激光晶化形成纳米硅材料的场电子发射性质研究

利用KrF准分子激光退火超薄非晶硅膜,并结合热退火技术制备了单层纳米硅薄膜并研究了薄膜的场电子发射性质.在晶化形成的纳米硅薄膜中可以观测到稳定的场电子发射现象,其开启电场从原始淀积的非晶硅薄膜的17V/μm降低到8.5V/μm,而场发射电流密度可以达到0.1mA/cm².激光晶化后形成的纳米硅材料的场电子发射特性的改善可以从薄膜表面形貌的改变以及高密度纳米硅的形成所导致的内部电场增强作用来解释. 关键词： 纳米硅 场发射 激光晶化     

Structure and electrical characterization of amorphous ErSiO films deposited by rf magnetron sputtering on Si (001)

Amorphous ErSiO films have been fabricated on p-type Si (001) substrates using rf magnetron sputtering technique. X-ray diffraction, high-resolution transmission electron microscopy, and atomic force microscopy were employed to investigate the samples. It is found that ErSiO film exhibits a flat surface, a sharp interface and superior electrical properties after post-deposition annealing in O₂ ambience for 30 min at 450°C. The effective dielectric constant of the film is measured to be 14.2, and the effective oxide thickness reaches 1.9 nm, with a low leakage current density of 1.1×10⁻⁴ A/cm² at an electric field of 1 MV cm⁻¹ after annealing at 450°C. The obtained characteristics make the amorphous ErSiO films a promising substitute for SiO₂ as a high-k gate dielectric.     

Influence of heat treatment on field emission characteristics of boron nitride thin films

Boron nitride (BN) nanometer thin films are synthesized on Si (1 0 0) substrates by RF reactive magnetron sputtering. Then the film surfaces are treated in the case of the base pressure below 5 × 10⁻⁴ Pa and the temperature of 800 and 1000 °C, respectively. And the films are studied by Fourier transform infrared spectra (FTIR), atomic force microscopic (AFM) and field emission characteristics at different annealing temperature. The results show that the surface heat treatment makes no apparent influence on the surface morphology of the BN films. The transformations of the sample emission characteristics have to do with the surface negative electron affinity (NEA) of the films possibly. The threshold electric fields are lower for BN samples without heat-treating than the treated films, which possibly ascribed to the surface negative electron affinity effect. A threshold field of 8 V/μm and the emission current of 80 μA are obtained. The surface NEA is still presence at the heat treatment temperature of 800 °C and disappeared at temperature of 1000 °C.     

Fabrication and sub-band-gap absorption of single-crystal Si supersaturated with Se by pulsed laser mixing

Selenium supersaturated silicon layers were fabricated by pulsed excimer laser induced liquid-phase mixing of thin Se films on Si(001) wafers. Sufficiently low Se coverage avoids destabilization of rapid epitaxial solidification, resulting in supersaturated solid solutions free of extended defects, as shown by transmission electron microscopy. The amount of retained Se depends on the original film thickness, the laser fluence, and the number of laser pulses irradiating the same spot on the surface. Using this method, Se has incorporated into the topmost 300 nm of the silicon with a concentration of 0.1 at.%. Channeling Rutherford backscattering spectrometry measurements show that the substitutional fraction can be as high as 75% of the total retained Se. These alloys exhibit strong sub-band-gap absorption with optical absorption coefficient ranging up to about 10⁴ cm⁻¹, thus making them potential candidates for applications in Si-based optoelectronic devices.     

