Nuclear magnetic resonance investigation of H, H2 and dopants in hydrogenated amorphous silicon and related materials

Nuclear magnetic resonance has been successfully applied to the study of the microstructure of hydrogenated amorphous silicon and related materials. It has been used to determine the local bonding and structural environment of the host atoms, the hydrogen, and the dopants. First, we review some of these NMR experimental results on the hydrogen microstructure in hydrogentaed amorphous semiconductors and compare the results on plasma deposited hydrogenated amorphous silicon (a-Si:H), remote hydrogen plasma deposited a-Si:H, thermally annealed a-Si:H, doped a-Si:H, microcrystalline Si and amorphous (Si, Ge):H alloys. A common feature is that these materials exhibit a heterogeneous distribution of hydrogen bonded to the semiconductor lattice in dilute and clustered phases. In addition, the lattice contains voids of varying number and size that contain non-bonded molecular hydrogen whose quantity is altered by deposition conditions and thermal treatment. Second, we review some aspects of the local bonding structure of dopants in a-Si:H. A significant fraction of the dopants are found to be in dopant-hydrogen clusters similar to those proposed to explain hydrogen passivation in crystalline silicon. Implications of the determined local structure on the doping efficiency are discussed.     

镶嵌有纳米硅的氮化硅薄膜键合特性分析

采用螺旋波等离子体化学气相沉积(HWPCVD)技术制备了非化学计量比的氢化氮化硅薄膜,对所沉积样品及氮气环境中920 ℃退火样品的微观结构及键合特性进行了分析。Raman散射结果表明,薄膜中过量硅以非晶纳米粒子形式存在,退火样品呈现纳米晶硅和氮化硅的镶嵌结构。红外吸收和可见光吸收特性比较结果显示,薄膜样品的微观结构依赖于化学计量比以及退火过程,硅含量较低样品因高的键合氢含量而表现出低的纳米硅表面缺陷态密度;退火过程将引起Si—H和N—H键合密度的减少,因晶态纳米颗粒的形成,退火样品表现出更高的结构无序度。     

Luminescence in amorphous semiconductors

A review of the luminescence properties of amorphous semiconductors is presented. The materials covered are chalcogenide glasses, silicon and arsenic. Luminescence spectra, excitation spectra, temperature dependences and lifetimes are described.

The radiative transition in chalcogenides is the recombination of an electron in the conduction band tail and a trapped hole. A strong electron-phonon coupling distorts the lattice near the trapped hole, lowering its energy. This interaction is responsible for the broadness of the luminescence band and its position at about half the band gap energy. The recombination centre is thought to be a charged dangling bond with density 10¹⁷ cm^-3 in arsenic chalcogenides and 10¹⁶ cm^-3 in selenium. The same centre is observed in the hole drift mobility, and thermally stimulated conductivity.

Luminescence in amorphous silicon also originates from recombination between the band tails and deep centres, with three separate transitions identified. In contrast to chalcogenides the electron-phonon coupling is not strong. The shape and intensity of the spectra are very sensitive to sample preparation and treatment, and correlate with other electrical and optical properties of Si.     

Ion beam deposition of a-Si:H

The ion beam deposition (IBD) of hydrogenated amorphous silicon is described. Hydrogen incorporation and bonding with the silicon network is evident from SIMS and infrared spectra; the latter show absorption bands centered at 2000cm^?1 and 630cm^?1 typical of monosilicon hydride bonding. IBD a-Si:H thin films are found to be free of microvoids and trace metallic impurities. Four probe conductivity measurements show that the ion beam deposition process yields high resistivity, hydrogenated amorphous silicon (?≥10⁹Ωcm). All of these measurements suggest a low density of defects states in the band gap.     

Amorphous carbon

The properties of various types of amorphous carbon and hydrogenated amorphous carbon are reviewed with particular emphasis on the effect of atomic structure on the electronic structure. It is shown how the proportion of sp³ and sp² sites not only defines the short-range order but also a substantial medium-range order. Medium-range order is particularly important in amorphous carbon because it is the source of its optical gap, whereas short-range order is usually sufficient to guarantee a gap in other amorphous semiconductors. The review discusses the following properties: short-range order and the radial distribution function, the infrared and Raman spectra, mechanical strength, the electronic structure, photoemission spectra, optical properties, electron energy-loss spectra, core-level excitation spectra, electrical conductivity, electronic defects and the electronic doping of hydrogenated amorphous carbon.     

Photoinduced effects and metastability in amorphous semiconductors and insulators

Amorphous semiconductors, being intrinsically metastable in nature, exhibit a wide variety of changes in their physical properties, particularly when photoinduced using bandgap illumination. This article reviews the photoinduced phenomena exhibited by amorphous semiconductors such as amorphous hydrogenated silicon (and other tetrahedrally coordinated materials) and chalcogenide glasses. Features exhibited in common by all types of amorphous semiconductors, whether in the experimentally observed photoinduced metastability or the theoretical models used to account for such behaviour, are stressed.     

