阅读说明：本技术 一种基于热电半导体的双功能薄膜传感器及其制备方法 (A kind of difunctional thin film sensor and preparation method thereof based on thermoelectric semiconductor ) 是由 黄海明 王雪强 李玮洁 于 2019-09-05 设计创作，主要内容包括：本发明公开了一种基于热电半导体的双功能薄膜传感器及其制备方法,属于传感器技术领域。本发明在基体表面制备温度传感器热电偶和热流传感器热电堆,热流传感器热电堆由多个热电偶阵列构成。在温度传感器热电偶周围覆盖Al<Sub>2</Sub>O<Sub>3</Sub>保护层,防止氧化。在热流传感器热电堆不同位置处上方覆盖不同厚度的热阻层,形成温差,用以检测热流；热电偶的电极材料为P型碳化硼半导体和N型碳化硼半导体,可实现2000℃以下热流的直接测量。利用塞贝克效应输出热电势,通过温度补偿处理后可输出温度。本发明在超高温条件下热稳定性好,结构可靠,灵敏度高,可为实现下一代高超声速导弹的热防护优化设计提供有效的技术支撑。(The invention discloses a kind of difunctional thin film sensor and preparation method thereof based on thermoelectric semiconductor, belongs to sensor technical field.The present invention is made of in matrix surface preparation temperature sensor thermocouple and heat flow transducer thermoelectric pile, heat flow transducer thermoelectric pile multiple thermocouple arrays.Al is covered around temperature sensor thermocouple 2 O 3 Protective layer prevents from aoxidizing.The thermoresistance layer that different-thickness is covered above at the heat flow transducer thermoelectric pile different location, forms the temperature difference, to detect hot-fluid；The electrode material of thermocouple is for p-type boron carbide semiconductor and N-type boron carbide semiconductor, it can be achieved that the direct measurement of 2000 DEG C or less hot-fluids.Thermoelectrical potential, exportable temperature after handling by temperature-compensating are exported using Seebeck effect.Present invention thermal stability under ultra-high temperature condition is good, and structure is reliable, high sensitivity, can provide effective technical support to realize the thermal protection optimization design of next-generation hypersonic missile.)

1. a kind of difunctional thin film sensor based on thermoelectric semiconductor, it is characterised in that: including matrix (1), protective layer (2), Thick thermoresistance layer (3), thin thermoresistance layer (4), heat flow transducer thermoelectric pile (5), conducting wire (8), cold-junction compensation end (9), compensation is led Line (10), temperature sensor thermocouple (11)；Described matrix (1) is covered on testee (12) surface；In described matrix (1) table Wheat flour is for temperature sensor thermocouple (11) and heat flow transducer thermoelectric pile (5), and the heat flow transducer thermoelectric pile (5) is by multiple Thermocouple arrays are constituted；The temperature sensor thermocouple (11) is made of P-type electrode (6) and N-type electrode (7), the p-type electricity Pole (6) connects at joint location with N-type electrode (7)；

Matcoveredn (2) are covered around the temperature sensor thermocouple (11)；The different positions of the heat flow transducer thermoelectric pile (5) It is covered with thick thermoresistance layer (3) and thin thermoresistance layer (4) above the place of setting, forms temperature under the thick thermoresistance layer (3) and thin thermoresistance layer (4) Difference, to detect hot-fluid；Thermoelectrical potential is exported using the Seebeck effect of electrode material, temperature is reflected by thermoelectrical potential；The temperature There is compensating wire (10) connection in the end of degree sensor thermocouple (11), is connected to cold-junction compensation end (9) and carries out temperature-compensating, Compensated temperature signal is input to computer by conducting wire (8)；Heat flow transducer thermoelectric pile (5) end has conducting wire (8) Connection, is input to computer for heat flow signal.

2. difunctional thin film sensor according to claim 1, it is characterised in that: described matrix (1) material is Al₂O₃Pottery Porcelain；The thermocouple is made of P-type electrode (6) and N-type electrode (7), and P-type electrode material (6) material is that p-type boron carbide is partly led Body, the N-type electrode material (7) are N-type boron carbide semiconductor；It is described thickness thermoresistance layer (3) and thin thermoresistance layer (4) material be Al₂O₃；Protective layer (2) material is Al₂O₃。

3. difunctional thin film sensor according to claim 2, it is characterised in that: the P-type electrode (6) and N-type electrode (7) with a thickness of 1~2 μm, length, width and the quantity of the P-type electrode (6) and N-type electrode (7) can be according to actual measurement demands It is adjusted；The thickness thermoresistance layer (3) is different with the thickness of thin thermoresistance layer (4), and thick thermoresistance layer (3) is with a thickness of 4~6 μm, thin heat Resistance layer (4) is with a thickness of 1~3 μm, for generating the temperature difference and preventing electrode from aoxidizing；The protective layer (2) is with a thickness of 1~3 μ M, for preventing electrode from aoxidizing.

