CN103266320A - High temperature oxidation resistant film sensor and production method thereof - Google Patents
High temperature oxidation resistant film sensor and production method thereof Download PDFInfo
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- CN103266320A CN103266320A CN2013102079422A CN201310207942A CN103266320A CN 103266320 A CN103266320 A CN 103266320A CN 2013102079422 A CN2013102079422 A CN 2013102079422A CN 201310207942 A CN201310207942 A CN 201310207942A CN 103266320 A CN103266320 A CN 103266320A
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Abstract
The invention belongs to a high temperature oxidation resistant film sensor and a production method thereof. The film sensor comprises a to-be-tested alloy substrate and a NiCrAlY alloy transition layer adhered on the top surface of the substrate, an aluminum oxide/aluminum nitride transition layer, an aluminum oxide/aluminum nitride ceramic insulating layer, a sensor function layer composed of electrodes, a Si3N4 isolating layer and an aluminum oxide protective layer arranged on the insulating layer are orderly arranged above the transition layer; the production method comprises surface treatment of alloy substrate, NiCrAlY alloy transition layer settling on the alloy substrate, precipitation, oxidation or nitriding treatment of metal aluminum, setting of Al2O3/AlN ceramic insulating layer, setting of film sensor function layer and Si3N4 isolating layer thereof, and setting of Al2O3 protective layer. The Si3N4 isolating layer in the invention can be used for effectively resisting the oxygen atom dissolved from the insulating layer and aluminum oxide protective layer at high temperature environment to diffuse to the function layer, the stability and reliability of the sensor at high temperature high pressure working environment can be improved, and relative and more accurate basic data is provided for the study and design of a turbine engine.
Description
Technical field
The invention belongs to thin film sensor design and production technical field, particularly a kind of with alloy materials such as turbine engine blade to be measured, combustion chamber inwalls as substrate, the method of resistance to high temperature oxidation thin film sensor directly is set on surfaces such as turbine engine blade to be measured, combustion chamber inwalls, this type of sensor can be widely used in the measurement of state parameters such as the temperature, strain on structural part surfaces such as turbine engine blade, combustion chamber inwall, for research and the design of turbine engine provides basic data more accurately.
Background technology
During modern aeroengine work, owing to turbine blade and combustion chamber are in the severe environment such as high temperature that fuel gas buring produces, high pressure, turbine blade and combustor surface temperature sharply raise, produce simultaneously bigger thermal strain, and the temperature distribution of turbine blade and combustor surface and thermal strain thereof are very big to performance and the influence in life-span of turbine engine, and often there is hot localised points in turbine blade surface and turbine blade etc. is produced serious harm.Therefore, in modern aeroengine design and experimental study, accurately performance perameters such as the temperature distribution of turbine blade and combustor surface and thermal strain are most important to the design of engine under the surveying work state.
The metal-base film sensor technology of preparing that adopts is on the alloy substrate, under the temperature and ar gas environment about 600 ℃ at present, adopts magnetically controlled sputter method deposition NiCrAlY(nichrome-chromium-aluminium-yttrium) the alloy transition layer; The NiCrAlY transition layer of preparation is heat-treated in vacuum and 1000 ℃ of temperature, and with at surperficial precipitating metal aluminium, the aluminium of separating out generates Al through heated oxide under normal pressure
2O
3(aluminum oxide) layer; Again at this Al
2O
3On the layer, adopt electron-beam vapor deposition method in 600～900 ℃ of temperature ranges and 10
-3～10
-2The thick about thick Al in the 20 μ m left and right sides of evaporation under the Pa vacuum
2O
3Ceramic insulating layer; Then at Al
2O
3Preparation thin film sensor functional layer on the ceramic insulating layer; Last under the temperature about 600 ℃, adopt electron-beam vapor deposition method evaporating Al on gained thin film sensor functional layer and insulation layer
2O
3Protective layer.But there is following defective at work in this type of thin film sensor: in hot environment, and Al
2O
3Ceramic insulating layer and Al
2O
3Al in the protective layer
2O
3Can decompose the generation Sauerstoffatom, the thin film sensor functional layer is in the well-oxygenated environment; And all very responsive to oxidation in common thin film sensor functional layer material, in common film thermocouple functional layer material, with the ITO(indium tin oxide) the thermopair film is example, ito thin film is a kind of n N-type semiconductorN, current carrier is mainly derived from alms giver Sn
4+In in the substitutionary oxydation indium
3+Two electronics that an electronics that discharges and the oxygen room that is in the Indium sesquioxide of going back ortho states discharge, and when ito thin film is oxidized, the oxygen room that is present in the ito thin film also can be filled up by Sauerstoffatom, the resistivity of ito thin film is sharply raise, carrier concentration descends, the conductivity variation has a strong impact on the important parameters such as Seebeck coefficient of film thermocouple; In the common thin film strain meter functional layer material, be example with the NiCr material in the metallic film, its electrical conduction mechanism is because valence electron is not fettered by atom and moves freely in metal, when part metals atom and oxygen are combined into oxide compound, electric conductivity is understood variation, and can influence the TCR(temperature coefficient of resistance of thin film strain meter to a certain extent) and the GF factor (strain factor).
