Bandgap narrowing in the layered oxysulfide semiconductor Ba_3Fe_2O_5Cu_2S_2: Role of FeO_2 layer

A new layered Cu-based oxychalcogenide Ba_3Fe_2O_5Cu_2S_2 has been synthesized and its magnetic and electronic properties were revealed. Ba_3Fe_2O_5Cu_2S_2 is built up by alternatively stacking [Cu_2S_2]^（2-） layers and iron perovskite oxide[（FeO_2）（BaO）（FeO_2）]^（2-）layers along the c axis that are separated by barium ions with Fe^（3＋） fivefold coordinated by a square-pyramidal arrangement of oxygen. From the bond valence arguments, we inferred that in layered CuC h-based（Ch =S, Se, Te） compounds the ＋3 cation in perovskite oxide sheet prefers a square pyramidal site, while the lower valence cation prefers the square planar sites. The studies on susceptibility, transport, and optical reflectivity indicate that Ba_3Fe_2O_5Cu_2S_2 is an antiferromagnetic semiconductor with a Ne′el temperature of 121 K and an optical bandgap of 1.03 eV. The measurement of heat capacity from 10 K to room temperature shows no anomaly at 121 K. The Debye temperature is determined to be 113 K. Theoretical calculations indicate that the conduction band minimum is predominantly contributed by O 2p and 3 d states of Fe ions that antiferromagnetically arranged in FeO_2 layers. The Fe 3d states are located at lower energy and result in a narrow bandgap in comparison with that of the isostructural Sr_3Sc_2O_5Cu_2S_2.

Considerations of dopant-dependent bandgap narrowing for accurate device simulation in abrupt HBTs

Heavy doping of the base in HBTs brings about a bandgap narrowing （BGN） effect, which modifies the intrinsic carrier density and disturbs the band offset, and thus leads to the change of the currents. Based on a thermionic-field-diffusion model that is used to the analyze the performance of an abrupt HBT with a heavydoped base, the conclusion is made that, although the BGN effect makes the currents obviously change due to the modification of the intrinsic carrier density, the band offsets disturbed by the BGN effect should also be taken into account in the analysis of the electrical characteristics of abrupt HBTs. In addition, the BGN effect changes the bias voltage for the onset of Kirk effects.

Accurate structural descriptor enabled screening for nitrogen and oxygen vacancy codoped TiO_(2) with a large bandgap narrowing

Nitrogen(N)doping has been widely adopted to improve the light absorption of TiO_(2).However,the newly introduced N-2p states are largely localized thus barely overlap with O-2p states in the valence band of TiO_(2),resulting in a shoulder-like absorption edge.To realize an apparent overlap between N-2p and O-2p states,charge compensation between N^(3-)and O^(2-)via electron transfer from oxygen vacancies(VO)to N dopants is one possible strategy.To verify this,in numerous doping configurations of N/VO-codoped anatase TiO_(2),we identified two types of VOposition independent N-dopant spatial orderings by efficient screening enabled with a newly designed structural descriptor.Compared with others,these two types of the N-dopant spatial orderings are highly beneficial for charge compensation to produce an apparent overlap between N-2p and O-2p states,therefore achieving a large bandgap narrowing.Furthermore,the two types of the N-dopant spatial orderings can also be generalized to N/VO-codoped rutile TiO_(2)for bandgap narrowing.

Eco-friendly glucose assisted structurally simplified high-efficiency tin-lead mixed perovskite solar cells

Achieving highly-efficient and stable perovskite solar cells(PSCs) with a simplified structure remains challenging, despite the tremendous potential for reducing preparation cost and facile processability by removing hole transport layer(HTL). In this work, eco-friendly glucose(Gl) as an interface modifier for HTL-free narrow bandgap tin-lead(Sn-Pb) PSCs is proposed. Gl not only enhances the wettability of the indium tin oxide to promote perovskite heterogeneous nucleation on substrate, but also realizes defect passivation by interacting with uncoordinated Pb^(2+) and Sn^(2+) in perovskite films. As a result, the quality of the perovskite films has been significantly improved, accompanied by reduced defects of bottom interface and optimized energy level structure of device, leading to an efficiency increase and a less nonradiative voltage loss of 0.102 V(for a bandgap of ~1.26 eV). Consequently, the optimized PSC delivers an unprecedented efficiency over 21% with high open-circuit voltage and enhanced stability, outperforming the control device. This work demonstrates a cost-effective approach to develop simplified structure high efficiency HTL-free Sn-Pb PSC.

