Challenges in Atomic-Scale Characterization of High-k Dielectrics and Metal Gate Electrodes for Advanced CMOS Gate Stacks

The decreasing feature sizes in complementary metal-oxide semiconductor （CMOS） transistor technology will require the replacement of SiO2 with gate dielectrics that have a high dielectric constant （high-k） because as the SiO2 gate thickness is reduced below 1.4 nm, electron tunnelling effects and high leakage currents occur in SiO2, which present serious obstacles to future device reliability. In recent years significant progress has been made on the screening and selection of high-k gate dielectrics, understanding their physical properties, and their integration into CMOS technology. Now the family of hafnium oxide-based materials has emerged as the leading candidate for high-k gate dielectrics due to their excellent physical properties. It is also realized that the high-k oxides must be implemented in conjunction with metal gate electrodes to get sufficient potential for CMOS continue scaling. In the advanced nanoscale Si-based CMOS devices, the composition and thickness of interfacial layers in the gate stacks determine the critical performance of devices. Therefore, detailed atomic- scale understandings of the microstructures and interfacial structures built in the advanced CMOS gate stacks, are highly required. In this paper, several high-resolution electron, ion, and photon-based techniques currently used to characterize the high-k gate dielectrics and interfaces at atomic-scale, are reviewed. Particularly, we critically review the research progress on the characterization of interface behavior and structural evolution in the high-k gate dielectrics by high-resolution transmission electron microscopy （HRTEM） and the related techniques based on scanning transmission electron microscopy （STEM）, including high-angle annular dark- field （HAADF） imaging （also known as Z-contrast imaging）, electron energy-loss spectroscopy （EELS）, and energy dispersive X-ray spectroscopy （EDS）, due to that HRTEM and STEM have become essential metrology tools for characterizing the dielectric gate stacks in the present and future generations of CMOS devices. In Section 1 of this review, the working principles of each technique are briefly introduced and their key features are outlined. In Section 2, microstructural characterizations of high-k gate dielectrics at atomic-scale by electron microscopy are critically reviewed by citing some recent results reported on high-k gate dielectrics. In Section 3, metal gate electrodes and the interfacial structures between high-k dielectrics and metal gates are discussed. The electron beam damage effects in high-k gate stacks are also evaluated, and their origins and prevention are described in Section 4. Finally, we end this review with personal perspectives towards the future challenges of atomic-scale material characterization in advanced CMOS gate stacks.

Selective hydrogenation improves interface properties of high-k dielectrics on 2D semiconductors

The integration of high-k dielectrics with two-dimensional(2D)semiconductors is a critical step towards high-performance nanoelectronics,which however remains challenging due to the high density of interface states and the damage to the monolayer 2D semiconductors.In this study,we propose a selective hydrogenation strategy to improve the interface properties while the 2D semiconductors are not affected.Using the interface of monolayer molybdenum disulfide(MoS_(2))and silicon nitride as an example,we show substantially improved interface properties for electronic applications after the interfacial hydrogenation,as evidenced by reduced inhomogeneous charge redistribution,increased band offset,and nearly intact electronic properties of MoS_(2).Importantly,this hydrogenation process selectively occurs only at the silicon nitride surface and is compatible with the current semiconductor fabrication process.We further show that this strategy is general and applicable to other interfaces between high-k dielectrics and 2D semiconductors such as hafnium dioxide(HfO_(2))on the monolayer MoS_(2).Our results demonstrate a simple yet viable way to improve the integration of high-k dielectrics on a broad range of 2D transition metal disulfide semiconductors,shedding light on practical electronic and optoelectronic applications.

Fabrication and characteristics of high-K HfO2 gate dielectrics on n-germanium

This paper reports that the high-K HfO2 gate dielectrics are fabricated on n-germanium substrates by sputtering Hf on Ge and following by a furnace annealing. The impacts of sputtering ambient, annealing ambient and annealing temperature on the electrical properties of high-K HfO2 gate dielectrics on germanium substrates are investigated. Experimental results indicate that high-K HfO2 gate dielectrics on germanium substrates with good electrical characteristics are obtained, the electrical properties of high-K HfO2 gate dielectrics is strongly correlated with sputtering ambient, annealing ambient and annealing temperature.

