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  • G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
  • G01J5/20—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using resistors, thermistors or semiconductors sensitive to radiation, e.g. photoconductive devices
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  • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
  • H10F30/10—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices being sensitive to infrared radiation, visible or ultraviolet radiation, and having no potential barriers, e.g. photoresistors
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  • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
  • H10F39/10—Integrated devices
  • H10F39/12—Image sensors
  • H10F39/15—Charge-coupled device [CCD] image sensors
  • H10F39/157—CCD or CID infrared image sensors
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Definitions

• the present invention relates to the use of thin layers based on iron monoxides and spinel oxides as a sensitive material for the detection of infrared radiation. infrared radiation detection.
• Thermal infrared detection devices like bolometric detectors, are able to absorb incident infrared radiation and convert it into heat. They generally comprise a sensitive element based on a material whose electrical resistance varies with temperature. The variation of temperature of the sensitive element causes a variation of the resistance of said sensitive element. These devices therefore make it possible, by means of a suitable electrical installation, known per se, to convert a modification of the temperature into an electrical signal.
• microbo meters having a plurality of microsensors arranged in the form of a matrix array of pixels.
• Each microsensor absorbs the infrared radiation that strikes it, and the resulting temperature variations of the sensitive material, present as a thin layer in each microsensor, induce a variation of the electrical resistance of said sensitive material.
• a measurement system known per se, evaluates the variations of the resistance and translates them into electrical signals. These electrical signals can be converted into images using an appropriate imaging device known per se.
• the present invention results more particularly from the discovery by the inventors that the combinations, in the form of thin layers, of iron monoxide with a spinel oxide also prove to be particularly effective as sensitive materials for the bolometric detection devices of the invention. infrared.
• the invention relates to the use as sensitive material in a thin layer for the bolometric detection of infrared radiation, of at least one combination of iron monoxide and spinel ferrite (s) (s). ) the chemical composition of which, apart from any doping agents present, meets the gross formula:
• Fe represents ferrous and / or ferric cations, identical or different
• - M represents metal cations, other than ferrous cations
• z represents the number of metal cations other than ferrous cations
• x is a number strictly less than 1 and strictly greater than 0.75.
• the terms "strictly greater or strictly inferior" exclude the value of the specified boundary.
• z can take values such that: 0 ⁇ z ⁇ 1.
• the material considered according to the invention is single-phase, has a structure of NaCl type and corresponds to the structural formula:
• Fe x (i -z ) .3 ⁇ + ⁇ M xz- ⁇ 0i-4 ⁇ represents the NaCl-type iron monoxide matrix in which the spinel aggregates are dispersed, with: ⁇ representing the number of M cations other than the ferrous cations, with within the "spinel aggregates", ⁇ representing the number of form units (Fe ⁇ M ⁇ O 4 ) aa contained in the set of "spinel aggregates", and M, Fe and O being as defined above.
• single-phase material means a material whose X-ray or electron diffraction pattern reveals only a system of lines, dots or rings attributable to a material of crystallographic structure. NaCl type.
• the material is considered according to the invention comprises a two-phase spinel oxide phase and a NaCl-type iron monoxide phase and can be defined as follows: ⁇ Fe 3-y M y O 4 + (l- ⁇ ) ( Fei -v M v) s O (III) wherein:
• Fe 3-y MyO4 represents a spinel oxide phase with: M, Fe and O being as defined above, v representing the number of cations M other than ferrous ions, present within the iron monoxide phase, representing the number of M cations other than the ferrous ions, present within the spinel phase, s being a number strictly less than 1 and strictly greater than 0.75, and ⁇ being a number satisfying the relation 0 ⁇ ⁇ l.
• two-phase material is understood to mean a material for which the X-ray or electron diffraction pattern reveals two systems of lines, dots or rings, one being characteristic of the material of spinel type, the other being characteristic of the NaCl type material.
• the present invention furthermore relates, according to another of its aspects, to a metrological device for the detection of infrared radiation or for infrared imaging, comprising at least one sensor provided with a sensitive element in the form of a thin layer of a single-phase material having a NaCl type structure or a two-phase material comprising a spinel oxide phase and an NaCl type oxide phase according to the present invention.
• It also relates, in another of its aspects, to a method of detecting infrared radiation or infrared imaging production, using a bo lomic device capable of absorbing incident radiation, converting it to heat, and communicating a portion of the heat generated to a sensitive element whose resistivity varies with temperature, wherein said device is as defined below.
