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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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.     

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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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.     

Morphology and constitution of the compound layer formed on nitrided Fe–4wt.%V alloy

The microstructure of the compound (“white”) layer formed on the surface of Fe–4wt.%V alloy, by nitriding in a gas mixture of ammonia and hydrogen at 580 °C, has been investigated by employing light and scanning electron microscopy, X-ray diffraction and electron probe microanalysis. The compound layer is dominantly composed of γ^|-Fe₄N nitride. Quantitative analysis of the composition data demonstrated that V is present in the compound layer as VN precipitates, i.e. V is not taken up significantly in (Fe, V) nitrides. A mechanism for compound-layer formation has been proposed.

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Thermal property evolution of metal based thermal barrier coatings with heat treatments

Predicting “in-service” lifetime of ceramic thermal barrier coatings (TBCs) is difficult due to the inherent brittle nature of ceramics used. Therefore, the study of metal-based thermal barrier coatings (MBTBCs) has been initiated to challenge the current problems of ceramic-based TBCs (CBTBCs) and create a new generation of thermal barrier coatings (TBCs). In this work, nano/amorphous structured MBTBCs, for use in internal combustion engines, have been produced using high frequency induction plasma spraying (IPS) of iron-based nanostructured alloy powders. Coatings were deposited by IPS using various spray parameters and heat treated up to 850 °C to study the thermal stability of the coating. The thermal diffusivity (α) properties of MBTBCs were measured using a laser flash method. Density (ρ) and specific heat (C _p ) of the MBTBCs were also measured for calculating thermal conductivity (k = αρC _p ).

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Melt synthesis of oxide phosphors with K2NiF4 structures: CaLa1? x Eu x GaO4

In order to synthesize compounds of various Perovskite-related structures, we have utilized a novel “melt synthesis technique” for phosphors rather than the conventional solid state reaction techniques. The solid state reactions require multi-step processes of heating/cooling with intermediate grindings to make homogeneous samples. However, for the melt synthesis, it is possible to make a homogeneous sample in a single step within a short period of time (1–60 s) due to the liquid phase reaction in the molten samples, which were melted by strong light radiation in an imaging furnace. In this study, we have prepared a red-phosphor CaLaGaO₄:Eu³⁺ which has a perovskite—related layered K₂NiF₄ structure. Well-crystallized CaLa_1−x Eu _x GaO₄ samples with the K₂NiF₄ structure have been obtained up to x = 0.25, but there was the formation of an olivine phase when x = 0.5–1.0. The red emission at 618 nm increased with the increasing value of x up to x = 0.25.

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Spark Plasma synthesis and diffusion of Cu and Ag in vanadium mixed valence oxides

Spark Plasma sintering (SPS) technique allows powders to be compacted at low temperature with a very short holding time. The powder loaded into a carbon die is heated via direct current pulses and simultaneously submitted to an uni-axial pressure of several MPa. Full density of the sample is achieved within minutes. This process is used to study Cu and Ag metals interactions with V₂O₅ oxide. Syntheses of M _x V₂O₅ phases (M = Cu, Ag) have been achieved within minutes. Thus Cu and Ag atoms penetrate microcrystals of V₂O₅ oxide at a high speed, shearing its crystal network and simultaneously rebuilding the crystal structures of the prototype networks β, β′, ε or δ M _x V₂O₅. To account for the formation of these phases identified by X-ray diffraction, structural mechanisms are proposed. Cu and Ag atomic diffusion parameters have been determined from energy dispersive X-ray spectroscopy (EDX) and electron micropobe analysis (EPMA) line scans. High values of diffusion coefficients have been determined. Cu atoms diffuse faster than Ag, D _Cu ≈ 4 × 10⁻⁸ m²/s and D _Ag ≈ 0.5–1 × 10⁻⁹ m²/s in ε and δ M _x V₂O₅ phases, respectively. Their formation may also be used as a model for further investigations into the diffusion mechanisms of atoms in solids and for a better understanding of the SPS process.

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Microstructure and stresses in a keatite solid–solution glass–ceramic

The microstructure of a translucent keatite solid–solution glass–ceramic (keatite s.s.) of the LAS-system (Li₂O–Al₂O₃–SiO₂) has been analyzed with SEM, AFM, XRF, XRD, and TEM. The glass–ceramic consists mainly of keatite s.s. with minor secondary phases such as zirconium titanate, gahnite and probably rutile. Furthermore the resistance to temperature differences (RTD) of this glass–ceramic was investigated. It is shown that, in spite of the relatively high coefficient of thermal expansion (CTE) of about 1 × 10⁻⁶ K⁻¹, an improved RTD can be achieved by special ceramization treatment. With this, compressive stresses in the first 100 μm to 150 μm are induced. These stresses can presumably be contributed to a difference in CTE between the surface-near zone and the bulk. Said CTE difference is caused by chemical gradients of CTE-relevant elements, such as Zn, K, and supposedly additional alkali elements such as Li. These stresses are useful to increase the strength and application range of glass–ceramics based on keatite s.s.

