Preparation of ITO thin films applied in nanocrystalline silicon solar cells

ITO thin films were prepared by changing the experimental parameters including gas flow ratio, sputtering pressure and sputtering time in DC magnetron sputtering equipment. The stable experimental parameters of Ar flow at 70 sccm, O₂ flow at 2.5 sccm ∼ 3.0 sccm, sputtering pressure around 0.5 Pa, and sputtering time of 80 s were obtained. Under these parameters, we had achieved the ITO thin films with low resistivity (<4 × 10⁻⁴ Ω ? cm) and high average transmissivity (95.48%, 350 nm ∼ 1100 nm). These ITO thin films were applied in nanocrystalline silicon solar cells as top transparent conductive layer. The solar cell test result showed that the open circuit voltage (Voc) was up to 534.9 mV and the short circuit current density (Jsc) was 21.56 mA/cm².     

Development of microcrystalline silicon carbide window layers by hot-wire CVD and their applications in microcrystalline silicon thin film solar cells

Microcrystalline silicon carbide (μc-SiC:H) thin films in stoichiometric form were deposited from the gas mixture of monomethylsilane (MMS) and hydrogen by Hot-Wire Chemical Vapor Deposition (HWCVD). These films are highly conductive n-type. The optical gap E₀₄ is about 3.0-3.2 eV. Such μc-SiC:H window layers were successfully applied in n-side illuminated n-i-p microcrystalline silicon thin film solar cells. By increasing the absorber layer thickness from 1 to 2.5 μm, the short circuit current density (j_SC) increases from 23 to 26 mA/cm² with Ag back contacts. By applying highly reflective ZnO/Ag back contacts, j_SC = 29.6 mA/cm² and η = 9.6% were achieved in a cell with a 2-μm-thick absorber layer.     

Novel aspects in thin film silicon solar cells-amorphous, microcrystalline and nanocrystalline silicon

The improvement of photodegradation of a-Si:H has been studied on the basis of controlling the subsurface reaction and gaseous phase reaction. We found that higher deposition temperature, hydrogen dilution and triode method are effective to reduce the SiH₂ density in the film and to suppress the photodegradation of solar cells. These results are explained in terms of the hydrogen elimination reaction in the subsurface region and the contribution of the higher silane radicals to the film growth. The high-rate deposition of μc-Si:H was obtained by means of a high-pressure method and further improvement in deposition rate and the film quality was achieved in combination with the locally high-density plasma, which enables effective dissociation of source gases without thermal damage. It was also found that the deposition pressure is crucial to improve the film quality for device. This technique was successfully applied to the solar cells and an efficiency of 7.9% was obtained at a deposition rate of 3.1 nm/s. The potential application of nanocrystalline silicon is also discussed.     

Surface passivation of crystalline silicon by Cat-CVD amorphous and nanocrystalline thin silicon films

In this work, we study the electronic surface passivation of crystalline silicon with intrinsic thin silicon films deposited by Catalytic CVD. The contactless method used to determine the effective surface recombination velocity was the quasi-steady-state photoconductance technique. Hydrogenated amorphous and nanocrystalline silicon films were evaluated as passivating layers on n- and p-type float zone silicon wafers. The best results were obtained with amorphous silicon films, which allowed effective surface recombination velocities as low as 60 and 130 cm s⁻¹ on p- and n-type silicon, respectively. To our knowledge, these are the best results ever reported with intrinsic amorphous silicon films deposited by Catalytic CVD. The passivating properties of nanocrystalline silicon films strongly depended on the deposition conditions, especially on the filament temperature. Samples grown at lower filament temperatures (1600 °C) allowed effective surface recombination velocities of 450 and 600 cm s⁻¹ on n- and p-type silicon.     