Crystallization Regulation and Morphological Evolution for HTM-free Tin-Lead (1.28eV) Alloyed Perovskite Solar Cells

There have been huge achievements of all-perovskite tandem solar cells,which recently realized the highest power conversion efficiency of 24.8%.However,the complex device structure and complicated manufacture processes severely restrict the further development of all-perovskite tandem solar cells.In this work,we successfully fabricated high-efficiency hole transport material-free(HTM-free)Sn−Pb alloyed narrow bandgap perovskite solar cells(PSCs)by introducing guanidinium thiocyanate(GASCN)and hydroiodic acid(HI)into the perovskite precursor solution.GASCN and HI play a positive synergy effect during perovskite crystallization process resulting in larger grain size,fewer surface defects,and lower trap density to suppress the Sn^(2+)oxidation degradation.Furthermore,they could effectively adjust the energy level of perovskite materials,reduce the energy level difference between perovskite and ITO resulting in more efficiently transport of free hole charge carriers.As a result,with adding GASCN and HI,the achieved highest power conversion efficiency of HTM-free devices increased from 12.58%to 17.85%,which is one of the highest PCEs among all values reported to date for the HTM-free narrow-bandgap(1.2-1.4 eV)Sn−Pb binary PSCs.Moreover,the optimized device shows improved environmental stability.Our additive strategy manifests a remarkable step towards the facile,cost-efficient fabrication of HTM-free perovskite-based tandem solar cells with both high efficiency and simple fabrication process.

Core-shell particles of C-doped CdS and graphene: A noble metal-free approach for efficient photocatalytic H_(2) generation

To achieve efficient photocatalytic H_(2) generation from water using earth-abundant and cost-effective materials,a simple synthesis method for carbon-doped CdS particles wrapped with graphene(C-doped CdS@G)is reported.The doping effect and the application of graphene as cocatalyst for CdS is studied for photocatalytic H_(2) generation.The most active sample consists of CdS and graphene(CdS-0.15G)exhibits promising photocatalytic activity,producing 3.12 mmol g^-(1) h^-(1) of H_(2) under simulated solar light which is^4.6 times superior than pure CdS nanoparticles giving an apparent quantum efficiency(AQY)of 11.7%.The enhanced photocatalytic activity for H_(2) generation is associated to the narrowing of the bandgap,enhanced light absorption,fast interfacial charge transfer,and higher carrier density(N_(D))in C-doped CdS@G samples.This is achieved by C doping in CdS nanoparticles and the formation of a graphene shell over the C-doped CdS nanoparticles.After stability test,the spent catalysts sample was also characterized to investigate the nanostructure.

Design and Synthesis of Acceptor-Donor-Acceptor Type Non-Fullerene Acceptors Using Oxindole-Based Bridge for Polymer Solar Cells Applications

Two acceptor-donor-acceptor(A-D-A)type non-fullerene acceptors(namely WH1 and WH7)containing the oxindole-based bridge are designed and synthesized for polymer solar cells(PSCs)applications.The bridge unit is introduced through a precursor(6-bromo-1-octylindoline-2,3-dione)that contains both bromine and carbonyl and provides the feasibility of the Pd-catalyzed cross-coupling reaction and the Knoevenagel condensation,respectively.This facile synthetic approach exhibits the potential to gain high performance non-fullerene acceptors through extendingπ-conjugated backbone with strong light-absorbing building blocks.The synthesis and properties of WH1 and WH7 are demonstrated with different endcap units,then PSCs are fabricated using PBDB-T:WH1 and PBDB-T:WH7 as the active layers,and attain an average power conversion efficiency(PCE)of 2.58%and 6.24%,respectively.Further device physics studies afford the deep insight of structure variation influence on the device performance.This work provides a facile non-fullerene acceptor design strategy and shows how structure variations impact the PSC performance.

