In situ reduction of graphene oxide dispersed in a polymer matrix

Silicon wafers coated with a film of Ag pattern are used for investigating roles of Ag in the fabrication of silicon nanowire arrays (SiNWs) by the electroless chemical etching technique. The diameter of SiNWs grown in the mixed AgNO₃/HF solution ranges from 20 to 250?nm. A growth mechanism for such obtained SiNWs is proposed and further experimentally verified. As a comparison as well as to better understand this chemical process, another popular topic on growing SiNWs in the H₂O₂/HF solution is also studied. Originating from different chemical reaction mechanisms, Ag film could protect the underneath Si in the AgNO₃/HF solution and it could, on the contrary, accelerate etching of the underneath Si in the H₂O₂/HF solution.     

Effect of temperature and silicon resistivity on the elaboration of silicon nanowires by electroless etching

The morphology of silicon nanowire (SiNW) layers formed by Ag-assisted electroless etching in HF/H₂O₂ solution was studied. Prior to the etching, the Ag nanoparticles were deposited on p-type Si(1 0 0) wafers by electroless metal deposition (EMD) in HF/AgNO₃ solution at room temperature. The effect of etching temperature and silicon resistivity on the formation process of nanowires was studied. The secondary ion mass spectra (SIMS) technique is used to study the penetration of silver in the etched layers. The morphology of etched layers was investigated by scanning electron microscope (SEM).     

Effects of silver and gold catalytic activities on the structural and optical properties of silicon nanowires

The metal-assisted chemical etching of silicon in an aqueous solution of hydrofluoric acid and hydrogen peroxide is established for the fabrication of large area, uniform silicon nanowire (SiNW) arrays. In this study, silver (Ag) and gold (Au) are considered as catalysts and the effect of different catalysts with various thicknesses on the structural and optical properties of the fabricated SiNWs is investigated. The morphology of deposited catalysts on the silicon wafer is characterized by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is shown that the morphology of the fabricated silicon nanostructures remarkably depends upon the catalyst layer thickness, and the catalyst etching time directly affects the structural and optical properties of the synthesized SiNWs. FESEM images show a linear increment of the nanowire length versus time, whereas the etching rate for the Au-etched SiNWs was lower than the Ag-etched ones. Strong light scattering in SiNWs caused the total reflection to decrease in the range of visible light, and this decrement was higher for the Ag-etched SiNW sample, with a longer length than the Au-etched one. A broadband visible photoluminescence (PL) with different peak positions is observed for the Au- and Ag-etched samples. The synthesized optically active SiNWs can be considered as a promising candidate for a new generation of nano-scale opto-electronic devices.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Bi-assisted chemical etching of silicon in HF/Co(NO3)2 solution

The morphology and the photoluminescence (PL) of Bi-assisted electroless etched p-type silicon in HF–Co(NO₃)₂–H₂O solution as a function of etching time were studied. The scanning electron microscopy (SEM) observations have shown that the morphology of etched layers strongly depends on the etching time and it was observed that macropores filled with silicon crystallites are formed for etching time higher than 50 min. Moreover, it was found that the PL spectra show a red emission with a peak centred at 640 nm. The PL peak intensity reaches a maximum for etching time of 50 min, and then it decreases with increasing etching time. The Fourier transform infrared (FTIR) measurements have shown a strong increase in intensities of the relevant Si–H and in the amount of oxide (absorption band at 1070 cm^?1) for long etching time which was ascribed to an increase in the number of Si crystallites formed in the macropores.     

Effects of silicon nanowires length on solar cells photovoltaic properties

Silicon nanowires (SiNWs) were produced by an electroless method on FZ-Si (100) wafer, in HF/AgNO₃ solution. The influence of etching time and temperature on SiNWs morphology were studied using FESEM images. Optical properties were also investigated by optical absorption spectroscopy and low-temperature photoluminescence at 4.2?K. Considering their role as active regions, photovoltaic properties of SiNWs solar cells were studied for their different lengths. Photovoltaic measurements were taken in 1 sun condition under AM 1.5 illumination supplied by a solar simulator. Measurements indicated a reduction in efficiency as SiNWs length increased, which might be attributed to increased dangling states on nanowires surfaces.     

