Electrical properties and degradation behavior of hydrogenated amorphous Si alloys for solar cells

The electrical properties and the degradation behavior of hydrogenated amorphous silicon alloys (a-Si_1–x A _x : H, with A=C, Ge, B, P) in designs of pin, pip, nin, and MOS structures are investigated by measuring the dark and light I(V) characteristics and the spectral response as well as the space-charge-limited current (SCLC), the time of flight (TOF) of carriers and the field effect (FE). These investigations give an overview of our recent work combined with new results emphasizing the physics of the a-Si:H pin solar cells. We discuss the stabilizing influence on the degradation behavior achieved by profiling the i layers of the pin solar cells with P and B. Two kinds of pin solar cells, namely glass/SnO₂/p(C)in/metal and glass/metal/pin/ITO, are investigated and an explanation of their different spectral response behavior is given. SCLC measurements lead to the conclusion that trapping is also involved in the degradation mechanism, as is recombination. TOF experiments on a-Si_1–x Ge _x : H pin diodes indicate that the incorporation of Ge widens the tail-state distribution below the conduction band. FE measurements showed densities of gap states of about 5×l0¹⁶cm^–3eV^–1.     

Superstrate p-i-n a-Si:H solar cells on textured ZnO:Al front transparent conduction oxide

Superstrate p-i-n amorphous silicon thin-film (a-Si:H) solar cells are prepared on SnO₂:F and ZnO:Al transparent conducting oxides (TCOs) in order to see the effect of TCO/p-layers on a-Si:H solar cell operation. The solar cells prepared on textured ZnO:Al have higher open circuit voltage V_oc than cells prepared on SnO₂:F. The presence of a thin microcrystalline p-type silicon layer (μc-Si:H) between ZnO:Al and p a-SiC:H plays a major role by causing an improvement in the fill factor as well as in V_oc of a-Si:H solar cells prepared on ZnO:Al TCO. Without any treatment of the p-i interface, we could obtain a high V_oc of 994 mV while keeping the fill factor (72.7%) and short circuit current density J_sc at the same level as for the cells on SnO₂:F TCO. This high V_oc value can be attributed to modification in the current transport in this region due to creation of a potential barrier.     

Phonon spectroscopy measurements at amorphous films

Phonon spectroscopy measurements were used to examine the scattering of high frequency phonons (300 GHz-1 THz) in amorphous materials. The experiments were done with the use of time and frequency resolved measurements of the phonon transmission behaviour through amorphous single films of different thicknesses. The typical film thicknesses were of the order of 10 nm. In contrast to the pure amorphous semiconductors Si and Ge our experiments show inelastic phonon scattering processes in the case of SiO₂ and SiH. This inelastic phonon scattering also occurs when the pure semiconductors Si and Ge are prepared in an O₂ or H₂ atmosphere, but is missing when the preparation process is done in an N₂ atmosphere. In films of the pure semiconductors a-Si and a-Ge we only found evidence to elastic scattering processes. In further experiments at heated a-SiH samples we could examine the atomical bonded hydrogen to be the center of the inelastic phonon scattering.The measurements and investigations described in this work were done in time of preparing a thesis at: Physikalisches Institut Teil 1, Universität Stuttgart, Pfaffenwaldring 57, D-70569 Stuttgart, Germany     

Potential of amorphous silicon for solar cells

This paper reviews recent developments in the field of amorphous-silicon-based thin-film solar cells and discusses potentials for further improvements. Creative efforts in materials research, device physics, and process engineering have led to highly efficient solar cells based on amorphous hydrogenated silicon. Sophisticated multijunction solar cell designs make use of its unique material properties and strongly suppress light induced degradation. Texture-etching of sputtered ZnO:Al films is presented as a novel technique to design optimized light trapping schemes for silicon thin-film solar cells in both p-i-n and n-i-p device structure. Necessary efforts will be discussed to close the efficiency gap between the highest stabilized efficiencies demonstrated on lab scale and efficiencies achieved in production. In case of a-Si:H/a-Si:H stacked cells prepared on glass substrates, significant reduction of process-related losses and the development of superior TCO substrates on large areas promise distinctly higher module efficiencies. A discussion of future perspectives comprises the potential of new deposition techniques and concepts combining the advantages of amorphous and crystalline silicon thin-film solar cells. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 14 June 1999     

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.     

