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。     

非晶态合金与氢相互作用的研究进展

非晶态合金在力学性能、耐磨耐蚀性、磁性等方面比传统晶态合金具有显著优势,是一类有优良应用前景的新型结构与功能材料.非晶态合金与氢相互作用可以产生很多有趣的物理化学现象和应用.本文从物理基础和材料应用两个方面评述非晶态合金和氢相互作用的研究进展,在物理基础研究方面,从氢在非晶态合金中的存在状态出发,讨论氢在非晶态合金中的溶解、分布、占位和扩散等相关物理问题,进而分析氢对非晶态合金的热稳定性、磁性、内耗、氢脆等的影响.在材料应用研究方面,对非晶态储氢合金、非晶态合金氢功能膜、吸氢改善非晶态合金的塑性和玻璃形成能力、氢致非晶化、利用非晶态合金制备纳米储氢材料等方面的研究进展进行评述.最后总结并展望有关非晶态合金与氢相互作用的研究和应用.     

Electrochemical insertion into and the detection of hydrogen in amorphous silicon solid electrolytes

The specific features of amorphous silicon are mainly contributed by the incorporation of hydrogen into the silicon during the vapour deposition process but, in spite of the considerable progress in the development of amorphous silicon cells, two major problems exist - light induced degradation and hydrogen evolution. As a result, there is a need to be able to measure and adjust the hydrogen content of the amorphous silicon. It is shown that this can be achieved using a potentiometric sensor, based on a proton conductor, and electrochemical tritation. Experiments show that it is possible to detect changes in hydrogen at all temperatures, using solid electrolytes, but that it is only possible to titrate hydrogen into the amorphous silicon at elevated temperatures. Paper presented at the 1st Euroconference on Solid State Ionics in Zakynthos, Greece, 11–18 Sept. 1994     

Effect of hydrogen on hardness of amorphous silicon

A comparative study of hardness of thin films of hydrogenated amorphous silicon (a-Si:H) and hydrogen-free amorphous silicon (a-Si) was carried out to reveal the role of hydrogen in the plastic properties of amorphous silicon. In addition, the effect of hydrogen on hardness was established by changing hydrogen concentration in the material using post-deposition processing of the samples. The hydrogen concentration in a-Si:H was decreased by thermal annealing. In a-Si hydrogen was introduced by plasma hydrogenation. The values of hardness of the as-prepared a-Si and a-Si:H films were determined by nanoindentation using depth profiling. Low-depth indentation was applied to evaluate the effect of post-hydrogenation. The results obtained show that the presence of hydrogen in the amorphous silicon network leads to the increase in hardness. The conducted experiments demonstrate that plasma hydrogenation can be used as an effective tool to increase the hardness of amorphous silicon. Hardness of a-Si:H of about 12.3–12.7 GPa is as high as of crystalline silicon, suggesting a-Si:H can be a substitute for crystalline silicon in some MEMS.     

Hydrogen permeability of amorphous and recrystallized iron alloys

The hydrogen permeability of amorphous and recrystallized Fe alloys is investigated. It is found that the surface layers of both samples are enriched with metalloids, which interfere with the penetration of hydrogen from the molecular and atomic phases. The kinetics of curves of flow transition to a steady state upon ion irradiation in an amorphous alloy points to processes of reversible capture. The penetrating flow demonstrates Arrhenius dependence on temperature in the case of recrystallized samples and nonmonotonic dependence on temperature in the case of amorphous samples. A model of hydrogen penetration is suggested, which includes the reemission and diffusion processes; and estimates are obtained of the energy of activation of thermodesorption and diffusion.     

Theory of hydrogen-related metastability in disordered silicon

Density functional electronic structure calculations are employed to examine hydrogen for a variety of configurations in silicon. A novel complex is found for hydrogen in amorphous silicon. The complex involves the breaking of a weak silicon bond to form two Si-H bonds with both hydrogens in between the original silicon atoms. This complex provides a microscopic model for new metastable complexes observed in amorphous silicon. Mechanisms for hydrogen-related metastability are discussed for amorphous and polycrystalline silicon.     

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.     

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.     