• iron oxide or iron oxide
• Fei O solid solutions of oxygen in FeO
• wustite The equilibrium of the electrostatic charges within Fei -z 0 implies the formation of ferric ions (Fe 3+ ) by oxidation of a small proportion of ferrous ions.
• ferrous ions make up the majority of iron monoxide cations.
• the formation of ferric ions is at the origin of structural defects, described in detail by C.R.A. Catlow and B.E.F. Fender (J. Phys., C8, 3267, (1975)) on the one hand, and F.
• Fei- z 0 oxides can thus be described by the formulas of the type: OL (Fe 2+ FeI + O 4 2 " ), (1-Aa) (Fe 1+ O 1 ' ) or: ⁇ (Fe 3 O 4) X (I - Aa) (FeO) if the divalent and trivalent cations are not differentiated.
• ⁇ (Fe 2+ Fe + O 4 - ) and ⁇ (Fe 3 O 4 ) in the preceding formulas refer to the spinel type aggregates, while the second parts of the preceding formulas represent a carbon monoxide. perfectly stoichiometric iron.
• the inventors have therefore found that the use of a combination of iron monoxide and ferrite (s) spinel (s) as a sensitive material for infrared detection devices Io metrics is particularly advantageous for obtaining a material having a moderate electrical resistivity, associated with a low noise sequence and very sensitive to temperature.
• the two phases can be characterized as diffraction of X-rays or electrons.
• the NaCl phase can, from a degree of presence too high in spinel phase, be difficult to characterize, although present. Nevertheless, the Mossbauer spectroscopy more particularly proposed to carry out this characterization of phases makes it possible, in such a case, to discern the two phases.
• Such a material is described as NaCl type and spinel ferrite according to the invention.
• x satisfies the condition 0.85 ⁇ x ⁇ 1, preferably 0.85 ⁇ x ⁇ 0.95 and even more preferably 0.85 ⁇ x ⁇ 0.90.
• Fe represents all iron cations (ferrous and ferric).
• M is a metal other than iron or a combination of two or more metals other than iron.
• M can be symbolized in the general formula I by the sequence x M oM 'x iM "X 2 wherein M, M', M '... are metal other than iron and Xo indexes , xi and x 2 represent the number of ions M, M ', M "...
• M may be a monovalent metal cation selected from Cu, Li, Na or divalent selected from Co, Ni, Zn, Cu, V, Mg, Mn or a metal cation selected from rare earths having an ionic radius compatible with a integration in the spinel oxide structure or in the structure of NaCl-type iron monoxide.
• the materials considered according to the invention may of course also contain other iron oxides and / or mixed oxides than the spinel ferrites and NaCl-type monoxides provided that their crude formulas remain in accordance with the empirical formula
• the materials may comprise, for example, Fe 2 O 3 , of type x or ⁇ , the material will then be three-phase.
• a material of the invention may further comprise an iron sesquioxide, in particular CC-Fe 2 O 3 .
• compositions of the iron monoxide or spinel phase, or else the monoxide and spinel oxide phases in the case of a biphasic material may be modified by doping agents, which are not represented by the formulas (I) to (III) and which are not necessarily part of the crystal lattice.
• doping agents which are not represented by the formulas (I) to (III) and which are not necessarily part of the crystal lattice.
• the use of a large number of doping agents has been described for this type of compounds.
• the presence of doping agents can for example facilitate the regulation of crystallization.
• the doping agents are present in the form of oxides in a weight proportion not exceeding 1 to 2% by weight, relative to the weight of the spinel oxide.
• Doping agents are for example silicon, phosphorus, boron, alkaline earth metals (in particular Ca, Ba, Sr), alkali metals (eg Na, K), gallium, germanium, arsenic, indium, antimony, bismuth, lead, etc.
• the materials used according to the invention may be amorphous or crystalline, and in particular they will preferably be in the form of thin films consisting of crystallites with a diameter of between 5 and 50 nm and preferably between 10 and 30 m.
• the obtaining of a thin layer of the sensitive material according to the invention, on a suitable substrate can be carried out according to the usual techniques, in particular by sputtering, starting from a target obtained in a conventional manner by sintering a mixture of oxide powders of the various metals chosen, and possibly of doping agents (the latter optionally being in the form of oxides).
• the layer can also be obtained by sputtering a metal target or an oxide-metal cermet with an oxygen-containing plasma.
