanoarchitecture with an appropriate free space between the NSs is consequently demonstrated to facilitate poly(3‐hexylthiophene) (P3HT) infiltration, resulting in superior interface properties, i.e., more efficient charge separation and less charge recombination, in the hybrid. Moreover, apart from the characteristics similar to the ZnO nanorod (NR) array, including vertical feature and single crystalline structure, the ZnO NS framework exhibits a slightly larger absorption edge and a faster electron transport rate. A notable efficiency of 0.88% is therefore attained in the ZnO NS‐P3HT hybrid solar cell, which is higher than that of the ZnO NR‐P3HT hybrid solar cell.     

Boosting the Efficiency of Perovskite Solar Cells with CsBr‐Modified Mesoporous TiO2 Beads as Electron‐Selective Contact

Rapid extraction of photogenerated charge carriers is essential to achieve high efficiencies with perovskite solar cells (PSCs). Here, a new mesoscopic architecture as electron‐selective contact for PSCs featuring 40 nm sized TiO₂ beads endowed with mesopores of a few nanometer diameters is introduced. The bimodal pore distribution inherent to these films produces a very large contact area of 200 m² g^?1 whose access by the perovskite light absorber is facilitated by the interstitial voids between the particles. Modification of the TiO₂ surface by CsBr further strengthens its interaction with the perovskite. As a result, photogenerated electrons are extracted rapidly producing a very high fill factor of close to 80% a V_OC of 1.14 V and a PCE up to 21% with negligible hysteresis.     

Dual Effect of ITO‐Interlayer on Inverted Top‐Illuminated Polymer Solar Cells: Wetting of Polyelectrolyte and Tuning of Cavity

Flexible inverted top‐illuminated polymer solar cells (IT‐PSCs) are fabricated by wetting of polyelectrolyte and designing a microcavity structure by laying an indium‐tin‐oxide (ITO) interlayer on top of an Ag reflector. The ITO‐coated Ag makes the surface hydrophilic, thereby improving wettability of polyethyleneimine (PEIE). This increased wettability of PEIE yields a reflective cathode with low work function of 3.73 eV. The ITO layer also tunes the light absorption spectrum in the active layer. Finite‐domain time‐difference simulation provides evidence that the ITO layer played a role in both the shift in resonant wavelength in the microcavity and confinement of the electric field to the active layer. Time‐dependent simulation suggests that the time to reach steady‐state light absorption is longer (6.6 fs) when a microcavity is present than when it is not present (3.8 fs); i.e., the microcavity increases light absorption in the active layer. The designed IT‐PSCs show a maximum photo‐conversion efficiency of 6.4% on plastic film and 6.1% on opaque copper foil; these are the highest values obtained by top‐illuminated PSCs on a metallic substrate. The IT‐PSCs have excellent mechanical flexibility and more stable in air than conventional normal structured devices.     

Self‐Assembled Quasi‐3D Nanocomposite: A Novel p‐Type Hole Transport Layer for High Performance Inverted Organic Solar Cells

Hole transport layer (HTL) plays a critical role for achieving high performance solution‐processed optoelectronics including organic electronics. For organic solar cells (OSCs), the inverted structure has been widely adopted to achieve prolonged stability. However, there are limited studies of p‐type effective HTL on top of the organic active layer (hereafter named as top HTL) for inverted OSCs. Currently, p‐type top HTLs are mainly 2D materials, which have an intrinsic vertical conduction limitation and are too thin to function as practical HTL for large area optoelectronic applications. In the present study, a novel self‐assembled quasi‐3D nanocomposite is demonstrated as a p‐type top HTL. Remarkably, the novel HTL achieves ≈15 times enhanced conductivity and ≈16 times extended thickness compared to the 2D counterpart. By applying this novel HTL in inverted OSCs covering fullerene and non‐fullerene systems, device performance is significantly improved. The champion power conversion efficiency reaches 12.13%, which is the highest reported performance of solution processed HTL based inverted OSCs. Furthermore, the stability of OSCs is dramatically enhanced compared with conventional devices. The work contributes to not only evolving the highly stable and large scale OSCs for practical applications but also diversifying the strategies to improve device performance.     

Thin Al2O3 passivated boron emitter of n‐type bifacial c‐Si solar cells with industrial process

We have presented thin Al₂O₃ (~4 nm) with SiN_x:H capped (~75 nm) films to effectively passivate the boron‐doped p⁺ emitter surfaces of the n‐type bifacial c‐Si solar cells with BBr₃ diffusion emitter and phosphorus ion‐implanted back surface field. The thin Al₂O₃ capped with SiN_x:H structure not only possesses the excellent field effect and chemical passivation, but also establishes a simple cell structure fully compatible with the existing production lines and processes for the low‐cost n‐type bifacial c‐Si solar cell industrialization. We have successfully achieved the large area (238.95 cm²) high efficiency of 20.89% (front) and 18.45% (rear) n‐type bifacial c‐Si solar cells by optimizing the peak sintering temperature and fine finger double printing technology. We have further shown that the conversion efficiency of the n‐type bifacial c‐Si solar cells can be improved to be over 21.3% by taking a reasonable high emitter sheet resistance. Copyright © 2017 John Wiley & Sons, Ltd.     

