TFSI钝化晶体硅表面性质的第一性原理研究

晶体硅表面钝化是高效率晶体硅太阳能电池的核心技术,直接影响晶体硅器件的性能。本文采用第一性原理方法研究了一种超强酸-双三氟甲基磺酰亚胺(TFSI)钝化晶体硅(001)表面。研究发现,TFSI的四氧原子结构能够与Si(001)表面Si原子有效成键,吸附能达到-5.124 eV。电子局域函数研究表明,TFSI的O原子与晶体硅表面的Si的成键类型为金属键。由态密度和电荷差分密度分析可知,Si表面原子的电子向TFSI转移,从而有效降低了Si表面的电子复合中心,有利于提高晶体硅的少子寿命。Bader电荷显示,伴随着TFSI钝化晶体硅表面的Si原子,表面Si原子电荷电量减少,而TFSI中的O原子和S原子电荷电量相应增加,进一步证明了TFSI钝化Si表面后的电子转移。该工作为第一性原理方法预测有机强酸钝化晶体硅表面的钝化效果提供了数据支撑。     

Polycrystalline silicon carbide film deposition using monomethylsilane and hydrogen chloride gases

A polycrystalline silicon carbide film is formed on a silicon surface by chemical vapor deposition using monomethylsilane gas along with hydrogen chloride gas in ambient hydrogen at atmospheric pressure. The film deposition is performed near 1000 K, at which temperature the monomethylsilane maintains a chemical bond between the silicon and carbon present in the molecular structure. The excess amount of silicon on the film surface is reduced using the hydrogen chloride gas. Although the film deposition stops within 1 min after beginning the supply of the monomethylsilane gas and hydrogen chloride gas, annealing at 1273 K in ambient hydrogen after the film deposition allows further deposition so that a thick silicon carbide film can be obtained.     

Porous silicon optical filters for biosensing applications

The surface of nanostructured silicon (porous silicon) was biofunctionalized by the deposition of 3-aminopropyltriethoxysilane from solution, leading to high density of amine groups covering the surface which would promote the further immobilization of biomolecules. In addition, porous silicon Bragg reflectors were developed for their use in the visible range. The optical behavior of these structures was previously designed by the use of a computational program, from which the optical constants and thickness of the individual porous silicon layers were determined. The possibility of using these structures as biosensors has been explored, based on the significant changes in the reflectance spectra before and after exposing the porous silicon optical structures to biomolecules. In particular, it is shown that there is a notable shift of the reflectance maximum associated to the Bragg reflector after immobilization of polyclonal mouse antibodies. Thus, the experimental results open the possibility of developing biosensors based on the variation of the position of the optical spectrum of porous silicon based devices.     

Generation of dislocations on polished surfaces of dislocation free silicon wafers

This paper describes investigations into the influence of wafer defects (surface defects) on the generation of process induced crystal defects in dislocation-free n-type silicon material of both Czochralski and zone-floating techniques. The surface defects are artificial defects, which were produced by scratching with definite forces. The behaviour of scratched silicon surfaces as well as that of scratched and polished silicon surfaces was studied at room temperature and after heat treatment. The experimental results are discussed.     

单晶硅外延生长晶化硅薄膜的研究

采用P型单晶硅片为衬底,并经混合酸溶液腐蚀抛光、清洗后,利用射频磁控溅射镀膜系统在其表面制备非晶硅薄膜;再结合快速光热退火工艺,于N2气氛下480℃退火30 min,得到晶化硅薄膜;利用光学金相显微镜、XRD衍射仪和拉曼散射光谱(Raman)仪对单晶硅衬底和晶化硅薄膜进行结构和性能表征.研究了混合酸溶液对单晶硅表面腐蚀效果、籽晶诱导外延生长晶化硅薄膜的物相结构和薄膜带隙.结果表明:采用混合酸溶液腐蚀后得到表面平整、光滑的单晶硅衬底;非晶硅薄膜经过快速退火后受籽晶诱导生成晶化硅薄膜,其晶相沿单晶硅衬底取向择优生长;随着非晶硅薄膜厚度从80 nm增加到280 nm,晶化后硅薄膜的表面粗糙度逐渐减小,晶化率从90.0;逐渐降低到37.0;;晶粒尺寸从6.65 nm逐渐减小到1.71 nm;带隙从1.18 eV逐渐升高到1.52 eV.     