4. a kind of preparation method for implementing difunctional thin film sensor described in claim 1, it is characterised in that: the thickness thermal resistance Layer (3), thin thermoresistance layer (4), heat flow transducer thermoelectric pile (5), protective layer (2), temperature sensor thermocouple (11) pass through photoetching It is prepared by technique and magnetron sputtering technique, comprising the following steps:

1) matrix (1) is provided and is cleaned；

It 2), will be in all P-type electrodes (6) pattern transfer to matrix (1) using mask plate by photoetching process；

3) P-type electrode (6) are generated by magnetron sputtering technique；

It 4), will be in all N-type electrodes (7) pattern transfer to matrix (1) using mask plate by photoetching process；

5) N-type electrode (7) are generated by magnetron sputtering technique；

6) pass through the protective layer (2) of magnetron sputtering technique covering densification around temperature sensor thermocouple (11)；

7) at heat flow transducer thermoelectric pile (5) different location top covering different-thickness thermoresistance layer, side is thick thermoresistance layer (3), the other side is thin thermoresistance layer (4)；

8) compensating wire (10) and conducting wire (8) are connected.

5. the preparation method of difunctional thin film sensor according to claim 4, it is characterised in that: sputtering P-type electrode (6) Target used is the adjacent carbon boride that 1-4- diaminobenzene is added.

6. the preparation method of difunctional thin film sensor according to claim 4, it is characterised in that: sputtering N-type electrode (7) Target used be between carbon boride (bis- carbon of 1-7-, 12 carborane), and it is 1% nickel or chromium that concentration is 4% that concentration, which is added,.

Technical field

The invention belongs to sensor technical field, the synthesis for being related to film heat flux sensor and film temperature sensor is set Meter and preparation, suitable for the detection of hypersonic aircraft surface temperature and hot-fluid, are equally applicable to other high-temperature services.

Background technique

Near space hypersonic missile have flying speed it is fast, can motor-driven, more trajectories variation selections, penetration ability it is strong and Can the outstanding advantages such as Impulse time sensitive target, the U.S., Russia, China etc. have all carried out relevant research and have achieved weight It is in progress.High temperature gas flow produces serious influence to the normal flight of aircraft after shock wave, and aircraft must be provided with thermal protection system System；But the heat load distribution born of aircraft accurately measure so far or blank or even heat protection design personnel also return The main reason for safety coefficient for not answering aircraft thermal protection is how many, the phenomenon is can not directly to measure hot-fluid and surface temperature Degree.With the development of thin-film material and high temperature thermoelectric semiconductor technology of preparing, micromation, filming, integrated superhigh temperature film Pyroelectric sensor has had the feasibility of development.In order to preferably feed the fast development of national defence aerospace industry, superhigh temperature oxidation Heat-flow measurement technology under environment is urgently to be resolved.The present invention gives full play to the capability of independent innovation, proposes superhigh temperature film-sensing The design and engineering preparation process of device.

Summary of the invention

The present invention is directed to realize to the superhigh temperature surfaces of the equipment such as hypersonic aircraft, punching engine carry out temperature and The direct measurement of hot-fluid overcomes the shortcomings of that current heat flow transducer response speed is slow, it is low to survey limiting temperature, is next-generation superb The thermal protection optimization design of velocity of sound guided missile provides effective technical support.

In order to achieve the above object, solution of the invention is as follows:

The present invention provides a kind of difunctional thin film sensor and preparation method thereof based on thermoelectric semiconductor, described difunctional Thin film sensor, including including matrix, protective layer, thick thermoresistance layer, thin thermoresistance layer, heat flow transducer thermoelectric pile, conducting wire, cold end temperature Spend compensating end, compensating wire, temperature sensor thermocouple；Described matrix is covered on testee surface；On described matrix surface Preparation temperature sensor thermocouple and heat flow transducer thermoelectric pile, the heat flow transducer thermoelectric pile is by multiple thermocouple arrays structures At；The thermocouple is made of P-type electrode and N-type electrode, and the P-type electrode connects at joint location with N-type electrode；It is described Matcoveredn is covered around temperature sensor thermocouple；Top is covered with difference at the heat flow transducer thermoelectric pile different location The thermoresistance layer of thickness forms the temperature difference under the thermoresistance layer, to detect hot-fluid；The end of the temperature sensor thermocouple has Compensating wire connection is connected to cold-junction compensation end and carries out temperature-compensating, and compensated temperature signal is input to meter by conducting wire Calculation machine；There is conducting wire connection in heat flow transducer thermoelectric pile end, and heat flow signal is input to computer.

