Failure mechanism of bulk silicon anode electrodes for lithium-ion batteries

Silicon has been investigated extensively as a promising anode material for rechargeable lithium-ion bat- teries. Understanding the failure mechanism of silicon-based anode electrodes for lithium-ion batteries is essential to solve the problem of low coulombic efficiency and capacity fading on cycling and also to further commercialize this very new energetic material in cells. To reach this goal, the structure changes of bulk silicon particles and electrode after cycling were studied using ex-situ scanning electron microscopy （SEM） and X-ray diffraction （XRD） techniques. The SEM images indicated that the microstructural changes of the bulk silicon particles during cycling led to a layer rupture of the electrode and then the breakdown of the conductive network and the failure of the electrode. The result contributes to the basic understanding of the failure mechanism of a bulk sil- icon anode electrode for lithium-ion batteries.

Research progress on silicon/carbon composite anode materials for lithium-ion battery

Silicon （Si） has been considered as one of the most promising anode material for tHe next generation lithium-ion batteries （LIBs） with high energy densities, due to its high theoretical capacity, abundant availability and environmental friendliness. However. silicon materials with low intrinsic electric and ionic conductivity suffer from huge volume variation during lithiation/delithiation processes leading to the pulverization of Si and subsequently resulting in severe capacity fading of the electrodes. Coupling of Si with carbon （C） realizes a favorable combination of the two materials properties, such as high lithiation capacity of Si and excellent mechanical and conductive properties of C. making silicon/carbon composite （Si/C） ideal candidates for LIBs anodes. In this review, recent progresses of Si/C materials utilized in LIBs are summarized in terms of structural design principles, material synthesis methods, morphological characteristics and electrochemical performances by highlighting the material structures. The mechanisms behind the performance enhancement are also discussed. Moreover, other factors that affect the performance of Si/C anodes, such as prelithiation, electrolyte additives, and binders, are also discussed. We aim to present a full scope of the Si/C-based anodes, and help understand and design future structures of Si/C anodes in LIBs,

Photoluminescence evolution in self-ion-implanted and annealed silicon

Si^＋ ion-implanted silicon wafers are annealed at different temperatures from room temperature to 950℃ and then characterized by using the photoluminescence （PL） technique at different recorded temperatures （RETs）. Plentiful optical features are observed and identified clearly in these PL curves. The PL spectra of these samples annealed in different temperature ranges are correspondingly dominated by different emission peaks. Several characteristic features, such as an R line, S bands, a W line, the phonon-assistant WTA and SiTO peaks, can be detected in the PL spectra of samples annealed at different temperatures. For the samples annealed at 800℃, emission peaks from the dislocations bounded at the deep energy levels of the forbidden band, such as D1 and D2 bands, can be observed at a temperature as high as 280 K. These data strongly indicate that a severe transformation of defect structures could be manipulated by the annealing and recorded temperatures. The deactivation energies of the main optical features are extracted from the PL data at different temperatures.

Effect of Pore Structures on the Electrochemical Performance of Porous Silicon Synthesized from Magnesiothermic Reduction of Biosilica

Two kinds of porous silicon（PS） were synthesized by magnesiothermic reduction of rice husk silica（RHS） derived from the oxidization of rice husks（RHs）. One was obtained from oxidization/reduction at 500 ℃ of the unleached RHs, the other was synthesized from oxidization/reduction at 650 ℃ of the acidleached RHs. The structural difference of the above PS was compared： the former had a high pore volume（PV, 0.31 cm3/g） and a large specific surface area（SSA, 45.2 m^2/g）, 138 % and 17 % higher than the latter, respectively. As anode materials for lithium ion batteries, the former had reversible capacity of 1 400.7 m Ah/g, 987 m Ah/g lower than the latter; however, after 50 cycles, the former had 64.5 % capacity retention（907 m Ah/g）, which was 41.2 % higher than the latter（555.7 m Ah/g）. These results showed that the electrochemical performance of PS was significantly affected by its pore structures, and low reduction temperature played the key role in increasing its porosity, and therefore improving its cycling performance.

The fabrication of nickel silicide ohmic contacts to n-type 6H-silicon carbide

This paper reports that the nickel silicide ohmic contacts to n-type 6H-SiC have been fabricated. Transfer length method test patterns with NiSi/SiC and NiSi2/SiC structure axe formed on N-wells created by N^＋ ion implantation into Si-faced p-type 6H-SiC epilayer respectively. NiSi and NiSi2 films are prepared by annealing the Ni and Si films separately deposited. A two-step annealing technology is performed for decreasing of oxidation problems occurred during high temperature processes. The specific contact resistance Pc of NiSi contact to n-type 6H-SiC as low as 1.78× 10^-6Ωcm^2 is achieved after a two-step annealing at 350 ℃for 20 min and 950℃ for 3 min in N2. And 3.84×10-6Ωcm^2 for NiSi2 contact is achieved. The result for sheet resistance Rsh of the N＋ implanted layers is about 1210Ω/□. X-ray diffraction analysis shows the formation of nickel silicide phases at the metal/n-SiC interface after thermal annealing. The surfaces of the nickel silicide after thermal annealing are analysed by scanning electron microscope.

