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中国 发明 在审

一种Ge掺Bi 【EN】A kind of Ge mixes Bi

申请(专利)号:CN201910377764.5国省代码:四川 51
申请(专利权)人:【中文】成都理工大学【EN】Chengdu University of Technology
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摘要:
【中文】本发明公开了一种Ge掺Bi2Te3热电薄膜制备方法,包括以下步骤:步骤1,将硅玻璃基片进行清洗,在丙酮中进行超声并进行干燥;步骤2,硅玻璃基片放入舱室进行烘干;步骤3,将硅玻璃基片放入磁控溅射基片台,进行溅射;步骤4,二次溅射,采用在线加热,真空保温去应力。本发明的优点在于:采用的是在线加热的方式,采用磁控溅射技术,改变Ge含量比,提高Bi2Te3薄膜的性能。对于真空条件下降温保护去应力,便于薄膜和基板之间进行结合。操作简单。 【EN】Paragraph:The invention discloses a kind of Ge to mix Bi2Te3Thermal electric film preparation method, comprising the following steps: step 1, silica glass substrate is cleaned, ultrasound is carried out in acetone and is dried;Step 2, silica glass substrate is put into cabin and is dried;Step 3, silica glass substrate is put into magnetron sputtering chip bench, is sputtered;Step 4, secondary sputtering, using on-line heating, vacuum heat-preserving destressing.The present invention has the advantages that using magnetron sputtering technique, changing Ge content ratio using the mode of on-line heating, improving Bi2Te3The performance of film.For cooling protection destressing under vacuum condition, convenient for being combined between film and substrate.It is easy to operate.Image:201910377764.GIF

主权项:
【中文】1.一种Ge掺BiTe热电薄膜制备方法,其特征在于,包括以下步骤: 步骤1,将硅玻璃基片进行清洗,在丙酮中进行超声,10-15min,然后将玻璃基片放入无水乙醇中进行再次超声,10-20min,将玻璃基片进行干燥; 步骤2,硅玻璃基片放入舱室进行烘干,同时进行抽真空,将舱室多余水分抽出,待达到所需要的真空度后开始磁控溅射基片台升温,将磁控溅射基片台温度预先升温到50℃,保温10分钟,待温度稳定后继续升温,反复升温到200℃后保温10分钟; 步骤3,将硅玻璃基片放入磁控溅射基片台,进行预溅射,预溅射时间为5-10min,充分将硅玻璃基片的表面进行清洗,去除表面附着物,便于BeTi薄膜的沉积; 步骤4,二次溅射,采用在线加热,真空保温去应力,溅射靶材与硅玻璃基片表面之间的距离为5cm。 【EN】1. a kind of Ge mixes BiTeThermal electric film preparation method, which comprises the following steps: Step 1, silica glass substrate is cleaned, carries out ultrasound in acetone, then glass substrate is put into nothing by 10-15min It carries out ultrasound, 10-20min again in water-ethanol glass substrate is dried; Step 2, silica glass substrate is put into cabin and is dried, while being vacuumized, and cabin excessive moisture is extracted out, to be achieved Start the heating of magnetron sputtering chip bench after required vacuum degree, magnetron sputtering chip bench temperature is warming up to 50 DEG C in advance, is protected Temperature 10 minutes, stablizes subsequent temperature of continuing rising to temperature, keeps the temperature 10 minutes after being warming up to 200 DEG C repeatedly; Step 3, silica glass substrate is put into magnetron sputtering chip bench, carries out pre-sputtering, the pre-sputtering time is 5-10min, sufficiently The surface of silica glass substrate is cleaned, surface attachments are removed, is convenient for BeTiThe deposition of film; Step 4, secondary sputtering, using on-line heating, vacuum heat-preserving destressing, between sputtering target material and silica glass substrate surface Distance is 5cm.