" method of thin film sensor is set at alloy substrate " disclosed in publication number is the patent documentation of CN102212823A, this inventive method is separated out certain thickness aluminium (Al) back at the NiCrAlY transition layer, is adopted the direct sputter layer of metal of the mode aluminium (Al) of magnetron sputtering, make sputter layer of metal aluminium (Al) and the aluminium (Al) of separating out be fused into one and be uniformly distributed in the surface of NiCrAlY transition layer, and then to this metallic aluminium (Al) layer carry out oxide treatment, to generate Al
2O
3Connect transition layer, again at Al
2O
3Connect on the transition layer and prepare Al
2O
3Ceramic insulating layer, thin film sensor functional layer and Al
2O
3Protective layer; The thickness of this method NiCrAlY transition layer is down to about 5 μ m of this invention from 100 traditional μ m, has reduced the difficulty of NiCrAlY transition layer preparation and cost, the while of preparation significantly and effectively improved security and reliability that thin film sensor uses under 1000 ℃ of environment; Has the thin and Al of NiCrAlY transition layer
2O
3The advantage that the linking intensity of ceramic insulating layer is high; But adopted Al
2O
3Ceramic insulating layer, film functional layer, Al
2O
3The traditional structure of protective layer very easily causes Al in hot environment
2O
3Insulation layer and Al
2O
3Al in the protective layer film
2O
3Decompose the Sauerstoffatom that produces and in functional layer, spread, thereby cause functional layer oxidation at high temperature, influence the performance of thin film sensor.
" a kind of metal-base film thermocouple and production method " disclosed in publication number is the patent documentation of CN101894904A, this invention adopts the good AlN ceramic insulating layer of high thermal conductivity coefficient and insulating property to replace the Al in the conventional metals base film thermocouple technology on the traditional technology method basis of deposit multilayer laminated film on the metal substrate
2O
3Ceramic insulating layer, thus temperature head and thickness of insulating layer between metal substrate and the surface of insulating layer reduced, and can effectively reduce measuring error, improve consistence and the reliability of thermopair measured temperature and metal substrate actual temperature to be measured; But because Al
2O
3Protective layer easily decomposites Sauerstoffatom to the oxidation of thin film sensor functional layer under hot environment, influence the defectives such as performance of thin film sensor.
In sum, in present metal-base film sensor preparation, no matter be to adopt traditional technology, or publication number is that two patented technologies of CN102212823A, CN101894904A all exist the thin film sensor functional layer easily oxidized in hot environment, the defectives such as stability, reliability and measuring accuracy when influencing its performance and work.
Summary of the invention
The objective of the invention is the defective at above background technology existence, improve a kind of resistance to high temperature oxidation thin film sensor of design and production method thereof, contact with Sauerstoffatom with the isolation sensor functional layer material, improve stability and reliability that sensor uses under the High Temperature High Pressure Working environment, for research and the design of turbine engine provides accordingly, more accurate basic data.
Resistance to high temperature oxidation thin film sensor of the present invention comprises alloy substrate to be measured and is attached to the NiCrAlY(nichrome-chromium-aluminium-yttrium of its end face) the alloy transition layer, the sensor function layer and the Si thereof that are followed successively by aluminum oxide/aluminium nitride transition layer, aluminum oxide/aluminium nitride ceramics insulation layer more than the transition layer, are formed by each electrode
3N
4Sealing coat and be located at protective layer of alumina on the sealing coat, key be when insulation layer be Al
2O
3The time, at Al
2O
3Insulation layer and Al
2O
3Si is set between the protective layer
3N
4Sealing coat, each electrode in the sensor function layer then is located in the sealing coat respectively; When insulation layer is AlN, after each electrode is located on the AlN insulation layer in the sensor function layer, at each electrode and the Al of AlN insulation layer and functional layer
2O
3Si is set between the protective layer
3N
4Sealing coat; Wherein NiCrAlY alloy transition layer is deposited on metal substrate end face, Al by magnetically controlled sputter method
2O
3/ AlN transition layer forms Al by the metallic aluminium that NiCrAlY alloy transition chromatography goes out through direct oxidation or nitriding treatment
2O
3/ AlN insulation layer then respectively with corresponding Al
2O
3Transition layer or AlN transition layer closely connect, sealing coat or by chemical vapour deposition in Al
2O
3Each electrode is located in this sealing coat or directly is deposited in AlN insulation layer and the functional layer on each electrode Al by chemical vapour deposition on the insulation layer and in the functional layer
2O
3Protective layer then evaporation in the upper surface of sealing coat.
