Efficient Carrier Multiplication in Self-Powered Near-Ultraviolet γ-InSe/Graphene Heterostructure Photodetector with External Quantum Efficiency Exceeding 161.

Carrier multiplication (CM) in semiconductors, the process of absorbing a single high-energy photon to form two or more electron-hole pairs, offers great potential for the high-response detection of high-energy photons in the ultraviolet spectrum. However, compared to two-dimensional semiconductors, conventional bulk semiconductors not only face integration and flexibility bottlenecks but also exhibit inferior CM performance. To attain efficient CM for ultraviolet detection, we designed a two-terminal photodetector featuring a unilateral Schottky junction based on a two-dimensional γ-InSe/graphene heterostructure. Benefiting from a strong built-in electric field, the photogenerated high-energy electrons in γ-InSe, an ideal ultraviolet light-absorbing layer, can efficiently transfer to graphene without cooling. It results in efficient CM within the graphene, yielding an ultrahigh responsivity of 468 mA/W and a record-high external quantum efficiency of 161.2% when it is exposed to 360 nm light at zero bias. This work provides valuable insights into developing next-generation ultraviolet photodetectors with high performance and low-power consumption.

One-Pot Colloidal Synthesis Enables Highly Tunable InSb Short-Wave Infrared Quantum Dots Exhibiting Carrier Multiplication.

Colloidal quantum dots (CQDs) are emerging materials for short-wave infrared (SWIR, ≈1100-3000 nm) photodetectors, which are technologically important for a broad array of applications. Unfortunately, the most developed SWIR CQD systems are Pb and Hg chalcogenides; their toxicity and regulated compositions limit their applications. InSb CQD system is a potential environmentally friendly alternative, whose bandgap in theory, is tunable via quantum confinement across the SWIR spectrum. However, InSb CQDs are difficult to exploit, due to their complex syntheses and uncommon reactive precursors, which greatly hinder their application and study. Here, a one-pot synthesis strategy is reported using commercially available precursors to synthesize-under standard colloidal synthesis conditions-high-quality, size-tunable InSb CQDs. With this strategy, the large Bohr exciton radius of InSb can be exploited for tuning the bandgap of the CQDs over a wide range of wavelengths (≈1250-1860 nm) across the SWIR region. Furthermore, by changing the surface ligands of the CQDs from oleic acid (OA) to 1-dodecanthiol (DDT), a ≈20-fold lengthening in the excited-state lifetime, efficient carrier multiplication, and slower carrier annihilation are observed. The work opens a wide range of SWIR applications to a promising class of Pb- and Hg-free CQDs.

Semiconductor quantum dots as a mechanism to enhance charge transfer processes in polymer solar cells.

The light trapping capability of thin film polymer solar absorber, composed of poly (3-hexylthiophene) and [6,6]-phenyl C61- butyric acid methyl ester (P3HT:PC60BM) blend, is improved using ZnS semiconductor quantum dots (QD) as third donor-acceptor (D:A) component. The inherent characteristics of the microwave-assisted synthesized ZnS QD, such as quantum size effect, and multiple exciton generation were leveraged in harvesting high energy photons, which resulted in a better exciton generation, dissociation, and effective charge transport in the polymer medium. The synthesized QD exhibited good phase purity, effective kinetic enhancement, and control of the aggregation process. Hence, the impact of ZnS QD on the performance of thin film polymer solar cells (TFPSC) is evident by a remarkable improvement in the measured photovoltaic parameters. Nonetheless, it is observed that the device performances are generally dependent on the concentration of the QD in the absorber layer. Consequently, the power conversion efficiency has increased by 58% at 3% concentration of QDs by weight. This is an interesting development of TFPSC fabricated under an ambient environment.

Plasmonic Nanoparticles on Graphene Absorber for Broadband High Responsivity 2D/3D Photodiode.

