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一种具有一维纳米阵列结构的薄膜热电偶及其制造方法 【EN】A kind of film thermocouple and its manufacturing method with one-dimensional nano-array structure

申请(专利)号:CN201910382177.5国省代码:北京 11
申请(专利权)人:【中文】中国航发北京航空材料研究院【EN】China Hangfa Beijing Institute of Aerial Materials
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摘要:
【中文】本发明属于薄膜热电偶制备技术,涉及一种具有一维纳米阵列结构的薄膜热电偶及其制造方法,包括基底,在基底上通过双靶磁控溅射工艺形成薄膜热电偶的电臂;对薄膜热电偶的一个电臂采用氧化铟锡靶材和贵金属靶材溅射,能够保证贵金属掺杂氧化铟锡的均匀性,同时保证在高温下的导电有较大的热电值输出,对薄膜热电偶的另一个电臂采用氧化锌靶材和贵金属靶材溅射;且设置双靶磁控溅射工艺的参数,使得溅射沉积形成的电臂为一维纳米阵列结构。提出一种具有一维纳米阵列结构的薄膜热电偶,这种薄膜热电偶的响应速度优于一般无特殊结构的薄膜热电偶,同时具有测温准确和抗疲劳的特点。 【EN】Paragraph:The invention belongs to film thermocouple technologies of preparing, are related to a kind of film thermocouple and its manufacturing method with one-dimensional nano-array structure, including substrate, form the electric arm of film thermocouple by double target magnetic control sputtering techniques in substrate;One electric arm of film thermocouple is sputtered using tin indium oxide target material and noble metal target material, it can guarantee the uniformity of precious metal doping tin indium oxide, guarantee that conduction at high temperature has biggish thermoelectricity value to export simultaneously, another electric arm of film thermocouple is sputtered using zinc oxide target and noble metal target material;And the parameter of double target magnetic control sputtering techniques is set, so that the electric arm that sputtering sedimentation is formed is one-dimensional nano-array structure.It is proposed a kind of film thermocouple with one-dimensional nano-array structure, the response speed of this film thermocouple is better than generally without the film thermocouple of special construction, while having the characteristics that thermometric is accurately and antifatigue.Image:201910382177.GIF

主权项:
【中文】1.一种具有一维纳米阵列结构的薄膜热电偶,其特征在于:包括基底,在基底上通过双靶磁控溅射工艺形成薄膜热电偶的电臂;对薄膜热电偶的一个电臂采用氧化铟锡靶材和贵金属靶材溅射,能够保证贵金属掺杂氧化铟锡的均匀性,同时保证在高温下的导电有较大的热电值输出,对薄膜热电偶的另一个电臂采用氧化锌靶材和贵金属靶材溅射;且设置双靶磁控溅射工艺的参数,使得溅射沉积形成的电臂为一维纳米阵列结构。 【EN】1. a kind of film thermocouple with one-dimensional nano-array structure, it is characterised in that: including substrate, by double in substrate The electric arm of target magnetic control sputtering technique formation film thermocouple;To an electric arm of film thermocouple using tin indium oxide target material and expensive Metal targets sputtering, can guarantee the uniformity of precious metal doping tin indium oxide, at the same the conduction for guaranteeing at high temperature have it is larger The output of thermoelectricity value, another electric arm of film thermocouple is sputtered using zinc oxide target and noble metal target material;And setting is double The parameter of target magnetic control sputtering technique, so that the electric arm that sputtering sedimentation is formed is one-dimensional nano-array structure.


