Characterization of pulsed laser crystallization of silicon thin film

Increases in the melt duration of silicon films were achieved by electrical current heating during and after pulsed excimer laser heating. When 50 nm thick amorphous silicon films formed on glass substrate were irradiated by 28-ns-pulsed excimer by applying 1.8 μs long pulsed-voltage at 100 V to the films, the silicon films were melted for the duration of the voltage pulse. The power threshold for heat energy for this long melting by the self-heating effect of the silicon films was 3.0×10⁵ W/cm². The high electrical conductivity of the silicon film (2.9×10⁻² S/cm) was found after regrowth of the silicon using a laser energy density of 360 mJ/cm² and a pulsed voltage of 150 V. The advantages of the long melt duration for large crystalline growth are discussed.     

Flexible amorphous and microcrystalline silicon tandem solar modules in the temporary superstrate concept

Encapsulated and series-connected amorphous silicon (a-Si:H) and microcrystalline silicon (μc-Si:H) based thin film silicon solar modules were developed in the superstrate configuration using an aluminum foil as temporary substrate during processing and a commodity polymer as permanent substrate in the finished module. For the development of μc-Si:H single junction modules, aspects regarding TCO conductivity, TCO reduction, deposition uniformity, substrate temperature stability and surface morphology were addressed. It was established that on sharp TCO morphologies where single junction μc-Si:H solar cells fail, tandem structures consisting of an a-Si:H top cell and a μc-Si:H bottom cell can still show a good performance. Initial aperture area efficiencies of 8.2%, 3.9% and 9.4% were obtained for fully encapsulated amorphous silicon (a-Si:H) single junction, microcrystalline silicon (μc-Si:H) single junction and a-Si:H/μc-Si:H tandem junction modules, respectively.     

Silicon-based thin-film solar cells fabricated near the phase boundary by VHF PECVD technique

The light-soaked and annealing behaviors for silicon (Si)-based thin-film single-junction solar cells fabricated near the phase boundary using a very-high-frequency plasma-enhanced chemical vapor deposition (VHF PECVD) technique are investigated. The hydrogen dilution ratio is changed in order to achieve wide band gap hydrogenated amorphous Si (a-Si:H) and narrow band gap hydrogenated microcrystalline Si (μc-Si:H) absorbers. Just below the a-Si:H-to-μc-Si:H transition, highly hydrogen-diluted a-Si:H solar cells with a good stability against light-soaking and fast annealing behavior are obtained. In contrast, the solar cell fabricated at the onset of the μc-Si:H growth is very unstable and its annealing behavior is slow. In the case of μc-Si:H solar cells with the crystal volume fraction of 43–53%, they show the lowest light-induced degradation among the fabricated solar cells. However, it is very difficult to recover the degraded μc-Si:H solar cells via thermal annealing.     

Crystallographic analysis of high quality poly-Si thin films deposited by atmospheric pressure chemical vapor deposition

Crystallinity of thin film polycrystalline silicon (poly-Si) grown by atmospheric pressure chemical vapor deposition has been investigated by X-ray diffraction measurement and Raman spectroscopy. Poly-Si films deposited at high temperatures of 850–1050°C preferred to 2 2 0 direction. By Raman spectroscopy, the broad peak of around 480–500 cm⁻¹ belonged to microcrystalline Si (μc-Si) phase was observed even for the poly-Si deposited at 950°C. After high-temperature annealing (1050°C) 3 3 1 direction of poly-Si increased. This result indicates that the μc-Si phase at grain boundary became poly-Si phase preferred to 3 3 1 direction by high-temperature annealing. Effective diffusion length of poly-Si films deposited at 1000°C was estimated to be 11.9–13.5 μm and 10.2–12.9 μm before and after annealing, respectively.     

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.     

Control of μc-Si/c-Si interface layer structure for surface passivation of Si solar cells

Outstanding passivation properties for p-type crystalline silicon surfaces were obtained by using very thin n-type microcrystalline silicon (μc-Si) layers with a controlled interface structure. The n-type μc-Si layers were deposited by the RF PE-CVD method with an insertion of an ultra-thin oxide (UTO) layer or an n-type amorphous silicon (a-Si : H) interface layer. The effective surface recombination velocity (SRV) obtained was very small and comparable to that obtained using thermal oxides prepared at 1000°C. The structural studies by HRTEM and Raman measurements suggest that the presence of UTO produces a very thin a-Si : H layer under the μc-Si. A crystal lattice discontinuity caused by these interface layers is the key to a small SRV.     

