Visible photoluminescence from a-Si : H/SiO2 superlattices fabricated by UHV evaporation

Hydrogenated amorphous-Si/SiO₂ (a-Si:H/SiO₂) superlattices with different a-Si : H thickness in the range of a few nanometers have been fabricated by ultra high vacuum evaporator (UHV evaporator). The photoluminescence (PL) of our superlattices is observed in the visible spectral region and the peak energy shifts to higher energy as the a-Si : H layer thickness decreases. The temperature dependence of the PL spectra reveals four sub-bands by fitting. Bands at 2.2, 1.9, 1.65 and 1.45 eV are detected and are attributed to E′δ centers, nonbridging-oxygen–hole centers (NBOHC), Si/SiO₂ interface and a-Si : H layer, respectively. We explain the overall blueshift of the PL spectra by the modification of the contribution of these sub-bands.     

A quantum chemical study of ZrO2 atomic layer deposition growth reactions on the SiO2 surface

Zirconium oxide (ZrO₂) is one of the leading candidates to replace silicon oxide (SiO₂) as the gate dielectric for future generation metal-oxide-semiconductor (MOS) based nanoelectronic devices. Experimental studies have shown that a 1–3 monolayer SiO₂ film between the high permittivity metal oxide and the substrate silicon is needed to minimize electrical degradation. This study uses density functional theory (DFT) to investigate the initial growth reactions of ZrO₂ on hydroxylated SiO₂ by atomic layer deposition (ALD). The reactants investigated in this study are zirconium tetrachloride (ZrCl₄) and water (H₂O). Exchange reaction mechanisms for the two reaction half-cycles were investigated. For the first half-reaction, reaction of gaseous ZrCl₄ with the hydroxylated SiO₂ surface was studied. Upon adsorption, ZrCl₄ forms a stable intermediate complex with the surface SiO₂–OH^* site, followed by formation of SiO₂–O–Zr–Cl^* surface sites and HCl. For the second half-reaction, reaction of H₂O on SiO₂–O–Zr–Cl^* surface sites was investigated. The reaction pathway is analogous to that of the first half-reaction; water first forms a stable intermediate complex followed by evolution of HCl through combination of a Cl atom from the surface site and an H atom from H₂O. The results reveal that the stable intermediate complexes formed in both half-reactions can lead to a slow film growth rate unless process parameters are adjusted to lower the stability of the complex. The energetics of the two half-reactions are similar to those of ZrO₂ ALD on ZrO₂ and as well as the energetics of ZrO₂ ALD on hydroxylated silicon. The energetics of the growth reactions with two surface hydroxyl sites are also described.     

Limitations of interface sharpness in a-Si:H/a-SiC:H multilayers

The goal of this work is to study the sharpness of interfaces in amorphous silicon based compositional multilayers (superlattices) by a number of different techniques and to discuss their limitations. From monitoring plasma transients during glow discharge deposition of a-Si:H/a-SiC:H multilayers, a lower limit of 3 Å for interface sharpness is estimated. Transmission electron microscopy (TEM) images yield an upper limit of 5–10 Å. These images directly show the increase in undulation from the substrate towards the film surface. From the comparison of simulated X-ray diffraction (XRD) spectra with measurements the interface sharpness is found to be between 5 and 8 Å. Using a series of multilayers with increasing number of interfaces, structural characteristics of the interfacial region can be extracted. For example, infrared absorption spectroscopy (FTIR) and elastic recoil detection (ERD) lead to an estimate of 1.1 × 10¹⁴ cm^-2 additional hydrogen atoms per single interface.     

硅锗量子阱结构在硅异质结太阳电池中应用的数值模拟

利用半导体工艺和器件仿真软件silvaco TCAD(Technology Computer Aided Design),模拟研究了采用硅/硅锗合金(silicon/silicon germanium alloy,Si/Si_(1-x)Ge_x)量子阱结构作为吸收层的薄膜晶体硅异质结太阳电池各项性能.模拟结果显示,长波波段光学吸收随锗含量的增加而增加,而开路电压则因Si_(1-x)Ge_x)层带隙的降低而下降.锗含量为0.25时,短路电流密度的增加补偿了开路电压的衰减,效率提升0.2%.氢化非晶硅/晶体硅(a-Si:H/c-Si)界面空穴密度以及Si_(1-x)Ge_x)量子阱的体空穴载流子浓度制约着空穴费米能级的位置,进而影响到开路电压的大小.随着锗含量增加,a-Si:H/c-Si界面缺陷对开压的影响降低,Si_(1-x)Ge_x)量子阱的体缺陷对开压的影响则相应增加.高效率含Si_(1-x)Ge_x)量子阱结构的硅异质结太阳电池的制备需要a-Si:H/c-Si界面缺陷的良好钝化以及高质量Si_(1-x)Ge_x)量子阱的生长.     