Structural and spectroscopic characterization of porous silicon carbide formed by Pt-assisted electroless chemical etching

A novel electroless method of producing porous silicon carbide (PSiC) is presented. Unlike anodic methods of producing PSiC, the electroless process does not require electrical contact during etching. Rather, platinum metal deposited on the wafer before etching serves as a catalyst for the reduction of a chemical oxidant, which combined with UV illumination injects holes into the valence band, the holes subsequently participating in the oxidation and dissolution of the substrate. The etchant is composed of HF and K₂S₂O₈ in water. Various porous morphologies are presented as a function of etchant concentration, time of etching, and SiC polytype. Wafer quality is of the utmost concern when utilizing the electroless wet etchant, since defects such as stacking faults, dislocations, and micropipes have a large impact on the resulting porous structure. Results of imaging and spectroscopic characterization indicate that the porous morphologies produced in this manner should be useful in producing sensors and porous substrates for overgrowth of low dislocation density epitaxial material.     

Au-assisted electroless etching of silicon in aqueous HF/H2O2 solution

The Au-assisted electroless etching of p-type silicon substrate in HF/H₂O₂ solution at 50 °C was investigated. The dependence of the crystallographic orientation, the concentration of etching solution and the silicon resistivity on morphology of etched layer was studied. The layers formed on silicon were investigated by scanning electron microscopy (SEM). It was demonstrated that although the deposited Au on silicon is a continuous film, it can produce a layer of silicon nanowires or macropores depending on the used solution concentration.     

The effects of surface modification on the electrical properties of p–n+ junction silicon nanowires grown by an aqueous electroless etching method

Although the aqueous electroless etching (AEE) method has received significant attention for the fabrication of silicon nanowires (SiNWs) due to its simplicity and effectiveness, SiNWs grown via the AEE method have a drawback in that their surface roughness is considerably high. Thus, we fabricated surface-modified p–n ⁺ junction SiNWs grown by AEE, wherein the surface roughness was reduced by a sequential processes of oxide growth using the rapid thermal oxidation (RTO) cycling process and oxide removal with a hydrofluoric acid solution. High-resolution transmission electron microscopy analysis confirmed that the surface roughness of the modified SiNWs was significantly decreased compared with that of the as-fabricated SiNWs. After RTO treatment, the wettability of the SiNWs had dramatically changed from superhydrophilic to superhydrophobic, which can be attributed to the formation of siloxane groups on the native oxide/SiNW surfaces and the effect of the nanoscale structure. Due to the enhancement in surface carrier mobility, the current density of the surface-modified p–n ⁺ junction SiNWs was approximately 6.3-fold greater than that of the as-fabricated sample at a forward bias of 4 V. Meanwhile, the photocurrent density of the surface-modified p–n ⁺ junction SiNWs was considerably decreased as a result of the decreases in the light absorption area, light absorption volume, and light scattering.     

Photoluminescence origin of lightly doped silicon nanowires treated with acid vapor etching

In this work, we carry out a comprehensive photoluminescence (PL) study to elucidate the origin of light emission from porous silicon nanowires (pSiNWs). SiNWs were first grooved in lightly doped Si wafer by silver assisted chemical etching, and then treated with an acid vapor emanating from HF/HNO₃ aqueous solution heated at 60 °C. Scanning and transmission electron microscopies were used to investigate the effect of the acid vapor etching on morphological properties of SiNWs. The as prepared pSiNWs exhibited a strong room temperature PL emission centered at 1.93 eV. An increase of the PL intensity was observed with the increase of HNO₃ in the acid solution. By varying the laser excitation density from 60 to 300 W/cm², we shed the light on the radiative recombination modes occurring within the Si nanocrystals (SiNCs) generated along the pSiNWs. We study as well the temperature-dependent PL of the pSiNWs in the range 10 to 300 K. Based on both laser excitation density and temperature-dependent PL, we propose a multilevel transition scheme resuming the PL origin taking into account the size distribution, shape and surface states of the SiNCs trimming the wire sidewalls.     

