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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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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Power loss calculation as a reliable methodology to assess the ohmic losses of the planar ohmic contacts formed on the photovoltaic devices

The front grid contact is particularly important and requires a low contact resistance which represents the resistance associated with the barrier at the interface of the metal and semiconductor contact structure. Often applied metal contacts are fired at a higher temperature (typically above 700 °C) in air ambient, which produces ohmic contact on both surface of the photovoltaic device. The specific contact resistance is one of the important device parameter on studying the interfacial properties of the metalization system. Therefore, a reliable methodology to assess the ohmic losses of the applied metal contact structure is required. It shows that it is rather simple and reliable to assess the electrical quality of the applied metal contacts by quantifying the total ohmic losses of the solar cell associated with the various resistive components of the solar cell normalized to unit cell area. It has been recently demonstrated that with a new experimental procedure, namely iteration method based on the calculation of power loss (ICPL) associated with the contact resistance of the front Ag thick-film metal contacts, a much reliable value of the specific contact resistance of the order of ≅10⁻⁵ Ω cm² can be extracted for the planar ohmic contacts. In this work, the specific contact resistance of the planar ohmic contacts formed on the heavily doped n⁺ region of the solar cells were studied on large number of finished cells by two independent methods: (i) standard three-point probe (TPP) and (ii) iteration technique based on the calculation of the power loss (ICPL) associated with the contact resistance of the front Ag contacts of the solar cell normalized to unit cell area. It shows that the value of specific contact resistance measured by both methods are desirably much lower than the expected value of 10⁻³ Ω  cm² for the screen-printed Ag metal contacts of the photovoltaic cells used for the A.M. 1.5 applications. Using the iteration, each resistive components of the solar cell normalized to unit cell area were directly evaluated. It is shown that by combining the measurements of specific contact resistance of the planar ohmic contacts and ohmic losses of the cell, it gives a direct and non-destructive diagnostic tool to qualitatively check the electrical quality of the applied Ag metal contacts.

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Comparative study of shunted bicrystal Josephson junctions

In order to optimize the series array performance of Y Ba₂Cu₃O_7−x (YBCO) grain boundary shunted junctions, a method to determine and control the junction resistance R_s and Au/YBCO contact resistivity ρ _c has been developed. 200 nm thick c-oriented YBCO films were grown by intermittent thermal coevaporation on bicrystal yttria-stabilized zirconia substrates. A gold contact overlayer of thickness d_n was deposited in situ. Normal junction resistances have been measured as a function of d_n and shunt width w. It was shown that, in accordance with theoretical estimates, the junction shunt resistance is essentially controlled by the c-axis Au/YBCO interface specific resistance and scales as . The product ρ _c ρ _n ≃ 3.10⁻¹⁴ Ω² cm ³ was estimated from the experimental data, leading to ρ _c ≈ 10⁻⁸ Ωcm ² for typical values of ρ _n for gold thin films.     

Re−Ni2B2C superconducting borocarbides: “In situ” growth of thin films, transport and point contact spectroscopy

High quality c-axis oriented films of the intriguing intermetallic superconducting compound YNi₂B₂C have been obtained “in situ” by magnetron sputtering on MgO substrates held at about 800°C. The films showed maximum T_c=15.3 K, †T_c≈0.1 K, room temperature resistivity ρ≈50μΩ·cm, critical current J_c≈10⁵ A/cm² and B_c2≈6 T. Superconducting films were also obtained on Al₂O₃ and LaAlO₃ single-crystal substrates. From the ρ(T) dependence a value of the Debye temperature Θ _D =330±20 K can be deduced. At low temperatures the resistivity follows a quadratic power law possibly indicative of a high value of the electron-phonon interaction parameter λ. In order to clarify the role of λ in these compounds, point contact spectroscopy measurements have been performed on YNi₂B₂C and HoNi₂B₂C bulk samples prepared by inductive melting using a Low Temperature Scanning Tunneling Microscope (LTSTM). In the point contact regime clear evidence of a superconducting gap have been found in both compounds, corresponding to a moderate strong coupling behaviour (2†/KT_c≈3.8).     