An n-Type All-Fused-Ring Molecule with Narrow Bandgap

All-fused-ringπ-conjugated molecules have received considerable attention because of their unique electronic structures,low conformation disorder,and excellent optoelectronic properties.Most all-fused-ring molecules are p-type organic semiconductors and possess medium bandgaps.In this work,we design and synthesize an all-fused-ring molecule(FM1)with an n-type property and narrow bandgap,which is a 10-fused-ring system composed of one electrondeficient benzotriazole core,two electron-rich thienopyrrole bridging units,and two electron-deficient malononitrile-functionalized end-cappers.FM1 exhibits low-lying highest occupied molecular orbit/lowest unoccupied molecular orbit energy levels of−5.77 eV/−3.89 eV,high electron mobility of 6.0×10^(−4)cm^(2)V^(−1)s^(−1),an optical bandgap of 1.50 eV,and a maximum absorption wavelength of 769nm.Because of the all-fused-ring skeleton,FM1 shows superior photostability and chemical stability.We use FM1 as an electron acceptor and successfully construct organic solar cell(OSC)devices with a decent power conversion efficiency(PCE)of 10.8%.Most importantly,the intrinsic stability of FM1 leads to its excellent OSC device stability.After irradiation with simulated solar light for 16 h,while control of the OSC device of the state-of-the-art small molecule electron acceptor shows a 46%decrease of PCE,the FM1’s unencapsulated OSC device exhibits only a 9%decrease of PCE.

Ga/GaSb nanostructures:Solution-phase growth for highperformance infrared photodetection

Gallium antimonide(GaSb)-based nanostructures have been reported via various vapor-phase synthetic routes while there is not a report on the growth of GaSb nanostructures via a complete one-step solution-phase synthetic strategy.Herein we report the design and synthesis of tadpole-like Ga/GaSb nanostructures by a one-step solution-phase synthetic route typically from the precursors of commercial triphenyl antimony(Sb(Ph)_(3))and trimethylaminogallium(Ga(NMe_(2))_(3))at 260°C in 1-octadecene.The GaSb nanocrystals are grown based on a solution–liquid–solid(SLS)mechanism with zinc blende phase,and their size and shape can be controlled in the procedures via manipulating the reaction conditions.Meanwhile,the tadpole-like Ga/GaSb nanostructures can be applied for the fabrication of a GaSb/Si nanostructured heterojunction-like photodetector over silicon wafer,which demonstrates excellent photoresponse and detection performances from wavelength of 405 to 1,064 nm with high photoresponding rate.Typically,the photodetector exhibits a high responsivity of 18.9 A·W^(−1),a superior detectivity of 1.1×10^(13)Jones,and an ultrafast response speed of 44 ns.The present work provides a new strategy to group III–V antimonide-based semiconducting nanostructures that are capable for the fabrication of photodetector with broadband,high-detectivity,and high-speed photodetecting performances.

Mixed 2D-Dion–Jacobson/3D Sn-Pb alloyed perovskites for efficient photovoltaic solar devices

Tin-lead(Sn-Pb)alloyed perovskites with tunable bandgaps hold great potential for constructing highly efficient single-junction and tandem photovoltaic devices.However,the efficiency and stability of Sn-Pb perovskite solar cells(PSCs)are greatly hampered by severe nonradiative recombination due to the easy oxidation of Sn(II).In this work,we report the construction of mixed dimensional two-dimensional(2D)Dion–Jacobson(DJ)and three-dimensional(3D)perovskites to improve the efficiency and stability of Sn-Pb alloyed PSCs.Introducing a small amount of 1,4-butanediammonium diiodide as spacer cations of DJ perovskites into precursor,the prepared mixed dimensional Sn-Pb alloyed perovskites exhibit reduced trap-state density due to the passivation of 2D DJ perovskites.As a result,nonradiative charge recombination is greatly suppressed.The prepared Sn-Pb alloyed PSCs based on 2D-DJ/3D heterojunction deliver a power conversion efficiency of 19.02%with an impressive fill factor of 80%.As well,improved device stability is realized due to the presence of DJ perovskites which serves as a protection barrier against oxidation and water invasion.

