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.     

Annealing optimization of silicon nitride film for solar cell application

Hydrogenated films of silicon nitride (SiNx:H) is commonly used as an antireflection coating as well as passivation layer in crystalline silicon solar cell. SiNx:H films deposited at different conditions in Plasma Enhanced Chemical Vapor Deposition (PECVD) reactor were investigated by varying annealing condition in infrared (IR) heated belt furnace to find the optimized condition for the application in silicon solar cells. By varying the gases ratio (R = NH₃/SiH₄ + NH₃) during deposition, the SiNx:H films of refractive indices 1.85-2.45 were obtained. Despite the poor deposition rate, the silicon wafer with SiNx:H film deposited at 450 °C showed the best effective minority carrier lifetime. The film deposited with the gases ratio of 0.57 shows the best peak of carrier lifetime at the annealing temperature of 800 °C. The single crystalline silicon solar cells fabricated in conventional industrial production line applying the optimized film deposition and annealing conditions on large area substrates (125 mm × 125 mm) were found to have the conversion efficiencies as high as 17.05 %. Low cost and high efficiency single crystalline silicon solar cells fabrication sequence employed in this study has also been reported in this paper.     

Hot Wire CVD for thin film triple junction cells and for ultrafast deposition of the SiN passivation layer on polycrystalline Si solar cells

We present recent progress on hot-wire deposited thin film solar cells and applications of silicon nitride. The cell efficiency reached for μc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.5%, in line with the state-of-the-art level for μc-Si:H n-i-p's for any method of deposition. Such cells, used in triple junction cells together with hot-wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.5% efficiency. The single junction μc-Si:H n-i-p cell is entirely stable under prolonged light soaking. The triple junction cell, including protocrystalline i-layers, is within 3% stable, due to the limited thicknesses of the two top cells. The application of SiN_x:H at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency. We have also achieved record high deposition rates of 7.3 nm/s for transparent and dense SiN_x;H. Hot-wire SiN_x:H is likely to be the first large commercial application of the Hot Wire CVD (Cat-CVD) technology.     

Microcrystalline silicon carbide alloys prepared with HWCVD as highly transparent and conductive window layers for thin film solar cells

Crystalline silicon carbide alloys have a very high potential as transparent conductive window layers in thin-film solar cells provided they can be prepared in thin-film form and at compatible deposition temperatures. The low-temperature deposition of such material in microcrystalline form (µc-Si:C:H) was realized by use of monomethylsilane precursor gas diluted in hydrogen with the Hot-Wire Chemical Vapor Deposition process. A wide range of deposition parameters has been investigated and the structural, electronic and optical properties of the µc-SiC:H thin films have been studied. The material, which is strongly n-type from unintentional doping, has been used as window layer in n-side illuminated microcrystalline silicon solar cells. High short-circuit current densities are obtained due to the high transparency of the material resulting in a maximum solar cell conversion efficiency of 9.2%.     

High efficiency microcrystalline silicon solar cells with Hot-Wire CVD buffer layer

Microcrystalline silicon (μc-Si:H) solar cells with i-layers deposited by hot wire chemical vapor deposition (HWCVD) exhibit higher open circuit voltage and fill factor than the cells with i-layers deposited by plasma enhanced (PE)-CVD. Inserting an intrinsic μc-Si:H p/i buffer layer prepared by HWCVD into PECVD cells nearly eliminates these differences. The influence of buffer layer properties on the performance of μc-Si:H solar cells was investigated. Using such buffer layers allows to apply high deposition rate processes for the μc-Si:H i-layer material yielding a high efficiency of 10.3% for a single junction μc-Si:H solar cell.     

Amorphous silicon thin film solar cells deposited entirely by hot-wire chemical vapour deposition at low temperature (< 150 °C)

Amorphous silicon n-i-p solar cells have been fabricated entirely by Hot-Wire Chemical Vapour Deposition (HW-CVD) at low process temperature < 150 °C. A textured-Ag/ZnO back reflector deposited on Corning 1737F by rf magnetron sputtering was used as the substrate. Doped layers with very good conductivity and a very less defective intrinsic a-Si:H layer were used for the cell fabrication. A double n-layer (µc-Si:H/a-Si:H) and µc-Si:H p-layer were used for the cell. In this paper, we report the characterization of these layers and the integration of these layers in a solar cell fabricated at low temperature. An initial efficiency of 4.62% has been achieved for the n-i-p cell deposited at temperatures below 150 °C over glass/Ag/ZnO textured back reflector.     

