Low Work Function Metal Research Articles

Self-Diffusion Effect Assisted TiO2/Li3PO4 Electron Selective Passivating Contact in Silicon Solar Cells Approaching 23% Efficiency.

Carrier selective contacts with passivation effects are considered to have a significant influence on the performance of crystalline silicon (c-Si) solar cells. It is essential for electron selective contact materials to meet the requirements of ultra-low contact resistance and excellent passivation effects. This work introduces a stack layer of Lithium Phosphate (Li3PO4) /Titanium Dioxide (TiO2) as a new electron selective passivating contact. It is found that the stack achieves an impressive contact resistivity (ρc) of 0.128mΩcm2 on n-type c-Si substrates with resistivity ranging from 1 to 3Ωcm (14.6mΩcm2 for the n-Si/a-Si:H/Li3PO4/TiO2/Al contact). Furthermore, it effectively reduces the surface recombination parameter (J0) to less than 4fA by incorporating a 6nm a-Si:H(i) layer. The characterization of the n-Si/Li3PO4/TiO2 interface reveals that phosphorus diffusion into silicon plays a crucial role in achieving the ultra-low contact resistivity, while the presence of PO4 3- groups helps in fixing hydrogen atoms to maintain the desired chemical passivation effect. Finally, a silicon heterojunction solar cell (SHJ) with a rear full-area configuration of a-Si:H/Li3PO4/TiO2/Al is successfully demonstrated achieving an impressive power conversion efficiency of 22.89%. The result proves the efficacy of employing hydrogen-rich low-work function metal oxide stacks as electron selective passivating contacts.

Electrochemical production of ammonia: Nitrate reduction over novel Cu-Ni-Al metallic glass nanoparticles used as highly active and durable catalyst

It is a great challenge to design and synthesize catalysts that can regulate both adsorption and desorption processes for electrocatalytic nitrate reduction to ammonia (NRA). Herein, amorphous Cu-Ni-Al nanometallic glasses (NG) were synthesized using a facile thermal evaporation coupled Joule heating method. The Cu50Ni25Al25-NG exhibits remarkable Faradaic efficiency (98.81 %) and NH3 yield-rate (211.14 μmol h−1cm−2) at an outstanding positive potential of −0.15 V vs. RHE. Aluminum atoms of low work-function when intercalated at different positions in Cu50Ni25Al25-NG enhance both adsorption and desorption processes during NRA. The oscillatory properties of surface potential detected by Kelvin-probe force microscopy demonstrate the diversity of active sites on Cu50Ni25Al25-NG. Two potential-regulated reaction mechanisms in NRA on the surface of Cu50Ni25Al25-NG were proposed using in-situ electrochemical Raman spectra. This work provides a new method for the preparation of multi-element NG enriched with low work-function metals and a new idea for the synthesis of synergistic catalytic-sites for NRAs.

Realizing n-type carbon nanotubes via halide perovskite nanowires Cs4MX5 inner filling

N-type carbon nanotubes (CNTs)-based field-effect transistors (FETs) have huge potential applications in low-power consumption tunnel FETs. However, the low-work function metal electrodes can achieve n-type CNTs, but they are easily oxidized due to poor environmental stability. Therefore, based on first-principles calculations, we proposed halide perovskite nanowires Cs4MX5 (M = Pb, Sn; X = Cl, Br, I) inner filling to achieve n-type single-walled CNTs (SWCNTs). The results indicated that all the perovskite nanowires located at the center of the SWCNTs possess high stability. Moreover, the diameter of SWCNTs is a crucial factor affecting the inner filling of perovskite nanowires with an optimal diameter of about 1.4 nm. Furthermore, all the perovskite nanowires Cs4MX5 are excellent electron donors, and the largest charge transfer is up to 1.72 e/nm for Cs4SnI5. Their interaction mechanism reveals that the low work function and the large internal bandgap are two important factors for cubic-phase nanowires to realize the n-type CNTs. Our findings provide some candidate materials and a feasible way to achieve n-type CNTs for applying CNTs-based FETs.

