TiO_(2)Electron Transport Layer with p-n Homojunctions for Efficient and Stable Perovskite Solar Cells

Low-temperature processed electron transport layer(ETL)of TiO_(2)that is widely used in planar perovskite solar cells(PSCs)has inherent low carrier mobility,resulting in insufficient photogenerated elec-tron transport and thus recombination loss at buried interface.Herein,we demonstrate an effective strategy of laser embedding of p-n homojunctions in the TiO_(2)ETL to accelerate electron transport in PSCs,through localized build-in electric fields that enables boosted electron mobility by two orders of magnitude.Such embedding is found significantly helpful for not only the enhanced crystallization quality of TiO_(2)ETL,but the fabrication of perovskite films with larger-grain and the less-trap-states.The embedded p-n homojunction enables also the modulation of interfacial energy level between perovskite layers and ETLs,favoring for the reduced voltage deficit of PSCs.Benefiting from these merits,the formamidinium lead iodide(FAPbI_(3))PSCs employing such ETLs deliver a champion efficiency of 25.50%,along with much-improved device stability under harsh conditions,i.e.,maintain over 95%of their initial efficiency after operation at maximum power point under continuous heat and illumination for 500 h,as well as mixed-cation PSCs with a champion efficiency of 22.02%and over 3000 h of ambient storage under humidity stability of 40%.Present study offers new possibilities of regulating charge transport layers via p-n homojunction embedding for high performance optoelectronics.

Highly efficient flexible perovskite solar cells with vacuum-assisted low-temperature annealed SnO2 electron transport layer

The demand for lightweight, flexible, and high-performance portable power sources urgently requires high-efficiency and stable flexible solar cells. In the case of perovskite solar cells(PSCs), most of the common electron transport layer(ETL) needs to be annealed for improving the optoelectronic properties,while conventional flexible substrates could barely stand the high temperature. Herein, a vacuumassisted annealing SnO_(2) ETL at low temperature(100℃) is utilized in flexible PSCs and achieved high efficiency of 20.14%. Meanwhile, the open-circuit voltage(V_(oc)) increases from 1.07 V to 1.14 V. The flexible PSCs also show robust bending stability with 86.8% of the initial efficiency is retained after 1000 bending cycles at a bending radius of 5 mm. X-ray photoelectron spectroscopy(XPS), atomic force microscopy(AFM), and contact angle measurements show that the density of oxygen vacancies, the surface roughness of the SnO_(2) layer, and film hydrophobicity are significantly increased, respectively. These improvements could be due to the oxygen-deficient environment in a vacuum chamber, and the rapid evaporation of solvents. The proposed vacuum-assisted low-temperature annealing method not only improves the efficiency of flexible PSCs but is also compatible and promising in the large-scale commercialization of flexible PSCs.

Composite electron transport layer for efficient N-I-P type monolithic perovskite/silicon tandem solar cells with high open-circuit voltage

Perovskite/silicon tandem solar cells(PSTSCs) have exhibited huge technological potential for breaking the Shockley-Queisser limit of single-junction solar cells. The efficiency of P-I-N type PSTSCs has surpassed the single-junction limit, while the performance of N-I-P type PSTSCs is far below the theoretical value. Here, we developed a composite electron transport layer for N-I-P type monolithic PSTSCs with enhanced open-circuit voltage(VOC) and power conversion efficiency(PCE). Lithium chloride(Li Cl) was added into the tin oxide(SnO_(2)) precursor solution, which simultaneously passivated the defects and increased the electron injection driving force at the electron transfer layer(ETL)/perovskite interface.Eventually, we achieved monolithic PSTSCs with an efficiency of 25.42% and V_(OC) of 1.92 V, which is the highest PCE and VOCin N-I-P type perovskite/Si tandem devices. This work on interface engineering for improving the PCE of monolithic PSTSCs may bring a new hot point about perovskite-based tandem devices.

