Boosting internal quantum efficiency via ultrafast triplet transfer to 2H-MoTe2 film.

Organic systems often allow to create two triplet spin states (triplet excitons) by converting an initially excited singlet spin state (a singlet exciton). An ideally designed organic/inorganic heterostructure could reach the photovoltaic energy harvest over the Shockley-Queisser (S-Q) limit because of the efficient conversion of triplet excitons into charge carriers. Here, we demonstrate the molybdenum ditelluride (MoTe2)/pentacene heterostructure to boost the carrier density via efficient triplet transfer from pentacene to MoTe2 using ultrafast transient absorption spectroscopy. We observe carrier multiplication by nearly four times by doubling carriers in MoTe2 via the inverse Auger process and subsequently doubling carriers via triplet extraction from pentacene. We also verify efficient energy conversion by doubling the photocurrent in the MoTe2/pentacene film. This puts a step forward to enhancing photovoltaic conversion efficiency beyond the S-Q limit in the organic/inorganic heterostructures.

Exciton-plasmon coupling and giant photoluminescence enhancement in monolayer MoS2through hierarchically designed TiO2/Au/MoS2ternary core-shell heterostructure.

Enhancing the light coupling efficiency of large-area monolayer molybdenum disulfide (1L-MoS2) is one of the major challenges for its successful applications in optoelectronics and photonics. Herein, we demonstrate a dramatically enhanced photoluminescence (PL) emission from direct chemical vapor deposited monolayer MoS2on a fluorine-doped TiO2/Au nanoparticle plasmonic substrate, where the PL intensity is enhanced by nearly three orders of magnitude, highest among the reported values. The formation of TiO2/Au/1L-MoS2ternary core-shell heterojunction is evidenced by the high-resolution transmission electron microscopy and Raman analyses. Localized surface plasmon resonance induced enhanced absorption and improved light coupling in the system was revealed from the UV-vis absorption and Raman spectroscopy analyzes. Our studies reveal that the observed giant PL enhancement in 1L-MoS2results from two major aspects: firstly, the heavy p-doping of the MoS2lattice is caused by the transfer of the excess electrons from the MoS2to TiO2at the interface, which enhances the neutral exciton emissions and restrains the trion formation. Secondly, the localized surface plasmon in Au NPs underneath the 1L-MoS2film initiates exciton-plasmon coupling between excitons of the 1L-MoS2and surface plasmons of the Au NPs at the MoS2/Au interface. The PL and Raman analyses further confirm the p-doping effect. We isolate the contributions of plasmon enhancement from the theoretical calculation of the field enhancement factor using the effective medium approximation of plasmonic heterostructure, which is in excellent agreement with the experimental data. This work paves a way for the rational design of the plasmonic heterostructure for the effective improvement in the light emission efficiency of 1L-MoS2, and may enable engineering the different contributions to enhance the optoelectronic performance of 2D heterostructures.

Precise Tuning of the Thickness and Optical Properties of Highly Stable 2D Organometal Halide Perovskite Nanosheets through a Solvothermal Process and Their Applications as a White LED and a Fast Photodetector.

Precise control of the thickness of large-area two-dimensional (2D) organometal halide perovskite layers is extremely challenging owing to the inherent instability of the organic component. Herein, a novel, highly reproducible, and facile solvothermal route is reported to synthesize and tailor the thickness and optical band gap of the organic-inorganic halide perovskite nanosheets (NSs). Our study reveals that self-assembly of randomly oriented perovskite nanorods leads to the growth of multilayered perovskite NSs at ∼100 °C, while at higher temperature, large-area few-layer to bilayer 2D NSs (CH3NH3PbBr3) are obtained through lattice expansion and layer separation depending precisely on the temperature. Interestingly, the thickness of the 2D NSs shows a linear dependence on the reaction temperature and thus enables precise tuning of the thickness from 14 layers to 2 layers, giving rise to a systematic increase in the band gap and appearance of excitonic absorption bands. Quantitative analysis of the change in the band gap with thickness revealed a strong quantum confinement effect in the 2D layers. The perovskite 2D NSs exhibit tunable color and a high photoluminescence (PL) quantum yield (QY) up to 84%. Through a careful analysis of the steady-state and time-resolved PL spectra, the origin of the lower PL QY in thinner NSs is traced to surface defects in the 2D layers, for the first time. A white light converter was fabricated using the composition-tuned 2D CH3NH3PbBrI2 NS on a blue light-emitting diode chip. The 2D perovskite photodetector exhibits a stable and very fast rise/fall time (24 µs/103 µs) along with high responsivity and detectivity of ∼1.93 A/W and 1.04 × 1012 Jones, respectively. Storage, operational, and temperature-dependent stability studies reveal high stability of the 2D perovskite NSs under the ambient condition with high humidity. The reported method is highly promising for the development of large-area stable 2D perovskite layers for various cutting-edge optoelectronic applications.

Large exciton binding energy, high photoluminescence quantum yield and improved photostability of organo-metal halide hybrid perovskite quantum dots grown on a mesoporous titanium dioxide template.