Low turn-on voltage AlGaN/GaN Schottky barrier diode with a low work function anode and high work function field plate

AlGaN/GaN Schottky barrier diodes (SBDs) with a low work function W anode and a high work function Ni field plate on sapphire substrates are investigated in this Letter. The low work function metal W leads to the low turn-on voltage, while the high work function metal Ni maintains the leakage current and increases the breakdown voltage. An ultralow turn-on voltage of 0.23 V determined by the positive fixed charge at the AlGaN/Si3N4 interface is achieved in this W/Ni SBD. More importantly, benefitting from the dual-metal anode/field plate structure, the on-resistance decreases from 7.99 to 5.53 Ω mm, and the breakdown voltage increases from 493 to 1219 V. In addition, the turn-on voltage decreases less than 57%, and the on-resistance increases less than 186% at a high temperature up to 120 °C. The W/Ni SBD with a cathode–anode length of 18 μm and a field plate length of 4 μm shows a low turn-on voltage of 0.23 V, a low on-resistance of 5.53 Ω mm, a leakage current of 0.65 mA/mm, and a high breakdown voltage of 1.21 kV, indicating a great potential for power electronic applications.

Atom layer deposited TiO2 electron transport layer for silicon heterojunction solar cells to achieve high performance

Silicon/compound heterojunction (SCH) solar cells based on p-type and n-type c-Si wafers using atom layer deposition-TiO2 and low work function metal as the electron transport layer and rear electrode are fabricated. Efficiencies of 20.6 % and 21.6 % are achieved on p-type and n-type silicon solar cells, respectively. High Voc exceeding 700 mV have been realized on both kinds of Si wafers. Special attention has been paid to the SCH solar cells based on p-type c-Si wafers in which the TiO2 electron transport layer serves as the emitter. Carrier transport mechanisms and junction characteristics of the SCH solar cells are analyzed based on dark J-V measurement. The formation of a strong inversion layer at the Si surface region is determined, which implies the high Voc potential of the SCH solar cells based on p-type Si. An optical loss analysis is performed along with a possible solution to further improve the Jsc. The feasibility of TiO2 applied as an efficient electron transport layer (emitter) in p-type SCH solar cells with high performance has been showed.

Characterization and Control of Carbon Nanotube Doping

Carbon nanotube FETs show great promise for beyond-Si and monolithic 3D electronics, however there are still fundamental questions to explore. In particular, controlled N- and P- doping is a fundamental process module which can be used to engineer semiconductor resistance in un-gated regions such as the contact or extension, as well as optimize band-to-band tunneling leakage [1-4]. To-date both N- and P- doping has been demonstrated for CNT, but the optimal strategies for doping control and carrier density quantification have not been determined. In this work, we present a study of N- and P- doping using solid-state dopants and doping control strategy using a dielectric barrier of tunable thickness. A TCAD evaluation reveals the tradeoffs between carrier density and mobility for increasing dielectric barrier thickness, and reveals the critical role of dielectric constant in optimizing performance of spacer doping [5]. Multiple characterization approaches under evaluation help to correlate doping strength to experimentally measurable quantities with insight into the doping mechanisms. Finally, we will summarize potential approaches for improving doping control and quantification, and progress towards integration of the doping in highly-scaled high-performance carbon nanotube FETs [6].[1] Z. Zhang, et al., “Complementary carbon nanotube metal-oxide-semiconductor field-effect transistors with localized solid-state extension doping,” Nature Electronics, 2023.[2] Q. Lin, et al., “Band-to-band Tunneling Leakage Current Characterization and Projection in Carbon Nanotube Transistors,” ACS Nano, 2023.[3] G. Zeevi, et al., “PN Junction and band to band tunneling in carbon nanotube transistors at room temperature,” Nanotechnology, 2021.[4] L. Liyanage, et al., “VLSI-compatible carbon nanotube doping technique with low work-function metal oxides,” Nano Letters, 2014.[5] C. Gilardi et al., “Barrier Booster for Remote Extension Doping and its DTCO for 1D & 2D FETs”, IEDM 2023[6] S.Li, et al., “High-performance and low parasitic capacitance CNT MOSFET: 1.2 mA/μm at VDS of 0.75 V by self-aligned doping in sub-20 nm spacer,” IEDM 2023.

