Cold Chemical Lamination—New Bonding Technique of LTCC Green Tapes

The low-temperature co-fired ceramic (LTCC) technology enables fabrication of sensors, actuators, microfludic devices² and fuel cells. The structures consist of screen-printed components, gas/liquid channels, reactive chambers and mixers. The lamination process determines the quality of such devices. Thermo-compression is the most popular bonding method. The LTCC green tapes are joined together at high temperature (up to 80°C) and high pressure (up to 30 MPa) for 2 to 15 minutes. The method allows good encapsulation of the LTCC structures, but the channels geometry is strongly affected by elevated temperature and pressure. Cold Chemical Lamination (CCL) is a new LTCC green tapes bonding technique, which allows for fabrication of 3D modules. A solvent-based method is used in the CCL lamination instead of the thermo-compression process. A special liquid agent is screen-printed on the green tape in the CCL method. The liquid melts the tape surface. Then the tapes are stacked and compressed at room temperature by a printing roll. The influence of the CCL and the thermo-compression methods on the chamber's geometry quality as well as basic electrical properties of screen-printed resistors (sheet resistance R_φ standard deviation of sheet resistance σ_R, variability coefficient of sheet resistance V_R, and long-term stability) are analyzed and compared in this paper. The bonding quality is examined by a scanning electron microscope (SEM).     

Novel cold chemical lamination bonding technique—A simple LTCC thermistor-based flow sensor

The LTCC technique enables fabrication of microfluidic devices. The structures consist of channels, chambers and screen-printed passives. The lamination is a quality-determining process in the manufacture of the fluidic modules. The commonly used bonding method is thermocompression. The tapes are joined together at high pressure (up to 30 MPa) and temperature (up to 80 °C) for 2–15 min. Although these parameters allow good LTCC module encapsulation, the quality of the chamber geometry is strongly affected by high pressure and temperature. The cold chemical lamination (CCL) technique presented in this paper, a solvent-based method, largely avoids these problems. A film of a special solvent is deposited on the green tape, and softens the surface. The tape layers are then stacked and compressed at low pressure, below 100 kPa, at room temperature. The fabrication of a simple LTCC thermistor-based flow sensor is presented here to compare both lamination methods. The test device consists of one buried thermistor screen printed on a bridge hanging in a gas/liquid channel. The basic sensor parameters (measurement range, working temperature, output signal, working pressure and measurement error) are analyzed.     

Low-pressure,thermo-compressive lamination

Lamination of green ceramic tapes is one of the most important technological processes in multilayer ceramic technology. Lamination affects the quality of all 3D structures (e.g., channels, chambers, membranes, etc.). Novel chemical methods of lamination reduce the deformation of 3D structures. However, these methods are useless in the fabrication of thin membranes and structures with thick-film electronic components or electric vias. Therefore, thermo-compressive lamination is still the best solution for the lamination of green ceramic tapes. Low-pressure thermo-compressive lamination with an insert material is presented in this paper. The influence of pressure and Low Temperature Cofired Ceramics (LTCC) material on the compressibility and shrinkage of LTCC, as well as the influence of the insert material on deflection and distortion of the membranes are presented and discussed in this paper.     

Influence of Cold Low Pressure Lamination Parameters on the Joining of Low Temperature Co‐Fired Ceramics Green Tapes and Sintered Alumina Substrates

In this study, laminates consisting of sintered alumina substrates and green Low Temperature Co‐fired Ceramics (LTCC) tapes have been produced via Cold Low Pressure Lamination which is based on adhesive tapes for joining of layers at room temperature and pressures <5 MPa. The influences of lamination parameters such as temperature, pressure, and time on the quality of the green and sintered multilayer stack have been determined. If the bottom LTCC layer of an alumina–LTCC–LTCC laminate is metallized by screen printing defects such as crack formation can occur due to stress formation caused by constrained sintering. By adapting the lamination parameters, these stresses can be avoided. Another defect observed is cavities which form along the printed circuit lines. This type of defect is caused by the shrinkage of the circuit line width during firing; by reducing the height of the conductor line during screen printing, the cavity size can be reduced. In addition, different screen‐printed metallization layouts have been tested to determine the influence of line and spaces on the quality of sintered laminates.     

