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     

Lowering of thickness of boron-doped microcrystalline hydrogenated silicon film by seeding technique

By using a seeding technique it has been possible to reduce the thickness of p-μc-Si:H film to 230 Å, with an improved electrical conductivity (0.93 S cm⁻¹) and lower optical absorption compared to those of conventional p-μc-Si:H layers without a seed layer, for use at the tunnel junction and as the top layer of a double junction n–i–p structured a-Si solar cell. Undoped-μc-Si:H has been used as the seed layer. The layers were prepared by the radio frequency plasma-enhanced chemical vapour deposition (RF-PECVD) method (13.56 MHz) at 40 mW/cm² rf power density and low substrate temperature (200 °C). The ultrathin seed layer (30 Å) enhances the growth of microcrystallinity of the p-type μc-Si:H film as confirmed by the results of transmission electron microscopy (TEM) analysis and Raman spectroscopy.     

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.     

Polycrystalline Si films formed by Al-induced crystallization (AIC) with and without Al oxides at Al/a-Si interface

Al-induced crystallization (AIC) without an Al oxide at the Al/a-Si interface (glass/Al/a-Si) was investigated in comparison with the case of an Al oxide (glass/Al/Al oxide/a-Si). The Si crystallization of Al/a-Si during AIC was much faster than that of Al/Al oxide/a-Si. The annealing of glass/Al/a-Si led to poly-Si films with small Si grains compared to that of glass/Al/Al oxide/a-Si. It is difficult to observe the influence of the crystallization temperatures (400–500°C) on the crystallization of glass/Al/a-Si. With annealing of glass/Al/a-Si at 300°C, the crystallization of a-Si occurred not only in the original Al layer but also in the original a-Si layer. With lowering crystallization temperature of glass/Al/Al oxide/a-Si, it is observed that poly-Si films become oriented preferentially in the (1 0 0) direction normal to the surface and had larger grains. These preferentially (1 0 0) oriented Si thin films can act as good seed layers for the growth of the active layers by liquid phase epitaxy.     

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.     

Back electrode formation for poly-Si thin film solar cells on glass having AIC-grown seeding layer

Various conductive materials (Al, Mo and TiN) were deposited onto glass substrates to evaluate whether poly-Si seed layers can be formed on such substrates by means of Al-induced crystallisation (AIC) of a-Si at low temperature around 450°C. The material located between the glass and the poly-Si film serves as the back electrode of a substrate-type thin-film solar cell configuration. The outcome of the investigation is that Mo is found to be not compatible with the AIC process. In contrast, Al and TiN showed moderate to good compatibility. TiN is the only viable choice for high-temperature applications (>540°C). Al has satisfactory back electrode properties whereas TiN has a medium high resistivity (120 μΩ cm) and an estimated low back reflectance at the near-infrared wavelengths critical for light trapping.     

Single-crystalline silicon solar cell with pp heterojunction of c-Si substrate and μc-Si : H film

Annealing effects of the single-crystalline silicon solar cells with hydrogenated microcrystaline silicon (μc-Si : H) film were studied to improve the conversion efficiency. Boron-doped (p⁺) μc-Si : H film was deposited in a RF plasma enhanced chemical vapor deposition system (RF plasma CVD) on the rear surface of the cell. With the optimized annealing conditions for the substrate, the conversion efficiency of 21.4% (AM1.5, 25°C, 100 mW/cm²) was obtained for 5 × 5 cm² area single crystalline-solar cell.     

Photothermal stability of encapsulated Si solar cells and encapsulation materials upon accelerated exposures