Ultrahigh performance passive radiative cooling by hybrid polar dielectric metasurface thermal emitters

Real-world passive radiative cooling requires highly emissive,selective,and omnidirectional thermal emitters to maintain the radiative cooler at a certain temperature below the ambient temperature while maximizing the net cooling power.Despite various selective thermal emitters have been demonstrated,it is still challenging to achieve these conditions sim-ultaneously because of the extreme difficulty in controlling thermal emission of photonic structures in multidimension.Here we demonstrated hybrid polar dielectric metasurface thermal emitters with machine learning inverse design,en-abling a high emissivity of~0.92 within the atmospheric transparency window 8-13μm,a large spectral selectivity of~1.8 and a wide emission angle up to 80 degrees,simultaneously.This selective and omnidirectional thermal emitter has led to a new record of temperature reduction as large as~15.4°C under strong solar irradiation of~800 W/m2,signific-antly surpassing the state-of-the-art results.The designed structures also show great potential in tackling the urban heat island effect,with modelling results suggesting a large energy saving and deployment area reduction.This research will make significant impact on passive radiative cooling,thermal energy photonics and tackling global climate change.

Design optimization of high breakdown voltage vertical GaN junction barrier Schottky diode with high-K/low-K compound dielectric structure

A vertical junction barrier Schottky diode with a high-K/low-K compound dielectric structure is proposed and optimized to achieve a high breakdown voltage(BV).There is a discontinuity of the electric field at the interface of high-K and low-K layers due to the different dielectric constants of high-K and low-K dielectric layers.A new electric field peak is introduced in the n-type drift region of junction barrier Schottky diode(JBS),so the distribution of electric field in JBS becomes more uniform.At the same time,the effect of electric-power line concentration at the p-n junction interface is suppressed due to the effects of the high-K dielectric layer and an enhancement of breakdown voltage can be achieved.Numerical simulations demonstrate that GaN JBS with a specific on-resistance(R_(on,sp)) of 2.07 mΩ·cm^(2) and a BV of 4171 V which is 167% higher than the breakdown voltage of the common structure,resulting in a high figure-of-merit(FOM) of 8.6 GW/cm^(2),and a low turn-on voltage of 0.6 V.

Improved performance of back-gate MoS2 transistors by NH3-plasma treating high-k gate dielectrics

NH3-plasma treatment is used to improve the quality of the gate dielectric and interface. Al2O3 is adopted as a buffer layer between HfO2 and MoS2 to decrease the interface-state density. Four groups of MOS capacitors and back-gate transistors with different gate dielectrics are fabricated and their C–V and I–V characteristics are compared. It is found that the Al2O3/HfO2 back-gate transistor with NH3-plasma treatment shows the best electrical performance: high on–off current ratio of 1.53 × 107, higher field-effect mobility of 26.51 cm2/V·s, and lower subthreshold swing of 145 m V/dec.These are attributed to the improvements of the gate dielectric and interface qualities by the NH3-plasma treatment and the addition of Al2O3 as a buffer layer.

The influence and explanation of fringing-induced barrier lowering on sub-100 nm MOSFETs with high-k gate dielectrics

The fringing-induced barrier lowering（FIBL） effect of sub-100 nm MOSFETs with high-k gate dielectrics is investigated using a two-dimensional device simulator.An equivalent capacitance theory is proposed to explain the physics mechanism of the FIBL effect.The FIBL effect is enhanced and the short channel performance is degraded with increasing capacitance.Based on equivalent capacitance theory,the influences of channel length,junction depth,gate/lightly doped drain（LDD） overlap length,spacer material and spacer width on FIBL is thoroughly investigated.A stack gate dielectric is presented to suppress the FIBL effect.

Study on the thermal stability and electrical properties of the high-k dielectrics (ZrO_2) _x(SiO_2)_(1-x)

(ZrO2)x(SiO2)1-x (Zr-Si-O) films with different compositions were deposited on p-Si(100) substrates by using pulsed laser deposition technique. X-ray photoelectron spectra (XPS) showed that these films remained amorphous after annealing at 800℃ with RTA process in N2 for 60 s. The XPS spectra indi- cated that Zr-Si-O films with x=0.5 suffered no obvious phase separation after annealing at 800℃, and no interface layer was formed between Zr-Si-O film and Si substrate. While Zr-Si-O films with x >0.5 suffered phase separation to precipitate ZrO2 after annealing under the same condition, and SiO2 was formed at the interface. To get a good interface between Zr-Si-O films and Si substrate, Zr-Si-O films with bi-layer structure (ZrO2)0.7(SiO2)0.3/(ZrO2)0.5(SiO2)0.5/Si was deposited. The electrical properties showed that the bi-layer Zr-Si-O film is of the lowest equivalent oxide thickness and good interface with Si substrate.

