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.

Amorphous BaTiO_(3) Electron Transport Layer for Thermal Equilibrium-Governed γ-CsPbl_(3) Perovskite Solar Cell with High Power Conversion Efficiency of 19.96%

Compared to organic-inorganic hybrid perovskites,the cesium-based allinorganic lead halide perovskite(CsPbI_(3))is a promising light absorber for perovskite solar cells owing to its higher resistance to thermal stress.Nonetheless,additional research is required to reduce the nonradiative recombination to realize the full potential of CsPbI_(3).Here,the diffusion of Cs ions participating in ion exchange is proposed to be an important factor responsible for the bulk defects inγ-CsPbI_(3)perovskite.Calculations based on first-principles density functional theory reveal that the[PbI_(6)]^(4-)octahedral tilt modifies the perovskite crystallographic properties inγ-CsPbI_(3),leading to alterations in its bandgap and crystal strain.In addition,by substituting amorphous barium titanium oxide(a-BaTiO_(3))for TiO_(2)as the electron transport layer,interfacial defects caused by imperfect energy levels between the electron transport layer and perovskite are reduced.High-resolution transmission electron microscopy and electron energy loss spectroscopy demonstrate that a-BaTiO_(3)forms entirely as a single phase,as opposed to Ba-doped TiO_(2)hybrid nanoclusters or separate domains of TiO_(2)and BaTiO_(3)phases.Accordingly,inorganic perovskite solar cells based on the a-BaTiO_(3)electron transport layer achieved a power conversion efficiency of 19.96%.

Gelation of Hole Transport Layer to Improve the Stability of Perovskite Solar Cells

To achieve high power conversion efficiency(PCE) and long-term stability of perovskite solar cells(PSCs), a hole transport layer(HTL) with persistently high conductivity, good moisture/oxygen barrier ability, and adequate passivation capability is important. To achieve enough conductivity and effective hole extraction, spiro-OMe TAD, one of the most frequently used HTL in optoelectronic devices, often needs chemical doping with a lithium compound(LiTFSI). However, the lithium salt dopant induces crystallization and has a negative impact on the performance and lifetime of the device due to its hygroscopic nature. Here, we provide an easy method for creating a gel by mixing a natural small molecule additive(thioctic acid, TA) with spiro-OMe TAD. We discover that gelation effectively improves the compactness of resultant HTL and prevents moisture and oxygen infiltration. Moreover, the gelation of HTL improves not only the conductivity of spiro-OMe TAD, but also the operational robustness of the devices in the atmospheric environment. In addition, TA passivates the perovskite defects and facilitates the charge transfer from the perovskite layer to HTL. As a consequence, the optimized PSCs based on the gelated HTL exhibit an improved PCE(22.52%) with excellent device stability.

Tailored PEDOT:PSS hole transport layer for higher performance in perovskite solar cells: Enhancement of electrical and optical properties with improved morphology

Precise control over the charge carrier dynamics throughout the device can result in outstanding performance of perovskite solar cells(PSCs).Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)is the most actively studied hole transport material in p-i-n structured PSCs.However,charge transport in the PEDOT:PSS is limited and inefficient because of its low conductivity with the presence of the weak ionic conductor PSS.In addition,morphology of the underlying PEDOT:PSS layer in PSCs plays a crucial role in determining the optoelectronic quality of the active perovskite absorber layer.This work is focused on realization of a non-wetting conductive surface of hole transport layer suitable for the growth of larger perovskite crystalline domains.This is accomplished by employing a facile solventengineered(ethylene glycol and methanol)approach resulting in removal of the predominant PSS in PEDOT:PSS.The consequence of acquiring larger perovskite crystalline domains was observed in the charge carrier dynamics studies,with the achievement of higher charge carrier lifetime,lower charge transport time and lower transfer impedance in the solvent-engineered PEDOT:PSS-based PSCs.Use of this solventengineered treatment for the fabrication of MAPbI3 PSCs greatly increased the device stability witnessing a power conversion efficiency of 18.18%,which corresponds to^37%improvement compared to the untreated PEDOT:PSS based devices.