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Amorphous and nano crystalline phase formation in Ni<Subscript>2</Subscript>MnGa ferromagnetic shape memory alloy synthesized by melt spinning

Melt spinning technique was used to synthesize Ni₂MnGa ferromagnetic shape memory alloy ribbons. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) analysis of the ribbon synthesized at lower wheel speed (20 m/s) reveal the formation of very fine clusters of austenitic phase of Ni₂MnGa. However at higher wheel speed (30 m/s) the formation of martensite and nanoparticles of Ni₂MnGa with a size range of 10–20 nm in the amorphous matrix is observed. Also an amorphous phase was observed at higher wheel speed in some areas of the ribbon. Annealing (1000 °C, 1 h) of the ribbon synthesized at higher wheel speed resulted in martensite and γ (gamma) phases. Amorphous phase, Ni₂MnGa nanoparticles, and the martensite phase are analyzed in detail.

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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.     

Growth of massive cementite layers; thermodynamic parameters and kinetics

Massive, pure cementite layers were grown on ferrite substrates by nitrocarburising in a dedicated NH₃/H₂/CO/N₂ containing gas atmosphere at temperatures in the range of 783–843 K. From the parabolic layer-growth constants, an “apparent” activation energy for cementite-layer growth of 109 ± 12 kJ/mol was obtained. This “apparent” activation energy can be subdivided into a positive contribution due to the activation energy for (tracer) diffusion of carbon in cementite and a negative contribution due to the temperature dependence of the difference of the carbon activity in cementite at the surface and at the interface cementite/ferrite.

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Redox processes at grain boundaries in barium titanate-based polycrystalline ferroelectrics semiconductors

Barium titanate, which is characterized by a positive temperature coefficient of resistance (PTCR), is widely used in practice. At the same time, it is unknown why only a small percentage of the introduced donor dopant takes part in the formation of PTCR effect, which phases appear at grain boundaries, how the introduced acceptor dopants affect the properties of grains. Elucidation of the above questions is of considerable scientific and practical interest. It has been shown that the phases Bа₆Ti₁₇O₄₀ and Y₂Ti₂O₇ precipitate on grains of barium titanate doped with donor dopant (yttrium). We identified paramagnetic impurities (iron, manganese, chromium) in starting reagents. These impurities can occupy titanium sites. Therefore, the part of the donor dopant that is spent on the charge exchange of acceptor dopants does not participate in the charge exchange of titanium Ti⁴⁺ → Ti³⁺, which is responsible for the appearance of PTCR effect in barium titanate. It has been found that an extra acceptor dopant (manganese) is distributed mainly at grain boundaries and in the grain outer layer. It has been shown that manganese ions introduced additionally (as acceptor dopants) increase the potential barrier at grain boundaries and form a high-resistance outer layer in PTCR ceramics. The resistance of grains, outer layers, and grain boundaries as a function of the manganese content has been investigated.

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A quenching apparatus for the gaseous products of the solar thermal dissociation of ZnO

Rapid cooling for avoiding the recombination of Zn vapor and O₂ derived from the solar thermal dissociation of ZnO is investigated using a thermogravimeter coupled to a quenching apparatus. The ZnO sample, which is placed in a cavity receiver and directly exposed to concentrated solar irradiation, underwent dissociation in the temperature range 1,820–2,050 K at a rate monitored by on-line thermogravimetry. The product gases were quenched by water-cooled surfaces and by injection of cold Ar at cooling rates from 20,000 to 120,000 K/s, suppressing the formation of ZnO in the gas phase and at the walls. Zinc content of the collected particles downstream varied in the range 40–94% for Ar/Zn(g) dilutions of 170 to 1,500.

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Optical switching of a photochromic bis-phenylazo compound in PMMA films

We present our results on a newly synthesized bis-phenylazo derivative, namely bisperfluoroalkylsulfonylamino- arylazomethylene-triphenyl-phosphorane (BAM-TPP). Thin films of BAM-TPP in polymethylmethacrylate (PMMA) matrix were prepared. The films (thickness, d < 60 μm) were exposed to UV-vis light with variable intensity in order to stimulate the photochromic reaction of BAM-TPP. The resulting absorption changes of the BAM-TPP/PMMA films were investigated by spectrophotometry. The absorption spectra reveal that BAM-TPP molecules in PMMA undergo photoisomerization with resulting decrease of absorbance in the range 500–700 nm. Finally, the time response of film transmittance at 514 nm under increasing CW light intensity was recorded, showing that the reverse photochromic process brings the absorbance back to its pristine value. The obtained films thus proved to be suitable for optical switching applications.