To overcome the image deterioration caused by pixel miniaturization resulting from the high-resolution trend of CIS (CMOS image sensor) technology, a photodiode working with an enhanced mechanism based on a distinctive device structure from the existing one is considerably required. In this study, our photodiode, consisting of gold nanoparticles/monolayer graphene/n-type trilayer MoS2/p-type Si bulk, achieved ultrafast rising/falling times of 28.6 ns/30.4 ns due to the spatially confined narrow depletion width (DW) resulting from the 2D/3D heterojunction. To compensate for the expected low absorbance due to the narrow DW, plasmonic gold nanoparticles on monolayer graphene are introduced, revealing broadband enhanced EQE of an average of 187% in the spectral range of 420-730 nm and the maximum EQE reaching 847% at 5 nW for a 520 nm wavelength. The broadband enhancement was further investigated through multiphysics simulation, and carrier multiplication in graphene was discussed for the reason for exceeding 100% EQE in our reverse biased photodiode.

Anisotropy of impact ionization in WSe2 field effect transistors.

Carrier multiplication via impact ionization in two-dimensional (2D) layered materials is a very promising process for manufacturing high-performance devices because the multiplication has been reported to overcome thermodynamic conversion limits. Given that 2D layered materials exhibit highly anisotropic transport properties, understanding the directionally-dependent multiplication process is necessary for device applications. In this study, the anisotropy of carrier multiplication in the 2D layered material, WSe2, is investigated. To study the multiplication anisotropy of WSe2, both lateral and vertical WSe2 field effect transistors (FETs) are fabricated and their electrical and transport properties are investigated. We find that the multiplication anisotropy is much bigger than the transport anisotropy, i.e., the critical electric field (ECR) for impact ionization of vertical WSe2 FETs is approximately ten times higher than that of lateral FETs. To understand the experimental results we calculate the average energy of the carriers in the proposed devices under strong electric fields by using the Monte Carlo simulation method. The calculated average energy is strongly dependent on the transport directions and we find that the critical electric field for impact ionization in vertical devices is approximately one order of magnitude larger than that of the lateral devices, consistent with experimental results. Our findings provide new strategies for the future development of low-power electric and photoelectric devices.

Carrier Relaxation and Multiplication in Bi Doped Graphene.

By introducing different contents of Bi adatoms to the surface of monolayer graphene, the carrier concentration and their dynamics have been effectively modulated as probed directly by the time- and angle-resolved photoemission spectroscopy technique. The Bi adatoms are found to assist acoustic phonon scattering events mediated by supercollisions as the disorder effectively relaxes the momentum conservation constraint. A reduced carrier multiplication has been observed, which is related to the shrinking Fermi sea for scattering, as confirmed by time-dependent density functional theory simulation. This work gives insight into hot carrier dynamics in graphene, which is crucial for promoting the application of photoelectric devices.

High Efficient Solar Cell Based on Heterostructure Constructed by Graphene and GaAs Quantum Wells.

Despite the fascinating optoelectronic properties of graphene, the power conversion efficiency (PCE) of graphene based solar cells remains to be lifted up. Herein, it is experimentally shown that the graphene/quantum wells/GaAs heterostructure solar cell can reach a PCE of 20.2% and an open-circuit voltage (Voc ) as high as 1.16 V at 90 K. The high efficiency is a result of carrier multiplication (CM) effect of graphene in the graphene/GaAs heterostructure. Especially, the external quantum efficiency (EQE) in the ultraviolet wavelength can be improved up to 72.2% based on the heterostructure constructed by graphene/In0.15 Ga0.85 As/GaAs0.75 P0.25 quantum wells/GaAs. The EQE increases as the light wavelength decreases, which indicates more carriers can be effectively excited by the higher energy photons through CM effect. Owing to these physical characters, the graphene/GaAs heterostructure solar cell will provide a possible way to exceed Shockley-Queisser (S-Q) limit.

Chiral Transport of Hot Carriers in Graphene in the Quantum Hall Regime.

Photocurrent (PC) measurements can reveal the relaxation dynamics of photoexcited hot carriers beyond the linear response of conventional transport experiments, a regime important for carrier multiplication. Here, we study the relaxation of carriers in graphene in the quantum Hall regime by accurately measuring the PC signal and modeling the data using optical Bloch equations. Our results lead to a unified understanding of the relaxation processes in graphene over different magnetic field strength regimes, which is governed by the interplay of Coulomb interactions and interactions with acoustic and optical phonons. Our data provide clear indications of a sizable carrier multiplication. Moreover, the oscillation pattern and the saturation behavior of PC are manifestations of not only the chiral transport properties of carriers in the quantum Hall regime but also the chirality change at the Dirac point, a characteristic feature of a relativistic quantum Hall effect.

