Positive Charge Buildup Research Articles

Compact model for single event transients and total dose effects at high temperatures for partially depleted SOI MOSFETs

This paper presents a compact model for partially depleted SOI MOSFETs, which allows for describing the total dose and the single event effects. It incorporates both temperature and charge buildup effects during irradiation. The developed model is implemented in a Verilog-A module. This original module can be coupled with Spice simulator, allowing for faster (time efficient) circuit simulations (comparing to numerical physical ones) at different bias, linear energy transfer ( LET), buildup charges and temperatures. Better efficiency and flexibility than the standard current source method is achieved thanks to the direct link between the module and the irradiated transistor through the partially depleted SOI CMOS body contact terminal. Mixed-mode simulations of a partially depleted SOI CMOS D flip–flop at different conditions (biases, LETs, temperatures, buildup charge densities) are used in order to validate the model. Well-known high tolerance of SOI circuits to a single event effects is demonstrated to be degraded with the total dose increase (appearing as a positive charge buildup), which is further enhanced at higher temperatures.

Comparison of electrical stress-induced charge carrier generation/trapping and related degradation of SiO 2 and HfO 2/SiO 2 gate dielectric stacks

We compare charge carrier generation/trapping related degradation in control oxide (SiO 2) and HfO 2/SiO 2 stack of an identical equivalent-oxide-thickness (EOT) during constant gate voltage stress of n-type metal-oxide-semiconductor (nMOS) capacitors. Irrespective of these two dielectrics, the kinetics of generation of both surface states and oxide-trapped positive charges are found to be similar. Our analysis shows that the positive oxide charge buildup during CVS is due to trapping of protons by the strained Si O Si bonds in either of the devices. We demonstrate that compared to SiO 2 devices, HfO 2 devices with an equal EOT better perform in CMOS logic applications. On the other hand, our results indicate that the control oxide is better in charge trapping memory devices. Furthermore, the lifetime of the control oxide devices is observed longer than that of HfO 2 devices at a given operating voltage.

Imination of Sulfides and Sulfoxides with Sulfonylimino‐λ3‐Bromane under Mild, Metal‐Free Conditions

Exposure of sulfides and sulfoxides to trifluoromethanesulfonylimino(aryl)-lambda(3)-bromane in dichloromethane at 0 degrees C results in a facile transfer of the sulfonylimino group to sulfur atoms and affords N-triflylsulfilimines and -sulfoximines in high yields under transition-metal-free conditions. Imination of (R)-methyl p-tolyl sulfoxide proceeded with predominant retention of configuration at the stereogenic sulfur center. The Hammett plot afforded rho values of -0.58 for para-substituted thioanisoles and -0.49 for their equivalent sulfoxides, which suggests a buildup of positive charge on the sulfur atoms of sulfides and sulfoxides in the transition state. Calculations suggest a bimolecular nucleophilic-substitution mechanism on the negatively charged nitrogen atom of the sulfonylimino-lambda(3)-bromane, which involves the attack of a sulfide from the opposite side to bromine(III).

Constant current stress-induced leakage current in mixed HfO 2–Ta 2O 5 stacks

The electrical characteristics of HfO 2–Ta 2O 5 mixed stacks under constant current stress (CCS) at gate injection with 20 mA/cm 2 and stressing times of 50 and 200 s have been investigated. A very weak effect of the stress on the global dielectric constant, on fast and slow states in the stack as well as on the dominant conduction mechanism is detected. The most sensitive parameter to the CCS is the leakage current. The stress-induced leakage current (SILC) is voltage and thickness dependent. The pre-existing traps govern the trapping kinetics and are a key parameter to evaluate the stress response. Two processes – positive charge build-up and new bulk traps generation – are suggested to be responsible for SILC: the domination of one of them depends on both the film thickness and the stressing time. The positive charge build-up is localized close to the gate electrode implying gate-induced defects could be precursors for it. It is established that unlike the case of single SiO 2 layer, the bulk traps closer to the gate electrode control SILC in the mixed Ta 2O 5–HfO 2-based capacitors.