High-density YSZ tapes fabricated via the multi-folding lamination process

A new method of ceramic processing to obtain high green and fully sintered yttria-stabilized zirconia (YSZ) ceramic parts has been studied. The procedure involved slip casting, multi-folding lamination, and sintering. A rheological study revealed correlation between compositional parameters and densities. A particular method of folding and lamination we named multi-folding lamination was proved to be an appropriate route to obtain dense, homogeneous green bodies, reaching density values of ca. 61%. Further studies on the sintered parts were performed in this work, obtaining YSZ sintered tapes suitable for the use in high temperature solid-state devices. This tapes, sintered at 1550 °C, reached values of 98% of theoretical density and average particle sizes within 1.7–12 μm.     

Factors Influencing the Green Body Properties and Shrinkage Tolerance of LTCC Green Tapes

Low-temperature co-fired ceramics (LTCC) is a powerful technology for the manufacture of integrated electronic devices. To fulfill the needs of miniaturization, the applied materials must be of constant quality and the manufacturing processes must be well controlled. The reproducibility in shrinkage is one of the most important quality issues of LTCC tapes. To guarantee the customer a narrow shrinkage tolerance, the tape producer must know the important influencing factors of tape manufacturing on shrinkage. In this work, the effects of slurry composition, tape-casting parameters like casting speed and opening of the blades, and tape handling on the sintering shrinkage behavior were investigated by using design of experiments. The investigation showed that the green density and therefore the shrinkage values of tapes depend considerably on the variation of the solvent mixture. Furthermore, significant interactions were quantified between the tape-casting velocity as well as the particle size and the shrinkage behavior. The shrinkage values were also influenced by mechanical deformations of the tapes before firing.     

Manufacture of 3D structures by cold low pressure lamination of ceramic green tapes

3D multilayer devices were generated by Laminated Object Manufacturing (LOM), a well-known rapid-prototyping technology. Divergent from this method, commercial ceramic green tapes were used which were laminated by Cold Low Pressure Lamination (CLPL). In contrast to thermo-compression, which works at pressures and elevated temperatures, CLPL allows to join particularly fine, complex structures with cavities or undercuts, because no mass flow occurs. This technique is based on gluing the adjacent tapes by means of an adhesive film at room temperature under a low pressure. After binder burnout and sintering the ceramic laminate has a homogenous and dense microstructure free of interfaces. This modified LOM technique is particularly suitable for the production of Micro Electro Mechanical Systems (MEMS).In the given paper commercial Low Temperature Co-fired Ceramic (LTCC) green tapes were used, which were structured by means of a high-frequency milling plotter and laminated by using CLPL. Various 3D devices of different shape with inlying cavities were manufactured. The quality of the fired and unfired structures of the devices were characterised by different methods and show a high quality surface of the multilayer structures. Process aspects of the CLPL technique are discussed. The results demonstrate the advantages of this method for the fabrication of MEMS.     

Tape casting of ferroelectric,dielectric, piezoelectric and ferromagnetic materials

Tape casting is a feasible method for preparing ceramic tapes with different electrical and magnetic properties for multilayer ceramic devices. This paper describes the tape casting process for several different electroceramic materials (BST, PZT, NZF and ZSB) utilising similar organic additive and solvent systems. The properties of tapes with different ceramic compositions before and after sintering are investigated, including surface roughness, shrinkage and microstructures. The parameters affecting the casting, shrinkage, lamination, thickness and tensile strength of green tape are also presented. This enables process design for tape which can be used in devices with true integration of dielectric and piezoelectric, ferroelectric and ferromagnetic layers in 3-dimensional multilayer structures.     