Mechanism and energetics of dimerization of SiH2 radicals on H-terminated Si(0 0 1)-(2×1) surfaces

The mechanism and energetics are presented of the dimerization of two adsorbed surface SiH₂ groups on the H-terminated Si(0 0 1)-(2 × 1) surface to form Si₂H₄ species during the initial stages of growth in plasma deposition of hydrogenated amorphous silicon (a-Si:H) films. The reactions are observed during classical molecular-dynamics (MD) simulations of a-Si:H film deposition from SiH₂ radical precursors impinging on an initially H-terminated Si(0 0 1)-(2 × 1) surface and substrate temperature, T, over the range 500T700 K. The Si₂H₄ species resulting from the surface SiH₂ dimerization reactions undergo surface conformational changes resulting in either a non-rotated (NRD) or a rotated dimer (RD) configuration. The RD configuration is found to be the energetically favorable one. The MD simulation results for the structure of the NRD and RD surface Si₂H₄ configurations corroborate with ab initio calculations of optimized adsorption configurations of SiH₂ radicals on crystalline Si surfaces, as well as results of STM imaging of the thermal decomposition of disilane on Si(0 0 1).     

H,Cl和F原子钝化Cu_2ZnSnS_4(112)表面态的第一性原理计算

采用基于密度泛函理论的第一性原理计算方法系统研究了Cu_2ZnSnS_4体相的晶格结构、能带、态密度及表面重构与H,Cl和F原子在Cu_2ZnSnS_4(112)表面上的吸附和钝化机理.计算结果表明:表面重构出现在以金属原子Cu-Zn-Sn终止的Cu_2ZnSnS_4(112)表面上,并且表面重构使表面发生自钝化;当单个H,Cl或F原子吸附在S原子终止的Cu_2ZnSnS_4(112)表面上时,相比于桥位(bridge)、六方密排(hcp)位和面心立方(fcc)位点,三种原子均在特定的顶位(top)吸附位点表现出最佳稳定性.当覆盖度为0.5 ML时,无论H,Cl还是F原子占据Cu_2ZnSnS_4(112)表面的2个顶位均具有最低的吸附能.以S原子终止的Cu_2ZnSnS_4(112)表面在费米能级附近的电子态主要由价带顶部Cu-3d轨道和S-3p轨道电子贡献,此即表面态.当H,Cl或F原子在表面的覆盖度达0.5 ML时,费米能级附近的表面态降低,其中H原子钝化表面态的效果最佳,Cl原子的效果次之,F原子的效果最差.表面态降低的主要原因在于吸附原子从S原子获得电子致使表面Cu原子和S原子在费米能级处的态密度峰几乎完全消失.     

硅异质结太阳电池的物理机制和优化设计

硅异质结太阳电池是一种由非晶硅薄膜层沉积于晶硅吸收层构成的高效低成本的光伏器件,是一种具有大面积规模化生产潜力的光伏产品.异质结界面钝化品质、发射极的掺杂浓度和厚度以及透明导电层的功函数是影响硅异质结太阳电池性能的主要因素.针对这些影响因素已经有大量的研究工作在全世界范围内展开,并且有诸多研究小组提出了器件效率限制因素背后的物理机制.洞悉物理机制可为今后优化设计高性能的器件提供准则.因此及时总结硅异质结太阳电池的物理机制和优化设计非常必要.本文主要讨论了晶硅表面钝化、发射极掺杂层和透明导电层之间的功函数失配以及由此形成的肖特基势垒;讨论了屏蔽由功函数失配引起的能带弯曲所需的特征长度,即屏蔽长度;介绍了硅异质结太阳电池优化设计的数值模拟和实践;总结了硅异质结太阳电池的研究现状和发展前景.     

