Nanocrystal and interface defects related photoluminescence in silicon-rich Al2O3 films

In this study, silicon nanocrystal-rich Al₂O₃ film has been prepared by co-sputtering a silicon and alumina composite target and subsequent annealing in N₂ atmosphere. The microstructure of the film has been characterized by infrared (IR) absorption, Raman spectra and UV-absorption spectra. Typical nanocrystal and interface defects related photoluminescence with the photon energy of 1.54 (IR band) and 1.69 eV (R band) has been observed by PL spectrum analysis. A post-annealing process in oxygen atmosphere has been carried out to clarify the emission mechanism. Despite the red shift of the spectra, enhanced emission of the 1.69 eV band together with the weak emission phenomenon of the 1.54 eV band has been found after the post-annealing. The R band is discussed to originate from silicon nanocrystal interface defects. The IR band is concluded to be a coupling effect between electronic and vibrational emissions.     

The role of carbon in the precipitation of oxygen in silicon

Oxygen precipitates were formed in Czochralski-grown silicon samples at different temperatures and for different lenghts of times of heat treatment. Precipitation was evident from infrared(IR) analysis of so treated samples. These samples were irradiated with 2 MeV electrons at near room temperature (310 K). Deep level transient spectroscopy measurements and IR measurements were performed on these samples. The results show directly that a single carbon atom or a carbon-oxygen complex can serve as nucleation centers for the oxygen precipitation.     

Interaction of oxygen and carbon impurities with the multiphonon infrared absorption bands of Silicon at low temperatures

Infrared absorptance measurements of polycrystalline silicon and single crystals of silicon having oxygen and carbon impurities were carried out at low temperatures in the wavelength range of multiphonon infrared absorption of silicon. Peak absorptance and frequencies were measured at temperatures from 10 to 130 K at intervals of 10 K. Absorptance-temperature curves were plotted for multiphonon bands and impurity bands. It has been observed that the three phonon band [2 TO (Γ) + TA (L)] exhibits a resonance-like behaviour with the anti-stretching mode of Si-O at low temperatures.     

Preparation of composition-controlled silicon oxynitride films by sputtering; deposition mechanism,and optical and surface properties

Silicon oxynitride films have been grown on silicon by current-controlled reactive sputtering. The content of oxygen in the films could be well controlled by regulating the sputtering current under the reactive gas of Ar+ N₂ with an oxygen content of around 3%. The atomic ratio of oxygen to nitrogen in the silicon oxynitride film became larger with increasing sputtering current. It has been found that electron irradiation of the silicon substrate induces adsorption of oxygen and nitrogen. The degree of oxygen adsorption was about ten times larger than that of nitrogen. This phenomenon is a key mechanism in controlling the film composition. The adsorptive mechanism might be explained by the phenomenon of surface activation by the electron bombardment. Utilizing this technique, wettability by germanium of silicon oxynitride films could be controlled by varying their oxygen and nitrogen contents. A better wetting condition was obtained from films with large atomic ratio of nitrogen to oxygen in the silicon oxynitride film.     

离子注入硅片快速退火后的红外椭偏光谱研究

离子注入硅片经高温退火后晶体结构缺陷会被修复,其在可见光波段下的光学性质趋于单晶硅,常规的可见光椭偏光谱法对掺杂影响的测量不再有效.本研究将测量波段扩展到红外区域(2—20μm),报道了利用红外椭偏光谱法测量经离子注入掺杂并高温退火的硅片掺杂层光学和电学性质的方法和结果.通过建立基于Drude自由载流子吸收的等效光学模型,得到了杂质激活后掺杂层的杂质浓度分布、电阻率和载流子迁移率等电学参数,以及掺杂层的红外光学常数色散关系,分析了这些参数随注入剂量的关系并对其物理机理给予了解释.研究表明,中远红外椭偏测量是表征退火硅片的有效方法,且测量波长越长,所能分辨的掺杂浓度越低.     

