CN100505355C - Pyroelectric infrared detector and composite film detecting member used therein - Google Patents
Pyroelectric infrared detector and composite film detecting member used therein Download PDFInfo
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- CN100505355C CN100505355C CNB2006100249202A CN200610024920A CN100505355C CN 100505355 C CN100505355 C CN 100505355C CN B2006100249202 A CNB2006100249202 A CN B2006100249202A CN 200610024920 A CN200610024920 A CN 200610024920A CN 100505355 C CN100505355 C CN 100505355C
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Abstract
The invention relates to a detecting element technique field of coextruded film pyroelectric infrared detector which is produced combining chemical method and physical method. The detecting element of pyroelectric infrared detector in the invention regards the monocrystalline silicon or complex with silica as substrate, porous silica membrane is the thermal insulation layer, dense silica film is transitional layer, platinum is base electrode, LNO film is down absorption layer and buffer layer, lead titanate iron conductive film is pyroelectric material, gold is upper electrode, LNO is upper absorption layer. The pyroelectric infrared detector in the invention can absorb more infrared radiation, and possesses less heat loss, so the infrared energy can be used by coextruded film in maximum degree, and LNO buffer layer increases the electrical property of PT to make detector possess perfect property. Besides, compounding the film with sol-gel processing, the evenness of componemt is high, temperature of process is low, it is easy to filming in large scale, without vacuum apparatus, the cost is low, and it is compatible with silicon integrated craft.
Description
Technical field
The present invention relates to a kind of detection unit technical field of the laminated film pyroelectric infrared detector in conjunction with the preparation of chemical method and physical method.
Background technology
Pyroelectric infrared detector is the receiving device that utilizes the pyroelectric effect detection infrared radiation of material.Have different electric dipole moments in the dielectric material, one of them does not produce owing to intermolecular positive and negative charge center does not overlap, and this dipole moment is called intrinsic electric dipole moment.Pyroelectricity material has the self poling effect, even do not having also there is electric dipole moment under the situation of external electric field.After pyroelectricity material was accepted to be detected the infrared radiation of object, its temperature changed, thereby distance between the dipole and bond angle change, and polarization intensity is changed.The polarization intensity size equals the dipole moment of unit volume, and its surface charge interior with appearing at crystalline electrode surface unit area is directly proportional, and therefore can survey the infrared energy that object radiation goes out by measuring the surface charge size.
Pyroelectric detector has the advantage that a lot of other Infrared Detectorss do not possess.At first, pyroelectric detector can be surveyed any making and survey the radiation that unit changes, promptly from the X ray to the microwave even particle; Secondly, its operating frequency is the wideest, both can be operated in several hertz even lower low frequency range, also can be operated in tens thousand of hertz high frequency region; In addition, because the pyroelectricity signal is proportional to the rate temperature change of device, so its response speed is very fast; Pyroelectric detector does not need refrigeration, does not require outer bias-field, reliability height, works long hours in addition, output signal is full TV compatibility.Pyroelectric infrared detector uses pottery and monocrystal material preparation more, generally adopts the integrated method of mixing, but that the problem of this method is complex process, rate of finished products is low, be difficult to realize high first number array.In addition, pottery and monocrystal material thickness are not easy attenuate, though adopt methods such as ion beam attenuate, chemical etching can obtain tens of microns thin slice, realize that integrated its rate of finished products of large tracts of land is lower, and cost is higher.Compare with monocrystal material with pottery, film pyroelectric detector thermal capacity is little, and response speed is fast; Can directly be deposited on the silicon chip, be easy to realize integrated with the silicon signal processing circuit; Cost of manufacture is low, is easy to realize suitability for industrialized production, has very much the potentiality of application.
The problem that the film-type pyroelectric infrared detector exists is to lack suitable absorbed layer material on the one hand, present infrared absorption layer structure mainly adopts melanism metal level, 1/4 wavelength absorption structure, thin metal absorbed layer etc., the shortcoming of melanism metal is that adhesive force is poor, 1/4 wavelength absorption structure is then to the thickness requirement strictness of electric heating film, and thin metal absorbed layer requires metal layer thickness accurate.