• the spinel type aggregates are generally not stabilized in the Fe 2 O 2 powders obtained by quenching from high temperatures (at least greater than 600 ° C.). Indeed, thermal energy is sufficient in this case to destroy the largest and most complex aggregates of defects.
• Fei- z O oxides in the "massive" state are semiconductors whose conductivity can reach several tens of Siemens per centimeter (S / cm).
• S / cm Siemens per centimeter
• spinel aggregates due to an increase in the oxidation state of the entire thin layer, tends to create a two-phase system comprising a NaCl type monoxide and a spinel oxide. These two-phase layers may also have semiconducting properties, due in particular to the electronic conduction by electron jumps ("hopping" according to Anglo-Saxon terminology) in the two phases present.
• cathodic sputtering technique that can be implemented to obtain a thin layer of the sensitive material according to the invention on a suitable substrate, it is a method for deposition on a substrate of thin films of any material, in an enclosure containing an inert gas, generally argon maintained at reduced pressure.
• the gas Under the influence of an electric field, the gas is ionized with formation of a luminescent plasma, and the shock of the ions incident on the material, called “target material” or “target”, which is fixed on a subject electrode. at a cathodic potential, causes, by a mechanical effect, the expulsion of surface atoms of the material that will be deposited on the substrate placed in front of the target.
• the composition of the deposit is close to the composition of the target material.
• the use of alternating voltages, in particular at high frequencies, has various advantages, in particular the spraying of insulating materials and the possibility of using lower starting voltages than in direct current.
• One such method is called radio frequency cathodic sputtering (or RF sputtering).
• the oxidation state of the deposited layer and therefore the nature of the oxide obtained depend on the conditions of the development.
• the partial pressure of oxygen regulated by the oxygen content of the target and / or by the addition of oxygen in the plasma, the pressure of the enclosure, the polarization of the substrate, the use of a magnetization, the distance from the target to the substrate as well as the electrical sputtering power, are parameters that strongly influence the state of oxidation and the nature of the deposited thin films.
• the material considered according to the invention can advantageously be implemented in the form of an amorphous or polycrystalline mono or biphase thin layer, thickness ranging from 10 to 500 nm, and in particular from 50 to 150 nm, consisting of crystallites whose average size varies between 5 and 50 nm, and in particular between 10 and 30 nm approximately.
• the thin layer When depositing mixtures of simple or mixed oxides, deposit possibly followed by a heat treatment in an oxidizing atmosphere, the thin layer can spontaneously adopt the crystal structure of NaCl, if it is single-phase, or of NaCl and spinel type if it is biphasic.
• the phases used according to the invention have semiconductor properties.
• the activation energy Ea can be calculated from two resistance measurements, R1 and R2, carried out at temperatures T1 and T2, respectively:
• the coefficient ⁇ is expressed in%. Kelvin "1 (% -K " 1 ).
• the electronic conduction in the transition metal oxides is achieved by the mixed valence states of the metal cations.
• the conduction is done by a jump transition mechanism, designated in English by the term "hopping".
• the electrical resistivity can thus be adjusted by modifying the number of cation pairs at different valence states by subjecting an oxide to oxidation-reducing treatments.
• the deposition of the mono- or biphasic thin layer it may be advantageous to carry out a heat treatment under an oxidizing atmosphere.
• the small thickness of the deposited layers and the small size of the crystallites facilitate oxidation at a moderate temperature, generally less than or equal to 300 ° C.
• This oxidation treatment makes it possible to increase the proportion of ferric ions (increase of x) in the oxides of the type (Fei- Z M Z ) X O and to reduce the electrical resistivity of the layer. It can also increase the variation of the resistivity with the temperature, which represents the property of sensitivity sought for the active materials of the bo Io metric devices or contribute to relax the mechanical stresses possibly present after deposition.
• This treatment is, however, adjusted so as to avoid the total oxidation of the monoxide phase and thus its total conversion into an oxide-spinel or corundum type. It is within the abilities of the person skilled in the art to determine, by simple routine experiments, the conditions of the oxidation treatment which may make it possible to obtain, for a given metal composition, the oxidation levels giving an optimum value. of the coefficient ⁇ , or a value of ⁇ greater, in absolute value, than a predetermined threshold value (for example> 1% .K ⁇ ⁇ ). Similarly, those skilled in the art are able to select, with such routine experiments, transition metal compositions which make it possible to obtain interesting resistivity properties, or to optimize the relative proportions of the metals of such compositions.