Carrier Multiplication in Transition Metal Dichalcogenides Beyond Threshold Limit.

Carrier multiplication (CM), multiexciton generation by absorbing a single photon, enables disruptive improvements in photovoltaic conversion efficiency. However, energy conservation constrains the threshold energy to at least twice bandgap (2 E g $ E_\text{g}$ ). Here, a below threshold limit CM in monolayer transition metal dichalcogenides (TMDCs) is reported. Surprisingly, CM is observed with excitation energy of only 1.75 E g $E_\text{g}$ due to lattice vibrations. Electron-phonon coupling (EPC) results in significant changes in electronic structures, which favors CM. Indeed, the strongest EPC in monolayer MoS2 leads to the most efficient CM among the studied TMDCs. For practical applications, chalcogen vacancies can further lower the threshold by introducing defect states within bandgap. In particular, for monolayer WS2 , CM occurs with excitation energy as low as 1.51 E g $E_\text{g}$ . The results identify TMDCs as attractive candidate materials for efficient optoelectronic devices with the advantages of high photoconductivity and efficient CM.

Hot Carrier Transport and Carrier Multiplication Induced High Performance Vertical Graphene/Silicon Dynamic Diode Generator.

Dynamic semiconductor diode generators (DDGs) offer a potential portable and miniaturized energy source, with the advantages of high current density, low internal impedance, and independence of the rectification circuit. However, the output voltage of DDGs is generally as low as 0.1-1 V, owing to energy loss during carrier transport and inefficient carrier collection, which requires further optimization and a deeper understanding of semiconductor physical properties. Therefore, this study proposes a vertical graphene/silicon DDG to regulate the performance by realizing hot carrier transport and collection. With instant contact and separation of the graphene and silicon, hot carriers are generated by the rebounding process of built-in electric fields in dynamic graphene/silicon diodes, which can be collected within the ultralong hot electron lifetime of graphene. In particular, monolayer graphene/silicon DDG outputs a high voltage of 6.1 V as result of ultrafast carrier transport between the monolayer graphene and silicon. Furthermore, a high current of 235.6 nA is generated due to the carrier multiplication in graphene. A voltage of 17.5 V is achieved under series connection, indicating the potential to supply electronic systems through integration design. The graphene/silicon DDG has applications as an in situ energy source for harvesting mechanical energy from the environment.

Hot carrier multiplication in plasmonic photocatalysis.

Light-induced hot carriers derived from the surface plasmons of metal nanostructures have been shown to be highly promising agents for photocatalysis. While both nonthermal and thermalized hot carriers can potentially contribute to this process, their specific role in any given chemical reaction has generally not been identified. Here, we report the observation that the H2-D2 exchange reaction photocatalyzed by Cu nanoparticles is driven primarily by thermalized hot carriers. The external quantum yield shows an intriguing S-shaped intensity dependence and exceeds 100% for high light intensities, suggesting that hot carrier multiplication plays a role. A simplified model for the quantum yield of thermalized hot carriers reproduces the observed kinetic features of the reaction, validating our hypothesis of a thermalized hot carrier mechanism. A quantum mechanical study reveals that vibrational excitations of the surface Cu-H bond is the likely activation mechanism, further supporting the effectiveness of low-energy thermalized hot carriers in photocatalyzing this reaction.

Escalated Photocurrent with Excitation Energy in Dual-Gated MoTe2.

Although van der Waals-layered transition metal dichalcogenides from transient absorption spectroscopy have successfully demonstrated an ideal carrier multiplication (CM) performance with an onset of nearly 2Eg, interpretation of the CM effect from the optical approach remains unresolved owing to the complexity of many-body electron-hole pairs. We demonstrate the escalated photocurrent with excitation photon energy by fabricating the dual-gate p-n junction of a MoTe2 film on a transparent substrate. Electrons and holes were efficiently extracted by eliminating the Schottky barriers in the metal contact and minimizing multiple reflections. The photocurrent was elevated proportionately to the excitation photon energy. The boosted quantum efficiency confirms the multiple electron-hole pair generation of >2Eg, consistent with CM results from an optical approach, pushing the solar cell efficiency beyond the Shockley-Queisser limit.