Spatial configuration engineering of perylenediimide-based non-fullerene electron transport materials for efficient inverted perovskite solar cells

Due to their excellent photoelectron chemical properties and suitable energy level alignment with perovskite,perylene diimide(PDI)derivatives are competitive non-fullerene electron transport material(ETM)candidates for perovskite solar cells(PSCs).However,the conjugated rigid plane structure of PDI units result in PDI-based ETMs tending to form large aggregates,limiting their application and photovoltaic performance.In this study,to restrict aggregation and further enhance the photovoltaic performance of PDI-type ETMs,two PDI-based ETMs,termed PDO-PDI2(dimer)and PDO-PDI3(trimer),were constructed by introducing a phenothiazine 5,5-dioxide(PDO)core building block.The research manifests that the optoelectronic properties and film formation property of PDO-PDI2 and PDO-PDI3 were deeply affected by the molecular spatial configuration.Applied in PSCs,PDO-PDI3 with threedimensional spiral molecular structure,exhibits superior electron extraction and transport properties,further achieving the best PCE of 18.72%and maintaining 93%of its initial efficiency after a 720-h aging test under ambient conditions.

Non-conjugated polymers as thickness-insensitive electron transport materials in high-performance inverted organic solar cells

Two non-conjugated polymers PEIE-DBO and PEIE-DCO, prepared by quaternization of polyethyleneimine ethoxylate by 1,8-dibromooctane and 1,8-dichlorooctane respectively, are developed as electron transport layer(ETL) in high-performance inverted organic solar cells(OSCs), and the effects of halide ions on polymeric photoelectric performance are fully investigated. PEIE-DBO possesses higher electron mobility(3.68×10-4 cm2 V-1s-1), higher conductivity and more efficient exciton dissociation and electron extraction, attributed to its lower work function(3.94 eV) than that of PEIE-DCO, which results in better photovoltaic performance in OSCs. The inverted OSCs with PTB7-Th: PC71BM as photoactive layer and PEIE-DBO as ETL exhibit higher PCE of 10.52%, 9.45% and 9.09% at the thickness of 9, 35 and 50 nm,respectively. To our knowledge, PEIE-DBO possesses the best thickness-insensitive performance in polymeric ETLs of inverted fullerene-based OSCs. Furthermore, PEIE-DBO was used to fabricate the inverted non-fullerene OSCs(PM6:Y6) and obtained a high PCE of 15.74%, which indicates that PEIE-DBO is effective both in fullerene-based OSCs and fullerene-free OSCs.

Toward high-efficiency perovskite solar cells with one-dimensional oriented nanostructured electron transport materials

The unique advantages of one-dimensional(1D)oriented nanostructures in light-trapping and chargetransport make them competitive candidates in photovoltaic(PV)devices.Since the emergence of perovskite solar cells(PSCs),1D nanostructured electron transport materials(ETMs)have drawn tremendous interest.However,the power conversion efficiencies(PCEs)of these devices have always significantly lagged behind their mesoscopic and planar counterparts.High-efficiency PSCs with 1D ETMs showing efficiency over 22%were just realized in the most recent studies.It yet lacks a comprehensive review covering the development of 1D ETMs and their application in PSCs.We hence timely summarize the advances in 1D ETMs-based solar cells,emphasizing on the fundamental and optimization issues of charge separation and collection ability,and their influence on PV performance.After sketching the classification and requirements for high-efficiency 1D nanostructured solar cells,we highlight the applicability of 1D TiO_(2)nanostructures in PSCs,including nanotubes,nanorods,nanocones,and nanopyramids,and carefully analyze how the electrostatic field affects cell performance.Other kinds of oriented nanostructures,e.g.,ZnO and SnO_(2)ETMs,are also described.Finally,we discuss the challenges and propose some potential strategies to further boost device performance.This review provides a broad range of valuable work in this fast-developing field,which we hope will stimulate research enthusiasm to push PSCs to an unprecedented level.

Inverted organic solar cells with solvothermal synthesized vanadium-doped TiO2 thin films as efficient electron transport layer

We investigated the effects of using different thicknesses of pure and vanadium-doped thin films of TiO2 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 TiO2nanoparticles were synthesized via the solvothermal method. Crystalline structure, morphology, and optical properties of pure and vanadium-doped TiO2 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 TiO2 thin films with thicknesses of 30 nm and 60 nm. The final results revealed that the best thickness of TiO2 thin films for our fabricated cells was 30 nm. The cell with vanadium-doped TiO2 thin film showed slightly higher power conversion efficiency and great Jsc of 10.7 mA/cm^2 compared with its pure counterpart. In the cells using 60 nm pure and vanadium-doped TiO2 layers, the cell using the doped layer showed much higher efficiency. It is remarkable that the external quantum efficiency of vanadium-doped TiO2 thin film was better in all wavelengths.

