Preparation of highly conductive p-type μc-Si:H window layer using lower concentration of hydrogen in the rf glow discharge plasma

Boron doped p-type hydrogenated microcrystalline silicon (μc-Si:H) films have been prepared by radio-frequency glow discharge method. Highly conductive p-type μc-Si:H films can be obtained even with lower concentration of hydrogen in the rf glow discharge plasma if chamber pressure is low. Effects of increase in hydrogen (H₂) flow rate and chamber pressure have been studied. The structural properties of the films have been studied by X-ray diffractometry. The electrical and optical characterization have been done by dark conductivity, Hall measurements and optical absorption measurements respectively. Film with conductivity 0.1(Ω-cm)⁻¹ with band gap 2.1 eV has been obtained.     

Characterization of undoped μc-SiO:H films prepared from (SiH4+CO2+H2)-plasma in RF glow discharge

Undoped hydrogenated microcrystalline silicon oxygen alloy films (μc-SiO:H) have been prepared from (SiH₄+CO₂+H₂)-plasma in RF glow discharge at a high H₂ dilution, moderately high RF power and substrate temperature. A detailed characterization of the films has been done by electrical, optical as well as structural studies, e.g., IR absorption spectroscopy, Raman scattering and transmission electron microscopy. The presence of a very small amount of oxygen induces the crystallization process, which fails to sustain at a higher oxygen dilution. At higher deposition temperature and in improved μc-network H content reduces, however, O incorporation is favoured. Sharp crystallographic rings in the electron diffraction pattern identify several definite planes of c-Si and no such crystal planes from c-SiO_X is detected.     

The creation of hydrogen radicals by the hot-wire technique and its application for μc-Si:H

A new method, Hot-wire assisted PECVD, is proposed for preparing μc-Si:H films. This method is constructed of two parts, plasma-enhanced CVD (PECVD) and hot-wire for exciting hydrogen. Both the crystalline grain size and the volume fraction of Si crystallites in the film are improved by this preparation method compared with those of the conventional PECVD. The results obtained are interpreted by the enhanced hydrogen-radical density. The importance of control of H radicals is discussed for the growth of the crystallite.     

Temperature dependence of absorption coefficient spectra for μc-Si films by resonant photothermal bending spectroscopy

Resonant photothermal bending spectroscopy (R-PBS) has been developed for estimating absorption coefficient spectra of thin film semiconductors. This technique has been applied to hydrogenated microcrystalline silicon (μc-Si:H) films at different measurement temperatures. It is found that absorption coefficient of μc-Si:H films at 0.7–1.1 eV is relevant for the localized states and decreases with increasing measurement temperature. The localized state exists at 0.7 eV in the band gap from the band edge. The origin of the absorption is also discussed.     

Microcrystalline silicon solar cell using p-a-Si:H window layer deposited by photo-CVD method

A p-a-Si:H layer, deposited by a photo-assisted chemical vapor deposition (photo-CVD) method, was adopted as the window layer of a hydrogenated microcrystalline silicon (μc-Si:H) solar cell instead of the conventional p-μc-Si:H layer. We verified the usefulness of p-a-Si:H for the p-layer of the μc-Si:H solar cell by applying it to SnO₂-coated glass substrate. It was found that the quantum efficiency (QE) characteristics and solar cell performance strongly depend on the p-a-Si:H layer thicknesses. We applied boron-doped nanocrystalline silion (nc-Si:H) p/i buffer layers to μc-Si:H solar cells and investigated the correlation of the p/i buffer layer B₂H₆ flow rate and solar cell performance. When the B₂H₆ flow rate was 0.2 sccm, there was a little improvement in fill factor (FF), but the other parameters became poor as the B₂H₆ flow rate increased. This is because the conductivity of the buffer layer decreases as the B₂H₆ flow rate increases above appropriate values. A μc-Si:H single-junction solar cell with ZnO/Ag back reflector with an efficiency of 7.76% has been prepared.     

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%).     

Extension of the a-Si:H electronic transport model to μc-Si:H: use of the μτ product to correlate electronic transport properties and solar cell performances

The aim of this communication is to show that it is possible to extend the model of the electronic transport developed for amorphous silicon (a-Si:H) to microcrystalline silicon (μc-Si:H). By describing the electronic transport with the μ⁰τ^R products (mobility×recombination time) as a function of the Fermi level, we observed the same behaviour for both materials, indicating a similar type of recombination. Moreover, applying the normalised μ⁰τ⁰ product (mobility×life-time) obtained by combining the photoconductivity (σ_photo) and the ambipolar diffusion length (L_amb) measured in individual layers, we are able, as in the case of a-Si:H, to predict the quality of the solar cells incorporating these layers as the active i layer.     

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.     

