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.

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.

Solvents incubatedπ-πstacking in hole transport layer for perovskite-silicon 2-terminal tandem solar cells with 27.21%efficiency

Room temperature sputtered inorganic nickel oxide(NiO_(x))is one of the most promising hole transport layers(HTL)for perovskite-sillion 2-terminal tandem solar cells with the aid of ultrathin and compact organic layers to passivate the surface defects.In this study,the aromatic solvent with different substituent groups was used to regulate the conformation of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)am ine](PTAA)layer.As a result,the single-junction perovskite solar cell(PSC)gained a power conversion efficiency(PCE)of 20.63%,contributing to a 27.21%efficiency for monolithic perovskite/silicon(double-side polished)2-terminal tandem solar cell,by applying the alkyl aromatic solvent to enhance theπ-πstacking of PTAA molecular chains.The tandem solar cell can maintain 95%initial efficiency after aging over 1000 h.This study provides a universal approach for improving the photovoltaic performance of NiO_(x)/polymer-based perovskite/silicon tandem solar cells and other single junction inverted PSCs.

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.

Improving the performance of arylamine-based hole transporting materials in perovskite solar cells： Extending π-conjugation length or increasing the number of side groups？

In this work, we prepared three simple arylamine-based hole transporting materials from commercially available starting materials. The effect of extending z-conjugation length or increasing the number of side groups compared with reference compound on the photophysical, electrochemical, hole mobility properties and performance in perovskite solar cells were further studied. It is noted that these two kinds of molecular modifications can significantly lower the HOMO level and improve the hole mobility, thus improving the hole injection from valence band of perovskite. On the other hand, the compound with more side groups showed higher hole injection efficiency due to lower HOMO level and higher hole mo- bility compared with the compound with extending π-conjugation length. The perovskite solar cells with the modified molecules as hole transporting materials showed a higher efficiency of 15.40% and 16.95%, respectively, which is better than that of the reference compound （13.18%）. Moreover, the compound with increasing number of side groups based devices showed comparable photovoltaic performance with that of conventional spiro-OMeTAD （16.87%）.

Highly efficient perovskite solar cells based on symmetric hole transport material constructed with indaceno[1,2-b:5,6-b’]dithiophene core building block

Two novel hole transport materials (HTMs) with indaceno[1,2-b:5,6-b’]dithiophene (IDT) as core building blocks,termed IDT1 and IDT2,were designed and synthesized.The side alkyl chains were introduced to regulate and control the morphology and stacking behavior of HTMs,and the peripheral triarylamine arms were introduced to adjust the energy levels and to facilitate efficient hole transport.Applied in mesoporous structured perovskite solar cells (PSCs),HTM IDT1 achieved higher power conversion efficiency (PCE,19.55%) and better stability than Spiro-OMeTAD (19.25%) and IDT2 (15.77%) based PSC.These results suggest the potential of IDTl as a promising HTM for PSCs.

Diketopyrrolopyrrole based D-π-A-π-D type small organic molecules as hole transporting materials for perovskite solar cells

Three novel diketopyrrolopyrrole （DPP） based small organic molecules were synthesized as hole transporting materials for perovskite solar cells. The effects of different donors and zr bridges on the performance of perovskite solar cells （PSCs） were discussed. The efficiency of TPADPP-1, TPADPP-2. PTZDPP-2 was 5.10%, 9.85% and 8.16% respectively. Compared to TPADPP-2, the voltage of PTZDPP-2 was higher. Because the electron-donatingability of phenothiazine based donor was larger than that of triphenylamine based donor, the HOMO level of PTZDPP-2 was lower than that of TPADPP-2. The results indicated that the diketopyrrolopyrrole based D-π-A-π-D type small organic molecule might be a promising hole trans- porting material in the perovskite solar cells.