Improvement of the efficiency of triple junction n-i-p solar cells with hot-wire CVD proto- and microcrystalline silicon absorber layers

Hot-wire chemical vapour deposition (HWCVD) was applied for the deposition of intrinsic protocrystalline (proto-Si:H) and microcrystalline silicon (μc-Si:H) absorber layers in thin film solar cells. For a single junction μc-Si:H n-i-p cell on a Ag/ZnO textured back reflector (TBR) with a 2.0 μm i-layer, an 8.5% efficiency was obtained, which showed to be stable after 750 h of light-soaking. The short-circuit current density (J_sc) of this cell was 23.4 mA/cm², with a high open-circuit voltage (V_oc) and fill factor (FF) of 0.545 V and 0.67.Triple junction n-i-p cells were deposited using proto-Si:H, plasma-deposited proto-SiGe:H and μc-Si:H as top, middle and bottom cell absorber layers. With Ag/ZnO TBR's from our lab and United Solar Ovonic LLC, respective initial efficiencies of 10.45% (2.030 V, 7.8 mA/cm², 0.66) and 10.50% (2.113 V, 7.4 mA/cm², 0.67) were achieved.     

A direct correlation between film structure and solar cell efficiency for HWCVD amorphous silicon germanium alloys

The film structure and H bonding of high deposition rate a-SiGe:H i-layers, deposited by HWCVD and containing ~ 40 at.% Ge, have been investigated using deposition conditions which replicate those used in n-i-p solar cell devices. Increasing the germane source gas depletion in HWCVD causes not only a decrease in solar cell efficiency from 8.64% to less than 7.0%, but also an increase in both the i-layer H preferential attachment ratio (PA) and the film microstructure fraction (R?). Measurements of the XRD medium range order over a wide range of germane depletion indicate that this order is already optimum for the HWCVD i-layers, suggesting that energetic bombardment of a-SiGe:H films may not always be necessary to achieve well ordered films. Preliminary structural comparisons are also made between HWCVD and PECVD device layers.     

Continuous hot-wire chemical vapor deposition on moving glass substrates

Hot Wire Chemical Vapor Deposition (HWCVD) is a very suitable technique for homogeneous deposition of thin films on continuously moving substrates in an in-line manufacturing system. This process is further aided by the fact that transport of insulating substrates (such as glass) during deposition can be easily arranged as the substrate is not part of the decomposition mechanism as in plasma enhanced CVD. Rigorous grounding of the moving substrates is not required, and no special care needs to be taken to make shields or liners equipotential planes. Moreover, as the creation of dust particles in the gas phase can be avoided, deposition could be undertaken with the substrates facing upward, thus further simplifying the mounting of the substrates. Amorphous as well as microcrystalline silicon thin films with device-quality properties have been achieved on moving substrates. The first p-i-n solar cells made with a 300-nm thick i-layer that was deposited on a linearly moving substrate already showed efficiencies of 6.4%, despite two air breaks that were needed in these tests.     

Hot wire CVD deposition of nanocrystalline silicon solar cells on rough substrates

In silicon thin film solar cell technology, frequently rough or textured substrates are used to scatter the light and enhance its absorption. The important issue of the influence of substrate roughness on silicon nanocrystal growth has been investigated through a series of nc-Si:H single junction p-i-n solar cells containing i-layers deposited with Hot-wire CVD. It is shown that silicon grown on the surface of an unoptimized rough substrate contains structural defects, which deteriorate solar cell performance. By introducing parameter v, voids/substrate area ratio, we could define a criterion for the morphology of light trapping substrates for thin film silicon solar cells: a preferred substrate should have a v value of less than around 1 × 10^- 6, correlated to a substrate surface rms value of lower than around 50 nm. Our Ag/ZnO substrates with rms roughness less than this value typically do not contain microvalleys with opening angles smaller than ~ 110°, resulting in solar cells with improved output performance. We suggest a void-formation model based on selective etching of strained Si-Si atoms due to the collision of growing silicon film surface near the valleys of the substrate.     

Recent advances in hot-wire CVD R&D at NREL: From 18% silicon heterojunction cells to silicon epitaxy at glass-compatible temperatures

Our research aiming to improve silicon photovoltaic materials and devices extensively utilizes hot-wire chemical vapor deposition (HWCVD). We have recently achieved 18.2% heterojunction silicon solar cells by applying HWCVD a-Si:H front and back contacts to textured p-type silicon wafers. This is the best reported p-wafer heterojunction solar cell by any technique. We have also dramatically improved the quality of HWCVD silicon epitaxy and recently achieved 11 μm of epitaxial growth at a rate of 110 nm/min.     