We have conducted a series of accelerated exposure test (AET) studies for various samples of crystalline-Si (c-Si) and amorphous-Si (a-Si) cells that were encapsulated with different superstrates, pottants, and substrates. Transmittance, fluorescence, color indices, impedance spectroscopy, laser optical beam induced current (OBIC), and light and dark current–voltage (I–V) measurements were used to characterize the samples. Nonuniform browning patterns of ethylene vinyl acetate (EVA) pottants were observed for glass/EVA/glass-encapsulated c-Si cell samples under solar simulator exposures at elevated temperatures. The EVA discolored gradually into a yellow–brown color when exposed under 7.5 ultraviolet (UV) suns at a black panel temperature (BPT) of 85°C, and very rapidly into a dark brown color when exposed under 9.0 UV suns at a BPT of 145°C. The latter conditions also caused extensive delamination of a polyolefin-based thermoplastic pottant laminated between two borosilicate plates. No visible color change of EVA could be observed for the c-Si cell samples heated in an oven at 85°C or exposed under 1.2 UV suns at BPT=60–65°C or 80–85°C. Under 1.2 UV suns exposure at a BPT of 60–65°C, the thin layers of EVA or silicone in the lightweight c-Si cell samples, which were laminated in a polymer/solar cell/polymer configuration with Tedlar or Tefzel films, did not discolor because of photobleaching reactions. In comparison, the polyester or nylon superstrate films turned yellow on laminates of polymer/a-Si/polymer minimodules, and significant delamination was observed for the polyester/EVA layers. For all c-Si cell samples tested, irregular changes in the I–V parameters were observed that could not be attributed only to transmittance changes of the superstrate/pottant layers. Under UV-transmitting polymer superstrate films, current/efficiency losses were greater for the c-Si and a-Si cells that were laminated with silicone-type adhesives than with EVA or polyethylene pottants.     

Thin CdS films prepared by metalorganic chemical vapor deposition

Polycrystalline CdS thin films have been deposited on borosilicate glass substrates coated with ITO film by metalorganic chemical vapor deposition using dimethyl cadmium and diethyl sulfide as source materials. The growth of CdS film occurred at substrate temperatures within the range of 280–360°C. The deposition rate increased with increasing VI/II molar ratio at any substrate temperature and showed a maximum value at the VI/II molar ratio of 4. The grain size of as-deposited CdS film prepared at substrate temperatures from 300°C to 360°C was about 0.1 μm. The CdS films consist of hexagonal form with a preferential orientation of the (0 0 2) plane parallel to the substrate. Thin CdS film with high optical transmittance was prepared at 350°C with the VI/II molar ratio of 4. The CdS film deposited by MOCVD may be used as a window layer for CdS/CdTe solar cell.     

Thin film poly-Si formation for solar cells by Flux method and Cat-CVD method

Two methods were examined for the formation of poly-Si films. One is flux method and the other is Cat-CVD method. Flux method was used for forming poly-Si seed films on glass substrates covered with rear electrode. Poly-Si films of a few μm grain size and of mainly (1 1 1) crystalline orientation were obtained at less than 600°C. To make the seed films function as BSF layer for solar cell, boron doping was applied and carrier concentration of 2×10¹⁹/cm³ was obtained which is suitable for highly efficient solar cells. Cat (catalytic)-CVD method was examined for forming poly-Si photo-active layers on the seed films. The films showed deposition gas pressure-dependent crystalline orientations and there was no amorphous incubation layer in (1 1 1) oriented films by Cat-CVD method when deposited on (1 1 1) oriented seed films prepared by Flux method. The electrical properties of the film are insufficient at present, may be due to high defect density and the film structure which allows impurity contaminations of oxygen and carbon after film deposition. Although the film quality needs to be improved, poly-Si films whose crystal fraction is more than 85% were obtained at deposition rate of up to around 40 Å/s. This result indicates high potential of Cat-CVD method for high throughput photo-active formation process necessary for low production cost thin film silicon solar cells.     

Oxidative photoelectrochemical technology with Ti/TiO2 anodes

Rutile and anatase TiO₂ films have been grown on Ti plates by thermal (500–800°C) and anodic oxidation followed by thermal annealing (400–500°C), respectively. The photoelectrochemical efficiency of these photoanodes, evaluated by current density measurements in the photooxidation of 4-methoxybenzyl alcohol in deaerated CH₃CN, has been determined. The photocurrent efficiency increases with the thickness of the TiO₂ rutile film up to 1 μm (the most efficient thickness). At the wavelengths furnished by the irradiation apparatus similar thicknesses of anatase and rutile films show nearly the same efficiencies. Anodic bias produces similar relative increases of current intensity in both crystalline forms.     