Structure of natural film on porous silicon surface founded by ellipsometry

Abstract

The multiple-angle-of-incidence ellipsometric studies of the natural film formed on the surface of porous silicon sample after its production and subsequent keeping in isopropyl alcohol have been performed. A new property of porous silicon with the natural film on its surface has been revealed which consists in a drastic change of the polarization characteristics of the reflected light wave after its keeping in alcohol. This property of porous silicon may be the basis for the development of liquid and gas sensors, polarization elements of optical devices etc. It was found that ellipsometric curves are described better by calculations in a two-layer model in comparison with a single-layer one of the investigated film. It was obtained that the outer layer of the film has smaller refractive index than the inner one. As a result of decoration the refractive indices of both layers decrease and further the changes of refractive indices and the redistribution of the thickness of both layers are found. It is suggested that the interaction of the alcohol molecules with silicon and its oxide environment occurs in the walls of the pores during the decoration.     

重掺硅衬底片的内吸除效应

本文研究了重掺p型(B)和重掺n型(P、As、Sb)硅单晶的内吸除效应.发现在本实验条件下,经过改进的内吸杂(IG)处理后,不同掺杂剂的重掺硅单晶片都出现了氧沉淀增强现象,但不同掺杂剂的重掺硅单晶中氧沉淀形态不同.且发现砷增强了硅片近表层区氧的外扩散.在相同的热处理条件下,不同掺杂剂的重掺硅清洁区宽度不同,重掺硼硅片的清洁区最窄,重掺砷的最宽.     

On the oxidation mechanism of microcrystalline silicon thin films studied by Fourier transform infrared spectroscopy

Insight into the oxidation mechanism of microcrystalline silicon thin films has been obtained by means of Fourier transform infrared spectroscopy. The films were deposited by using the expanding thermal plasma and their oxidation upon air exposure was followed in time. Transmission spectra were recorded directly after deposition and at regular intervals up to 8 months after deposition. The interpretation of the spectra is focused on the Si-H_x stretching (2000-2100 cm⁻¹), Si-O-Si (1000-1200 cm⁻¹), and O_xSi-H_y modes (2130-2250 cm⁻¹). A short time scale (< 3 months) oxidation of the crystalline grain boundaries is observed, while at longer time scales, the oxidation of the amorphous tissue and the formation of O-H groups on the grain boundary surfaces play a role. The implications of this study on the quality of microcrystalline silicon exhibiting no post-deposition oxidation are discussed: it is not sufficient to merely passivate the surface of the crystalline grains and fill the gap between the grains with amorphous silicon. Instead, the quality of the amorphous silicon tissue should also be taken into account, since this oxidation can affect the passivating properties of the amorphous tissue on the surface of the crystalline silicon grains.     

三氯氢硅和氢气系统的气相沉积三维模拟

建立了氢气和三氯氢硅系统的多晶硅气相沉积反应模型,通过Chemkin4.0耦合气相反应、表面反应机理,利用流体力学软件Fluent 6.3.26数值求解.根据模拟结果绘制了进气温度、进气组成、沉积表面温度以及反应压力与硅沉积速率的关系曲线,阐述了这些条件对于硅沉积速率的影响,同时把模拟结果与文献中的实验数据和计算结果进行对比.结果表明,硅沉积速率随反应温度和反应压力的提高而提高,随进气温度的提高而提高,当氢气摩尔组成低于0.8时,与氢气物质的量组成成正比,氢气物质的量组成大于0.8时,与氢气摩尔组成成反比.     

Cracking assisted nucleation in chemical vapor deposition of silicon nanoparticles on silicon dioxide

Deposition of sub-monolayer silicon on SiO₂/Si(1 0 0) greatly facilitates nucleation in subsequent thermal chemical vapor deposition (CVD) of silicon nanoparticles. Sub-monolayer seeding is accomplished using silicon atoms generated via disilane decomposition over a hot tungsten filament. The hot-wire process is nonselective towards deposition on silicon and SiO₂, is insensitive to surface temperature below 825 K, and gives controlled coverages well below 1 ML. Thermal CVD of nanoparticles at 1×10⁻⁴ Torr disilane and temperatures ranging from 825 to 925 K was studied over SiO₂/Si(1 0 0) surfaces that had been subjected to predeposition of Si or were bare. Seeding of the SiO₂ surface with as little as 0.01 ML is shown to double the nanoparticle density at 825 K, and densities are increased twenty fold at 875 K after seeding the surface with 30% of a monolayer.     