Summary of the invention
One of purpose of the present invention is exactly to overcome the deficiency that existing film-type pyroelectric infrared detector is surveyed unit, and a kind of detection unit that is easy to prepare and have the laminated film pyroelectric infrared detector of nickel acid lanthanum LNO absorbed layer and resilient coating is provided.
Another object of the present invention provides a kind of above-mentioned this novel pyroelectric infrared detector of surveying unit that has, and this detector can be the unit, also can be polynary detection array.
A further object of the invention provides the preparation method of the detection unit of above-mentioned this laminated film pyroelectric infrared detector with nickel acid lanthanum LNO absorbed layer and resilient coating.
Find that after deliberation nickel acid lanthanum LNO conductive oxide film has INFRARED ABSORPTION performance preferably, is easy to preparation, with electric heating film similar crystal structure is arranged, and is suitable as the absorbed layer material; Most of heat of detector absorption all scatters and disappears by silicon substrate on the other hand, can not effectively absorb for electric heating film, porous silica have lower thermal conductivity and with the semiconductor technology compatibility, preparation layer of silicon dioxide porous membrane between substrate and hearth electrode can effectively reduce hot-fluid from electric heating film scattering and disappearing to substrate.Because the porous silica surface ratio is more coarse, therefore need preparation one deck compact silicon dioxide film to reduce its surface roughness again.
Therefore, for reaching above-mentioned purpose, the technical scheme that the present invention takes is:
A kind of detection unit of pyroelectric infrared detector, be that complex with monocrystalline silicon or itself and silicon dioxide is a substrate, the porous silica film is a thermal insulation layer, the compact silicon dioxide film is a transition zone, platinum is hearth electrode, and nickel acid lanthanum LNO film is following absorbed layer and resilient coating, and lead titanates PT ferroelectric thin film is a pyroelectricity material, Au is a top electrode, and nickel acid lanthanum LNO film is last absorbed layer.
A kind of novel pyroelectric infrared detector, it surveys unit is to be substrate with monocrystalline silicon, the porous silica film is a thermal insulation layer, the compact silicon dioxide film is a transition zone, Pt is a hearth electrode, and nickel acid lanthanum LNO film is following absorbed layer and resilient coating, and lead titanates PT ferroelectric thin film is a pyroelectricity material, the Au gold is a top electrode, and nickel acid lanthanum LNO film is last absorbed layer.
The preparation method that described pyroelectric infrared detector is surveyed unit is as follows:
Pt electrode and Au electrode all adopt the preparation of direct current sputtering method in the pyroelectric infrared detector detection unit, and each layer of all the other except that substrate all adopts the sol-gel process preparation.
Preparation method's concrete steps that pyroelectric infrared detector is surveyed unit are:
The preparation of g, porous silica film thermal insulation layer: with tetraethoxysilane, glycerol and deionized water is raw material, and ammoniacal liquor is catalyst, adopts sol-gal process at SiO
2Preparation porous silica film PS on the/Si substrate;
The preparation of h, compact silicon dioxide film DS transition zone: with tetraethoxysilane, ethanol and deionized water is raw material, and hydrochloric acid is catalyst, adopts sol-gal process at PS/SiO
2Preparation compact silicon dioxide film DS on the/Si substrate;
I, adopt under the dc sputtering argon gas atmosphere at DS/PS/SiO
2Preparation Pt electrode on the/Si substrate;
The preparation of absorbed layer and resilient coating under j, the nickel acid lanthanum LNO film: with lanthanum nitrate, nickel acetate is raw material, and EGME is a solvent, and monoethanolamine is that chelating agent prepares nickel acid lanthanum
3Elder generation's liquid solution adopts sol-gal process at Pt/DS/PS/SiO
2The nickel acid lanthanum LNO film of preparation different-thickness on the/Si substrate;
The preparation of k, lead titanates PT ferroelectric thin film pyroelectricity material: with lead acetate, butyl titanate is raw material, and EGME is a solvent, and acetylacetone,2,4-pentanedione is that intercalating agent prepares lead titanates PT elder generation liquid solution, adopts sol-gal process at LNO/Pt/DS/PS/SiO
2Preparation lead titanates PT ferroelectric thin film on the/Si substrate;
1, adopts under the dc sputtering argon gas atmosphere at PT/LNO/Pt/DS/PS/SiO
2Preparation Au electrode on the/Si substrate, and prepare nickel acid lanthanum LNO film thereon as last absorbed layer.
