Applying analytical and numerical methods for the analysis of microcrystalline silicon solar cells

The results of numerical device simulations for p–i–n diodes and the closed-form expression of the current–voltage characteristics developed for p–n diodes are compared. It is shown that the closed-form expression correctly predicts the functional relationship between material parameters and device performance of p–i–n diodes. The ideality factor between 1 and 2 is analyzed in detail. The effect of the defect density, the intrinsic carrier concentration, the mobility and the built-in potential on device performance are demonstrated. These insights are applied to analyze microcrystalline silicon thin-film solar cells deposited by chemical vapor deposition at temperatures below 250 °C.     

Intrinsic microcrystalline silicon: A new material for photovoltaics

Microcrystalline silicon (μc-Si:H) prepared by plasma-enhanced chemical vapor deposition (PECVD) has been investigated as material for absorber layers in solar cells. The deposition process has been adjusted to achieve high deposition rates and optimized solar cell performance. In particular, already moderate variations of the crystalline vs. amorphous volume fractions were found to effect the electronic material – and solar cell properties. Such variation is readily achieved by changing the process gas mixture of silane to hydrogen. Best cell performance was found for material near the transition to the amorphous growth regime. With this optimized material efficiencies of 7.5% for a 2 μm thick μc-Si:H single solar cell and 12% for an a-Si:H/μc-Si:H stacked solar cell have been achieved.     

Relationship between Raman crystallinity and open-circuit voltage in microcrystalline silicon solar cells

A series of nip-type microcrystalline silicon (μc-Si:H) single-junction solar cells has been studied by electrical characterisation, by transmission electron microscopy (TEM) and by Raman spectroscopy using 514 and 633 nm excitation light and both top- and bottom-illumination. Thereby, a Raman crystallinity factor indicative of crystalline volume fraction is introduced and applied to the interface regions, i.e. to the mixed amorphous-microcrystalline layers at the top and at the bottom of entire cells. Results are compared with TEM observations for one of the solar cells. Similar Raman and electrical investigations have been conducted also on pin-type μc-Si:H single-junction solar cells. Experimental data show that for all nip and pin μc-Si:H solar cells, the open-circuit voltage linearly decreases as the average of the Raman crystallinity factors for top and bottom interface regions increases.     

The application of grating couplers in thin-film silicon solar cells

As an alternative to randomly textured transparent conductive oxides as front contact for thin-film silicon solar cells, the application of periodic light grating couplers was studied. The periods and groove depths of transparent gratings made of zinc oxide were tuned independently from each other and varied between 1 and 4 μm and 100 and 600 nm, respectively. The one-dimensional grating couplers were realized using photolithography. We have analysed the optical properties of the gratings and the properties of amorphous and microcrystalline silicon solar cells incorporating these grating couplers. The achieved results are discussed with respect to the performance of cells deposited on flat and randomly textured substrates.     

Studies on microstructure of silicon thin films and its effect on solar cells

Intrinsic microcrystalline silicon films have been deposited at high-power–high-pressure regime. Effects of pressure and hydrogen dilution on the microstructures of the films have been investigated. Crystalline size decreases at high pressure although the deposition rate increases up to 10 Å/s. Microstructure depends sensitively on pressure as well as on hydrogen dilution of silane. Single junction solar cells have been fabricated with Si films having different degrees of crystallinity and grain size and the performances have been studied.     

Total SiH4/H2 pressure effect on microcrystalline silicon thin films growth and structure

The effect of the total SiH₄/H₂ gas pressure (1–10 Torr) on the growth rate, the film crystallinity and the nature of hydrogen bonding of microcrystalline silicon thin films deposited by 13.56 MHz plasma-enhanced chemical vapour deposition (PECVD) was investigated under well-controlled discharge conditions. The deposition rate presents an optimum for 2.5 Torr, which does not follow the trend of silane consumption that increases with pressure and is attributed to an increase in plasma density. The film crystallinity increases with pressure from 1–2.5 Torr and then remains almost the same, whereas the films deposited at 1 Torr are highly stressed. On the other hand, hydrogen bonding is also drastically affected.     