The p recombination layer in tunnel junctions for micromorph tandem solar cells

A new tunnel recombination junction is fabricated for n–i–p type micromorph tandem solar cells. We insert a thin heavily doped hydrogenated amorphous silicon (a-Si:H) p + recombination layer between the n a-Si:H and the p hydrogenated nanocrystalline silicon (nc-Si:H) layers to improve the performance of the n–i–p tandem solar cells. The effects of the boron doping gas ratio and the deposition time of the p-a-Si:H recombination layer on the tunnel recombination junctions have been investigated. The current-voltage characteristic of the tunnel recombination junction shows a nearly ohmic characteristic, and the resistance of the tunnel recombination junction can be as low as 1.5 ·cm 2 by using the optimized p-a-Si:H recombination layer. We obtain tandem solar cells with open circuit voltage V oc = 1.4 V, which is nearly the sum of the V oc s of the two corresponding single cells, indicating no V oc losses at the tunnel recombination junction.     

Vis-NIR characteristics of amorphous germanium films and electrical properties of a-Ge/<Emphasis Type="Italic">p</Emphasis>-Si heterostructures obtained by pulsed-laser deposition method

Optical properties of a-Ge films (glass substrate) and electrical properties of a-Ge/p-Si heterostructures obtained by the pulsed-laser deposition method have been studied. It is shown that optical properties of a-Ge films can be well explained by the Tauc model for amorphous semiconductors. The dependence of optical gap on the film thickness is obtained for a-Ge films. Forward-bias current-voltage characteristics of the a-Ge/p-Si heterostructures are satisfactorily approximated by the relation for current density J = CV ^m , where m varies from 1.45 to 1.95 depending on the applied forward bias and a-Ge film thickness. Also, for the mentioned heterostructure (a-Ge film thickness is 400 nm) nearly quadratic dependence of the current density is observed, which indicates the predominance of the space-charge-limited current.     

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.     

Three dimensional a-Si:H thin-film solar cells with silver nano-rod back electrodes

We present three dimensional (3-D) amorphous silicon (a-Si:H) thin-film solar cells with silver nano-rods as back electrodes, which are fabricated by low cost nano imprint lithography (NIL). After conformal deposition of thin metal and semiconductor layers, we can achieve a dome-shaped geometry, which is shown to be effective in reducing the reflectance at the front surface due to the graded refractive index effect. In addition, the enhancement of the diffused reflectance over a broad wavelength in this dome-shaped geometry provides light trapping due to the increase in the effective light propagation length. Using this 3-D solar cell, we achieved 54% increase in short circuit current density and 45% increase in the conversion efficiency compared to the control cells with flat Ag surfaces. This 3-D structure can be also used for improving light harvesting in various photovoltaic devices regardless of materials and structures.     

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。     

Reflectivity modeling of Si-based amorphous superlattices

The structural properties of superlattices composed by hydrogenated amorphous silicon/silicon carbide (a-Si:H/a- Si_1 − xC_x:H) and silicon/germanium (a-Si:H/a-Ge:H), deposited by the plasma-enhanced chemical vapor deposition (PECVD) technique, were analyzed by means of small-angle X-ray diffraction. The relevant structural parameters, such as the multilayer period, the individual layer thickness, the width of the interface and the optical constants, were determined by modeling the experimental reflectivity. The model was based on the dynamical diffraction theory, including material mixing at the interface, interface roughness and random variation of component thickness. In addition, the effect of the direct beam and background on the measured intensities were considered.     

N-type amorphous silicon-based bilayers for cost-effective thin-film silicon photovoltaic devices

We investigate the improvement of p–i–n type thin-film silicon (Si) solar cells by employing a hydrogenated n-type amorphous Si (n-a-Si:H)-based bilayer. The initial conversion efficiency (η) of a-Si:H single-junction solar cells is improved from 9.2 to 10.0%. The developed n-a-Si:H-based bilayer is also suitable for a-Si:H/hydgrogenated microcrystalline Si (μc-Si:H) double-junction solar cells, and thus initial η is improved from 10.4 to 10.8%. With a further optimization, initial η of 11.3% and stabilized η of 10.1% are achieved. Since the n-a-Si:H-based bilayer is easily formed using a conventional process, it can be a promising option for cost-effective mass production of large-area thin-film Si solar modules.     