The impurity heterogeneities in the surface layer of silicon with an atomically clean surface

The electrical and photoelectrical properties of the surface region of silicon after evaporation in vacuum used in obtaining an atomically clean surface at the subsequent epitaxy are studied. The formation kinetics of a p-layer at 1300 and 1350 °C for the heating time of 10 to 10³ s is investigated. The effective values of holes mobility in p-layers are independent on a decrease of layer thicknesses down to 0.2μm at the concentration of acceptors of 10¹⁷ to 10¹⁸ cm⁻³ (294 K). The concentrations of doping impurities in the surface region of silicon before and after thermal treatment are determined by the method of mass-spectrometric analysis. The peculiarities of transport and building-in of doping impurities of the III and V groups at epitaxy and the possible nature of acceptor levels are discussed. A concentration profile of acceptors and donors from the surface deep into the silicon bulk is determined by the methods of layer-by-layer etching and of C-V characteristics. An effective built-in electric field is due to acceptor and donor distribution, which favours drift separation of minor radiation-generated current carriers in the p-n structure. The high-sensitive and fast-responding photoreceivers have been produced. The given detectability reaches 2 × 10¹² cm Hz^1/2/W at a wavelength of 1.06μm.     

基于POLO钝化接触结构的晶硅电池技术及其研究进展

多晶硅氧化物(POLO)结构是在晶硅表面依次生长一层极薄的界面氧化层与多晶硅层所形成的钝化接触结构。基于POLO结构的钝化接触技术不仅能够获得优异的表面钝化特性,而且避免了金属与晶硅表面的直接接触,极大地降低了金属与晶硅表面的接触复合。目前应用POLO钝化接触结构制作的小面积晶硅太阳能电池转换效率高达26.1%,制作的大面积晶硅太阳能电池产业化效率已经超过24.5%。同时POLO钝化接触技术应用于晶硅电池的制作可以承受高温工艺,兼容现有的晶硅电池产业化设备,是未来极具产业化潜力的钝化接触技术方案。本文主要综述了POLO钝化接触结构中载流子的传输机理及相应的量化参数表征方法;对比了POLO结构制备中界面氧化层生长、多晶硅层的沉积、掺杂及氢化处理的方法;总结了多晶硅层的寄生吸收效应、晶硅表面形貌结构、掺杂浓度分布对POLO结构钝化接触特性的影响;简述了POLO钝化接触技术的研究进展及当前POLO电池制作面临的技术难点。     

Silicon on spinel: The interaction between deposition constituents and the substrate surface

The examination of the growth of silicon on flame fusion and Czochralski spinel prior to complete coverage of the substrate provides information on the chemical interaction between the deposition constituents and the substrate material. The flame fusion spinel appears to be eroded primarily by silicon, while the Czochralski spinel is eroded by both hydrogen and silicon. The hole mobilities in (111) silicon deposited in helium on the Czochralski spinel are similar to the mobilities in (111) silicon deposited in hydrogen on the flame fusion spinel. The semiconducting properties of silicon on the Czochralski spinel are degraded by annealing the substrate in hydrogen, and are unaffected by annealing the substrate in helium. The substrate surface work damage appears to be removed as the result of reduction of the spinel by silicon during the deposition of silicon on the Czochralski spinel in helium. Both the electrical data of 1 μm thick films and the physical nature of the deposits prior to complete coverage of the substrate lead to the conclusion that the hole mobilities in silicon on spinel are limited primarily by the impurities introduced into the deposit by reaction of the substrate with the deposition constituents, and that the impurities are incorporated into the deposit mainly prior to complete coverage of the surface and are concentrated in a thin layer in the silicon near the silicon-substrate interface.     

镁离子掺杂多孔硅的蓝光发射

用电化学方法对多孔硅薄膜进行了镁离子的化学掺杂.用荧光分光光度计分析了样品的光致发光特性,发现镁掺杂增强了多孔硅的蓝光发射,当镁离子浓度增大到0.002mol/L时,可使蓝光强度达到多孔硅红光强度的一半.红外吸收谱表明,掺镁多孔硅的表面形成较完整的Si-O-Si网络结构,分析结果认为,多孔硅的蓝光光激发主要发生在多孔硅的纳米硅粒中,光发射主要发生在多孔硅中包裹纳米硅SiOx层中的发光中心上,对实验结果进行了合理的解释.     