Hydrogen in crystalline and amorphous silicon: A first principles molecular dynamics study

Structural and dynamical properties of hydrogen in crystalline and amorphous silicon are analyzed by ab initio molecular dynamics simulations. In the crystalline case we focus mainly on the diffusion process of an isolated positively charged hydrogen impurity at high temperature, finding important dynamical effects. In the amorphous case we analyze the local order and the dynamical properties corresponding to an atomic hydrogen concentration of 11%, typical of a device quality material. We find that hydrogen atoms form monohydride complexes and show interesting clustering effects. In both crystalline and amorphous cases, our results are in good agreement with available experimental data and give unique insight into the microscopic details of hydrogen incorporation in silicon.     

Pulsed laser deposition of photosensitive a-Si thin films

Si films have been fabricated by pulsed KrF excimer laser deposition (PLD) through the use of various Si targets and deposition conditions. The deposits consisted of droplets and homogeneous films, which were assigned to be crystalline and amorphous silicon, respectively, by the micro Raman scattering measurements. Not only the crystalline but also the amorphous Si part scarcely (<1 atomic %) contained hydrogen regardless of whether or not the films are prepared in the presence of H₂ gas. Conditions were explored to reduce the droplet formation and to produce photosensitive films. Amorphous Si films with photosensitivity (C_ph/C_d) exceeding 10³ were obtained, and they exhibited high stability against light soaking. Thus, PLD is a promising method to fabricate photosensitive and photostable a-Si films.     

Growth characteristics of amorphous-layer-free nanocrystalline silicon films fabricated by very high frequency PECVD at 250 ℃

Amorphous-layer-free nanocrystalline silicon films were prepared by a very high frequency plasma enhanced chemical vapor deposition(PECVD) technique using hydrogen-diluted SiH4 at 250 C.The dependence of the crystallinity of the film on the hydrogen dilution ratio and the film thickness was investigated.Raman spectra show that the thickness of the initial amorphous incubation layer on silicon oxide gradually decreases with increasing hydrogen dilution ratio.High-resolution transmission electron microscopy reveals that the initial amorphous incubation layer can be completely eliminated at a hydrogen dilution ratio of 98%,which is lower than that needed for the growth of amorphous-layer-free nanocrystalline silicon using an excitation frequency of 13.56 MHz.More studies on the microstructure evolution of the initial amorphous incubation layer with hydrogen dilution ratios were performed using Fourier-transform infrared spectroscopy.It is suggested that the high hydrogen dilution,as well as the higher plasma excitation frequency,plays an important role in the formation of amorphous-layer-free nanocrystalline silicon films.     

Preparation of hydrogenated amorphous germanium by reactive thermal evaporation

Hydrogenated amorphous germanium was prepared by the thermal evaporation of high purity polycrystalline germanium in an atmosphere of hydrogen plasma produced by high voltage AC discharge of molecular hydrogen. The addition of hydrogen during the thermal evaporation of germanium is shown to improve the electrical properties of the resulting amorphous germanium films considerably by saturation of dangling bonds, if the dissociation of molecular hydrogen takes place. Hydrogenated sample deposited at 200°C has shown a high resistivity and an activation type conduction (with an activation energy of 0.38–0.39 eV) in measuring temperature range (above room temperature).     

Interaction between Intermetallic Compounds <Emphasis Type="Italic">R</Emphasis>Ni<Subscript>3</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Gd,Dy) and Hydrogen at Low Temperatures

The hydride phases of the intermetallic compounds GdNi₃ and DyNi₃ are synthesized at room temperature and at 273 K under a hydrogen pressure of 1–30 bar. The phase composition of the obtained samples is established using the X-ray diffraction method and the crystal-lattice parameters of the hydride phase are determined. The crystal phases are synthesized at room temperature under a hydrogen pressure of about 1 bar. At 273 K and under a pressure of 30 bar, amorphous samples are formed. The desorption of hydrogen from amorphous hydrides at 573 K leads to the formation of well-crystallized samples of the initial intermetallides. The amorphous samples are formed due to the ordering of hydrogen atoms in the metallic matrix of the hydride at low temperatures.     

