Hysteresis effect on traps of Si3N4 sensing membranes for pH difference sensitivity

The mechanism of different pH sensitivities on single and stacked layer silicon nitride (Si₃N₄)-electrolyte insulator semiconductor (EIS) structures was investigated for the application of an inorganic ion sensitive field effect transistor (ISFET) and reference field effect transistor (REFET) pair. The capacitance-voltage (C-V) hysteresis effect of the EIS structures was measured. In addition, pH sensitivity was evaluated with different sweep directions and ranges of the substrate bias. Based on the hysteresis results, a pH-dependent trapping effect was found to decrease the pH sensitivity on a single Si₃N₄ sensing membrane EIS structure.     

Study of front-side connected chemical field effect transistor for water analysis

Front-side connected, N-channel, normally-off, chemical field effect transistor (ChemFET) microsensors including a SiO₂/Si₃N₄ pH-sensitive gate have been fabricated using a standard P-well silicon technology. The fabrication and packaging processes are described and sensor properties and performances are demonstrated through pH measurements. Finally, the front-side connected ChemFETs microsensors have been adapted to the detection of ions thanks to polyHEMA/siloprene-based ionosensitive membranes. Application is performed through the NH₄⁺ and NO₃⁻ ions detection in artificial solutions, evidencing quasi-Nernstian responses (s≈50 mV/pH) in the appropriate detection ranges. This microsensor will be used for the monitoring of environmental pollution and more precisely for ground water analysis.     

A study on the improved programming characteristics of flash memory with Si3N4/SiO2 stacked tunneling dielectric

The programming characteristics of memories with different tunneling-layer structures (Si₃N₄, SiO₂ and Si₃N₄/SiO₂ stack) dielectrics are investigated using 2-D device simulator of MEDICI. It is theoretically confirmed that the memory with the SiO₂/Si₃N₄ stacked tunneling layer exhibits better programming characteristics than ones with single tunneling layer of SiO₂ or Si₃N₄ for programming by channel hot electron (CHE) injection. A 10-μs programming time with a threshold-voltage shift of 5 V can be obtained for the memory with SiO₂/Si₃N₄ stacked tunneling layer at V_cg = 10 V and V_ds = 3.3 V. This is attributed to the fact that the floating-gate voltage is close to drain voltage for the stacked tunneling dielectric (TD), and thus the CHE injection current is the largest. Furthermore, optimal substrate concentration is determined to be 5 × 10¹⁶–2 × 10¹⁷ cm⁻³, by considering a trade-off between the programming characteristics and power dissipation/lifetime of the devices. Lastly, the effects of interface states on the programming characteristics are investigated. Low interface-state density gives short programming time and small post-programming control-gate current.     

Development of pNH4-isfets microsensors for water analysis

Front-side connected, N-channel, normally-off, SiO₂/Si₃N₄ chemical field effect transistor (ChemFET) microsensors have been fabricated using a standard P-well silicon technology. These ChemFETs microsensors were adapted to ammonium ion detection thanks to photosensitive polysiloxane (PSX) polymer containing nonactine as an ionophore. The ammonium-sensitive membrane has been deposited either manually by micropipette, either by spin coating and patterned using photolithography technique. Both processes have been studied and compared through the ammonium ion determination. The manually deposed layers have been characterised by thickness non-reproducibility. Therefore, spin-coated layers have good reproducibility, but their thickness of 30 μm has been responsible for an increase of the ISFET threshold voltage and a decrease of its bias current. Nevertheless, in both cases, good sensitivities have been shown on the (1-5) pNH₄ range even if saturation phenomena have been evidenced for the lowest concentrations. These pNH₄-ISFETs microsensors are developed for the monitoring of environmental pollution and more precisely for ground water analysis.     

Mechanism of selective Si3N4 etching over SiO2 in hydrogen-containing fluorocarbon plasma

This paper describes the mechanism of selective Si₃N₄ etching over SiO₂ in capacitively-coupled plasmas of hydrogen-containing fluorocarbon gas, including CHF₃, CH₂F₂ and CH₃F. The etch rate of Si₃N₄ and SiO₂ is investigated as a function of O₂ percentage in all plasma gases. Addition of O₂ in feed gases causes plasma gas phase change especially H density. The SiO₂ etch rate decreases with increase of O₂ percentage due to the decline of CF_x etchant. The Si₃N₄ etch rate is found to be strong correlated to the H density in plasma gas phase. H can react with CN by forming HCN to reduce polymer thickness on Si₃N₄ surface and promote the removal of N atoms from the substrate. Thus the Si₃N₄ etch rate increases with H intensity. As a result, a relative high selectivity of Si₃N₄ over SiO₂ can be achieved with addition of suitable amount of O₂ which corresponds to the maximum of H density.     

