太阳电池中新腐蚀液实现纳米黑硅表面的一步腐蚀制备

通过引入添加剂,调节腐蚀溶液的pH值,实现了一步法制备黑硅表面. 在取得低表面反射率的同时,减小了黑硅层的腐蚀深度,对于16 min腐蚀的黑硅层,其表面加权平均反射率可达5%(300～1200 nm),但腐蚀深仅约为200 nm. 减小腐蚀深度能够降低黑硅太阳电池的表面复合速率,从而提高太阳电池性能,尤其是开路电压及填充因子. 以新腐蚀液制备的黑硅为衬底,在常规太阳电池产线上制备大面积p-Si黑硅太阳电池,实现了15.63%的转换效率,具有高的开路电压(624.32 mV)和填充因子(77.88%),改进了大面积黑硅太阳电池的性能.     

Excellent passivation of thin silicon wafers by HF‐free hydrogen plasma etching using an industrial ICPECVD tool

In this work, hydrogen plasma etching of surface oxides was successfully accomplished on thin (～100 µm) planar n‐type Czochralski silicon wafers prior to intrinsic hydrogenated amorphous silicon [a‐Si:H(i)] deposition for heterojunction solar cells, using an industrial inductively coupled plasma‐enhanced chemical vapour deposition (ICPECVD) platform. The plasma etching process is intended as a dry alternative to the conventional wet‐chemical hydrofluoric acid (HF) dip for solar cell processing. After symmetrical deposition of an a‐Si:H(i) passivation layer, high effective carrier lifetimes of up to 3.7 ms are obtained, which are equivalent to effective surface recombination velocities of 1.3 cm s^–1 and an implied open‐circuit voltage (V_oc) of 741 mV. The passivation quality is excellent and comparable to other high quality a‐Si:H(i) passivation. High‐resolution transmission electron microscopy shows evidence of plasma‐silicon interactions and a sub‐nanometre interfacial layer. Using electron energy‐loss spectroscopy, this layer is further investigated and confirmed to be hydrogenated suboxide layers. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Metastability of amorphous silicon from silicon network rebonding

We propose a network rebonding model for light-induced metastability in amorphous silicon, involving bonding rearrangements of silicon and hydrogen atoms. Nonradiative recombination breaks weak silicon bonds and generates dangling bond-floating bond pairs, with very low activation energies. The transient floating bonds annihilate, generating local hydrogen motion. Charged defects are also found. Support for these processes is found with tight-binding molecular dynamics simulations. The model accounts for major experimental features of the Staebler-Wronski effect including electron-spin resonance data, the t(1/3) kinetics of defect formation, two types of metastable dangling bonds, and hysteretic annealing.     

Extremely low surface recombination in 1 Ω cm n‐type monocrystalline silicon

A key requirement in the recent development of highly efficient silicon solar cells is the outstanding passivation of their surfaces. In this work, plasma enhanced chemical vapour deposition of a triple layer dielectric consisting of amorphous silicon, silicon oxide and silicon nitride, charged extrinsically using corona, has been used to demonstrate extremely low surface recombination. Assuming Richter's parametrisation for bulk lifetime, an effective surface recombination velocity S_eff = 0.1 cm/s at Δn = 10¹⁵ cm^–3 has been obtained for planar, float zone, n ‐type, 1 Ω cm silicon. This equates to a saturation current density J_0s = 0.3 fA/cm², and a 1‐sun implied open‐circuit voltage of 738 mV. These surface recombination parameters are among the lowest reported for 1 Ω cm c‐Si. A combination of impedance spectroscopy and corona‐lifetime measurements shows that the outstanding chemical passivation is due to the small hole capture cross section for states at the interface between the Si and a‐Si layer which are hydrogenated during nitride deposition. (© 2016 The Authors. Phys. Status Solidi RRL published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

EPR investigation of a-Si:H aerosol particles formed under silane thermal decomposition