Infrared ellipsometry study of the oxidation mechanisms of hydrogenated amorphous silicon

A detailed study of the oxidation of plasma deposited amorphous silicon (a-Si : H) using infrared phase modulated ellipsometry (IRPME) is presented. a-Si : H is found to be resistant against air oxidation confirming previous measurements. A 5–6 Å thick oxide layer at the surface of a-Si : H is observed after a few months of exposure to air. The extreme sensitivity of IRPME is emphasized. In particular Si-O-Si and (O_n)Si-H stretching vibrations are identified at the film surface at the submonolayer level. The oxidation mechanisms are discussed. The weak reactivity of a-Si : H with atmosphere is correlated with the presence of a hydrogen rich thin layer at the top surface.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

Surface tension and density measurements for indium and uranium using a sessile-drop apparatus with glow discharge cleaning

The sessile-drop method is used to measure the surface tension and density of liquid indium and uranium under high vacuum. Measurements are made over the temperature range 156–500°C for In and at the melting point for U. Surface oxides are efficiently removed with a glow discharge system. Drop profiles are captured by photograph and processed using nonlinear regression to yield the surface tension and density. In this regression procedure, normal distances from calculated profiles to data points are minimized. For indium, the density and surface tension measurements yield _mp = 7.05 × 10³kg/m³, d/dT = −0.776 kg/m³·°C, and γ_mp = 0.568 N/m, dγ/dT = −9.45 × 10⁻⁵ N/m·°C. The results for uranium at the melting point are _mp = 17.47 × 10³ kg/m³ and γ_mp = 1.653 N/m.     

Desorption of H2 from W(110) and Fe covered W(110) surfaces

The kinetics of H₂ desorption from H/W(110) and H/Fe₁/W(110) were studied by measuring work function changes Δø vs time at a number of temperatures. Combination with previously determined Δø vs coverage data and differentiation at various fixed coverages gave rate vs T data from which activation energies of desorption could be obtained. E vs coverage results agree well with previously determine ΔH_des results. In the case of H/Fe₁/W(110) this includes a rise from 20 to 30 kcal mol⁻¹ of H₂ at H/Fe = H/W > 0.3. Plots of rate −dθ/dt vs θ (θ being coverage in units of H/W) vary much more steeply than θ² at most coverages for both systems. The θ dependence can be explained almost quantitatively in terms of the variations of ΔH_des and surface entropy S_s with coverage, by assuming that rates of desorption are equal to the equilibrium rates of adsorption. The latter can be formulated thermodynamically, except for a sticking coefficient, s. Values for s(θ, T) can also be obtained and show relatively little temperature dependence.     

Surface diffusion of dysprosium on the W(1 1 1) facet

Diffusion of dysprosium on the (1 1 1) facet of a tungsten micromonocrystal was investigated by means of spectral analysis of field emission current fluctuations. The experimental spectral density functions of the current fluctuations were analysed by using Gesley and Swanson’s theoretical spectral density function, which enables to determine the surface diffusion coefficient D for dysprosium. Derived from the temperature dependence of D, the diffusion activation energy E is presented for some Dy coverages θ_(1 1 1). In the temperature range 400–600 K, the E first drops from 1.25 eV per atom at θ₍₁₁₁₎≈0.25 ML to 0.48 eV per atom at θ₍₁₁₁₎≈1 ML (corresponding to the minimum of the work function of the system), then increases to 1.03 eV per atom at θ₍₁₁₁₎≈1.3 ML. The results are discussed from the aspects of the substrate structure and interaction in the adsorbed layer.     

