Picosecond-laser structuring of amorphous-silicon thin-film solar modules

Laser scribing with nanosecond (ns) diode pumped solid-state laser sources is the industry standard in the fabrication of silicon-based thin-film photovoltaic (TFPV) modules. Reducing the interconnection area is one of the on-going challenges for the next generation of TFPV modules. In this regard, replacing ns laser sources by picosecond (ps) laser sources is one of the logical steps. Ps-laser pulses reduce the heat-affected zones compared to ns pulses, and thus enable a reduction of the interconnection zone. This work describes the substrate-side ablation of fluorine-doped tin oxide, amorphous silicon (a-Si:H) and a-Si:H with an aluminum layer on top, using a 10-ps laser with a wavelength of 1064 nm. The investigation of single-pulse ablation and trench scribing demonstrates that the complete monolithic interconnection can be achieved at the fundamental wavelength. In addition, the evaluation of the ablation efficiency shows that the best trench quality is achieved at the efficiency maximum.     

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.     

Effect of hydrogen on surface texturing and crystallization of a-Si:H thin film irradiated by excimer laser

Hydrogenated amorphous silicon (a-Si:H) thin films have been considered for use in solar cell applications because of their significantly reduced cost compared to crystalline bulk silicon. However, their overall efficiency and stability are lower than that of their bulk crystalline counterpart. Limited work has been performed on simultaneously solving the efficiency and stability issues of a-Si:H. Previous work has shown that surface texturing and crystallization on a-Si:H thin film can be achieved through a single-step laser processing, which can potentially alleviate the disadvantages of a-Si:H in solar cell applications. In this study, hydrogenated and dehydrogenated amorphous silicon thin films deposited on glass substrates were irradiated by KrF excimer laser pulses and the effect of hydrogen on surface morphologies and microstructures is discussed. Sharp spikes are focused only on hydrogenated films, and the large-grained and fine-grained regions caused by two crystallization processes are also induced by presence of hydrogen. Enhanced light absorptance is observed due to light trapping based on surface geometry changes of a-Si:H films, while the formation of a mixture of nanocrystalline silicon and original amorphous silicon after crystallization suggests that the overall material stability can potentially improve. The relationship between crystallinity, fluence and number of pulses is also investigated. Furthermore, a step-by-step crystallization process is introduced to prevent the hydrogen from diffusing out in order to reduce the defect density, and the relationship between residue hydrogen concentration, fluence and step width is discussed. Finally, the combined effects show that the single-step process of surface texturing and step-by-step crystallization induced by excimer laser processing are promising for a-Si:H thin-film solar cell applications.     

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     

Investigation of laser scribing of a-Si:H from the film side for solar modules using a UV laser with ns pulses

This paper investigates laser scribing of a-Si:H layers from the film side with a ns pulsed UV laser for thin-film solar modules. We compared the contact resistance for several scribing methods and find that a low contact resistance is only achieved for double scribing methods (i.e. scribing the same line twice). Furthermore, we find that for such double scribing methods the alignment between the laser spots of the first and second sub-scribes is critical for good-quality contacts. In order to analyze these results in more detail, we examined the morphology and chemical composition at the surface of the laser lines using scanning electron microscopy, X-ray photoelectron spectroscopy and secondary ion mass spectrometry. From this analysis, we conclude that a good alignment between the first and second scribes results in less re-deposition of silicon in the form of SiO₂ on the surface, which explains differences in contact resistance found for the various scribing methods. As a good alignment between the two sub-scribes is difficult to obtain, these double scribing methods are not attractive for industrial application. We developed a new scribing method for which alignment between the two scribes is not critical, and demonstrate that we can obtain high-quality contacts with this method.     

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.     

Numerical analysis of Excimer laser assisted processing of multi-layers for the tailored dehydrogenation of amorphous and nano-crystalline silicon films

The application of the striking electrical and optical properties of amorphous and nano-crystalline silicon in photovoltaic, photonic and nano-electronic devices is attracting increasing attention. In particular, its use both on polymeric substrates and in Integrated Circuit technology for the development of enhanced new devices has shown that processing techniques to produce amorphous hydrogenated and nano-crystalline silicon films avoiding high substrate temperatures are of great importance. A promising strategy to achieve this purpose is the combination of Hot-Wire Chemical Vapor Deposition at 150 °C with Excimer Laser Annealing, thus maintaining the substrate at relatively low temperature during the complete process.In this work we present a numerical analysis of Excimer Laser Annealing, performed at room temperature, of a multilayer structure of thin alternating a-Si:H and nc-Si films deposited on glass and grown by Hot-Wire Chemical Vapor Deposition. A set of two different layer thicknesses a-Si:H (25 nm)/nc-Si (100 nm) and a-Si:H (30 nm)/nc-Si (60 nm) were analysed for a total structure dimension of 900 nm. The aim is to determine the probable temperature profile to achieve controlled localized in depth dehydrogenation.Temperature distribution has been calculated inside the multilayer during the irradiation by a 193 nm Excimer laser, 20 ns pulse length, with energy densities ranging from 50 to 300 mJ/cm². Calculations allowed us to estimate the dehydrogenation effect in the different layers as well as the structural modifications of the same layers as a function of the applied laser energy.The numerical results have been compared to the experimental ones obtained in similar multilayer structures that have been analysed through Raman spectroscopy and TOF-SIMS in depth profiling mode.     

