The present invention relates to a method for manufacturing an infrared detection element using the temperature dependence of spontaneous polarization of ferroelectrics. As an infrared detection element generally used for consumer appliances, there is a pyroelectric infrared detection element using the characteristics of changing of spontaneous polarization due to temperature changes.
In the pyroelectric infrared detection element, infrared light supplied to an infrared detection element periodically interrupted by a chopper. According to temperature dependence of the infrared detection element synchronized with the interruption frequency by the chopper, the infrared detection element is charged. The charge is amplified by an amplifier and read as a current or a voltage, thus infrared light is detected.
An example of a conventional pyroelectric infrared detection element already put into practical use is shown in
Further, to solve such problems of the infrared detection element using a pyroelectric substance, production of an infrared detection element using a thin pyroelectric film has been tried. An example of a conventional infrared detection element using a thin pyroelectric film is shown in
However, a pyroelectric property of such a thin polycrystalline BST film, particularly ferroelectricity that is a basis for development of the pyroelectricity, is far inferior to that of BST ceramics sintered at a high temperature. Moreover, the thinner the film is made, the more degraded are the ferroelectricity and the pyroelectric property in the prior art. Namely, when a thin polycrystalline pyroelectric film is used, the infrared detection element can be made thin and small. There is, however, a problem arises that the detection sensitivity is greatly reduced.
To make rapid improvement in the ferroelectric property and the pyroelectric property of such a thin pyroelectric film, a method for using a thin single-crystalline pyroelectric film by epitaxial growth has been proposed (see Japanese Patent No.3094753).
A manufacturing process of a conventional infrared detection element using the thin single-crystalline pyroelectric film is exemplary shown in
The infrared detector composed of a thin single-crystalline PZT film with the heat resistant support, which is manufactured through such a complicated process as described, proved that the sensitivity is far higher than that of a detector composed of a thin polycrystalline film. However, there are problems in the infrared detector that the manufacturing process is complicated, that the yield rate is low, and that the cost is high.
Having made a number of experiments and theoretical analyses to improve the performance of an infrared detector using such a thin single-crystalline pyroelectric film, the inventors have found for the first time limits or problems on use of the thin single-crystalline pyroelectric film supported in the air. The discovered problems will be described hereunder in detail.
BaTiO3, one of the ferroelectrics for example, shows a primary phase transition in a following manner as temperature rises from a low temperature; rhombohedral crystal→rhombic crystal→tetragonal crystal→cubic crystal. Further, when the temperature becomes lower from a high temperature, a primary phase transition, from cubic crystal to tetragonal crystal occurs inversely. In the course of the phase transition from the cubic crystal to the tetragonal crystal due to the temperature decrease, a and b axes shrink by about 0.005 Å and c axis extends by 0.01 Å, from their original length of 4.01 Å at the curie temperature. With the phase transition, spontaneous polarization of 18 μC/cm2 is generated in the crystal.
This discontinuous change of the lattice constant in the phase transition of the ferroelectrics brings about a discontinuous change in the temperature property of the spontaneous polarization. The discontinuous changes of the spontaneous polarization with the temperature in the neighborhood of the Curie temperature make accurate temperature measurement unable in the neighborhood of the Curie temperature.
The present invention provides a method for manufacturing an infrared detection element, which eliminates a discontinuous primary phase transition of ferroelectrics based on the fact described, and enables the accurate temperature measurement even in the neighborhood of the Curie temperature.
Further, the present invention is made to provide a method for manufacturing an infrared detection device incorporating the infrared detection element.
A method for manufacturing an infrared detection element according to the present invention has steps of:
providing a single-crystalline base layer with a thickness of 50 nm to 10 μm having a principal surface,
forming a first electrode layer on a principal surface of the single-crystalline layer,
forming a single-crystalline or a unidirectioally oriented ferroelectric layer on the first electrode layer, so that a distortion of which is elastically constrained by the single-crystalline base layer in a plain parallel to the principal surface of the single-crystalline base layer, and
forming a second electrode layer on the ferroelectric layer.
In the method for manufacturing an infrared detection element according to the present invention, the elastic restriction on the ferroelectric layer is not sufficient when the thickness of the single-crystalline base layer is less than 50 nm. However, when the thickness of the single-crystalline base layer is more than 10 μm, heat capacity becomes large and the response to infrared light thus becomes slow.
Further, in the method for manufacturing an infrared detection element of according to the present invention, it is preferable that the ferroelectric layer has the perovskite structure so that the amount of charge in the ferroelectric layer may change depending on the temperature change caused by irradiation of infrared light.
Further, in the method for manufacturing an infrared detection element according to the present invention, it is preferable that the ferroelectric layer has a main component of Ba1-xSrxTiO3 (0≦×≦1).