Influence of H2O/DEZ ratio on LPCVD ZnO:B films for application in a-Si:H/μc-Si:H tandem solar cells

In this study, boron doped zinc oxide (ZnO:B) films were prepared at different water to diethyl zinc (H₂O/DEZ) flow ratios from 0.6 to 1.4 by a low pressure chemical vapor deposition (LPCVD) technique. It is found that the morphology of ZnO:B films varies from small leaf-like to pyramidal surface structures with the increasing H₂O/DEZ flow ratio. The rough ZnO:B films deposited at a relatively H₂O/DEZ flow ratio such as 1.2 or 1.4 show a high haze value of up to 28 % at 600 nm and $\mathrm{a} (11\overline{2}0)$ preferential crystallographic orientation. All ZnO:B films were applied in hydrogenated amorphous silicon/microcrystalline silicon tandem solar cells (a-Si:H/μc-Si:H) as front electrodes. The efficiency of the solar cells increases with the increasing H₂O/DEZ flow ratio, which is attributed to a high spectral response mainly in the long-wavelength range and the consequent enhancement of short-circuit current. A high-efficiency a-Si:H/μc-Si:H tandem solar cell of 10 % was achieved. The H₂O/DEZ ratio is an important process parameter to tune the material properties of LPCVD ZnO:B films and the performances of corresponding silicon thin film solar cells.     

Determination of electron-diffusion length from photocurrent characteristics of the structure ITO/a-SiC:H(p-type)/a-Si:H/a-Si:H(n-type)/Pd

In this study the electron diffusion length L _n is determined from the relative spectral response of the photocurrent characteristics of the p/i/n sandwich structure ITO/a-SiC:H(p-type)/a-Si:H/a-Si:H(n-type)/Pd. The techniques used for the preparation of the a-Sic:H and a-Si:H amorphous films were glow-discharge and rf magnetron sputtering, respectively. The thickness of the p-type, intrinsic and n-type layer were 400 Å, 7000 Å and 600 Å, respectively. The response of the short-circuit current density J _sc was measured versus the photon energy hv at both constant light intensity and constant temperature. The electron diffusion length was found to be 0.31 m by means of the method of Agarwala and Tewary. Although, in the case of single crystals many diffusion length measurements have been made, there are only few papers for amorphous silicon this films [1]. As it is well-known, the diffusion length of the charge carriers is the most important parameter from the point of view of solar cell applications [2]. In order to obtain a high efficiency in a solar cell all carriers created under illumination in the intrinsic layer should reach the electrodes [3]. In the case that the thickness of the intrinsic layer is much larger than the diffusion length, not all carriers can reach the electrodes and, accordingly, a low efficiency results [4]. On the other hand, carriers which reach the electrodes without thermalizing do not contribute to the photocurrent and finally the efficiency of the solar cell is negatively affected. In order to avoid such an effect to a large extent, the thickness of the amorphous layers in a p/i/n solar cell must be conveniently chosen compared to the diffusion length of the carriers.Here it is aimed to determine the electron diffusion length. In order to achieve this goal, the photocurrent characteristics of an ITO/a-SiC:H(p-type)/a-Si:H/a-Si:H(n-type)/Pd structure was measured versus the photon energy at constant light intensity and constant temperature. In order to determine the electron diffusion length, the method of Agarwala and Tewary [5] was utilized.     

a-Si:H/c-Si 异质结太阳电池 J-V 曲线的 S-Shape 现象

通过异质结界面分析与 AMPS 模拟计算研究了 a-Si:H/c-Si 异质结太阳电池在低温工作、a-Si:H 层低掺杂、高价带补偿以及高界面态时光态 J-V 曲线出现 S-Shape 现象的物理过程,总结了 S-Shape 现象的物理原因.分析结果表明,当空穴输运受到界面势垒的限制时,空穴在 c-Si 界面附近聚集,能带重新分配,c-Si 耗尽区的电场减小,更多的电子从 c-Si 准中性区反转至 c-Si 界面及耗尽区与空穴复合,复合速率显著增大,光电流的损失显著增大,光态 J-V< 关键词： 模拟 异质结太阳电池 a-Si:H/c-Si 异质结     

Understanding of a-Si:H(p)/c-Si(n) heterojunction solar cell through analysis of cells with point-contacted p/n junction

We fabricated point-contacted a-Si:H(p)/c-Si(n) heterojunction solar cells using patterned SiO₂ and investigated their electrical properties using the light current–voltage (I–V) curve and Suns-V_oc measurements. The light I–V curves showed bias-dependent changes according to the applied voltage in the point-contacted cells, especially in the samples with a long distance between the point-contacted junctions. The Suns-V_oc measurements showed that the bias-dependence of the light I–V curves did not originate from the recombination in the SiO₂/Si or a-Si:H(p)/c-Si(n) interface, but from the series resistances. It is possible to explain the bias-dependent light I–V curve in terms of the conductivity of a-Si:H(p) and difference in the electrical contact properties between a-Si:H(p), ZnO and c-Si(n). These results mean that the electrical properties of the a-Si:H(p) layer and the contact properties with this layer are also critical to obtain a high J_sc and fill factor in n-type based Si heterojunction solar cells.     