TiO_2 composite electron transport layers for planar perovskite solar cells by mixed spray pyrolysis with precursor solution incorporating TiO_2 nanoparticles

Perovskite solar cells with planar structure are attractive for their simplified device structure and reduced hysteresis effect. Compared to conventional mesoporous devices, TiO2 porous scaffold layers are removed in planar devices. Then, compact TiO2 electron transport layers take the functions of extracting electrons, transporting electrons, and blocking holes. Therefore, the properties of these compact TiO2 layers are important for the performance of solar cells. In this work, we develop a mixed spray pyrolysis method for producing compact TiO2 layers by incorporating TiO2 nanoparticles with dif- ferent size into the precursor solutions. For the optimized nanoparticle size of 60 nm, a power conversion efficiency of 16.7% is achieved, which is obviously higher than that of devices without incorporated nanoparticles （9.9%）. Further in- vestigation reveals that the incorporation of nanoparticles can remarkably improve the charge extraction and recombination processes.

Electron transport properties of TiO_2 shell on Al_2O_3 core in dye-sensitized solar cells

The performance of dye-sensitized solar cells （DSSCs） is strongly affected by the properties of semiconductor nanoparticles. In this work, we used TiO2 particles prepared by TiC14 hydrolysis n times on A1203 films （A/T（n））, and investigated morphology, photoelectric, and electron transport properties of A/T（n）. The TiO2 shell was composed of 10-20 nm nanoparticles and the number of nanoparticles increased with increasing TIC14 treatment times. The highest photoelectric conversion efficiency of 3.23% was obtained as A/T（4）. IMPS results indicated that electron transport rate was high enough to conduct current, and was not the dominating effect to limit the Jsc. Jsc was mainly determined by dye loading on TiO2 and the interconnection of TiO2. These may provide a new strategy for preparing semiconductor working electrodes for DSSC.

Highly soluble dendritic fullerene derivatives as electron transport material for perovskite solar cells

A series of shape-persistent polyphenylene dendritic C_(60)derivatives as the electron transport materials were designed and synthesized via a catalyst-free Diels-Alder[4+2]cycloaddition reaction.These increasing hyperbranched scaffolds could effectively enhance the solubility;notably,both first and second generation dendrimers,C_(60)-G1 and C_(60)-G2,demonstrated more than 5 times higher solubilities than pristine C_(60).Furthermore,both simulated and experimental data proved their promising solution-processabilities as electron-transporting layers(ETLs)for perovskite solar cells.As a result,the planar p-i-n structural perovskite solar cell could achieve a maximum power conversion efficiency of 14.7%with C_(60)-G2.

Alleviating Interfacial Recombination of Heterojunction Electron Transport Layer via Oxygen Vacancy Engineering for Efficient Perovskite Solar Cells Over 23%

Electron transport layer(ETL)is pivotal to charge carrier transport for PSCs to reach the Shockley-Queisser limit.This study provides a fundamental understanding of heterojunction electron transport layers(ETLs)at the atomic level for stable and efficient perovskite solar cells(PSCs).The bilayer structure of an ETL composed of SnO_(2) on TiO_(2) was examined,revealing a critical factor limiting its potential to obtain efficient performance.Alteration of oxygen vacancies in the TiO_(2) underlayer via an annealing process is found to induce manipulated band offsets at the interface between the TiO_(2) and SnO_(2) layers.In-depth electronic investigations of the bilayer structure elucidate the importance of the electronic properties at the interface between the TiO_(2) and SnO_(2) layers.The apparent correlation in hysteresis phenomena,including current density-voltage(J-V)curves,appears as a function of the type of band alignment.Density functional theory calculations reveal the intimate relationship between oxygen vacancies,deep trap states,and charge transport efficiency at the interface between the TiO_(2) and SnO_(2) layers.The formation of cascade band alignment via control over the TiO_(2) underlayer enhances device performance and suppresses hysteresis.Optimal performance exhibits a power conversion efficiency(PCE)of 23.45%with an open-circuit voltage(V_(oc))of 1.184 V,showing better device stability under maximum power point tracking compared with a staggered bilayer under one-sun continuous illumination.