等离子体诱导碳纳米管到纳米金刚石的相变

采用氢等离子体，实现了碳纳米管向金刚石的结构相变，并实现了金刚石的高密度成核，有效成核密度可达10\+\{11\}／cm\+2以上，处于目前金刚石成核密度的最高行列，为制备优质的金刚石薄膜提供了保证.高分辨透射电镜、x射线衍射和拉曼光谱都证实了金刚石的形成.同时，对纳米金刚石晶粒的生成机理进行了初步探讨. 关键词： 等离子体 碳纳米管 纳米金刚石 结构相变     

相变区硅薄膜拉曼和红外光谱分析

采用等离子体增强化学气相沉积(PECVD)技术制备了一系列不同氢稀释率下的硅薄膜,采用拉曼散射光谱和傅里叶红外光谱技术研究了非晶/微晶相变区硅薄膜的微观结构变化,将次晶结构(paracrystalline structure)引入到非晶/微晶相变区硅薄膜结构中,提出了次晶粒体积分数(f_p),用来表征硅薄膜中程有序程度。结果表明,氢稀释率的提高导致硅薄膜经历了从非晶硅到微晶硅的相变过程,在相变区靠近非晶相的一侧,硅薄膜表现出氢含量高、结构致密和中程有序度高等特性,氢在薄膜的生长中主要起到表面钝化作用。在相变区靠近微晶相的一侧,硅薄膜具有氢含量低、晶化率高和界面体积分数小等特性,揭示了氢的刻蚀作用主控了薄膜生长过程。采用扫描电子显微镜对样品薄膜的表面形貌进行分析,验证了拉曼散射光谱和傅里叶红外光谱的分析结果。非晶/微晶相变区尤其是相变区边缘硅薄膜结构特性优良,在太阳能电池应用中适合用作硅基薄膜电池本征层。     

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 storage in different carbon materials: Influence of the porosity development by chemical activation

The hydrogen adsorption capacity of different types of carbon nanofibers (platelet, fishbone and ribbon) and amorphous carbon have been measured as a function of pressure and temperature. The results showed that the more graphitic carbon materials adsorbed less hydrogen than more amorphous materials. After a chemical activation process, the hydrogen storage capacities of the carbon materials increased markedly in comparison with the non-activated ones.BET surface area of amorphous carbon increased by a factor of 3.5 and the ultramicropore volume doubled, thus increasing the hydrogen adsorption by a factor of 2. However, BET surface area in platelet CNFs increased by a factor of 3 and the ultramicropore volume by a factor of 6, thus increasing the hydrogen storage by a factor of 4.5. The dependency of hydrogen storage capacity of carbon materials on the BET surface area was evaluated using both a condensation model and experimental results. Comparison of data suggests that the hydrogen adsorption capacity clearly depends on the pore structure and so, on the accessibility to the internal surface.     

Hydrogen evolution in amorphous silicon carbide

The influence of the hydrogen content and its evolution in the annealing treatments of the structural properties of hydrogenated amorphous silicon carbide (a-SiC:H) prepared by plasma enhanced chemical vapour deposition under different deposition conditions have been studied. The results indicate how strongly hydrogen affects the presence of defects in the amorphous network of the samples.     

Tight-binding molecular dynamics study of the hydrogen-induced structural modifications in tetrahedral amorphous carbon

A tight-binding molecular dynamics study of the structural evolution in tetrahedral amorphous carbon networks under dynamic hydrogen saturation is presented. The incorporation of hydrogen results in higher degrees of network disorder in second-neighbour distances, and initiates orbital re-hybridization that relaxes network stress. Using the simulated structures, numerical tests are performed to verify the effectiveness of a new structural order parameter for tetrahedrally-bonded solids. It is found that the island of accessible information, within the order parameter field shows a linear dependence between the fluctuations in first- and second-nearest-neighbour distances at a preferred orientation of 36°. A comparison with similar studies on hydrogenated amorphous silicon suggests that the local network structure of tetrahedrally-bonded amorphous solids obey the same ordering rule irrespective of differences in chemical species.     

Mössbauer study of Fe−Zr amorphous alloys hydrogenated at different cathodic potentials

Mössbauer spectroscopy was used for studying the effect of hydrogenation on amorphous Fe₉₀Zr₁₀ and Fe₈₉Zr₁₁ alloys electrolytically charged to high hydrogen content. The differences observed between the room temperature Mossbauer spectra of uncharged and hydrogenated amorphous alloys can be attributed to a change in the Curie temperature. Up to a certain hydrogen content the Curie temperature increases with the hydrogen concentration while the Curie temperature goes thorough a maximum as the hydrogen content increases.