热化学气相沉积法在硅纳米丝上合成碳纳米管

利用热化学气相沉积法在负载不同厚度催化剂的硅纳米丝(SiNW)表面生长碳纳米管(CNTs),探讨了生长条件对所合成SiNW-CNT的结构和场发射特性的影响.这种类似树状的三维结构具有较高碳纳米管表面密度及降低的电场筛除效应等潜在优势.使用拉曼光谱( Raman)、电子显微镜(SEM)、透射电子显微镜(TEM)、能量扩散分光仪(EDS)分析了碳纳米管的结构性质,并在高真空下施加电场测得碳纳米管的场发射特性.结果表明:随硅纳米丝上负载催化剂镍膜厚度的变化,所合成碳纳米管的表面特性、结晶结构及功函数改变,导致电子发射难易程度的改变,进一步影响碳纳米管的场发射特性.     

The effect of argon dilution on deposition of microcrystalline silicon by microwave plasma enhanced chemical vapor deposition

Microwave plasma-enhanced chemical vapor deposition (PECVD) is a very promising method for industrial scale fabrication of microcrystalline silicon solar cells since the technique is well applicable for large areas, and high deposition rates can be obtained. We have investigated the effect of Ar dilution on the growth process and the material properties of microcrystalline silicon. The major benefit of Ar addition in the MWPECVD process, using H₂ and SiH₄ as reactant gases, is an improved stabilization of the plasma, in particular at low pressure and MW power. We show, however, that material properties of the microcrystalline silicon layers deteriorate if we partly substitute H₂ by Ar during the deposition. The density of the layers - as expressed by the refractive index - decreases, and the defect density (measured by Fourier transform photocurrent spectroscopy) increases with increasing Ar flow. Investigation of the plasma by optical emission study shows that Ar atoms play a very active role in the dissociation processes of H₂ and SiH₄. Substitution of H₂ by Ar decreases the SiH^? emission and increases the Si^? emission. On the other hand, the H_α/H_β ratio increases upon substitution of H₂ by Ar. The latter effect shows that Ar addition does not lead to higher electron temperatures and we conclude that the changes of SiH^? and Si^? emissions are due to dissociation of SiH₄ by Ar^? (quenching reactions). The precise role of Ar in MWPECVD of microcrystalline silicon needs further investigation, but we conclude that the usage of this gas should be minimized in order to maximize the quality of the silicon layers.     

Effects of rf power on the structural properties of carbon nitride thin films prepared by plasma enhanced chemical vapour deposition

Carbon nitride (CN_x) thin films were deposited by radio frequency plasma enhanced chemical vapour deposition (rf PECVD) technique from a gas mixture of methane (CH₄), hydrogen (H₂) and nitrogen (N₂). The effects of rf power on the structural properties of CN_x thin films were discussed in this paper. It was found that rf power had significant effects on the growth rate, structural and morphological properties of the deposited films. The point of transition of the growth rate trend marked the equilibrium condition for primary and secondary reactions in growth kinetics of the film with respect to rf power. The films grown at this optimum rf power were most ordered in structure with high surface roughness and had the lowest N incorporation. This work showed that H etching effects and ion bombardment effects increase with increase in rf power and strongly influenced the structure of the CN_x films.     

Optimization of organized silicon nanowires growth inside porous anodic alumina template using hot wire chemical vapor deposition process

A Hot Wire assisted Chemical Vapor Deposition (HWCVD) process has been developed for producing high-density arrays of parallel, straight and organized silicon nanowires (SiNWs) inside vertical Porous Anodic Alumina (PAA) templates, exploring temperatures ranging from 430 °C to 600 °C, and pressures varying between 2.5 and 7.5 mbar. In order to prevent parasitic amorphous silicon (a-Si) deposit and to promote the crystalline SiNWs growth, we used a tungsten hot wire to partially crack H₂ into atomic hydrogen, which acts like a selective etchant regarding a-Si. Here we describe the optimization route we followed to limit the deposit of a-Si onto the surface of the porous membrane and on the walls of the pores, which led to the possibility to grow SiNWs inside the PAA membranes. Such an approach has high potentialities for device realization, like PIN junctions, FETs or electrodes for Li-ion batteries.     