Improving the performance and stability of inverted perovskite solar cell modules by cathode interface engineering

Perovskite solar cells (PSCs) represent a highly promising photovoltaic technology wherein a low-work function metal cathode is essential for efficient electron collection. The effectiveness of PSCs is significantly enhanced by a well-designed cathode interface layer (CIL). Characterized by their simple structure and impressive modification capabilities, small-molecule CILs hold considerable commercial potential for advancing the performance of PSCs. Herein, we synthesized a conjugated small-molecule CIL, named FY1, for modulating the cathode interface of inverted PSCs to enhance the power conversion efficiency (PCE) and long-term stability. FY1 not only optimized the molecule/metal contact to reduce traps but also uniformly improved the efficiency and speed of extracting photogenerated electrons, facilitating their effective extraction at the cathode interface. FY1 modification reduced the work function of Ag, subsequently lowering the energy barrier for electron transfer from the electron transport layer to the external cathode metal. By employing FY1 as a CIL, a record-high PCE of 23.72 % and a fill factor of 82.3 % were achieved in inverted PSCs. Furthermore, FY1 modification increased the PCE of PSC modules with an active area of 14 cm2 to 21.8 %; after continuous illumination for 850 h, it retained approximately 98.5 % of the initial efficiency. These findings show that FY1 can assist in unlocking the full potential of this emerging photovoltaic technology.

An energy-band modulated p-GaN/InGaN/AlN p-channel MESFET with high ION/IOFF ratio and steep subthreshold swing

In this work, we report on the high-performance p-GaN/InGaN/AlN multi-heterostructure p-channel metal–semiconductor field effect transistors (MESFETs) with energy-band modulated quantum well-like InGaN channel and low work function metal tungsten (W) as the gate material. A negative threshold voltage (VTH) of −0.35 V is achieved by precisely controlling the self-aligned etching depth at the active region. Benefiting from the enhanced hole confinement, the ION/IOFF ratio and subthreshold swing of the fabricated-channel MESFET are extracted to be 1.2 × 107 and 66 mV/dec, respectively, at room temperature. The idealized Schottky interface with TMAH and post-gate-annealing treatment shows an ultra-low voltage hysteresis of 0.08 V extracted at subthreshold area in the dual-sweep transfer curves.

Improved field emission properties of reduced graphene oxide decorated with indium nanoparticles

Low work function metals decoration of graphene is a effective method for the improvement of electron field emission properties. Indium, a relatively lower work function metal, is used to decorate reduced graphene oxide (RGO) films for the first time by simple and efficient solution process combined with magnetron sputtering method and the field emission properties are investigated. At continue voltage mode, the indium decorated RGO films display lower turn-on and threshold field as well as better emission stability than those of pristine RGO films. Moreover, the field emission performance of indium decorated RGO films is affected by the spacing between the cathode and anode. At pulse voltage mode, the indium decorated RGO films show approximately 10 times higher maximum emission current density compared to that at continue voltage mode. The calculation results by density functional theory indicate that the indium decoration of RGO significantly increases the density of states (DOS) near Fermi level and reduces the work function.

Direct Observation of Contact Reaction Induced Ion Migration and its Effect on Non-Ideal Charge Transport in Lead Triiodide Perovskite Field-Effect Transistors.