说明书

【中文】

一种具有一维纳米阵列结构的薄膜热电偶及其制造方法

技术领域

本发明属于表面温度测试技术,涉及一种在硬质或柔性基底表面生长具有一维纳米阵列结构的两种热电臂薄膜,从而实现快速、准确获取固体表面的温度数据。

背景技术

随着航空发动机推重比的提高,现有的金属基热电偶电极材料难以适应高温、高压、高氧化性气氛下的测温工作。例如,常用的Pt-Rh合金系列的薄膜热电偶在大于900℃的环境下,Rh氧化严重,直接影响测温精度和寿命,且大推重比航空发动机的涡轮前温度已经接近或超越了Pt-Rh合金系列薄膜热电偶的测温上限[ChenX M,GregoryOJ,AmaniM.Thin-film thermocouples based on the system In2O3–SnO2[J].Journal of the AmericanCeramic Society,2011,94,854.]。因此,现有的薄膜热电偶无法满足未来先进航空发动机高温部件温度测试的需要。随着陶瓷发动机的开发,陶瓷薄膜热电偶已成为研究热点。薄膜热电偶的核心为薄膜热电材料,不同的热电材料具有不同的温度使用范围。基于航空发动机高温、高压和易氧化的环境特点,具有高熔点、抗氧化双重优势的氧化物陶瓷热电材料成为航空发动机测温热电偶的首选,同时氧化物热电材料具有比纯贵金属热电偶更大的热电势输出(高赛贝克系数),与发动机陶瓷热障涂层的热膨胀系数更为接近,在高温下与基底有较强的结合力,并能大幅降低成本[Tougas I M,Amani M,Gregory O J.Metallic andceramic thin film thermocouples for gas turbine engines[J].Sensors,2013,13,15324.]。可以预见,由氧化物材料组成的热电偶能够大幅提升温度测量的抗干扰能力和精确度,更能满足新一代航空发动机温度测试的需要。国内外常用的氧化物热电材料为纯In2O3,电导率和Seebeck系数有待进一步提升。近年来,各国科研人员均发现设计材料的特殊纳米结构或沿不同晶面择优生长可以进一步提升热电材料的电导率和Seebeck系数,同时增加的纳米晶界能够显著降低热导率,从而获得性能更加优异的热电材料[Feng J J,Zhu W,Deng Y.An overview of thermoelectric films:Fabrication techniques,classification,and regulation methods[J].Chinese Physics B,2018,4,047210.]。基于优异热电性能的热电材料,有望获得响应时间更快,测试精密度更高(输出热电势高),抗氧化能力强的高温薄膜热电偶,为航空发动机高温部件温度动态监测,失效诊断提供有力支撑。

本申请中涉及的高温为1000℃以上。

发明内容

本发明的目的是:制备一种响应速度快,测温准确和抗疲劳的薄膜热电偶

本发明的技术方案是:一种具有一维纳米阵列结构的薄膜热电偶,包括基底,在基底上通过双靶磁控溅射工艺形成薄膜热电偶的电臂;对薄膜热电偶的一个电臂采用氧化铟锡靶材和贵金属靶材溅射,能够保证贵金属掺杂氧化铟锡的均匀性,同时保证在高温下的导电有较大的热电值输出,对薄膜热电偶的另一个电臂采用氧化锌靶材和贵金属靶材溅射;且设置双靶磁控溅射工艺的参数,使得溅射沉积形成的电臂为一维纳米阵列结构。一维纳米阵列结构能够显著的提高热电臂材料的热电ZT值,进而提高薄膜热电偶的电压输出值,提高测温的准确性,同时能够使薄膜热电偶的响应速度显著高于无特殊结构的薄膜热电偶。

进一步的,所述基底为金属氧化物或氧化硅材质。优选地,金属氧化物为氧化铝。氧化铝与氧化铟锡、氧化锌具有相近的晶格参数,能够增强热电臂与基底的结合力,保证热电偶在高温下不失效。

进一步的,所述基底为硬质基底或柔性基底。

上述薄膜热电偶的制备方法,包括如下步骤:

步骤1、通过双靶磁控溅射工艺在基底上溅射沉积电臂,对第一个电臂采用采用氧化铟锡靶材射频功率溅射和贵金属靶材直流功率溅射,氧化铟锡靶材的射频功率与贵金属靶材的直流功率之比为4:1~5:1;对第二个电臂采用氧化锌靶材射频功率溅射和贵金属靶材直流功率溅射,对应氧化铟锡靶材的射频功率与对应贵金属靶材的直流功率之比为4:1~5:1;氧化物的射频功率与对应贵金属靶材的直流功率之比能够保证热电臂材料中氧化物与贵金属的成分比例,使得热电ZT值达到最优,保证薄膜热电偶的测温精度。