Synthesis of silicon carbide nanowires by solid phase source chemical vapor deposition

In this paper, we report a simple approach to synthesize silicon carbide (SiC) nanowires by solid phase source chemical vapor deposition (CVD) at relatively low temperatures. 3C-SiC nanowires covered by an amorphous shell were obtained on a thin film which was first deposited on silicon substrates, and the nanowires are 20–80 nm in diameter and several μm in length, with a growth direction of [200]. The growth of the nanowires agrees well on vapor-liquid-solid (VLS) process and the film deposited on the substrates plays an important role in the formation of nanowires.     

射频功率对微晶硅薄膜微结构和光电性能的影响

采用射频等离子体增强化学气相沉积(rf-PECVD)技术,在玻璃和硅衬底上沉积微晶硅(μc-Si:H)薄膜。利用拉曼光谱、AFM和电导率测试对不同射频功率下沉积的薄膜的结构特性及光电性能进行分析。研究表明:随着射频功率的增加,薄膜的晶化率和沉积速率也随之增加,而当射频功率增加到一定的程度,晶化率和沉积速率反而减小。薄膜的暗电导率与晶化率的变化情况相对应。     

The structure and optical properties of silicon nanowires prepared by inductively coupled plasma chemical vapor deposition

Silicon nanowires were prepared by vapor-liquid-solid (VLS) mechanism at a growth temperature as low as 380 °C in an inductively coupled plasma chemical vapor deposition system. The nanowires consist of crystalline core surrounded by a thick amorphous silicon shell. An increase in plasma power produces dense and long nanowires with thick amorphous shell, accompanied with a thick uncatalyzed amorphous silicon film on the silicon substrate. Small catalyst nanoparticles are easier activated by plasma to grow the dense and thin nanowires in comparison with the large-size nanoparticles. Moreover, an enhanced optical absorption is achieved due to the strong light trapping and anti-reflection effects in the thin and tapered silicon nanowires with high density.     

Structural and optical properties of four-hexagonal polytype nanocrystalline silicon carbide films deposited by plasma enhanced chemical vapor deposition technique

Four-hexagonal polytype films of nanocrystalline silicon carbide (4H-nc-SiC) were deposited by plasma enhanced chemical vapor deposition method with more than 3×10⁴ W m⁻² threshold of power density, high hydrogen dilution ratio, and bias pretreatment. The source gases were silane, methane and hydrogen. Our work showed that under conditions similar to those used for the growth of μc-SiC—except a higher power densities over a threshold, a bigger bias pretreatment on substrates, and a moderate bias deposition—nc-SiC films could indeed be achieved. The Raman spectra and transmission electron microscopy diffraction patterns demonstrated that the as-grown films from the H₂-CH₄-SiH₄ plasma consist of amorphous network and phase-pure crystalline silicon carbide which has the 4H polytype structure. The microcolumnar 4H-SiC nanocrystallites of a mean size of approximately 1.6×10⁻⁸ m in diameter are encapsulated by amorphous SiC networks. The photoluminescence spectra of 4H-SiC at room temperature, peaking at 8.10×10⁻⁷ m using a wavelength of 5.145×10⁻⁷ m of argon ion laser, were obtained at room temperature; the luminescence mechanism is thought to be related to transitions in the energy band gap which could be ascribed to the surface states and defects in the structure of 4H-SiC nanocrystalline in these films due to its small size. The as-grown films showed an optical transmittance of 89% at 6.58×10⁻⁷ m. This higher transmittance is believed to be from the small size and amorphous matrix.     