Growth of single-walled carbon nanotubes on silicon nanowires

Single-walled carbon nanotubes (SWNTs) have been grown on silicon nanowires (SiNWs) by ethanol chemical vapor deposition (CVD) with Co catalysts. We have found that a surface SiO_x layer of SiNWs is necessary for the formation of active Co catalysts. In fact, the yield of the SWNT/SiNW heterojunctions gradually decreases as the thickness of the surface SiO_x layer decreases. Since thin SiNWs are transparent to an electron beam, the Co nanoparticles on SiNWs can be easily observed as well as SWNTs by TEM. Therefore, the relationship between the diameters of each SWNT and its catalyst nanoparticle has been investigated. The diameters of SWNTs are equal to or slightly smaller than those of the catalyst nanoparticles.     

Formation of aligned silicon nanowire on silicon by electroless etching in HF solution

It was demonstrated that the etching in HF-based aqueous solution containing AgNO₃ and Na₂S₂O₈ as oxidizing agents or by Au-assisted electroless etching in HF/H₂O₂ solution at 50 °C yields films composed of aligned Si nanowire (SiNW). SiNW of diameters ∼10 nm were formed. The morphology and the photoluminescence (PL) of the etched layer as a function of etching solution composition were studied. The SiNW layers formed on silicon were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and photoluminescence. It was demonstrated that the morphology and the photoluminescence of the etched layers strongly depends on the type of etching solution. Finally, a discussion on the formation process of the silicon nanowires is presented.     

Reflectivity of porous-pyramids structured silicon surface

The antireflection of porous-pyramids structured silicon surface has been studied. The porous surface is formed by stain etching in HF/Fe(NO₃)₃ aqueous solution after textured in KOH/IPA solution. Reflectivity measurements show an overall reflectance of 4.2% for porous-pyramids textured silicon surface in the range from 400 to 900 nm. An optimal etching time of 30 min is obtained when both reflectivity and photo-generated carriers lifetime are considered. This technique may be probably used in the texturization process for high-efficiency silicon solar cells.     

Formation of Si nanowires by the electrochemical reduction of porous Ni/SiO2 blocks in molten CaCl2

Silicon nanowires (SiNWs) were prepared by the electrochemical reduction of solid Ni/SiO₂ blocks in molten CaCl₂ at 1173 K. The SiNWs have diameter distributions ranging from 80 to 350 nm, and the nickel–silicon droplets are found on the tips of the nanowires. The growth mechanism of SiNWs was investigated, which confirmed that the nano-sized nickel–silicon droplets formed at the Ni/SiO₂/CaCl₂ three-phase interline. The droplets lead to the oriented growth of SiNWs. Formation of nano-sized nickel–silicon droplets suggests that this method could be a potential way to produce nano-sized metal silicides.     

Preparation and surface modification of silicon nanowires under normal conditions

Preparation and surface modification of silicon nanowires (SiNWs) grown by the metal catalyzed solution method under normal conditions (room temperature, 1 atm) had been studied in this paper. Firstly, SiNWs using a simple solution method via electroless metal deposition (EMD) of silver under room temperature, standard pressure had been prepared. The influence of the growth parameters such as solution concentration, etching time on the SiNWs formation had been studied. Secondly, the surface modification of SiNWs with platinum and copper had been investigated. The results indicated that the SiNWs modified with Pt and Cu showed different surface morphologies. Pt modification on SiNWs presented in the form of nanoparticles, whereas Cu modification in the form of membrane. Therefore, the Pt modified SiNWs have more vast surface-to-bulk ratio than the unmodified ones, and SiNWs modified with copper nanoparticles will lead to the smaller surface-to-bulk ratio. So the platinum-modified SiNWs have a promising application in sensors’ field.     

Fabrication and field emission properties of multi-walled carbon nanotube/silicon nanowire array

Silicon nanowire (SiNW) arrays were fabricated on silicon wafers by the metal-assisted chemical etching method. Varied average diameters of SiNW arrays were realized through further treatment in a mixed agent of HF and HNO₃ of certain concentrations. After the treatment, there were more than 93% SiNWs with diameters smaller than 100 nm. The tip of each SiNW was subsequently wrapped with multi-walled carbon nanotubes (MWCNTs) with chemical vapor deposition method. The as-fabricated MWCNT/SiNW arrays were fabricated into electric field emitters, with turn-on field of 2.0 V/μm (current density: 10 μA/cm²), much lower than that of SiNW array (5.0 V/μm). The turn-on electric field of MWCNT/SiNW array decreased with the decreasing of the average diameter of SiNWs, indicating the performance of the field emission is relative to the morphology of SiNWs. As the SiNW array is uniform in height and easy to fabricate, the MWCNT/SiNW array shows potential applications in flat electric display.     