Preparation of single-crystal-like MgO films on Si and orientation control of platinum films on MgO/Si

Growth of a Pt/MgO bilayer on Si(100) was investigated by pulsed-laser deposition. The growth modes of both MgO and platinum films are layer-by-layer growth, which were revealed by in situ reflection high energy electron diffraction observations. Two kinds of orientations of platinum films, viz. epitaxially (100) and (111)-oriented platinum films, were obtained on the same MgO(100)/Si(100) substrate only by varying the laser fluence. The effect of laser fluence on the orientation of platinum films is briefly discussed. The platinum films prepared in our experiments are epitaxially grown and exhibit atomic-scale surface flatness. It is believed that the improvement in the quality of platinum films can be attributed to the perfectly single-crystalline quality of the MgO buffer layer, which was further confirmed by the excellent dielectric properties. For a 150 nm thick MgO film, the leakage current density was found to be 10^-7 Acm^-2 with an electric field of 8×10⁵ Vcm^-1 and the relative dielectric constant (_r) was 10.6. PACS 68.55.Jk; 81.15.Fg; 85.50.Gk     

Field emission from a-GaN films deposited on Si (100)

Amorphous gallium nitride (a-GaN) films have been deposited on Si (100) substrates using ion-assisted deposition. The deposited films were characterised by X-ray diffraction (XRD) and atomic force microscopy (AFM). XRD confirms the amorphous nature of the films and AFM showed nanostructures in the films. The field electron emission from the film was obtained in a probe-hole field emission microscope, and the current-voltage (I-V) characteristics were studied. The corresponding Fowler-Nordheim (F-N) plots showed a linear behaviour. A current density of 0.1 A/cm² has been obtained for 1.2 V/μm electric field. The field emission current-time (I-t), curves were recorded at a current level of 500 nA for 3 h. The field emission behaviour is compared with that of crystalline GaN as reported in literature.     

Enhanced field emission from ZnO nanopencils by using pyramidal Si(1 0 0) substrates

Zinc oxide nanopencil arrays were synthesized on pyramidal Si(1 0 0) substrates via a simple thermal evaporation method. Their field emission properties have been investigated: the turn-on electric field (at the current density of 10 μA/cm²) was about 3.8 V/μm, and the threshold electric field (at the current density of 1 mA/cm²) was 5.8 V/μm. Compared with similar structures grown on flat Si substrates, which were made as references, the pyramidal Si-based ZnO nanopencil arrays appeared to be superior in field emission performance, thus the importance of the non-flat substrates has been accentuated. The pyramidal Si substrates could not only suppress the field screening effect but also improve the field enhancement effect during the field emission process. These findings indicated that using non-flat substrates is an efficient strategy to improve the field emission properties.     

Effects of sputtering pressure on the field emission properties of N-doped SrTiO3 thin films coated on Si tip arrays

The influence of sputtering pressure on the electron emission properties of Si tips coated with N-doped SrTiO₃ ultrathin films was investigated. X-ray diffraction studies revealed that the N-doped SrTiO₃ films deposited at different pressures remain the perovskite structure. However, the threshold electric field of electron emission decreased markedly when the sputtering pressure is increased, and reached a minimum value of 17.37 V/μm while deposited at 1.6 Pa. The decrease in the threshold field is attributed to the narrowed band gap and the lowered surface energy of SrTiO₃ thin films with nitrogen doped, as confirmed using spectroscopic ellipsometry and water contact angle measurement. Furthermore, it is revealed using XPS that such sputtering pressure dependence is accompanied with the change of nitrogen bonding state in the films, which changes from poorly screened γ-N₂ state to atomic β-N state when the sputtering pressure is increased. A mechanism of bonding and band-forming was proposed for the enhanced electron emission with nitrogen incorporation in the sputtered SrTiO₃ films.     