说明书

【中文】

一种Ge掺Bi2Te3热电薄膜制备方法

技术领域

本发明涉及化学镀膜技术领域,特别涉及一种高性能Ge掺杂的Bi2Te3薄膜的制备方法。

背景技术

碲化铋(Bi2Te3)基化合物是当前室温下性能最好的商用热电材料,对Bi2Te3基热电材料进行纳米低维化和掺杂改性可以进一步提高其热电性能。

磁控溅射技术是目前研究较多的热电材料薄膜制备方法之一,碲化铋是近室温应用的重要热电材料。磁控溅射技术是薄膜制备的有效工业方法,近年来对使用磁控溅射技术合成的Bi2Te3热电薄膜进行了广泛的研究。由于电子和声子的量子经典尺寸效应,与块体热电器件相比较,薄膜热电器件有更高的热电转换效率。作为薄膜热电器件的重要组成部分,p型模块与n型模块的复合稳定性成为影响薄膜热电器件转化效率的关键因素之一。通过掺杂Ge元素和改变掺杂浓度的方法调节微流子的传输特性,在引入掺杂离子的同时,伴随着晶体结构的改变,长程有序结构受到破坏,微流子在近费米面的传输受到影响,从而影响热电薄膜材料热电性能的提高。

发明内容

本发明针对现有技术的缺陷,提供了一种Ge掺Bi2Te3热电薄膜制备方法,能有效的解决上述现有技术存在的问题。

为了实现以上发明目的,本发明采取的技术方案如下:

一种Ge掺Bi2Te3热电薄膜的制备方法,包括以下步骤:

步骤1,将硅玻璃基片进行清洗,在丙酮中进行超声10-15min,然后将玻璃基片放入无水乙醇中进行再次超声,10-20min,将玻璃基片进行干燥;

步骤2,硅玻璃基片放入舱室进行烘干,同时进行抽真空,将舱室多余水分抽出,待达到所需要的真空度后开始磁控溅射基片台升温,将磁控溅射基片台温度预先升温到50℃,保温10分钟,待温度稳定后继续升温,反复升温到200℃后保温10分钟;

步骤3,将硅玻璃基片放入磁控溅射基片台,进行预溅射,预溅射时间为5-10min,充分将硅玻璃基片的表面进行清洗,去除表面附着物,便于Be2Ti3薄膜的沉积;

步骤4,二次溅射,采用在线加热,真空保温去应力,溅射靶材与硅玻璃基片表面之间的距离为5cm。

作为优选,步骤3中磁控溅射基片台的功率为40w,气压为0.4pa,采用直流电压。

作为优选,步骤4中二次溅射中磁控溅射基片台转速为25r·min,功率为40w,气压为0.4pa,采用射频电源。

进一步地,采用的靶材为纯度99.99%Be2Ti3合金靶材。

进一步地,采用的靶材规格为50.8*4mm。

进一步地,Be2Ti3薄膜的平均厚度为2.4μm。

与现有技术相比本发明的优点在于:采用的是在线加热的方式,采用磁控溅射技术,改变Ge掺杂含量比,提高Bi2Te3薄膜的性能。对于真空条件下降温保护去应力,便于薄膜和基板之间进行结合。操作简单。

附图说明

图1为本发明实施例Be2Ti3薄膜的PF图。

具体实施方式

为使本发明的目的、技术方案及优点更加清楚明白,以下举实施例,对本发明做进一步详细说明。

本发明实验采用了组合式溅射镀膜系统(COSCOS)。该系统由主真空室,多样品台,磁控溅射枪和真空泵系统组成。该室通过涡轮分子泵(600r/s)与旋转泵混合泵送。溅射的工作压力由反馈控制的自动闸阀系统精确设定和保持。可以在不中断真空条件的情况下,立即将多个基板安装在真空室内并旋转改变。可以将样品中的一个加热至1300K,同时,通过与自身被循环水冷却的铜块接触,将其他样品冷却至温度100K以下。基板位于加热位置、溅射靶溅射的方向也可以改变。相较于一般磁控溅射系统,对于样品台,基板温度的不控制型,通过精准的电脑温控程序实现精确温度升温。