Above-mentioned alloy substrate is Ni base alloy sheets or stainless steel substrate.Si
3N
4Sealing coat adopts the PECVD(plasma enhanced chemical vapor deposition) the method preparation, when being Al
2O
3During insulation layer, Si
3N
4Separation layer thickness is 2.5-3 μ m, and each electrode is located on the position, middle section of this sealing coat in the functional layer; When being the AlN insulation layer, Si
3N
4Separation layer thickness is 1.5-1.8 μ m.
The production method of above-mentioned high temperature resistance etching resistant film sensor comprises:
A. the surface treatment of alloy substrate: elder generation, back adopt acetone and ethanol that the surface of alloy substrate to be measured is cleaned, and clean to be placed on drying under the nitrogen atmosphere;
B. at alloy substrate deposition NiCrAlY alloy transition layer: adopt conventional magnetically controlled sputter method with the NiCrAlY alloy deposition on the alloy substrate after the processing of step A, as transition layer, must be with the composite base plate of NiCrAlY alloy transition layer;
C. separating out of metallic aluminium: step B gained composite base plate is placed in the vacuum heat treatment furnace, 10
-3-10
-4Be heated to 900-1300 ℃, constant temperature to metallic aluminium under the Pa vacuum condition and separate out the thickness on surface and reach 1-2 μ m and end, cool to normal temperature then with the furnace;
D. oxidation or nitriding treatment:
D1. when oxide treatment, under oxygen atmosphere, at the uniform velocity be warming up to 900-1100 ℃ after, constant temperature 4-10h(hour), what make the metallic aluminium layer thickness is completely oxidized to Al more than 50%
2O
3The back, be cooled to room temperature, obtain Al
2O
3Layer;
D2. when nitriding treatment, under vacuum atmosphere, in stove, inject highly purified nitrogen to furnace pressure 10
3-10
5Behind the Pa, at the uniform velocity be warming up to 1000-1200 ℃ and constant temperature 10-16h(hour) after carry out nitriding treatment to metallic aluminium layer thickness 50-30% by fully nitrogenize, be cooled to room temperature, obtain the AlN layer;
E., Al is set
2O
3/ AlN ceramic insulating layer:
E1. Al ought be set
2O
3During ceramic insulating layer, adopt conventional vacuum vapour deposition, will place under vacuum atmosphere and 500-600 ℃ through the composite base plate after the step D1 oxide treatment, adopt high purity Al
2O
3Be the evaporation raw material, at the Al of composite base plate
2O
3The thick Al of surface deposition 3-10 μ m that connects transition layer
2O
3The pottery, as insulation layer;
E2. when the AlN ceramic insulating layer is set, composite base plate behind step D2 nitriding treatment is placed under the vacuum atmosphere, adopting high purity metal Al is sputtering target material, then in 1: the ratio of 4-10 feeds nitrogen and argon gas, under 500-800 ℃ and 0.1-2.0Pa sputter (work) pressure, adopt magnetron sputtering method deposit the thick AlN ceramic layer of 3-10 μ m, as insulation layer;
F., thin film sensor functional layer and Si are set
3N
4Sealing coat:
F1. working as insulation layer is Al
2O
3During ceramic insulating layer, at first will be placed the CVD treatment unit by the composite base plate that step e 1 makes, adopt SiH
4/ NH
3As source of the gas, adopting the PECVD(plasma enhanced chemical vapor deposition) method is deposited on silicon nitride on the composite base plate, and its thickness reaches till 1～1.2 μ m, obtains Si
3N
4Sealing coat basic unit; Then under vacuum atmosphere, with argon gas as reaction medium, under normal temperature and 0.1-1.2Pa sputter (work) pressure, adopt reactive magnetron sputtering method at Si
3N
4Each thin film sensor functional layer is set in the sealing coat basic unit; Adopt the PECVD method at Si at last
3N
4Covering a layer thickness on sealing coat basic unit and the thin film sensor functional layer is the Si of 1.5～1.8 μ m
3N
4Layer makes itself and Si
3N
4Sealing coat basic unit is fused into one, as Si
3N
4Sealing coat;
F2. when insulation layer is the AlN ceramic insulating layer, under vacuum atmosphere, with argon gas as reaction medium, under normal temperature and 0.1-1.2Pa sputter (work) pressure, adopt reactive magnetron sputtering method directly at the AlN ceramic insulating layer each thin film sensor to be set; Adopting the PECVD method then is the Si of 1.5～1.8 μ m at AlN ceramic insulating layer and thin film sensor covering one layer thickness
3N
4Layer is as Si
3N
4Sealing coat.