Novel field‐effect passivation for nanostructured Si solar cells using interfacial sulfur incorporation

Surface passivation of a nanostructured Si solar cells plays a crucial role in collecting photogenerated carriers by mitigating carrier recombination at surface defect sites. Interface modification by additional sulfur (S) incorporation is proposed to enhance the field‐effect passivation performance. Here, we report that simple annealing in a H₂S ambient induced additional negative fixed charges at the interface between atomic‐layer‐deposited Al₂O₃ and nanostructured Si. Annealing at various temperatures allowed us to control the S concentration and the fixed charge density. The optimized S incorporation at the interface significantly enhanced the negative fixed charge density and the minority carrier lifetime up to ~5.9 × 10¹² cm⁻² and ~780 μs, respectively. As a result, the internal quantum efficiency was nearly two times higher in the blue response region than that of control cells without S incorporation. Copyright © 2017 John Wiley & Sons, Ltd.     

Fabrication,Optical Modeling,and Color Characterization of Semitransparent Bulk‐Heterojunction Organic Solar Cells in an Inverted Structure

Semitransparent inverted organic photodiodes are fabricated with a Baytron PH500 ethylene‐glycol layer/silver grid as the top electrode. Reasonable performances are obtained under both rear‐ and front‐side illumination and efficiencies up to 2% are achieved. Some light is shed on visual prospects through optical simulations for a semitransparent device of poly(3‐hexylthiophene) (P3HT) and the C60 derivative 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl[6,6]C₇₁ (PC70BM) in the inverted structure. These calculations allow the maximum efficiency achievable to be predicted for semitransparent cells based on P3HT:PC70BM versus the transparency perception for a human eye. The simulations suggest that low‐bandgap materials such as poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)] (PCPDTBT) have a better potential for semitransparent devices. In addition, the color range recognized by the human eye is predicted by the optical simulation for some semitransparent devices including different active layers.     

Constructing Safe and Durable High‐Voltage P2 Layered Cathodes for Sodium Ion Batteries Enabled by Molecular Layer Deposition of Alucone

Sodium ion batteries are a promising next‐generation energy storage device for large‐scale applications. However, the high voltage P2–O2 phase transition (>4.25 V vs Na/Na⁺) and metal dissolution of P2 layered cathodes into the electrolyte result in severe capacity fading, which is a major setback to fabricate high energy devices. Hence, it is essential to design an appropriate strategy to enhance interfacial behaviors to obtain safe and stable high voltage sodium ion batteries. Herein, an ultrathin alucone layer deposited through molecular layer deposition (MLD) is employed to stabilize the structure of a P2‐type layered cathode cycled at a high cut‐off voltage (>4.45 V) for the first time. The alucone coated P2‐type Na_0.66Mn_0.9Mg_0.1O₂ (NMM) cathode exhibits an 86% capacity retention after 100 cycles between 2 and 4.5 V at 1 C, demonstrating substantial improvement compared to pristine (65%) and Al₂O₃‐coated (71%) NMM cathodes. Furthermore, the mechanically robust and conductive nature of the organometallic thin film enhances the rate capability relative to the pristine NMM electrode. This work reveals that the MLD of alucone on cathodes is a promising approach to improve the cycle stability of sodium ion batteries at high cut‐off voltages.     

Inverted Layer‐By‐Layer Fabrication of an Ultraflexible and Transparent Ag Nanowire/Conductive Polymer Composite Electrode for Use in High‐Performance Organic Solar Cells

A highly flexible and transparent conductive electrode based on consecutively stacked layers of conductive polymer (CP) and silver nanowires (AgNWs) fully embedded in a colorless polyimide (cPI) is achieved by utilizing an inverted layer‐by‐layer processing method. This CP‐AgNW composite electrode exhibits a high transparency of >92% at wavelengths of 450–700 nm and a low resistivity of 7.7 Ω ?^?1, while its ultrasmooth surface provides a large contact area for conductive pathways. Furthermore, it demonstrates an unprecedentedly high flexibility and good mechanical durability during both outward and inward bending to a radius of 40 μm. Subsequent application of this composite electrode in organic solar cells achieves power conversion efficiencies as high as 7.42%, which represents a significant improvement over simply embedding AgNWs in cPI. This is attributed to a reduction in bimolecular recombination and an increased charge collection efficiency, resulting in performance comparable to that of indium tin oxide‐based devices. More importantly, the high mechanical stability means that only a very slight reduction in efficiency is observed with bending (<5%) to a radius of 40 μm. This newly developed composite electrode is therefore expected to be directly applicable to a wide range of high‐performance, low‐cost flexible electronic devices.     

Hybrid Templated Synthesis of Crack‐Free,Organized Mesoporous TiO2 Electrodes for High Efficiency Solid‐State Dye‐Sensitized Solar Cells

Organic/inorganic hybrid templates, i.e., aluminium oxide (Al₂O₃) nanoparticles grafted with poly(oxyethylene) methacrylate, Al₂O₃‐POEM, are synthesized via surface‐initiated atom transfer radical polymerization (ATRP), as confirmed by Fourier transform‐infrared spectroscopy (FT‐IR) and thermogravimetric analysis (TGA). Upon combining the Al₂O₃‐POEM with titanium(IV) isopropoxide (TTIP), hydrophilic TTIP is selectively confined in the hydrophilic POEM chains through hydrogen bonding interactions. Following the calcination at 450 °C and the selective etching of Al₂O₃ with NaOH, the OM‐TiO₂ films with high surface areas, good interconnectivity, and anatase phase are obtained. The solid‐state dye‐sensitized solar cells (ssDSSCs) fabricated with OM‐TiO₂ photoelectrodes and a polymerized ionic liquid (PIL) show a high energy conversion efficiency of 7.3% at 100 mW cm^?2, which is one of the highest values for ssDSSCs. The high cell performance is due to the well‐organized structure, resulting in improved dye loading, excellent pore filling of electrolyte, enhanced light harvesting, and reduced charge recombination.