High energy electron fluxes in dc-augmented capacitively coupled plasmas. II. Effects on twisting in high aspect ratio etching of dielectrics

In high aspect ratio (HAR) plasma etching of holes and trenches in dielectrics, sporadic twisting is often observed. Twisting is the randomly occurring divergence of a hole or trench from the vertical. Many causes have been proposed for twisting, one of which is stochastic charging. As feature sizes shrink, the fluxes of plasma particles, and ions in particular, into the feature become statistical. Randomly deposited charge by ions on the inside of a feature may be sufficient to produce lateral electric fields which divert incoming ions and initiate nonvertical etching or twisting. This is particularly problematic when etching with fluorocarbon gas mixtures where deposition of polymer in the feature may trap charge. dc-augmented capacitively coupled plasmas (dc-CCPs) have been investigated as a remedy for twisting. In these devices, high energy electron (HEE) beams having narrow angular spreads can be generated. HEEs incident onto the wafer which penetrate into HAR features can neutralize the positive charge and so reduce the incidence of twisting. In this paper, we report on results from a computational investigation of plasma etching of SiO2 in a dc-CCP using Ar/C4F8/O2 gas mixtures. We found that HEE beams incident onto the wafer are capable of penetrating into features and partially neutralizing positive charge buildup due to sporadic ion charging, thereby reducing the incidence of twisting. Increasing the rf bias power increases the HEE beam energy and flux with some indication of improvement of twisting, but there are also changes in the ion energy and fluxes, so this is not an unambiguous improvement. Increasing the dc bias voltage while keeping the rf bias voltage constant increases the maximum energy of the HEE and its flux while the ion characteristics remain nearly constant. For these conditions, the occurrence of twisting decreases with increasing HEE energy and flux.

Synthesis of Oxorhenium(V) Complexes with Diamido Amine Ancillary Ligands and Their Role in Oxygen Atom Transfer Catalysis

The detailed syntheses of complexes of the form [Re(O)(X)(RNCH(2)CH(2))(2)N(Me)] (X = Me, Cl, I, R = mesityl, C(6)F(5)), 1-3, incorporating diamidoamine ancillary ligands are described. X-ray crystal structures for the complexes [Re(O)(Me)((C(6)F(5))NCH(2)CH(2))(2)N(Me)], 1a, [Re(O)(I)((C(6)F(5))N CH(2)CH(2))(2)N(Me)], 3a, and [Re(O)(I)((Mes)NCH(2))(2)N(Me)], 3b, are reported. The geometry about the metal center in 1a is best described as a severely distorted square pyramid with the oxo ligand in the apical position. In contrast, the geometry about the metal center in 3a is best described as a severely distorted trigonal bipyramid, with the iodo ligand occupying the apical position and the diamido nitrogens and the oxo ligand occupying the equatorial plane. The catalytic activities of these complexes for oxygen atom transfer, OAT, from pyridine-N-oxides, PyO, to PPh(3) were also examined. The reactions exhibited a clear dependence on the diamido ligand substituent and the X ligand (Me, I, Cl) attached to the metal, with the combined effect that electron-withdrawing substituents on the diamido ligand and poor sigma donors directly attached to the metal center increases the rate of catalytic activity. The kinetics of OAT from pyridine-N-oxides to Re were also investigated. The reactions displayed clean first order kinetics in Re and saturation kinetics for the dependence on PyO. Changing the PyO substrate had no effect on the saturation value, k(sat), suggesting that the OAT reaction in these five-coordinate complexes appears to be governed by isomerization of the starting complex. Attempts to isolate a postulated Re(VII) intermediate were not successful because of hydrolytic degradation. The product of hydrolytic degradation [((C(6)F(5))N(H)CH(2)CH(2)))(2)NH(Me)][X], (X = ReO(4)(-), or I(-)), 4 can be isolated, and its X-ray crystal structure is reported. Although the Re(VII) intermediate could not be isolated, its activity in OAT reactions was probed by competition experiments with PPh(3) and four para-substituted triarylphosphines (p-X-Ph)(3)P (X = OMe, Me, Cl, CF(3)). These experiments led to a Hammett that yielded a reaction constant of rho = -0.30 +/- 0.01. This data suggests a positive charge buildup on phosphorus for the OAT reaction and is consistent with the nucleophilic attack of phosphorus on an electrophilic metal oxo.