A pre-hydrogen glow method to improve the reproducibility of intrinsic microcrystalline silicon thin film depositions in a single-chamber system

Material property differences are observed in hydrogenated microcrystalline silicon (μc-Si:H) thin films deposited under the same nominal conditions in a single-chamber plasma enhanced chemical vapor deposition system but at different stages of chamber history during prolonged usage. This phenomenon is called system shift, which results from the increase of powder coverage on the surface of the cathode and the coatings on other areas in the chamber. We propose a pre-hydrogen glow method to suppress the system shifting. Experimental results show that this method is very effective to reduce the non-reproducibility in μc-Si:H depositions for prolonged usage of the deposition system. In addition, the μc-Si:H films deposited with the pre-hydrogen glow have an improved structural homogeneity along the film thickness.     

Substrate temperature and hydrogen dilution: parameters for amorphous to microcrystalline phase transition in silicon thin films

Amorphous to microcrystalline phase transition in hydrogenated silicon (Si:H) is realized separately with the variations of substrate temperature and hydrogen dilution. The Raman spectroscopy reveals structural transformations and marks the transition. It occurs at 450°C with 10% silane concentration, whereas that is noted at 250°C with a silane concentration of 4.5%. The material evolved in the transition region is a well-developed amorphous matrix containing a small fraction (12%) of crystallites. A uniform distribution of small (100 Å) crystallites in the films is observed by transmission electron microscopy. The transition material is photosensitive.     

The effect of transient depletion of source gases on the properties of microcrystalline silicon solar cells

In is paper, the transient behavior of silane molecules in the initial plasma ignition stage on the properties of microcrystalline silicon films is studied using tailored initial SiH₄ density method, and the results are analyzed by Raman spectroscopy and spectroscopic ellipsometry. Compared with standard plasma ignition conditions, tailored initial SiH₄ density conditions result higher crystallinity in the interface between substrate and bulk film. Finally, tailored and standard conditions are used in i-layer deposition processes of p-i-n and n-i-p solar cells. It is demonstrated that tailored initial SiH₄ density conditions is helpful for the efficiency improvement of n-i-p solar cells and standard plasma ignition conditions for p-i-n solar cells.     

Material properties of microcrystalline silicon for solar cell application

The paper reviews the material requirements of microcrystalline silicon (μc-Si) in terms of the device operation and configuration for thin film solar cells and thin film transistors (TFTs). We investigated the material properties of μc-Si films deposited by using 13.56 MHz plasma-enhanced chemical vapor deposition (PECVD) from a conventional H₂ dilution in SiH₄. Two types of intrinsic μc-Si films deposited at the high pressure narrow electrode gap and the low pressure wide electrode gap were studied for the solar cell absorption layers. The material properties were characterized using dark conductivity, Raman spectroscopy, and transmission electron microscope (TEM) measurements. The μc-Si quality and solar cell performance were mainly determined by microstructure characteristics. Solar cells adopting the optimized μc-Si film demonstrated high stability with no significant changes in solar cell performance after air exposure for six months and subsequent illumination for over 300 h. The results can be explained that low ion bombardment and high atomic hydrogen density under the PECVD condition of the high pressure narrow electrode gap produce high-quality μc-Si films for solar cell application.     

Influence of the substrate geometrical parameters on microcrystalline silicon growth for thin-film solar cells

The effect of substrate morphology on the growth and electrical properties of single-junction microcrystalline silicon cells is investigated. A large variety of V-shaped and U-shaped substrates are characterized by scanning electron microscopy (SEM) and the growth of thin-film microcrystalline silicon (μc-Si:H) devices is observed by cross-sectional transmission electron microscopy (TEM). It is shown that enhanced electrical properties of solar cells are obtained when U-shaped substrates are used and the effect is universal, i.e. independent of the substrate or feature size. U-shaped substrates prevent the formation of two dimensional “cracks”, which are identified as zones of porous material, from propagating throughout the active part of the solar cell. A numerical growth simulation program reproduces satisfactorily these experimental observations. According to these simulations, shadowing effect due to surface morphology and low adatom surface diffusion length are responsible for the formation of cracks in μc-Si:H material.     