离子束反应溅射沉积SiO2薄膜的光学特性

 主要研究采用离子束反应溅射（RIBS）制备SiO2薄膜的折射率、消光系数、化学计量比与氧气在氩氧混合工作气体中含量及其沉积速率的关系。研究结果表明：RIBS制备的SiO2薄膜在0.63 μm处折射率n= 1.48,消光系数小于10-5;随着沉积速率的增加,薄膜的折射率和消光系数随之变大,当沉积速率超过0.3 nm/s,即使是在纯氧环境溅射,折射率值也不低于1.5;通过对红外透射光谱的主吸收峰位置研究得到沉积的SiO2薄膜为缺氧型,化学计量比不超过1.8,且红外吸收峰位置和SiO2折射率存在对应关系,因此在不加热衬底情况下使用RIBS制备SiO2薄膜时,会限制沉积速率的提高。     

脉冲激光辐照p型硅单晶向n型转化

本文研究了p型硅单晶用红宝石脉冲激光辐照之后向n型转化的效应。这个效应与补偿杂质有关。实验结果表明:脉冲激光辐照之后补偿杂质浓度增加,补偿杂质磷分布发生变化,杂质补偿度大于7％的样品在被激光辐照的区域较容易转变为n型导电。这个效应与硅单晶中氧含量、晶面和晶体生长方式无关。 关键词：     

X-ray Photoelectron Spectroscopy of silicon oxynitride layers obtained by low-energy ion implantation

Simultaneous oxygen and nitrogen low-energy ion implantation in silicon single crystals have been used to obtain surface layers of silicon oxynitride. In-depth concentration profiles, measured by XPS, showed all the possible tetrahedral configurations of silicon with the neighboring atoms. The most important feature of these profiles has been found to be the accumulation of a so-called Si³⁺ state just below the surface and about 20 nm deep. This amphoteric state has interesting properties for impurity passivation or electron trapping.     

Diffuse x-ray scattering study of the formation of microdefects in heat-treated dislocation-free large-diameter silicon wafers

Diffuse x-ray scattering (DXS) is used to study the formation of microdefects (MDs) in heat-treated dislocation-free large-diameter silicon wafers with vacancies. The DXS method is shown to be efficient for investigating MDs in silicon single crystals. Specific defects, such as impurity clouds, are found to form in the silicon wafers during low-temperature annealing at 450°C. These defects are oxygen-rich regions in the solid solution with diffuse coherent interfaces. In the following stages of decomposition of the supersaturated solid solution, oxide precipitates form inside these regions and the impurity clouds disappear. As a result of the decomposition of the supersaturated solid solution of oxygen, interstitial MDs form in the silicon wafers during multistep heat treatment. These MDs lie in the {110} planes and have nonspherical displacement fields. The volume density and size of MDs forming in the silicon wafers at various stages of the decomposition are determined.     

Iron contamination in ion implanted silicon,as revealed by x-ray and electron diffraction

A surface contamination effect was detected by double-crystal x-ray diffraction analysis of silicon wafers implanted with silicon ions at different doses and energies after annealing at 700 °C.The hypothesis of recoiled oxygen from the native oxide, as the impurity responsible for surface strain, was excluded by x-ray characterization of a series of samples implanted through thermally grown silicon oxides. The surface positions of the strain, resulting from x-ray analysis after 700 °C annealing and the analysis of the electron diffraction patterns, taken on particles originated from precipitation of the impurity by 1000 °C heating, allowed to conclude that the contamination phenomenon is due to iron atoms coming from the ion implanter.     

Covalency and compression effects on the isomer shift of substitutional119Sn impurities in group IV semiconductors

Since substitutional tin is an isovalent impurity in group IV semiconductors, it represents an almost ideal probe for the study of the variation of the chemical bond in these materials using the isomer shift measurements. To obtain a realistic formula for the isomer shifts in this case, the impurity problem has been formulated in such a way as to include both the band structure and compression effects on the¹¹⁹Sn impurity. The increase of the isomer shift values measured on the impurity¹¹⁹Sn when going from diamond to silicon and germanium host crystals, is interpreted in terms of increasing dehybridization of the homopolar bond in these materials. The lattice relaxation around the tin impurity, due to its large size, seems to be relatively small, if any, in silicon and germanium, while a shift of the neighbouring carbon atoms outwards by 18% of the nearest neighbour distance has to be assumed to explain the experimental value of the isomer shift of substitutional tin in diamond.     