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.

Improved performance of organic light-emitting diodes with dual electron transporting layers

In this study the performance of organic light-emitting diodes （OLEDs） are enhanced significantly, which is based on dual electron transporting layers （13phen/CuPc）. By adjusting the thicknesses of Bphen and CuPc, the maximal luminescence, the maximal current efficiency, and the maximal power efficiency of the device reach 17570 cd/m^2 at 11 V, and 5.39 cd/A and 3.39 lm/W at 3.37 mA/cm^2 respectively, which are enhanced approximately by 33.4%, 39.3%, and 68.9%, respectively, compared with those of the device using Bphen only for an electron transporting layer. These results may provide some valuable references for improving the electron injection and the transportation of OLED.

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.

TTA as a potential hole transport layer for application in conventional polymer solar cells

Hole transport layers(HTLs)play a vital role in organic solar cells(OSCs).In this work,a derivative of tetrathiafulvalene with four carboxyl groups TTA was introduced as a novel HTL to fabricate OSC with high performance.Displaying a better energy level match between HTL and active layers,the TTA based devices show a peak power conversion efficiency of 9.09%,which is comparable to the devices based on PEDOT:PSS.The favorable surface morphology recorded via atomic force microscopy,low series loss and charge recombination indicated by electrochemical impedance spectroscopy,synchronously verify the potential of TTA for application in OSCs as a valid kind of HTLs.

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.

TiO_(2)/SnO_(2)electron transport double layers with ultrathin SnO_(2)for efficient planar perovskite solar cells

The electron transport layer(ETL)plays an important role on the performance and stability of perovskite solar cells(PSCs).Developing double ETL is a promising strategy to take the advantages of different ETL materials and avoid their drawbacks.Here,an ultrathin SnO_(2)layer of~5 nm deposited by atomic layer deposit(ALD)was used to construct a TiO_(2)/SnO_(2)double ETL,improving the power conversion efficiency(PCE)from 18.02%to 21.13%.The ultrathin SnO_(2)layer enhances the electrical conductivity of the double layer ETLs and improves band alignment at the ETL/perovskite interface,promoting charge extraction and transfer.The ultrathin SnO_(2)layer also passivates the ETL/perovskite interface,suppressing nonradiative recombination.The double ETL achieves outstanding stability compared with PSCs with TiO_(2)only ETL.The PSCs with double ETL retains 85%of its initial PCE after 900 hours illumination.Our work demonstrates the prospects of using ultrathin metal oxide to construct double ETL for high-performance PSCs.

Charge transfer modification of inverted planar perovskite solar cells by NiO_(x)/Sr:NiO_(x)bilayer hole transport layer

Perovskite solar cells(PSCs) are the most promising commercial photoelectric conversion technology in the future.The planar p–i–n structure cells have advantages in negligible hysteresis, low temperature preparation and excellent stability.However, for inverted planar PSCs, the non-radiative recombination at the interface is an important reason that impedes the charge transfer and improvement of power conversion efficiency. Having a homogeneous, compact, and energy-levelmatched charge transport layer is the key to reducing non-radiative recombination. In our study, NiO_(x)/Sr:NiO_(x)bilayer hole transport layer(HTL) improves the holes transmission of NiO_(x)based HTL, reduces the recombination in the interface between perovskite and HTL layer and improves the device performance. The bilayer HTL enhances the hole transfer by forming a driving force of an electric field and further improves J_(sc). As a result, the device has a power conversion efficiency of 18.44%, a short circuit current density of 22.81 m A·cm^(-2) and a fill factor of 0.80. Compared to the pristine PSCs, there are certain improvements of optical parameters. This method provides a new idea for the future design of novel hole transport layers and the development of high-performance solar cells.