High-Efficiency Silicon Solar Cells—Materials and Devices Physics

High-efficiency Si solar cells have attracted great attention from researchers, scientists, engineers of photovoltaic (PV) industry for the past few decades. Many researchers, scientists, and engineers in both academia and industry seek solutions to improve the cell efficiency and reduce the cost. This desire has drawn stronger support from major funding agencies and industry and stimulated a growing number of major research and research infrastructure programs, and a rapidly increasing number of publications in this filed. This article reviews materials, devices, and physics of high-efficiency Si solar cells developed over the last 20 years and presents representative examples of superior performances and competitive advantages. In this paper there is a fair number of topics, not only from the material viewpoint, introducing various materials that are required for high-efficiency Si solar cells, such as base materials (FZ-Si, CZ-Si, MCZ-Si, and multi-Si), emitter materials (diffused emitter and deposited emitter), passivation materials (Al-BSF, high-low junction, SiO₂, SiO_x, SiN_x, Al₂O₃ and a-Si:H), and other functional materials (antireflective layer, transparent conductive oxide and metal electrode), but also from the device and physics point of view, elaborating on physics, cell concept, development, and status of most types of high-efficiency Si solar cells, including passivated emitter and rear contact (PERC), passivated emitter and rear locally diffused (PERL), passivated emitter and rear totally-diffused (PERT), Pluto, PANDA, interdigitated back-contacted (IBC), emitter-wrap-through (EWT), metallization-wrap-through (MWT), heterojunction with intrinsic thin-layer (HIT), and so on. Finally, the technical data of these high-efficiency Si solar cells has been tabulated.     

Quantum emission efficiency of nanocrystalline and amorphous Si quantum dots

The paper presents the comparison of emission efficiencies for crystalline Si quantum dots (QDs) and amorphous Si nanoclusters (QDs) embedded in hydrogenated amorphous (a-Si:H) films grown by the hot wire-CVD method (HW-CVD) at the variation of technological parameters. The correlations between the intensities of different PL bands and the volumes of Si nanocrystals (nc-Si:H) and/or an amorphous (a-Si:H) phase have been revealed using X-ray diffraction (XRD) and photoluminescence (PL) methods. These correlations permit to discuss the PL mechanisms in a-Si:H films with embedded nc-Si QDs. The QD parameters of nc-Si:H and a-Si:H QDs have been estimated from PL results and have been compared (for nc-Si QDs) with the parameters obtained by the XRD method. Using PL and XRD results the relations between quantum emission efficiencies for crystalline (η_cr) and amorphous (η_am) QDs have been estimated and discussed for all studied QD samples. It is revealed that a-Si:H films prepared by HW-CVD with the variation of wire temperatures are characterized by better passivation of nonradiative recombination centers in comparison with the films prepared at the variation of substrate temperatures or oxygen flows.     

后退火增强氢化非晶硅钝化效果的研究

在本征氢化非晶硅(a-Si:H(i))/晶体硅(c-Si)/a-Si:H(i)异质结构上溅射ITO时, 发现后退火可大幅增加ITO/a-Si:H(i)/c-Si/a-Si:H(i)的少子寿命(从1.7 ms到4 ms). 这一增强效应可能的三个原因是: ITO/a-Si:H(i)界面场效应作用、退火形成的表面反应层影响以及退火对a-Si:H(i)材料本身的优化, 但本文研究结果表明少子寿命增强效应与ITO和表面反应层无关; 对不同沉积温度制备的a-Si:H(i)/c-Si/a-Si:H(i)异质结后退火的研究表明: 较低的沉积温度(<175 ℃)后退火增强效应显著, 而较高的沉积温度(>200 ℃)后退火增强效应不明显, 可以确定“低温长高温后退火”是获得高质量钝化效果的一种有效方式; 采用傅里叶红外吸收谱(FTIR)研究不同沉积温度退火前后a-Si:H(i)材料本身的化学键构造, 发现退火后异质结少子寿命大幅提升是由于a-Si:H(i)材料本身的结构优化造成的, 其深层次的本质是通过材料的生长温度和退火温度的优化匹配来控制包括H含量、H键合情况以及Si原子无序性程度等微观因素主导作用的一种竞争性平衡, 对这一平衡点的最佳控制是少子寿命大幅提升的本质原因.