Study of hot wire chemical vapor deposition technique for silicon thin film

Micro and multi-crystalline silicon thin films have been prepared in the growing rate of more than 10 Å/S by hot wire (HW) CVD. The crystallite size of the films ranges from 0.1 to 1 μm. The effects of processing parameters on the property of the films have been systematically studied. The energy gap ranges from 1.5 to 1.12 eV when substrate temperature changes from 250°C to 450°C. The conductivity of the doped films is as high as 10 (Ω cm)⁻¹. An anomalous behavior of hot palladium wire in an atmosphere of silane at low pressure is reported and preliminarily explained. The reason why tungsten wire is easy to break during silicon thin film deposition by hot wire CVD is discussed.     

Deposition of hydrogenated amorphous silicon (a-Si:H) films by hot-wire chemical vapor deposition (HW-CVD) method: Role of substrate temperature

Hydrogenated amorphous silicon (a-Si:H) thin films were deposited from pure silane (SiH₄) using hot-wire chemical vapor deposition (HW-CVD) method. We have investigated the effect of substrate temperature on the structural, optical and electrical properties of these films. Deposition rates up to 15 Å s⁻¹ and photosensitivity 10⁶ were achieved for device quality material. Raman spectroscopic analysis showed the increase of Rayleigh scattering in the films with increase in substrate temperature. The full width at half maximum of TO peak (Γ_TO) and deviation in bond angle (Δθ) are found smaller than those obtained for P-CVD deposited a-Si:H films. The hydrogen content in the films was found <1 at% over the range of substrate temperature studied. However, the Tauc's optical band gap remains as high as 1.70 eV or much higher. The presence of microvoids in the films may be responsible for high value of band gap at low hydrogen content. A correlation between electrical and structural properties has been found. Finally, the photoconductivity degradation of optimized a-Si:H film under intense sunlight was also studied.     

Influence of silane flow on structural, optical and electrical properties of a-Si:H thin films deposited by hot wire chemical vapor deposition (HW-CVD) technique

The electrical, structural and optical properties of hydrogenated amorphous silicon (a-Si:H) films deposited from pure silane (SiH₄) using hot wire chemical vapor deposition (HW-CVD) technique are systematically studied as a function of silane flow rate between 5 and 30 sccm. We found that the properties are greatly affected by the silane flow rate over the range we studied. The device quality a-Si:H films with a photosensitivity >10⁵ were deposited by HW-CVD at a deposition rate >10 Å s⁻¹ using low silane flow rate. However, a-Si:H films deposited at higher silane flow rate and/or higher deposition rates show degradation in their structural and electrical properties. The FTIR studies indicate that the hydrogen bonding in a-Si:H films shifts from mono-hydrogen (Si–H) to di-hydrogen (Si–H₂) and (Si–H₂)_n complexes when films were deposited at higher silane flow rate. The hydrogen content in the a-Si:H films increases with increase in silane flow rate and was found to be less than 10 at.%. The Raman spectra show increase in disorder and the Rayleigh scattering with increase in silane flow rate. The optical band gap also shows an increasing trend with silane flow rate. Therefore, only the hydrogen content cannot be accounted for the increase in the optical band gap. We think that the increase in the optical band gap may be due to the increase in the voids. These voids reduce the effective density of material and increase the average Si–Si distance, which is responsible for the increase in the band gap. Silane flow rate of 5 sccm, appears to be an optimum flow rate for the growth of mono-hydrogen (Si–H) bonded species having low hydrogen content (4.25 at%) in a-Si:H films at high deposition rate (12.5 Å s⁻¹), high photosensitivity (10⁵) and small structural disorder.     

Simple and fast fabrication of a-Si:H/c-Si hetero-junction solar cells by dual-chamber hot wire chemical vapor deposition

One of the fabrication issues in hetero-junction crystalline Si solar cells is the overhead time between the deposition steps of the top and bottom surfaces, because flipping of the progressing wafer is necessary to process the both sides of the wafer. To reduce the overall processing time by reducing the overhead time, we propose a dual-chamber deposition system, where thin films on the top and bottom surfaces of the Si wafer are simultaneously deposited. We have evaluated the proposed deposition system by demonstrating fabricated hetero-junction crystalline Si solar cells, which were compared with solar cells fabricated by a conventional plasma-enhanced chemical deposition system. We have obtained the power conversion efficiency of 15.5% from solar cells fabricated by our dual-chamber system; and additional analyses confirmed that the proposed dual-chamber system is, in principle, competitive with conventional systems in terms of the fabricated solar cell performance. This novel concept for the fabrication of a hetero-junction crystalline Si solar cell is expected to lay an important foundation in the future thin film crystalline Si based photovoltaic industry.     