Applications of microcrystalline hydrogenated cubic silicon carbide for amorphous silicon thin film solar cells

We demonstrated the fabrication of n-i-p type amorphous silicon (a-Si:H) thin film solar cells using phosphorus doped microcrystalline cubic silicon carbide (μc-3C-SiC:H) films as a window layer. The Hot-wire CVD method and a covering technique of titanium dioxide TiO₂ on TCO was utilized for the cell fabrication. The cell configuration is TCO/TiO₂/n-type μc-3C-SiC:H/intrinsic a-Si:H/p-type μc- SiC_x (a-SiC_x:H including μc-Si:H phase)/Al. Approximately 4.5% efficiency with a V_oc of 0.953 V was obtained for AM-1.5 light irradiation. We also prepared a cell with the undoped a-Si_1−xC_x:H film as a buffer layer to improve the n/i interface. A maximum V_oc of 0.966 V was obtained.     

Intrinsic microcrystalline silicon prepared by hot-wire chemical vapour deposition for thin film solar cells

Microcrystalline silicon (μc-Si:H) prepared by hot-wire chemical vapour deposition (HWCVD) at low substrate temperature T_S and low deposition pressure exhibits excellent material quality and performance in solar cells. Prepared at T_S below 250 °C, μc-Si:H has very low spin densities, low optical absorption below the band gap, high photosensitivities, high hydrogen content and a compact structure, as evidenced by the low oxygen content and the weak 2100 cm⁻¹ IR absorption mode. Similar to PECVD material, solar cells prepared with HWCVD i-layers show increasing open circuit voltages V_oc with increasing silane concentration. The best performance is achieved near the transition to amorphous growth, and such solar cells exhibit very high V_oc up to 600 mV. The structural analysis by Raman spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM) shows considerable amorphous volume fractions in the cells with high V_oc. Raman spectra show a continuously increasing amorphous peak with increasing V_oc. Crystalline fractions X_C ranging from 50% for the highest V_oc to 95% for the lowest V_oc were obtained by XRD. XRD-measurements with different incident beam angles, TEM images and electron diffraction patterns indicate a homogeneous distribution of the amorphous material across the i-layer. Nearly no light induced degradation was observed in the cell with the highest X_C, but solar cells with high amorphous volume fractions exhibit up to 10% degradation of the cell efficiency.     

Room temperature synthesis of nanocrystalline silicon by aluminium induced crystallization for solar cell applications

The aim of this study is to synthesis large area, plastic compatible of p-type nanocrystalline silicon through conventional sputter system. The growth of and p-type doping of nanocrystalline silicon onto plastic substrates using D.C. magnetron sputtering was investigated. The film properties were examined by Raman spectroscopy, X-ray Diffraction, scanning electron microscopy and energy dispersive spectrometry. Nanocrystalline silicon was achieved with careful control of ion bombardment energy. Through a narrow experimental, window room temperature, nanocrystalline silicon can be synthesised on aluminium. It is believed the aluminium reduces the required energy for crystallite nucleation. PN junction was formed through sputtering of Al/Al-Si/n-type Si/AZO structure. The I-V characteristic showed good rectifying behaviour and confirms p-type doping via aluminium induced crystallization.     

Photoconductivity spectroscopy in hydrogenated microcrystalline silicon thin films

Steady-state photoconductivity and sub-bandgap absorption measurements by the dual-beam photoconductivity (DBP) method were carried out on undoped hydrogenated microcrystalline silicon thin films prepared by VHF-PECVD and hot-wire chemical vapor deposition. The results are compared with those of the constant-photocurrent method (CPM) and photothermal deflection spectroscopy (PDS). It is found that DBP, CPM, and PDS provide complementary data on the optoelectronic processes in microcrystalline silicon.     