Novel hole transport layer of nickel oxide composite with carbon for high-performance perovskite solar cells

A depth behavioral understanding for each layer in perovskite solar cells （PSCs） and their inter[acial interactions as a whole has been emerged for further enhancement in power conversion efficiency （PCE）. Herein, NiO@Carbon was not only simulated as a hole transport layer but also as a counter electrode at the same time in the planar heterojunction based PSCs with the program wxAMPS （analysis of microelectronic and photonic structures）-lD. Simulation results revealed a high dependence of PCE on the effect of band offset between hole transport material （HTM） and perovskite layers. Meanwhile, the valence band offset （AEv） of NiO-HTM was optimized to be -0.1 to -0.3 eV lower than that of the perovskite layer. Additionally, a barrier cliff was identified to significantly influence the hole extraction at the HTM/absorber interface. Conversely, the AEv between the active material and NiO@Carbon-HTM was derived to be -0.15 to 0.15 eV with an enhanced efficiency from 15% to 16%.

The Hole Transport Characteristics of 1,4,5,8,9 and 11-Hexaazatriphenylene-Hexacarbonitrile by Blending

The hole transport characteristics of molecule blends of 1, 4, 5, 8, 9 and 11-hexaazatriphenylene-hexacarbonitrile （HAT-CN）： N,N＇-di（naphthalene-l-yl）-N,N＇-diphenyl-benzidine （NPB） and HAT-CN： 4,4＇-cyclohexylidenebis[N,N- bis（4-methylphenyl）benzenamine] （TAPC） with various NPB and TAPC mixing concentrations （5 90wt%） are studied. When the concentration is in the range of 5-80wt%, it is found that the hole conductions in the two blends are space-charge-limited current （SCLC） with free trap distributions. The current-voltage characteristics of the two blends show SCLC with exponentiM trap distributions at the concentration of 90wt%. The hole mo- bilities of the two blends are very close （10^-4-10^-3 cm2 V^-1 s-X ）, the dependence of electric field and temperature can be described by the modified Poole-Frenkel model. The hole mobility and activation energy of the two blends depending on concentration are similar.

Non-peripherally octaalkyl-substituted nickel phthalocyanines used as non-dopant hole transport materials in perovskite solar cells

This report presents two non-perihperally octaalkyl-substituted nickel phthalocyanines(NiPcs),namely,NiEt2Pc and NiPr_(2)Pc,for use as dopant-free hole transport materials in perovskite solar cells(PSCs).The length extension of the alkyl chains from ethyl to propyl significantly tunes the NiPcs’energy levels,thus reducing charge carrier recombination at the perovskite/hole transport layer(HTL)interface and leading to higher open-circuit voltage(VOC)and short-circuit current density(JSC)observed for the NiPr_(2)Pc-based PSC.And higher charge carrier mobility,higher thin film crystallinity,and lower surface roughness of the NiPr_(2)Pc HTL compared with that of the NiEt2Pc one also lead to higher JSC and fill factor(FF)observed for the NiPr_(2)Pc-based device.Consequently,the NiPr_(2)Pc-based PSC exhibits a higher power conversion efficiency(PCE)of 14.07%than that of the NiEt2Pc-based device(8.63%).

A novel phenoxazine-based hole transport material for efficient perovskite solar cell

Based on the previous research work in our laboratory, we have designed and synthesized a small-molecule, hole transport material （HTM） POZ6-2 using phenoxazine （POZ） as central unit and dicyanovinyl units as electron-withdrawing terminal groups. Through the introduction ofa 2-ethyl-hexyl bulky chain into the POZ core unit, POZ6-2 exhibits good solubility in organic solvents. In addition, POZ6-2 possesses appropriate energy levels in combination with a high hole mobility and conductivity in its pristine form. Therefore, it can readily be used as a dopant-flee HTM in perovskite solar cells （PSCs） and a conversion efficiency of 10.3% was obtained. The conductivity of the POZ6-2 layer can be markedly enhanced via doping in combination with typical additives, such as 4-tert-butylpyridine （TBP） and lithium bis（trifluoromethanesulfonyl） imide （LiTFS1）. Correspondingly, the efficiency of the PSCs was further improved to 12.3% using doping strategies. Under the same conditions, reference devices based on the well-known HTM Spiro-OMeTAD show an efficiency of 12.8%.

Multiple methoxy-substituted hole transporter for inverted perovskite solar cells

Inverted organic-inorganic hybrid perovskite solar cells(i-PSC)with low temperature processed interlayers and weak hysteresis behaviors have shown great potential for commercialization[1-5].However,their relatively lower power conversion efficiency(PCE)and inferior reproducibility than conventional PSCs limit further developments.These problems are largely determined by the hole transporting layer(HTL)and the quality of the upper perovskite film[6-8];in particular,the latter is considerably influenced by the surface property of the underlying HTL.