钙钛矿/硅叠层太阳电池中平面a-Si:H/c-Si异质结底电池的钝化优化及性能提高

最近,旋涂法制备的钙钛矿/平面硅异质结高效叠层太阳电池引起人们广泛关注,主要原因是相比于绒面硅衬底制备的钙钛矿/硅叠层太阳电池,其制备工艺简单、制备成本低且效率高.对于平面a-Si:H/c-Si异质结电池, a-Si:H/c-Si界面的良好钝化是获得高转换效率的关键,进而决定了钙钛矿/硅异质结叠层太阳电池的性能.本文主要从硅片表面处理、a-Si:H钝化层和P型发射极等方面展开研究,通过对硅片表面的氢氟酸(HF)浸泡时间和氢等离子体预处理气体流量、a-Si:H钝化层沉积参数、钝化层与P型发射极(I/P)界面富氢等离子体处理的综合调控,获得了相应的优化工艺参数.对比研究了p-a-Si:H和p-nc-Si:H两种缓冲层材料对I/P界面的影响,其中高电导、宽带隙的p-nc-Si:H缓冲层既能够降低I/P界面的缺陷态,又可以增强P型发射层的暗电导率,提高了前表面场效应钝化效果.通过上述优化,制备出最佳的P-type emitter layer/aSi:H(i)/c-Si/a-Si:H(i)/N-type layer (inip)结构样品的少子寿命与implied-Voc分别达到2855μs和709 mV,表现出良好的钝化效果.应用于平面a-Si:H/c-Si异质结太阳电池,转换效率达到18.76%,其中开路电压达到681.5 mV,相对于未优化的电池提升了34.3 mV.将上述平面a-Si:H/c-Si异质结太阳电池作为底电池,对应的钙钛矿/硅异质结叠层太阳电池的开路电压达到1780 mV,转换效率达到21.24%,证明了上述工艺优化能够有效地改善叠层太阳电池中的硅异质结底电池的钝化及电池性能.     

过渡区p型氢化硅氧薄膜结构和光电特性的研究

采用射频等离子体增强化学气相沉积技术,利用二氧化碳(CO_2)、氢气(H_2)、硅烷(SiH_4)和乙硼烷(B_2H_6)作为气源,制备出一系列p型氢化硅氧薄膜.利用拉曼光谱、傅里叶变换红外光谱和暗电导测试,研究了不同二氧化碳流量对薄膜材料结构和光电特性的影响,获得了从纳米晶相向非晶相转变的过渡区P层.研究表明:随着二氧化碳流量从0增加到1.2 cm~3·min~(-1),拉曼光谱的峰值位置从520 cm~(-1)逐渐移至480 cm~(-1).材料红外光谱表明,随着二氧化碳流量的增加,薄膜中的氧含量逐渐增加,氢键配置逐渐由硅单氢键转换为硅双氢键.P层SiO:H薄膜电导率从3S/cm降为8.3×10~(-6)S/cm.所有p型SiO:H薄膜的光学带隙(Eopt)都在1.82—2.13 eV之间变化.在不加背反射电极的条件下,利用从纳米晶相向非晶相转变的过渡区P层作为电池的窗口层,且在P层和I层之间插入一定厚度的缓冲层,制备出效率为8.27%的非晶硅薄膜电池.     

分子动力学模拟H原子与Si的表面相互作用

通过分子动力学模拟了入射能量对H原子与晶Si表面相互作用的影响. 通过模拟数据与实验数据的比较, 得到H原子吸附率随入射量的增加 呈先增加后趋于平衡的趋势. 沉积的H原子在Si表面形成一层氢化非晶硅薄膜, 刻蚀产物(H₂, SiH₂, SiH₃和SiH₄)对H原子吸附率趋于平衡有重要影响, 并且也决定了样品的表面粗糙度. 当入射能量为1 eV时, 样品表面粗糙度最小. 随着入射能量的增加, 氢化非晶硅薄膜中各成分(SiH, SiH₂, SiH₃)的量以及分布均有所变化. 关键词： 分子动力学 吸附率 表面粗糙度 氢化非晶硅薄膜     

Isothermal desorption of hydrogen from polycrystalline diamond films

The kinetics of isothermal H₂ desorption from polycrystalline diamond are studied in real time. The surface H coverage (θ_H) is measured by mass analyzing the recoiled H₊ ion signal during the desorption. We find that the H₂ desorption is 1st order in θ_H with an activation energy of 69 ± 6 kcal/mol and a prefactor of 10^{10.5 ± 0.9} s⁻¹. We suggest that formation of a C---C π-bond on the clean surface plays a key role in H₂ desorption from diamond, a view consistent with previous theoretical calculations of H₂ desorption from diamond.     

In situ study of the Si-H bond in a-Si:H ultrathin films

A preliminary in situ analysis of the growth mechanisms and vibrational properties of plasma deposited amorphous silicon (a-Si:H) ultrathin films (d_f<200 Å) is presented. The hydrogen incorporation, as a function of the film thickness and the influence of the nature of the substrate on the early stage of the growth are studied by a new infrared phase modulated ellipsometer (IRPME). The Si-H bond (near 1990 cm^-1) is evidenced for the first time on films as thin as 5 Å. This new ellipsometer offers extremely high resolution thanks to a very small noise (0.02° in ψ and Δ).     