Nanoporous SiO_x coated amorphous silicon anode material with robust mechanical behavior for high-performance rechargeable Li-ion batteries

Silicon is a promising anode material for rechargeable Li-ion battery (LIB) due to its high energy density and relatively low operating voltage. However, silicon based electrodes suffer from rapid capacity degradation during electrochemical cycling. The capacity decay is predominantly caused by (i) cracking due to large volume variations during lithium insertion/extraction and (ii) surface degradation due to excessive solid electrolyte interface (SEI) formation. In this work, we demonstrate that coating of a-Si thin film with a Li-active, nanoporous SiOx layer can result in exceptional electrochemical performance in Li-ion battery. The SiOx layer provides improved cracking resistance to the thin film and prevent the active material loss due to excessive SEI formation, benefiting the electrode cycling stability. Half-cell experiments using this anode material show an initial reversible capacity of 2173 mAh g^-1 with an excellent coulombic efficiency of 90.9%. Furthermore, the electrode shows remarkable capacity retention of ~97% after 100 cycles at C/2 charging rate. The proposed anode architecture is free from Liinactive binders and conductive additives and provides mechanical stability during the charge/discharge process.

Performance of n-type silicon/silver composite anode material in lithium ion batteries: A study on effect of work function matching degree

In this paper, two types of silicon（Si） particles ball-milled from n-type Si wafers, respectively, with resistivity values of 1 Ω·cm and 0.001 Ω·cm are deposited with silver（Ag）. The Ag-deposited n-type 1-Ω·cm Si particles（nl-Ag） and Ag-deposited n-type 0.001-Ω·cm Si particles（n0.001-Ag） are separately used as an anode material to assemble coin cells,of which the electrochemical performances are investigated. For the matching of work function between n-type 1-Ω·cm Si（nl） and Ag, nl-Ag shows discharge specific capacity of up to 683 mAh·g^-1 at a current density of 8.4 A·g^-1, which is40% higher than that of n0.001-Ag. Furthermore, the resistivity of nl-Ag is lower than half that of n0.001-Ag. Due to the mismatch of work function between n-type 0.001-Ω·cm Si（n0.001） and Ag, the discharge specific capacity of n0.001-Ag is 250.2 mAh·g^-1 lower than that of nl-Ag after 100 cycles.

Thermal annealing induced photocarrier radiometry enhancement for ion implanted silicon wafers

An experimental study on the photocarrier radiometry signals of As^＋ ion implanted silicon wafers before and after rapid thermal annealing is performed. The dependences of photocarrier radiometry amplitude on ion implantation dose （1×10^11-1×10^16/cm^2）, implantation energy （20-140 keV） and subsequent isochronical annealing temperature （500- 1100℃ are investigated. The results show that photocarrier radiometry signals are greatly enhanced for implanted samples annealed at high temperature, especially for those with a high implantation dose. The reduced surface recombination rate resulting from a high built-in electric field generated by annealing-activated impurities in the pn junction is believed to be responsible for the photocarrier radiometry signal enhancement. Photocarrier radiometry is contactless and can therefore be used as an effective in-line tool for the thermal annealing process monitoring of the ion-implanted wafers in semiconductor industries.

Study on the defect-related emissions in the light self-ion-implanted Si films by a silicon-on-insulator structure

This paper reports that the Si＋ self-ion-implantation are conducted on the silicon-on-insulator wafers with the 2SSi＋ doses of 7 ×1012, 1 × 1013, 4 × 1013, and 3× 1014 cm-2, respectively. After the suitable annealing, these samples are characterized by using the photoluminescence technique at different recorded temperatures. Plentiful emission peaks are observed in these implanted silicon-on-insulator samples, including the unwonted intense P~ band which exhibits a great potential in the optoelectronic application. These results indicate that severe transformation of the interstitial clusters can be manipulated by the implanting dose at suitable annealing temperatures. The high critical temperatures for the photoluminescence intensity growth of the two signatures are well discussed based on the thermal ionization model of free exciton.