G. capping oxidation aluminium protective layer: under vacuum atmosphere and 500-800 ℃ of temperature, adopt electron-beam vapor deposition method at Si
3N
4Insulation surface evaporation protective layer of alumina, reach 1.0-2.0 μ m to thickness and end; Thereby make film thermocouple of the present invention.
The above vacuum atmosphere, its vacuum tightness are 10
-3-10
-5Pa; Magnetron sputtering method is direct current magnetron sputtering process, radio-frequency magnetron sputter method or medium frequency magnetron sputtering method, and the metal A l purity as sputtering target material is not less than 99.99wt% in the step e 2.At highly purified nitrogen described in the step D2, for purity is not less than 99.99% nitrogen; Conventional vacuum vapour deposition described in the step D1, its vacuum tightness are 10
-3-10
-5Pa, and described employing high purity Al
2O
3Be evaporation raw material, raw material A l
2O
3Purity be not less than 99.99wt%.The plasma enhanced chemical vapor deposition of PECVD(described in the step F) method, its SiH
4/ NH
3Gas source and flow amount is than being SiH
4: NH
3=1:9, back of the body end vacuum tightness are 6.0 * 10
-4Pa, operating air pressure are 60Pa, and depositing temperature is 270 ℃, and radio frequency power is 20W, and all Si described in the step F
3N
4The same process parameter is adopted in the preparation of layer.
Because Si
3N
4Film also has remarkable anti-oxidant and insulating property and the good ability that stops sodium ion, shelters water vapour and metal diffusing except having high chemical stability, high resistivity, the high characteristic of hardness; And the Si that arranges among the present invention
3N
4Sealing coat effectively the Sauerstoffatom that under hot environment, decomposites of barrier insulating layer and protective layer of alumina to the diffusion of functional layer, protection sensor function layer steady operation under hot environment.
Description of drawings
Fig. 1 is embodiment 1 thin film sensor structural representation (A-A sectional view);
Fig. 4 is the vertical view (B-B sectional view) of Fig. 1
Among the figure: 1. alloy substrate to be measured, 2. alloy transition layer, 3.Al
2O
3Transition layer, 4.Al
2O
3Ceramic insulating layer, 5.Si
3N
4Sealing coat, 6-1,6-2.(film) sensor function layer electrode, 6-3. lead terminal 7.Al
2O
3Protective layer.
Fig. 2 is embodiment 2 thin film sensor structural representations (A-A sectional view);
Among the figure: 1. alloy substrate to be measured, 2. alloy transition layer, 3.Al
2O
3Transition layer, 4.Al
2O
3Ceramic insulating layer, 5.Si
3N
4Sealing coat, 6-1,6-2.(film) sensor function layer electrode, 7.Al
2O
3Protective layer.
Fig. 3 is embodiment 3 thin film sensor structural representations (A-A sectional view);
Among the figure: 1. alloy substrate to be measured, 2. alloy transition layer, 3-1. gold aluminium lamination, 3-2.AlN layer, 4.AlN ceramic insulating layer, 5-1,5-2.(film) sensor function layer electrode, 6.Si
3N
4Sealing coat, 7.Al
2O
3Protective layer.