The power source effect on SiOx coating deposition by plasma enhanced chemical vapor deposition

SiOx coatings were prepared by capacitively coupled plasma enhanced chemical vapor deposition on polyethyleneterephtalate substrates in 23 kHz middle-frequency and radio frequency power supplies, respectively, where hexamethyldisiloxane was used as gas source. The influences of discharge conditions on gas phase intermediate species and active radicals for SiOx formation was investigated by mass spectrometry as real-time in-situ diagnosis. The deposited SiOx coating chemical structures were also analyzed by Fourier transform infrared spectroscopy. Meanwhile, the film barrier property, oxygen transmission rate, was measured at 23 °C and 50% humidity circumstance. The better barrier property was obtained in the MF power source depositing SiOx coated PET.     

微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石

研究了衬底温度、核化密度、衬底表而预处理等工艺参数对微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石的影响.采用扫描电镜、X-射线衍射、喇曼光谱和红外光谱对样品进行了表征.结果表明:从高核化密度生长的金刚石膜中探测不到碳化硅;不论对硅衬底进行抛光预处理还是未抛光预处理,从低核化密度牛长的金刚石厚膜中总能探测到碳化硅.碳化硅生长在硅衬底上未被金刚石覆盖的地方,或者是在金刚石晶核之间的空洞处.碳化硅形成和金刚石生长是同时发生的两个竞争过程.此研究结果为制备金刚石和碳化砟复合材料提供了一种新的方法.     

Silicon nanostructures fabricated by Au and SiH4 co-deposition technique using hot-wire chemical vapor deposition

In this study, the fabrication of Si nanostructures by Au and SiH₄ co-deposition technique using hot-wire chemical vapor deposition was demonstrated. A high deposition rate of 2.7 nm/s and a high density of silicon nanostructures with a diameter of about 140 nm were obtained at T_s of 250 °C. An increase in T_s led to a significant reduction in the size of the nanostructures. However, coalescence on the nanostructures was observed at T_s of 400 °C. The Si nanostructures exhibited a highly crystalline structure, which was induced by Au crystallites. The crystallite size and crystallinity of the Si nanostructures amplified with the increase in T_s. The presence of nanostructures enhanced the surface roughness of the samples and clearly reduced the reflection, especially in the visible region.     

Electrical properties/Doping efficiency of doped microcrystalline silicon layers prepared by hot-wire chemical vapor deposition

Microcrystalline silicon (μc-Si) doped films were prepared by hot-wire chemical vapor deposition (HWCVD) to investigate the doping efficiency. The incorporation probability of different dopant atoms into the solid-phase is always increasing with the doping gas concentrations, but very different for the doping gases used: trimethylboron (TMB), boron trifluoride (BF₃) and phosphine (PH₃). At the same doping gas concentration in the process gas the incorporation of phosphorus atoms into the solid μc-Si phase is much larger than that of boron atoms with respect to the dissociation probability of the doping gases. The electron and hole concentrations, estimated from Hall measurements, are directly related to the solid phase concentration of the doping atoms and independent of the type of dopant and the doping gas used. This results in an equal doping efficiency of about 20 % for the incorporated B and P atoms in doped HWCVD μc-Si films. For the dopant atom concentration regime investigated the doping efficiency of B atoms is in good agreement with corresponding PECVD doping efficiencies however, the doping efficiency of P atoms is considerably lower for our n-doped films.     

爆炸辅助气相沉积法制备炭纳米线的研究

根据爆炸辅助气相沉积法生长碳纳米管的机理,设计了两种制备炭纳米线的方案:(1)使用低活性铁-镍二元金属催化剂;(2)对钴催化剂作用下碳纳米管的生长实施冷冻。透射电子显微镜显示这两种方法制备的炭纳米线均为纳米颗粒组装而成,具有非常粗糙的表面。其中,使用铁-镍二元催化剂所制炭纳米线直径分布不均匀,黏结情况严重;而在冷冻钴催化剂作用下炭纳米管生长过程所得的炭纳米线直径分布比较均匀,黏结情况也大为减少。这两种纳米线的差别与金属催化剂的活性有关。光催化降解亚甲基蓝实验表明:冷冻碳纳米管生长所得炭纳米线具有良好的催化辅助功能,可以提高ZnS纳米晶的光催化活性。     

Non-uniform deposition in the early stage of hot-wire chemical vapor deposition of silicon: The charge effect approach