Further, in the method for manufacturing an infrared detection element according to the present invention, the first electrode layer is a noble metal layer such as Au, Pt or a conductive oxide layer of the perovskite structure and having a thickness of preferably 1 μm or less, thereby effectively transferring the elastic restrictive force of the single-crystalline layer to the ferroelectric layer.
Further, in the method for manufacturing an infrared detection element according to the present invention, it is preferable that the single-crystalline layer is a single-crystalline silicon layer having a surface oriented to (001) direction and the ferroelectric layer is grown so as to have a surface oriented to (001) direction through an epitaxial growth or any other manufacturing method.
Further, in the method for manufacturing an infrared detection element according to the present invention, it is preferable that the a and b axes of the ferroelectric layer are formed within a surface parallel to the principal surface of the semiconductor layer and the c axis of the ferroelectric layer is formed in a direction perpendicular to the principal surface of the semiconductor layer.
Further, the method for manufacturing an infrared detection element according to the present invention has steps of:
forming a silicon single-crystalline base layer with a thickness of 50 nm to 10 μm having a principal surface,
forming a first electrode layer on a principal surface of the single-crystalline layer,
forming a single-crystalline ferroelectric layer by an epitaxial growth or an unidirectioally oriented ferroelectric layer by orientation growth on the principal surface of the single-crystalline base layer, and
forming a second electrode layer formed on the ferroelectric layer.
Further, the method for manufacturing an infrared detection element according to the present invention has steps of:
forming a single-crystalline base layer with a thickness of 50 nm to 10 μm having a principal surface,
forming a first electrode layer on the principal surface of the single-crystalline layer,
forming a first ferroelectric layer on the first electrode layer, which is composed of a single-crystalline layer or a unidirectioally oriented layer, and a distortion of which is elastically constrained by the single-crystalline base layer in a plain parallel to the principal surface of the single-crystalline base layer,
forming an infrared detection element having a second electrode layer on the ferroelectric layer,
forming a third electrode layer on the principal surface of the single-crystalline base layer,
forming a second ferroelectric layer on the first electrode layer, which is composed of a first single-crystalline layer or a unidirectioally oriented layer, and a distortion of which is elastically constrained by the single-crystalline base layer in a plain parallel to the principal surface of the single-crystalline base layer,
forming a reference cell having a fourth electrode layer on the ferroelectric layer, and
forming an infrared reflection film on the reference cell.
To consider the theory of a discontinuous primary phase transition of ferroelectrics, the inventors simulated the relation between the lattice constant and the temperature of a single crystal BaTiO3 introducing the Legendre transformation.
As shown with the lines (1) in
On the other hand, as shown in the property (2) of the single crystal BaTiO3 when the “a” and “b” axes are fixed and the “c”axis is not fixed, it is seen that the lattice constant of the “a” and “b” axes and that of the “c”axis slowly change at a lower side of the Curie temperature (about 132° C.). This is due to the occurrence of a continuous secondary phase transition between a tetragonal crystal and a cubit crystal instead of the primary phase transition by restricting the movement of the single crystal BaTiO3 in the directions of the “a”, “b” and “c” axes and by not restricting the movement in “c” axis, even though the single crystalline BaTiO3 have a tetragonal crystal structure on the lower side and a cubic crystal structure on the higher side of the Curie temperature (about 132° C.).
Further, the inventors simulated the relation between the spontaneous polarization and the temperature of the single crystal BaTiO3 based on the results shown in
As shown with the line (1) in
On the other hand, as shown with the property (2) in
In the aforementioned experiment, BaTiO3 is used as a ferroelectric material. However, other ferroelectric materials such as BST or PLT can be used with an equal effect. When BaTiO3 is used as a ferroelectric, the Curie temperature for restricting the distortion of the crystal within a surface is higher than a room temperature of, for example, 112° C. However, when BST having a composition of about Ba0.5 Sr0.5TiO3, in which a part of Ba of BaTiO3 is replaced with Sr is used, the Curie temperature can be selected to be a temperature close to the room temperature, which is convenient to the infrared detection element.
Based on the result described, the present invention provides an infrared detection element having a single-crystalline base layer with a thickness of 50 nm to 10 μm having a principal surface, a first electrode layer formed on the principal surface of the single-crystalline layer, a ferroelectric layer formed on the first electrode layer being composed of a single-crystalline layer or a unidirectioally oriented layer so that distortion in crystalline structure of the ferroelectric layer in a plain parallel to the principal surface of the single-crystalline base layer is elastically constrained by the single-crystalline base layer, and a second electrode layer formed on the ferroelectric layer, wherein an amount of a charge changes in accordance with a change in a temperature caused by irradiation of infrared light and the amount the charge is detected as an electric signal from the first and second electrode layers.
More specifically, a highly sensitive infrared detection element can be realized exhibiting a property shown lines (2) in
The thickness of the single-crystalline layer forming the base substrate for the ferroelectric layer is selected between 50 nm and 10 μm. The reason is that when the thickness is less than 50 nm, the lattice constant of the ferroelectric layer cannot be constrained sufficiently in a plain parallel to the surface of the substrate. Further, the reason is that when the thickness is selected larger than 10 μm, heat capacity becomes large, which make it difficult for heat radiate quickly, and sensitivity gets worse. More preferably, the thickness is between 200 nm and 2 μm.