由于失去了电子而产生了一个正离子,因为这对于其它电子而言是个“空位”,所以通常把它叫做“空穴”,而这种材料被称为“P”型半导体。在这样的材料中传导主要是由带正电的空穴引起的,因而在这种情况下电子是“少数载流子”。传导性是由于有多余的负离子引起的,所以称为“N”型。也有些材料的传导性是由于材料中有多余的正离子,但主要还是由于有大量的电子引起的,因而(在N型材料中)电子被称为“多数载流子”由于在溅射过程中采用在线加热的方式,随着温度的升高,Bi2Te3晶体结构发生改变,由于溅射速率的改变,使得Te/Bi元素比例发生变化,从而导致晶粒生长过程中出现一定程度的缺陷,导致载流子浓度发生变化,在320摄氏度时发生p-n型的转变。

薄膜中的应力受多方面因素的影响,其中薄膜沉积工艺、热处理工艺以及材料本身的机械特性是主要影响因素。按照应力的产生根源将薄膜内的应力分为热应力和本征应力,通常所说的残余应力就是这两种应力的综合作用,是一种宏观应力。应力在作用方向上有张应力和压应力之分。若薄膜具有沿膜面膨胀的趋势则基底对薄膜产生压应力;相反,薄膜沿膜面的收缩趋势造成张应力。一般定义张应力为正值薄膜应力,压应力为负值。薄膜中的残余应力又可定义为两种应力:一种是平均应力,另一种是微区应力。

要消除薄膜中的热应力,最根本的方法就是选用热膨胀系数相同的薄膜和基片材料。其次是让成膜温度与薄膜的测量温度或使用温度相同。热应力作为薄膜应力的一部分,受温度的影响而易于控制,这样通过热应力的变化与本征应力相互作用,调整薄膜的宏观应力,可能起到改善应力的效果。通过改变工艺参数控制应力。镀膜过程中工艺参数的改变会直接影响薄膜中的最终残余应力水平,通过调整镀膜时的基底温度、工作气压、沉积速率等工艺参数可以控制薄膜中应力的大小,甚至会改变应力的性质。

在真空(0.4Pa)条件下进行溅射,真空保持,通过改变大气压从而影响薄膜的结构、成分、晶粒尺寸以及各种缺陷的的数量和分布。对于溅射镀膜,随着反应腔内溅射气压的增大,高能离子(粒子)的浓度增大,使得气体分子自由程减小,存在严重相互碰撞的散射现象,从而减小了气体分子的能量,原子喷丸效应削弱,增大了沉积粒子流的倾斜分量,致使膜结构疏松,压应力越来越小,变为张应力,张应力先增大再减小,满足界面电子密度连续的条件,从而不会造成薄膜的形变,消除薄膜中产生内应力。

玻璃Be2Ti3薄膜在线加热条件下实现p-n型转变的方法,将玻璃基片(10*10mm)进行清洗,在丙酮中进行超声,10-15min,然后将玻璃基片放入无水乙醇中进行再次超声,10-20min,将玻璃基片进行干燥。

其次,将玻璃基片放入磁控溅射基片台,进行溅射,首先预溅射5-10min,充分将玻璃基片的表面进行清洗,去除表面附着物,便于Be2Ti3薄膜的沉积,磁控溅射基片台的功率为40w,气压为0.4pa,采用直流电压;

开始溅射,采用在线加热,真空保温去应力,溅射靶材与玻璃基片表面之间的距离为5cm,磁控溅射基片台转速为25r·min,功率为40w,气压为0.4pa,采用射频电源;

升温模式为在溅射的开始阶段,对舱室进行烘干,同时进行抽真空,将舱室多余水分抽出,待达到所需要的真空度后开始磁控溅射基片台升温,将磁控溅射基片台温度预先升温到50℃,保温10分钟,待温度稳定后继续升温,反复升温到200℃后保温10分钟,稳定后开始溅射,溅射时间为5min,Be2Ti3薄膜的平均厚度为2.4μm,真空降温去应力。

在掺杂条件下,通过掺杂不同浓度Ge元素提高Bi2Te3薄膜性能的显著提高。

由图1可以看出通过本工艺合成薄膜性能大幅度提高。

本领域的普通技术人员将会意识到,这里所述的实施例是为了帮助读者理解本发明的实施方法,应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合,这些变形和组合仍然在本发明的保护范围内。

【EN】

A kind of Ge mixes Bi2Te3Thermal electric film preparation method

Technical field

The present invention relates to plated film technical field, in particular to a kind of Bi of high-performance Ge doping2Te3The preparation of film

Method.