TiO_2 nanoparticle-based electron transport layer with improved wettability for efficient planar-heterojunction perovskite solar cell

The electron transport layer （ETL） plays an important role in planar heterojunction perovskite solar cell （PSCs）, by affecting the light-harvesting, electron injection and transportation processes, and especially the crystal- lization of perovskite absorber. In this work, we utilized a commercial TKD-TiO2 nanoparticle with a small diameter of 6 nm for the first time to prepare a compact ETL by spin coating. The packing of small-size particles endowed TKD-TiO2 ETL an appropriate surface-wettability, which is beneficial to the crystallization of perovskite deposited via solution-processed method. The uniform and high-transmittance TKD-TiO2 films were successfully incorporated into PSCs as ETLs. Further careful optimization of ETL thickness gave birth to a highest power conversion efficiency of 11.0%, which was much higher than that of PSC using an ETL with the same thickness made by spray pyrolysis. This TKD-TiO2 provided a universal solar material suitable for the further large-scale production of PSCs. The excellent morphology and the convenient preparation method of TKD-TiO2 film gave it an extensive application in photovoltaic devices.

Cross-linked polyelectrolyte reinforced SnO_(2)electron transport layer for robust flexible perovskite solar cells

SnO_(2)electron transport layer(ETL)is a vital component in perovskite solar cells(PSCs),due to its excellent photoelectric properties and facile fabrication process.In this study,we synthesized a water-soluble and adhesive polyelectrolyte with ethanolamine(EA)and poly-acrylic acid(PAA).The linear PAA was crosslinked by EA,forming a 3D network that stabilized the SnO_(2)nanoparticle dispersion.An organic–inorganic hybrid ETL is developed by introducing the cross-linked PAA-EA into SnO_(2)ETL,which prevents nano particle agglomeration and facilitates uniform SnO_(2)film formation with fewer defects.Additionally,the PAA-EA-modified SnO_(2)facilitated a uniform and compact perovskite film,enhancing the interface contact and carrier transport.Consequently,the PAA-EA-modified PSCs exhibited excellent PCE of 24.34%and 22.88%with high reproducibility for areas of 0.045 and 1.00 cm~2,respectively.Notably,owing to structure reinforce effect of PAA-EA in SnO_(2)ETL,flexible device demonstrated an impressive PCE of 23.34%while maintaining 90.1%of the initial PCE after 10,000 bending cycles with a bending radius of 5 mm.This successful approach of polyelectrolyte reinforced hybrid organic–inorganic ETL displays great potential for flexible,large-area PSCs application.

SnO2-based electron transporting layer materials for perovskite solar cells: A review of recent progress

In recent years, due to their high photo-to-electric power conversion efficiency(PCE)(up to 23%(certified)) and low cost, perovskite solar cells(PSCs) have attracted a great deal of attention in photovoltaics field. The high PCE can be attributed to the excellent physical properties of organic–inorganic hybrid perovskite materials, such as a long charge diffusion length and a high absorption coefficient in the visible range. There are different diffusion lengths of holes in electrons in a PSC device, and thus the electron transporting layer(ETL) plays a critical role in the performance of PSCs. An alternative for TiO2, to the most common ETL material is SnO2, which has similar physical properties to TiO2 but with much higher electron mobility, which is beneficial for electron extraction. In addition, there are many facile methods to fabricate SnO2 nanomaterials with low cost and low energy consumption. In this review paper, we focus on recent developments in SnO2 as the ETL of PSCs. The fabrication methods of SnO2 materials are briefly introduced. The influence of multiple Sn O2 types in the ETL on the performance of PSCs is then reviewed. Different methods for improving the PCE and long-term stability of PSCs based on SnO2 ETL are also summarized. The review provides a systematic and comprehensive understanding of the influence of different Sn O2 ETL types on PSC performance and potentially motivates further development of PSCs with an extension to SnO2-based PSCs.