Embodiment
Embodiment 1: with the basic alloy sheets of nickel (Ni) as alloy substrate 1 to be measured, prepare ITO thermopair thin film sensor and to choose silicon nitride be example as protective layer material thereon:
1) surface treatment of alloy substrate: adopting the basic alloy sheets of nickel (Ni) of (length * wide * thick) 30 * 95 * 5mm is alloy substrate 1 to be measured, and elder generation, back adopt acetone and ethanol that the surface of alloy substrate to be measured is cleaned, and cleans and is placed on drying under the nitrogen atmosphere;
2) at alloy substrate deposition NiCrAlY alloy transition layer: it is 6.0 * 10 that the Ni base alloy substrate 1 that cleans up is placed vacuum tightness
-4In the vacuum of Pa (namely the carrying on the back end vacuum) environment, be target with the NiCrAlY alloy, the input purity be the 99.999%(volume percent) argon gas as the sputter medium, be under the condition of 0.6Pa at 500 ℃ of temperature, power 300W, sputtering pressure (operating pressure), adopt dc magnetron sputtering method with the NiCrAlY alloy deposition on Ni base alloy substrate 1, deposit thickness 12 μ m, must cover the composite base plate of NiCrAlY alloy transition layer 2;
3) separating out of metallic aluminium: with step 2) composite base plate that makes is put into vacuum heat treatment furnace, 5 * 10
-4After rising to 1000 ℃ under the Pa vacuum condition, with the heat-up rate of 10 ℃/min, constant temperature (processing) 5h, under vacuum condition, cool to normal temperature with the furnace then; This process separates out the Al element in the transition layer to the surface, forms the thick metal aluminium lamination of the about 1.2 μ m of one deck on the transition layer surface;
4) oxide treatment: the composite base plate that step 3) makes being put into atmosphere sintering furnace, feed purity and be 99.999% oxygen, rise to 1000 ℃, constant temperature with the heat-up rate of 5 ℃/min and handle 5h, is Al with the metal aluminium lamination complete oxidation on composite base plate surface
2O
3The back, stop to heat and continue logical oxygen and end up to being cooled to room temperature, obtain separating out a layer 3(Al with the metallic aluminium of NiCrAlY alloy transition layer and abundant oxidation
2O
3Layer) composite base plate;
5) Al is set
2O
3Ceramic insulating layer: with the composite base plate after step 4) is handled the back of the body end vacuum be 6.0 * 10
-4Under the condition of Pa, to adopt purity be the Al of 99.999wt%
2O
3Being the evaporation raw material, is evaporation under the condition of 60mA at 550 ℃, evaporation electronic beam current, with Al
2O
3Be deposited on the composite base plate, get the Al that thickness is 8 μ m
2O
3Ceramic insulating layer 4;
6) thin film sensor functional layer and Si thereof are set
3N
4Sealing coat: at first will be placed back of the body end vacuum tightness by the composite base plate that step 5) makes is 6.0 * 10
-4In the CVD treatment unit of Pa, adopt SiH
4/ NH
3(throughput ratio is SiH
4: NH
3=1:9) as source of the gas, back of the body end vacuum tightness is 6.0 * 10
-4Pa, operating air pressure are 60Pa, and depositing temperature is 270 ℃, and radio frequency power is 20W, adopt the PECVD(plasma enhanced chemical vapor deposition) method is Si
3N
4Be deposited on the composite base plate, obtain the Si that thickness is 1 μ m
3N
4Sealing coat basic unit; Be 8.0 * 10 in back of the body end vacuum then
-4Pa is target with argon gas as reaction medium, ITO and Pt, room temperature, and power be that 150W, operating air pressure are under the condition of 0.8Pa, adopt conventional magnetically controlled sputter method at Al
2O
3The surface of ceramic insulating layer 4 deposits 2, thickness successively and is the ITO-Pt thermopair of 1 μ m as (film) sensor function layer 6; At last adopt the PECVD method of same process parameter at Si again
3N
4Deposition one layer thickness is the Si of 1.5 μ m on sealing coat basic unit and the sensor function layer
3N
4Layer makes itself and Si
3N
4Sealing coat basic unit is fused into one, as Si
3N
4Sealing coat 5.
7) Al is set
2O
3Protective layer: the back of the body end vacuum be 6.0 * 10
-4Pa, employing purity are the Al of 99.999wt%
2O
3Being the evaporation raw material, is under the condition of 60mA at 550 ℃, evaporation electronic beam current, still adopts conventional electrical beam evaporation method at Si
3N
4 Sealing coat 5 surperficial evaporating Al
2O
3 Protective layer 7 is to (film) sensor Si
3N
4Sealing coat 5 upper surfaces 1.5 μ m are thick to be ended; Thereby make metal-base film sensor of the present invention.
As the Pt-ITO film thermocouple that this example is made, adopt the Pt-ITO film thermocouple of traditional technology preparation, 300 ℃～1000 ℃ temperature ranges, guarantee the drift stabilization of thermoelectric force in ± 5%, sustainable work 5h; After selecting this paper novel thin film structure for use, can extend to 8h 300 ℃～1000 ℃ sustainable working hours of temperature range, and the repeatability of thermoelectric force rate curve, the linear lag improve all.Si
3N
4Sealing coat effectively stops Al
2O
3Insulation layer and Al
2O
3The Sauerstoffatom that protective layer decomposites under hot environment is protected sensor function layer steady operation under hot environment to the diffusion of functional layer.