From Mono‐ to Poly‐Substituted Frameworks: A Way of Tuning the Acidic Character of CcH in o‐Carborane Derivatives

The incorporation of iodine atoms onto the boron vertices of the o-carborane framework causes, according to spectroscopic data, a uniform increase in the acidic character of the C(c)-H (C(c)= cluster carbon) vertices, whereas the incorporation of methyl groups onto the boron vertices of the o-carborane framework reduces their acidity. Methyl groups when attached to boron are electron-withdrawing in boron clusters, whereas iodine atoms bonded to boron act as electron donors. This has been proven on B-methyl and B-iodinated o-carboranes with NMR spectroscopy measurements and DFT calculations of natural bond orbital (NBO) charges, which show a cumulative buildup of positive cluster-only total charge (CTC) on B-methyl o-carboranes and a cumulative buildup of negative cluster-only total charge for B-iodinated o-carboranes.

Effects of Si implantation on the total dose hardness of fully-depleted SIMOX wafers

Total dose hardened fully-depleted SOI materials are fabricated on separation by implanted oxygen (SIMOX) materials by silicon ion implantation and annealing. The ID–VG characteristics of pseudo-MOS transistors pre- and post-irradiation are tested with 60Co gamma rays. The chemical bonds and the structure of Si in the buried oxide are also studied by X-ray photoelectron spectroscopy and cross-sectional high-resolution transmission electron microscopy, respectively. The results show that Si nanocrystals in the buried oxide produced by ion implantation are efficient deep electron traps, which can significantly compensate positive charge buildup during irradiation. Si implantation can enhance the total-dose radiation tolerance of the fully-depleted SOI materials.

Mechanism of positive charge generation in the bulk of HfAlO/SiO 2 stack

We have investigated electrical stress-induced positive charge buildup in a hafnium aluminate (HfAlO)/silicon dioxide (SiO 2) dielectric stack (equivalent oxide thickness = 2.63 nm) in metal–oxide–semiconductor (MOS) capacitor structures with negative bias on the TaN gate. Various mechanisms of positive charge generation in the dielectric have been theoretically studied. Although, anode hole injection (AHI) and valence band hole tunneling are energetically favorable in the stress voltage range studied, the measurement results can be best explained by the dispersive proton transport model.

Fabrication of Total-Dose-Radiation-Hardened (TDRH) SOI wafer with embedded silicon nanoclusters

Si ion-implantation and post annealing of silicon wafers prior to wafer bonding were used to radiation-harden the thermal oxide layer of Silicon on Insulator structures. After grinding and polishing, Total-Dose-Radiation-Hardened SOI (TDRH-SOI) wafers with several-micron-thick device layers were prepared. Electrical characterization before and after X-ray irradiation showed that the flatband voltage shift induced by irradiation was reduced by this preprocessing. Photoluminescence Spectroscopy (PL), Transmission Electron Microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) results indicated that the improvement of the total dose response of the TDRH-SOI wafer was associated with formation of Si nanoclusters in the implanted oxide layer, suggesting that these were the likely candidates for electron and proton trapping centers that reduce the positive charge buildup effect in the buried oxide.

Impact of Nitridation on Negative and Positive Charge Buildup in SiC Gate Oxides

We report on the effect of nitridation on the negative and positive charge buildup in SiC gate oxides during carrier injection. We observe that the incorporation of nitrogen at the SiO2/SiC interface can enhance the reliability of the interface by suppressing the generation of interface states upon electron injection but that it can also degrade the oxide by creating additional hole traps. We relate these phenomena to the passivation of atomic-level defects by nitrogen.