Fabrication of selective-emitter silicon heterojunction solar cells using hot-wire chemical vapor deposition and laser doping

The Si heterojunction (HJ) solar cells were fabricated on the textured p-type mono-crystalline Si (c-Si) substrates using hot-wire chemical vapor deposition (HWCVD). In view of the potential for the bottom cell in a hybrid junction structure, the microcrystalline Si (μc-Si) film was used as the emitter with various PH₃ dilution ratios. Prior to the n-μc-Si emitter deposition, a 5 nm-thick intrinsic amorphous Si layer (i-a-Si) was grown to passivate the c-Si surface. In order to improve the indium-tin oxide (ITO)/emitter front contact without using the higher PH₃ doping concentration, a laser doping technique was employed to improve the ITO/n-μc-Si contact via the formation of the selective emitter structure. For a cell structure of Ag grid/ITO/n-μc-Si emitter/i-a-Si/textured p-c-Si/Al-electrode, the conversion efficiency (AM1.5) can be improved from 13.25% to 14.31% (cell area: 2 cm × 2 cm) via a suitable selective laser doping process.     

Hot-wire CVD deposited n-type μc-Si films for μc-Si/c-Si heterojunction solar cell applications

Phosphorous-doped microcrystalline silicon (μc-Si) films were prepared using hot-wire chemical vapor deposition (HWCVD). Structural, electrical and optical properties of these thin films were systematically studied as a function of PH₃ gas mixture ratio. We report recent results for p-type crystalline silicon-based heterojunction (HJ) solar cells using the HWCVD n-μc-Si film to form an n-p junction. The surface morphology of the crystalline Si substrate after hydrogen treatment was examined using atomic force microscopy. A transfer length method was used to modify the indium-tin-oxide (ITO) deposition parameters in order to reduce front ITO/n-μc-Si contact resistance. In our best solar cell sample (1 cm²) without any buffer layer, the conversion efficiency of 15.1% has been achieved with an open circuit voltage of 0.615 V, fill factor of 0.71 and short circuit current density of 34.6 mA/cm² under 100 mW/cm² condition. The spectral response of this cell will also be discussed.     

Simulated body fluid (SBF) adsorption onto a-SiC:H thin films deposited by hot wire chemical vapor deposition (HWCVD)

Hydrogen amorphous silicon carbon (a-SiC:H) film deposited by the Hot Wire Chemical Vapor Deposition (HWCVD) technique on silicon substrates were soaked in simulated body fluid (SBF). Characterization of the film with different soaking durations in SBF was carried out by Fourier Transform Infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and contact angle measurements. It was found that the relative amounts of carbon in the a-SiC:H film surface decreases with increase in soaking period. XPS results showed the adsorption of Ca and Mg on the a-SiC:H surface. This indicates the formation of negatively charged surface possibly due to formation of silanol groups or dissolution of carbon to SBF confirming the bioactivity of the material. Contact angle decreased from 74° to 65° during 30 days of soaking in the body fluid. Present study is an attempt to observe the interaction of a-SiC:H film prepared by HWCVD technique with the body environment for its future suitability as artificial heart valve and stent coating materials.     

Plasma deposition of n-SiOx nanocrystalline thin film for enhancing the performance of silicon thin film solar cells

In this paper, we firstly optimized the properties of n-SiO_x nanocrystalline thin film through tuning deposition parameters by plasma enhanced chemical vapor deposition, so that we can actively control the properties of materials obtained. Secondly, we proposed using n-SiO_x/Al as back reflector for amorphous silicon (a-Si:H) solar cells. Compared to Al single-layer as back reflector, adding an n-SiO_x layer into the back reflector could improve the solar cell performance, which not only enhances the short circuit current density by an improvement of spectral response in the wavelength range of 550-750 nm, but also improves the open circuit voltage. With an optimized n-SiO_x/Al back reflector, a-Si:H solar cells with an intrinsic layer thickness of 270 nm show 13.1% enhancement in efficiency. In addition, a-Si:H/μc-Si:H tandem solar cells with n-SiO_x as intermediate reflector were also researched. As a result, it evidently balanced the current matching between top and bottom cell.     

Modelization of hafnium silicate chemical vapor deposition using tetrakis-diethyl-amino-hafnium and tetrakis-dimethyl-amino-silane

The Chemical Vapor Deposition growth mechanism of a hafnium silicate film deposited by means of the co-flow of two precursors, TDEAH (tetrakis-diethyl-amino-hafnium) and 4DMAS (tetrakis-dimethyl-amino-silane), is characterized. Typical growth kinetics demand that the deposition rate increases and the silicon concentration remain stable with increasing reactor pressure. Though the deposition rate follows the expected growth kinetics, the silicon concentration in the silicate does not and exhibits an abnormal increase with increasing reactor pressure. To understand this atypical behavior the formation of pure HfO₂ from TDEAH and pure SiO_x from 4DMAS is first studied. Experimental results show that whereas the HfO₂ deposition is well behaved and fits a diffusion-based model defined by assuming diffusion of TDEAH through a boundary layer, the deposition of SiO_x with 4DMAS requires Hf-O nucleation sites and self-saturates after a single Si―O monolayer is formed. Based on these observations, a model is developed for hafnium silicate formation. The Atomic Layer Deposition like behavior of 4DMAS decomposition results in a deposition rate and film stoichiometry that are weakly sensitive to the 4DMAS partial pressure, and instead are driven by the TDEAH reaction. Since TDEAH operates within a transport-limited regime, the deposition rate is insensitive to substrate temperature, and is only controlled by the TDEAH partial pressure and the gas phase kinematics, rendering the process robust and easily controllable with excellent reproducibility.     