Embodiment 2: with the basic alloy sheets of nickel (Ni) as alloy substrate to be measured, and prepare K type NiCr-NiSi thermopair thin film sensor thereon:
The concrete implementation step 1 of present embodiment), 2), 3), 4), 5), 6) with application for a patent for invention prospectus CN102212823A in the embodiment A, B, C, D, E, F processing condition and parameter corresponding identical;
7) thin film sensor functional layer and Si thereof are set
3N
4Sealing coat: at first will by step 6) make composite base plate place the back of the body end vacuum tightness be 6.0 * 10
-4In the CVD treatment unit of Pa, adopt SiH
4/ NH
3(throughput ratio is SiH
4: NH
3=1:9) as source of the gas, back of the body end vacuum tightness is 6.0 * 10
-4Pa, operating air pressure are 60Pa, and depositing temperature is 270 ℃, and radio frequency power is 20W, adopt the PECVD method with Si
3N
4Be deposited on the composite base plate, obtain the Si that thickness is 1 μ m
3N
4Sealing coat basic unit; Be 6.0 * 10 in back of the body end vacuum then
-4Pa is target with argon gas as reaction medium, Ni90Cr10 and Ni97Si3, room temperature, and power be that 100W, operating air pressure are under the condition of 0.4Pa, adopt conventional magnetically controlled sputter method at Si
3N
4The surface of sealing coat basic unit deposits 2, thickness successively and is the NiCr-NiSi thermopair of 1 μ m as (film) sensor function layer 6-1,6-2; At last adopt the PECVD method of same process parameter at Si again
3N
4Deposition one layer thickness is the Si of 1.5 μ m on sealing coat basic unit and the sensor function layer
3N
4Layer makes itself and Si
3N
4Sealing coat basic unit is fused into one, as Si
3N
4Sealing coat 5.
8) Al is set
2O
3Protective layer: the back of the body end vacuum be 6.0 * 10
-4Pa, employing purity are the Al of 99.999wt%
2O
3Being the evaporation raw material, is under the condition of 60mA at 550 ℃, evaporation electronic beam current, still adopts conventional electrical beam evaporation method at Si
3N
4 Sealing coat 5 surperficial evaporating Al
2O
3 Protective layer 7 is to (film) sensor Si
3N
4Sealing coat 5 upper surface 1.5m are thick to be ended; Thereby make metal-base film sensor of the present invention.
Embodiment 3: with the basic alloy sheets of nickel (Ni) as alloy substrate to be measured, and prepare K type NiCr-NiSi thermopair thin film sensor thereon:
The concrete implementation step 1 of present embodiment), 2), 3), 4), 5) with application for a patent for invention prospectus CN101894904A in the open embodiment 1), 2), 3), 4), 5) processing condition and parameter be corresponding identical;
6) thin film sensor functional layer and Si thereof are set
3N
4Sealing coat: be 6.0 * 10 in back of the body end vacuum at first
-4Pa, be target with argon gas as reaction medium, Ni90Cr10 and Ni97Si3, room temperature, and power be that 100W, operating air pressure are under the condition of 0.4Pa, adopt conventional magnetically controlled sputter method to deposit 2, thickness successively on the surface of AlN ceramic insulating layer 4 and be the NiCr-NiSi thermopair of 1 μ m as (film) sensor function layer 5-1,5-2; Then the gained composite base plate being placed back of the body end vacuum tightness is 6.0 * 10
-4In the CVD treatment unit of Pa, adopt SiH
4/ NH
3(throughput ratio is SiH
4: NH
3=1:9) as source of the gas, back of the body end vacuum tightness is 6.0 * 10
-4Pa, operating air pressure are 60Pa, and depositing temperature is 270 ℃, and radio frequency power is 20W, adopt the PECVD method with Si
3N
4Be deposited on the composite base plate, obtain the Si that thickness is 1.5 μ m
3N
4Layer is as Si
3N
4Sealing coat 6;
7) Al is set
2O
3Protective layer: the back of the body end vacuum be 6.0 * 10
-4Pa, employing purity are the Al of 99.999wt%
2O
3Being the evaporation raw material, is under the condition of 60mA at 550 ℃, evaporation electronic beam current, still adopts conventional electrical beam evaporation method at sensor function layer 5-1,5-2 and Si
3N
4Sealing coat 6 surperficial evaporating Al
2O
3Protective layer 7 is to (film) sensor Si
3N
4Sealing coat 6 upper surfaces 1.5 μ m are thick to be ended; Thereby make metal-base film sensor of the present invention.
