A Highly Conductive Titanium Oxynitride Electron-Selective Contact for Efficient Photovoltaic Devices

High-quality carrier-selective contacts with suitable electronic properties are a prerequisite for photovoltaic devices with high power conversion efficiency (PCE). In this work, an efficient electron-selective contact, titanium oxynitride (TiO_xN_y), is developed for crystalline silicon (c-Si) and organic photovoltaic devices. Atomic-layer-deposited TiO_xN_y is demonstrated to be highly conductive with a proper work function (4.3 eV) and a wide bandgap (3.4 eV). Thin TiO_xN_y films simultaneously provide a moderate surface passivation and enable a low contact resistivity on c-Si surfaces. By implementation of an optimal TiO_xN_y-based contact, a state-of-the-art PCE of 22.3% is achieved for a c-Si solar cell featuring a full-area dopant-free electron-selective contact. Simultaneously, conductive TiO_xN_y is proven to be an efficient electron-transport layer for organic photovoltaic (OPV) devices. A remarkably high PCE of 17.02% is achieved for an OPV device with an electron-transport TiO_xN_y layer, which is superior to conventional ZnO-based devices with a PCE of 16.10%. Atomic-layer-deposited TiO_xN_y ETL on a large area with a high uniformity may help accelerate the commercialization of emerging solar technologies.     

Specific contact resistance measurements of the screen-printed Ag thick film contacts in the silicon solar cells by three-point probe methodology and TLM method

The specific contact resistance of the screen-printed Ag contacts in the silicon solar cells has been investigated by applying two independent test methodologies such as three-point probe (TPP) and well-known transfer length model (TLM) test structure respectively. This paper presents some comparative results obtained with these two measurement techniques for the screen-printed Ag contacts formed on the porous silicon antireflection coating (ARC) in the crystalline silicon solar cells. The contact structure consists of thick-film Ag metal contacts patterned on the top of the etched porous silicon surface. Five different contact formation temperatures ranging from 725 to 825 °C for few minutes in air ambient followed by a short time annealing step at about 450 °C in nitrogen ambient was applied to the test samples in order to study the specific contact resistance of the screen-printed Ag metal contact structure. The specific contact resistance of the Ag metal contacts extracted based on the TPP as well as TLM test methodologies has been compared and verified. It shows that the extraction procedure based on the TPP method results in specific contact resistance, ρ _c  = 2.15 × 10⁻⁶ Ω-cm² indicating that screen-printed Ag contacts has excellent ohmic properties whereas in the case of TLM method, the best value of the specific contact resistance was found to be about ρ _c  = 8.34 × 10⁻⁵ Ω-cm². These results indicate that the ρ _c value extracted for the screen-printed Ag contacts by TPP method is one order of magnitude lower than that of the corresponding value of the ρ _c extracted by TLM method. The advantages and limitations of each of these techniques for quantitatively evaluating the specific contact resistance of the screen-printed Ag contacts are also discussed.     

SEM and specific contact resistance analysis of screen-printed Ag contacts formed by fire-through process on the shallow emitters of silicon solar cell

The SEM and specific contact resistance measurements of the Ag metal contact formed by applying a fire-through process on the shallow emitter region of the silicon solar cell have been investigated. The metal contact consists of screen-printed Ag paste patterned on the silicon nitride (Si₃N₄) deposited over the n⁺-Si emitter region of the solar cell. The sintering step consists of a rapid firing step at 800 °C or above in air ambient. This is followed by an annealing step at 450 °C in nitrogen ambient. It enables to drive the Ag metal paste onto the Si₃N₄ layer and facilitates the formation of an Ag metal/p-Si contact structure. It serves as the top metallization for the screen-printed silicon solar cell. The SEM measurement shows that sintering of the Ag metal paste at 800 °C or above causes the Ag metal to firmly coalesce with the underlying n⁺-Si surface. A thin layer of conductive glassy layer is also presents at the interface of the Ag metal and n⁺-Si surface. The electrical quality of the contact structure was characterized by measuring the specific contact resistance, ρ _c (in Ω-cm²) using the iteration technique based on the power loss calculation for the solar cell. It shows that best value of ρ _c  = 2.53 × 10⁻⁵ Ω-cm² is estimated for the Ag metal contact sintered at temperature above 800 °C. This value of ρ _c is two orders of magnitude lower than the typical value of ρ _c  = 3 × 10⁻³ Ω-cm² reported previously for the Ag contacts of the solar cell. Such low value of ρ _c for the Ag metal contacts indicates that fire-through process results in excellent ohmic properties. The plot of the ρ _c versus impurity doping level (N _s ) shows that measured value of the ρ _c follows a linear relationship with the N _s as predicted by the theory for the heavily doped semiconductor surface. Hence, carrier injection across the Schottky barrier height is quite appropriate to explain the observed ohmic properties of the Ag metal contacts on the n⁺-Si surface of the silicon solar cell.