Beneficial effect of the present invention: the porous silica film for preparing among the present invention has bigger porosity, so pyroconductivity is lower, can reduce thermal loss; The compact silicon dioxide film can effectively reduce the surface roughness of porous membrane, improves the interface of itself and electrode; And nickel acid lanthanum LNO film can effectively reduce the leakage current density and the dielectric loss of lead titanates PT film as resilient coating; Nickel acid lanthanum LNO film has good INFRARED ABSORPTION performance, can be used as the absorbed layer material, prepares nickel acid lanthanum LNO film up and down respectively at lead titanates PT film and can improve absorption to infrared energy.Therefore the absorption infrared radiation that the pyroelectric infrared detector among the present invention can be more, has less heat loss, thereby infrared energy can farthest be utilized by electric heating film, and nickel acid lanthanum LNO resilient coating improved the electric property of lead titanates PT, makes detector have excellent performance.In addition, with sol-gel process built up membrane microcell component uniformity height, the technical process temperature is low, is easy to the large tracts of land film forming, does not need vacuum equipment, and cost is low, and with silicon integrated technique compatibility.
Description of drawings
Fig. 1 is the infrared absorption spectroscopy of different-thickness nickel acid lanthanum LNO film.
Fig. 2 is that preparation is at LNO/Pt/DS/PS/SiO
2The dielectric constant of the lead titanates PT film the on/Si substrate is with the change curve of frequency.
Fig. 3 is that preparation is at LNO/Pt/DS/PS/SiO
2The dielectric loss of the lead titanates PT film the on/Si substrate is with the change curve of frequency.
Fig. 4 is that preparation is at LNO/Pt/DS/PS/SiO
2The leakage current density of the lead titanates PT film the on/Si substrate is with the change curve of electric field strength.
Fig. 5 surveys meta structure schematic diagram, the 1st, last absorbed layer, the 2nd, top electrode, the 3rd, electric heating film, the 4th, following absorbed layer and resilient coating, the 5th, hearth electrode, the 6th, transition zone, the 7th, thermal insulation layer, the 8th, substrate.
Embodiment
The concrete preparation method of each layer film is as follows in the laminated film pyroelectric infrared detector:
1, the preparation of porous silica film:
After 0.05mol tetraethoxysilane, 0.05mol glycerol and 0.5mol deionized water fully mixed, add 0.16g ammoniacal liquor.Stir after 40 hours, obtain even colloidal sol, add the 16.56g mass concentration again and be 5% polyvinyl alcohol (PVA) solution, stir, the middling speed qualitative filter paper filters the colloidal sol that obtains clear.With colloidal sol at substrate SiO
2The last rotation of/Si applies rotating speed 3000r/min, time 30s, 550 ℃ of following heat treatment 60min.Prepare the two-layer thick porous silica film (PS) of 2000nm altogether with the method, the porous membrane porosity is about 57.7%.
The concrete manufacturing process of PVA solution is: respectively take by weighing PVA and deionized water at 1: 19 according to mass ratio, water-bath is heated to 100 ℃ after swelling on the blender stirs 6h then, after treating that the PVA particle dissolves fully, use the middling speed quantitative filter paper to filter while hot, obtain mass concentration and be 5% PVA solution.
2, the preparation of compact silicon dioxide film:
After tetraethoxysilane, ethanol and deionized water mixed according to mol ratio at 1: 4: 4, the pH value that adds the concentrated hydrochloric acid regulator solution is about 2, stir after 24 hours, the ethanol that adds original consumption twice dilutes solution, after stirring, obtain homogeneous transparent colloidal sol with the filtration of middling speed quantitative filter paper.With colloidal sol at substrate PS/SiO
2The last rotation of/Si applies rotating speed 3000r/min, time 20s, 550 ℃ of following heat treatment 60min.Prepare the thick compact silicon dioxide film (DS) of one deck 170nm with the method, porosity is less than 2%.