Claims (10)
1. resistance to high temperature oxidation thin film sensor, comprise alloy substrate to be measured and be attached to the NiCrAlY(nichrome-chromium-aluminium-yttrium of its end face) the alloy transition layer, the sensor function layer and the Si thereof that are followed successively by aluminum oxide/aluminium nitride transition layer, aluminum oxide/aluminium nitride ceramics insulation layer more than the transition layer, are formed by each electrode
3N
4Sealing coat and be located at protective layer of alumina on the sealing coat, key be when insulation layer be Al
2O
3The time, at Al
2O
3Insulation layer and Al
2O
3Si is set between the protective layer
3N
4Sealing coat, each electrode in the sensor function layer then is located in the sealing coat respectively; When insulation layer is AlN, after each electrode is located on the AlN insulation layer in the sensor function layer, at each electrode and the Al of AlN insulation layer and functional layer
2O
3Si is set between the protective layer
3N
4Sealing coat; Wherein NiCrAlY alloy transition layer is deposited on metal substrate end face, Al by magnetically controlled sputter method
2O
3/ AlN transition layer forms Al by the metallic aluminium that NiCrAlY alloy transition chromatography goes out through direct oxidation or nitriding treatment
2O
3/ AlN insulation layer then respectively with corresponding Al
2O
3Transition layer or AlN transition layer closely connect, sealing coat or by chemical vapour deposition in Al
2O
3Each electrode is located in this sealing coat or directly is deposited in AlN insulation layer and the functional layer on each electrode Al by chemical vapour deposition on the insulation layer and in the functional layer
2O
3Protective layer then evaporation in the upper surface of sealing coat.
2. by the described resistance to high temperature oxidation thin film sensor of claim 1, it is characterized in that described alloy substrate is Ni base alloy sheets or stainless steel substrate.
3. by the described resistance to high temperature oxidation thin film sensor of claim 1, it is characterized in that described Si
3N
4Sealing coat adopts the preparation of PECVD method, when insulation layer is Al
2O
3The time, Si
3N
4Separation layer thickness is 2.5-3 μ m, and each electrode is located on the position, middle section of this sealing coat in the functional layer; When insulation layer is AlN, Si
3N
4Separation layer thickness is 1.5-1.8 μ m.
4. by the production method of the described resistance to high temperature oxidation thin film sensor of claim 1, comprising:
A. the surface treatment of alloy substrate: elder generation, back adopt acetone and ethanol that the surface of alloy substrate to be measured is cleaned, and clean to be placed on drying under the nitrogen atmosphere;
B. at alloy substrate deposition NiCrAlY alloy transition layer: adopt conventional magnetically controlled sputter method with the NiCrAlY alloy deposition on the alloy substrate after the processing of step A, as transition layer, must be with the composite base plate of NiCrAlY alloy transition layer;
C. separating out of metallic aluminium: step B gained composite base plate is placed in the vacuum heat treatment furnace, 10
-3-10
-4Be heated to 900-1300 ℃, constant temperature to metallic aluminium under the Pa vacuum condition and separate out the thickness on surface and reach 1-2 μ m and end, cool to normal temperature then with the furnace;
D. oxidation or nitriding treatment:
D1. when oxide treatment, under oxygen atmosphere, at the uniform velocity be warming up to 900-1100 ℃ after, constant temperature 4-10h, what make the metallic aluminium layer thickness is completely oxidized to Al more than 50%
2O
3The back, be cooled to room temperature, obtain Al
2O
3Layer;
D2. when nitriding treatment, under vacuum atmosphere, in stove, inject highly purified nitrogen to furnace pressure 10
3-10
5Behind the Pa, at the uniform velocity be warming up to carry out behind 1000-1200 ℃ and the constant temperature 10-16h nitriding treatment to metallic aluminium layer thickness 50-30% by nitrogenize fully, be cooled to room temperature, obtain the AlN layer;
E., Al is set
2O
3/ AlN ceramic insulating layer:
E1. Al ought be set
2O
3During ceramic insulating layer, adopt conventional vacuum vapour deposition, will place under vacuum atmosphere and 500-600 ℃ through the composite base plate after the step D1 oxide treatment, adopt high purity Al
2O
3Be the evaporation raw material, at the Al of composite base plate
2O
3The thick Al of surface deposition 3-10 μ m that connects transition layer
2O
3The pottery, as insulation layer;
E2. when the AlN ceramic insulating layer is set, composite base plate behind step D2 nitriding treatment is placed under the vacuum atmosphere, adopting high purity metal Al is sputtering target material, then in 1: the ratio of 4-10 feeds nitrogen and argon gas, under 500-800 ℃ and 0.1-2.0Pa sputtering pressure, adopt the thick AlN ceramic layer of magnetron sputtering method deposition 3-10 μ m, as insulation layer;