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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.     

Analysis on the interfacial properties of transparent conducting oxide and hydrogenated p-type amorphous silicon carbide layers in p-i-n amorphous silicon thin film solar cell structure

Quantitative estimation of the specific contact resistivity and energy barrier at the interface between transparent conducting oxide (TCO) and hydrogenated p-type amorphous silicon carbide (a-Si_1 − xC_x:H(p)) was carried out by inserting an interfacial buffer layer of hydrogenated p-type microcrystalline silicon (μc-Si:H(p)) or hydrogenated p-type amorphous silicon (a-Si:H(p)). In addition, superstrate configuration p-i-n hydrogenated amorphous silicon (a-Si:H) solar cells were fabricated by plasma enhanced chemical vapor deposition to investigate the effect of the inserted buffer layer on the solar cell device. Ultraviolet photoelectron spectroscopy was employed to measure the work functions of the TCO and a-Si_1 − xC_x:H(p) layers and to allow direct calculations of the energy barriers at the interfaces. Especially interface structures were compared with/without a buffer which is either highly doped μc-Si:H(p) layer or low doped a-Si:H(p) layer, to improve the contact properties of aluminum-doped zinc oxide and a-Si_1 − xC_x:H(p). Out of the two buffers, the superior contact properties of μc-Si:H(p) buffer could be expected due to its higher conductivity and slightly lower specific contact resistivity. However, the overall solar cell conversion efficiencies were almost the same for both of the buffered structures and the resultant similar efficiencies were attributed to the difference between the fill factors of the solar cells. The effects of the energy barrier heights of the two buffered structures and their influence on solar cell device performances were intensively investigated and discussed with comparisons.     

Specific contact resistance and metallurgical process of the silver-based paste for making ohmic contact structure on the porous silicon/p-Si surface of the silicon solar cell

Porous silicon has been considered as a promising optoelectronic material for developing a variety of optoelectronic devices and sensors. In the present study, the electrical properties and metallurgical process of the screen-printed Ag metallization formed on the porous silicon surface of the silicon solar cell have been investigated. The contact structure consists of thick-film Ag metal contact patterned on the top of the porous silicon surface. The sintering process consists of a rapid firing step at 750–825 °C in air ambient. It results in the formation of a nearly perfect contact structure between the Ag metal and porous silicon/p-Si structure that forms the top metalization for the screen-printed silicon solar cells. The SEM picture shows that Ag metal firmly coalesces with the silicon surface with a relatively smooth interfacial morphology. This implies that high temperature fire-through step has not introduced any signs of adverse effect of junction puncture or excessive Ag indiffusion, etc. The three-point probe (TPP) method was applied to estimate the specific contact resistance, ρ _c (Ω-cm²) of the contact structure. The TPP measurement shows that contact structure has excellent ohmic properties with ρ _c = 1.2 × 10⁻⁶ Ω-cm² when the metal contact sintered at 825 °C. This value of the specific contact resistance is almost three orders of magnitude lower than the corresponding value of the ρ _c = 7.35 × 10⁻³ Ω-cm² obtained for the contact structure sintered at 750 °C. This improvement in the specific contact resistance indicates that with increase in the sintering temperature, the barrier properties of the contact structure at the interface of the Ag metal and porous silicon structure improved which in turn results a lower specific contact resistance of the contact structure.     