Degradation behavior of Ta 2O 5 stacks and its dependence on the gate electrode

Response of 8 nm Ta 2O 5 stacks with Al and Au gate electrodes to voltage stress at room temperature and at 100 °C is investigated. Stress-induced leakage current (SILC) reveals significant gate dependence and distinct difference to SILC in SiO 2. The mechanisms for SILC generation and stress degradation are discussed. Unlike SiO 2, pre-existing traps and positive charge build-up are recognized as a key factor for generation of SILC in Ta 2O 5 stacks.

Extension of the Measurement Range of MOS Dosimeters Using Radiation Induced Charge Neutralization

This work proposes a new measurement technique to extend the dose range of MOS dosimeters. The technique consists on alternating stages of positive oxide charge buildup with stages of radiation induced charge neutralization, maintaining a uniform sensitivity along the whole measurement. The technique was applied with 70 nm MOS dosimeters, extending the dose measurement range from less than a kilogray to more than 675 kGy without showing wear effects. An initial saturation of interface traps creation ensures repeatability in the responses.

Constant voltage stress induced current in Ta2O5 stacks and its dependence on a gate electrode

Response of 8 nm Ta2O5 stacks with different gates (Al, W and Au) to voltage stress at gate injection is studied by probing under various voltage/time conditions at room temperature and at 100 °C. A stress-induced leakage current (SILC) is detected in all samples and reveals gate dependence. It is established that the pre-existing traps actually govern this response, and the impact of gate-induced defects is stronger. The Au-gated devices are the most susceptible to the stress degradation. Two processes—electron trapping at pre-existing traps and positive charge build-up—are suggested to be responsible for generation of SILC. It is concluded that despite some gate effects, the origin of CVS degradation in this particular high-k dielectric is different from that in SiO2.

Synthesis and bioorthogonal coupling chemistry of a novel cyclopentenone-containing unnatural tyrosine analogue

Herein we report the synthesis of a novel amino acid with orthogonal functionality to the natural amino acid side chains. Tyrosine was O-alkylated with a cyclic 5-membered α,β-unsaturated ketone ring ( 5). We have established that this amino acid analogue can undergo cycloaddition reactions in aqueous media with in situ generated nitrones. Nitrone formation occurred by micellar catalysis can undergo aqueous 1,3-dipolar cycloaddition reactions with the unnatural Tyr. We also performed a linear free energy analysis of the one pot bioconjugation reaction in water using cyclopentenone as a model for the Tyr analogue and seven different aryl nitrones. We found that the Hammett ρ value was −0.94, suggesting that the reaction occurs in a concerted fashion with a slight positive charge buildup in the transition state. The Hammett ρ value also suggests that the bioconjugation reaction is tolerant of different substituents and thus may be useful for introducing novel functionality into peptides and proteins containing the Tyr analogue 5. The aqueous 1,3-dipolar cycloaddition reactions, that use nitrones to trap the O-alkylated Tyr 5, establish a novel strategy for rapid, water compatible bioconjugation reactions.

Research on total-dose hardening for H-gate PD NMOSFET/SIMOX by ion implanting into buried oxide

In this work, we investigate the back-gate I-V characteristics for two kinds of NMOSFET/ SIMOX transistors with H gate structure fabricated on two different SOI wafers. A transistors are made on the wafer implanted with Si+ and then annealed in N2, and B transistors are made on the wafer without implantation and annealing. It is demonstrated experimentally that A transistors have much less back-gate threshold voltage shift ΔVth than B transistors under X-ray total dose irradiation. Subthreshold charge separation technique is employed to estimate the build-up of oxide charge and interface traps during irradiation, showing that the reduced ΔVth for A transistors is mainly due to its less build-up of oxide charge than B transistors. Photoluminescence (PL) research indicates that Si implantation results in the formation of silicon nanocrystalline (nanocluster) whose size increases with the implant dose. This structure can trap electrons to compensate the positive charge build-up in the buried oxide during irradiation, and thus reduce the threshold voltage negative shift.