Inhibiting interfacial transport loss for efficient organic nonfullerene solar cells and photodetectors

Nonfullerene organic solar cells(OSCs) and photodetectors have received tremendous interest due to their rapidly progressed power conversion efficiency(PCE) and wide range photoresponse to nearinfrared region, respectively. Further optimization of the interfacial transport layer is one of the key factors toward enhanced performance. Herein, we reported a general multi-component electron transport layer(ETL) strategy to achieve better energy level alignments and interfacial contact for both OSCs and photodetectors. The binary polymer:molecule blend based ETL can overcome low crystallinity and selfaggregation issue in neat polymer and molecule ETL, respectively. The mixed blend provides a more tunable platform to optimize the interfacial morphology and creates more efficient charge-transporting pathways. We showcase that the PNDIT-F3N:PDINN binary ETL exhibits its strength in a series of nonfullerene OSCs with enhanced fill factor and current density, achieving a champion PCE approaching 19%. Additionally, self-powered organic photodetectors with lower dark current and high detectivity were achieved with the same binary ETL strategy. Detailed morphology and device characterizations reveal that the binary ETL modulates the interfacial interface to deliver a more favorable energy level alignment, facilitating carrier extraction and transport. We believe these findings could provide insight into the design of ETL with sufficient interfacial tunability for organic optoelectronic devices.

High-Performance Inverted Perovskite Solar Cells with Sol-Gel-Processed Sliver-Doped NiO_(x)Hole Transporting Layer

Nickel oxide(NiO_(x))has been established as a highly efficient and stable holetransporting layer(HTL)in perovskite solar cells(PSCs).However,existing deposition methods for NiO_(x)have been restricted by high-vacuum processes and fail to address the energy level mismatch at the NiO_(x)/perovskite interface,which has impeded the development of PSCs.Accordingly,we explored the application of NiO_(x)as a hybrid HTL through a sol-gel process,where a NiO_(x)film was pre-doped with Ag ions,forming a p/p^(+)homojunction in the NiO_(x)-based inverted PSCs.This innovative approach offers two synergistic advantages,including the enlargement of the built-in electric field for facilitating charge separation,optimizing energy level alignment,and charge transfer efficiency at the interface between the perovskite and HTL.Incorporating this hybrid HTL featuring the p/p^(+)homojunction in the inverted PSCs resulted in a high-power conversion efficiency(PCE)of up to 19.25%,significantly narrowing the efficiency gap compared to traditional n-i-p devices.Furthermore,this innovative strategy for the HTL enhanced the environmental stability to 30 days,maintaining 90%of the initial efficiency.

Simplified p-i-n Perovskite Solar Cells with a Multifunctional Polyfullerene Electron Transporter

In prevailing p-i-n perovskite solar cells(PSCs),solution-processible fullerene molecules are widely used as electron-transporting layers(ETLs)but they typically suffer from poor uniformity and undesirable stability issues.Additionally,a separate bathocuproine(BCP)layer is needed to block hole tran sfer,increasing fabrication complexity and cost.Here,we address these limitations by develo ping a novel polymeric ETL(named PF BCP)synthesized by polymerizing C_(60)with BCP.This innovative material achieves both efficient electron transport and hole blocking,while its excellent uniformity minimizes interface recombination and enhances stability.Consequently,our blade-coated PSCs utilizing PFBCP achieve a high power conversion efficiency exceeding 22%and retain 91%of initial efficiency after 1200 h of light exposure.This development not only paves the way for commercially viable PSCs but also opens avenues for future ETL design to realize even more efficient and stable PSCs.