Heteroatom engineering on spiro-type hole transporting materials for perovskite solar cells

A series of spiro-type hole transporting materials, spiro-OMe TAD, spiro-SMe TAD and spiro-OSMe TAD,with methoxy, methylsulfanyl or half methoxy and half methylsulfanyl terminal groups are designed and prepared. The impact of varied terminal groups on bulk properties, such as photophysical, electrochemical, thermal, hole extraction, and photovoltaic performance in perovskite solar cells is investigated.It is noted that the terminal groups of the hole transporting material with half methoxy and half methylsulfanyl exhibit a better device performance and decreased hysteresis compared with all methoxy or methylsulfanyl counterparts due to better film-forming ability and improved hole extraction capability.Promisingly, the spiro-OSMe TAD also shows comparable performance than high-purity commercial spiro-OMe TAD. Moreover, the highest power conversion efficiency of the optimized device employing spiro-OSMe TAD exceeding 20% has been achieved.

Decorating hole transport material with −CF_(3) groups for highly efficient and stable perovskite solar cells

The hole transport material (HTM) plays an extremely important role to determine the power conversion efficiency (PCE) and the stability of perovskite solar cells (PSCs). Herein, we report an effective strategy to improve the performance of HTMs by introducing −CF_(3) groups via the rational decorative mode. Upon direct attachment or nonconjugated alkoxyl bridging of −CF_(3) groups on the terminal diphenylamines, the resulting molecular HTMs, i.e., 2,7-BCzA4CF_(3) and 2,7-BCzA4OCCF_(3), show distinct properties. Compared with 2,7-BCzA4CF_(3), the nonconjugated alkoxyl bridging −CF_(3) group-based 2,7-BCzA4OCCF_(3) exhibits better thermal stability, hydrophobicity, and a dramatically upgraded hole mobility by 135.7-fold of magnitude to 1.71 × 10^(−4) cm^(2) V^(−1) S^(−1). The PSCs with 2,7-BCzA4OCCF_(3) as HTM exhibit an PCE of up to 20.53% and excellent long-term stability, maintaining 92.57% of their performance for 30 days in air with humidity of 30% without encapsulation. This work provides beneficial guidelines for the design of new HTMs for efficient and stable PSCs.

Enhanced Photovoltage for Inverted Perovskite Solar Cells Using Delafossite CuCrO_(2) Hole Transport Material

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS)has been widely adopted as hole transport material(HTM)in inverted perovskite solar cells(PSCs),due to high optical transparency,good mechanical flexibility,and high thermal stability;however,its acidity and hygroscopicity inevitably hamper the long-term stability of the PSCs and its energy level does not match well with perovskite materials with a relatively low open-circuit voltage.In this work,p-type delafossite CuCrO_(2)nanoparticles synthesized through hydrothermal method was employed as an alternative HTM for triple cation perovskite[(FAPbI_(3))_(0.87)(MAPbBr_(3))_(0.13)]_(0.92)(CsPbI_(3))_(0.08)(possessing better photovoltaic performance and stability than conventional CH3NH3PbI3)based inverted PSCs.The average open-circuit voltage of PSCs increases from 908 mV of the devices with PEDOT:PSS HTM to 1020 m V of the devices with CuCrO_(2)HTM.Ultraviolet photoemission spectroscopy demonstrates the energy band alignment between CuCrO_(2)and perovskite is better than that between PEDOT:PSS and perovskite,the electrochemical impedance spectroscopy indicates CuCrO_(2)-based PSCs exhibit larger recombination resistance and longer charge carrier lifetime than PEDOT:PSS-based PSCs,which contributes to the high VOCof CuCrO_(2)HTM-based PSCs.