Aluminium-induced crystallisation of silicon on glass for thin-film solar cells

Aluminium-induced crystallisation of amorphous silicon is studied for the formation of continuous polycrystalline silicon thin-films on low-temperature glass substrates. It is shown to be a promising alternative to laser crystallisation and solid-phase crystallisation. Silicon grain sizes of larger than 10 μm are achieved at temperatures of around 475°C within annealing times as short as 1 h. The Al doping concentration of the poly-Si films depends on the annealing temperature, as revealed by Hall effect measurements. A poly-Si/Al/glass structure presented here can serve as a seeding layer for the epitaxial growth of polycrystalline silicon thin-film solar cells, or possibly as the base material with the back contact incorporated.     

Light trapping effect of patterned back surface reflectors in substrate-type single and tandem junction thin-film silicon solar cells

Light trapping is a key issue to boost the efficiency of thin-film Si solar cells including μc-Si:H. In this paper, effect of textured back reflectors on light trapping in μc-Si:H cells has been investigated with self-orderly patterned Al substrates obtained by anodic oxidation. With increase in the period of the patterned substrates from 0 to 1.1 μm, the short circuit current densities of 1-μm-thick μc-Si:H cells on the patterned substrates significantly increase from 18 to over 24 mA/cm², which is attributed to the improved light trapping in the infrared region. It has been clarified that this enhanced light-trapping effect in longer wavelengths is mainly attributed to the improved light scattering at the rear side by comparing μc-Si:H solar cells with polished and as-deposited front surfaces. The effectiveness of the patterned Al substrates has also been demonstrated in an a-Si:H/μc-Si:H tandem cell with a bottom cell thickness of 1 μm, showing a higher conversion efficiency than the reference cell.     

First-principles analysis of electrochemical hydrogen storage behavior for hydrogenated amorphous silicon thin film in high-capacity proton battery

Silicon material electrodes as proton carriers for high-capacity proton battery have only been proposed for such a short period of time that their physicochemical properties and electrochemical hydrogen storage behavior during charge and discharge processes remain nearly uncharted territory. Herein, the hydrogenated amorphous silicon (a-Si:H) thin film electrodes are prepared by radio frequency sputtering followed by ex-situ hydrogenation. The electrochemical properties of a-Si:H electrodes are tested experimentally, and the electrochemical hydrogen storage behaviors of a-Si:H electrodes are analyzed by first-principles calculations. The results show that the hydrogenation process significantly increases the electrochemical capacity of the electrodes and reduces the band gap of the electrode structure. The electrode exhibits weak conductivity during the initial charging, but the instability of the electrode electronic structure during the later charging results in a slight fluctuation of the electrochemical charging process. The a-Si:H electrode have better electrochemical hydrogen storage/release reversibility than non-hydrogenated electrodes, but this reversibility is weakened by oxygen atoms covered on the electrode surface. The electrochemical hydrogen storage process is easier to accomplish than the electrochemical desorption process of hydrogen evolution reaction for the a-Si:H electrodes. The a-Si:H thin film electrode is more stable on the Ni(111) substrate surface and the good conductivity of the electrode/substrate interface provides convenient conditions for the free transport of electrons in the electrochemical charge/discharge processes. We believe that these results perfectly explain the microscopic mechanisms responsible for the electrode reaction and electrochemical behavior of a-Si:H electrodes in this type of proton battery, and have a certain reference value in understanding the physicochemical properties and electrochemical hydrogen storage behavior of silicon material electrodes applied to other types of batteries during charge/discharge processes.     