Photoconductivity Multiplication in Semiconducting Few-Layer MoTe2.

We report efficient photoconductivity multiplication in few-layer 2H-MoTe2 as a direct consequence of an efficient steplike carrier multiplication with near unity quantum yield and high carrier mobility (∼45 cm2 V-1 s-1) in MoTe2. This photoconductivity multiplication is quantified using ultrafast, excitation-wavelength-dependent photoconductivity measurements employing contact-free terahertz spectroscopy. We discuss the possible origins of efficient carrier multiplication in MoTe2 to guide future theoretical investigations. The combination of photoconductivity multiplication and the advantageous bandgap renders MoTe2 as a promising candidate for efficient optoelectronic devices.

Carrier Multiplication in PbS Quantum Dots Anchored on a Au Tip using Conductive Atomic Force Microscopy.

Carrier multiplication (CM) is the amplification of the excited carrier density by two times or more when the incident photon energy is larger than twice the bandgap of semiconductors. A practical approach to demonstrate the CM involves the direct measurement of photocurrent in the device. Specifically, photocurrent measurement in quantum dots (QDs) is typically limited by high contact resistance and long carrier-transfer length, which yields a low CM conversion efficiency and high CM threshold energy. Here, the local photocurrent is measured to evaluate the CM quantum efficiency from a QD-attached Au tip of a conductive atomic force microscope (CAFM) system. The photocurrent is efficiently measured between the PbS QDs anchored on a Au tip and a graphene layer on a SiO2 /Si substrate as a counter electrode, yielding an extremely short channel length that reduces the contact resistance. The quantum efficiency extracted from the local photocurrent data with an incident photon energy exhibits a step-like behavior. More importantly, the CM threshold energy is as low as twice the bandgap, which is the lowest threshold energy of optically observed QDs to date. This enables the CAFM-based photocurrent technique to directly evaluate the CM conversion efficiency in low-dimensional materials.

Extremely Efficient Photocurrent Generation in Carbon Nanotube Photodiodes Enabled by a Strong Axial Electric Field.

Carbon nanotube (CNT) photodiodes have the potential to convert light into electrical current with high efficiency. However, previous experiments have revealed the photocurrent quantum yield (PCQY) to be well below 100%. In this work, we show that the axial electric field increases the PCQY of CNT photodiodes. Under optimal conditions, our data suggest PCQY > 100%. We studied, both experimentally and theoretically, CNT photodiodes at room temperature using optical excitation corresponding to the S22, S33, and S44 exciton resonances. The axial electric field inside the pn junction was controlled using split gates that are capacitively coupled to the suspended CNT. Our results give new insight into the photocurrent generation pathways in CNTs and the field dependence and diameter dependence of PCQY.

Enhanced Multiple Exciton Generation in PbS|CdS Janus-like Heterostructured Nanocrystals.

Generating multiple excitons by a single high-energy photon is a promising third-generation solar energy conversion strategy. We demonstrate that multiple exciton generation (MEG) in PbS|CdS Janus-like heteronanostructures is enhanced over that of single-component and core/shell nanocrystal architectures, with an onset close to two times the PbS band gap. We attribute the enhanced MEG to the asymmetric nature of the heteronanostructure that results in an increase in the effective Coulomb interaction that drives MEG and a reduction of the competing hot exciton cooling rate. Slowed cooling occurs through effective trapping of hot-holes by a manifold of valence band interfacial states having both PbS and CdS character, as evidenced by photoluminescence studies and ab initio calculations. Using transient photocurrent spectroscopy, we find that the MEG characteristics of the individual nanostructures are maintained in conductive arrays and demonstrate that these quasi-spherical PbS|CdS nanocrystals can be incorporated as the main absorber layer in functional solid-state solar cell architectures. Finally, based upon our analysis, we provide design rules for the next generation of engineered nanocrystals to further improve the MEG characteristics.