The migration of ionic defects and electrochemical reactions with metal electrodes remains one of the most important research challenges for organometal halide perovskite optoelectronic devices. There is still a lack of understanding of how the formation of mobile ionic defects impact charge carrier transport and operational device stability, particularly in perovskite field-effect transistors (FETs), which tend to exhibit anomalous device characteristics. Here, the evolution of the n-type FET characteristics of one of the most widely studied materials, Cs0.05 FA0.17 MA0.78 PbI3, is investigated during repeated measurement cycles as a function of different metal source-drain contacts and precursor stoichiometry. The channel current increases for high work function metals and decreases for low work function metals when multiple cycles of transfer characteristics are measured. The cycling behavior is also sensitive to the precursor stoichiometry. These metal/stoichiometry-dependent device non-idealities are correlated with the quenching of photoluminescence near the positively biased electrode. Based on elemental analysis using electron microscopy the observations can be understood by an n-type doping effect of metallic ions that are created by an electrochemical interaction at the metal-semiconductor interface and migrate into the channel. The findings improve the understanding of ion migration, contact reactions, and the origin of non-idealities in lead triiodide perovskite FETs.

Stepwise photoassisted decomposition of carbohydrates to H2

Stepwise photoassisted decomposition of carbohydrates to H2

Ab-initio study of Schottky barrier heights at metal-diamond (1 1 1) interfaces

Diamond electronic devices have attracted great attention in the field of high power and high frequency applications due to their excellent properties. For diamond electronics, metal and diamond contacts are important for the electronic device performance, with Schottky barrier heights (SBHs) playing a crucial role in the transmission properties of diamond devices. To make sense of their electrical characteristics, the interface supercells of diamond (111) with diverse metals have been explored using first-principles calculations. Clear metal-induced gap states (MIGS) can be observed at the interface, resulting in an enhanced Fermi-level pinning effect, with a pinning factor of 0.3. The results surprisingly show that there is a larger transverse tunneling probability and a smaller longitudinal tunneling probability for all diamond contact interfaces. All interfaces studied are p-type contacts with the metal Fermi level close to the diamond valance band edge. The low work function metals such as Sc and Ti are excellent at generating Schottky contacts with relatively higher SBHs (∼1.0 eV ± 0.6 eV). Pt and Ni have a smallest barrier height of ∼ 0.5 eV, making them ideal for ohmic electrodes with low contact resistance. The calculated SBHs are within the range of the experimental findings. This work gives insight into the electrical structural changes at the contact interface between metal and diamond, which provides a theoretical basis for selecting suitable electrodes for high-power diamond devices.

Low leakage current and high breakdown voltage of AlGaN/GaN Schottky barrier diodes with wet-etching groove anode

AlGaN/GaN heterojunction epitaxies with wide bandgap, high critical electric field as well as high density and high mobility two-dimensional electron gas have shown great potential applications in the next-generation high-power and high-frequency devices. Especially, with the development of Si-based GaN epitaxial technique with big size, GaN devices with low cost also show great advantage in consumer electronics. In order to improve the rectification efficiency of AlGaN/GaN Schottky barrier diode (SBD), low leakage current and low turn-on voltage are important. The GaN Schottky barrier diode with low work-function metal as anode is found to be very effective to reduce turn-on voltage. However, the low Schottky barrier height makes the Schottky interface sensitive to damage to groove surface, which leads to a high leakage current. In this work, a novel wet-etching technique with thermal oxygen oxidation and KOH corrosion is used to prepare the anode groove, and the surface roughness of groove decreases from 0.57 to 0.23 nm, compared with that of the dry-etching surface of groove. Meanwhile, the leakage current is suppressed from 1.5 × 10<sup>–6</sup> to 2.6 × 10<sup>–7</sup> A/mm. Benefiting from the great corrosion selectively of hot KOH solution to AlGaN barrier layer and GaN channel layer after thermal oxygen oxidation, the spikes of the edge of groove region caused by the nonuniform distribution of plasma in the cavity is improved, and the breakdown voltage of the fabricated AlGaN/GaN SBDs is raised from –1.28 to –1.73 kV.