Effect of the sintering temperature on the photocatalytic activity of ZnO+Zn2TiO4 thin films

ZnO+Zn₂TiO₄ thin films were obtained by the sol–gel method, the precursor solutions were prepared using two Ti/Zn ratios: 0.49 and 0.69. The films were deposited on glass slide substrates and sintered at temperatures in the 200–600 °C range in increments of 50 °C, with the goal of studying the dependence of the photocatalytic activity (PA) on the annealing temperature. The films were characterized by X-ray diffraction and UV–Vis spectroscopy. The PA was evaluated by measuring the UV–Vis absorption spectra of the methylene blue in aqueous solution before and after photobleaching, using the Lambert–Beer's principle. The higher photocatalytic activities were obtained from the films with sintering temperature around 450 °C, for both Ti/Zn ratios studied.     

Comparison of electrochromic amorphous and crystalline tungsten oxide films

A detailed systematic study of the tungsten oxide thin films has been carried out using WO₃ films after they were annealed at progressively increasing temperatures ranging from 350°C to 450°C in oxygen environments. The structural properties of the films were characterized using X-ray diffraction and Raman spectroscopy. The amorphous WO₃ films remain as an amorphous phase up to 385°C and begin to crystallize at 390°C and then are completely crystallized at 450°C. Absorption peaks of the films are found to shift to a higher energy side with increasing annealing temperature up to 385°C and then shift abruptly to a lower energy as the films begin to crystallize at 390°C. Deconvolution of the absorption spectra shows that there are two different polaron transitions in the amorphous WO₃ films.     

High-efficiency μc-Si/c-Si heterojunction solar cells

P-type microcrystalline silicon (μc-Si (p)) on n-type crystalline silicon (c-Si(n)) heterojunction solar cells is investigated. Thin boron-doped μc-Si layers are deposited by plasma-enhanced chemical vapor deposition on CZ-Si and the V_oc of μc-Si/c-Si heterojunction solar cells is higher than that produced by a conventional thermal diffusion process. Under the appropriate conditions, the structure of thin μc-Si films on (1 0 0), (1 1 0), and (1 1 1) CZ-Si is ordered, so high V_oc of 0.579 V is achieved for 2×2 cm² μc-Si/multi-crystalline silicon (mc-Si) solar cells. The epitaxial-like growth is important in the fabrication of high-efficiency μc-Si/mc-Si heterojunction solar cells.     

Structural and electrical studies of plasma-deposited polycrystalline silicon thin-films for photovoltaic application

Plasma-deposited polycrystalline Si films [or microcrystalline Si (μc-Si) films] produced by plasma enhanced chemical vapor deposition (PECVD) have attracted considerable attention as novel, low-cost and stable materials for the photovoltaic i-layer in p–i–n junction thin-film solar cells. The μc-Si films prepared under various deposition conditions show widely various microstructures, from a crystalline–amorphous mixed state to an almost perfect crystalline state, with different crystallographic orientations. These structural changes directly influence the carrier transport properties that play a dominant role in determining photovoltaic performance. Furthermore, obtaining a uniform built-in electric field throughout the i-layer is a crucial issue for achieving excellent photovoltaic performance. To obtain a uniform electric field, the following terms should be required for the i-layer: ‘truly’ intrinsic characteristic (or not n-type characteristics) as well as structural uniformity in the growth direction without an incubation layer. Here, structural properties of μc-Si for achieving truly intrinsic characteristics are reviewed with an emphasis on collations with the crystalline volume function and the degree of (2 2 0) crystallographic preferential orientation in the crystalline phase. In addition, we reviewed a growth mechanism for the μc-Si film that is actually used in the photovoltaic i-layer in highly efficient solar cells: hybrid-phase growth consisting of conventional vapor-phase growth at the surface and the solid-phase crystallization that simultaneously occurs in the film. That growth is very effective in producing structural uniformity along the growth direction and for formation of crystallites directly on the underlying doped layer.     