On the origin of photoluminescence in heavily-doped silicon

The origin of the photoluminescence in heavily-doped silicon is examined. Transient photoluminescence data for Si(P) are presented and used to identify the “Low Level” emission bands in terms of recombination of impurity band electrons with holes bound to acceptor sites. The “High Level” bands are attributed to recombination of impurity band electrons with free holes. The energies of the band gap and optical band gap in heavily-doped silicon are determined from the photoluminescence measurements.     

Comparison of different gettering techniques for Cu–p+ versus polysilicon and oxygen precipitates

We performed measurements of gettering efficiencies for Cu in silicon wafers with competing gettering sites. Epitaxial wafers (p/p+) boron-doped with a polysilicon back side allowed us to compare p+ gettering with polysilicon gettering. We further measured metal distributions in p+/p- epitaxial test wafers, with the p- substrate wafers pretreated for oxygen precipitation to compare p+ gettering with oxygen precipitate gettering. Our test started with a reproducible spin-on contamination in the 10¹² atoms/cm² range, followed by thermal treatment in order to redistribute the metallic impurity. Wafers were then analyzed by a novel wet chemical layer-by-layer etching technique in combination with inductively coupled plasma mass spectrometry. This led to “stratigraphical” concentration profiles of the impurity, with typical detection limits of 5–10×10¹² atoms/cm³. Twenty-five percent of the total Cu contamination in the p/p+/poly wafer was found in the p+ layer, whilst 75% was gettered by the polysilicon. Obviously, polysilicon exhibits a stronger gettering than p+ silicon, but due to the large distance from the front surface, polysilicon was less effective in reducing impurities from the front side of a wafer compared with p+ gettering. An epitaxial layer p+ on top of p- substrates with oxygen precipitates gettered 50% of the total Cu; while the other 50% of the Cu was measured in the p- substrate wafer with oxygen precipitates. Without oxygen precipitates, 100% of the spiked Cu contamination was detected inside the p+ layer. Gettering by oxygen precipitates thus occurs in the same temperature range as that where p+ silicon begins to getter Cu. Received: 3 September 2001 / Accepted: 17 October 2001 / Published online: 27 March 2002     

Diffusion in porous silicon carbide

By the example of vanadium and erbium diffusion in porous silicon carbide, the semiconductor porous structure modification during thermal annealing has been simulated and the effect of this modification on impurity diffusion has been considered. A comparison of calculated and experimental profiles of the erbium and vanadium distributions in porous silicon carbide shows that the consideration of porous structure modification due to vacancy redistribution makes it possible to adequately describe diffusion in the porous semiconductor.     

Gettering of metallic impurities in photovoltaic silicon

 This work addresses the issue of structural defect-metallic impurity interactions in photovoltaic silicon and their effect on minority carrier diffusion length values. Aluminium and phosphorus segregation gettering studies were performed on photovoltaic silicon in order to gain insight into these interactions and quantify the effect of gettering on solar cell performance. Integrated circuit grade silicon was also studied for comparative purposes. Additionally, a novel rapid thermal annealing technique, designed to dissolve metallic impurity precipitates, and Deep Level Transient Spectroscopy were utilized to determine the as-grown impurity concentration in both grades of materials. Significant differences in gettering responses between the two grades of silicon are observed. Gettering treatments greatly improve I.C. grade silicon with a specific gettering temperature providing the optimal response. Photovoltaic grade silicon does not respond as well to the gettering treatments and, in some cases, the material degrades at higher gettering temperatures. The degradation is primarily observed in dislocated regions of multicrystalline photovoltaic silicon. Additionally, these dislocated regions were found to possess the highest as-grown metallic impurity concentration of all the materials studied. The dislocation-free photovoltaic silicon has a higher diffusion length relative to dislocated silicon but could not be improved by the gettering methods employed in this study. A model is presented to describe these phenomena where the high concentration of metallic impurities at dislocations produce relatively low minority carrier diffusion lengths as well as the degrading response with higher gettering temperatures while microdefects create an upper limit to the photovoltaic grade material’s diffusion length. Received: 21 June 1996/Accepted: 2 September 1996     