这一功率比例既保证贵金属的掺杂比例又保证形成一维纳米阵列的特殊结构。

步骤2、将溅射沉积的两个电臂置于氮气气氛中进行退火,通过退火提高电臂与基底的结合性能。

步骤3、在基底上磁控溅射沉积形成二氧化硅高阻层,且所述高阻层覆盖基底和电臂,不覆盖接电端。优选地,在磁控溅射时,在接电端上覆盖掩模板。

进一步的,溅射时的基底加热温度与工作气压同时增大或同时减小。

进一步的,步骤2完成后在各电臂后端磁控溅射沉积形成接电端,每个接电端磁控溅射两次,第一次溅射靶材为钛金属,第二次溅射靶材为贵金属,每次溅射后均进行退火处理。这项工艺能够使热电臂材料和接电端形成欧姆接触。

进一步的,所述射频功率不大于100W;所述直流功率不大于20W。

进一步的,SiO2高阻层厚度不大于100nm。

本发明的优点是:提出一种具有一维纳米阵列结构的薄膜热电偶,这种薄膜热电偶的响应速度优于一般无特殊结构的薄膜热电偶,同时具有测温准确和抗疲劳的特点。本发明响应时间更快,测试精密度更高(输出热电势高),抗氧化能力强的高温薄膜热电偶,为航空发动机高温部件温度动态监测,失效诊断提供有力支撑。

附图说明

图1是实施例1在氧化铝片上生长的氧化锌掺杂铱的扫描电镜断面照片。

图2是实施例1在氧化铝片上生长的氧化铟锡掺杂铱的扫描电镜断面照片。

图3是实施例1在氧化铝片上生长的薄膜热电偶照片.

其中:1-基底、2-第一电臂、3-第二电臂。

具体实施方式

实施例1:氧化铝基底上制备具有一维纳米阵列结构的薄膜热电偶

步骤1、通过双靶磁控溅射工艺在基底上溅射沉积电臂,对第一个电臂采用氧化铟锡靶材射频功率溅射和铱靶材直流功率溅射,氧化铟锡靶材的射频功率与铱靶材的直流功率之比为4:1~5:1;靶基距为d=90mm;氧化铝基底的加热温度为250℃;氩气压强为1Pa;对氧化铟锡靶材施加射频功率为70W;对铱靶材施加直流功率为15W;溅射沉积时间1h;自然冷却至室温。对第二个电臂采用氧化锌靶材射频功率溅射和贵金属靶材直流功率溅射,对应氧化铟锡靶材的射频功率与对应铱靶材的直流功率之比为4:1~5:1;靶基距为d=90mm;基底加热温度200℃;氩气压强为1Pa;对氧化锌靶材施加射频功率为70W;对铱靶材施加直流功率为15W;溅射沉积时间1h;自然冷却至室温,取出

步骤2、将溅射沉积的两个电臂置于氮气气氛中进行退火,退火温度300℃,退火时间0.5h;

步骤3、利用电极掩模版溅射一层Ti金属膜(通用溅射方法),在Ti膜上再溅射一层Pd电极,在100℃温度下,退火时间0.5h。

步骤4、在基底上磁控溅射沉积形成二氧化硅高阻层,且所述高阻层覆盖基底和电臂,不覆盖接电端。

实施例2:氧化硅基底上制备具有一维纳米阵列结构的薄膜热电偶

步骤1、通过双靶磁控溅射工艺在基底上溅射沉积电臂,对第一个电臂采用氧化铟锡靶材射频功率溅射和铱靶材直流功率溅射,氧化铟锡靶材的射频功率与铱靶材的直流功率之比为4:1~5:1;靶基距为d=70mm;氧化硅基底的加热温度为200℃;氩气压强为0.5Pa;对氧化铟锡靶材施加射频功率为100W;对铱靶材施加直流功率为20W;溅射沉积时间1h;自然冷却至室温。对第二个电臂采用氧化锌靶材射频功率溅射和贵金属靶材直流功率溅射,对应氧化铟锡靶材的射频功率与对应铱靶材的直流功率之比为4:1~5:1;靶基距为d=70mm;基底加热温度200℃;氩气压强为0.5Pa;对氧化锌靶材施加射频功率为90W;对铱靶材施加直流功率为20W;溅射沉积时间1h;自然冷却至室温,取出