Synthesis and magnetic properties of Ni–SiO2 nanocomposites

Nanocomposite Ni_(1 − x)/(SiO₂)_x soft magnetic materials were synthesized by a simple sol–gel combined hydrogen reduction method. The crystal structure of the particles was determined by X-ray diffraction (XRD). The shapes and sizes of the metal particles embedded in the SiO₂ matrix were determined by transmission electron microscopy (TEM), and magnetic properties were measured by the vibrating samples magnetometer (VSM). The obtained nanocomposite material is composed of nanoparticles coated with a thin SiO₂ layer, and with the content of the silicon increase, the thickness of the silica shells increase and the saturation magnetization decrease. The diameter of Ni particle in the sample is about 30–40 nm. The influence of the Ni content and preparation conditions on the microstructures and magnetic properties were discussed.     

Application of power loss calculation to estimate the specific contact resistance of the screen-printed silver ohmic contacts of the large area silicon solar cells

The establishment of a suitable contact formation methodology is a critical part of the technological development of any metal-to-semiconductor contact structure. Many test structures and methodologies have been proposed to estimate the specific contact resistance (ρ_c) of the planar ohmic contacts formed on the heavily doped semiconductor surface. These test structures are usually processed on the same wafer to monitor a particular process. In this study, new experimental procedure has been evolved to assess the value of ρ_c of the screen-printed front silver (Ag) thick-film metal contact to the silicon surface. The essential feature of this methodology is that it is an iteration technique based on the calculation of power loss associated with various resistive components of the solar cell normalized to the unit cell area. Therefore, this method avoids the complexity of making the design of any lay out of a standard contact resistance test structure like transmission line model (TLM) or Kelvin resistor, etc. It was shown that value of specific contact resistance of the order of 1.0 × 10⁻⁵ Ω−cm ² is measured for the Ag metal contacts formed on the n⁺ silicon surface. This value is much lower than the ρ_c data previously reported for the screen-printed Ag contacts. The sintering process of the front metal contact structure at different furnace setting is carried out to understand the possible wet interaction and metal contact formation as a function of the firing. Therefore, the study is further extended to study the peak firing temperature dependence of the ρ_c of screen-printed Ag metal contacts. It will help to assess the specific contact resistance of the ohmic contacts as a function of firing temperature of sintering process.

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Photovoltaic performance of dye-sensitized solar cells fabricated with polyvinylidene fluoride–polyacrylonitrile–silicondioxide hybrid composite membrane

Electrospun fibrous membranes of hybrid composites of polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN) and silicon dioxide (SiO₂) (PVdF–PAN–SiO₂) are prepared with different proportions of SiO₂ (3, 5 and 7% w/w). The field emission scanning electron microscopy (FE-SEM) reveals that these membranes have three-dimensional, fully interconnected network structures, which are combined with micropores of fine SiO₂ distribution. The surface roughness of the membranes increases with increasing the SiO₂ content. It is found that 7 wt% SiO₂/PVdF–PAN electrolyte membrane has the highest ionic conductivity (6.96 × 10⁻² S cm⁻¹) due to the large liquid electrolyte uptake (about 570%). As the concentration of SiO₂ nanoparticles increase, the contact angle value also increases, ranging from 135.70° to 140.60° which indicates that the membrane has higher hydrophobicity. The dye sensitized solar cells (DSSCs) are fabricated using the hybrid composite membrane with PVdF–PAN with 7 wt % SiO₂. Its photovoltaic performance exhibits an open circuit voltage (V_oc) of 0.79 V and a short circuit current 11.6 mA cm⁻² at an incident light intensity of 100 mW cm⁻², producing an efficiency of 5.61%. DSSC, using the hybrid composite electrospun membrane which shows more stable photovoltaic performance than other assembled DSSCs.     

Wide optical bandgap p-type μc-Si:Ox:H prepared by Cat-CVD and comparisons to p-type μc-Si:H

Oxygen-impurity boron-doped hydrogenated microcrystalline silicon (p-μc-Si:O_x:H) films have been deposited using catalytic chemical vapor deposition (Cat-CVD). Pure silane (SiH₄), hydrogen (H₂), oxygen (O₂), and diluted diborane (B₂H₆) gases were used. The tungsten catalyst temperature (T_fil) was varied from 1900 to 2100 °C and films were deposited on glass substrates at temperatures of 100 to 300 °C. Different catalyst-to-substrate distances were employed and single- or double-coiled filaments were used. In addition to p-μc-Si:O_x:H deposition, we have also deposited conventional p-type microcrystalline silicon (p-μc-Si:H) in order to compare their electrical and optical properties to p-μc-Si:O_x:H.     