Background technique

Bismuth telluride (Bi2Te3) based compound is performance is best under current room temperature commercial thermoelectric material, to Bi2Te3Base heat

Electric material carries out nanometer low-dimensional and doping vario-property can be further improved its thermoelectricity capability.

Magnetron sputtering technique is to study more one of thermoelectric film preparation method at present, and bismuth telluride is that nearly room temperature is answered

Important thermoelectric material.Magnetron sputtering technique is effective commercial run of film preparation, in recent years to using magnetron sputtering skill

The Bi of art synthesis2Te3Thermal electric film conducts extensive research.Due to the quantum classics dimensional effect of electronics and phonon, with block

Thermo-electric device compares, and thin film thermoelectric device has higher conversion efficiency of thermoelectric.Important composition portion as thin film thermoelectric device

Point, the stable composition of p-type module and N-shaped module becomes one of the key factor for influencing thin film thermoelectric device transformation efficiency.It is logical

Overdoping Ge element and the method for changing doping concentration adjust the transmission characteristic of miniflow, while introducing Doped ions, companion

With the change of crystal structure, long range ordered structure is destroyed, and miniflow is affected in the transmission of nearly Fermi surface, thus shadow

Ring the raising of thermoelectric film material thermoelectricity capability.

Summary of the invention

The present invention in view of the drawbacks of the prior art, provides a kind of Ge and mixes Bi2Te3Thermal electric film preparation method, can be effective

Solve the above-mentioned problems of the prior art.

In order to realize the above goal of the invention, the technical solution adopted by the present invention is as follows:

A kind of Ge mixes Bi2Te3The preparation method of thermal electric film, comprising the following steps:

Step 1, silica glass substrate is cleaned, carries out ultrasound 10-15min in acetone, then puts glass substrate

Enter to carry out ultrasound, 10-20min again in dehydrated alcohol that glass substrate being dried;

Step 2, silica glass substrate is put into cabin and is dried, while being vacuumized, and cabin excessive moisture is extracted out, to

Start the heating of magnetron sputtering chip bench after vacuum degree required for reaching, magnetron sputtering chip bench temperature is warming up to 50 in advance

DEG C, 10 minutes are kept the temperature, stablizes subsequent temperature of continuing rising to temperature, keeps the temperature 10 minutes after being warming up to 200 DEG C repeatedly;

Step 3, silica glass substrate being put into magnetron sputtering chip bench, carries out pre-sputtering, the pre-sputtering time is 5-10min,

Sufficiently the surface of silica glass substrate is cleaned, removes surface attachments, is convenient for Be2Ti3The deposition of film;

Step 4, secondary sputtering, using on-line heating, vacuum heat-preserving destressing, sputtering target material and silica glass substrate surface it

Between distance be 5cm.

Preferably, the power of magnetron sputtering chip bench is 40w, air pressure 0.4pa, using DC voltage in step 3.

Preferably, magnetron sputtering chip bench revolving speed is 25rmin, power 40w, air pressure in secondary sputtering in step 4

For 0.4pa, using radio-frequency power supply.

Further, the target used is purity 99.99%Be2Ti3Alloy target material.

Further, the target specification used is 50.8*4mm.

Further, Be2Ti3The average thickness of film is 2.4 μm.

Compared with prior art the present invention has the advantages that using on-line heating mode, using magnetron sputtering skill

Art changes Ge doping content ratio, improves Bi2Te3The performance of film.For cooling protection destressing under vacuum condition, it is convenient for film

It is combined between substrate.It is easy to operate.

Detailed description of the invention

Fig. 1 is Be of the embodiment of the present invention2Ti3The PF of film schemes.

Specific embodiment

To make the objectives, technical solutions, and advantages of the present invention more comprehensible, by the following examples, to the present invention do into

One step is described in detail.