High-Performance Graphene/ß-Ga2O3 Heterojunction Deep-Ultraviolet Photodetector with Hot-Electron Excited Carrier Multiplication.

Solar-blind ultraviolet (SBUV) detection has important applications in wireless secure communication, early warning, and so forth. However, the desired key device for SBUV detection and high-sensitivity and low-noise "sandwich" photodetector with large detective area is difficult to be fabricated because it is usually hard for traditional wide band gap semiconductors to boast both high conductivity and high SBUV transparency. Here, we proposed to use graphene as the transparent conductive layer to form graphene/ß-Ga2O3 heterojunction. With the help of large-area graphene and hot carrier multiplication, a SBUV photodetector with large detective area, low dark current, and high sensitivity was successfully assembled. Its photoresponsivity is 1-3 orders of magnitude higher than that of the conventional SBUV photodetectors, and its response speed can rival the best device ever reported.

Asymmetric Optical Transitions Determine the Onset of Carrier Multiplication in Lead Chalcogenide Quantum Confined and Bulk Crystals.

Carrier multiplication is a process in which one absorbed photon excites two or more electrons. This is of great promise to increase the efficiency of photovoltaic devices. Until now, the factors that determine the onset energy of carrier multiplication have not been convincingly explained. We show experimentally that the onset of carrier multiplication in lead chalcogenide quantum confined and bulk crystals is due to asymmetric optical transitions. In such transitions most of the photon energy in excess of the band gap is given to either the hole or the electron. The results are confirmed and explained by theoretical tight-binding calculations of the competition between impact ionization and carrier cooling. These results are a large step forward in understanding carrier multiplication and allow for a screening of materials with an onset of carrier multiplication close to twice the band gap energy. Such materials are of great interest for development of highly efficient photovoltaic devices.

Efficient Steplike Carrier Multiplication in Percolative Networks of Epitaxially Connected PbSe Nanocrystals.

Carrier multiplication (CM) is a process in which a single photon excites two or more electrons. CM is of interest to enhance the efficiency of a solar cell. Until now, CM in thin films and solar cells of semiconductor nanocrystals (NCs) has been found at photon energies well above the minimum required energy of twice the band gap. The high threshold of CM strongly limits the benefits for solar cell applications. We show that CM is more efficient in a percolative network of directly connected PbSe NCs. The CM threshold is at twice the band gap and increases in a steplike fashion with photon energy. A lower CM efficiency is found for a solid of weaker coupled NCs. This demonstrates that the coupling between NCs strongly affects the CM efficiency. According to device simulations, the measured CM efficiency would significantly enhance the power conversion efficiency of a solar cell.

Carrier Multiplication Mechanisms and Competing Processes in Colloidal Semiconductor Nanostructures.

Quantum confined semiconductor nanoparticles, such as colloidal quantum dots, nanorods and nanoplatelets have broad extended absorption spectra at energies above their bandgaps. This means that they can absorb light at high photon energies leading to the formation of hot excitons with finite excited state lifetimes. During their existence, the hot electron and hole that comprise the exciton may start to cool as they relax to the band edge by phonon mediated or Auger cooling processes or a combination of these. Alongside these cooling processes, there is the possibility that the hot exciton may split into two or more lower energy excitons in what is termed carrier multiplication (CM). The fission of the hot exciton to form lower energy multiexcitons is in direct competition with the cooling processes, with the timescales for multiplication and cooling often overlapping strongly in many materials. Once CM has been achieved, the next challenge is to preserve the multiexcitons long enough to make use of the bonus carriers in the face of another competing process, non-radiative Auger recombination. However, it has been found that Auger recombination and the several possible cooling processes can be manipulated and usefully suppressed or retarded by engineering the nanoparticle shape, size or composition and by the use of heterostructures, along with different choices of surface treatments. This review surveys some of the work that has led to an understanding of the rich carrier dynamics in semiconductor nanoparticles, and that has started to guide materials researchers to nanostructures that can tilt the balance in favour of efficient CM with sustained multiexciton lifetimes.