Dimethyl acridine-based self-assembled monolayer as a hole transport layer for highly efficient inverted perovskite solar cells

Self-assembled monolayers(SAMs)have recently emerged as excellent hole transport materials in inverted perovskite solar cells(PSCs)owing to their ability to minimize parasitic absorption,regulate energy level alignment,and passivate perovskite defects.Herein,we design and synthesize a novel dimethyl acridinebased SAM,[2-(9,10-dihydro-9,9-dimethylacridine-10-yl)ethyl]phosphonic acid(2PADmA),and employ it as a hole-transporting layer in inverted PSCs.Experimental results show that the 2PADmA SAM can modulate perovskite crystallization,facilitate carrier transport,passivate perovskite defects,and reduce nonradiative recombination.Consequently,the 2PADmA-based device achieves an enhanced power conversion efficiency(PCE)of 24.01%and an improved fill factor(FF)of 83.92%compared to the commonly reported[2-(9H-carbazol-9-yl)ethyl]phosphonic acid(2PACz)-based control device with a PCE of 22.32%and FF of 78.42%,while both devices exhibit comparable open-circuit voltage and short-circuit current density.In addition,2PADmA-based devices exhibit outstanding dark storage and thermal stabilities,retaining approximately~98%and 87%of their initial PCEs after 1080 h of dark storage and 400 h of heating at 85°C,respectively,both considerably superior to the control device.

Bithiophene-based cost-effective hole transport materials for efficient n-i-p perovskite solar cells

Charge transport materials constitute a relatively large portion of the cost in the production of perovskite solar cells(PSCs).Therefore,developing cheap and efficient charge transport materials is of great significance for the commercialization of PSCs.In this study,three low-cost hole transport materials(HTMs),specifically 4,4'-(3,3'-bis(4-methoxy-2,6-dimethylphenyl)-[2,2'-bithiophene]-5,5'-diyl)bis(N,N-bis(4-methoxyphenyl)aniline)(TP-H),4,4'-(3,3'-bis(4-methoxy-2,6-dimethylphenyl)-[2,2'-bithiophene]-5,5'-diyl)bis(3-methoxy-N,N-bis(4-methoxy-phenyl)aniline)(TP-OMe),and 4,4'-(3,3'-bis(4-methoxy-2,6-dimethylphenyl)-[2,2'-bithiophene]-5,5'-diyl)bis(3-fluoro-N,N-bis(4-methoxyphenyl)aniline)(TP-F),were designed and synthesized using a bulky group-substi-tuted 2,2'-bithiophene core and methoxy-or F-functionalized triphenylamine derivatives.Compared to the HTMs without F atoms,TP-F using F substitution exhibited enhanced intermolecular packing,a lower highest occupied molecular orbital energy level,and increased hole mobility and conductivity.The PSC incorporating the doped TP-F as the hole transport layer achieved the highest power conversion efficiency(over 24%)among the three devices.The high performance of TP-F can be attributed to the passivation effect of S and F atoms on uncoordinated Pb2+within the perovskite(PVSK)film,which significantly reduces the density of defect states and the incidence of trap-mediated recombination in PSCs.This study demonstrates the effec-tiveness of the 3,3'-bis(4-methoxy-2,6-dimethylphenyl)-2,2'-bithiophene building block for constructing cost-effective HTMs and highlights the impact of F substitution on enhancing the photovoltaic performance of PSCs.

Thermally Evaporated ZnSe for Efficient and Stable Regular/Inverted Perovskite Solar Cells by Enhanced Electron Extraction

Electron transport layers(ETLs)are crucial for achieving efficient and stable planar perovskite solar cells(PSCs).Reports on versatile inorganic ETLs using a simple film fabrication method and applicability for both low-cost planar regular and inverted PSCs with excellent efficiencies(>22%)and high stability are very limited.Herein,we employ a novel inorganic ZnSe as ETL for both regular and inverted PSCs to improve the efficiency and stability using a simple thermal evaporation method.The TiO_(2)-ZnSe-FAPbl_(3)heterojunction could be formed,resulting in an improved charge collection and a decreased carrier recombination further proved through theoretical calculations.The optimized regular PSCs based on TiO_(2)/ZnSe have achieved 23.25%efficiency with negligible hysteresis.In addition,the ZnSe ETL can also effectively replace the unstable bathocuproine(BCP)in inverted PSCs.Consequently,the ZnSe-based inverted device realizes a champion efficiency of 22.54%.Moreover,the regular device comprising the TiO_(2)/ZnSe layers retains 92%of its initial PCE after 10:00 h under 1 Sun continuous illumination and the inverted device comprising the C_(60)/ZnSe layers maintains over 85%of its initial PCE at 85℃for 10:00 h.This highlights one of the best results among universal ETLs in both regular and inverted perovskite photovoltaics.