Binding of sulfonium‐ion analogues of di‐epi‐swainsonine and 8‐epi‐lentiginosine to Drosophila Golgi α‐mannosidase II: The role of water in inhibitor binding

Retaining glycosidases operate by a two-step catalytic mechanism in which the transition states are characterized by buildup of a partial positive charge at the anomeric center. Sulfonium-ion analogues of the naturally occurring glycosidase inhibitors, swainsonine and 8-epi-lentiginosine, in which the bridgehead nitrogen atom is replaced by a sulfonium-ion, were synthesized in order to test the hypothesis that a sulfonium salt carrying a permanent positive charge would be an effective glycosidase inhibitor. Initial prediction based on computational docking indicated three plausible binding modes to Drosophila Golgi alpha-mannosidase II (dGMII), the most likely being close to that of swainsonine. Observation of the binding of di-epi-thioswainsonine and 8-epi-thiolentiginosine to dGMII from crystallographic data, however, revealed an orientation different from swainsonine in the active site. Screening these two compounds against dGMII shows that they are inhibitors with IC(50) values of 2.0 and 0.014 mM, respectively. This dramatic difference in affinity between the two compounds, which differ by only one hydroxyl group, is rationalized in terms of bound water molecules and the water molecule substructure in the active site, as identified by comparison of high resolution X-ray crystal structures of several dGMII-inhibitor complexes.

Effect of nanoclusters induced by Si implantation on total dose radiation response of a SOI wafer

Si ion implantation with subsequent annealing was used to improve the irradiation hardness of SOI wafers. The reduced negative shifts in the threshold voltage of the n-channel transistors showed that the total dose radiation hardness was remarkably enhanced by this modification process, and the pseudo-MOS method was used to test the Id–VG characteristics of the SOI samples before and after irradiation. Photoluminescence (PL) spectra demonstrated that Si nanoclusters were formed during annealing in the buried oxide of the implanted samples, which were possibly the main candidates for charge compensation. X-ray photoelectron spectroscopy (XPS) results also suggested that reduction of the threshold voltage shifts was accompanied with the formation of Si nanoclusters near the peak of the implants. Furthermore, the effect of positive charge buildup can be partly reduced as a result of the improvement on proton trapping in the bulk of the oxide due to the implantation induced nanoclusters.

An Analysis of the Effects of Low-Energy Electron Irradiation of AlGaN/GaN HFETs

The effects of low energy (0.45 MeV) electron radiation on the gate and drain currents of Al0.27Ga0.73N/GaN HFETs are investigated using IV and CV measurements. Following irradiation, the gate and drain currents increase at low temperatures and reach a saturation level. The gate leakage currents do not fully account for the drain current increase. Following a room temperature anneal, the gate and drain currents return to pre-irradiation levels. These results are explained by the buildup of positive charge in the AlGaN layer at low temperature and traps formed via a complexing precursor in the AlGaN layer near the interface. The positive charge increases the carrier concentration in the 2DEG and hence the drain current. The traps act as trap-assisted-tunneling centers that increase the gate leakage current.

Toward Selective Reactions with CH Bonds: A Rationale for the Regio- and Stereochemistry of Dichlorocarbene Insertions into Cyclic Hydrocarbons

DFT calculations have been performed to study the course of dichlorocarbene insertion reactions into alkanes and to better understand the regio- and stereoselectivities observed. At the B3LYP/6-31G(d) level of theory, the selectivity of dichlorocarbene insertions into a number of hydrocarbons agrees well with the obtained experimental results. The reactivity of a specific C-H bond is determined by the capacity of the remaining alkyl fragment to effectively delocalize the partial positive charge buildup during the reaction. This activity can readily be estimated by calculation of the hydride transfer potential (HTP). A comparison with the structure and the stability of the corresponding cation is useful to emphasize the origins of the selectivity. Dichlorocarbene is also predicted to react efficiently with acidic C-H bonds through a nucleophilic-electrophilic mechanism. In principle, an attack of a carbene on an appropriately substituted three-membered ring may lead to fragmentation of the molecule.