Interface-state suppression of AlGaN/GaN Schottky barrier diodes with post-anode-annealing treatment

Owing to the high density and high mobility of two-dimensional electron gas (2DEG) induced by strong spontaneous polarization and piezoelectric polarization effect, AlGaN/GaN Schottky barrier diodes (SBDs) with high output current density and low on-resistance have proved to be a promising candidate. Anode of GaN SBD is the core structure, which affects the device performance such as turn-on voltage, reverse current, on-resistance, and breakdown voltage. Therefore, idealized Schottky junction with low interface state density is very important in achieving high-performance GaN SBD. In this work, AlGaN/GaN SBD with low work-function metal W as anode is fabricated, and the post-anode-annealing (PAA) treatment is found to be effective in promoting the bonding reaction between anode metal and GaN in the anode region. Comparing with GaN SBDs without PAA treatment, the interface state density decreases from 9.48×10<sup>15</sup> eV<sup>–1</sup>·cm<sup>–2</sup> to 1.77×10<sup>13</sup> eV<sup>–1</sup>·cm<sup>–2</sup> after PAA treatment. The reverse leakage current is reduced by two orders, which ascribes to the idealized anode interface with low interface state density. Meanwhile, the influence of interface state on carriers in the forward conduction process is also suppressed, and the differential on-resistance of the fabricated GaN SBDs decreases from 17.05 Ω·mm to 12.57 Ω·mm. It is obvious that the PAA process proves to be an effective method to suppress the interface states density at M/S interface, thus significantly improving the performance of GaN SBD, which is the key technology in fabricating the high-performance GaN device.

The Investigation of the Influence of a Cu2O Buffer Layer on Hole Transport Layers in MAPbI3-Based Perovskite Solar Cells.

The passivation engineering of the hole transport layer in perovskite solar cells (PSCs) has significantly decreased carrier accumulation and open circuit voltage (Voc) loss, as well as energy band mismatching, thus achieving the goal of high-power conversion efficiency. However, most devices incorporating organic/inorganic buffer layers suffer from poor stability and low efficiency. In this article, we have proposed an inorganic buffer layer of Cu2O, which has achieved high efficiency on lower work function metals and various frequently used hole transport layers (HTLs). Once the Cu2O buffer layer was applied to modify the Cu/PTAA interface, the device exhibited a high Voc of 1.20 V, a high FF of 75.92%, and an enhanced PCE of 22.49% versus a Voc of 1.12 V, FF of 69.16%, and PCE of 18.99% from the (PTAA/Cu) n-i-p structure. Our simulation showed that the application of a Cu2O buffer layer improved the interfacial contact and energy alignment, promoting the carrier transportation and reducing the charge accumulation. Furthermore, we optimized the combinations of the thicknesses of the Cu2O, the absorber layer, and PTAA to obtain the best performance for Cu-based perovskite solar cells. Eventually, we explored the effect of the defect density between the HTL/absorber interface and the absorber/ETL interface on the device and recommended the appropriate reference defect density for experimental research. This work provides guidance for improving the experimental efficiency and reducing the cost of perovskite solar cells.

Fermi Level Depinning in Two-Dimensional Materials Using a Fluorinated Bilayer Graphene Barrier

Strong Fermi level pinning (FLP) - often attributed to metal-induced gap states at the interfacial contacts - severely reduces the tunability of the Schottky barrier height of the junction and limits applications of the 2D materials in electronics and optoelectronics. Here, we show that fluorinated bilayer graphene (FBLG) can be used as a barrier to effectively prevent FLP at metal/2D materials interfaces. FLBG can be produced via short exposure (1-3 min) to SF6 plasma that fluorinates only the top layer of a bilayer graphene with covalent C-F bonding, while the bottom layer remains intrinsic, resulting in a band gap opening of about 75 meV. Inserting FBLG between the metallic contacts and a layer of MoS2 reduces the Schottky barrier height dramatically for the low-work function metals (313 and 260 meV for Ti and Cr, respectively) while it increases for the high-work function one ( 160 meV for Pd), corresponding to an improved pinning factor. Our results provide a straightforward method to generate atomically thin dielectrics with applications not only for depinning the Fermi level at metal/transition metal dichalcogenide (TMD) interfaces but also for solving many other problems in electronics and optoelectronics

