Characterization of materials for integrated pyroelectric sensors

doi:10.1016/0924-4247(91)87023-V

Sensors and Actuators A: Physical

Volume 26, Issues 1–3, March 1991, Pages 407-411

Dedicated to Professor Dr K. H. Härdtl on the occasion of his 60th birthday.

https://doi.org/10.1016/0924-4247(91)87023-V Get rights and content

Abstract

The pyroelectric element in an integrated IR sensor is usually in good thermal contact with the silicon chip. To characterize materials for these applications, heat sink figures of merit are introduced and various materials are compared. Integrated arrays with the materials poly(vinylidene fluoride) (PVDF) and LiTaO₃ are realized. The measured specific detectivity of arrays with 40 μm thick PVDF is D* = 1.4 × 10⁷ cm √Hz/W.

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Fig. 5 shows the frequency dependence of the dielectric constant (ε) and the dielectric loss (tanδ) at RT. The values obtained for both poled samples are in the range of values of 8–9 (at 1 kHz) reported for ε for poled samples [45–48]. There is little difference between the differently processed samples, but smaller values were obtained for the EFC-P and conventionally poled samples as a result of dipole moment orientation.
Uniform thin films of poly(vinylidene fluoride)-trifluoroethylene copolymers were spin-coated and their functional electrical properties were investigated after corona poling. The copolymers were poled in the gel state at room temperature (RT) without stretching or annealing treatment. This E-field crystallisation processing method at RT leads to the formation of improved ferroelectric and pyroelectric properties in the investigated thin films. That processing method has great potential for ferroelectric material coatings on thermally highly sensitive substrates. The selected composition (∼1 µm thick composites of 65/35 mol% PVDF-TrFE) of the copolymer produced a pyroelectric coefficient value of 36 ± 3 µC/m²K¹, a dielectric constant of 9, and a dielectric loss of about 0.018 at a frequency of 1 kHz under ambient conditions.
An accurate dynamic method for determining pyroelectric coefficient of ferroelectric materials
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A lot of methods for pyroelectric coefficient measurement have been developed in literatures which, however, are not accurate enough, as a result, there is no standard device for pyroelectric coefficient measurement hitherto. In this work, a dynamic method has been reported and successfully applied back propagation neural network (BPNN) to the control of thermo electric cooler (TEC). It averts poor calculative ability of monolithic computing machine by taking advantage of powerful calculative ability of Matlab on PC and therefore realizes sinusoidal-wave and triangular-wave temperature control with high accuracy. Practical p measurement results for classic ferroelectric materials such as polyvinylidene fluoride (PVDF), lithium tantalate (LT) and lead zirconium titanate (PZT) samples revealed that relative measurement error with sinusoidal-wave temperature control was less than 10%, implying its good accuracy and practical ability.
Universal Curie constant and pyroelectricity in doped ferroelectric HfO<inf>2</inf> thin films
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The figures of merit are all linearly proportional or proportional to the square of the pyroelectric coefficient which is highest in Hf0.5Zr0.5O2. The figures of merit for the voltage and current sensitivity is roughly 70% and 50% of LiTaO3 [42], a leading commercial pyroelectric material which is neither CMOS compatible nor shown to be capable of being grown into 3-dimensional capacitor structures. The clear process advantages and ability to fabricate high surface area devices with ferroelectric HfO2 make the films more attractive for embedded energy harvesting applications than the leading pyroelectric materials.
Pyroelectric coefficients are measured for Si, Sr, La, Al, and Gd doped HfO₂ thin films as well as the solid-solution Hf_0.5Zr_0.5O₂ composition from 280 to 440 K. Pyroelectric currents show sensitivity to the dopant used to stabilize ferroelectricity in HfO₂. Large pyroelectric coefficients up to 70 μC cm⁻² K⁻¹ were measured in films with the largest remanent polarization magnitudes, La-doped HfO₂ and Hf_0.5Zr_0.5O₂. A temperature-driven ferroelectric to antiferroelectric-like transition influences the pyroelectric coefficient and is found only in Si-doped HfO₂ thin films. The transition is shown to produce a decrease in the Curie constant with temperature and thus deviates from the Curie law, although most ferroelectric films reported here obey the Curie law. Independent measurements of the remanent polarization, relative permittivity, and pyroelectric coefficient are used to extract the Curie constants of the thin films. The fundamental thermodynamic relationship between the dielectric, ferroelectric, and pyroelectric properties of ferroelectric HfO₂ thin films are established based on Landau theory with a universal Curie constant of 5.8 × 10⁻⁷ ± 0.46 × 10⁻⁷ K C V⁻¹ m⁻¹ (Landau coefficient, α₀ = 1.72 × 10⁶ ± 0.138 × 10⁶ V m K⁻¹ C⁻¹) for ferroelectric HfO₂ independent of doping concentration and dopant type. An electro-thermal coupling factor of 1.9 × 10⁻³ and a voltage responsivity figure of merit of 0.085 m²/C illustrate the promising potential of ferroelectric HfO₂ thin films for use in embedded energy harvesting and infrared sensing circuits.