Described matrix material is Al₂O₃Ceramics；The thermocouple is made of P-type electrode and N-type electrode, the P-type electrode material Material is p-type boron carbide semiconductor, and the N-type electrode material is N-type boron carbide semiconductor, and thickness is 1 μm；The thickness thermoresistance layer It is Al with thin thermal resistance layer material₂O₃, the thickness thermoresistance layer is with a thickness of 5 μm, and the thin thermoresistance layer is with a thickness of 2 μm, for generating the temperature difference And prevent electrode from aoxidizing；The protective layer material is Al₂O₃, with a thickness of 2 μm, for preventing electrode from aoxidizing.

The difunctional thin film sensor is prepared by photoetching process and magnetron sputtering technique, and process is as follows.

(1) matrix is provided and is cleaned；

It (2), will be in all P-type electrode pattern transfers to matrix using mask plate by photoetching process；

(3) P-type electrode is generated by magnetron sputtering technique；

It (4), will be in all N-type electrode pattern transfers to matrix using mask plate by photoetching process；

(5) N-type electrode is generated by magnetron sputtering technique；

(6) pass through the protective layer of magnetron sputtering technique covering densification around temperature sensor thermocouple；

(7) at the heat flow transducer thermoelectric pile different location above cover the thermoresistance layer of different-thickness, side is thick thermal resistance Layer, the other side are thin thermoresistance layer；

(8) compensating wire and conducting wire are connected.

Beneficial effects of the present invention: the present invention can directly measure superhigh temperature and hot-fluid, next-generation high to realize The thermal protection optimization design of supersonic missile provides effective technical support；Response time is in Microsecond grade, it can be achieved that instantaneous measurement； Using new electrode materials, temperature detected may be up to 2000 DEG C, higher than traditional metallic thermocouple electrode material, be suitble to It is used under hyperthermal environments；The Seebeck coefficient of Boron Carbide Thermoelectrical Materials is tradition between 200 μ of μ V/ DEG C~300 V/ DEG C 5~10 times of Metal Substrate thermocouple probes material, sensor have higher sensitivity and smaller resolution ratio；Double function Energy thin film sensor keeps preferable linear relationship, thermostabilization between the thermoelectrical potential and temperature of output between 600~2000 DEG C Property is good；It is designed using thermoelectric pile formula, the output signal and measuring accuracy of sensor can be improved；By heat flow transducer and temperature sensing Device is integrated, can measure hot-fluid and temperature simultaneously；Preparation process of the invention is simple, can quantify to produce, and reduces manufacturing cost, improves Benefit.

Detailed description of the invention

Fig. 1 is the difunctional thin film sensor equal axes axonometric drawing of the present invention；

Fig. 2 is the A direction view of the difunctional thin film sensor in Fig. 1；

Fig. 3 is the B direction view of the difunctional thin film sensor in Fig. 1；

Fig. 4 is the C direction view of the difunctional thin film sensor in Fig. 1；

In figure: 1-matrix, 2-protective layers, 3-thick thermoresistance layers, 4-thin thermoresistance layers, 5-heat flow transducer thermoelectric piles, 6-P-type electrodes, 7-N-type electrodes, 8-conducting wires, 9-cold-junction compensation ends, 10-compensating wires, 11-temperature sensors heat Galvanic couple, 12-testees.

Specific embodiment

The difunctional thin film sensor: including matrix 1, protective layer 2, thick thermoresistance layer 3, thin thermoresistance layer 4, heat flow transducer Thermoelectric pile 5, conducting wire 8, cold-junction compensation end 9, compensating wire 10, temperature sensor thermocouple 11；Described matrix 1 be covered on by Survey 12 surface of object；In 1 surface preparation temperature sensor thermocouple 11 (for measuring temperature) of described matrix and heat flow transducer Thermoelectric pile 5 (for measuring hot-fluid), the heat flow transducer thermoelectric pile 5 are made of multiple thermocouple arrays；The temperature sensing Device thermocouple 11 is made of P-type electrode 6 and N-type electrode 7, and the P-type electrode 6 connects at joint location with N-type electrode 7；Institute State 11 surrounding of temperature sensor thermocouple covering matcoveredn 2；Top covering at 5 different location of heat flow transducer thermoelectric pile There are thick thermoresistance layer 3 and thin thermoresistance layer 4, the temperature difference is formed under the thick thermoresistance layer 3 and thin thermoresistance layer 4, to detect hot-fluid；It utilizes The Seebeck effect of electrode material exports thermoelectrical potential, reflects temperature by thermoelectrical potential；The end of the temperature sensor thermocouple 11 There is the connection of compensating wire 10 at end, is connected to cold-junction compensation end 9 and carries out temperature-compensating, compensated temperature signal passes through conducting wire 8 It is input to computer；There is the connection of conducting wire 8 in 5 end of heat flow transducer thermoelectric pile, and heat flow signal is input to computer.