Effect of Friction on Inhomogeneous Shrinkage Behavior of Structured LTCC Tapes

Vias, cavities, and other cutouts are significant inhomogeneities in low temperature co-fired ceramics (LTCC) tapes and lead to inhomogeneous shrinkage during sintering, which has a negative effect on the quality of the final multilayer device. The influence of such cutouts on the shrinkage behavior of LTCC tapes was investigated by an exact measurement of the geometry before and after sintering and by in situ observations with an optical dilatometer. The investigations show a strong influence of cutouts on the magnitude of shrinkage inhomogeneities. This effect is more pronounced, if the tapes become thinner, the dimensions of the cutouts become larger, or their position becomes less centric. It is shown that the most important factor on the occurrence of shrinkage inhomogeneities in tapes with cutouts is the static friction of the LTCC material on the setter. Severe warpage is caused by interlocking effects, which occur at bumps of the rough setter surface when the inner edges of the cutouts are pulled over the setter. By using a separating agent between the LTCC tape and the setter, the static friction could be minimized, which eliminates the sintering inhomogeneities.     

Effect of Particle Shape on Anisotropic Packing and Shrinkage Behavior of Tape-Cast Glass–Ceramic Composites

In this study, the influence of particle shape anisometry and particle alignment in tape-cast green sheets on the shrinkage behavior of low-temperature co-fired ceramics (LTCCs) was investigated quantitatively. A new method for the characterization of particle shape with the use of a particle image analyzer is presented, and its application to real material systems demonstrated. A commercial LTCC system and three developed composite powders with different average particle sizes were analyzed. After tape casting, particle alignment in the green sheets was analyzed using image analysis of SEM micrographs of cross sections. The investigations showed that the degree of particle alignment correlates significantly with the particle shape and size of the materials. A further increase in particle orientation was seen after the lamination process. Additionally, the powder packing of both single layers and laminates was analyzed by mercury porosity. The anisotropic shrinkage behavior during the sintering process was determined by means of optical dilatometry. The data obtained on the particle morphology, particle orientation in the tapes, and their effects on the shrinkage anisotropy will be discussed.     

Influence of Low-Temperature Co-Fired Ceramics Green Tape Characteristics on Shrinkage Behavior

To establish a better understanding of the complex densification and shrinkage processes of low-temperature co-fired ceramics (LTCC) and to improve the dimensional control in the manufacture of LTCC multilayer devices, the influence of glass, composite, and microstructural green tape characteristics on the densification and shrinkage behavior of LTCC materials, with special focus on the development of anisotropy, was investigated. To study the influence of these factors, a commercial LTCC system was analyzed regarding chemical and microstructural composition as well as sintering behavior. The results of the analysis showed that the commercial LTCC system is composed of alumina as a ceramic filler and a CaO–SiO₂–B₂O₃–Al₂O₃ glass. Based on these results, a similar glass was produced. To understand the mechanisms of densification, its wetting behavior and viscosity as a function of temperature were investigated. As developed glass was mixed with an alumina powder and milled down to average grain sizes of 1, 2, and 3 μm, respectively. From these composite powders, slurries were prepared and tape cast. The sintering kinetics including onset temperature, development of viscous flow as well as phase development of both commercial and internally developed LTCC tapes LTCC tapes in relation to their modified composition and green tape structures were analyzed in situ by means of optical dilatometry, thermo-mechanical analysis (TMA), and high-temperature-X-ray diffraction. The viscous behavior of the glass-filler composites was determined by means of cyclic dilatometry in a TMA device.     