Effect of Cumulative Nanosecond Laser Pulses on the Plasma Emission Intensity and Surface Morphology of Pt-and Ag-Ion Deposited Silicon

In this work, the laser induced plasma plume characteristics and surface morphology of Pt- and Ag-ion deposited silicon were studied. The deposited silicon was exposed to cumulative laser pulses. The plasma plume images produced by each laser shot were captured through a computer controlled image capturing system and analyzed with image-J software. The integrated optical emission intensity of both samples showed an increasing trend with increasing pulses. Agion deposited silicon showed higher optical emission intensity as compared to Pt-ion deposited silicon, suggesting that more damage occurred to the silicon by Ag ions, which was confirmed by SRIM/TRIM simulations. The surface morphologies of both samples were examined by optical microscope showing thermal, exfoliational and hydrodynamical sputtering processes along with the re-deposition of the material, debris and heat affected zones＇ formation. The crater of Ption deposited silicon was deeper but had less lateral damage than Agion deposited silicon. The novel results clearly indicated that the ion deposited silicon surface produced incubation centers, which led to more absorption of incident light resulting into a higher emission intensity from the plasma plume and deeper crater formation as compared to pure silicon. The approach can be effectively utilized in the laser induced breakdown spectroscopy technique, which endures poor limits of detection.

Local Tuning of the Surface Potential in Silicon Carriers by Ion Beam Induced Intrinsic Defects

The immobilization of biomaterials on a carrier is the first step for many different applications in life science and medicine. The usage of surface-near electrostatic forces is one possible approach to guide the charged biomaterials to a specific location on the carrier. In this study, we investigate the effect of intrinsic defects on the surface potential of silicon carriers in the dark and under illumination by means of Kelvin probe force microscopy. The intrinsic defects were introduced into the carrier by local, stripe-patterned ion implantation of silicon ions with a fluence of 3 × 1013 Si ions/cm2 and 3 × 1015 Si ions/cm2 into a p-type silicon wafer with a dopant concentration of 9 × 1015 B/cm3. The patterned implantation allows a direct comparison between the surface potential of the silicon host against the surface potential of implanted stripes. The depth of the implanted silicon ions in the target and the concentration of displaced silicon atoms was simulated using the Stopping and Range of Ions in Matter (SRIM) software. The low fluence implantation shows a negligible effect on the measured Kelvin bias in the dark, whereas the large fluence implantation leads to an increased Kelvin bias, i.e. to a smaller surface work function according to the contact potential difference model. Illumination causes a reduced surface band bending and surface potential in the non-implanted regions. The change of the Kelvin bias in the implanted regions under illumination provides insight into the mobility and lifetime of photo-generated electron-hole pairs. Finally, the effect of annealing on the intrinsic defect density is discussed and compared with atomic force microscopy measurements on the 2nd harmonic. In addition, by using the Baumgart, Helm, Schmidt interpretation of the measured Kelvin bias, the dopant concentration after implantation is estimated.

Realization of conformal doping on multicrystalline silicon solar cells and black silicon solar cells by plasma immersion ion implantation

Emitted multi-crystalline silicon and black silicon solar cells are conformal doped by ion implantation using the plasma immersion ion implantation （PⅢ） technique. The non-uniformity of emitter doping is lower than 5 %. The secondary ion mass spectrometer profile indicates that the PⅢ technique obtained 100-rim shallow emitter and the emitter depth could be impelled by furnace annealing to 220 nm and 330 nm at 850 ℃ with one and two hours, respectively. Furnace annealing at 850 ℃ could effectively electrically activate the dopants in the silicon. The efficiency of the black silicon solar cell is 14.84% higher than that of the mc-silicon solar cell due to more incident light being absorbed.

Parameter analysis for gate metal-oxide-semiconductor structures of ion-implanted 4H silicon carbide metal-semiconductor field-effect transistors

From the theoretical analysis of the thermionic emission model of current-voltage characteristics, this paper extracts the parameters for the gate Schottky contact of two ion-implanted 4H-SiC metal-semiconductor field-effect transistors （sample A and sample B for three and four times multiple ion-implantation channel region respectively） fabricated in the experiment, including the ideality factor, the series resistance, the zero-field barrier height, the interface oxide capacitance, the interface state density distribution, the neutral level of interface states and the fixed space charge density. The methods to improve the interface of the ion-implanted Schottky contact are given at last.

Improvement of total-dose irradiation hardness of silicon-on-insulator materials by modifying the buried oxide layer with ion implantation

The hardening of the buried oxide （BOX） layer of separation by implanted oxygen （SIMOX） silicon-on-insulator （SOI） wafers against total-dose irradiation was investigated by implanting ions into the BOX layers. The tolerance to total-dose irradiation of the BOX layers was characterized by the comparison of the transfer characteristics of SOI NMOS transistors before and after irradiation to a total dose of 2.7 Mrad（SiO2）. The experimental results show that the implantation of silicon ions into the BOX layer can improve the tolerance of the BOX layers to total-dose irradiation. The investigation of the mechanism of the improvement suggests that the deep electron traps introduced by silicon implantation play an important role in the remarkable improvement in radiation hardness of SIMOX SOI wafers.