步骤2、将溅射沉积的两个电臂置于氮气气氛中进行退火,退火温度500℃,退火时间2h;

步骤3、利用电极掩模版溅射一层Ti金属膜(通用溅射方法),在Ti膜上再溅射一层Pt电极,在100℃温度下,退火时间0.5h。

步骤4、在基底上磁控溅射沉积形成二氧化硅高阻层,且所述高阻层覆盖基底和电臂,不覆盖接电端。

【EN】

A kind of film thermocouple and its manufacturing method with one-dimensional nano-array structure

Technical field

The invention belongs to surface temperature measuring technologies, and being related to a kind of grow in hard or flexible substrates surface has a wiener

Two kinds of thermoelectric arm films of rice array structure, to realize the temperature data for quickly, accurately obtaining the surface of solids.

Background technique

With the raising of aero-engine thrust ratio, existing Metal Substrate thermocouple probes material is difficult to adapt to high temperature, height

Thermometric work under pressure, high oxidative atmosphere.For example, the film thermocouple of common Pt-Rh alloy series is being greater than 900 DEG C

Under environment, Rh oxidation is serious, directly affects temperature measurement accuracy and service life, and the turbine inlet temperature of big thrust loading aero-engine is

The thermometric upper limit [ChenX M, GregoryOJ, AmaniM.Thin- close or that surmounted Pt-Rh alloy series film thermocouple

film thermocouples based on the system In2O3–SnO2[J].Journal of the American

Ceramic Society,2011,94,854.].Therefore, existing film thermocouple is unable to satisfy the following advanced aero engine

The needs of high-temperature component temperature test.With the exploitation of ceramic engine, ceramic membrane thermocouple has become research hotspot.Film

The core of thermocouple is thin film thermoelectric materials, and different thermoelectric materials has different temperature use scopes.Based on aeroplane engine

Machine high temperature, high pressure and oxidizable environmental quality, with high-melting-point, anti-oxidant double dominant oxide ceramics thermoelectric material at

For the first choice of aero-engine temperature thermocouple, simultaneous oxidation object thermoelectric material has the thermoelectricity bigger than pure noble-metal thermocouple

Gesture exports (high Seebeck coefficient), with the thermal expansion coefficient of engine ceramic heat-barrier coating more closely, at high temperature with substrate

There is stronger binding force, and cost [Tougas I M, Amani M, Gregory O J.Metallic and can be greatly reduced

ceramic thin film thermocouples for gas turbine engines[J].Sensors,2013,13,

15324.].It is contemplated that the anti-interference ability and essence of temperature measurement can be substantially improved in the thermocouple being made of oxide material

Exactness is more able to satisfy the needs of aero-engine temperature test of new generation.Common oxide pyroelectric material is pure both at home and abroad

In2O3, conductivity and Seebeck coefficient need to be further improved.In recent years, various countries scientific research personnel has found the spy of designing material

Different nanostructure or the conductivity and Seebeck coefficient that thermoelectric material can be further promoted along different crystal face preferential growths, together

When increased nanometer crystal boundary can significantly reduce thermal conductivity, thus obtain more excellent performance of thermoelectric material [Feng J J,

Zhu W,Deng Y.An overview of thermoelectric films:Fabrication techniques,

classification,and regulation methods[J].Chinese Physics B,2018,4,047210.].Base

It in the thermoelectric material of excellent thermoelectricity capability, is expected to obtain the response time faster, test precision is higher (output thermoelectrical potential is high), resists

The strong high temperature film thermocouple of oxidability, is the dynamic monitoring of high-temperature unit of aircraft engine temperature, and failure diagnosis provides strong

Support.