• the method of obtaining a sensitive layer according to the invention therefore consists in depositing a layer having a chemical composition close to (Fei Z M Z) X Y and to perform if necessary treatment of oxidation possibly improving the value of ⁇ , in order to select the compositions whose The absolute value of ⁇ is, for example, greater than 1 0 Zo 1 K -1 or another desired value while maintaining a low resistivity and a low electron noise.
• the thin layer is generally deposited on one or more layers capable of providing the mechanical rigidity, the absorption of infrared radiation and the electrical connections of the sensitive layer This thin layer or all of the layers can be deposited on a sacrificial structure.
• a metric device for the detection of infrared radiation or for infrared imaging, comprising at least one sensor provided with a sensitive element in the form of a layer thin material as defined above.
• the senor which is inserted into a housing having an infrared-transparent entrance window, comprises a membrane capable of absorbing infrared radiation and converting it into heat, said membrane being disposed so as to be exposed to incident infrared radiation having passed through the entrance window, and so as to transmit a portion of the heat thus produced to said sensing element.
• Figure 1 is shown a simplified view of such a device.
• the bolometric device which is represented therein comprises a thin membrane 10 capable of absorbing infrared radiation, and suspended above a support 13 via anchoring points 11.
• a sensitive layer 14 is deposited on the membrane 10. Under the effect of infrared radiation, the membrane heats up and transmits its temperature to the layer 14.
• the electrical interconnection between the sensitive layer 14 and the reading elements (not shown) arranged on the substrate is ensured by a layer, generally metallic, not shown, passing through the anchoring points 11.
• the sensitivity of the thermal detection is significantly improved by introducing isolation arms 12 between the support substrate and the membrane in order to limit the thermal losses of the latter.
• the resistivity variations of the sensitive layer are recorded using two electrodes connected to a suitable reading circuit. The electrodes can be coplanar or sandwiched.
• the support substrate may consist of an electronic circuit integrated on a silicon wafer comprising, on the one hand, devices for stimulating and reading temperature variations and on the other hand
• the multiplexing components are used to serialize the signals from the different thermometers and transmit them to a small number of outputs in order to be exploited by a conventional imaging system.
• the membrane on which is deposited the thin layer of material according to the invention may consist for example of one or more layer (s) dielectric (s) including SiO, SiN.
• Electrodes including TiN having a high absorption of infrared radiation.
• the electrodes may be either affixed to the surface of the outer layer or enclosed between the two layers.
• the thin layer of material according to the invention is deposited on this membrane according to one of the techniques described above.
• FIG. 2 shows two integration variants of a thin layer of material according to the invention in a coplanar electrode detector.
• the structure supporting a thin layer of material according to the invention consists of two insulating layers enclosing metal electrodes.
• the insulating layer deposited on the metal layer has contact openings so as to connect the ferrite sensitive element.
• the structure supporting a thin layer of material according to the invention consists of a single insulating layer on which metal electrodes directly in contact with the ferrite sensitive element rest.
• the etching of a thin layer of material according to the invention makes it possible to release the material in the region of the isolation arms and in the regions separating the detectors from each other.
• the bolometric devices in accordance with the invention may comprise a plurality of sensors in the form of a matrix array of pixels.
• a sensor network can be connected for example to a CCD matrix or CMOS.
• the device of the invention then constitutes an infrared camera.
• the BO IO metric devices of the invention can also be integrated in so-called monolithic structures, collectively manufactured by the microelectronics processes that have been developed for silicon.
• CMOS or CCD type of multiplexing circuit can be manufactured by directly connecting a matrix of sensitive elements to a CMOS or CCD type of multiplexing circuit.
• the support substrate may consist of an integrated electronic circuit comprising, on the one hand, stimulus and reading devices and, on the other hand, the multiplexing components which make it possible to serialize the signals coming from the different detectors and to transmit them to a number reduced outputs to be exploited by a conventional imaging system.
• the insulating supports are made in the form of thin layers having for example a thickness of 5 to 100 nm.
• These insulating elements for example SiN, SiO, ZnS, etc.
• PECVD plasma-assisted chemical vapor deposition
• the etching of these materials is generally performed by plasma etching methods.
• the metallic materials constituting the electrodes (for example Ti, TiN, Pt, etc.) are preferably deposited by sputtering.
• the shape of the electrodes is defined by chemical etching or plasma methods.
• the thickness of the electrodes is for example between 5 nm and 100 nm.