Low-temperature formation of nanocrystalline SiC particles and composite from three-layer Si/C/Si film for the novel enhanced white photoluminescence

In this article, nanocrystalline silicon carbide (nc-SiC) and composite have been synthesized at an annealing temperature as low as 750 °C through the thermal reaction of Si/C/Si multilayers deposited on the Si(100) substrate by ultra-high-vacuum ion beam sputtering (UHV IBS) compared with the conventional thermal formation of crystalline SiC (c-SiC) nanostructures above 1,000 °C. The evolution of microstructure and reaction between C and Si was examined by Raman spectroscopy, Fourier transform infrared spectrometer (FTIR), high-resolution field emission scanning electron microscope (HR-FESEM), and high-resolution transmission electron microscopy. The c-SiC nanoparticles (np-SiC) of around 20–120 nm in diameter appeared on the top and bottom of the three-layer film with a particle density of around 2.63 × 10¹⁰ cm⁻² after 750 °C annealing. The composite of nc-SiC and Si nanocrystals (nc-Si) size below 5 nm embedded in an amorphous SiC (a-SiC) matrix appeared at the interface between the Si and C layers. Efficient thermal energy is the driving force for the formation of nc-SiC and composite through interdiffusion between C and Si. The broad visible photoluminescence (PL) spectrum of 350–750 nm can be obtained from the annealed composite Si/C/Si multilayer and deconvoluted into four bands of blue (~430 nm), green (~500 nm), green–yellow (~550 nm), and orange (~640 nm) emission, corresponding to the emission origins from nc-SiC, sp² carbon clusters, np-SiC, and nc-Si, respectively.     

Controlled fabrication of Si nanostructures by high vacuum electron beam annealing

Silicon nanostructures, called Si nanowhiskers, have been successfully synthesized on Si(1 0 0) substrate by high vacuum electron beam annealing (EBA). Detailed analysis of the Si nanowhisker morphology depending on annealing temperature, duration and the temperature gradients applied in the annealing cycle is presented. A correlation was found between the variation in annealing temperature and the nanowhisker height and density. Annealing at 935 °C for 0 s, the density of nanowhiskers is about 0.2 μm⁻² with average height of 2.4 nm grow on a surface area of 5×5 μm, whereas more than 500 nanowhiskers (density up to 28 μm⁻²) with an important average height of 4.6 nm for field emission applications grow on the same surface area for a sample annealed at 970 °C for 0 s. At a cooling rate of −50 °C s⁻¹ during the annealing cycle, 10–12 nanowhiskers grew on a surface area of 5×5 μm, whereas close to 500 nanowhiskers grew on the same surface area for samples annealed at the cooling rate of −5 °C s⁻¹. An exponential dependence between the density of Si nanowhiskers and the cooling rate has been found. At 950 °C, the average height of Si nanowhiskers increased from 4.0 to 6.3 nm with an increase of annealing duration from 10 to 180 s. A linear dependence exists between the average height of Si nanowhiskers and annealing duration. Selected results are presented showing the possibility of controlling the density and the height of Si nanowhiskers for improved field emission properties by applying different annealing temperatures, durations and cooling rates.     

Growth of AgInSe<Subscript>2</Subscript> on Si(100) substrate by thermal evaporation technique

AgInSe₂ films were prepared by a thermal evaporation technique onto Si(100) substrates at a pressure of 10⁻⁵ mbar. Structural and optical properties of films deposited at 300 and 473 K have been investigated. The film composition was studied by energy dispersive analysis through X-rays. X-ray diffraction patterns indicate that AgInSe₂ films have chalcopyrite structure with strong preferred orientation in the (112) direction. Average vertical crystallite size of 25 nm was observed. The optical energy gaps of 1.20 and 1.90 eV were obtained due to the fundamental absorption edge and a transition originating from crystal field splitting, respectively. Field emission scanning electron microscopy shows loosely packed grains of spherical symmetry with some facets.     

Effect of Si ion irradiation on polycrystalline CdS thin film grown from novel photochemical deposition technique

CdS thin films have been deposited from aqueous solution by photochemical reactions. The solution contains Cd(CH₃COO)₂ and Na₂S₂O₃, and pH is controlled in an acidic region by adding H₂SO₄. The solution is illuminated with light from a high-pressure mercury-arc lamp. CdS thin films are formed on a glass substrate by the heterogeneous nucleation and the deposited thin films have been subjected to high-energy Si ion irradiations. Si ion irradiation has been performed with an energy of 80 MeV at fluences of 1×10¹¹, 1×10¹², 1×10¹³ and 1×10¹⁴ ions/cm² using tandem pelletron accelerator. The irradiation-induced changes in CdS thin films are studied using XRD, Raman spectroscopy and photoluminescence. Broadening of the PL emission peak were observed with increasing irradiation fluence, which could be attributed to the band tailing effect of the Si ion irradiation. The lattice disorder takes place at high Si ion fluences.     