Effect of dielectric material on the uniformity of nanosecond pulsed dielectric barrier discharge

Dielectric barrier discharge(DBD)is considered as a promising technique to produce large volume uniform plasma at atmospheric pressure,and the dielectric barrier layer between the electrodes plays a key role in the DBD processes and enhancing discharge uniformity.In this work,the uniformity and discharge characteristics of the nanosecond(ns)pulsed DBD with dielectric barrier layers made of alumina,quartz glass,polycarbonate(PC),and polypropylene(PP)are investigated via discharge image observation,voltage-current waveform measurement and optical emission spectral diagnosis.Through analyzing discharge image by gray value standard deviation method,the discharge uniformity is quantitatively calculated.The effects of the space electric field intensity,the electron density(Ne),and the space reactive species on the uniformity are studied with quantifying the gap voltage Ug and the discharge current Ig,analyzing the recorded optical emission spectra,and simulating the temporal distribution of Ne with a one-dimensional fluid model.It is found that as the relative permittivity of the dielectric materials increases,the space electric field intensity is enhanced,which results in a higher Ne and electron temperature(Te).Therefore,an appropriate value of space electric field intensity can promote electron avalanches,resulting in uniform and stable plasma by the merging of electron avalanches.However,an excessive value of space electric field intensity leads to the aggregation of space charges and the distortion of the space electric field,which reduce the discharge uniformity.The surface roughness and the surface charge decay are measured to explain the influences of the surface properties and the second electron emission on the discharge uniformity.The results in this work give a comprehensive understanding of the effect of the dielectric materials on the DBD uniformity,and contribute to the selection of dielectric materials for DBD reactor and the realization of atmospheric pressure uniform,stable,and reactive plasma sources.

BE-SONOS flash memory along with metal gate and high-k dielectrics in tunnel barrier and its impact on charge retention dynamics

We investigate the effect of a high-k dielectric in the tunnel layer to improve the erase speed-retention trade-off. Here, the proposed stack in the tunnel layer is AlLaO_3/Hf AlO/SiO_2. These proposed materials possess low valence band offset with high permittivity to improve both the erase speed and retention time in barrier engineered silicon-oxide-nitride-oxide-silicon（BE-SONOS）. In the proposed structure Hf Al O and AlLaO_3 replace Si_3N_4 and the top SiO_2 layer in a conventional oxide/nitride/oxide（ONO） tunnel stack. Due to the lower conduction band offset（CBO） and high permittivity of the proposed material in the tunnel layer, it offers better program/erase（P/E） speed and retention time. In this work the gate length is also scaled down from 220 to 55 nm to observe the effect of high-k materials while scaling, for the same equivalent oxide thickness（EOT）. We found that the scaling down of the gate length has a negligible impact on the memory window of the devices. Hence, various investigated tunnel oxide stacks possess a good memory window with a charge retained up to 87.4%（at room temperature） after a period of ten years. We also examine the use of a metal gate instead of a polysilicon gate, which shows improved P/E speed and retention time.

Achieving Synergistic Improvement in Dielectric and Energy Storage Properties of All-Organic Poly(Methyl Methacrylate)-Based Copolymers Via Establishing Charge Traps

How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote theε_(r)and E_(b)of linear poly(methyl methacrylate)(PMMA)copolymers.The PMMA-based random copolymer films(P(MMA-co-MHT)),block copolymer films(PMMA-b-PMHT),and PMMA-based blend films were prepared to investigate the effects of sequential structure,phase separation structure,and modification method on dielectric and energy storage properties of PMMA-based dielectric films.As a result,the random copolymer P(MMA-coMHT)can achieve a maximumε_(r)of 5.8 at 1 kHz owing to the enhanced orientation polarization and electron polarization.Because electron injection and charge transfer are limited by the strong electrostatic attraction ofπ-conjugated benzophenanthrene group analyzed by the density functional theory(DFT),the discharge energy density value of P(MMA-co-PMHT)containing 1 mol%MHT units with the efficiency of 80%reaches15.00 J cm^(-3)at 872 MV m^(-1),which is 165%higher than that of pure PMMA.This study provides a simple and effective way to fabricate the high performance of polymer dielectrics via copolymerization with the monomer of P-type semi-conductive polymer.