Template-free synthesis of carbon doped TiO_2 mesoporous microplates for enhanced visible light photodegradation

报道了一种在乙酸蒸汽中蒸发有机钛源(Ti(i-Pr O)_4),无模版合成碳掺杂介孔Ti O_2微板块的方法.该微板块由纳米晶组成,具有统一的介孔结构和微米级厚度.制备过程的副产有机物经炭化后对Ti O_2形成了表面和/或间隙碳掺杂,特别是源于乙酸的羧基最终与Ti O_2形成双齿螯合结构,强吸电子特性使羧基在价带边引入了带尾,导致Ti O_2带隙大幅减小(1.84 e V).独特的形貌和显著缩减的带隙,使该Ti O_2微板块显示出较高的可见光苯酚降解活性和优良的固-液分离性能.

A Verilog-A large signal model for InP DHBT including thermal effects

A large signal model for InP/InGaAs double heterojunction bipolar transistors including thermal effects has been reported,which demonstrated good agreements of simulations with measurements.On the basis of the previous model in which the double heterojunction effect,current blocking effect and high current effect in current expression are considered,the effect of bandgap narrowing with temperature has been considered in transport current while a formula for model parameters as a function of temperature has been developed.This model is implemented by Verilog-A and embedded in ADS.The proposed model is verified with DC and large signal measurements.

A chlorinated non-fullerene acceptor for efficient polymer solar cells

Improving the performance and reducing the manufacturing costs are the main directions for the development of organic solar cells in the future.Here,the strategy that uses chemical structure modification to optimize the photoelectric properties is reported.A new narrow bandgap(1.30 eV)chlorinated non-fullerene electron acceptor(Y15),based on benzo[d][1,2,3] triazole with two 3-undecylthieno[2’,3’:4,5] thieno[3,2-b] pyrrole fused-7-heterocyclic ring,with absorption edge extending to the near-infrared(NIR) region,namely A-DA’D-A type structure,is designed and synthesized.Its electrochemical and optoelectronic properties are systematically investigated.Benefitting from its NIR light harvesting,the fabricated photovoltaic devices based on Y15 deliver a high power conversion efficiency(PCE) of 14.13%,when blending with a wide bandgap polymer donor PM6.Our results show that the A-DA’D-A type molecular design and application of near-infrared electron acceptors have the potential to further improve the PCE of polymer solar cells(PSCs).

Polymerizing small molecular acceptors for efficient all-polymer solar cells

All-polymer solar cells(all-PSCs)have received attention due to their morphological stability under thermal and mechanical stresses.Currently,the highest reported power conversion efficiency of all-PSCs is over 17%,achieved by utilizing polymerized small molecular acceptors(PSMAs).However,the need for higher regiospecificity to avoid forming isomers during polymerization of SMAs still challenges the further applications of all-PSCs.From this perspective,we focus on some recent studies and highlight the importance of controlling the regioregularity of PSMAs.In particular,integrating PSMAs with regioregularity endows the polymer acceptors with good absorption,superior backbone ordering,and optimal blend morphology compared with those obtained from regiorandom one.Moreover,the distinctive features that are derived from these regioregular PSMAs,such as the possibility of repeatable synthesis and reproducible device performance,herald a brighter future for scaling-up and commercializing all-PSCs.We expect this integrated strategy will inspire researchers to devote more efforts to further narrow the efficiency gap between the PSCs based on SMAs and PSMAs.Finally,we discuss the existing challenges and future prospects of PSMAs as new platform for further advancing all-PSCs.

Molecular engineering of Y-series acceptors for nonfullerene organic solar cells

The power conversion efficiencies(PCEs)of single-junction organic solar cells(OSCs)have surpassed 19%,owing to the emerging Y-series nonfullerene acceptors(NFAs).Undoubtedly,the power and flexibility of chemical design has been a strong driver for this rapid efficiency improvement in the OSC field.Over the course of the past 3 years,a variety of modifications have been made to the structure of the Y6 acceptor,and a large number of Y-series NFAs have been reported to further improve performance.Herein,we present our insights into the rationale behind the Y6 acceptor and discuss the design principles toward high-performance Y-series NFAs.It is clear that structural modifications through choice of heteroatom,soluble chains,πspacers,central cores,and end groups alter the material characteristics and properties,contributing to distinctive photovoltaic performance.Subsequently,we analyze various design strategies of Y-series-containing materials,including polymerized small-molecule acceptors(PSMA),non-fused-ring acceptors(NFRA),and all-fused-ring acceptors(AFRA).This review is expected to be of value in providing effective molecular design strategies for high-performance NFAs in future innovations.