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.     

激光限制结晶技术制备nc-Si/SiO2多层膜

在等离子体增强化学气相淀积系统中，采用aSi:H层淀积和原位等离子体氧化相结合的逐层生长技术制备了aSi:H/SiO_2多层膜.在激光诱导限制结晶原理基础上，使用KrF准分子脉冲激光为辐照源，对aSi:H/SiO_2多层膜进行辐照，使纳米级厚度的aSi:H子层晶化.Raman散射谱和电子衍射谱的结果表明，经过激光辐照后纳米Si颗粒在原始的aSi:H子层内形成，晶粒尺寸可以根据aSi:H层的厚度精确控制.还研究了样品的光致发光（PL）特性以及激光辐照能量密度对PL性质的影响. 关键词： 脉冲激光 多层膜 限制结晶     

Selective ablation with UV lasers of a-Si:H thin film solar cells in direct scribing configuration

Monolithical series connection of silicon thin-film solar cells modules performed by laser scribing plays a very important role in the entire production of these devices. In the current laser process interconnection the two last steps are developed for a configuration of modules where the glass is essential as transparent substrate. In addition, the change of wavelength in the employed laser sources is sometimes enforced due to the nature of the different materials of the multilayer structure which make up the device. The aim of this work is to characterize the laser patterning involved in the monolithic interconnection process in a different configurations of processing than the usually performed with visible laser sources. To carry out this study, we use nanosecond and picosecond laser sources working at 355 nm of wavelength in order to achieve the selective ablation of the material from the film side. To assess this selective removal of material has been used EDX (energy dispersive using X-ray) analysis, electrical measurements and confocal profiles. In order to evaluate the damage in the silicon layer, Raman spectroscopy has been used for the last laser process step. Raman spectra gives information about the heat affected zone in the amorphous silicon structure through the crystalline fraction calculation. The use of ultrafast sources, such as picoseconds lasers, coupled with UV wavelength gives the possibility to consider materials and substrates different than currently used, making the process more efficient and easy to implement in production lines. This approach with UV laser sources working from the film side offers no restriction in the choice of materials which make up the devices and the possibility to opt for opaque substrates.     

Interaction of ultra-short laser pulses with CIGS and CZTSe thin films

The thin-film solar cell technologies based on complex quaternary chalcopyrite and kesterite materials are becoming more attractive due to their potential for low production costs and optimal spectral performance. As in all thin-film technologies, high efficiency of small cells might be maintained with the transition to larger areas when small segments are interconnected in series to reduce photocurrent and related ohmic losses in thin films. Interconnect formation is based on the three scribing steps, and the use of a laser is here crucial for performance of the device. We present our simulation and experimental results on the ablation process investigations in complex CuIn_1?x Ga _x Se₂ (CIGS) and Cu₂ZnSn(S,Se)₄ (CZTSe) cell’s films using ultra-short pulsed infrared (~1 μm) lasers which can be applied to the damage-free front-side scribing processes. Two types of processes were investigated—direct laser ablation of ZnO:Al/CIGS films with a variable pulse duration of a femtosecond laser and the laser-induced material removal with a picosecond laser in the ZnO:Al/CZTSe structure. It has been found that the pulse energy and the number of laser pulses have a significantly stronger effect on the ablation quality in ZnO:Al/CIGS thin films rather than the laser pulse duration. For the thin-film scribing applications, it is very important to carefully select the processing parameters and use of ultra-short femtosecond pulses does not have a significant advantage compared to picosecond laser pulses. Investigations with the ZnO:Al/CZTSe thin films showed that process of the absorber layer removal was triggered by a micro-explosive effect induced by high pressure of sublimated material due to a rapid temperature increase at the molybdenum-CZTSe interface.     

Amorphous thin-film solar cells

This report gives an overview of the present status of thin-film solar cells made from hydrogenated amorphous semiconductors (a-Si:H, a-Ge:H) together with new results emphasizing the physics of amorphous materials and devices. Preparation techniques, quality and performances of a-Si:H and a-Ge:H films as well as solar cells with pin structures are reviewed. Dark and light current-voltage I(V) characteristics and spectral response measurements give information about photovoltaic diodes and allow further insights into the physics of these kinds of materials and solar cells. Simulation calculations and device modelling of such solar cells have increased our understanding of amorphous semiconductors and their devices. The introduction of pin/pin stacked and/or tandem structures has improved the long-term stability and conversion efficiency of amorphous solar cells.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

Optimization of laser patterning of textured gallium-doped zinc oxide for amorphous silicon photovoltaics