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.     

Deposition of thin film silicon using the pulsed PECVD and HWCVD techniques

We report on the use of pulsed plasma-enhanced chemical vapor deposition (P-PECVD) technique and show that “state-of-the-art” amorphous silicon (a-Si:H) materials and solar cells can be produced at a deposition rate of up to 15 Å/s using a modulation frequency in the range 1–100 kHz. The approach has also been developed to deposit materials and devices onto large area, 30 cm×40 cm, substrates with thickness uniformity (<5%), and gas utilization rate (>25%). We have developed a new “hot wire” chemical vapor deposition (HWCVD) method and report that our new filament material, graphite, has so far shown no appreciable degradation even after deposition of 500 μm of amorphous silicon. We report that this technique can produce “state-of-the-art” a-Si:H and that a solar cell of p/i/n configuration exhibited an initial efficiency approaching 9%. The use of microcrystalline silicon (μc-Si) materials to produce low-cost stable solar cells is gaining considerable attention. We show that both of these techniques can produce thin film μc-Si, dependent on process conditions, with 1 1 1 and/or 2 2 0 orientations and with a grain size of approx. 500 A. Inclusion of these types of materials into a solar cell configuration will be discussed.     

Improved quality a-SiC:H films prepared by photo chemical vapour decomposition of silane and acetylene

Hydrogenated amorphous and microcrystalline silicon carbon alloy films have been grown by photo-CVD using C₂H₂ as a source gas of carbon. The hydrogenated amorphous silicon carbon (a-SiC:H) film with a band gap of ~2.0 eV prepared at a very low hydrogen (LD) concentration exhibits better photo-electronic properties compared to that at high hydrogen dilution (HD) having a similar optical gap. Notwithstanding a high deposition rate, the high photosensitivity ( 10⁶), the low density of the defect states ( 6 × 10¹⁶cm⁻³) and the Urbach energy parameter (72 meV) for the a-SiC:H film prepared at low hydrogen dilution and pressure are impressive. On the other hand, low pressure along with high hydrogen dilution have been found to be conducive to microcrystalline silicon carbon alloy (μc-Si:H) formation. Interestingly, crystallites are of silicon while carbon remains in the amorphous and grain boundary regions.     

Microcrystalline silicon thin film solar modules on glass

We developed microcrystalline silicon (μc-Si:H) thin film solar modules on textured ZnO-coated glass. The single junction (p–i–n) cell structure was prepared by plasma-enhanced chemical vapour deposition (PECVD) at substrate temperatures below 250 °C. Front ZnO and back contacts were prepared by sputtering. A process for the monolithic series connection of μc-Si:H cells by laser scribing was developed. These microcrystalline p–i–n modules showed aperture area efficiencies up to 8.3% and 7.3% on aperture areas of 64 and 676 cm², respectively. The temperature coefficient of the efficiency was −0.4%/K.     

Reduction of plasma-induced damage by electron beam excited plasma CVD

The electron beam excited plasma (EBEP-) CVD has succeeded in making nano-crystaline films. On the other hand, the existence of the plasma-induced damage by EBEP-CVD has been confirmed using the hydrogen plasma by measuring the photoluminescence (PL). After plasma exposure, broad band peak appears in the region of 1.0–0.78 eV (1.2–1.6 μm), and intensity of bound exciton peak with energy of 1.093 eV, which is measured and the non-irradiated silicon has been decreased. The same experiment was also performed with RF plasma and the peak appeared not only for EBEP but also for conventional RF plasma. The damage peak tends to disappear over 420°C of the substrate temperature. The damage recovery analysis has been done in relation to the annealing temperature of the substrate after the plasma exposure. Exciton peak has been increased by increasing the temperature especially at 350°C. Furthermore, plasma-induced peak intensity has been decreased at temperature higher than 500°C. Similar peak has been observed in the samples irradiated with high-energy protons. Therefore, positive ions in the plasma are thought to be the source of the damage of the silicon. The origin of the plasma-induced defect in Si is also considered. According to these results, the electric potential of substrate was controlled in order to avoid collision with positive ions in the plasma. When it was set to zero, plasma-induced peaks did not appear.     