Further, to sufficiently fix the lattice constant of the ferroelectric layer in the plain parallel to the surface of the substrate, the thickness of the ferroelectric layer is preferably thinner than that of the single-crystalline layer of the base.
Further, a semiconductor crystal such as silicon or a compound semiconductor single crystal such as SiGe or GaAs may be used for the single-crystalline base layer.
Further, a silicon single-crystalline substrate having a surface oriented to (100) direction is preferable for the epitaxial growth or oriented growth of the ferroelectric layer.
Further, a conductive oxide having a perovskite structure is preferable for the first electrode layer. The reason is that the bonding between the single-crystalline base layer forming the base substrate and the ferroelectric layer forming the upper layer is made strong and the single-crystalline base layer constraines the ferroelectric layer in the plain parallel to the surface of the substrate more strongly. Furthermore, the reason is that when a conductive oxide having the perovskite structure is used as the first electrode layer, the crystallinity of the ferroelectric layer is improved.
As shown in
The single-crystalline or single-oriented ferroelectric layer 5 composed of Sr1-xBaxTiO3 is formed on the first electrode layer 4. The single-crystalline base layer 3 elastically constraines distortion of the crystal structure of the ferroelectric layer 5 in a plain parallel to the surface of the single-crystalline base layer 3. The distortion in a direction perpendicular to the surface of the single-crystalline base layer 3 is not constrained but is free. When the semiconductor layer 5 has the perovskite structure, for example, directions of “a” and “b” axes are oriented in the plain parallel to the surface of the single-crystalline base layer 3 and “c” axis is oriented in the direction perpendicularly to the surface.
A second electrode layer 6 is formed on the ferroelectric layer 5. The second electrode layer 6 preferably has crystallinity and conductivity. For example, a conductive oxide such as SrRuO3 is preferable having the perovskite structure.
The infrared detection element thus formed can detect infrared light accurately with a high sensitively even in the neighborhood of the Curie temperature.
A method for manufacturing the infrared detection element and infrared detector using the element will be described.
In a first step, a hollow 12 is formed in the neighborhood of the surface of a silicon substrate 11,having a surface oriented to (100) direction as shown in
A method for forming the hollow 12 is described below.
As shown in
In a second step, as shown in
In a third step, as shown in
In a fourth step, as shown in
In a fifth step, an inter-layer insulating film 17 composed of silicone oxide is formed on the reference cell D by the CVD method and then an is formed on the inter-layer insulating film 17. The infrared reflection film 18 prevents the temperature due to infrared light from being transmitted to the reference cell D. In this way, an infrared detector is manufactured.
The operation principle of the infrared detection element will be explained by referring to
As shown by dashed lines in
In the infrared detection element of the sense cell S, a potential is applied between the first and the second electrode layers 4, 6 and the magnitude P1 of a turnover charge of the ferroelectric layer 5 is detected as a voltage or a current. With respect to the reference cell D with no infrared light being irradiated, the hysteresis curve of which is shown by solid lines in
In the infrared detector, the circumferential part of the ceiling 3 of the hollow 12 formed in the silicon substrate 11 is cut off (FIGS. 10(a) and (b) ). Namely, the sense cell S composed of the single-crystalline base layer 3, the first electrode layer 4 (lower electrode layer), the ferroelectric layer 5, and the second electrode layer 6 (upper electrode layer) is separated from the silicon substrate 11 except for an end portion of the sense cell S.
With the main portion of the infrared detection element being separated from the silicon substrate 11 as described, high sensitivity of the cell is realized since an electric distortion is easily generated in the ferroelectric layer 5 and since the amount of heat leaking from the periphery of the sense cell S can be reduced, when the infrared light is irradiated to the sense cell S causing a change in the temperature of the ferroelectric layer 5. In the infrared detector shown in
In the infrared detector shown in
In a second step, as shown in
In a third step, as shown in
In a fourth step, as shown in
By selective etching for the sacrifice layer 32 in the manner described, the infrared detection element is formed.
According to the present invention, it is possible to measure a temperature accurately with high precision even of a substance in the neighborhood of the Curie temperature by elastically constraining the crystal structure of the single crystalline layer in the plain parallel to the surface of the base single-crystalline layer, on which the ferroelectric layer is formed and by preventing the discontinuous primary phase transition due to the change of the temperature.
Number | Date | Country | Kind |
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2001-074541 | Mar 2001 | JP | national |
This is a divisional application of Ser. No. 10/097,405, filed on Mar. 15, 2002.
Number | Date | Country | |
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Parent | 10097405 | Mar 2002 | US |
Child | 10901110 | Jul 2004 | US |