Ionographic patterns with amorphous/crystalline contrast

Ion irradiation of thin layers of crystalline semiconductors induces a phase transition to the amorphous state. The concomitant optical contrast between unirradiated, crystalline, and irradiated, amorphous, material may be used for pattern fabrication in the submicron range. This process will be explained by the example of silicon single-crystal layers on sapphire.International Patents pending     

a-Si:H/a-SiNx:H超晶格薄膜光致发光性质的研究

本文报道了a-Si:H/a-SiNx:H超晶格薄膜光致发光某些性质的研究。实验发现,这种超晶格薄膜光致发光的强度和峰值能量随交替层a-Si:H厚度,测量温度及光照时间等而变化。同时还发现,在阴、阳两极上,利用GD法沉积的样品,发光强度和峰值能量也有所不同。文中对这些实验结果作了初步解释。     

硅基混合集成技术的研究进展

硅基光电子集成技术(PICs)为高速宽带光互连和光通信的发展提供了一种低成本的有效方案,受到人们的高度重视.目前将III-V族和锗等半导体化合物集成到硅衬底的方法主要分为两类:异质结外延生长和异质材料的键合.低温下晶片键合的方法克服了异质结外延生长中的生长温度高、晶格失配和材料热膨胀系数非共容性的缺点,为大规模的异质(不同半导体材料)集成提供了可能.文章综述了近几年来一些常用的键合方法,并对低温键合方法的发展动向做了展望.     

氢化非晶硅薄膜中氢含量及键合模式的红外分析

Fourier红外透射(FTIR)谱技术是研究氢化非晶硅（a-Si∶H）薄膜中氢的含量（CH）及硅—氢键合模式（Si-Hn）最有效的手段.对用等离子体化学气相沉积（PCVD）方法在不同的衬底温度（Ts）下制备出的氢化非晶硅薄膜，通过红外透射光谱的基线拟合、高斯拟合分析，得到了薄膜中的氢含量，硅氢键合模式及其组分，并分析了这些参量随衬底温度变化的规律.     

Microstructure of hydrogenated silicon thin films prepared from silane diluted with hydrogen

We report results obtained from FTIR and TEM measurements carried out on silicon thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) from silane diluted with hydrogen. The hydrogen content, the microstructure factor, the mass density and the volume per Si-H vibrating dipoles were determined as a function of the hydrogen dilution. Hydrogen dilution of silane results in an inhomogeneous growth during which the material evolves from amorphous hydrogenated silicon (a-Si:H) to microcrystalline hydrogenated silicon (μc-Si:H). With increasing dilution the transition from amorphous to microcrystalline phase appears faster and the average mass density of the films decreases. The μc-Si:H films are mixed-phase void-rich materials with changing triphasic volume fractions of crystalline and amorphous phases and voids. Different bonding configurations of vibrating Si-H dipoles were observed in the a-Si:H and μc-Si:H. The bonding of hydrogen to silicon in the void- and vacancy-dominated mechanisms of network formation is discussed.     

Hydrogen effusion: a probe for surface desorption and diffusion

Hydrogen effusion results are discussed for hydrogenated amorphous silicon (a-Si:H) and related alloys as well as for crystalline silicon (c-Si). It is demonstrated that depending on the microstructure of the material, hydrogen effusion gives information on hydrogen diffusion or surface desorption. The results suggest for compact a-Si:H and for ion implanted c-Si a similar hydrogen diffusion process, which is a trap limited motion of atomic hydrogen. Hydrogen effusion from defect-free c-Si and from void-rich amorphous semiconductors is limited by surface desorption. Both hydrogen diffusion and desorption depend on the Fermi energy if hydrogen bonds to the host material are broken.     

Anodic oxidation during electrostatic bonding

During electrostatic bonding, anodic oxidation of the anode material, for instance silicon, is thought to be the essential step in the bonding mechanism, leading to the formation of a permanent, strong and vacuum-tight bond. Despite the perceived importance of this step in the bonding mechanism of this well-established bonding technique, there is little experimental evidence for anodic oxidation during electrostatic bonding. One reason is that a thin (approximately 10–20?nm) amorphous anodic oxide layer is difficult to detect adjacent to an amorphous cation-depleted glass. Here, silicon–Pyrex and aluminium–Pyrex electrostatic bonds are made and the anodic oxidation process is studied directly using transmission electron microscopy. The consumption of silicon is demonstrated by the movement of the crystalline–amorphous interface compared with a marker under the original silicon–Pyrex interface. The formation of an anodic silica layer can also be demonstrated using electron-energy-loss spectrometry. An amorphous reaction layer 5–20?nm thick is formed during the bonding cycle. For aluminium anode materials bonded at 450°C a nanocrystalline γ-Al₂O₃ reaction layer is formed, which can be readily detected by transmission electron microscopy. At a bonding temperature of 350°C, no such crystalline reaction layer can be detected between Pyrex and aluminium.     