Pyroelectric and electrocaloric effects and their applications
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In this chapter, applications based on pyroelectricity and electrocaloric effects in ferroelectric thin films with a fluorite structure are reviewed. It is known that giant pyroelectricity and electrocaloric effects can occur near phase transitions between ferroelectric and paraelectric crystal phases. Compared to conventional ferroelectrics, fluorite-structure ferroelectrics are theoretically expected to exhibit a phase transition over a much broader temperature range. As a result, they are highly promising for pyroelectric energy harvesting and electrocaloric cooling because a large entropy change can be induced across a wide temperature range. Moreover, large electric fields can be applied due to their high breakdown field strength, which can be related to a larger electronic bandgap compared to conventional perovskite-structured materials. Therefore, large quantities of conversion between thermal and electrical energy can be achieved over the wide temperature and electric field ranges. Furthermore, the pyroelectricity of fluorite-type ferroelectrics for infrared sensor application has also been examined. Even from the very first reports on this topic, pyroelectric voltage figures of merit of these new materials were comparable to those of other promising candidates. Therefore, fluorite-type ferroelectrics are highly promising for the aforementioned applications from both theoretical and experimental considerations.
Ferroelectric phase transitions in nanoscale HfO<inf>2</inf> films enable giant pyroelectric energy conversion and highly efficient supercapacitors
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While FI is lower than most materials in Table 1 it is almost twice as high compared to PVDF [10]. Additionally, the signal-to-noise FOM FD is also comparable to PVDF [10]. The electrothermal coupling factors k2 for Si:HfO2 calculated here are more than one order of magnitude higher compared to the best values reported so far and even two and a half orders of magnitude higher than for example PVDF and many other materials [4,10].
Temperature- and field-induced phase transitions in ferroelectric nanoscale TiN/Si:HfO₂/TiN capacitors with 3.8 to 5.6 mol% Si content are investigated for energy conversion and storage applications. Films with 5.6 mol% Si concentration exhibit an energy storage density of ~40 J/cm³ with a very high efficiency of ~80% over a wide temperature range useful for supercapacitors. Furthermore, giant pyroelectric coefficients of up to −1300 µC/(m² K) are observed due to temperature dependent ferroelectric to paraelectric phase transitions. The broad transition region is related to the grain size distribution and adjustable by the Si content. This strong pyroelectricity yields electrothermal coupling factors k² of up to 0.591 which are more than one order of magnitude higher than the best values ever reported. This enables pyroelectric energy harvesting with the highest harvestable energy density ever reported of 20.27 J/cm³ per Olsen cycle. Possible applications in infrared sensing are discussed. Inversely, through the electrocaloric effect an adiabatic temperature change of up to 9.5 K and the highest refrigerant capacity ever reported of 19.6 J/cm³ per cycle is achievable. This might enable energy efficient on-chip electrocaloric cooling devices. Additionally, low cost fabrication of these films is feasible by existing semiconductor process technology.
The electrical response of the modified lead titanate-based thick films
2009, Physica B: Condensed Matter
The modified lead titanate (PT) based thick films were fabricated using thick film transfer (TFT) technique. The pyroelectric and dielectric behavior ascertained plausible usage as infrared detectors for these films. The conduction processes in these films are represented by the development of an equivalent circuit model that portrays a near perfect dielectric material containing traps. Various “materials’ figures-of-merit” of modified PT films are determined for their potential use as infrared detector. Based on existing information these material properties are found to be reasonable.

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Characterization of materials for integrated pyroelectric sensors

Abstract

Sensors and Actuators

Sensors and Actuators A

Pyroelectric devices and materials

Rep. Prog. Phys.

A simple technique to interface pyroelectric materials with silicon substrates for infrared detection

Ferroelectrics Lett.