C≡N-based carbazole-arylamine hole transporting materials for perovskite solar cells: Substitution position matters

Hole transporting materials(HTMs)containing passivating groups for perovskite materials have attracted much attention for efficient and stable perovskite solar cells(PSCs).Among them,C≡N-based molecules have been proved as efficient HTMs.Herein,a series of novel C≡N functionalized carbazole-arylamine derivatives with variable C≡N substitution positions(para,meta,and ortho)on benzene-carbazole skeleton(on the adjacent benzene of carbazole)were synthesized(p-HTM,m-HTM and o-HTM).The experimental results exhibit that the substitution positions of the Ctriple bondN unit on HTMs have minor difference on the HOMO energy level and hydrophobicity.m-HTM has a relatively lower glass transition temperature compared with that of p-HTM and o-HTM.The functional theory calculations show that the C≡N located on meta position exposed very well,and the exposure direction is also the same with the methoxy.Upon applying these molecules as HTMs in PSCs,their device performance is found to sensitively depend on the substitution position of the C≡N unit on the molecule skeleton.The devices using m-HTM and o-HTM exhibit better performance than that of p-HTM.Moreover,m-HTM-based devices exhibit better light-soaking performance and long-term stability,which could be resulted from better interaction with the perovskite according to DFT results.Moreover,we further prepared a HTM with two C≡N units on the symmetrical meta position of molecular skeleton(2m-HTM).Interestingly,2m-HTM-based devices exhibit relatively inferior performance compared with that of the m-HTM,which could be resulted from weak negative electrical character of C≡N unit on 2m-HTM.The results give some new insights for designing ideal HTM for efficient and stable PSCs.

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.

D-π-D molecular layer electronically bridges the NiO_(x) hole transport layer and the perovskite layer towards high performance photovoltaics

Nickel oxide (NiO_(x)) has significant cost and stability advantages over poly[bis (4-phenyl)(2,4,6-trimethyl phenyl)amine](PTAA) for inverted p-i-n perovskite solar cells (PSCs),but the poor NiO_(x)/perovskite contact stemming from some reactive species at the interface led to suboptimal device performance.To solve this problem,we take a multiple donor molecule approach,using 3,3’-(4,8-bis(hexylthio)benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl)bis(10-(6-bromohexyl)-10H-phenoxazine)(BDT-POZ) as an example,to modify the NiO_(x)/perovskite interface.The primary goal was to reduce the under-coordinated Ni^(≥3+) cations via electron transfer from the donor molecules to NiO_(x),thus mitigating the detrimental reactions between perovskite and NiO_(x).Equally importantly,the hole extraction at the interface was greatly enhanced after the organic donor modification,since the hydrophobic species atop NiO_(x) not only enabled pinhole-free crystallization of the perovskite but also properly tuned the interfacial energy level alignment.Consequently,the PSCs with NiO_(x)/BDT-POZ HTL achieved a high power conversion efficiency (PCE) up to 20.16%,which compared excellently with that of the non-modified devices (17.83%).This work provides a new strategy to tackle the exacting issues that have so far impeded the development of NiO_(x) based 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.

Pyridine-triphenylamine hole transport material for inverted perovskite solar cells

In the light of superior interaction between pyridine unit and perovskite,a facile star-shaped triphenylamine-based hole transport material(HTM)incorporating pyridine core(coded as H-Pyr)is designed and synthesized.A reference HTM with benzene core,coded as H-Ben,is also prepared for a comparative study.The effects of varying core on HTMs are investigated by comparing the photophysical,electrochemical and hole mobility properties.It is found that pyridine core exhibits better conjunction and decreased dihedral angles with triphenylamine side arms than that of benzene,leading to obviously better hole mobility and well-matched work function.The perovskite film prepared on H-Pyr also shows improved crystallization than on H-Ben.Photoluminescence and electrochemical impedance studies indicate improved charge extraction and reduced recombination in the H-Pyr-based perovskite solar cells.Consequently,H-Pyr-based device exhibits higher efficiency than H-Ben-based one.After doping with a Lewis acid,tris(pentafluorophenyl)borane,H-Pyr-based device delivers a champion efficiency of 17.09%,which is much higher compared with 12.14% of the device employing conventional poly(3,4-ethy lenedioxythiophene)polystyrene sulfonate(PEDOT:PSS)as HTM.Moreover,the H-Pyr-based device displays good long-term stability that the power conversion efficiency remains over 80% of the initial value after storage in ambient(relative humidity=50±5%)for 20 days.