3, adopt under the dc sputtering argon gas atmosphere at DS/PS/SiO
2Pt electrode on the/Si substrate about preparation thickness 200nm.Pressure is 1 * 10
-1Mbar, electric current are 25mA, and the sputtering time of Au is 20min, and the sputtering time of Pt is 40min.
4, the preparation of nickel acid lanthanum LNO film:
Nickel acid lanthanum LNO elder generation the synthetic of liquid solution is at room temperature to carry out, and concentration is 0.2Mol/L.At first take by weighing the nickel acetate of 0.004mol, in the 20ml mixed liquor of 9: 1 EGME of volume ratio and monoethanolamine, constantly stir up to dissolving fully, the lanthanum nitrate that takes by weighing 0.004mol then joins in the mixed solution, constantly stir up to dissolving fully, the solution that obtains is filtered the navy blue nickel acid lanthanum LNO elder generation liquid solution that obtains clear with the middling speed quantitative filter paper.With first liquid solution at Pt/DS/PS/SiO
2Go up rotation on the/Si substrate and apply, rotary speed is 3000r/min, and time 20s, the wet film that obtains directly put into 500 ℃ Muffle furnace preliminary treatment 20min.Be cooled to room temperature after the taking-up, apply thin film down, move in circles up to the film that obtains desired thickness, at last with this film at 650 ℃ of following heat treatment 60min.Make the nickel acid lanthanum LNO film that thickness is respectively 50nm, 100nm, 150nm and 200nm different-thickness altogether.
5, the preparation of lead titanates PT film:
At first butyl titanate is dissolved in the acetylacetone,2,4-pentanedione, mol ratio is 1: 2, stirred under the room temperature 2 hours, simultaneously, lead acetate (with the mol ratio of butyl titanate be 1: 1) in EGME, be heated to 120 ℃ of dissolvings.The mixture of titanium and acetylacetone,2,4-pentanedione is joined in the EGME solution of lead acetate.Solution is stirred 30min down at 80 ℃, filter the PbTiO of the 0.3Mol/L that obtains yellow transparent with the middling speed quantitative filter paper
3Elder generation's liquid solution.At LLNO/Pt/DS/PS/SiO
2On/Si the substrate, adopt the method for spin coated to prepare lead titanates PT film, rotary speed is 3000r/min, and the time is 20s.The wet film that obtains is directly put into 500 ℃ Muffle furnace preliminary treatment 20min.After film applies preliminary treatment through 10 times, at 600 ℃ of following heat treatment 60min.With 10 layers of lead titanates PT ferroelectric thin film that about 500nm is thick of the method preparation.
6, adopt under the dc sputtering argon gas atmosphere at PT/LNO/Pt/DS/PS/SiO
2Au electrode on the/Si substrate about preparation thickness 100nm, and prepare nickel acid lanthanum LNO film thereon as last absorbed layer.Pressure is 1 * 10
-1Mbar, electric current are 25mA, and the sputtering time of Au is 20min, and the sputtering time of Pt is 40min.
Claims (5)
1, a kind of detection unit of pyroelectric infrared detector, it is characterized in that: be that complex with monocrystalline silicon or itself and silicon dioxide is a substrate, the porous silica film is a thermal insulation layer, the compact silicon dioxide film is a transition zone, Pt is a hearth electrode, and nickel acid lanthanum LNO film is following absorbed layer and resilient coating, and lead titanates PT ferroelectric thin film is a pyroelectricity material, Au is a top electrode, and nickel acid lanthanum LNO film is last absorbed layer.
2, the detection unit of pyroelectric infrared detector as claimed in claim 1 is characterized in that: porous silica film thermal insulation layer thickness is 2000nm, and porosity is 57.7%; Compact silicon dioxide film transition bed thickness 170nm, porosity is less than 2%; The Pt electrode is 200nm; Nickel acid lanthanum LNO film thickness is respectively 50nm, 100nm, 150nm and 200nm; Lead titanates PT ferroelectric thin film is 500nm; The Au electrode is 100nm.