Structural characterization and optoelectronic properties of GaN thin films on Si(111) substrates using pulsed laser deposition assisted by gas discharge

GaN films have been grown on Si(111) substrates with a thin AlN buffer layer using pulsed laser deposition (PLD) assisted by gas discharge. The crystalline quality, surface morphology and optoelectronic properties of the deposited films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL) spectroscopy, and room-temperature Van der Pauw–Hall measurements. The influence of the deposition temperature in the range 637–1037 K on the crystallinity of GaN films, the laser incident energy in the range 150–250 mJ/pulse on the surface morphology and the optoelectronic properties were systematically studied. The XRD analysis shows that the crystalline quality of the GaN films improves with increasing deposition temperature to 937 K, but further increase of the deposition temperature to 1037 K leads to the degradation of the crystalline quality. AFM results show that the surface roughness of the GaN films can be decreased with increasing laser incident energy to 220 mJ/pulse. Further increase of the laser incident energy to 250 mJ/pulse leads to an increase in the surface roughness. The optoelectronic properties of GaN films were also improved by increasing the laser incident energy to 220 mJ/pulse. GaN films which have a n-type carrier concentration of 1.26×10¹⁷ cm^-3 and a mobility of 158.1 cm²/Vs can be deposited at a substrate temperature of 937 K, a deposition pressure of 20 Pa and a laser incident energy of 220 mJ/pulse. Their room-temperature PL spectra exhibit a strong band-edge emission at 365 nm. PACS 81.15.Fg; 81.05.Ea; 78.20.-e; 73.61.Ey; 78.66.Fd     

Controlled fabrication of Si nanostructures by high vacuum electron beam annealing

Silicon nanostructures, called Si nanowhiskers, have been successfully synthesized on Si(1 0 0) substrate by high vacuum electron beam annealing (EBA). Detailed analysis of the Si nanowhisker morphology depending on annealing temperature, duration and the temperature gradients applied in the annealing cycle is presented. A correlation was found between the variation in annealing temperature and the nanowhisker height and density. Annealing at 935 °C for 0 s, the density of nanowhiskers is about 0.2 μm⁻² with average height of 2.4 nm grow on a surface area of 5×5 μm, whereas more than 500 nanowhiskers (density up to 28 μm⁻²) with an important average height of 4.6 nm for field emission applications grow on the same surface area for a sample annealed at 970 °C for 0 s. At a cooling rate of −50 °C s⁻¹ during the annealing cycle, 10–12 nanowhiskers grew on a surface area of 5×5 μm, whereas close to 500 nanowhiskers grew on the same surface area for samples annealed at the cooling rate of −5 °C s⁻¹. An exponential dependence between the density of Si nanowhiskers and the cooling rate has been found. At 950 °C, the average height of Si nanowhiskers increased from 4.0 to 6.3 nm with an increase of annealing duration from 10 to 180 s. A linear dependence exists between the average height of Si nanowhiskers and annealing duration. Selected results are presented showing the possibility of controlling the density and the height of Si nanowhiskers for improved field emission properties by applying different annealing temperatures, durations and cooling rates.     