Herein, we demonstrated a novel synthetic route to grow size-tunable hybrid perovskite (CH3NH3PbI3 and CH3NH3PbBr3) quantum dots (QDs) using a Fluorine-doped TiO2 (F-TiO2) mesoporous template and these QDs exhibit large exciton binding energy, high photoluminescence quantum yield and improved photostability. The pore size in F-TiO2 template is tuned by varying the HF molar concentration during its solvothermal growth and size of the perovskite QDs embedded in F-TiO2 pores is tuned in the range 1.7-5.1 nm, as revealed from the TEM analysis. A systematic blue-shift in UV-visible absorption edge, as well as photoluminescence (PL) spectrum, is observed with the reduced size of the perovskite QDs due to strong quantum confinement. The CH3NH3PbI3 QD with average size ∼1.7 nm exhibits ∼47 nm blue shift in the PL spectra, ∼43 fold enhancement in PL intensity and ∼25% PL quantum yield (QY). On the other hand, CH3NH3PbBr3 QD of similar size exhibits dramatically enhanced (∼124 times) PL emission with narrow line width and a PLQY of ∼57%, which is significant for the template-assisted growth of perovskite QDs film. The quantitative analysis of the PL emission energy vs QD size shows an excellent fit with the Brus equation confirming the strong quantum confinement effect in the perovskite QDs. Analysis of low-temperature PL spectra reveals very high exciton binding energy (162-272 meV) for the QDs as compared to the bulk film (32 meV) due to the high effective dielectric constant, and high electron-hole recombination probability in the QDs, which is consistent with the extremely high PLQY and stable emission from the QDs. The blue shift of the PL peak with increasing temperature is explained on the basis of localization effect. Time-resolved PL analysis for both the perovskite QDs reveals faster life time compared to their bulk counterparts, confirming the significant radiative recombination of carriers in the QDs at the room temperature. The CH3NH3PbBr3 QDs embedded in porous F-TiO2 template maintain its initial PL intensity up to several hours (≥10 h) under the UV laser exposure (18mW), while that of the bulk film decreases to <67%. Thus, template grown hybrid perovskite QDs exhibiting high photostability and very high PLQY demonstrated here are promising for the next generation optoelectronic applications.

Shape Tailored TiO2 Nanostructures and Their Hybrids for Advanced Energy and Environmental Applications: A Review.

Shape tailored TiO2 nanostructures with various dimensionality (zero to three dimension) have unique physicochemical and functional properties that facilitates its efficient energy and environment applications, e.g., solar light driven photocatalytic hydrogen generation and decontamination of organic/inorganic toxic pollutants, CO2 reduction into the hydrocarbon fuels, solar cells, supercapacitors and lithium-ion batteries etc. However, the wide band gap nature and the fast recombination of the photogenerated charge carriers in TiO2 usually limit its overall performance under solar light illumination. In this review, we present a state of the art on the fabrication techniques of shape tailored TiO2 nanostructures and the strategies employed to make the system catalytically more efficient. Though shape tailored TiO2 nanostructures with large specific surface area and highly energetic (001) facet exposed TiO2 nanostructures (2D and 3D) can enhance the photocatalytic efficiency to a reasonable extent, further surface engineering is needed for the modification of the electronic band arrangement, visible light sensitization and efficient charge separation. Herein, TiO2 heterostructures (HSs) with metal/non-metal doping, surface fluorination, plasmonic noble metal nanoparticles (NPs) and coupling with the narrow band gap suitable semiconductor (type-II) are discussed in details covering from zero dimensional to three dimensional heterostructures. The synthesis strategies, charge transfer mechanism and their participation in the photocatalysis are elaborated. Though one dimensional TiO2 HSs have been widely studied, we present the recent development of critical surface engineering strategies of two and three dimensional systems, which give rise to the excellent properties including the enlargement of surface area, light absorption capability and efficient separation of electrons/holes resulting in the superior performance in advanced applications. Based on recent breakthroughs in the field, future directions and outlook of the field are presented at the end.

Trion-Inhibited Strong Excitonic Emission and Broadband Giant Photoresponsivity from Chemical Vapor-Deposited Monolayer MoS2 Grown in Situ on TiO2 Nanostructure.