The effects of inner electrode shape on the performance of dielectric barrier discharge reactor for oxidative removal of NO and SO_(2)

Seagoing vessels are responsible for more than 90%of global freight traffic,but meanwhile,emission pollutants(NO_(x)and SO_(x))of seagoing vessels also cause serious air pollution.Nonthermal plasma(NTP)combined with wet scrubbing technology is considered to be a promising technology.In order to improve the oxidation efficiency and energy efficiency of the NTP reactor,the screw and rod inner electrodes of dielectric barrier discharge(DBD)reactor were investigated.To analyze the mechanism,the optical emission spectra(OES)of NTP were measured and numerical calculation was applied.The experiment results show that the NO oxidation removal efficiency of screw electrode is lower than that of rod electrode.However,the SO_(2)removal efficiency of screw electrode is higher.According to the OES experiment and numerical calculation,the electric field intensity of the screw electrode surface is much higher than that of the rod electrode surface,and it is easier to generate N radicals to form NO.For the same energy density condition,the OH radical generation efficiency of the screw electrode reactor is similar to that of the rod electrode,but the gas temperature in the discharge gap is higher.Therefore,the SO2 oxidation efficiency of the thread electrode is higher.This study provides guidance for the optimization of oxidation efficiency and energy consumption of DBD reactor.

Solvation Effects on the Dielectric Constant of 1 M LiPF6 in Ethylene Carbonate:Ethyl Methyl Carbonate 3:7

We report the dielectric constant of 1 M LiPF_(6)in EC:EMC 3∶7 w/w(ethylene carbonate/ethyl methyl carbonate)in addition to neat EC:EMC 3∶7 w/w.Using three Debye relaxations,the static permittivity value,or dielectric constant,is extrapolated to 18.5,which is compared to 18.7 for the neat solvent mixture.The EC solvent is found to strongly coordinate with the Li^(+)cations of the salt,which results in a loss of dielectric contribution to the electrolyte.However,the small amplitude and large uncertainty in relaxation frequency for EMC cloud definitive identification of the Li^(+)solvation shell.Importantly,the loss of the free EC permittivity contribution due to Li^(+)solvation is almost completely balanced by the positive contribution of the associated LiPF_(6)salt,demonstrating that a significant quantity of dipolar ion pairs exists in 1 M LiPF_(6)in EC:EMC 3∶7.

Dielectric anisotropy in liquid crystal mixtures with nematic and smectic phases

The modulation of dielectric anisotropy(△ε)is pivotal for elucidating molecular interactions and directing the alignment of liquid crystals.In this study,we combine liquid crystals with opposing dielectric anisotropies to explore the impact of varying concentrations on their properties.We report the sign-reversal of△εin both the nematic and smectic A phases of these mixed liquid crystals,alongside a dual-frequency behaviour across a broad temperature spectrum.Our research further quantifies the influence of mixture ratios under various temperatures and electric field frequencies.This exploration may pave the way for the discovery of new physical phenomena.

Boron nitride silicone rubber composite foam with low dielectric and high thermal conductivity

Silicone rubber(SR)is widely used in the field of electronic packaging because of its low dielectric properties.In this work,the porosity of the SR was improved,and the dielectric constant of the SR foam was reduced by adding expanded microspheres(EM).Then,the thermal conductivity of the system was improved by combining the modified boron nitride(f-BN).The results showed that after the f-BN was added,the dielectric constant and dielectric loss were much lower than those of pure SR.Micron-sized modified boron nitride(f-mBN)improved the dielectric and thermal conductivity of the SR foam better than that of nano-sized modified boron nitride(f-nBN),but f-nBN improved the volume resistivity,tensile strength,and thermal stability of the SR better than f-mBN.When the mass ratio of f-mBN and fnBN is 2:1,the thermal conductivity of the SR foam reaches the maximum value of 0.808 W·m^(-1)·K^(-1),which is 6.5 times that before the addition.The heat release rate and fire growth index are the lowest,and the improvement in flame retardancy is mainly attributed to the high thermal stability and physical barrier of f-BN.

Influences of divalent ion substitution on the magnetic and dielectric properties of W-type barium ferrite

Saturation magnetization,magneto-crystalline anisotropy field,and dielectric properties are closely related to microwave devices applied at different frequencies.For regulating the magnetic and dielectric properties of W-type barium ferrites,single-phase BaMe_(2)Fe_(16)O_(27)(Me=Fe,Mn,Zn,Ni,Co) with different Me ions were synthesized by the high-temperature solid-state method.The saturation magnetization(Ms) range from 47.77 emu/g to 95.34 emu/g and the magnetic anisotropy field(H_a) range from 10700.60 Oe(1 Oe=79.5775 A·m^(-1)) to 13739.57 Oe,depending on the type of cation substitution in the hexagonal lattice.The dielectric permittivity and dielectric loss decrease with increasing frequency of the AC electric field in the low-frequency region,while they almost remain constant in the high-frequency region.The charac teristics of easy regulation and preparation make it a potential candidate for use in microwave device applications.