Deep trapping of implanted Na+ and Li+ ions near the Si/SiO2 interface in metal-oxide-silicon structures

Na⁺ and Li⁺ ions have been implanted in the oxide layer of MOS structures with doses ranging from 3 × 10¹¹ to 3 × 10¹³ ions/cm². Part of the implanted ions can be retraced as mobile ions: this fraction decreased with increasing dose. The trapping of the mobile ions near the Si/SiO₂ interface has been investigated by means of the thermally stimulated ionic current (TSIC) technique. The average energy depth of the ionic traps appeared to increase with increasing dose. Moreover, we found that Li⁺ ions are trapped deeper than Na⁺ ions under equivalent experimental conditions. The influence of the applied electric field on the detrapping has been studied. In the case of 3 × 10¹³ Na⁺ implantation, the barrier lowering corresponds with the Poole-Frenkel theory. We have also paid attention to the effects of bias-temperature stress treatments on the trapping kinetics. We observed a decrease of the mobile ion current after long BTS treatments.     

New ISFET interface circuit design with temperature compensation

An integrated and new interface circuit with temperature compensation has been developed to enhance the ISFET readout circuit stability. The bridge-type floating source circuit suitable for sensor array processing has been proposed to maintain reliable constant drain-source voltage and constant drain current (CVCC) conditions for measuring the threshold voltage variation of ISFET due to the corresponding hydrogen ion concentration in the buffer solution. The proposed circuitry applied to Si₃N₄ and Al₂O₃-gate ISFETs demonstrate a variation of the drain current less than 0.1 μA and drain-source voltage less than 1 mV for the buffer solutions with the pH value changed from 2 to 12. In addition, the scaling circuitry with the V_T temperature correction unit (extractor) and LABVIEW software are used to compensate the ISFET thermal characteristics. Experimental results show that the temperature dependence of the Si₃N₄-gate ISFET sensor improved from 8 mV/°C to less than 0.8 mV/°C.     

Effects of CH2F2 and H2 flow rates on process window for infinite etch selectivity of silicon nitride to ArF PR in dual-frequency CH2F2/H2/Ar capacitively coupled plasmas

The process window for the infinite etch selectivity of silicon nitride (Si₃N₄) layers to ArF photoresist (PR) and ArF PR deformation were investigated in a CH₂F₂/H₂/Ar dual-frequency superimposed capacitive coupled plasma (DFS-CCP) by varying the process parameters, such as the low frequency power (P_LF), CH₂F₂ flow rate, and H₂ flow rate. It was found that infinitely high etch selectivities of the Si₃N₄ layers to the the ArF PR on both the blanket and patterned wafers could be obtained for certain gas flow conditions. The H₂ and CH₂F₂ flow rates were found to play a critical role in determining the process window for infinite Si₃N₄/ArF PR etch selectivity, due to the change in the degree of polymerization. The preferential chemical reaction of hydrogen with the carbon in the hydrofluorocarbon (CH_xF_y) layer and the nitrogen on the Si₃N₄ surface, leading to the formation of HCN etch by-products, results in a thinner steady-state hydrofluorocarbon layer and, in turn, in continuous Si₃N₄ etching, due to enhanced SiF₄ formation, while the hydrofluorocarbon layer is deposited on the ArF photoresist surface.     

Flux-adjusted phase transformation from Ca2SiO4 to Ca3Si2O7 with Eu2+ activator for white light emitting diodes

Eu2+ -activated reddish-orange-emitting Ca3Si2O7 phosphors were synthesized with the addition of NH4Cl flux.When the phosphors were synthesized in a nominal composition of (Ca0.99Eu0.01)3Si2O7 without flux addition,a Ca3Si2O7 phase responsible for reddish-orange emission was identified to coexist with an intermediate phase of a-Ca2SiO4 for green emission.With the addition of NH4Cl flux,a-Ca2SiO4 was suppressed while the pure phase Ca3Si2O7 was obtained as the flux content was 3 wt%.Through varying the amount of flux,the emission color of samples can be tuned from green to reddish-orange,corresponding to the phase transformation from a-Ca2SiO4 to Ca3Si2O7.Through optimizing the doping concentration of Eu2+ ,the optimized photoluminescence (PL) properties for reddish-orange emission can be achieved,which makes this kind of phosphor prospective in the applications of the phosphor-converted white light emitting diodes (PC-WLEDs).     