Amorphous silicon/p-type crystalline silicon heterojunction solar cells with a microcrystalline silicon buffer layer

Undoped hydrogenated amorphous silicon (a-Si:H)/p-type crystalline silicon (c-Si) structures with and without a microcrystalline silicon (μc-Si) buffer layer have been investigated as a potential low-cost heterojunction (HJ) solar cell. Unlike the conventional HJ silicon solar cell with a highly doped window layer, the undoped a-Si:H emitter was photovoltaically active, and a thicker emitter layer was proven to be advantageous for more light absorption, as long as the carriers generated in the layer are effectively collected at the junction. In addition, without using heavy doping and transparent front contacts, the solar cell exhibited a fill factor comparable to the conventional HJ silicon solar cell. The optimized configuration consisted of an undoped a-Si:H emitter layer (700 Å), providing an excellent light absorption and defect passivation, and a thin μc-Si buffer layer (200 Å), providing an improved carrier collection by lowering barrier height at the interface, resulting in a maximum conversion efficiency of 10% without an anti-reflective coating.     

Evolution of microstructure and phase in amorphous, protocrystalline, and microcrystalline silicon studied by real time spectroscopic ellipsometry

Real time spectroscopic ellipsometry has been applied to develop deposition phase diagrams that can guide the fabrication of hydrogenated silicon (Si:H) thin films at low temperatures (<300°C) for highest performance electronic devices such as solar cells. The simplest phase diagrams incorporate a single transition from the amorphous growth regime to the mixed-phase (amorphous+microcrystalline) growth regime versus accumulated film thickness [the a→(a+μc) transition]. These phase diagrams have shown that optimization of amorphous silicon (a-Si:H) intrinsic layers by RF plasma-enhanced chemical vapor deposition (PECVD) at low rates is achieved using the maximum possible flow ratio of H₂ to SiH₄ that can be sustained while avoiding the a→(a+μc) transition. More recent studies have suggested that a similar strategy is appropriate for optimization of p-type Si:H thin films. The simple phase diagrams can be extended to include in addition the thickness at which a roughening transition is detected in the amorphous film growth regime. It is proposed that optimization of a-Si:H in higher rate RF PECVD processes further requires the maximum possible thickness onset for this roughening transition.     

Low-temperature a-Si:H/ZnO/Al back contacts for high-efficiency silicon solar cells

The paper analyses the electronic transport of high-efficiency silicon solar cells with high-quality back contacts that use a sequence of amorphous (a-Si) and microcrystalline (μc-Si) silicon layers prepared at a maximum temperature of 220 °C. Our best solar cells having diffused emitters with random texture and full-area a-Si/μc-Si contacts have an independently confirmed efficiency of 21.0%. An alternative concept uses a simplified a-Si layer sequence combined with Al-point contacts and yields a confirmed efficiency of 19.3%. Analysis of the internal quantum efficiency (IQE) shows that both types of back contacts lead to effective diffusion lengths L_eff exceeding the wafer thickness considerably. Fill factor limitations for the full area contacts result from non-ideal diode behavior, possibly due to the injection dependence of the interface recombination velocity.     

Low-temperature growth of thick intrinsic and ultrathin phosphorous or boron-doped microcrystalline silicon films: Optimum crystalline fractions for solar cell applications

The growth kinetics and optoelectronic properties of intrinsic and doped microcrystalline silicon (μc-Si:H) films deposited at low temperature have been studied combining in situ and ex situ techniques. High deposition rates and preferential crystallographic orientation for undoped films are obtained at high pressure. X-ray and Raman measurements indicate that for fixed plasma conditions the size of the crystallites decreases with the deposition temperature. Kinetic ellipsometry measurements performed during the growth of p-(μc-Si:H) on transparent conducting oxide substrates display a remarkable stability of zinc oxide, while tin oxide is reduced at 200°C but stable at 150°C. In situ ellipsometry, conductivity and Kelvin probe measurements show that there is an optimum crystalline fraction for both phosphorous- and boron-doped layers. Moreover, the incorporation of p-(μc-Si:H) layers produced at 150°C in μc-Si:H solar cells shows that the higher the crystalline fraction of the p-layer the better the performance of the solar cell. On the contrary, the optimum crystalline fraction of the p-layer is around 30% when hydrogenated amorphous silicon (a-Si:H) is used as the intrinsic layer of p–i–n solar cells. This is supported by in situ Kelvin probe measurements which show a saturation in the contact potential of the doped layers just above the percolation threshold. In situ Kelvin probe measurements also reveal that the screening length in μc-Si:H is much higher than in a-Si:H, in good agreement with the good collection of microcrystalline solar cells     