Influence of doping Nb5+ and Mn2+ on the PTCR effects of Ba0.92Ca0.05(Bi0.5Na0.5)0.03TiO3 ceramics

As a positive temperature coefficient of resistivity (PTCR) material, Ba_0.92Ca_0.05(Bi_0.5Na_0.5)_0.03TiO₃ ceramics with donor doping of Nb⁵⁺ and acceptor doping of Mn²⁺ were prepared by a conventional mixed oxide method. The influence of contents of Nb⁵⁺ and Mn²⁺ on the microstructure and PTCR characteristics of Ba_0.92Ca_0.05(Bi_0.5Na_0.5)_0.03TiO₃ ceramics sintered at 1,360°C for 2 h was investigated. The result showed that the Curie temperature (T _c) was shifted to a lower temperature with increasing of the content of Nb⁵⁺ and the resistance jump (ρ_max/ρ_min) was enhanced with doping of Mn²⁺. The grain size of ceramic sample decreased with increasing of contents of donor Nb⁵⁺ and acceptor Mn²⁺. The Ba_0.92Ca_0.05(Bi_0.5Na_0.5)_0.03TiO₃ ceramic with 0.4 mol%Nb⁵⁺ and 0.04 mol%Mn²⁺ exhibited a low ρ_RT of 5.0 × 102 Ω cm, a typical PTCR effect of ρ_max/ρ_min > 10³, and a T _c of 158°C.     

Studying diffusion in multilayer thin-film structures on silicon by the contact melting technique

Features of the contact melting in thin-film structures comprising an aluminum layer with a thickness of h ₁ = 5 μm and a metal (Ti, Ni, Mo) or semiconductor (Si, Ge) sublayer (h ₂ = 0.1 μm) on a single crystal silicon plate (h ₃ = 500 μm) have been studied. The contact melting was caused by single rectangular electric pulses with a current density of j < 9 × 10¹⁰ A/m² and a duration of τ = 100–1000 μs passing through the Al layer. The duration and rate of melting in the samples were determined using voltage waveforms measured by an oscillograph. A method has been developed based on an analysis of the mechanisms of contact interaction in the Al film—sublayer system (with allowance for experimental data on the time of sublayer dissolution in the Al film) for estimating the coefficients of mutiphase diffusion of the system components during the passage of a current pulse.     

Influence of ion-induced interfacial chemical reactivity on contact resistance

Contact resistance measurements of chromium contacts deposited by partially ionized beam deposition on transparent conducting indium tin oxide (ITO) were performed. These provide a direct experimental evidence of the influence of interfacial chemical interaction on the contact resistance. The interfacial reactivity is controlled by modifying the energy and flux of ionized chromium atoms deposited on ITO employing a specially designed partially ionized deposition system with very high ionization efficiency. The true contact resistivityρ _c is obtained by iteratively correcting the experimentally measured values for the finite sheet resistance of the ITO layer.ρ _c decreases linearly with the energy of the ionized chromium. Auger sputter profiling shows no structural modifications at the interface due to a change in the energy of the chromium atoms, confirming that the observed change in the contact resistivity is directly related to interfacial chemical bonding of the atoms with the oxygen atoms in the ITO leading to a local increase of carrier concentration and lower interfacial resistance.     

XPS study of palladium sensitized nano porous silicon thin film

Nano porous silicon (PS) was formed on p-type monocrystalline silicon of 2–5 Ω cm resistivity and (100) orientation by electrochemical anodization method using HF and ethanol as the electrolytes. High density of surface states, arising due to its nano structure, is responsible for the uncontrolled oxidation in air and for the deterioration of the PS surface with time. To stabilize the material PS surface was modified by a simple and low cost chemical method using PdCl₂ solution at room temperature. X-ray photoelectron spectroscopy (XPS) was performed to reveal the chemical composition and the relative concentration of palladium on the nanoporous silicon thin films. An increase of SiO₂ formation was observed after PdCl₂ treatment and presence of palladium was also detected on the modified surface. I–V characteristics of Al/PS junction were studied using two lateral Al contacts and a linear relationship was obtained for Pd modified PS surface. Stability of the contact was studied for a time period of around 30 days and no significant ageing effect could be observed.     

Rapid processing of low-cost, high-efficiency silicon solar cells

Rapid and potentially low-cost processing techniques are analyzed and applied toward the fabrication of high-efficiency Si solar cells. (i) A technology that can simultaneously form the phosphorus emitter, boron BSF, andin situ oxide in a single high-temperature furnace step or: simultaneously diffused, textured, and AR coated process (STAR) is presented. (ii) A high quality screen-printed (SP) contact methodology is developed that results in fill factors of 0·785–0·790 on monocrystalline Si. (iii) Aluminum back surface field (Al-BSF) formation is studied in detail to establish the process conditions that result in optimal BSF action. (iv) Screen-printing of Al conductor paste and rapid thermal processing (RTP) are integrated into the BSF procedure, and effective recombination velocities (S _eff) as low as 200 cm/s are demonstrated on 2·3 Ω-cm Si with this rapid thermal processing of screen-printed contacts, Al alloyed BSF processes. (v) A novel passivation scheme consisting of a dielectric stack (plasma silicon nitride on top of a rapid thermal oxide) is developed to reduce the surface recombination velocity (S) to ≈ 10 cm/s at the 1·3 Ω-cm Si surface. The important feature of this stack passivation scheme is its ability to withstand a high-temperature anneal (700–850°C) without degradation in surface recombination velocity. This feature is critical for most current commercial processes that utilize SP contact firing. (vi) Finally, the individual processes are integrated to form high-efficiency, manufacturable devices. Solar cell efficiencies of 17% and >19% are achieved on FZ Si with SP and evaporated (photolithography) contacts, respectively.     