Formation and nature of swirl defects in silicon

Point defect agglomerates in dislocation-free silicon crystals, usually called “swirls”, have been investigated by means of high-voltage electron microscopy. It was found that a single swirl defect consists of a dislocation loop or a cluster of dislocation loops. By contrast experiments it could be shown that these loops are formed by agglomeration of self-interstitial atoms. Generally the loops have a/2〈110〉 Burgers vectors, but in specimens with high concentrations of carbon (～10¹⁷ cm^?3) and oxygen (～10¹⁶ cm^?3) also dislocation loops including a stacking fault were observed. In crystals grown at growth rates higher thanv=4 mm/min no swirls are observed; lower growth rates do not markedly affect the size and shape of the dislocation loops. With decreasing impurity content (particulary of oxygen and carbon) the swirl density decreases, whereas the dislocation loop clusters become larger and more complex. A model is presented which describes the formation of swirls in terms of agglomeration of silicon self-interstitials and impurity atoms.     

用四探针及阳极氧化方法测量硅中扩散层杂质分布

本文讨论了:(1)用阳极氧化法在硅片表面去层的技术;(2)用四探针测量扩散层面电导的方法;(3)用阳极氧化去层及四探针测量面电导方法求得扩散层精细杂质分布。文中着重讨论了实验技术中的实际问题,如如何在阳极氧化过程中取得精细而均匀的去层(300—1500?);如何控制及测量去层厚度;测量面电导及杂质分布时的误差来源及减小误差的措施。以典型的磷在硅中扩散的杂质分布测量为例:扩散深度为4.9μm,测量间距为400—1600?,面电导测量误差估计小于3％,杂质分布误差估计小于20％。简单地提出了一些测量中尚待进一步解决的问题。     

Oxidation study of silicon nanoparticle thin films on HOPG

Thin films of silicon nanoparticles (diameter 5-10 nm) were deposited on highly oriented pyrolytic graphite (HOPG) by low-pressure DC magnetron sputtering. The effect of different room-temperature oxidation techniques was investigated using XPS sputter-depth profiling. Both oxygen treatment during deposition (using an argon-oxygen mixture in the sputter gas) as well as post-deposition oxidation techniques (exposure to oxygen plasma beam, ambient air conditions) were studied. In all cases oxidation was found to involve the whole film down to the film/substrate interface, indicating a network of open pores. Depending on the type of oxidation between 15 and 25 at% of oxygen, mostly associated with low oxidation states of silicon, were detected in the interior of the film and attributed to oxidized surfaces of the individual silicon nanoparticles. The highest oxygen concentrations were found at the very film surface, reaching levels of 25-30% for films exposed to air or prepared by reactive magnetron sputtering. For the oxygen plasma-treated films even oxygen surface concentrations around 45% and fully oxidized silicon (i.e., SiO₂) were achieved. At the Si/HOPG interface formation of silicon carbide was observed due to intermixing induced by Ar-ion beam used for sputter-depth profiling.     

Oxygen depth profiling of high pressure DC-sputtered amorphous silicon

We have measured the in-depth oxygen concentration of high pressure DC-sputtered a-Si films. The measurements were performed by means of AES and IR spectroscopy, immediately after sample preparation and after air exposure during two weeks. We found that post incorporation of oxygen is not located at the thin film surface, supporting the idea that a-Si films prepared by high pressure sputtering present an open pore network, as it has been previously proposed.     

Specular reflectance of silicon and germanium at variable angles of incidence in the infrared region

The results of systematic measurements of specular reflectances of both single as well as double surface polished silicon and germanium at glancing angles of incidence from 10° to 70° in the infrared (IR) region of 2.5–25 μm have been discussed. The experimental results have been explained by comparison with the theoretical reflectance data obtained using Fresnel's theory.