The dangling bond defects were investigated in a-Si:H particles formed under silane thermal decomposition in flow reactor. EPR together with hydrogen evolution method were used. The experimental results allowed us to conclude that there are two kinds of dangling bond defects in a-Si:H aerosol particles. The defects of the first kind are localized on the surface of interconnected microvoids and microchannels (surface dangling bonds) and those of the second kind are embedded in amorphous silicon network (volume dangling bonds). The thermal equilibration of dangling bonds and temperature dependence of equilibrium dangling bond concentration were investigated. It was found that at temperatures > 400 K the dangling bond concentrationNApplied Magnetic Resonance _s reversibly depends on sample temperature. The volume dangling bond concentration increases with temperature increasing (the effective activation energy of dangling bond formationU > 0), and the surface dangling bond concentration decreases with temperature increasing (U < 0). It has been found that EPR line is considerably asymmetric for samples with high hydrogen content and for low hydrogen content the EPR line is weakly asymmetric. A conclusion was drawn that the asymmetry degree depends on amorphous silicon lattice distortions. This conclusion has been confirmed by EPR spectra simulations.     

Influence of microwave plasma microprocessing on the electronic properties of the (100)Si surface

The feasibility of controlling the electronic properties of the semiconductor surface by varying conditions for its processing is considered. The study of electron transverse transport in heterostructures based on a (100)Si single crystal and a tunnel-thin film of hydrogenized amorphous silicon carbide shows that the form of the I–V characteristic of such structures depends on the density of dangling bonds on the surface. They arise when silicon single crystals of a given orientation are subjected to microprocessing by a highly ionized microwave plasma in different plasma-forming media to obtain an atomically clean surface.     

Electronic structure and band alignment of 9,10-phenanthrenequinone passivated silicon surfaces

In this work we demonstrate that the room-temperature deposition of the organic molecule 9,10-phenanthrenequinone (PQ) reduces the surface defect density of the silicon (100) surface by chemically bonding to the surface dangling bonds. Using various spectroscopic measurements we have investigated the electronic structure and band alignment properties of the PQ/Si interface. The band-bending at the PQ-passivated silicon surface is negligible for both n- and p-type substrates, demonstrating a low density of surface defects. Finally we show that PQ forms a semiconducting wide-bandgap type-I heterojunction with silicon.     

Direct role of hydrogen in the Staebler-Wronski effect in hydrogenated amorphous silicon

We report a hydrogen-related defect that establishes the direct role of hydrogen in stabilizing the silicon dangling bonds created in the Staebler-Wronski effect in hydrogenated amorphous silicon. A specific NMR signal due to paired hydrogen atoms occurs only after optical excitation, exists at an intensity that is consistent with the density of optically induced silicon dangling bonds, and anneals at temperatures that are consistent with the annealing of the optically induced silicon dangling bonds. At this defect the hydrogen atoms are 2.3+/-0.2 A apart.     

Chemical reactions of chlorine on a vicinal Si(100) surface studied by ESDIAD

The reaction of Cl₂ on a vicinal Si(100) surface has been studied by ESDIAD. This type of surface possesses two types of sites: pairs of dangling bonds on Si---Si terrace dimers, and single dangling bonds on the 2-atom layer high steps. The reactivity of these two sites is compared. For low coverages the step dangling bonds are identified as the preferred Cl bonding site after 673 K-annealing. Upon higher temperature annealing and SiCl₂(g) desorption, the terrace-site Cl species are depleted more rapidly than the step-site Cl species. Extensive isothermal etching under a continuous Cl₂ flux at 800 K is found to produce a disordered surface structure. Heating to 1123 K causes a reordering of the surface.     

4H-SiC纳米薄膜的微结构及其光电性质研究

采用新设计的电极结构的等离子体增强化学气相沉积(PECVD)技术,在高功率密度、高氢稀释比、低温、偏压及低反应气压的条件下,在衬底表面形成双等离子流,增加了衬底表面SiC的成核概率,增强成核作用,形成纳米晶.采用高H2等离子体刻蚀弱的、扭曲的、非晶Si—C及Si—Si和Si—H等键时,由于H等离子体对纳米SiC晶粒与非晶态键的差异刻蚀作用,产生自组织生长,发生晶化.Raman光谱和透射电子衍射(TEM)的测试结果表明,纳米晶SiC是4HSiC多型结构.电子显微照片表明平均粒径为16nm,形状为微柱体.实验结果指出,SiC纳米晶的形成必须经过偏压预处理成核,并且其晶化存在一个功率密度阈值;当低于这一功率密度阈值时,晶化消失;当超过这一阈值时,纳米晶含量随功率密度的提高而增加.随着晶化作用的加强,电导率增加. 关键词： 4H-SiC PECVD 纳米结构 多型薄膜 纳米电子学     