Front-side metal electrode optimization using fine line double screen printing and nickel plating for large area crystalline silicon solar cells

Industrial applicable fine-line double printing and nickel plating method was applied to single crystalline silicon (c-Si) solar cells. As the finger widths decreased, the efficiency and short circuit current density (J_SC) linearly increased. Although the increase of the J_SC was caused by the reduction of shadowing loss due to the decrease of finger width, the fill factor (FF) was slowly decreased due to increase of contact resistance. The FF of the cells using the fine line was enhanced by using a double printing and nickel plating. c-Si solar cells with the dimensions of 12.5 cm × 12.5 cm, double printed finger width of 50 μm due to spreadability of paste, a finger spacing of 2.4 μm, and aluminum back surface field were fabricated, achieving an increase of J_SC and efficiencies of up to about 0.62 mA/cm² and 0.38% compared to a reference cell at 79.8% of the FF, respectively.     

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.     

Effect of rapid thermal annealing time on Au/SiOx film prepared by hot wire assisted plasma enhanced chemical vapour deposition technique

In this study, nanocomposite material consisting of silicon suboxide (SiO_x) film embedded with gold nanoparticles (Au NPs) was synthesized using hybrid technique combining hot wire evaporation and plasma enhanced chemical vapour deposition (PECVD) method. As prepared Au/SiO_x films were rapid thermal annealed at constant temperature of 800 °C for different annealing times from 30 to 120 s. The use of tungsten filament for Au evaporation allowed the effective reduction of the silicon content. Depth profiling analysis confirmed the embedded in structure of Au/SiO_x film. FESEM, UV/VIS/NIR and PL spectroscopy were utilized to study the structural and optical properties of annealed Au/SiO_x film for different times. Embedded Au NPs diffused towards the surface of SiO_x film agglomerate and increased in size with an increase in annealing time. Localized surface plasmon resonance (LSPR) peak induced by Au NPs in SiO_x, which is dependent on annealing time, was clearly observed in optical spectra. Intensity and position of the PL peak located at 580 nm experienced a decrease and red-shift, as annealing time increased.     

Characterization of SiNx/a-Si:H crystalline silicon surface passivation under UV light exposure

One of the most promising solution for crystalline silicon surface passivation in solar cell fabrication consists in a low temperature (< 400 °C) Plasma Enhanced Chemical Vapor Deposition of a double layer composed by intrinsic hydrogenated amorphous silicon (a-Si:H) and hydrogenated amorphous silicon nitride (SiN_x). Due to the high amount of hydrogen in the gas mixture during the double layer deposition, the passivation process results particularly useful in case of multi-crystalline silicon substrates in which hydrogenation of grain boundaries is very needed. In turn the presence of hydrogen inside both amorphous layers can induce metastability effects. To evaluate these effects we have investigated the stability of the silicon surface passivation obtained by the double layer under ultraviolet light exposure. In particular we have verified that this double layer is effective to passivate both p- and n-type crystalline silicon surface by measuring minority carrier high lifetime, via photoconductance-decay. To get better inside the passivation mechanisms, strongly connected to the charge laying inside the SiN_x layer, we have collected the Infrared spectra of the SiN_x/a-Si:H/c-Si structures and we have monitored the capacitance-voltage profiles of Al/SiN_x/a-Si:H/c-Si Metal Insulator Semiconductor structures at different stages of UltraViolet (UV) light exposure. Finally we have verified the stability of the double passivation layer applied to the front side of solar cell devices by measuring their photovoltaic parameters during the UV light exposure.     

Effect of oxygen to argon ratio on the properties of thin SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films deposited by r.f. sputtering

Energy Dispersive X-ray and X-ray Photoelectron (XPS) spectroscopies show that SiO _x films deposited by reactive r.f. magnetron sputtering at partial pressure ratios R between oxygen and argon in a wide range (1–0.005) have compositions close to the stoichiometric one. For these films high temperature annealing at 1,000 °C shifts the band in the Fourier Transform-Infrared spectrum due to the Si–O–Si stretching vibration to values typical of stoichiometric SiO₂. Further decrease of R leads to splitting of the Si 2p XPS line indicating increase of the Si content and formation of a second phase in a SiO₂ matrix. The electrical properties of test MOS structures with SiO _x gate dielectric, regarding defect density in the oxide and at the SiO _x /c-Si interface, degrade with the decrease of R. High temperature annealing at 1,000 °C strongly improves the properties of all films regarding leakage current and properties of the interface.     