Influence of short-term annealing on the conductivity of porous silicon and the transition resistivity of an aluminum-porous silicon contact

Measurements were made of the transition resistivities of an aluminum-porous silicon contact and the resistivity of the surface region of the porous material after short-term annealing in an inert medium at temperatures between 300 and 550 °C. It was shown that the parameters of the contacts are determined by the pore morphology, the annealing temperature, and the plasma-chemical etching process. For porous silicon formed on p-Si, annealing reduces the transition resistivities by several orders of magnitude. In this case, the resistivity of the surface region of porous silicon decreases sharply. The results are analyzed from the point of view of the passivating effect of hydrogen in the porous silicon. Pis’ma Zh. Tekh. Fiz. 24, 45–51 (March 26, 1998)     

Modified sol-gel process for the preparation of BaTiO3 and PbTiO3 ferroelectric films

A modified method for preparing barium and lead titanate films is suggested, which combines precipitation from solution and elements of sol-gel processing. The ∼1-μm-thick BaTiO₃/Pt and PbTiO₃/Pt films deposited on Pt foil are transparent, show good adhesion, and have the 1 : 1 : 3 stoichiometry. The films are finegrained, with a mean grain size of 0.1–0.2 μm. The barium titanate films are characterized byt _C = 110-125°C, ε₂₀ = 167-500, tanδ₂₀ = 0.015-0.06, ε_max = 1050,P _s= 3.2 μC/cm²,E _c = 14 kV/cm, ρ = (5-7) × 10⁹ Ω cm, andV _br = 80-150 kV/cm. The lead titanate films are characterized byc/a = 1.056, ε₂₀ = 105-110, tanδ₂₀ = 0.11-0.16,P _s = 4.1 μC/cm²,E _c = 34 kV/cm, ρ = (0.8-3.0) × 10⁹ Ω cm, andV _br = 50-100 kV/cm.     

Ion beam and thermally-induced interface reaction between highT c superconductor thin film and metal overlayer

Ion beam and thermally-induced interface reactions between highT _c superconducting thin film of Y₁Ba₂Cu₃O_7−x and metal overlayer of Ag are studied with a view to control the interfacial property of contact resistance. The interface reaction is induced by 100 keV Ar⁺ ion beam with different ion dose values ranging from 5 × 10¹³ to 3×10¹⁴ ions/cm². The YBaCuO film-metal interface is characterized by using the small angle XRD to study the structural properties of the interfacial phases. The electrical property of the interface, specifically contact resistance, has been investigated for different dose values and thermal treatments. Three-probe vs four-probe configuration has been adopted to measure the contact resistance.     

Synthesis and characterization of mesoporous silicon directly from pure silica sodalite single crystal

Mesoporous silicon granules with high surface area were synthesized directly from pure silica sodalite single crystals, with the starting shape retained. The sodalite single crystals were reduced by a magnesiothermal process in vacuum at 630 °C. The X-ray diffraction patterns indicate the presence of crystal silicon. Transmission electron microscopy studies reveal that the obtained silicon granules are composed of a monocrystalline surface with an island-like mesoporous internal structure. The results of N₂ adsorption and desorption analysis indicate that the surface area is around 308 m² g⁻¹ and the single point pore volume is 0.37 cm³ g⁻¹. The photoluminescence emission centered at 2.7 eV may be due to both an oxidized surface and quantum confinement effects. These results reveal that the silicon granules possess a different microstructure from those of etched silicon films. The present synthetic design correlates the microporous zeolite and mesoporous silicon together and gives a new way for enlarging the structural diversity of porous silicon crystal.     