Ultrafast deposition of silicon nitride and semiconductor silicon thin films by hot wire chemical vapor deposition

The technology of Hot Wire Chemical Vapor Deposition (HWCVD) or Catalytic Chemical Vapor Deposition (Cat-CVD) has made great progress during the last couple of years. This review discusses examples of significant progress. Specifically, silicon nitride deposition by HWCVD (HW-SiN_x) is highlighted, as well as thin film silicon single junction and multijunction junction solar cells. The application of HW-SiN_x at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency and preliminary tests of our transparent and dense material obtained at record high deposition rates of 7.3 nm/s yielded 14.9% efficiency. We also present recent progress on Hot-Wire deposited thin film solar cells. The cell efficiency reached for (nanocrystalline) nc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.6%. Such cells, used in triple junction cells together with Hot-Wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.9% efficiency. Further, in our research on utilizing the HWCVD technology for roll-to-roll production of flexible thin film solar cells we recently achieved experimental laboratory scale tandem modules with HWCVD active layers with initial efficiencies of 7.4% at an aperture area of 25 cm².     

Electronic transport properties of microcrystalline silicon thin films prepared by VHF-PECVD

Steady-state photocarrier grating (SSPG) and steady-state photoconductivity, _ph, experiments have been carried out to investigate the electronic transport properties of undoped hydrogenated microcrystalline silicon (c-Si : H) films prepared with very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). Material with different crystalline volume fractions was obtained by variation of the silane concentration (SC) in the process gas mixture. Pure amorphous silicon material was investigated for comparison. The ambipolar diffusion length, L_amb, which is dominated by the minority carrier properties, is obtained both from the best fit to the experimental photocurrents ratio, , versus grating period (), and from the Balberg plot for the generation rates between 10¹⁹ and 10²¹ cm^–3 s^–1. L_amb increases from 86 nm with increasing SC and peaks around 200 nm for the SC=5.6% and decreases again for higher SCs. L_amb values obtained from the intercept of the Balberg plot result in a small difference of around 5% for most of the samples. Minority carrier mobility-lifetime ()-products are much lower than those of majority carriers, however, both majority and minority carrier -products in microcrystalline silicon are higher than those of undoped hydrogenated amorphous silicon. The grating quality factor (₀) changes from 0.70 to 1.0 indicating almost negligible surface roughness present in the samples.     

Mechanical properties of amorphous and microcrystalline silicon films

Hydrogen-free amorphous silicon (a-Si) films with thickness of 4.5-6.5 μm were prepared by magnetron sputtering of pure silicon. Mechanical properties (hardness, intrinsic stress, elastic modulus), and film structure (Raman spectra, electron diffraction) were investigated in dependence on the substrate bias and temperature. The increasing negative substrate bias or Ar pressure results in simultaneous reducing compressive stress, the film hardness and elastic modulus. Vacuum annealing or deposition of a-Si films at temperatures up to 600 °C saving amorphous character of the films, results in reducing compressive stress and increasing the hardness and elastic modulus. The latter value was always lower than that for monocrystalline Si(111). The crystalline structure (c-Si) starts to be formed at deposition temperature of ∼ 700 °C. The hardness and elastic modulus of c-Si films were very close to monocrystalline Si(111). Phase transformations observed in the samples at indentation depend not only on the load and loading rate but also on the initial phase of silicon. However, the film hardness is not too sensitive to the presence of phase transformations.     

Some physical properties of Sn-doped CdO thin films prepared by chemical bath deposition

Undoped and Sn-doped CdO thin films were prepared by the chemical bath deposition method by means of a procedure that improves the deposition efficiency. All as-grown films were crystallized in the cubic structure of cadmium peroxide (CdO₂) and transformed into CdO with a cubic structure after an annealing process. The as-grown films have a high resistivity (> 10⁶ Ω cm) and an optical bandgap around 3.6 eV. Undoped CdO displays an optical bandgap around 2.32–2.54 eV and has an electrical conductivity of 8 × 10^− 4 Ω cm. The Sn incorporation into CdO produces a blue shift in the optical bandgap (from 2.55 to 2.84 eV) and a decrease in the electrical conductivity.The deposition procedure described here gives colloid-free surface thin films as indicated by the surface morphology analysis.     