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%).     

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.     

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.     

CuGaxSey chalcopyrite-related thin films grown by chemical close-spaced vapor transport (CCSVT) for photovoltaic application: Surface- and bulk material properties, oxidation and surface Ge-doping

Device-grade ternary Cu-Ga-Se chalcopyrite thin films used for photovoltaic energy conversion have been prepared by a novel chemical close-spaced vapor transport (CCSVT) technique developed for a deposition on areas of up to 10×10 cm². A two-step process has been developed which allows the fine tuning of the film composition and the electronic properties. The extension of deposition times in the two-step process led to final film compositions with [Ga]/[Cu] ratios ranging from 0.9 to 5.7, allowing the study of the structural phase transitions. In this paper the main focus of interest is related to the material properties of the device-grade thin films prepared by CCSVT technique. We present our recent studies on (i) the growth, compositional, structural and electronic structural properties, (ii) the degradation under ambient conditions and (iii) the feasibility of n-type doping this p-type semiconducting material by germanium. Thin films were grown with chalcopyrite (1:1:2) and CuGaSe₂-related defect compound structures (DC) with stoichiometries of CuGa₃Se₅ and CuGa₅Se₈. In order to derive the DC structure, X-ray and neutron powder diffraction investigations have been carried out on powders of these CuGaSe₂-related compounds grown by elemental synthesis (powder) and CCSVT (thin films), respectively. We found no hints for an ordering of defects, as proposed in the past and giving name to the so-called Ordered Defect Compounds (ODC) in this and related structures. From our results a growth model is presented for CuGa₃Se₅ formation in gallium-rich CCSVT-grown CuGa_xSe_y films. The chemical and electronic surface and interface structure of CuGaSe₂ thin films with bulk [Ga]/[Cu] ratios between 0.94 and 1.39 is investigated by X-ray and UV-excited photoelectron spectroscopy (XPS and UPS, respectively). A transition of the Cu:Ga:Se surface composition from 1:1:2 for the Cu-rich bulk sample to 1:3:5 for the sample with the highest bulk [Ga]/[Cu] ratio is observed. Simultaneously, a downward shift of the valence band maximum position with respect to the Fermi energy is found. The comparison of the estimated conduction band minimum with that of CdS reveals the formation of a pronounced “cliff-like” conduction band offset at the respective interface.Furthermore, the CuGaSe₂ thin film degradation under ambient as well as under thermal conditions of CuGaSe₂ thin films has been studied by XPS. During thermal oxidation, the formation of predominantly Ga₂O₃ and some amount of SeO₂ were observed, but no copper oxides could be detected in the near-surface region of the thin films. The same oxides are found after native oxidation in air under ambient conditions. An additional sodium oxide compound formed at the thin film surface, Na_xO and Na₂CO₃ after thermal and native oxidation, respectively.Germanium ion implantation technique of the near-surface region of CuGaSe₂ thin films has been used in order to prove the feasibility of n-type doping. In photoluminescence (PL) studies, the occurrence of a new emission line is identified as Ge related and explained as a donor-acceptor-pair (DAP) recombination. The precise role the Ge is playing in this doping of CuGaSe₂ is revealed by X-ray absorption spectroscopy (XANES and EXAFS) and ab initio calculations based on the density functional theory. The studies indicate that the incorporated Ge atoms preferentially occupy Ga sites when relaxation around the dopant is taken into account. Additionally, our corresponding theoretical band structure model predicts the existence of additional localized electronic acceptor and donor defect bands within the band gap of CuGaSe₂ originating from a strong covalent interaction between Ge 4s and Se 4p states for Ge atoms tetrahedrally surrounded by the Se nearest-neighbor atoms. A theoretically predicted anti-bonding Ge-Se4sp³ defect band appearing well above the Fermi level for the Ge¹⁺_Ga point defect system can be directly linked to a Ge-dopant-related donor-acceptor-pair transition as observed in our photoluminescence spectra.     

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.