Multi-phase structured silicon carbon nitride thin films prepared by hot-wire chemical vapour deposition

In this work, Silicon Carbon Nitride (Si-C-N) thin films were deposited by Hot Wire Chemical Vapour Deposition (HWCVD) technique from a gas mixture of silane (SiH₄), methane (CH₄) and nitrogen (N₂). Six sets of Si-C-N thin films were produced and studied. The component gas flow rate ratio (SiH₄:CH₄:N₂) was kept constant for all film samples. The total gas flow-rate (SiH₄ + CH₄ + N₂) was changed for each set of films resulting in different total gas pressure which represented the deposition pressure for each of these films ranging from 40 to 100 Pa. The effects of deposition pressure on the chemical bonding, elemental composition and optical properties of the Si-C-N were studied using Fourier transform infrared (FTIR) spectroscopy, Auger Electron Spectroscopy (AES) and optical transmission spectroscopy respectively. This work shows that the films are silicon rich and multi-phase in structure showing significant presence of hydrogenated amorphous silicon (a-Si:H) phase, amorphous silicon carbide (a-SiC), and amorphous silicon nitride (a-SiN) phases with Si-C being the most dominant. Below 85 Pa, carbon content is low, and the films are more a-Si:H like. At 85 Pa and above, the films become more Si-C like as carbon content is much higher and carbon incorporation influences the optical properties of the films. The properties clearly indicated that the films underwent a transition between two dominant phases and were dependent on pressure.     

Localized oxidation influence from conductive atomic force microscope measurement on nano-scale I-V characterization of silicon thin film solar cells

Nano-scale current-voltage (I-V) characteristics of hydrogenated microcrystalline silicon (μc-Si:H) prepared by Hot-Wire CVD (HWCVD) technique have been studied by Conductive Atomic Force Microscope (Conductive-AFM) under atmospheric conditions. It is demonstrated that a local modification is caused by the current, detected as a dramatic decrease in the forward biased current of I-V characteristics with the number of repeated scans. On the other hand, smaller change of reverse biased current is observed after the repeated scans. On the base of these results, we discuss and demonstrate the validity of our proposed new junction characterization method at the nanometer scale; that is, simultaneous nano-scale Topographical and Current-Voltage Imaging (TCVI) for Silicon (Si) thin film solar cells.     

Non-uniform deposition in the early stage of hot-wire chemical vapor deposition of silicon: The charge effect approach

The deposition behavior in hot-wire chemical vapor deposition (HWCVD) of silicon was investigated, focusing on the thickness uniformity of films deposited on silicon and glass substrates, and based on the previous suggestion that a major depositing flux in HWCVD should be negatively charged nanoparticles. The deposition was performed using a 20%-SiH₄-80%-H₂ gas mixture at a 450 °C substrate temperature under a working pressure of 66.7 Pa (0.5 Torr). Non-uniform depositions for three hot-wire temperatures, 1590 °C, 1670 °C, and 1800 °C, and on the silicon and glass substrates were compared. The non-uniformity was most pronounced at 1800 °C and more pronounced on the glass substrate. On the glass substrate, the deposition rate was highest at the corner and lowest at the center, which was attributed to the fastest charge removal, to a conducting stainless steel substrate holder, at the corner. Once the entire glass substrate was deposited with silicon, the growth rate tended to become uniform, possibly due to the high charge removal rate of silicon. The observed deposition behavior indicated that the major depositing flux is negatively charged.     

Hot-wire chemical vapor deposition and characterization of polycrystalline silicon thin films using a two-step growth method

A two-step growth method was proposed to reduce the amorphous incubation layer in the initial growth of polycrystalline silicon (poly-Si) films prepared by hot-wire chemical vapor deposition (HWCVD). In the two-step growth process, a thin seed layer was first grown on the glass substrate under high hydrogen dilution ratios (φ ≥ 0.9), and then a thick overlayer was subsequently deposited upon the seed layer at a lower φ value. The effect of various deposition parameters on the structural properties of poly-Si films was investigated by Raman spectroscopy and transmission electron microscopy. Moreover, the electrical properties, such as dark and photo conductivities, of poly-Si films were also measured. It was found that the Si incubation layer could be suppressed greatly in the initial growth of poly-Si with the two-step growth method. In the subsequent poly-Si film thickening, a lower φ value of the reactant gases can be applied to enhance the deposition rate. Therefore, a high-quality poly-Si film can be fabricated via a two-step growth method with a sufficient growth rate using HWCVD.