氢化非晶硅叠层薄膜对单晶硅表面钝化研究

采用等离子体增强化学气相沉积法生长的单层本征氢化非晶硅薄膜对单晶硅片进行钝化,结果表明增加氢稀释比有利于减少薄膜中的缺陷,增强钝化效果,过量的氢稀释比会导致非晶硅在硅片表面的外延晶化生长,降低钝化效果。退火导致非晶硅晶化程度增加,降低了钝化效果,同时退火提升了薄膜的质量,改变了H键合方式,增强了钝化效果。因此,单层氢化非晶硅只有在合适的氢稀释比和退火温度才可以获得最佳钝化效果。为了提高非晶硅薄膜对硅片的钝化效果,采用具有高低氢稀释比的叠层本征非晶硅薄膜对硅片进行钝化。因此将高氢稀释比沉积的非晶硅薄膜叠层生长于低氢稀释比的薄膜之上,避免非晶硅在硅片表面的外延生长。在退火过程中,高氢稀释比薄膜中的氢扩散到低氢稀释比薄膜中,有效地钝化了非晶硅中和单晶硅表面的悬挂键,改善了非晶硅/硅片的界面质量,叠层钝化后硅片的少子寿命为7.36 ms,隐含开路电压为732 mV。     

微晶硅薄膜的结构及光学性质的研究

借助RF-PECVD辅助RTP技术，采用高沉积气压的技术路线制备了优质的微晶硅薄膜，并利用拉曼光谱、反射谱和透射谱分别研究了微晶硅的晶化率和光学性质.实验中发现微晶硅的吸收边出现了相对红移，此相对红移可归结于薄膜晶化率的提高和带尾态密度的降低. 关键词： 微晶硅 拉曼光谱 快速热处理 红移     

Theory of spin-dependent recombination in semiconductors

The pair model of spin-dependent recombination of carriers in semiconductors, as discussed by Kaplan, Solomon and Mott, is solved exactly in several limiting cases. The model accounts for the large influence of a saturating microwave field in ESR experiments on recombination in crystalline and amorphous silicon. Further, the effect of a static magnetic field on recombination is explored.     

Influence of substrate in photothermal measurements of thin film absorption

In photothermal measurements of low optical absorption coefficients, as in the case of thin films of amorphous semiconductors, the substrate absorption can play a non-negligible role. In this paper, the substrate influence is discussed and generalized on the basis of a theoretical model of a two-layer absorbing sample, and the interaction of the thermal and optical parameters which control the photothermal process in the sample is shown. Some experimental results obtained on thin films of amorphous silicon carbide deposited on different substrates are presented and discussed.     

Photoluminescence spectra of laser-synthesized Si/C/N ultrafine powders

Ultrafine Si/C/N ceramic powders were synthesized by a CO₂-laser-induced reaction between silane (SiH₄), ammonia (NH₃) and acetylene (C₂H₂). The powders were characterized by infrared (IR) reflection and photoluminescence (PL) spectroscopy. From the infrared reflection spectra of Si/C/N powders, we have identified the causes of the strong photoluminescence present in these powders. The photoluminescence spectra of Si/C/N powders originate from the presence of hydroxylated and amorphous silicon (a-SiO₂) formed at the porous surface of these powders. We have shown that different chemical bonding between Si, C and N atoms, the degree of crystallinity of ternary powders and their porosity strongly influence the processes at their surface, i.e. the formation of amorphous silicon and silanole. Received: 16 June 2000 / Accepted: 24 June 2000 / Published online: 9 November 2000     

半导体中定域模,准定域模晶格振动的光谱研究

本文讨论了用光学方法研究杂质诱发定域化振动模的理论模型,分门别类地论述了半导体中杂质诱发的定域模、禁带模、共振模和准定域模晶格振动及非晶态半导体的晶格振动谱,给出了它们的综合结果。半导体中杂质诱发定域模已被人们广为研究,作者主要以自己的结果阐述了禁带模、共振模、准定域模和非晶态半导体振动谱研究在近年来取得的重要进展。除以较多篇幅研究各种定域化振动模的位置外,本文还从键—电荷模型出发讨论了杂质诱发振动吸收带的强度。     

Dependence of vibrational density of states and Raman spectra on size in non-polar and polar nano-crystalline semiconductors

The vibrational density of states (VDOS) of Si, diamond, SiC, and InSb clusters has been calculated using the cluster model for various cluster sizes. The results show that the peak frequency of optical-like bands of VDOSs of non-polar nano-crystalline (NC) semiconductors varies with size, but that of polar NC semiconductors does not vary with size. We attribute the origin of this different behavior of non-polar and polar NC semiconductors to different interactions in the optical-like modes of them. That is, the deformation potentials for the non-polar NC semiconductors and electrostatic potentials for the polar NC semiconductors. According to the amorphous crystal (aC) model, Raman spectra are directly related to VDOS. In this Letter, it is verified that the aC model can be applied to NC semiconductors. Calculated VDOS are compared with observed Raman spectra of corresponding samples, which show agreement.