Highly efficient bifacial semitransparent perovskite solar cells based on molecular doping of CuSCN hole transport layer

Coper thiocyanate(CuSCN)is generally considered as a very hopeful inorganic hole transport material(HTM)in semitransparent perovskite solar cells(ST-PSCs)because of its low parasitic absorption,high inherent stability,and low cost.However,the poor electrical conductivity and low work function of CuSCN lead to the insufficient hole extraction and large open-circuit voltage loss.Here,2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane(F4TCNQ)is employed to improve conductivity of CuSCN and band alignment at the CuSCN/perovskite(PVK)interface.As a result,the average power conversion efficiency(PCE)of PSCs is boosted by≈11%.In addition,benefiting from the superior transparency of p-type CuSCN HTMs,the prepared bifacial semitransparent n-i-p planar PSCs demonstrate a maximum efficiency of 14.8%and 12.5%by the illumination from the front side and back side,respectively.We believe that this developed CuSCN-based ST-PSCs will promote practical applications in building integrated photovoltaics and tandem solar cells.

Improvement of Performance of Organic Light-Emitting Diodes with Both a MoO3 Hole Injection Layer and a MoO3 Doped Hole Transport Layer

We improve the performance of organic light-emitting diodes （OLEDs） with both a MoO3 hole injection layer （HIL） and a MoO3 doped hole transport layer （HTL）, and present a systematical and comparative investigation on these devices. Compared with OLEDs with only MoO3 HIL or MoO3 doped HTL, OLEDs with both MoO3 HIL and MoO3 doped HTL show superior performance in driving voltage, power efficiency, and stability. Based on the typical NPB/Alq3 heterojunction structure, OLEDs with both MoO3 HIL and MoO3 doped HTL show a driving voltage of 5.4 V and a power efficiency of 1.41 lm/W for 1000 cd/m2, and a lifetime of around 0. 88 h with an initial luminance of 5268 cd/m2 under a constant current of 190 mA/cm2 operation in air without encapsulation. While OLEDs with only MoO3 HIL or MoO3 doped HTL show higher driving voltages of 6.4 V or 5.8 V and lower power efficiencies of 1.201m/W or 1.341m/W for 1000cd/m2, and a shorter lifetime of 0.33 or 0.60h with an initial luminance of around 5122 or 5300cd/m2 under a constant current of 200 or 216mA/cm2 operation. Our results demonstrate clearly that using both MoO3 HIL and MoO3 doped HTL is a simple and effective approach to simultaneoasly improve both the hole injection and transport efficiency, resulting from the lowered energy barrier at the anode interface and the increased hole carrier density in MoO3 doped HTL.

Fabrication of Perovskite-Type Photovoltaic Devices with Polysilane Hole Transport Layers

Perovskite-type photovoltaic devices with polysilane hole transport layers were fabricated by a spin-coating method. In the present work, poly(methyl phenylsilane) (PMPS) and decaphenylcyclopentasilane (DPPS) were used as the hole transport layers. First, structural and optical properties of the PMPS and DPPS films were investigated, and the as-prepared PMPS and DPPS films were amorphous. Optical absorption spectra of the amorphous PMPS and DPPS showed some marked features due to the nature of polysilanes. Then, microstructures, optical and photovoltaic properties of the perovskite-type photovoltaic devices with polysilane hole transport layers were investigated. Current density-voltage characteristics and incident photon to current conversion efficiency of the photovoltaic devices with the polysilane layers showed different photovoltaic performance each other, attributed to molecular structures of the polysilanes and Si content in the present hole transport layers.