Elaboration of heterojunction solar cells by the deposit of tin oxide thin films on silicon by APCVD

We present in this paper the experimental results concerning the deposition of tin oxide SnO₂ on silicon substrate by the technique of Atmospheric Pressure Chemical Vapour Deposition (APCVD). The obtained Si-SnO₂ heterostructure is used for photovoltaic application. The properties of tin oxide thin films deposited by APCVD technique depends on three parameters which are the deposition temperature, the deposition time and the oxygen pressure. We have obtained the optimal value of each parameter by the measurement of the open-circuit voltage of the obtained Si-SnO₂ heterostructure. So, at the temperature of 490 °C during 12 min of deposition time under oxygen pressure of 1 bar we have obtained tin oxide thin layers exhibiting the best optoelectronic and morphology characteristics. These thin films are polycrystalline and present a resistivity of 1.3 · 10^− 3 Ω cm and a refractive index of 1.72. The Si-SnO₂ heterojunction solar cell that has an area of 2 × 1.5 cm² is characterised by the current-voltage I(V) measurement. It gives an open circuit voltage of 0.45 V and a short circuit current of 74 mA.     

Effect of HCl addition on the crystalline fraction in silicon thin films prepared by hot-wire chemical vapor deposition

In an effort to increase the crystalline fraction of silicon films directly deposited on a glass substrate by hot-wire chemical vapor deposition, the effect of HCl addition was studied. The silicon film was deposited on a glass substrate at 320 °C under a reactor pressure of 1333 Pa at the wire temperature of 1600 °C with 10%SiH₄–90%He at a fixed flow rate 100 standard cubic centimeter per minute (sccm) and HCl varied at 0, 10, 16 and 28 sccm. With increasing HCl, the crystalline fraction of silicon was increased as revealed by Raman spectra but the growth rate was decreased.     

Nanostructure, electrical and optical properties of p-type hydrogenated nanocrystalline silicon films

In this paper, p-type hydrogenated nanocrystalline (nc-Si:H) films were prepared on corning 7059 glass by plasma-enhanced chemical vapor deposition (PECVD) system. The films were deposited with radio frequency (RF) (13.56 MHz) power and direct current (DC) biases stimulation conditions. Borane (B₂H₆) was a doping agent, and the flow ratio η of B₂H₆ component to silane (SiH₄) was varied in the experimental. Films’ surface morphology was investigated with atomic force microscopy (AFM); Raman spectroscopy, X-ray diffraction (XRD) was performed to study the crystalline volume fraction X_c and crystalline size d in films. The electrical and optical properties were gained by Keithly 617 programmable electrometer and ultraviolet-visible (UV-vis) transmission spectra, respectively. It was found that: there are on the film surface many faulty grains, which formed spike-like clusters; increasing the flow ratio η, crystalline volume fraction X_c decreased from 40.4% to 32.0% and crystalline size d decreased from 4.7 to 2.7 nm; the optical band gap E_g^opt increased from 2.16 to 2.4 eV. The electrical properties of p-type nc-Si:H films are affected by annealing treatment and the reaction pressure.     

Low-temperature PECVD deposition of highly conductive microcrystalline silicon thin films

In this paper, we present the characterization results of doped n-type microcrystalline hydrogenated-silicon (c-Si : H) films deposited in a plasma-enhanced chemical vapor deposition in the temperature range between 70 and 250 °C. The interest in these films arises from the fact that they combine the high optical absorption of amorphous silicon with the electronic behavior of the crystalline silicon, making them interesting for the production of large electronic devices such as solar cells, image sensors, and flat panels. It is shown that n-type c-Si : H films with high electrical conductivity can be obtained even at low temperature deposition, around 120 °C (=2.9 S cm^–1). The structural properties of the films have been studied by Raman and infrared spectroscopy that allowed for the determination of the crystalline fraction. Electrical measurements were performed by a.c. impedance spectroscopy, Hall effect, and dark conductivity. Characteristics suitable for application in electronic devices were obtained with the developed deposition parameters set-up; the best dark conductivity values were around 1 S cm^–1 for deposition temperatures within the 120–140 °C range. Some conclusions regarding the correlation between electrical and structural properties are presented for the considered temperature range.     