F., thin film sensor functional layer and Si are set
3N
4Sealing coat:
F1. working as insulation layer is Al
2O
3During ceramic insulating layer, at first will be placed the CVD treatment unit by the composite base plate that step e 1 makes, adopt SiH
4/ NH
3As source of the gas, adopt the PECVD method that silicon nitride is deposited on the composite base plate, its thickness reaches till 1～1.2 μ m, obtains Si
3N
4Sealing coat basic unit; Then under vacuum atmosphere, with argon gas as reaction medium, under normal temperature and 0.1-1.2Pa sputtering pressure, adopt reactive magnetron sputtering method at Si
3N
4Each thin film sensor functional layer is set in the sealing coat basic unit; Adopt the PECVD method at Si at last
3N
4Covering a layer thickness on sealing coat basic unit and the thin film sensor functional layer is the Si of 1.5～1.8 μ m
3N
4Layer makes itself and Si
3N
4Sealing coat basic unit is fused into one, as Si
3N
4Sealing coat;
F2. when insulation layer is the AlN ceramic insulating layer, under vacuum atmosphere, with argon gas as reaction medium, under normal temperature and 0.1-1.2Pa sputtering pressure, adopt reactive magnetron sputtering method directly at the AlN ceramic insulating layer each thin film sensor to be set; Adopting the PECVD method then is the Si of 1.5～1.8 μ m at AlN ceramic insulating layer and thin film sensor covering one layer thickness
3N
4Layer is as Si
3N
4Sealing coat.
G. capping oxidation aluminium protective layer: under vacuum atmosphere and 500-800 ℃ of temperature, adopt electron-beam vapor deposition method at Si
3N
4Insulation surface evaporation protective layer of alumina, reach 1.0-2.0 μ m to thickness and end; Thereby make film thermocouple of the present invention.
5. by the production method of the described resistance to high temperature oxidation thin film sensor of claim 4, it is characterized in that its vacuum tightness is 10 at the described vacuum atmosphere of step D-step F
-3-10
-5Pa.
6. by the production method of the described resistance to high temperature oxidation thin film sensor of claim 4, it is characterized in that highly purified nitrogen described in the step D2, be not less than 99.99% nitrogen for purity.
7. by the production method of the described resistance to high temperature oxidation thin film sensor of claim 4, it is characterized in that conventional vacuum vapour deposition described in the step e 1, its vacuum tightness are 10
-3-10
-5Pa, and described employing high purity Al
2O
3Be evaporation raw material, raw material A l
2O
3Purity be not less than 99.99wt%.
8. press the production method of the described resistance to high temperature oxidation thin film sensor of claim 4, it is characterized in that magnetron sputtering method described in the step e 2 is direct current magnetron sputtering process, radio-frequency magnetron sputter method or medium frequency magnetron sputtering method, and be not less than 99.99wt% as the metal A l purity of sputtering target material.
9. by the production method of the described resistance to high temperature oxidation thin film sensor of claim 4, it is characterized in that PECVD method described in the step F, its SiH
4/ NH
3Gas source and flow amount is than being SiH
4: NH
3=1:9, back of the body end vacuum tightness is 6.0 * 10
-4Pa, operating air pressure are 60Pa, and depositing temperature is 270 ℃, and radio frequency power is 20W.
10. press the production method of the described resistance to high temperature oxidation thin film sensor of claim 4, it is characterized in that in the performing step C process, after the thickness that metallic aluminium is separated out reaches 100-300nm, cool to normal temperature with the furnace, must separate out the composite base plate of layer with NiCrAlY alloy transition layer and metallic aluminium; Before the performing step D, can carry out the operation of splash-proofing sputtering metal aluminium lamination, the composite base plate after handling through step C adopts conventional magnetically controlled sputter method, is 6.0 * 10 in back of the body end vacuum tightness
-4Pa, operating air pressure are under 0.5Pa and the room temperature condition, the Al that is not less than 99.99wt% in purity is target, be to be not less than 99.999% argon gas as the sputter medium metallic aluminium to be deposited on aluminium and to separate out on the layer with volume percent purity, the thickness that the metallic aluminium that makes deposition is fused into one with the metallic aluminium of separating out and is uniformly distributed in NiCrAlY transition layer surface reaches 1-2 μ m to be ended, and changes step D then and carries out oxidation or nitriding treatment.
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