Structural, optical and electrical characterizations of μc-Si:H films deposited by PECVD

The effects of the silane concentration f on the structural, optical and electrical properties of undoped hydrogenated silicon films prepared in a plasma-enhanced chemical vapour deposition system have been studied. The electrical conductivity and Hall mobility appear to be controlled by microstructures induced by silane concentration and a clear electrical transport transition from crystalline to amorphous phase has been found when 3%<f<4%. A two-phase model has been used to discuss the electrical properties.     

p-doped μc-Si:H window layers prepared by hot-wire CVD for amorphous solar cell application

We report on boron-doped μc-Si:H films prepared by hot-wire chemical vapor deposition (HWCVD) using silane as a source gas and trimethylboron (TMB) as a dopant gas and their incorporation into all-HW amorphous silicon solar cells. The dark conductivity of these films was in the range of 1–10 (Ω cm)⁻¹. The open circuit voltage V_oc of the solar cells was found to decrease from 840 mV at low hydrogen dilution H-dil=91% to 770 mV at high H-dil =97% during p-layer deposition which can be attributed to the increased crystallinity at higher H-dil and to subsequent band edge discontinuity between μc-Si:H p- and amorphous i-layer. The short circuit current density J_sc and the fill factor FF show an optimum at an intermediate H-dil and decrease for the highest H-dil. To improve the conversion efficiency and the reproducibility of the solar cells, an amorphous-like seed layer was incorporated between TCO and the bulk p-layer. The results obtained until now for amorphous solar cells with and without the seed layer are presented. The I–V parameters for the best p–i–n solar cell obtained so far are J_sc=13.95 mA/cm², V_oc=834 mV, FF=65% and η=7.6%, where the p-layers were prepared with 2% TMB. High open circuit voltages up to 847 mV could be achieved at higher TMB concentrations.     

Absorption coefficient spectra of μc-Si in the low-energy region 0.4–1.2 eV

Optical absorption spectra in the low-energy region 0.4–1.2 eV is reported for μc-Si:H using a photothermal deflection spectroscopy technique. Absorption coefficient spectra in the low-energy region contain important information related to defects and hydrogen. It is demonstrated that there is a good correlation between electron spin densities and integrated absorption coefficient spectra from 0.7 to 1.2 eV. The amount of the hydrogen molecules in microvoids is much larger in μc-Si:H than that in a-Si:H. Light illumination effects in PDS spectra has also been studied from a view point of photo degradation of the μc-Si:H.     

Numerical modelling of trap-assisted tunnelling mechanism in a-Si:H and μc-Si n/p structures and tandem solar cells

The trap-assisted tunnelling theory was developed to describe the tunnelling of charge carriers via bandgap energy levels in structures based on hydrogenated amorphous silicon and microcrystalline silicon. Its implementation into ASPIN numerical simulator is explained. Models that were verified on n/p single junctions were applied in the tunnel recombination junction area of a tandem solar cell. Thus, it is possible to study a multi-layer solar cell without separately simulating any of its components.     

Optimization of n-doping in n-type a-SI : H/p-type textured c-Si heterojunction for photovoltaic applications

In this paper is investigated an heterostructure based on p-doped textured wafers of crystalline silicon on which we deposited a buffer of lightly n-doped amorphous layer and an n⁺-doped layer. In particular, the effect of n-doping of amorphous silicon on the photovoltaic characteristics of the heterojunctions is studied. Starting from an extensive analysis of the doping efficiency of phosphine in microdoped materials we fabricated several devices varying the PH₃/SiH₄ ratio in the PECVD system. An optimum value of this ratio is found at 10⁻², corresponding to the maximum of the photovoltaic efficiency of 11.5%.     

Microcrystallisation in Si:H: the effect of gas pressure in Ar-diluted SiH4 plasma

Using noble gas argon as a diluent of SiH₄ in RF glow discharge, undoped μc-Si:H thin films have been developed at a low power density of 30 mW/cm². It has been found that the gas pressure is a critical factor for the growth of μc-Si:H films. Undoped μc-Si:H films having σ_D10⁻⁶ S/cm and ΔE<0.57 eV have been obtained at and above a critical pressure of 0.8 Torr. When the RF power density is increased to 90 mW/cm², a more crystalline as well as highly conducting (σ_D10⁻⁴ S/cm) μc-Si:H film has been achieved at a deposition rate of 30 Å/min, which is much higher than that attained from H₂-diluted SiH₄ plasma, by conventional approach. The crystallinity of the films has been identified by the sharp Raman peak at 520 cm⁻¹ and a large number of micrograins in the TEM micrographs. The metastable state of Ar, denoted as Ar^*, plays the crucial role in inducing microcrystallisation by transferring its de-excitation energy at the surface of the growing film. A mechanism has been proposed to explain the dependence of the formation of μc-Si:H film on the working gas pressure in the plasma.     