Synthesis of highly conductive boron-doped p-type hydrogenated microcrystalline silicon (μc-Si:H) by a hot-wire chemical vapor deposition (HWCVD) technique

Boron-doped hydrogenated microcrystalline silicon (μc-Si:H) films were prepared using hot-wire chemical vapor deposition (HWCVD) technique. Structural, electrical and optical properties of these thin films were systematically studied as a function of B₂H₆ gas (diborane) phase ratio (Variation in B₂H₆ gas phase ratio, dopant gas being diluted in hydrogen, affected the film properties through variation in doping level and hydrogen dilution). Characterization of these films from low angle X-ray diffraction and Raman spectroscopy revealed that the high conductive film consists of mixed phase of microcrystalline silicon embedded in an amorphous network. Even a small increase in hydrogen dilution showed marked effect on film microstructure. At the optimized deposition conditions, films with high dark conductivity (0.08 (Ω cm)⁻¹) with low charge carrier activation energy (0.025 eV) and low optical absorption coefficient with high optical band gap (2.0 eV) were obtained. At these deposition conditions, however, the growth rate was small (6 Å/s) and hydrogen content was large (9 at%).     

Enhancement of the optical absorption of thin-film of amorphorized silicon for photovoltaic energy conversion

In this study we report for the first time a method for simple, precise and single-step generation of thin film of amorphous silicon (a-Si) on silicon substrate induced by laser pulses with the frequency of megahertz under ambient conditions for solar cell fabrication. Also, the effect of laser parameters such as pulse width is investigated by developing an analytical model for the calculation of the non-dimensional surface temperature with various pulse widths; it was found from experimental and analytical results that for a constant power and repetition rate, an increase in the pulse duration corresponds to a significant increase in the surface temperature which results in an increase in the amount of amorphorized material as well as improvement of light absorption. A Scanning Electron Microscope (SEM), scanning near-field optical microscope (SNOM), a Micro-Raman, Energy Dispersive X-ray (EDX) spectroscopy and an optical spectrometer were used to analyze the optical and material properties of the amorphorized thin layer on Si-substrate.     

Spatial distribution of high-density microwave plasma for fast deposition of microcrystalline silicon film

The high-density microwave plasma utilizing a spokewise antenna was successfully applied to fast deposition of highly crystallized and photoconductive microcrystalline silicon (μc-Si:H) film at low temperatures. Among various deposition parameters, spatial distribution of ion energy (IDF) mainly determines film crystallinity. The best crystallinity was obtained at the axial distance, Z from the quartz glass plate, where the spread of mean ion energy is minimum. By optimizing the axial distance, Z and total pressure, highly crystallized and photoconductive μc-Si:H film could be fabricated with a high deposition rate of 47 Å/s at 50 mTorr in SiH₄ and Ar plasma.     

Experimental studies and limitations of the light trapping and optical losses in microcrystalline silicon solar cells

This study addresses the potential of different approaches to improve the generated current in silicon thin-film solar cells and modules. Decreasing the carrier concentration in the front contact has proven to increase the quantum efficiency and the cell-current density significantly. Additionally, an optically improved ZnO/Ag back reflector and the optimized light incoupling by anti-reflection layers were studied. In this contribution, we show the potential of the different optical components and discuss combinations thereof in order to obtain a maximized cell-current density in silicon thin-film solar cells. Limitations of the cell-current density are discussed with respect to theoretical calculations.     

Rough ZnO layers by LP-CVD process and their effect in improving performances of amorphous and microcrystalline silicon solar cells

Doped ZnO layers deposited by low-pressure chemical vapour deposition technique have been studied for their use as transparent contact layers for thin-film silicon solar cells.Surface roughness of these ZnO layers is related to their light-scattering capability; this is shown to be of prime importance to enhance the current generation in thin-film silicon solar cells. Surface roughness has been tuned over a large range of values, by varying thickness and/or doping concentration of the ZnO layers.A method is proposed to optimize the light-scattering capacity of ZnO layers, and the incorporation of these layers as front transparent conductive oxides for p–i–n thin-film microcrystalline silicon solar cells is studied.