The deposition behavior in hot-wire chemical vapor deposition (HWCVD) of silicon was investigated, focusing on the thickness uniformity of films deposited on silicon and glass substrates, and based on the previous suggestion that a major depositing flux in HWCVD should be negatively charged nanoparticles. The deposition was performed using a 20%-SiH₄-80%-H₂ gas mixture at a 450 °C substrate temperature under a working pressure of 66.7 Pa (0.5 Torr). Non-uniform depositions for three hot-wire temperatures, 1590 °C, 1670 °C, and 1800 °C, and on the silicon and glass substrates were compared. The non-uniformity was most pronounced at 1800 °C and more pronounced on the glass substrate. On the glass substrate, the deposition rate was highest at the corner and lowest at the center, which was attributed to the fastest charge removal, to a conducting stainless steel substrate holder, at the corner. Once the entire glass substrate was deposited with silicon, the growth rate tended to become uniform, possibly due to the high charge removal rate of silicon. The observed deposition behavior indicated that the major depositing flux is negatively charged.     

Silicon nanowire growth on glass substrates using hot wire chemical vapor deposition

We report here, the first observation of silicon nanowire growth via the VLS route at 400 °C using the HWCVD technique with gold (Au) as catalyst. The supersaturation of the alloy droplet, due to a large flux of atomic silicon generated due to efficient dissociation of the silane over the hot wire, leads to the precipitation of Si nanowires. The hot wire process plays a dual role in the entire nanowire growth. Firstly, the atomic hydrogen generated from the hot wire leads to the formation of the metal nanoclusters. Secondly, it offers a continuous supply of silicon atoms enabling efficient diffusion of Si into the Si-Au eutectic alloy leading to the growth of dense silicon nanowires as observed in the SEM. The Raman and TEM data show that the Si nanowires are amorphous in nature. Precise tuning of the hot wire CVD process parameters gives rise to a high density of silicon nanowires having diameters as small as 50 nm and lengths of about a few microns.     

Mechanical properties of carbon-modified silicon oxide barrier films deposited by plasma enhanced chemical vapor deposition on polymer substrates

Cohesive and adhesive properties of silicon oxide barrier coatings deposited from an oxygen/hexamethyldisiloxane gas mixture by plasma enhanced chemical vapor deposition, with controlled incorporation of carbon on 12 μm thick polyethylene terephtalate films were investigated. The reactor was equipped with a 2.45 GHz slot antenna plasma source and a 13.56 MHz-biased substrate holder. The two plasma sources were operated separately or in a dual mode. It was found that no or negligible internal stresses were introduced in the silicon oxide coatings as long as the increase of energy experienced by the film was compensated by the densification of the oxide. For a range of process parameters and carbon content on the changes of the crack onset strain, adhesion, and cohesion were found to be similar. Generally a high crack onset strain or good adhesion and cohesion were measured for films with an increased carbon content, although this was obtained at the expense of the gas barrier performance. Promising approaches towards high-barrier thin films with good mechanical integrity are proposed, based on coatings with a gradient in the carbon content and in the mechanical properties, on nano-composite laminates, and on organo-silane treatments.     

Direct growth of large grain polycrystalline silicon films on aluminum-induced crystallization seed layer using hot-wire chemical vapor deposition

Large grain polycrystalline silicon (poly-Si) films on glass substrates have been deposited on an aluminum-induced crystallization (AIC) seed layer using hot-wire chemical vapor deposition (HWCVD). A poly-Si seed layer was first formed by the AIC process and a thicker poly-Si film was subsequently deposited upon the seed layer using HWCVD. The effects of AIC annealing parameters on the structural and electrical properties of the poly-Si seed layers were characterized by Raman scattering spectroscopy, field-emission scanning electron microscopy, and Hall measurements. It was found that the crystallinity of seed layer was enhanced with increasing the annealing duration and temperature. The poly-Si seed layer formed at optimum annealing parameters can reach a grain size of 700 nm, hole concentration of 3.5 × 10¹⁸ cm^− 3, and Hall mobility of 22 cm²/Vs. After forming the seed layer, poly-Si films with good crystalline quality and high growth rate (> 1 nm/s) can be obtained using HWCVD. These results indicated that the HWCVD-deposited poly-Si film on an AIC seed layer could be a promising candidate for thin-film Si photovoltaic applications.     