Selective formation of silicon nanowires on pre-patterned substrates

In this paper, the selective growth of silicon nanowires (SiNWs) was studied. With the aid of photolithography, the vertically aligned silicon nanowires were selectively formed on the patterned substrates via an electroless metal deposition (EMD) method under normal conditions (room temperature, 1 atm). Low-pressure chemical vapor deposition (LPCVD) silicon nitride was used as the masking layer for SiNWs preparation. The scanning electron microscope was used to examine the etching results. Both the patterned and the unpatterned silicon substrates were used for study. The results indicated that the growth rates of the SiNWs upon the patterned and the unpatterned substrates are different. For the patterned substrates, the growth rate of SiNWs is dependent upon the pattern shape. The influence of length-to-width ratio for the rectangular-shaped patterns was studied. It is concluded that by designing the proper length-to-width ratio, the nanowires with different lengths can be fabricated simultaneously on the same substrate.     

碱溶液修饰硅纳米线阵列绒面

提出用碱溶液修饰硅纳米线阵列制作太阳能绒面的方法。实验中首先采用金属催化化学腐蚀法在Si(100)基底上制备了定向排列的硅纳米线阵列,然后将纳米线阵列浸入碱溶液中进行修饰,修饰时间分别为10,30,50,60,90s。通过扫描电子显微镜(SEM)对硅纳米线阵列进行形貌分析,采用太阳能测试系统附带的积分球测量纳米线阵列绒面结构的反射光谱。通过测量和分析发现硅纳线阵列在碱溶液中修饰30s时表面分布均匀,在400～1000nm波段的综合反射率低于4%。结果表明碱溶液修饰纳米线阵列的方法能够有效分散束状硅纳米线阵列,明显降低绒面的反射率,并且初步分析了碱溶液修饰硅纳米线阵列的分散机理。     

Characteristics of silicon solar cell emitter with a reduced diffused phosphorus inactive layer

The diffusion of phosphorus using a phosphorous oxychloride (POCl₃) source in silicon has been used widely in crystalline silicon solar cells. The thermal diffusion process in the furnace consists of two steps: pre-deposition and drive-in. The phosphorous doping profile via thermal diffusion often exhibits high concentrations in the surface-near emitter, which result in a recombination increase. This layer, called the dead layer, should be inhibited in order to fabricate high efficiency silicon solar cells. In this paper, the amount of the POCl₃ flow rate was varied during the pre-deposition process in order to minimize the dead layer, and the characteristics of the phosphosilicate glass (PSG) and emitter were analyzed. From the secondary ion mass spectroscopy (SIMS) and electrochemical capacitance–voltage profiler (ECV) measurements, the emitter formed using a POCl₃ flow rate of 1000 sccm contained the least amount of inactive dopant and resulted in reasonable performance in the silicon solar cell. As the POCl₃ flow rate increased, the doped silicon wafer included electrically inactive P near the surface, which functions as a defect degrading the electrical performance of the emitter. As a result of this, the removal of the dead layer containing the inactive P was attempted through dipping the doped wafer in a HF solution. After this process, the emitter saturation current density and implied V_oc were improved. The completed solar cells and their external quantum efficiencies at a short wavelength also demonstrated improved performance. A quantitative analysis of the emitter can provide a deeper understanding of methods to improve the electrical characteristics of the silicon solar cell.     

硅纳米线阵列的光学特性

在常温常压条件下,采用改进的金属催化化学腐蚀方法在n型单晶硅片(100)上制备了大面积垂直于硅衬底、直径均匀、排列整齐的硅纳米线阵列。分析了样品的表面形貌和反射谱,纳米线直径为10~50 nm。在腐蚀时间分别为15,30,60 m in时,纳米线长度分别为9,17,34μm。样品的减反射性能优异,在300~1 000nm波段,得到了2.4%的反射率。初步分析了纳米线阵列的减反射机制和不同腐蚀时间样品的反射率差异。