Zero Shrinkage of LTCC by Self-Constrained Sintering

Low shrinkage in x and y direction and low tolerances of shrinkage are an indispensable precondition for high-density component configuration. Therefore, zero shrinkage sintering technologies as pressure-assisted sintering and sacrificial tapes have been introduced in the low-temperature co-fired ceramics (LTCC) production by different manufacturers. Disadvantages of these methods are high costs of sintering equipment and an additional process step to remove the sacrificial tapes. In this article, newly developed self-constrained sintering methods are presented. The new technology, HeraLock^®, delivers LTCC modules with a sintering shrinkage in x and y direction of less than 0.2% and with a shrinkage tolerance of ±0.02% without sacrificial layers and external pressure. Each tape is self-constrained by integration of a layer showing no shrinkage in the sintering temperature range of the LTCC. Large area metallization, integration of channels, cavities and passive electronic components are possible without waviness and camber. Self-constrained laminates are an alternative way to produce zero shrinkage LTCC. They consist of tapes sintering at different temperature intervals. Precondition for a successful production of a self-constrained LTCC laminate is the development of well-adapted material and tapes, respectively. This task is very challenging, because sintering range, high-temperature reactivity and thermal expansion coefficient have to be matched and each tape has to fulfill specific functions in the final component, which requires the tailoring of many properties as permittivity, dielectric loss, mechanical strength, and roughness. A self-constrained laminate is introduced in this article. It consists of inner tapes sintering at especially low-temperature range between 650°C and 720°C and outer tapes with an as-fired surface suitable for thin-film processes.     

Mechanical and lamination properties of alumina green tapes obtained by aqueous tape-casting

Mechanical characterisation and lamination were carried out on alumina green tapes prepared by aqueous tape casting using two acrylic emulsions having different glass transition temperatures (T_g) as binders. The tensile strength and strain were strongly dependent on the binder nature and content. Namely, the mechanical properties of the green tapes reflected those of the binders at room temperature: the green tapes obtained with the higher T_g binder showed a brittle behaviour, whereas those obtained with the lower T_g binder showed an elastoplastic behaviour. The mechanical properties of the green tapes prepared by mixing the two acrylic binders lies in between, giving the possibility of tailoring the flexibility and strength in the range of the values obtained for pure binders. Lamination gave rise to an increase of both green and sintered densities, compared with monolayer specimens, whatever the composition of the binder system. Such improvements significantly depended on lamination pressure, but were insensitive to lamination temperature for the two temperatures tested higher than the T_g of the two binders. ©     

Influence of processing and conduction materials on properties of co-fired resistors in LTCC structures

The motivation of this study is the need for fundamental understanding of the effects of processing conditions on the electrical properties of low-temperature co-fired ceramic (LTCC) tapes, those screen printed with commercial thick-film pastes of electronic components for increased reliability. The method of the study is realized by analyzing the physical and chemical effects of mono/multilayer firing and firing temperatures on the temperature coefficient of resistance (TCR) and sheet resistance (SR) values of the positive temperature coefficient (PTC) resistors screen-printed on LTCC tapes. The results are discussed with respect to the information obtained by the scanning electron microscopy (SEM), electro dispersive X-ray analysis (EDXS), X-ray and dilatometry analysis. It is shown that the content of pastes combined with varying processing conditions result in deviation from expected TCR and SR values due to the chemical and/or mechanical reactions.     

Innovative strategy for designing proton conducting ceramic tapes and multilayers for energy applications

Aim of this work is to present, for the first time, the use of Dynamic Mechanical Analysis as a tool to characterize the thermo-mechanical behavior of green tapes defining the process conditions for the subsequent lamination step. This method was applied on tapes of protonic conductors, key-materials for different applications in the energy sector, from gas separation membranes to solid oxide fuel cells and electrolyzers. The pore former (rice starch) content was found to considerably affect the thermomechanical behavior (elastic and storage moduli, elongation to break, viscosity) of the tape and therefore the lamination process. The temperature required for a proper lamination increases from 50 up to 75 °C passing from the system without rice starch to the one with the highest pore former amount. This work identifies for the first time an optimal lamination viscosity (10¹⁰ Pa s), regardless the tapes formulation, required for a suitable adhesion among the layers.     

Roles of Poly(propylene glycol) during Solvent-Based Lamination of Ceramic Green Tapes

Solvent lamination of alumina green tapes is readily accomplished using a mixture of ethanol, toluene, and poly(propylene glycol), or PPG. After lamination, the PPG is clearly present as a discrete film at the interface between the laminated tapes, and direct particle–particle contact does not, in general, exist across the joined surfaces. This condition, however, does not generate delamination during firing. Instead, stacks of green tapes laminated using this mixture routinely sinter to full density and no evidence of original joint persists through the firing process. This paper presents the results of experiments undertaken to determine the role of PPG in the lamination process and, specifically, the mechanism by which it is redistributed during subsequent processing. PPG slowly diffuses through the organic binder film at room temperature. The PPG diffusion rapidly increases as the temperature is increased to 80°C. The key to the efficiency of adhesives during green-tape lamination is mutual solubility of the nonvolatile component of the glue and the base polymeric binder.     