Laser scribing process of in-house textured gallium-doped zinc oxide (GZO) is optimized, aiming to improve the performance of amorphous silicon (a-Si:H) photovoltaic (PV) modules. The reasons for different scribing quality of textured GZO and SnO₂:F scribed at 1064 nm with pulse duration of 40 ns were analyzed. Apart from separation resistance, quality of the scribed lines was evaluated by laser scan microscopy from three-dimensional images. Other types of lasers, such as laser with shorter pulse duration, laser at 355 nm and laser with Gaussian-to-tophat converter, were used to smooth the edges and flatten the bottoms of the scribed lines. The proper laser scribing realizes the advantages of textured GZO films used as front contacts in PV modules. A short-circuit current density of 14.3 mA/cm² and an initial aperture area efficiency of 8.8% were obtained on 16 cm × 16 cm textured GZO coated glass scribed at 355 nm with pulse duration of 40 ns.     

Physical mechanism of silicon ablation with long nanosecond laser pulses at 1064 nm through time-resolved observation

Nanosecond (ns) laser ablation can provide a competitive solution for silicon micromachining in many applications. However, most of the previous studies focus on ns lasers at visible or ultraviolet (UV) wavelengths. The research is very limited for ns lasers at infrared (e.g., 1064 nm) wavelengths (which often have the advantage of much lower cost per unit average output power), and the research is even less if the ns laser also has a long pulse duration on the order of ∼100 ns. In this paper, time-resolved observation using an ICCD (intensified charge-coupled device) camera has been performed to understand the physical mechanism of silicon ablation by 200-ns and 1064-nm laser pulses. This kind of work has been rarely reported in the literature. The research shows that for the studied conditions, material removal in laser silicon ablation is realized through surface vaporization followed by liquid ejection that occurs at a delay time of around 200-300 ns. The propagation speed is on the order of ∼1000 m/s for laser-induced plasma (ionized vapor) front, while it is on the order of ∼100 m/s or smaller for the front of ejected liquid. It has also been found that the liquid ejection is very unlikely due to phase explosion, and its exact underlying physical mechanism requires further investigations.     

Ablation of microstructures applying diffractive elements and UV femtosecond laser pulses

A new method for simple and economic fabrication of diffractive optical elements (DOEs) with three and four phase levels, by UV nanosecond (ns) laser ablation is presented. The technique is based on the combination of two sequentially generated complementary 2-level phase elements. During the fabrication, complete ablative removal of a highly absorbing silicon suboxide layer by pixelated backside illumination ensures the necessary high precision and optical quality. Full functionality of the new DOEs is demonstrated by fabricating micro-structures using UV femtosecond pulses.     

a-Si ∶H/SiO2多量子阱材料制备及其光学性能和微结构研究

利用等离子体增强化学气相沉积技术制备了a-Si ∶H/SiO₂多量子阱结构材料.对a-Si ∶H/SiO₂多量子阱样品分别进行了3种不同的热处理,其中样品经1100 ℃高温退火可获得尺寸可控的nc-Si:H/SiO₂量子点超晶格结构,其尺寸与非晶硅子层厚度相当.比较了a-Si ∶H/SiO₂多量子阱材料与相同制备工艺条件下a-Si ∶H材料的吸收系数,在紫外/可见短波段前者的吸收系数明显增大,光学吸收边蓝移,说明该材料 关键词： 多量子阱 量子限制效应 光学吸收 能带结构     

Silicon grain arrays prepared using a pattern crystallization technique of pulsed-excimer laser irradiation

Silicon grain arrays were prepared using a pattern crystallization technique of pulsed KrF excimer laser irradiation. The precursor material was hydrogenated amorphous silicon (a-Si:H) thin films deposited on single crystal Si wafers by plasma-enhanced chemical vapor deposition. It was shown that Si grains with a uniform size and a well-defined periodicity embedded in the a-Si:H matrix were obtained by this simple technique. The grain size was less than 2 μm. Relativly strong photo-luminescence with two peaks at 720 and 750 nm was observed at room temperature. We expect to reduce Si grain sizes by optimizing the growth conditions of a-Si:H thin films and controlling the temperature distribution in the film during laser irradiation. Received: 21 November 2000 / Accepted: 12 December 2000 / Published online: 9 February 2001     

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.     

Effect of charged deep states in hydrogenated amorphous silicon on the behavior of iron oxides nanoparticles deposited on its surface

Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe₃O₄/Fe₂O₃) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their “orientation ordering” in an energetically favourable position.     

FABRICATION AND CHARACTERIZATION OF THE SIZE-CONTROLLED AND PATTERNED nc-Si DOTS

A new method of phase-modulated excimer laser crystallization is adopted to fabricate the patterned nanometer-sized crystalline silicon (nc-Si) dots within the sandwiched structure (a-SiN_x:H/a-Si:H/a-SiN_x:H) films. The results of transmission electron microscopy, electron diffraction and Raman scattering show the ultra-thin and single-layer nc-Si films were patterned in the lateral direction and the size of crystallites is controlled by the thickness of as-deposited a-Si film in the longitudinal direction. The effects of the laser energy density on the structures of the samples and the crystallization mechanism are discussed.