Fatigue Resistance of RCA Modified Asphalt Based on Dielectric Properties

In order to study the anti-fatigue performance of RCA modified asphalt (RMA),the performance of RMA and 90#matrix asphalt with different modifier content were measured by asphalt penetration,ductility,softening point,Brookfield viscosity,rheological index,infrared spectrum and dielectric constant test.This paper discusses the changes of asphalt basic indexes,fatigue properties and asphalt components based on dielectric properties under different modifier contents,and analyzes the grey correlation degree between components and asphalt pavement performance indexes.The results show that the optimum content of RCA modifier is 16.7%of the asphalt quality according to the penetration,ductility,softening point,Brockfield viscosity,viscosity temperature curve and fatigue life.In the phase angle-strain curve,there is disorder in the latter part of the curve.According to the strain (ε_(d)) corresponding to the disorder point,a new fatigue failure criterion is proposed and proved.Based on the new asphalt fatigue failure criterion,the fatigue prediction model of asphalt mixture is improved,and the fatigue life predicted by the improved fatigue model is compared with the fatigue life obtained by four-point bending fatigue test.The results show that the proposed new asphalt fatigue failure criterion is reasonable,and the fatigue life predicted by the improved asphalt mixture fatigue prediction model is accurate.The research method of classifying asphalt components based on dielectric properties is simple and effective,and the components have a high correlation with the road performance of base asphalt and modified asphalt.

Surface charge characteristics in a three-electrode surface dielectric barrier discharge

The surface charge characteristics in a three-electrode surface dielectric barrier discharge(SDBD)are experimentally investigated based on the Pockels effect of an electro-optical crystal. The actuator is based on the most commonly used SDBD structure for airflow control, with an exposed electrode supplied with sinusoidal AC high voltage, a grounded encapsulated electrode and an additional exposed electrode downstream supplied with DC voltage. The ionic wind velocity and thrust can be significantly improved by increasing DC voltage although the plasma discharge characteristics are virtually unaffected. It is found that the negative charges generated by the discharge of the three-electrode structure accumulate on the dielectric surface significantly further downstream in an AC period compared to the actuator with a two-electrode structure. The negative charges in the downstream region increase as the DC voltage increases.In addition, the DC voltage affects the time required for the positive charge filaments to decay.The positive DC voltage expands the ionic acceleration zone downstream to produce a greater EHD force. The amplitude of the DC voltage affects the electric field on the dielectric surface and is therefore a key factor in the formation of the EHD force. Further research on the surface charge characteristics of a three-electrode structure has been conducted using a pulse power to drive the discharge, and the same conclusions are drawn. This work demonstrates a link between surface charge characteristics and EHD performance of a three-electrode SDBD actuator.

Enhancing the Performance of Perovskite Light-Emitting Diodes via Synergistic Effect of Defect Passivation and Dielectric Screening

Metal halide perovskites,particularly the quasi-two-dimensional perovskite subclass,have exhibited considerable potential for next-generation electroluminescent materials for lighting and display.Nevertheless,the presence of defects within these perovskites has a substantial influence on the emission efficiency and durability of the devices.In this study,we revealed a synergistic passivation mechanism on perovskite films by using a dual-functional compound of potassium bromide.The dual functional potassium bromide on the one hand can passivate the defects of halide vacancies with bromine anions and,on the other hand,can screen the charged defects at the grain boundaries with potassium cations.This approach effectively reduces the probability of carriers quenching resulting from charged defects capture and consequently enhances the radiative recombination efficiency of perovskite thin films,leading to a significant enhancement of photoluminescence quantum yield to near-unity values(95%).Meanwhile,the potassium bromide treatment promoted the growth of homogeneous and smooth film,facilitating the charge carrier injection in the devices.Consequently,the perovskite light-emitting diodes based on this strategy achieve a maximum external quantum efficiency of~21%and maximum luminance of~60,000 cd m^(-2).This work provides a deeper insight into the passivation mechanism of ionic compound additives in perovskite with the solution method.

Reconfigurable(4, 6^(2)) and(4, 8^(2)) Archimedean plasma photonic crystals in dielectric barrier discharge

Archimedean photonic crystal has become a research area of great interest due to its various unique properties. Here, we experimentally demonstrate the realization of reconfigurable(4, 6^(2))and(4, 8^(2)) Archimedean plasma photonic crystals(APPCs) by use of dielectric barrier discharges in air. Dynamical control on both the macrostructures including the lattice symmetry and the crystal orientation, and the microstructures including the fine structures of scattering elements has been achieved. The formation mechanisms of APPCs are studied by time-resolved measurements together with numerical simulations. Large omnidirectional band gaps of APPCs have been obtained. The tunable topology of APPCs may offer new opportunities for fabricating multi-functional and highly-integrated microwave devices.