Quench-condensed indium-hydrogen films. II. Changes in electric and superconducting characteristics near the metal-insulator transition

Electrical and superconducting properties of indium films condensed in a H₂ atmosphere (pressurep _{H 2}=6×10⁻⁶ to 1.4×10⁻⁴ Torr) onto a substrate cooled with liquid helium are investigated. As hydrogen content is increased, a continuous increase in residual resistivity ρ* is observed, permitting systematic study of the resistance vs. temperature dependenceR(T) and the superconducting transition temperatureT _c on approaching the metal-insulator transition (MIT). With regard to ρ*, four regimes of conductivity can be observed: (1) conductivity with a positive temperature resistance coefficient (TRC), (2) conductivity with a small, constant, negative TRC, (3) conductivity under weak localization with ΔR (T) ∼ln T or type corrections, (4) hopping conductivity.T _c rises continuously with ρ* and reaches its peak (∼5.2K) in the second regime. A further increase of ρ* leads to a decrease ofT _c and complete suppression of superconductivity. The experimental dependenceR(T) is compared with theory. TheT _c variation on approaching the MIT and the relation between Mooij's rule and the superconducting properties are discussed.     

Oxidation Resistance and Magnetic Properties of SmCo7?x Si x Permanent Magnetic Alloys

The crystal structure, oxidation resistance, and magnetic properties of SmCo_7−x Si _x (x=0, 0.4, 0.6, and 0.9) permanent magnetic alloys were investigated systematically. It is found that the addition of silicon in the as-cast SmCo₇ ingot plays an important role in stabilizing TbCu₇ phase and improving inherent oxidation resistance. For the bulk nanocrystalline SmCo_7−x Si _x magnets, the oxidation resistance remarkably enhances but the corresponding Curie temperature T _c and maximum energy product (BH)_max exhibit a decreasing trend with the increase in Si content x. For the typical SmCo_6.4Si_0.6 nanocrystalline magnet, its final mass gain was about 1.71 mg/cm² after oxidation at 500 °C for 100 h, indicating the enhanced inherent oxidation resistance. Its T _c and (BH)_max were about 708 °C and 35.4 kJ/m³, respectively.     

Structure and properties of polyethyleneterephthalate crystallized by annealing in the highly oriented state

The structure of polyethyleneterephthalate bristles drawn about five times in the amorphous state and subsequently crystallized at temperatures between 100 and 260‡ C has been studied by means of small-angle X-ray scattering. In addition density, heat of fusion and wide-angle scattering behaviour were measured. For comparison, similar experiments were carried out with undrawn samples. The results showed that the degree of crystallinity of PET cannot be calculated from density data on the basis of a simple two-phase model, since the effective densitiesρ _c ^* andρ _a ^* of the crystalline and amorphous regions depend strongly on crystallization and drawing conditions. With rising crystallization temperature the size of the mosaic blocks building up the crystalline layers and their longitudinal mutual order increase whereas the volume fraction of the crystalline region is only rather slightly effected by the annealing temperature. The difference between the effective densityρ _c ^* and the “X-ray density”ρ _c of the crystalline layers is supposed to be caused by lattice vacancies in the boundaries of the mosaic blocks.     

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

The isochoric heat capacity of pure methanol in the temperature range from 482 to 533 K, at near-critical densities between 274.87 and 331.59 kg· m⁻³, has been measured by using a high-temperature and high-pressure nearly constant volume adiabatic calorimeter. The measurements were performed in the single- and two-phase regions including along the coexistence curve. Uncertainties of the isochoric heat capacity measurements are estimated to be within 2%. The single- and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from experimental data for each measured isochore. The critical temperature (T_c = 512.78±0.02K) and the critical density (ρ_c = 277.49±2 kg · m⁻³) for pure methanol were derived from the isochoric heat-capacity measurements by using the well-established method of quasi-static thermograms. The results of the C_VVT measurements together with recent new experimental PVT data for pure methanol were used to develop a thermodynamically self-consistent Helmholtz free-energy parametric crossover model, CREOS97-04. The accuracy of the crossover model was confirmed by a comprehensive comparison with available experimental data for pure methanol and values calculated with various multiparameter equations of state and correlations. In the critical and supercritical regions at 0.98T_c≤ T ≤ 1.5T_c and in the density range 0.35ρ_c ≤ ρ leq 1.65 ρ_c, CREOS97-04 represents all available experimental thermodynamic data for pure methanol to within their experimental uncertainties.     

Effect of temperature on thermally induced defects in silicon

Deep level transient spectroscopy has been used to study thermally activated defects in silicon. It has been observed that different annealing temperatures activate different defects in silicon, which were lying on inactive sites before annealing. Two deep mid-gap levels at energy positions E _c −0.48 eV and E _c −0.55 eV were found to be introduced by different heat treatments. It is also noted that heat treatment at 1,250 °C suppresses the concentration of deep level at E _c −0.23 eV and enhances the concentration of deep level at E _c −0.25 eV, while heat treatment at 950 °C has an opposite effect. Annealing response of the level at E _c −0.48 eV is found different to the annealing response of the level at E _c −0.55 eV which suggests them two different levels.