多孔硅层的剥离及反射率研究

通过改变电化学腐蚀电流密度的大小成功剥离了多孔硅层,并分析了多孔硅层的剥离机理,测量了多孔硅层的反射率曲线.结果表明:影响多孔硅层剥离的主要因素是多孔硅的形成临界电流密度,当电化学腐蚀的电流密度增大到100mA/cm2时,已经大于多孔硅的临界形成电流,从而发生了硅片表面的电化学抛光,并且多孔硅层对从近紫外到近红外的整个波段反射率都较低.     

Catalyzed-assisted growth of well-aligned silicon oxide nanowires

Bulk quantity and ultra-long silicon oxide nanowires on micrometer-sized solid tin balls have been synthesized by typical chemical vapor deposition via a vapor–liquid–solid process. Low melting point tin droplets can be used as an effective catalyst for the large-scale growth of highly aligned silicon oxide nanowires. Observations using scanning electron microscopy indicate that numerous nanowires simultaneously nucleate, grow at nearly the same rate, and simultaneously stop growing. The silicon oxide nanowires have a uniform diameter distribution about 60 nm and are well-aligned. A model for the growth of silicon oxide nanowires on the surface of the tin balls was proposed. The Sn balls on the substrate come from the thermal evaporating SnCl₂ powders, and one of the reactants, Si, on the surface of a Sn ball come from the silicon wafer. Silicon reacts with oxygen to form silicon oxide nanowires on the surface of a liquid Sn ball.     

X-ray electrono-optical and SIMS characterization of Si crystals implanted with Bi ions before and after rapid thermal annealing

The purpose of the presented paper is to find out what kinds of information on surface layer structure of implanted silicon after rapid thermal annealing can be acquired by such non-destructive methods as X-ray diffractometry and its complementary RHEED technique. The experiments were performed on Si crystals implanted with Bi ions. The studies showed that using the anomalous X-ray transmission of the wavelength of 1.54 Å we are able to determine the defect concentration introduced by ion implantation with different doses as well as the effects of defect annealing. It was also shown using the REED that the surface layer of ca. 50 Å thick remains amorphous after RTA probably due to the oxidation. The measurements by using SIMS pointed also out that at the crystal surface there was a small amount of Bi atoms accumulated after RTA.     

低表面浓度磷掺杂的高方阻P-N结发射极制备工艺

制备P-N结发射极的常规扩散工艺主要包括预淀积和高温推阱两个步骤。本文采用在高温推阱之后施加一步保温过程的工艺方案,在p型多晶硅片上制备了低表面浓度磷掺杂的高方阻发射极,研究了不同保温温度对P-N结发射极的方阻和磷原子掺杂分布的影响。结果表明,当完成高温推阱后,在650~750 ℃温度范围内施加保温工艺所得P-N结的方阻值反向升高,同时二次离子质谱(SIMS)测试结果表明,硅片表层区域的磷原子掺杂浓度相应降低。与常规扩散工艺相比,采用在700 ℃下保温15 min时所得P-N结的方阻升高约3.2 Ω/□,所得相应太阳能电池光电转换效率E_ff达到18.69%,比产线工艺提高约0.23%。     

预处理对超纳米金刚石薄膜表面质量的影响

本文研究了金刚石粉手工研磨及超声波震荡两种预处理方法对硅片衬底及超纳米金刚石膜表面粗糙度和形貌的影响,利用表面轮廓仪、X射线衍射分析(XRD)、激光拉曼、场发射扫描电子显微镜(FE-SEM)对衬底及超纳米金刚石膜进行表征.结果表明,由于衬底轮廓的遗传特性,手工研磨的硅片上沉积的超纳米金刚石膜表面粗糙度远高于超声震荡的硅片上沉积的超纳米金刚石膜.     

Preparation and characterization of Si sheets by renewed SSP technique

Silicon sheets from powder (SSP) ribbons have been prepared by modified SSP technique using electronic-grade (9N purity) silicon powder. The surface morphology, crystallographic quality, composition and electric properties of the SSP ribbons were investigated by surface profiler, X-ray diffraction (XRD), scanning electron microscopy (SEM), metallurgical microscope, Auger electron spectroscopy (AES) and four-point probe apparatus, respectively. The results show that the SSP ribbon made from electronic-grade silicon powder is a suitable candidate for the substrates of crystalline silicon thin film (CSiTF) solar cells, which could meet the primary requirements of CSiTF solar cell process on the substrates, including surface smoothness, crystallographic quality, purity and electric conductivity, etc.