Nanocrystalline silicon thin films on PEN substrates

We study the structural and electrical properties of intrinsic layer growth close to the transition between amorphous silicon (a-Si:H) and nanocrystalline silicon (nc-Si:H), deposited on glass and PEN without intentional heating. These samples showed different behaviour in Raman shift and XRD spectra when compared with that of samples deposited at 200 °C. Electrical properties of these films also reflect the transition between a-Si:H and nc-Si:H, and put in evidence some differences between the microstructure of the films grown on PEN and on glass.P- and n-doped layers were deposited onto glass substrate without intentional heating and at 100 °C with thicknesses ranging from 1000 nm to 35 nm. Conductivity measurements indicate the capability of doping this material, but, for very thin layers, substrate heating was found to be essential.     

Correlation of structural and optoelectronic properties of thin film silicon prepared at the transition from microcrystalline to amorphous growth

Photovoltaic properties of 4 µm thick microcrystalline silicon p–i–n solar cells have been studied, over a range of crystallinity determined using Raman spectroscopy. Low-crystallinity material (below 10%) appears to absorb disproportionately strongly in the infrared, possibly due to increased light scattering or to relaxation of the crystal momentum selection rule. A minimum in solar cell efficiency is observed under AM1.5 illumination when V_OC ≈ 580 mV, with blue response most strongly affected. This is consistent with a reduction in electron mobility to a value below that of amorphous silicon for low-crystallinity material, in agreement with time-of-flight measurements.     

Formation of microcrystalline silicon films using rapid crystal aluminum induced crystallization under low-temperature rapid thermal annealing

The process of obtaining thin film solar cells using the method of aluminum-induced crystallization under rapid thermal annealing (RTA) was investigated. 200-nm-thick amorphous Si (a-Si) film was deposited on a glass substrate using an ultra-high vacuum ion beam sputtering system. A 50-nm-thick crystal aluminum layer was then evaporated and deposited onto the a-Si film. In contrast to conventional furnace annealing, RTA can supply rapid thermal energy so that a-Si can be induced into microcrystalline-Si (μc-Si) in a short time at low temperatures. The crystal Al may promote the crystallization reaction because its surface energy is higher than 0.89 N/m, which is the minimum energy required to produce the (111) orientation. Free Si atoms are induced at the interface of the Al and Si sub-layers by the diffusion of Al along the grain boundaries. The Raman spectrum shows that the sample could be induced to crystallize at 350 °C. After the aluminum was etched, the maximum grain size was 4 μm. The carrier mobility was between 6.2 cm²/Vs and 18.8 cm²/Vs. The proposed method can be used to obtain μc-Si with reduced energy and time during the thermal annealing.     

Determination of the optical properties of non-uniformly thick non-hydrogenated sputtered silicon thin films on glass

An improved envelope method (EM) is presented in this paper that allows the determination of the refractive index (n_f) and absorption coefficient (_f) of non-uniformly thick, absorbing films on a slightly absorbing substrate from a single transmission measurement. The limitation of the previous version of the EM [R. Swanepoel, J. Phys. E: Sci. Inst. 17 (1984) 896] only permitted the evaluation of samples that exhibited a transparent region in the near infrared (NIR). As an initial test of the improved EM, n_f and _f of a 0.5-μm thick epitaxially grown silicon-on-sapphire (SOS) film were determined over the range of 1.1–3.2 eV, with increased absorption being observed at the silicon: sapphire interface. Subsequently, sputtered amorphous silicon (a-Si) films, which exhibit absorption throughout the visible–NIR spectrum, were successfully characterised and a definite trend towards lower absorption coefficients for films deposited at higher temperatures was observed. After the a-Si films were subjected to solid phase crystallisation (SPC), increased sub-bandgap absorption was attributed to higher defect levels in the films, which also resulted in amorphous features remaining in the Raman spectra.