High temperature involved in the application is 1000 DEG C or more.

Summary of the invention

The purpose of the present invention is: prepare a kind of fast response time, the accurate and antifatigue film thermocouple of thermometric

The technical scheme is that a kind of film thermocouple with one-dimensional nano-array structure, including substrate, in base

The electric arm of film thermocouple is formed on bottom by double target magnetic control sputtering techniques;Indium oxide is used to an electric arm of film thermocouple

Tin target and noble metal target material sputtering, can guarantee the uniformity of precious metal doping tin indium oxide, while guaranteeing at high temperature

Conduction has biggish thermoelectricity value to export, and is splashed to another electric arm of film thermocouple using zinc oxide target and noble metal target material

It penetrates;And the parameter of double target magnetic control sputtering techniques is set, so that the electric arm that sputtering sedimentation is formed is one-dimensional nano-array structure.It is one-dimensional

Nano array structure can significantly improve the thermoelectricity ZT value of thermoelectric arm material, and then improve the voltage output of film thermocouple

Value, improves the accuracy of thermometric, while the film that the response speed of film thermocouple can be made to be significantly higher than no special construction is warm

Galvanic couple.

Further, the substrate is metal oxide or oxidation silicon material.Preferably, metal oxide is aluminium oxide.

Aluminium oxide and tin indium oxide, zinc oxide have similar lattice parameter, can enhance the binding force of thermoelectric arm and substrate, guarantee heat

Galvanic couple does not fail at high temperature.

Further, the substrate is hard substrate or flexible substrates.

The preparation method of above-mentioned film thermocouple, includes the following steps:

Step 1 passes through double target magnetic control sputtering technique sputtering sedimentation electric arm in substrate, uses oxygen to first electric arm

Change the sputtering of indium tin target radio-frequency power and the sputtering of noble metal target material dc power, the radio-frequency power and noble metal of tin indium oxide target material

The ratio between dc power of target is 4:1~5:1;To second electric arm using the sputtering of zinc oxide target radio-frequency power and noble metal target

The sputtering of material dc power, the ratio between the radio-frequency power of corresponding tin indium oxide target material and dc power of corresponding noble metal target material are 4:1

~5:1;The ratio between the radio-frequency power of oxide and dc power of corresponding noble metal target material can guarantee to aoxidize in thermoelectric arm material

The component ratio of object and noble metal guarantees the temperature measurement accuracy of film thermocouple so that thermoelectricity ZT value is optimal.

This power proportions had not only guaranteed the doping ratio of noble metal but also had guaranteed to be formed the special construction of one-dimensional nano-array.

Two electric arm of sputtering sedimentation are placed in nitrogen atmosphere and anneal by step 2, improve electric arm and base by annealing

The binding performance at bottom.

Step 3, magnetron sputtering deposits to form silica resistive formation in substrate, and resistive formation covering substrate and electricity

Arm does not cover power connection end.Preferably, in magnetron sputtering, the coverage mask plate on power connection end.

Further, substrate heating temperature when sputtering increases simultaneously with operating air pressure or reduces simultaneously.

Further, it deposits to form power connection end in each electric arm rear end magnetron sputtering after the completion of step 2, each power connection end magnetic control

Twice, first time sputtering target material is titanium for sputtering, and second of sputtering target material is noble metal, is carried out at annealing after sputtering every time

Reason.This technique can make thermoelectric arm material and power connection end form Ohmic contact.

Further, the radio-frequency power is not more than 100W;The dc power is not more than 20W.

Further, SiO2Resistive formation thickness is not more than 100nm.

The invention has the advantages that proposing a kind of film thermocouple with one-dimensional nano-array structure, this thin film thermoelectric

Even response speed is better than generally without the film thermocouple of special construction, while having the characteristics that thermometric is accurately and antifatigue.This

Invent the response time faster, test precision is higher (output thermoelectrical potential is high), and the strong high temperature film thermocouple of oxidation resistance is

High-temperature unit of aircraft engine temperature dynamic monitoring, failure diagnosis provide strong support.