Hydrogen adsorption on the silicon (001) surface and on a step on the (111) surface

Adsorption of atomic hydrogen on an ideal (001) silicon surface is investigated in the present paper. Saturation of one of the two dangling bonds of a silicon atom on this surface by hydrogen removes the interaction (hybridization) between them, resulting in the appearance of a bonding and an antibonding chemisorption state associated with the attacked dangling bond, and in the shift of the peak of the remaining unsaturated dangling bond to the energy typical of a surface state of the (111) surface. Further saturation leads to the disappearance of this peak from the energy spectrum. An analogous situation occurs for the silicon atom with two dangling bonds on a step on the (111) surface, when hydrogen is chemisorbed. Both examples testify to the local chemical nature of Shockley surface states in silicon.The authors thank A. N. Sorokin for useful discussions.     

Photo-Induced Metastable Effects in Hydrogenated Amorphous Silicon (a-Si:H)

Light induced changes of electronic properties are studied in glow discharge deposited a-Si: H-films by ESR, field effect, DLTS and electronic transport. These effects are caused by silicon dangling bonds generated by recombination processes, which raise the density of states near midgap. The concomitant increase of potential fluctuations indicates that these defects are inhomogeneously distributed.     

Fabrication and characterization of polycrystalline silicon nanowires with silver-assistance by electroless deposition

Single crystal silicon wafers are widely used as the precursors to prepare silicon nanowires by employing a silver-assisted chemical etching process. In this work, we prepared polycrystalline silicon nanowire arrays by using solar-grade multicrystalline silicon wafers. The chemical composition and bonding on the surface of silicon nanowire arrays were characterized by Fourier Transform Infrared spectroscope, and X-ray photoelectron spectroscope. The photoluminescence spectra of silicon nanowires show red light emissions centered around 700 nm. Due to the passivation effect of Si dangling bonds by concentrated HNO₃ aqueous solution, the photoluminescence intensities are improved by 2 times. The influences of surface chemical states on the wettability of silicon nanowire arrays were also studied. We obtained a superhydrophobic surface on the as-etched silicon nanowire arrays without surface modification with any organic low-surface-energy materials, and realized the evolution from superhydrophobicity to superhydrophilicity via surface modifications with HNO₃ solutions.     

Suppression of the fractal conductivity channel and superlocalization effects in porous a-Si:H

The temperature dependence of the hopping conductivity and the relaxation kinetics of the transient current in porous amorphous silicon are investigated after treatment in a hydrogen plasma at 200 °C. It is discovered that posthydrogenation of the material increases the dimension of the conducting channel from 2.5 to 3, while suppressing and slowing the relaxation of the transient current. The results obtained are attributed to passivation of the electrically active dangling bonds on the pore surface by hydrogen. It is concluded that electron transport in porous amorphous silicon in the temperature range T>T*, where T* lies in the range 130–270 K and depends on the density of states, takes place between superlocalized states of the internal surface, which is enriched with dangling bonds and acts as a fractal percolation system. When the temperature is lowered below T*, a transition to one-dimensional hopping conduction in the bulk silicon regions occurs. Zh. éksp. Teor. Fiz. 112, 926–935 (September 1997)     