Doping of a-SiCX:H films including μc-Si:H by hot-wire CVD and their application as a wide gap window for heterojunction solar cells

Impurity doping using B₂H₆ gas using hot-wire CVD has been tried for hydrogenated amorphous silicon-carbon (a-SiC_X:H) alloy films including hydrogenated microcrystalline silicon (μc-Si:H) with carbon content, C/(Si+C), of about 28%. The dark- and photoconductivities of B-doped samples are larger than those of undoped samples. The activation energy for dark conductivity of the B-doped sample with the doping gas ratio, B₂H₆/(SiH₄+CH₄), of about 0.054% is 0.17 eV. This value is smaller than that of the undoped sample. The P-doped samples also show larger dark- and photoconductivities and smaller activation energy than the undoped samples.     

Influence of hydrogen dilution on structural, electrical and optical properties of hydrogenated nanocrystalline silicon (nc-Si:H) thin films prepared by plasma enhanced chemical vapour deposition (PE-CVD)

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were deposited from pure silane (SiH₄) and hydrogen (H₂) gas mixture by conventional plasma enhanced chemical vapour deposition (PE-CVD) method at low temperature (200 °C) using high rf power. The structural, optical and electrical properties of these films are carefully and systematically investigated as a function of hydrogen dilution of silane (R). Characterization of these films with low angle X-ray diffraction and Raman spectroscopy revealed that the crystallite size in the films tends to decrease and at same time the volume fraction of crystallites increases with increase in R. The Fourier transform infrared (FTIR) spectroscopic analysis showed at low values of R, the hydrogen is predominantly incorporated in the nc-Si:H films in the mono-hydrogen (SiH) bonding configuration. However, with increasing R the hydrogen bonding in nc-Si:H films shifts from mono-hydrogen (SiH) to di-hydrogen (SiH₂) and (SiH₂)_n complexes. The hydrogen content in the nc-Si:H films decreases with increase in R and was found less than 10 at% over the entire studied range of R. On the other hand, the Tauc's optical band gap remains as high as 2 eV or much higher. The quantum size effect may responsible for higher band gap in nc-Si:H films. A correlation between electrical and structural properties has been found. For optimized deposition conditions, nc-Si:H films with crystallite size 7.67 nm having good degree of crystallinity (84% ) and high band gap (2.25 eV) were obtained with a low hydrogen content (6.5 at%). However, for these optimized conditions, the deposition rate was quite small (1.6 Å/s).     

The role of the ZnO buffer layer in Al/Si interdiffusion in α-Si : H solar cells on flexible substrates

Results of a study on the interdiffusion of Al and α-Si : H, occurring in cells grown on a KAPTON/Al substrate, are presented. Cell parameters of a series of cells grown at temperatures ranging from 100°C to 200°C are presented for KAPTON/Al and KAPTON/Al/ZnO substrates, where a thin ZnO buffer layer was inserted for the latter series of substrates. It is demonstrated that the implementation of this buffer layer results in a significant increase in cell efficiency. With SIMS and SXPS depth profiles, it is demonstrated that cells grown on substrates without the ZnO layer are destroyed as a result of the interdiffusion of α-Si : H and Al, and that the presence of the ZnO buffer layer impedes this process. It is argued that, apart from the well-known enhanced reflectance and resulting improved cell characteristics caused by the insertion of this buffer layer, the main effect of the buffer layer (in cells grown on aluminized flexible substrates) is to impede the interdiffusion of Al and α-Si : H at the semi-conductor/metal interface.     

Synthesis of a-Si:H/μc-Si:H multilayer structures by hot wire chemical vapor deposition (HW-CVD) technique: Study of opto-electronic and photovoltaic properties

Multilayer structures of the type a-Si:H/μc-Si:H were fabricated for the first time by hot wire chemical vapor deposition (HW-CVD) technique. These multilayers were studied for their opto-electronic and photovoltaic properties as a function of a-Si:H sublayer thickness. The microcrystalline phase of a-Si (μc-Si:H) of thickness 250 Å have been used to create drift field in these multilayer structures. The quantum size and photovoltaic effects are observed in these multilayer structures. The persistent photoconductivity measurements clearly indicate the existence of interface defects and spatial charge separation due to the formation of p-n junction field. The best photovoltaic performance was obtained with the fill factor 0.4062 and conversion efficiency (η) 2.08% over an active area of 0.0132 cm². The advantage in these multilayer structures is that no hazardous gases are involved in the fabrication process because no intentional doping is performed and all depositions were carried out in a single deposition chamber.     

The influence of metal contacts and ZnO buffer-layer on the low-temperature crystallization of α-Si : H in flexible solar cells

It is demonstrated that crystallization of α-Si : H in cells grown on metallized polymer substrates occurs at temperatures below 160°C. X-ray diffraction and Raman studies indicate that the extent of crystallization is larger for silver than for aluminum coated polymers, and increases with deposition temperature. Results are presented for the strong impediment of the crystallization of α-Si : H with the insertion of a thin ZnO buffer-layer between the metal and α-Si : H. It is further demonstrated that aluminum crystallizes when α-Si:H is deposited onto it.