3, a kind of pyroelectric infrared detector is characterized in that: the detection unit of this pyroelectric infrared detector is the detection unit of the arbitrary described pyroelectric infrared detector of claim 1～2, and this detection unit can use separately, also can be polynary detection array.
4, the described pyroelectric infrared detector of claim 1 is surveyed the preparation method of unit, and this method is that all the other each layers except that substrate all adopt the sol-gel process preparation, and Pt electrode and Au electrode all adopt the preparation of direct current sputtering method.
5, pyroelectric infrared detector as claimed in claim 4 is surveyed the preparation method of unit, and it is characterized in that: the step that this method is concrete is:
The preparation of a, porous silica film thermal insulation layer: with tetraethoxysilane, glycerol and deionized water is raw material, and ammoniacal liquor is catalyst, adopts sol-gal process at SiO
2Preparation porous silica film PS on the/Si substrate;
The preparation of b, compact silicon dioxide film DS transition zone: with tetraethoxysilane, ethanol and deionized water is raw material, and hydrochloric acid is catalyst, adopts sol-gal process at PS/SiO
2Preparation compact silicon dioxide film DS on the/Si substrate;
C, adopt under the dc sputtering argon gas atmosphere at DS/PS/SiO
2Preparation Pt electrode on the/Si substrate;
The preparation of absorbed layer and resilient coating under d, the nickel acid lanthanum LNO film: with lanthanum nitrate, nickel acetate is raw material, and EGME is a solvent, and monoethanolamine is that chelating agent prepares nickel acid lanthanum LNO elder generation liquid solution, adopts sol-gal process at Pt/DS/PS/SiO
2The nickel acid lanthanum LNO film of preparation different-thickness on the/Si substrate;
The preparation of e, lead titanates PT ferroelectric thin film pyroelectricity material: with lead acetate, butyl titanate is raw material, and EGME is a solvent, and acetylacetone,2,4-pentanedione is that chelating agent prepares lead titanates PT elder generation liquid solution, adopts sol-gal process at LNO/Pt/DS/PS/SiO
2Preparation lead titanates PT ferroelectric thin film on the/Si substrate;
F, adopt under the dc sputtering argon gas atmosphere at PT/LNO/Pt/DS/PS/SiO
2Preparation Au electrode on the/Si substrate, and prepare nickel acid lanthanum LNO film thereon as last absorbed layer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101201271B (en) * | 2007-12-21 | 2010-05-26 | 云南民族大学 | Internal modulation type ferro-electricity non-refrigeration infrared focal plane prober |
| CN101862505B (en) * | 2010-07-15 | 2014-07-30 | 四川大学 | Self-electroosmosis hydrogel adhesive film |
| CN103943771A (en) * | 2014-05-12 | 2014-07-23 | 中国科学院上海硅酸盐研究所 | Relaxation ferroelectric monocrystal pyroelectric infrared detector and preparation method thereof |
| CN104846370A (en) * | 2015-04-20 | 2015-08-19 | 河南师范大学 | Preparation method of gold-lanthanum nickelate layered composite conductive thin film material |
| CN106289539A (en) * | 2016-09-06 | 2017-01-04 | 西安交通大学 | A kind of method and apparatus for real-time monitoring chemical reaction process |
| CN106872052B (en) * | 2017-02-17 | 2019-12-13 | 电子科技大学 | Absorption film system structure of wide-spectrum pyroelectric detector and preparation method thereof |
| CN108198897B (en) * | 2017-12-12 | 2020-08-04 | 南京邮电大学 | Graphene field effect transistor quantum dot photoelectric detector and preparation method thereof |
| WO2020157029A1 (en) * | 2019-01-29 | 2020-08-06 | Trinamix Gmbh | Optical detector |
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Non-Patent Citations (2)
| Title |
|---|
| LNO薄膜的射频磁控溅射制备及其电学性能与红外吸收性能. 王震东，赖珍荃，范定环，张景基，黄志明.南昌大学学报(理科版)，第29卷第6期. 2005 |
| LNO薄膜的射频磁控溅射制备及其电学性能与红外吸收性能. 王震东，赖珍荃，范定环，张景基，黄志明.南昌大学学报(理科版)，第29卷第6期. 2005 * |
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