2D material-based heterostructures often prepared by wet transfer technique suffers from poor interface and contamination issues and it results in inferior device performance. Herein, we report an in situ chemical vapor deposition (CVD) growth of MoS2@TiO2 core-shell heterojunction with single-layer MoS2 (1L-MoS2) as the shell and 3D TiO2 nanoflower (NF) as the core for multifunctional optoelectronic applications. We explore a powerful approach to switch the trions in 1L-MoS2 into neutral excitons by developing a core-shell heterostructure with TiO2 and demonstrate a giant photoluminescence (PL) enhancement in the 1L-MoS2 shell. 3D TiO2 NFs with average diameter ∼1 µm are uniformly coated with 1L-MoS2 shell by in situ CVD technique, resulting in ∼83- and ∼30-fold enhancement in PL intensity at room temperature from the 1L-MoS2 shell on TiO2 NFs as compared to that of 1L-MoS2 grown on Ti and sapphire substrate, respectively. This high PL enhancement is attributed to the migration of excess electrons from MoS2 to TiO2, leading to a heavy p-doping in the MoS2 lattice, as evidenced by the Raman and X-ray photoelectron spectroscopy analyses. Additionally, the formation of the core-shell heterojunction facilitates the suppression of nonradiative recombination of the excitons even at the room temperature, as revealed from the low-temperature PL study. The charge transfer-induced p-doping effect in 1L-MoS2 is verified from the oxygen plasma treatment of the 1L-MoS2@Ti and it shows similar PL enhancement. Further, the 1L-MoS2@TiO2 p-n heterojunction is demonstrated as a high-performance broadband photodetector owing to its favorable band alignment and high absorption in the spectral range of 300-900 nm. The heterojunction photodetector exhibits a record high responsivity and detectivity of ∼35.9 A W-1 and 1.98 × 1013 jones, respectively, in the UV region, and ∼18.5 A W-1 and 1.09 × 1013 jones, respectively, in the visible region. As compared to the 1L-MoS2@Ti and 1L-MoS2@SiO2 with slow photoresponse, 1L-MoS2@TiO2 heterojunction exhibits more than 1 order of magnitude faster photoresponse (rise/fall time ∼33.7/28.2 ms), which is attributed to the fast photogenerated carrier transport at the p-n heterojunction due to the large built-in electric field. This high-performance 1L-MoS2@TiO2 core-shell heterojunction grown by a novel in situ CVD technique is promising for the cutting-edge optoelectronic applications.

Multifunctional Ag nanoparticle decorated Si nanowires for sensing, photocatalysis and light emission applications.

We report on the fabrication of Ag nanoparticle (NP) decorated mesoporous Si nanowire (NW) heterostructure (HS) by a simple and low cost chemical process. The as-grown Si NWs are mesoporous in nature and the Ag NP decorated Si NWs (Ag@Si NWs) exhibit broadband light emission, ultralow reflectance, efficient photocatalytic degradation of organic dyes and excellent sensitivity for the detection of organic molecules over a wide range of concentration. The broadband white light photoluminescence emission from the bare Si NWs is explained on the basis of quantum confinement effect in Si NCs/NWs and the nonbridging oxygen hole center defects in the SiSiOx interface. High work function of the noble metal NPs facilitates the effective separation of the photoinduced electron-hole pairs in Si NWs, which enables the Ag@Si NWs to exhibit high photocatalytic efficiency for the degradation of organic dye. The Ag@Si NWs exhibited high potential and sensitivity for the selective and quantitative detection of different organic molecules at extremely low concentration down to 10-12 M by surface-enhanced Raman scattering and 10-11 M by fluorescence-based detection. These versatile properties of the Ag@Si NWs open up opportunities for a variety of energy and environmental applications, such as white light emission, solar cell, artificial photosynthesis, disposal of organic pollutant and bio-chemical sensors etc.

Mechanism of strong visible light photocatalysis by Ag2O-nanoparticle-decorated monoclinic TiO2(B) porous nanorods.

We report on the ultra-high rate of photodegradation of organic dyes under visible light illumination on Ag2O-nanoparticle-decorated (NP) porous pure B-phase TiO2 (TiO2(B)) nanorods (NRs) grown by a solvothermal route. The as-grown TiO2(B) NRs are found to be nanoporous in nature and the Ag2O NPs are uniformly decorated over its surface, since most of the pores work as nucleation sites for the growth of Ag2O NPs. The effective band gap of the TiO2(B)/Ag2O heterostructure (HS), with a weight ratio of 1:1, has been significantly reduced to 1.68 eV from the pure TiO2(B) band gap of 2.8 eV. Steady state and time-resolved photoluminescence (PL) studies show the reduced intensity of visible PL and slower recombination dynamics in the HS samples. The photocatalytic degradation efficiency of the TiO2(B)/Ag2O HS has been investigated using aqueous methyl orange and methylene blue as reference dyes under visible light (390-800 nm) irradiation. It is found that photodegradation by the TiO2(B)/Ag2O HS is about one order of magnitude higher than that of bare TiO2(B) NRs and Ag2O NPs. The optimized TiO2(B)/Ag2O HS exhibited the highest photocatalytic efficiency, with 88.2% degradation for 30 min irradiation. The corresponding first order degradation rate constant is 0.071 min(-1), which is four times higher than the reported values. Furthermore, cyclic stability studies show the high stability of the HS photocatalyst for up to four cycles of use. The major improvement in photocatalytic efficiency has been explained on the basis of enhanced visible light absorption and band-bending-induced efficient charge separation in the HS. Our results demonstrate the long-term stability and superiority of the TiO2(B)/Ag2O HS over the bare TiO2(B) NRs and other TiO2-based photocatalysts for its cutting edge application in hydrogen production and environmental cleaning driven by solar light photocatalysis.