Low-Sintering High-k Materials for an LTCC Application

High-k LTCC tapes with ultralow sintering temperatures were developed from lead-free perovskite powders. Lowering of the sintering temperature from 1250°C down to 900°C has been achieved by means of ultrafine ceramic powders in combination with suitable sintering aids. The tape-casting process has been optimized for ultrafine powders with an enhanced sintering activity. Low-sintering high-k tapes of a thickness down to 40 μm, suitable for LTCC processing, were obtained. The sintering behavior of these high-k tapes has been studied and compared with other LTCC materials. Dielectric properties of the high-k material have been investigated on a multilayer test structure consisting of up to 20 dielectric layers. After metallization with an Ag conductor, the green tapes were stacked and laminated. Sintering of these multilayer stacks at 900°C gives dense ceramic samples. Permittivities up to 2000 have been obtained, together with low dielectric losses. Material compatibility with several Ag/Au-thick-film-paste systems has been tested.     

Fabrication of embedded microfluidic channels in low temperature co-fired ceramic technology using laser machining and progressive lamination

This paper describes the application of laser micromachining techniques for the fabrication of microfluidic channels in low temperature co-fired ceramic, LTCC, technology. It is shown that embedded cavities can be successfully realised by employing a recently proposed progressive lamination process with no additional fugitive material. Various microfluidic structures have been fabricated and X-ray imaging has been used to assess the quality of the embedded channels after firing. The problem of achieving accurate alignment between LTCC layers is addressed such that deeper channels, spanning more than one layer, can be fabricated using a pre-lamination technique. A number of possible applications for the presented microfluidic structures are discussed and an H-filter particle separator in LTCC is demonstrated.     

Design and Fabrication of Transparent and Gas‐Tight Optical Windows in Low‐Temperature Co‐Fired Ceramics

Low‐temperature co‐fired ceramics (LTCC) enable the fabrication of microfluidic elements such as channels and embedded cavities in electrical devices. Hence, LTCC facilitate the realization of complex and integrated microfluidic devices. Examples can be applied in many areas like reaction chambers for synthesis of chemical compounds. However, for many applications it is necessary to have an optically transparent interface to the surroundings. The integration of optical windows in LTCC opens up a wide field of new and innovative applications such as the observation of chemiluminescent reactions. These chemical reactions emit electromagnetic radiation and thus offer a method for noninvasive detection. Thin glasses (≤500 μm) were bonded by thermocompression onto a LTCC substrate. As the bonding agent, a glass frit paste was used. Borosilicate glasses, fused silica as well as silicon were successfully bonded onto LTCC. To join materials with a large coefficient of thermal expansion mismatch (i.e., fused silica and LTCC), it is necessary to limit the heat input to the bond interface. Therefore, a heating structure was integrated into the LTCC substrate beneath the bond interface. This bonding process provides a gas‐tight optical port with a high bond strength.     

Graphical based characterisation and modelling of material gradients in porosified LTCC

The chemical composition of low temperature cofired ceramics (LTCC) allows to locally embed air into sintered substrates by a selective wet chemical etch process. Therefore, LTCC substrate with areas of low permittivity can be created without material combination. The presented graphical method of material component contrast images enables the evaluation of their most important material properties which are their component distribution, their porosification gradient and their residual bearing surface. The graphical method, including focused ion beam and scanning electron microscopy analyses, is applied to different commercially available LTCC types having two porosification states each. Derived mathematical models, which are suitable for finite element method implementation, allow the characterisation of the effective permittivity reduction while keeping a maximum residual surface area for, e.g., metallisation purposes. The shape of the optimum material distribution function features an ‘air pocket’ of small width and a depth being dependent on the application specific operating frequency.