Influence of activated polymer on the etching rate of SiO2 in CF4 + H2 plasma

The reactive ion etching (RIE) of SiO₂ in CF₄ + H₂ plasma is considered. The influence of activated polymer on the RIE rate of SiO₂ in CF₄ + H₂ plasma is determined by extrapolation of experimentally measured kinetics of the etching rate. It is found that the increased surface coverage by CF₂ radicals suppresses the RIE rate of SiO₂ in CF₄ + H₂ plasma during the initial stages of the etching process. The formation of activated polymer becomes pronounced when adsorbed CF₂ radicals are slowly activated. The activated polymer intensifies the etching reaction and enhances the etching rate. At the same time, the activated polymer intensifies the polymerization reactions. The increased surface coverage by the polymer suppresses the RIE rate of SiO₂ in CF₄ + H₂ plasma at later stages of the etching process.     

Optically induced charge storage in ion implanted SiO2

Charge storage in MOS structures with an ion implanted oxide layer has been investigated. The electrons generated by internal photoemission are captured in SiO₂ traps which are created by the implantation of Kr⁺ and N⁺ ions at energies of 50–290 keV and a fluence up to 10¹⁴ cm^?2. The charge storage results in a voltage shift of the high frequency C-V-curve. The dependence of electron storage on exposure time has been measured and compared with approximative calculations. The discharge of traps occurs by heating treatment and hints at the existence of deep oxide traps combined with structural lattice defects.     

Two Layer Surface Exfoliation on Si3N4/Si by Sequential Implantation of He and H Ions

n-Type Si(100) wafers with a thermally grown Si₃N₄ layer (∼170 nm) were sequentially implanted with 160 keV He ions at a dose of 5 × 10¹⁶ cm⁻² and 110 keV H ions at a dose of 1 × 10¹⁶ cm⁻². Depending on the annealing temperature, surface exfoliations of two layers were observed by optical microscopy and atomic force microscopy. The first layer exfoliation was found to correspond to the top Si₃N₄ layer, which was produced at lower annealing temperatures. The other was ascribed to the implanted Si layer, which was formed at higher temperatures. The possible exfoliation processes are tentatively discussed, and potential applications of such phenomena are also suggested.     

Breakdown properties of metal/NIDOS SiO2/silicon structures

NIDOS/SiO₂/silicon structures have been annealed in a nitrogen (N₂) ambient and X-ray photoelectron spectroscopy (XPS) characterization has been performed in order to definitively demonstrate the nitrogen atoms out-diffusion from the nitrogen doped silicon (NIDOS) film towards the buried oxide layer. The nitridation of the SiO₂ layer is related to the competition between nitrogen atoms out-diffusion phenomena on one side into the underlying oxide layer and on the other side into an oxynitride layer grown during annealing. In order to analyse and optimize the corresponding MIS process, different structures such as metal/SiO₂/silicon, metal/(NH₃-‘nitrided’)SiO₂/silicon, metal/(N₂O-nitrided)SiO₂/silicon, metal/poly-Si*/SiO₂/silicon (* indicates deposited from disilane Si₂H₆) and metal/NIDOS/SiO₂/silicon have been realized and compared by capacitance–voltage, current–voltage and ageing under constant current injection experiments. The optimization of the NIDOS-nitridation process gives the highest charge-to-breakdown for the lowest nitridation level or even for no intentional nitridation. The dielectric breakdown improvement should therefore not be related to the nitridation phenomena alone but also to the intrinsic properties of the polysilicon layer itself.     

Novel iron (III) phthalocyanine derivative functionalized semiconductor based transducers for the detection of citrate

In the present work, we report a novel citrate-selective sensor based on iron (III) phthalocyanine chloride-C-monoamido-Poly-n-Butyl Acrylate (Fe(III)MAPcCl-P-n-BA) modified silicon nitride and Ion sensitive field effect transistor (ISFET) structures for the electrochemical determination and estimation of the pathophysiological range of citrate. The developed capacitive sensor based on Fe(III)MAPcCl-P-n-BA had a Nernstian sensitivity of (−20.2 ± 1.3) mV/decade with a detection limit of about 7 × 10⁻⁷ M and a linear range from 10⁻⁶ M to 10⁻¹ M (RSD = 6.2%). Then, the performance of the Fe(III)MAPcCl-P-n-BA functionalized ISFET structure towards the detection of citrate has been investigated. A Nernstian sensitivity of about (−19.8 ± 1.0) mV/decade in the range from 10⁻⁶ M to 10⁻¹ M was achieved (RSD = 4.8%) which covered the pathologically important clinical range of citrate. The detection limit was about 4 × 10⁻⁷ M. The number of available recognition sites N_s and the complexation constant pK were calculated using the enhanced site binding model. A side by side comparison of the developed chemical sensors based on electrolyte-insulator-Semi conductor (EIS) and ISFET structures showed similar characteristics which proves the successful miniaturization of the semiconductor based transducer. The obtained experimental data of the Fe(III)MAPcCl-P-n-BA functionalized ISFET structure were used to validate the TopSPICE ISFET/MEMFET macromodel. The obtained theoretical sensitivity was in good agreement to the experimental one which proves the successful design of the developed ISFET/MEMFET macromodel.     