Detailed description of the invention

Fig. 1 is the scanning electron microscope cross-section photographs for the Zinc oxide doped iridium that embodiment 1 is grown on alumina wafer.

Fig. 2 is the scanning electron microscope cross-section photographs for the tin indium oxide doped iridium that embodiment 1 is grown on alumina wafer.

Fig. 3 is the film thermocouple photo that embodiment 1 is grown on alumina wafer

Wherein: 1- substrate, the first electric arm of 2-, the second electric arm of 3-.

Specific embodiment

Embodiment 1: preparation has the film thermocouple of one-dimensional nano-array structure in alumina substrate

Step 1 passes through double target magnetic control sputtering technique sputtering sedimentation electric arm in substrate, uses indium oxide to first electric arm

The sputtering of tin target radio-frequency power and the sputtering of iridium target dc power, the radio-frequency power of tin indium oxide target material and the direct current function of iridium target

The ratio between rate is 4:1~5:1;Target-substrate distance is d=90mm;The heating temperature of alumina substrate is 250 DEG C;Ar pressure is 1Pa;It is right

It is 70W that tin indium oxide target material, which applies radio-frequency power,;Applying dc power to iridium target is 15W;Sputtering sedimentation time 1h;Naturally cold

But to room temperature.Second electric arm is sputtered using zinc oxide target radio-frequency power and noble metal target material dc power sputters, it is corresponding

The ratio between the radio-frequency power of tin indium oxide target material and dc power of corresponding iridium target are 4:1~5:1;Target-substrate distance is d=90mm;Base

200 DEG C of bottom heating temperature;Ar pressure is 1Pa;Applying radio-frequency power to zinc oxide target is 70W;Direct current is applied to iridium target

Power is 15W;Sputtering sedimentation time 1h;Cooled to room temperature is taken out

Two electric arm of sputtering sedimentation are placed in nitrogen atmosphere and anneal by step 2, and 300 DEG C of annealing temperature, when annealing

Between 0.5h;

Step 3 sputters one layer of Ti metal film (general sputtering method) using electrode mask version, sputters one layer again on Ti film

Pd electrode, at a temperature of 100 DEG C, annealing time 0.5h.

Step 4, magnetron sputtering deposits to form silica resistive formation in substrate, and resistive formation covering substrate and electricity

Arm does not cover power connection end.

Embodiment 2: preparation has the film thermocouple of one-dimensional nano-array structure in oxidation silicon base

Step 1 passes through double target magnetic control sputtering technique sputtering sedimentation electric arm in substrate, uses indium oxide to first electric arm

The sputtering of tin target radio-frequency power and the sputtering of iridium target dc power, the radio-frequency power of tin indium oxide target material and the direct current function of iridium target

The ratio between rate is 4:1~5:1;Target-substrate distance is d=70mm;The heating temperature for aoxidizing silicon base is 200 DEG C;Ar pressure is 0.5Pa;

Applying radio-frequency power to tin indium oxide target material is 100W;Applying dc power to iridium target is 20W;Sputtering sedimentation time 1h;From

So it is cooled to room temperature.Second electric arm is sputtered using zinc oxide target radio-frequency power and noble metal target material dc power sputters,

The ratio between the radio-frequency power of corresponding tin indium oxide target material and dc power of corresponding iridium target are 4:1~5:1;Target-substrate distance is d=

70mm;200 DEG C of substrate heating temperature;Ar pressure is 0.5Pa;Applying radio-frequency power to zinc oxide target is 90W;To iridium target

Application dc power is 20W;Sputtering sedimentation time 1h;Cooled to room temperature is taken out

Two electric arm of sputtering sedimentation are placed in nitrogen atmosphere and anneal by step 2, and 500 DEG C of annealing temperature, when annealing

Between 2h;

Step 3 sputters one layer of Ti metal film (general sputtering method) using electrode mask version, sputters one layer again on Ti film

Pt electrode, at a temperature of 100 DEG C, annealing time 0.5h.

Step 4, magnetron sputtering deposits to form silica resistive formation in substrate, and resistive formation covering substrate and electricity

Arm does not cover power connection end.

图1
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