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Hybrid organic–inorganic materials based on polypyrrole and 1,3-dithiole-2-thione-4,5-dithiolate (DMIT) containing dianions

The synthesis of hybrid materials by electropolymerization of pyrrole and inorganic complexes based on the DMIT ligand (1,3-dithiole-2-thione-4,5-dithiolate), e.g. [NEt₄]₂[M(DMIT) _n ] (M = Ni, Pd or Pd, n = 2; M = Sn, n = 3], in acetonitrile solution is reported. Spectroscopic data showed that DMIT-containing anions, [M(DMIT) _n ]²⁻, were inserted into the polypyrrole framework without chemical modification during the electropolymerization process. Cyclic voltammetry showed that materials obtained were electroactive, undergoing redox processes related to both the conducting polymer and the counteranions. The electrochemical results also suggest that, in the case of the transition metal containing films, the counteranions are not trapped in the PPy matrix but undergo anion exchange during the redox cycle of PPy. However, an opposite behaviour was observed with the film with [M(DMIT) _n ]²⁻. The films exhibit good thermal stabilities and have conductivity values expected for semiconductors. This study of these hybrid materials highlights the importance of targeting specific materials for specific applications.

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A comparison of impression and compression creep behavior of polycrystalline Sn

This paper reports on the application of a miniaturized impression creep test to measure the creep behavior of pure polycrystalline Sn, and compares the results to compression creep data on the same sample, in order to experimentally determine a scaling constant to formulate the equivalent uniaxial creep constitutive law from the impression creep data. The creep parameters determined via impression and compression creep are found to be identical, with n ∼ 5 and Q ∼ 42 kJ/mol, indicating that over the tested stress–temperature range, the mechanism is core diffusion controlled dislocation creep. In conjunction with results from previous modeling work, a single conversion factor, κⁿ/C, which depends on material properties, is shown to be usable for converting the impression creep relation to the equivalent uniaxial creep relation, and the experimentally determined value of κⁿ/C for polycrystalline Sn is very close to that obtained via modeling.

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The synthesis and characterisation of grafted random styrene butadiene for biomedical applications

The work undertaken investigates the spectral, thermal and surface characteristics of a random styrene butadiene rubber (SBR) with monomeric graft(s) of acrylic acid (AA), N-vinyl-2-pyrrolidinone (NVP) or N-isopropylacrylamide (NIPAAm) synthesised using UV polymerisation. The grafted materials were characterised by differential scanning calorimetry (DSC), modulated differential scanning calorimetry (MDSC), attenuated total reflectance infrared Fourier transform spectrometry (ATR-FTIR) and atomic force microscopy (AFM). Thermograph analysis has shown an endothermic transition occurring at ~75 °C for all random SB-g-NVP copolymers, whereas the T _g value for random SB copolymer was found at 60 °C, thus suggesting that a chemical reaction between styrene and NVP had occurred. Similar thermal profiles to that of random SB-g-NVP copolymers were evident when random SB was UV polymerised with AA. When NIPAAm was grafted onto random SB, a notable exothermic transition was evident in all samples tested using DSC. It was established using MDSC that this exothermic transition was caused by the breakdown of crosslinks as a result of UV polymerisation.

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Time-lapse photography of the β-Sn/α-Sn allotropic transformation

When tin transforms from the β to α phase it undergoes a dramatic process. The crystal structure changes from tetragonal to diamond cubic; the material properties transform from a ductile metal to a brittle semiconductor; however the most notable change is the decrease in density, which goes from 7.31 g/cm³ to 5.77 g/cm³ [1]. It can be calculated that this decrease in density is equivalent to an increase in volume of about 26% [2]. Due to this volume increase and the brittleness, the transformed material progressively cracks and eventually falls apart. This could potentially be a threat for tin-rich alloys used in electronics in low temperature applications. Due to the optimal transformation temperature of approximately 240 K and the long time required for the transformation, a direct observation of the phenomenon has not been possible. This study proposes a new method for observing the β/α transformation in situ using a time-lapse photographic technique. This study concentrates on pure tin, but the applicability of the method opens new possibilities for studying the phenomenon for other tin alloys, such as the two commonly encountered eutectics of SnCu and SnAgCu.

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