Investigation of the lateral spread of erbium ions implanted in silicon crystal

The erbium ions at energy of 400 keV and dose of 5× 10^15 ions/cm^2 were implanted into silicon single crystals at room temperature at the angles of 0°,45° and 60°. The lateral spread of 400 keV erbium ions implanted in silicon sample was measured by the Rutherford backscattering technique. The results show that the measured values were in good agreement with those obtained from the prediction of TRIM＇98 （Transport of Ions in Matter） and SRIM2006 （Stopping and Range of Ions in Matter） codes.

Study of the lateral distribution of neodymium ions implanted in silicon

Due to the need to reduce electronic device sizes, it is very important to consider the depth and lateral distribution of ions implanted into a crystalline target. This paper reports that Nd ions with energies of 200 keV to 500 keV and dose of 5× 10^15 ions/cm2 are implanted into Si single crystals at room temperature under the angles of 0°, 30°, and 45°, respectively. The lateral spreads of 200 keV-500 keV Nd ions implanted in Si sample are measured by Rutherford backscattering technique. The results show that the measured values are in good agreement with those obtained from the prediction of SRIM2010 codes.

Investigation of the inhibiting outdiffusion of erbium atoms to a silicon-on-insulator surface after annealing at high temperature

The annealing behaviour of 400 keV Er ions at a fluence of 2×10^15 cm^-2 implanted into silicon-on-insulator（SOI） samples is investigated by Rutherford backscattering spectrometry of 2.1 MeV He^2＋ ions with a multiple scattering model.It is found that the damage close to the SOI surface is almost removed after being annealed in O2 and N2 atmospheres,successively,at ℃,and that only a small number of the Er atoms segregated to the surface of the SOI sample,whereas a large number of Er atoms diffused to a deeper position because of the affinity of Er for oxygen.For the SOI sample co-implanted with Er and O ions,there is no evident outdiffusion of Er atoms to the SOI surface after being annealed in N2 atmosphere at ℃.

TEM Observation of Si0.99C0.01 Thin Films with Arsenic-Ion-, Boron-Ion-, and Silicon-Ion-Implantation Followed by Rapid Thermal Annealing

Strained Si and its related materials, such as strained SiGe and strained silicon-carbon alloy (Si-C), are receiving tremendous interest due to their high carrier mobility. In this study we carry out a basic investigation of the change in microstructure of ion-implanted Si-C solid solution caused by rapid thermal annealing, because it is very important to realize a field-effect transistor made of this new material. The microstructures of arsenic-ion-, boron-ion-, and silicon-ion-implanted Si0.99C0.01 specimens upon thermal annealing are observed using transmission electron microscopy, and it is revealed that the rate of solid-state crystallization of ion-implanted Si-C is slower than that of the ion-implanted Si.

In-situ synthesis of interconnected SWCNT/OMC framework on silicon nanoparticles for high performance lithium-ion batteries

In spite of silicon has a superior theoretical capacity, the large volume expansion of Si anodes during Li^+ insertion/extraction is the bottle neck that results in fast capacity fading and poor cycling performance. In this paper, we report a silicon, single-walled carbon nanotube, and ordered mesoporous carbon nanocomposite synthesized by an evaporation-induced self-assembly process, in which silicon nanoparticles and single-walled carbon nanotubes were added into the phenolic resol with F-127 for co-condensation. The ordered mesoporous carbon matrix and single-walled carbon nanotubes network could effectively accommodate the volume change of silicon nanoparticles, and the ordered mesoporous structure could also provide efficient channels for the fast transport of Li-ions. As a consequence, this hybrid material exhibits a reversible capacity of 861 mAh g^(-1) after 150 cycles at a current density of 400 mAg^(-1). It achieves significant improvement in the electrochemical performance when compared with the raw materials and Si nanoparticle anodes.

Combined frequency- and time-domain photocarrier radiometry characterization of ion-implanted and thermally annealed silicon wafers

A combined frequency-swept and quasi-time-domain photocarrier radiometry （PCR） technique was developed to characterize thermally annealed silicon wafers with B＋, P＋, and As＋ ion implantation at doses ranging from 1 ×1011 cm-2 to 1 ×1016 cm-2. The implantation dose dependence of the PCR amplitude, the frequency dependencies of the PCR amplitude and phase, as well as the quasi-time-domain PCR waveforms were simultaneously employed to analyze all the ion-implanted silicon samples. The dependence of the effective lifetime on the implantation dose has been investigated and shown to be related to the trap density and the lifetime extracted from the transient PCR signals.