Post deposition annealing temperature effect on silicon quantum dots embedded in silicon nitride dielectric multilayer prepared by hot-wire chemical vapor deposition

The preparations of the 20-period of a Si quantum dot (QD)/SiN_x multilayer in a hot-wire chemical vapor deposition (HWCVD) chamber is presented in this paper. The changes in the properties of Si-QDs after the post deposition annealing treatment are studied in detail. Alternate a-Si:H and SiN_x layers are grown in a single SiN_x deposition chamber by cracking SiH₄, and SiH₄ + NH₃, respectively at 250 °C. The as-deposited samples are annealed in the temperature range of 800 °C to 950 °C to grow Si-QDs. All the samples are characterized by confocal micro Raman, transmission electron microscope (TEM), and photoluminescence (PL) to study the changes in the film structures after the annealing treatment. The micro Raman analysis of the samples shows the frequency line shifting from 482 cm^− 1 to 500 cm^− 1 indicating the Si transition from an amorphous to a crystalline phase. The TEM micrograph inspection indicates the formation of Si-QDs of size 3 to 5 nm and a density of 5 × 10¹²/cm². The high resolution TEM micrographs show an agglomeration of Si-QDs with an increase in the annealing temperature. The PL spectra show a peak shifting from 459 nm to 532 nm with increasing the annealing temperature of the film.     

Growth of silicon nanoclusters on different substrates by plasma enhanced chemical vapor deposition

We report an atomic force microscopy study of the early stages of growth of silicon nanoclusters formed on different substrates by plasma-enhanced chemical vapor deposition, using dichlorosilane (SiH2CI2) and hydrogen (H2) as reactive gases. (100) n-type single crystalline silicon, fused silica, amorphous silicon nitride and corning glass, were used as substrates for the growth of the nanoclusters, which were formed at low substrate temperature (200 degrees C). The diameter, height and number density of the clusters were controlled by the deposition time and pressure. It was found that not only the plasma conditions but also the surface characteristics of the substrate influence the cluster density, shape, and size. For the ordered silicon surface and the amorphous fused silica, the nanoclusters result oval in shape and exhibit preferential growth along the surface. When deposited over amorphous silicon nitride and corning glass, the density of nanoclusters increases and there is a tendency toward columnar growth since the diameter of the nanoclusters tends to decrease. We conclude that although the specific features of the nanoclusters originate from the chlorine chemistry introduced by the SiHxCly deposition precursor and the chemical stability of chlorine-terminated surfaces under hydrogen plasma, the surface quality and roughness also plays an important role on the nucleation and mobility of the species. The combination of both effects gives rise to the different nanostructured growths observed.     

Fabrication of selective-emitter silicon heterojunction solar cells using hot-wire chemical vapor deposition and laser doping

The Si heterojunction (HJ) solar cells were fabricated on the textured p-type mono-crystalline Si (c-Si) substrates using hot-wire chemical vapor deposition (HWCVD). In view of the potential for the bottom cell in a hybrid junction structure, the microcrystalline Si (μc-Si) film was used as the emitter with various PH₃ dilution ratios. Prior to the n-μc-Si emitter deposition, a 5 nm-thick intrinsic amorphous Si layer (i-a-Si) was grown to passivate the c-Si surface. In order to improve the indium-tin oxide (ITO)/emitter front contact without using the higher PH₃ doping concentration, a laser doping technique was employed to improve the ITO/n-μc-Si contact via the formation of the selective emitter structure. For a cell structure of Ag grid/ITO/n-μc-Si emitter/i-a-Si/textured p-c-Si/Al-electrode, the conversion efficiency (AM1.5) can be improved from 13.25% to 14.31% (cell area: 2 cm × 2 cm) via a suitable selective laser doping process.