Effect of the Si excess on the structure and the optical properties of Nd-doped Si-rich silicon oxide

Nd-doped Si-rich silicon oxide thin films were produced by radio frequency magnetron co-sputtering of three confocal cathodes: Si, SiO₂, and Nd₂O₃, in pure argon plasma at 500 °C. The microstructure and optical properties of the films were investigated versus silicon excess and post-deposition annealing treatment by means of ellipsometry and Fourier transform infrared spectrometry as well as by the photoluminescence method. A notable emission from Nd³⁺ ions was obtained for the as-deposited sample, while the films annealed at 900 °C showed the highest peak intensity. The maximum emission was observed for the films with 4.7 at% of Si excess.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.     

Nanosecond laser ablation and deposition of silicon

Nanosecond-pulsed KrF (248 nm, 25 ns) and Nd:YAG (1064 nm, 532 nm, 355 nm, 5 ns) lasers were used to ablate a polycrystalline Si target in a background pressure of <10⁻⁴ Pa. Si films were deposited on Si and GaAs substrates at room temperature. The surface morphology of the films was characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Round droplets from 20 nm to 5 μm were detected on the deposited films. Raman Spectroscopy indicated that the micron-sized droplets were crystalline and the films were amorphous. The dependence of the properties of the films on laser wavelengths and fluence is discussed.     

Influence of surface morphology on the field emission properties of planar SiC/Si heterostructures formed by ion beam synthesis

The electron field emission properties of planar SiC/Si heterostructures with various surface morphology formed by high dose C⁺ implantation into Si using a metal vapor vacuum arc ion source were investigated. An implant energy of 35 keV was used with doses of 8×10¹⁷, 1×10¹⁸ and 1.2×10¹⁸ ions/cm⁻² with subsequent annealing in Ar at 1200 °C for various times. X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy showed that a thin stoichiometric SiC surface layer is formed and the surface work function is about 4.5 eV. Atomic force microscopy indicated that the size and density of the densely distributed small protrusions formed on the surface vary with preparation conditions. Results showed that there is an optimum annealing time for the corresponding implant dose at which a remarkably low turn-on field of about 1 V/μm is observed. The density and size of the small protrusions on the surface are believed to be the main factors affecting the field emission properties.     

Field electron emission of carbon-based nanocone films

Diamond nanocone, graphitic nanocone, and mixed diamond and graphitic nanocone films have been synthesized through plasma enhanced hot filament chemical vapor deposition (HFCVD). The field emission properties of these films have been experimentally investigated. The studies have revealed that all three kinds of nanocone films have excellent field electron emission (FEE) properties including low turn-on electric field and large emission current at low electric field. Compared with the diamond nanocone films (emission current of 86 μA at 26 V/μm with the turn-on field of 10 V/μm), the graphitic nanocone films exhibit higher FEE current of 1.8×10² μA at 13 V/μm and a lower turn-on filed of 4 V/μm. The mixed diamond and graphitic nanocone films have been found to posses FEE properties similar to graphitic nanocone films (emission current of 1.7×10² μA at 20 V/μm with the turn-on field of 5 V/μm), but have much better FEE stability than the graphitic nanocone films. PACS 81.07.Bc; 81.05.Uw; 79.70.+q     

First comparison of electric field induced second harmonic of near-infrared femtosecond laser pulses in reflection and transmission generated from Si/SiO<Subscript>2</Subscript> interfaces of a silicon membrane

For the first time electric field induced second harmonic (EFISH) generation of femtosecond (fs) laser pulses (λ=800 nm, τ=75±5 fs, rep. rate=80 MHz, E _pulse≤10 nJ) is observed in transmission through a thin free-standing silicon (Si) membrane of 10-μm thickness and compared to the well-known EFISH results in reflection by use of the z-scan technique. EFISH in reflection and transmission unequivocally originate from the front and rear Si/SiO₂ interfaces, respectively, with SiO₂ being the natural oxide on the Si surfaces. Frequency conversion is enhanced by photoinduced electric fields across the Si/SiO₂ interfaces caused by charge-carrier injection from Si into the oxide. The z-scan results and time-dependent measurements allow comparison of the EFISH signal amplitudes and time constants detected in transmission and reflection, demonstrating the need for further investigation.