New materials and deposition techniques for highly efficient silicon thin film solar cells

This paper reviews recent efforts to provide the scientific and technological basis for cost-effective and highly efficient thin film solar modules based on amorphous (a-Si:H) and microcrystalline (μc-Si:H) silicon. Textured ZnO:Al films prepared by sputtering and wet chemical etching were applied to design optimised light-trapping schemes. Necessary prerequisite was the detailed knowledge of the relationship between film growth, structural properties and surface morphology obtained after etching. High rate deposition using plasma enhanced chemical vapour deposition at 13.56 MHz plasma excitation frequency was developed for μc-Si:H solar cells yielding efficiencies of 8.1% and 7.5% at deposition rates of 5 and 9 Å/s, respectively. These μc-Si:H solar cells were successfully up-scaled to a substrate area of 30×30 cm² and applied in a-Si:H/μc-Si:H tandem cells showing initial test cell efficiencies up to 11.9%.     

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.     

Application of real-time spectroscopic ellipsometry for characterizing the structure and optical properties of microcrystalline component layers of amorphous semiconductor solar cells

Over the past few years, we have applied real-time spectroscopic ellipsometry (RTSE) to probe hydrogenated amorphous silicon (a-Si:H)-based solar cell fabrication on the research scale. From RTSE measurements, the microstructural development of the component layers of the cell can be characterized with sub-monolayer sensitivity, including the time evolution of (i) the bulk layer thickness which provide the deposition rates, and (ii) the surface roughness layer thickness which provide insights into precursor surface diffusion. In the same analysis, RTSE also yields the optical properties of the growing films, including the dielectric functions and optical gaps. Results reported earlier have been confined to p-i-n and n-i-p cells consisting solely of amorphous layers, because such layers are found to grow homogeneously, making data analysis relatively straightforward. In this study, we report the first results of an analysis of RTSE data collected during the deposition of an n-type microcrystalline silicon (μc-Si:H) component layer in an a-Si:H p-i-n solar cell. Such an analysis is more difficult owing to (i) the modification of the underlying i-layer by the H₂-rich plasma used in doped μc-Si:H growth and (ii) the more complex morphological development of μc-Si:H, including surface roughening during growth.     

Microcrystalline silicon and the impact on micromorph tandem solar cells

Intrinsic microcrystalline silicon opens up new ways for silicon thin-film multi-junction solar cells, the most promising being the “micromorph” tandem concept. The microstructure of entirely microcrystalline p–i–n solar cells is investigated by transmission electron microscopy. By applying low pressure chemical vapor deposition ZnO as front TCO in p–i–n configurated micromorph tandems, a remarkable reduction of the microcrystalline bottom cell thickness is achieved. Micromorph tandem cells with high open circuit voltages of 1.413 V could be accomplished. A stabilized efficiency of around 11% is estimated for micromorph tandems consisting of 2 μm thick bottom cells. Applying the monolithic series connection, a micromorph module (23.3 cm²) of 9.1% stabilized efficiency could be obtained.     

Hydrogenated nanocrystalline silicon p-layer in amorphous silicon n–i–p solar cells

This paper describes an investigation into the impacts of hydrogenated nanocrystalline silicon (nc-Si:H) p-layer on the photovoltaic parameters, especially on the open-circuit voltage (V_oc) of n–i–p type hydrogenated amorphous silicon (a-Si:H) solar cells. Raman spectroscopy and transmission electron microscopy (TEM) analyses indicate that this p-layer is a diphasic material that contains nanocrystalline grains with size around 3–5 nm embedded in an amorphous silicon matrix. Optical transmission measurements show that the nc-Si:H p-layer has a wide band gap of 1.9 eV. Using this nanocrystalline p-layer in n–i–p a-Si:H solar cells, the cell performances were improved with a V_oc of 1.042 V, whereas the solar cells deposited under similar conditions but incorporating a hydrogenated microcrystalline silicon (μc-Si:H) p-layer exhibit a V_oc of 0.526 V.