1 material of described matrix is Al₂O₃Ceramics；6 material of P-type electrode is p-type boron carbide semiconductor, the N-type electrode 7 materials are N-type boron carbide semiconductor, and thickness is 1 μm；The thermal resistance layer material is Al₂O₃, the thickness thermoresistance layer 3 is with a thickness of 5 μ M, the thin thermoresistance layer 4 is with a thickness of 2 μm, for generating the temperature difference and preventing electrode from aoxidizing；2 material of protective layer is Al₂O₃, with a thickness of 2 μm, for preventing electrode from aoxidizing.

The temperature sensor thermocouple 11, heat flow transducer thermoelectric pile 5, protective layer 6, thick thermoresistance layer 3 and thin thermoresistance layer 4 It is prepared by photoetching process and magnetron sputtering technique, detailed process is as follows:

◆ photoetching process

(1) matrix cleans

Matrix first is impregnated with suds, then rinses matrix surface with deionized water, while closely being contacted with brush Surface generates the cleaning action of high-energy, removes particle contamination and organic matter, super to matrix using acetone, deionized water later Sound cleans 15 minutes, is finally wiped again with acetone one time, sees whether that there are also pollutants under an optical microscope.

(2) prebake conditions

By the matrix after cleaning up 120 DEG C at a temperature of toast 15 minutes, removal is adsorbed on the moisture on surface, sufficiently It dries and keeps clean, photoresist is enable preferably to adhere on matrix.

(3) spin coating

In the uniform spin coating photoresist of matrix surface.

(4) soft baking

After gluing, photoresist still in liquid condition, 90 DEG C at a temperature of toast 30 minutes, remove a large amount of in photoresist Solvent influence the solubility of exposure in order to avoid the stickness on ultraviolet exposure machine sample stage.

(5) exposure+development

P-type electrode mask edition territory is placed, changes the property of part photoresist by the irradiation of exposure machine ultraviolet light, property The photoresist that matter changes is removed with developer solution.

(6) hard baking

100 DEG C at a temperature of toast 30 minutes, eliminate brought moisture in developing process, keep matrix and photoresist Good adhesion property.

(7) P-type electrode material is sputtered, P-type electrode film thickness is made to reach 1 μm.

(8) it removes photoresist

(9) the identical preparation process for using step (5)~(8) prepares N-type electrode using N-type electrode material, and thickness reaches 1μm。

(10) pass through the protective layer of magnetron sputtering technique covering densification around temperature sensor thermocouple.

(11) at the heat flow transducer thermoelectric pile different location above the heat of different-thickness is covered by magnetron sputtering technique Resistance layer, side are the thick thermoresistance layer with a thickness of 5 μm, and the other side is the thin thermoresistance layer with a thickness of 2 μm.

◆ sputtering technology

(1) prepare before plating

Keep vacuum chamber clean.

When cleaning target, is first cleaned with lint-free cloth, then cleaned with alcohol, then rinsed with deionized water, dried after flushing Target removes moisture removal, guarantees that the adhesive force between photoresist and matrix will not reduce.

(2) it is packed into target

Sputtering target material is fitted into target source, sputtered substrate is put into corresponding position.

(3) it vacuumizes

Low valve is evacuated down to 3Pa, molecular pump is evacuated down to 1.5 × 10^-3Pa。

(4) it is filled with inert gas-argon gas

(5) sputtering forms film

Highdensity argon ion arc column bombards target material surface, sputters target atom to make film.It is first when sputter coating First baffle is adjusted prevents the impurity on target from falling on pallet the quality for influencing plated film to the surface of tray surface.So After open AC power source, when reach setting power when, target baffle is removed, at this time can there is a phenomenon where glow discharge, start Sputtered film.The thickness of sputtered film was controlled by the time, and since timing occurring glow discharge, required for reaching Power supply is closed after thickness.

◆ the explanation about target

When sputtering P-type electrode, target used is the adjacent carbon boride that 1-4- diaminobenzene is added.

Sputter N-type electrode when, target used be between carbon boride (bis- carbon of 1-7-, 12 carborane), and be added concentration be The chromium that 1% nickel or concentration are 4%.

When sputtering protective layer, thick thermoresistance layer, thin thermoresistance layer, target used is Al₂O₃。

Preparation is completed, temperature sensor and heat flow transducer are integrated on same matrix.