薄膜硅/晶体硅异质结电池中本征硅薄膜钝化层的性质及光发射谱研究

本文采用甚高频等离子体化学气相沉积技术 (VHF-PECVD) 制备薄膜硅/晶体硅异质结电池中的本征硅薄膜钝化层, 光发射谱 (OES) 测量技术研究了硅薄膜沉积过程中等离子体发光谱随时间的变化. 结果表明: 在实验优化条件下等离子体发光谱很快达到稳定 (大约25 s), 并且SiH^*/H_α^* 的比值随时间变化较小, 避免了生长过程中硅薄膜结构的不均匀性, 这主要是SiH₄没有完全耗尽避免了SiH₄的反向扩散. 进一步研究了沉积参数对稳态发光谱和硅薄膜性质的影响, 结果表明: 随着硅烷浓度增加, H_α^*峰强度减小, SiH^*峰强度增加, 薄膜从微晶转变成非晶, 非晶硅薄膜钝化效果好; 随着沉积气压增大, H_α^*和 SiH^*峰强度先增加后减小, 高气压下H_α^*和 SiH^*峰强度下降主要是反应前驱物的聚合形成高聚合物, 不利于形成高质量的硅薄膜, 因此钝化效果下降; 随着反应功率密度增加, H_α^*和 SiH^*峰强度增大, 当功率密度为150 mW/cm² 趋于饱和, 硅薄膜的致密度和钝化效果也开始下降, 50 mW/cm²的低功率密度下硅薄膜钝化效果差可能是由于原子H 浓度低, 不能完全钝化单晶硅表面的悬挂键. 关键词： 薄膜硅 异质结 光发射谱 钝化     

Epitaxial silicon oxynitride layer on a 6H-SiC(0001) surface

Hydrogen-gas etching of a 6H-SiC(0001) surface and subsequent annealing in nitrogen atmosphere leads to the formation of a silicon oxynitride (SiON) epitaxial layer. A quantitative low-energy electron diffraction analysis revealed that the SiON layer has a hetero-double-layer structure: a silicate monolayer on a silicon nitride monolayer via Si-O-Si bridge bonds. There are no dangling bonds in the unit cell, which explains the fact that the structure is robust against air exposure. Scanning tunneling spectroscopy measured on the SiON layer shows a bulk SiO2-like band gap of approximately 9 eV. Great potential of this new epitaxial layer for device applications is described.     

Study of hydrogenated AlN as an anti‐reflective coating and for the effective surface passivation of silicon

Stacks of aluminum oxide and silicon nitride are frequently used in silicon photovoltaics. In this Letter, we demonstrate that hydrogenated aluminum nitride can be an alternative to this dual‐layer stack. Deposited on 1 Ω cm p‐type FZ silicon, very low effective surface recombination velocities of 8 cm/s could be reached after firing at 820 °C. This excellent passivation is traced back to a high density of fixed charges at the interface of approximately –1 × 10¹² cm^–2 and a very low interface defect density below 5 × 10¹⁰ eV^–1 cm^–2. Furthermore, spectral ellipsometry measurements reveal that these aluminum nitride layers have ideal optical properties for use as anti‐reflective coatings. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of a weak magnetic field on microplasticity of silicon crystals

The possibility of magnetic ordering at dangling bonds in dislocation cores has been investigated theoretically. It has been experimentally shown that magnetic ordering in dislocations affects the spin-dependent effects occurring in dislocation crystals of silicon. It has been found that preliminary magnetic treatment of silicon crystals in a weak magnetic field leads to the suppression of the electroplastic effect induced in silicon crystals excited by an electric current. It has been assumed that a change in the microplasticity under the combined action of a magnetic field and an electric current is caused by a weakening of spin-dependent recombination at dislocation dangling bonds.     

Materials with on-demand refractive indices in the terahertz range

We demonstrate the possibility to create materials with chosen refractive indices and a strong birefringence in the terahertz range by etching of patterns with appropriate filling factors in a dielectric substrate. We show that by using deep inductive plasma etching of silicon wafers, it is possible to achieve a birefringence as high as 1.2 in an 80 microm thick layer. The resulting stacks were used as building blocks for a photonic crystal displaying sharp defect mode peaks in transmittance.     

Fatigue effect in luminescence of glow discharge amorphous silicon at low temperatures

Fatigue in the luminescence was observed in glow discharge amorphous silicon at 4.2 K and 77 K. This fatigue was not recovered by infra-red illumination, but by heating the sample at higher temperatures. These results are interpreted in terms of enhancement of non-radiative recombination associated with dangling bonds created by high optical excitation.