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.     

Microcrystalline silicon carbide thin films grown by HWCVD at different filament temperatures and their application in n-i-p microcrystalline silicon solar cells

To optimize the performance of microcrystalline silicon carbide (µc-SiC:H) window layers in n-i-p type microcrystalline silicon (µc-Si:H) solar cells, the influence of the rhenium filament temperature in the hot wire chemical vapor deposition process on the properties of µc-SiC:H films and corresponding solar cells were studied. The filament temperature T_F has a strong effect on the structure and optical properties of µc-SiC:H films. Using these µc-SiC:H films prepared in the range of T_F = 1800-2000 °C as window layers in n-side illuminated µc-Si:H solar cells, cell efficiencies of above 8.0% were achieved with 1 µm thick µc-Si:H absorber layer and Ag back reflector.     

Ultra-high quality surface passivation of crystalline silicon wafers in large area parallel plate reactor at 40 MHz

We use a new in-house, large area and automated deposition system: the usable deposition area is 410 × 520 mm with RF-frequency of 40 MHz. We deposit intrinsic a-Si:H layer on flat p-type or n-type c-Si wafers after performing an HF dip. The overall recombination of these double-side passivated c-Si wafers is measured with an effective lifetime measurement set-up. We pay particular attention to the uniformity of the passivation obtained on the whole deposition area.We point out a major role of hydrogen dilution on quality of c-Si passivation. Excellent uniformity is obtained on the whole area with implied open-circuit voltages (V_oc) in a ± 1.5% range. We achieve excellent passivation with overall lifetimes approaching 7 ms (at Δn ≈ 4.5·10¹⁴ cm^− 3) resulting in implied V_oc of 708 mV on p-type c-Si; and lifetimes superior to 4.7 ms resulting in implied V_oc of 726 mV on n-type c-Si (S_eff less than 2 cm/s for both). These results open the way to very high efficiency heterojunction solar cell fabrication in large area reactors.     

Performance evaluation of tungsten sulphoselenides as a material for non-conventional energy devices

Values of thermal power factor S²/ρ at room temperature and its variation with temperature have been studied for mixed crystals of tungsten dichalcogenides i.e. WS_xSe_2−x (0 ≤ x ≤ 2) synthesized in single crystal form by a chemical vapour transport technique. Photoelectrochemical (PEC) solar cells have also been fabricated using this material. Various solar cell parameters e.g. open circuit voltage (V_oc), short circuit current (I_sc), fill factor (FF) and efficiency (η) have been determined for the entire series of WS_xSe_2−x. All results on thermoelectric and PEC behaviour have been carefully studied and their implications have been thoroughly discussed.     

Effect of N2O/SiH4 flow ratios on properties of amorphous silicon oxide thin films deposited by inductively-coupled plasma chemical vapor deposition with application to silicon surface passivation

Silicon oxide (SiO_x) thin films have been deposited at a substrate temperature of 300 °C by inductively-coupled plasma chemical vapor deposition (ICP-CVD) using N₂O/SiH₄ plasma. The effect of N₂O/SiH₄ flow ratios on SiO_x film properties and silicon surface passivation were investigated. Initially, the deposition rate increased up to the N₂O/SiH₄ flow ratio of 2/1, and then decreased with the further increase in N₂O/SiH₄ flow ratio. Silicon oxide films with refractive indices of 1.47-2.64 and high optical band-gap values (>3.3 eV) were obtained by varying the nitrous oxide to silane gas ratios. The measured density of the interface states for films was found to have minimum value of 4.3 × 10¹¹ eV⁻¹ cm⁻². The simultaneous highest τ_eff and lowest density of interface states indicated that the formation of hydrogen bonds at the SiO_x/c-Si interface played an important role in surface passivation of p-type silicon.