Increased performance of an organic light-emitting diode by employing a zinc phthalocyanine based composite hole transport layer

We demonstrate that the electroluminescent performances of organic light-emitting diodes are significantly improved by employing a zinc phthalocyanine （ZnPc）-based composite hole transport layer （c-HTL）. The optimum ris-（8-hydroxyquinoline）aluminum （Alq3）-based organic light-emitting diode with a c-HTL exhibits a lower turn-on voltage of 2.8 V, a higher maximum current efficiency of 3.40 cd/A and a higher maximum power efficiency of 1.91 lm/W, which are superior to those of the conventional device （turn-on voltage of 3.8 V, maximum current efficiency of 2.60 cd/A, and maximum power efficiency of 1.21 lm/W）. We systematically studied the effects of different kinds of N’-diphenyl-N,N’-bis（1-naphthyl）（1,1’-biphenyl）-4,4’diamine （NPB）：ZnPc c-HTL. Meanwhile, we also investigate their mechanisms different from that in the case of using ZnPc as buffer layer. The specific analysis is based on the absorption spectra of the hole transporting material and current density–voltage characteristics of the corresponding hole-only devices.

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.

Optical and NH₃Gas Sensing Properties of Hole-Transport Layers Based on PEDOT: PSS Incorporated with Nano-TiO₂

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) incorporated with nanocrystalline TiO2 powder (PEDOT:PSS+nc-TiO2) films were prepared by spin-coating technique. SEM surface morphology, UV-Vis spectra and NH3 gas sensing of were studied. Results showed that the PEDOT:PSS+nc-TiO2 film with a content of 9.0 wt% of TiO2 is most suitable for both the hole transport layer and the NH3 sensing. The responding time of the sensor made from this composite film reached a value as fast as 20 s. The rapid responsiveness to NH3 gas was attributed to the efficient movement of holes as the major charge carriers in PEDOT:PSS+nc-TiO2 composite films. Useful applications in organic electronic devices like light emitting diodes and gas thin film sensors can be envisaged.

Stabilizing semi-transparent perovskite solar cells with a polymer composite hole transport layer

Semi-transparent perovskite solar cells(ST-PSCs)have broad applications in building integrated photovoltaics.However,the stability of ST-PSCs needs to be improved,especially in n-i-p ST-PSCs since the doped 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene(Spiro-OMeTAD)is unstable at elevated temperatures and high humidity.In this work,aπ-conjugated polymer poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophene-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)](PBDB-T)is selected to form a polymer composite hole transport layer(HTL)with Spiro-OMeTAD.The sulfur atom of the thiophene unit and the carbonyl group of the polymer interact with the undercoordinated Pb2+at the perovskite surface,which stabilizes the perovskite/HTL interface and passivates the interfacial defects.The incorporation of the polymer also increases the glass transition temperature and the moisture resistance of Spiro-OMeTAD.As a result,we obtain ST-PSCs with a champion efficiency of 13.71%and an average visible light transmittance of 36.04%.Therefore,a high light utilization efficiency of 4.94%can be obtained.Moreover,the encapsulated device can maintain 84%of the initial efficiency after 751 h under continuous one-sun illumination(at 30%relative humidity)at the open circuit and the unencapsulated device can maintain 80%of the initial efficiency after maximum power tracking for more than 1250 h under continuous one-sun illumination.

Recent advances of Cu-based hole transport materials and their interface engineering concerning different processing methods in perovskite solar cells

In recent years, perovskite solar cells (PSCs) have become a much charming photovoltaic technology and have triggered enormous studies worldwide, owing to their high efficiency, low cost and ease of preparation. The power conversion efficiency has rapidly increased by more than 6 times to the current 25.5% in the past decade. Hole transport materials (HTMs) are an indispensable part of PSCs, which great affect the efficiency, the cost and the stability of PSCs. Inorganic Cu-based p-type semiconductors are a kind of representative inorganic HTMs in PSCs due to their unique advantages of rich variety, low cost, excellent hole mobility, adjustable energy levels, good stability, low temperature and scalable processing ability. In this review, the research progress in new materials and the control of photoelectric properties of Cu-based inorganic HTMs were first summarized systematically. And then, concerning different processing methods, advances of the interface engineering of Cu-based hole transport layers (HTLs) in PSCs were detailly discussed. Finally, the challenges and future trends of Cu-based inorganic HTMs and their interface engineering in PSCs were analyzed.