Organic field-effect transistor with extended indium tin oxide gate structure for selective pH sensing

In this study, organic field-effect transistors (OFETs) with extended gate structure were fabricated for selective pH sensing applications. Indium tin oxide (ITO) was used as extended gate electrode as well as an active layer for H⁺ sensing. The threshold voltage of the fabricated ion-selective OFET was varied by the changes in the electrochemical potential at the ITO electrode surface upon its exposure to buffer solutions with variable pH values. The sensor showed excellent linearity and a high sensitivity of 57–59 mV/pH in the pH range of 2–12. The selectivity of the ITO sensing layer to H⁺ ions was also investigated by measuring the interfering effect of Ca²⁺ and K⁺ ions in the buffer pH solutions. The results showed that the Ca²⁺ and K⁺ ions weakly interfere with the selective pH sensing of the ITO-extended gate OFET sensor device.     

激光合成非晶态Si3N4粉末

本文描述了大功率CO2激光辐照SiH4+NH3的快速流动气体合成Si3H4超细粉末的实验,揭示了激光谱线变化对合成反应的影响。讨论了粉末红外吸收光谱的畸变现象等。     

Gated Mesoporous SiO2 Nanoparticles Using K+‐Stabilized G‐Quadruplexes

The K⁺‐induced formation of G‐quadruplexes provides a versatile motif to lock or unlock substrates trapped in the pores of mesoporous SiO₂ nanoparticles, MP‐SiO₂ NPs. In one system, the substrate is locked in the MP‐SiO₂ NPs by K⁺‐ion‐stabilized G‐quadruplex units, and the pores are unlocked by the elimination of K⁺ ions using Kryptofix [2.2.2] (KP) or 18‐crown‐6‐ether (CE) from the G‐quadruplexes. In the second system, the substrate is locked in the pores by means of K⁺‐stabilized aptameric G‐quadruplex/thrombin units. Unlocking of the pores is triggered by the dissociation of the aptamer/thrombin complexes through the KP‐ or CE‐mediated elimination of the stabilizing K⁺ ions. In the third system, duplex DNA units lock the pores of MP‐SiO₂ NPs, and the release of the entrapped substrate is stimulated by the K⁺‐ion‐induced dissociation of the duplex caps through the formation of the K⁺‐stabilized G‐quadruplexes. The latter system is further implemented to release the anti‐cancer drug, doxorubicin, in the presence of K⁺ ions, from the MP‐SiO₂ NPs. Preliminary intracellular experiments reveal that doxorubicin‐loaded MP‐SiO₂ NPs lead to effective death of breast cancer cells.     

激光诱导SiH4等离子体反应碎片的产生机制

Using the technique of optical emission spectroscopy,time-dependence of fragment in SiH₄ laser plasma is measured.After analyzing the evolution and reaction progress of fragments,we proposed that si.H and si⁺ were the first reaction products,but Si₂ SiH and Si²⁺ the second ones.This conclusion is further verified by the experimental results of Si390.6nm and SiH412.8nm emission lines in various conditions.     

Study on Nitridation-Induced Residual Stress near Si/SiO2 Interface in n-MOSFETs

本文借助氩离子(Ar     

Investigation on bias stress effects in n-type PDI8-CN2 thin-film transistors

In this contribution, we investigate the bias stress phenomenon in n-type PDI8-CN₂ thin-film transistors fabricated by evaporation on both bare and hexamethyldisyloxane (HMDS)-treated SiO₂ gate dielectrics. Since the morphological properties of PDI8-CN₂ films are poorly influenced by the SiO₂ treatment, all the differences observed in the DC electrical response and the bias stress performances of these devices can be mainly ascribed to the interface chemistry between the dielectric and the semiconductor. In long-term bias stress experiments, performed in vacuum keeping the devices under fixed voltage polarization, the I_DS(t) decaying behavior shows to saturate when transistors on HMDS-treated substrates were considered. According to our findings, the BS physical origin is related to the occurrence of electrochemical reactions where PDI8-CN₂ molecules interact with H₂O, producing O₂ and protons (H⁺) which can initially diffuse in the SiO₂ layer barrier. Hence, the possibility that the bias stress effect in these n-type devices can be ruled by the H⁺ back-diffusion process, occurring from the SiO₂ bulk towards the dielectric-semiconductor interface during the prolonged application of positive V_GS voltages, is discussed.