微晶硅锗薄膜作为近红外光吸收层在硅基薄膜太阳电池中的应用

采用射频等离子体增强化学气相沉积技术,制备了具有一定晶化率不同Ge含量的氢化微晶硅锗(μcSi1-xGex:H)薄膜.通过Ⅹ射线荧光谱、拉曼光谱、X射线衍射谱、傅里叶红外谱、吸收系数谱和电导率的测试,表征了μc-Si_(1-x)Ge_x:H的材料微结构随Ge含量的演变.研究表明:提高Ge含量可以增强μc-Si_(1-x)Ge_x:H薄膜的吸收系数.将其应用到硅基薄膜太阳电池的本征层中可以有效提高电池的短路电流密度(J_(sc)).特别是在电池厚度较薄或陷光不充分的情况下,长波响应的提高会更为显著.应用ZnO衬底后,在Ge含量分别为9%和27%时,μc-Si_(1-x)Ge_x:H太阳电池的转换效率均超过了7%.最后,将μc-Si_(1-x)Ge_x:H太阳电池应用在双结叠层太阳电池的底电池中,发现μc-Si_(0.73)Ge_(0.27):H底电池在厚度为800 nm时即可得到比1700 nm厚微晶硅(μc-Si:H)底电池更高的长波响应.以上结果体现μc-Si_(1-x)Ge_x:H太阳电池作为高效近红外光吸收层,在硅基薄膜太阳电池中应用的前景.     

超薄高速率单结微晶硅薄膜电池及其叠层电池

采用甚高频等离子体增强化学气相沉积技术, 基于优化表面形貌及光电特性的溅射后腐蚀ZnO:Al衬底, 将通过调控工艺参数获得的器件质量级高速微晶硅(μupc-Si:H )材料(沉积速率达10.57 Å/s)应用到微晶硅单结电池中, 获得了初始效率达7.49%的高速率超薄微晶硅单结太阳电池(本征层厚度为1.1 μm). 并提出插入n型微晶硅和p型微晶硅的隧穿复合结, 实现了非晶硅顶电池和微晶硅底电池之间的低损电连接, 由此获得了初始效率高达12.03% (V_oc=1.48 eV, J_sc=11.67 mA/cm², FF=69.59%)的非晶硅/微晶硅超薄双结叠层电池(总厚度为1.48 μm), 为实现低成本生产太阳电池奠定了基础.     

On interface properties of ultra-thin and very-thin oxide/a-Si:H structures prepared by oxygen based plasmas and chemical oxidation

Amorphous hydrogenated silicon (a-Si:H) belongs still to most promising types of semiconductors for its utilization in fabrication of TFTs and thin film solar cell technology due to corresponding cheap a-Si:H-based device production in comparison with, e.g. crystalline silicon (c-Si) technologies. The contribution deals with both two important modes of preparation of very-thin and ultra-thin silicon dioxide films in the surface region of a-Si:H semiconductor (oxygen plasma sources and liquid chemical methods) and electrical, optical and structural properties of produced oxide/semiconductor structures, respectively. Dominant aim is focused on investigation of oxide/semiconductor interface properties and their comparison and evaluation from view of utilization of used technological modes in the nanotechnological industry. Following three basic types of oxygen plasma sources were used for the first time in our laboratories for treatments of surfaces of a-Si:H substrates: (i) inductively coupled plasma in connection with its applying at plasma anodic oxidation; (ii) rf plasma as the source of positive oxygen ions for plasma immersion ion implantation process; (iii) dielectric barrier discharge ignited at high pressures.The liquid chemical manner of formation SiO₂/a-Si:H structures uses 68 wt% nitric acid aqueous solutions (i.e., azeotropic mixture with water). Their application in crystalline Si technologies has been presented with excellent results in the formation of ultra-thin SiO₂/c-Si structures [H. Kobayashi, M. Asuha, H.I. Takahashi, J. Appl. Phys. 94 (2003) 7328].Passivation of surface and interface states by liquid cyanide treatment is additional original technique applied after (or before) formation of almost all formed thin film/a-Si:H structures. Passivation process should be used if high-quality electronical parameters of devices can be reached.