Electrical contact properties between Yb and few-layer WS2

The charge injection mechanism from contact electrodes into two-dimensional (2D) dichalcogenides is an essential topic for exploiting electronics based on 2D channels, but remains not well understood. Here, low-work function metal ytterbium (Yb) was employed as contacts for tungsten disulfide (WS2) to understand the realistic injection mechanism. The contact properties in WS2 with variable temperature (T) and channel thickness (tch) were synergetically characterized. It is found that the Yb/WS2 interfaces exhibit a strong pinning effect between energy levels and a low contact resistance (RC) value down to 5 kΩ μm. Cryogenic electrical measurements reveal that RC exhibits weakly positive dependence on T until 77 K as well as a weakly negative correlation with tch. In contrast to the non-negligible RC values extracted, an unexpectedly low effective thermal injection barrier of 36 meV is estimated, indicating the presence of significant tunneling injection in the subthreshold regime and the inapplicability of the pure thermionic emission model to estimate the height of the injection barrier.

Low-Work Function Metals Boost Selective and Fast Scission of Methanol C–H Bonds

Low-Work Function Metals Boost Selective and Fast Scission of Methanol C–H Bonds

Current transport mechanism of AlGaN-channel Schottky barrier diode with extremely low leakage current and high blocking voltage of 2.55 kV

This Letter presents work on lateral AlGaN-channel Schottky barrier diodes (SBDs) with impressive reverse blocking characteristics and low onset voltage (VON). A low reverse current (IR) of 28 nA/mm and low VON of 0.60 V are obtained by utilizing an AlGaN back barrier layer with high Al composition and low work function metal as the anode. The fabricated AlGaN-channel SBD with an anode–cathode distance (LAC) of 30 μm achieves a high blocking voltage of 2.55 kV and a power figure-of-merit of 363 MW/cm2. Meanwhile, the current transport mechanism of AlGaN-channel SBDs goes through thermionic emission, thermionic field emission, and trap-assisted tunneling as the reverse bias is gradually increased. The thermal activation energy (EA) is calculated to be 141.3 meV at high reverse bias. IR at 475 K is only 3 μA/mm, which shows an adequate barrier height for rectifying at high temperature even with low VON. The AlGaN-channel SBDs show great promise for next-generation power electronics with balanced forward and reverse characteristics.

(INVITED) Opto-electronic properties of solution-synthesized MoS2 metal-semiconductor-metal photodetector

We report a simple fabrication method for metal-semiconductor-metal (MSM) photodetectors using solution-synthesized MoS2 films as the semiconductor channel and pure indium for the metal contacts. Resonance Raman spectroscopy has been used to confirm the growth of ultra-thin MoS2 films. Due to the low work function of indium, the back-to-back indium-MoS2 Schottky junctions formed relatively low Schottky barrier height (0.43 eV), which has been calculated using the thermionic field emission model. Moreover, the MSM device shows good responsivity (22 mA/W) under white light illumination. The MoS2-MSM device possesses higher photoelectrical response in the visible and near IR region compared to UV due to the indirect bandgap of ultra-thin MoS2 film which has been estimated to be 1.38 eV. These findings reveal the significance of using low work function metals like indium as contacts for layered transition metal dichalcogenides (TMDC) films (produced by low cost solution-based techniques), particularly MoS2, in order to design semiconductor devices with efficient opto-electronic performance.