• the electrodes which extend in the isolation arms are connected to the input stage of the read circuit by conventional methods of contact recovery, and are adapted to the structure of the micro-bridge (similar to the anchor points). 11 of Figure 1).
• the material is deposited in the form of a thin layer according to the invention, using one of the techniques described above. Its etching can be carried out chemically (HCl, H3PO4) or by specific plasma etching processes, or by ion milling.
• the invention also relates to a method for detecting infrared radiation or producing infrared imaging, using a bolometric device capable of absorbing incident radiation, converting it to heat, and imparting a portion of the generated heat to a sensing element whose resistivity varies with temperature, wherein said device is as previously defined.
• the device of the invention is usable in many fields of application, for example in the military field (devices for sighting and night exploration), in the industrial field (parts control), in the field of safety ( detection of fires, identification of victims in smoke-filled rooms, night surveillance of sites, assistance with night driving of vehicles), or in the medical field (blood circulation mapping, mammography, etc.).
• FIG. 1 schematically represents a simplified perspective view of an embodiment of a metric bolometric device according to the invention
• FIGS. 2A and 2B illustrate two variants of integration of a thin layer of the material according to the invention. the invention in a device Io metric according to the invention
• Io metric Io metric according to the invention
• FIG. 3 represents the evolution of the electrical properties of the material according to example 3 as a function of the annealing temperature.
• a magnetite target is prepared from a mixture comprising 48% (by mass) of magnetite, 48% of water and 4% of an organic binder (polyvinyl alcohol). This mixture is then ground to obtain grains smaller than 200 microns. Then press the powder under 55 tons in a matrix of 10 cm using a hydraulic press. The ceramic obtained is then debonded and densified by sintering at 860 ° C. under an argon atmosphere to prevent the formation of the oxide Ot-Fe 2 O 3 . A 65% densified magnetite ceramic target is then obtained.
• the development of the thin layer is carried out with an SCM400 (Alcatel CIT) type sputtering frame, operating in radio-frequency mode.
• SCM400 Alcatel CIT
• the thin films are deposited on a series substrate 1.2 mm thick.
• the filing conditions are as follows: - Argon plasma
• Target distance-substrate 80 mm
• Radiocrystallographic analysis shows that the thin layers consist of an NaCl type iron monoxide phase.
• the electrical properties of the films in the raw state of deposit are as follows:
• Radiocrystallographic analysis shows that the thin layers consist of a NaCl type iron monoxide phase and a Fe 3 O 4 spinel phase.
• the electrical properties of the films are as follows:
• Thin layers based on a two - phase material according to the invention Thin films of magnetite Fe 3 O 4 and FeO are prepared with the method described in Example 1 and using the same target.
• the substrates are identical, but the deposition conditions differ, and are as follows:
• Argon plasma chamber pressure 0.5 Pa
• Target distance substrate 80 mm
• Thickness of the deposit 100 nm
• Radiocrystallographic analysis shows that the thin layers consist of an NaCl type iron monoxide phase and a Fe 3 O 4 spinel oxide phase.
• the electrical properties are modified by thermal treatments under air (treatment time: 2 hours) allowing oxidation of iron monoxide NaCl type spinel Fe 3 O 4 .
• the results are presented in FIG. 3A, and show that such oxidation treatments make it possible to improve the sensitivity ⁇ .
• Thin layers based on a single-phase material according to the invention The required quantities of oxides (0.95 mol of NiO, 1.025 mol of Fe 2 O 3 ) are mixed and finely ground.
• the powder is chamotte at 700 ° C.
• the process for obtaining the sintered target is analogous to Example 1.
• the sintering temperature is 1300 ° C. in air.
• Thin films are deposited on a 1.2 mm thick glass substrate.
• the filing conditions are as follows:
• Argon plasma chamber pressure 0.5 Pa
• a ferrite powder is obtained by co-precipitation of oxalates from zinc and iron sulphates precipitated in ammonium oxalate.
• the oxalate is then decomposed at 700 ° C. under air so as to obtain a mixture composed of ZnFe 2 O 4 and alpha-Fe 2 O 3 .
• the process for obtaining the sintered target is similar to Example 1.
• the sintering is carried out at a temperature of 990 ° C. under nitrogen.
• Thin films are deposited on a 1.2 mm thick glass substrate.
• the deposit conditions are as follows: Argon Plasma
• Thickness of the deposit 100 nm
• Radiocrystallographic analysis shows that these thin layers consist of a single phase of NaCl type.
• the electrical properties of the films are as follows

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