Poly-Si thin films by metal-induced growth for photovoltaic applications

Poly-Si films were produced using a metal-induced growth technique by sputtering from an n-type Si target onto a 50 nm thick Co seed-layer at 625°C. Silicon grew heteroepitaxially on the CoSi₂ layer formed due to the reaction between the sputtered Si atoms and Co at the beginning stage of deposition. A 5 μm thick Si film with grain features up to 1 μm was produced on the thin and flexible tungsten substrate by using a two-step sputtering method. The films also have a natural texture structure on the surface that is strongly recommended in thin-film solar cells in order to obtain high current density by increasing incident light trapping. After post-sputtering annealing at 700°C, the measured minority carrier lifetime for poly-Si film was 1.33 μs which shows the film to be suitable for photovoltaic applications. To explore the photovoltaic applications by using MIG poly-Si films, Au/n-Si Schottky photodiodes were fabricated due to the process simplicity. The effects of different parameters, which include film doping density, active-layer thickness, Si film surface conditions and hydrogenation, were studied. It was found that with the increasing of doping density, the open-circuit voltage (V_oc) increased while short-circuit current density (J_sc) decreased. Increasing the poly-Si active-layer thickness tended to improve the light absorption with an increased J_sc, but the V_oc was decreased due to a higher value of reverse saturation current. Because the metal/semiconductor interface condition facilitates the carrier transport in Schottky devices, the earlier study of modifying the Si surface by polishing showed an improved V_oc. The overall photo response was further improved by plasma hydrogenation.     

Study of the solid phase crystallization behavior of amorphous sputtered silicon by X-ray diffraction and electrical measurements

In situ X-ray diffraction (XRD) measurements have been used to study the amorphous-to-crystalline transformation in hydrogenated amorphous silicon (a-Si:H) thin films deposited by DC-Magnetron Sputtering at 300°C. The a-Si:H layers of 2.85 μm thickness were solid phase crystallized (SPC) and the crystallization kinetic was studied from in situ XRD measurements and also by in situ electrical conductance measurements during isothermal annealing at 630°C. The apparition and the evolution of the (1 1 1) peak in the XRD spectra during the annealing of the layer permit to follow the SPC kinetic which is the same as the electrical conductance kinetic (G=f(t)) performed in the same annealing conditions as in the XRD experiment. Several isothermal annealings at different temperatures permit to extract the characteristic parameters of the crystallization from the G=f(t) evolutions. These parameters are the thermally activated crystallization characteristic time and its activation energy.     

Hydrogen, fluorine ion implantation effects on polycrystalline silicon grain boundaries

The influences of hydrogen and fluorine ion implantation on polycrystalline silicon (poly-Si) grain boundaries have been investigated. Effective passivation of poly-Si grain boundaries was achieved by hydrogen ion implantation at 300–400°C. From fluorine implantation experiments, we confirmed that fluorine atoms in poly-Si were redistributed with a diffusion tail after annealing at above 600°C. A diffusion tail of fluorine redistribution was not observed in single crystalline silicon. We think that it is possible to passivate poly-Si grain boundaries by controlling the diffusion of fluorine.     

Routine instrumental procedures to characterise the mineralogy of modern and ancient silica sinters

Tightly constrained determinative methods can be used to characterise the silica minerals (opal-A, opal-CT, opal-C, quartz, moganite) and physical properties of silica sinters. Optimal X-ray powder diffraction operating parameters indicate silica lattice order/disorder using untreated, dry, <106 μm powders scanned at 0.6° 2θ/min with a step size of 0.01° from 10–40° 2θ and an internal Si standard. Simultaneous differential thermal and thermogravimetric analysis of 15.0±0.1 mg sinter samples of <106 μm grain size, at a heating rate of 20°C/min in dry air, identify thermal events associated with dehydration, organic combustion, and changes of state. Where abundant organic matter is present, nitrogen is the preferred atmosphere for thermal analysis. Thermogravimetric-determined water contents of sinters differ from Penfield determinations reflecting the differing nature of the two techniques. Laser Raman microprobe techniques can be used to explore the mineralogy of particular sinter morphologies and habits down to 10 μm diameter. The nature of the silica species present can assist in characterising individual sinter deposits and, combined with textural, density and/or porosity determinations, can lead to a better understanding of the hydrology and paleohydrology of a geothermal prospect.     

Different phases of indium selenide prepared by annealing In/Se bilayer at various temperatures: Characterization studies

Thin films of indium selenide were prepared by annealing Indium/Selenium stack layers at different temperatures ranging from 100 to 400 °C. Structural and optical characterizations were done using X-ray diffraction and optical absorption studies, respectively. Compositional analysis was done by employing Rutherford backscattering spectroscopy and X-ray photoelectron spectroscopy confirmed the compound formation. Photosensitivity and sheet resistance of these samples were also determined at room temperature. It was found that multi-phased films were formed at lower annealing temperatures and single phase films at higher annealing temperatures. A structural re-orientation as well as a phase transformation from β-In₂Se₃ to γ-In₂Se₃ was observed on annealing at 400 °C.