Present invention experiment uses combined type sputter coating system (COSCOS).The system is by main vacuum chamber, various sample platform,

Ion Sputter Magnetron Gun and vacuum pump system composition.The room mixes pumping with rotary pump by turbomolecular pump (600r/s).Sputtering

Operating pressure is accurately set and is kept by the Automatic slucie valve system of feedback control.Can in the case where not break vacuum condition,

Multiple substrates are mounted in vacuum chamber immediately and rotate change.One in sample can be heated to 1300K, meanwhile, lead to

It crosses and is contacted with itself by the copper billet of circulating water, other samples are cooled to temperature 100K or less.Substrate be located at heating location,

The direction of sputtering target sputtering also can change.Compared to general magnetic control sputtering system, for sample stage, substrate temperature is not controlled

Type realizes accurate temperature heating by accurately computer temperature control program.

A cation is produced due to losing electronics, because this is " vacancy ", an institute for other electronics

Usually it is called in " hole ", and this material is referred to as " P " type semiconductor.Conduction is mainly by band in such material

Caused by the hole of positive electricity, thus electronics is " minority carrier " in this case.Conductibility be due to have it is extra bear from

Caused by son, so being known as " N " type.Also the conductibility of some materials is gone back due to there is extra cation in material, but mainly

Be due to caused by having a large amount of electronics, thus (in n type material) electronics be referred to as " majority carrier " due to sputtering

In journey by the way of on-line heating, as the temperature rises, Bi2Te3Crystal structure changes, due to changing for sputter rate

Become, so that Te/Bi element ratio changes, so as to cause occurring a degree of defect in Growing Process of Crystal Particles, causes to carry

It flows sub- concentration to change, the transformation of p-n junction occurs at 320 degrees Celsius.

Stress in film is influenced by many factors, wherein thin film deposition processes, heat treatment process and material sheet

The mechanical property of body is major influence factors.The stress in film is divided into thermal stress according to the generation root of stress and intrinsic is answered

Power, usually said residual stress are exactly the comprehensive function of both stress, are a kind of macro-stresses.Stress is on action direction

It is divided into tensile stress and compression.Substrate generates compression to film if film has the trend expanded along film surface;On the contrary, thin

Film causes tensile stress along the tendencies toward shrinkage of film surface.The general tensile stress that defines is positive value membrane stress, and compression is negative value.In film

Residual stress may be defined as two kinds of stress again: one is mean stress, another kind is micro-sized stress.

The thermal stress in film is eliminated, the most fundamental method is exactly to select the identical film of thermal expansion coefficient and base sheet

Material.Followed by allow film-forming temperature identical as the measurement temperature of film or use temperature.The a part of thermal stress as membrane stress,

It is influenced by temperature and easily controllable, is interacted in this way by the variation of thermal stress and intrinsic stress, adjust the macroscopic view of film

Stress may play the effect for improving stress.By changing process parameter control stress.The change of technological parameter in coating process

The final residual stress that will have a direct impact in film is horizontal, base reservoir temperature, operating air pressure, deposition rate when by adjusting plated film

Equal technological parameters can control the size of stress in film, or even can change the property of stress.

It is sputtered under the conditions of vacuum (0.4Pa), vacuum is kept, and influences the knot of film by changing atmospheric pressure

Structure, ingredient, crystallite dimension and various defects quantity and distribution.For sputter coating, with sputtering pressure in reaction chamber

Increase, the concentration of energetic ion (particle) increases so that gas molecule free path reduces, and there is the scattering seriously mutually collided

Phenomenon, to reduce the energy of gas molecule, atom shot peening effect weakens, and increases the tilt component of deposited particles stream, causes

Keep membrane structure loose, compression is smaller and smaller, becomes tensile stress, and tensile stress first increases and reduces again, meets interface electron density company

Continuous condition is eliminated in film so that the deformation of film will not be caused and generates internal stress.

Glass Be2Ti3Under the conditions of film on-line heating realize p-n junction transformation method, by glass substrate (10*10mm) into

Row cleaning, carries out ultrasound in acetone, then glass substrate is put into dehydrated alcohol and carries out ultrasonic again, 10- by 10-15min

Glass substrate is dried 20min.

Secondly, glass substrate is put into magnetron sputtering chip bench, sputtered, first pre-sputtering 5-10min, sufficiently by glass

The surface of glass substrate is cleaned, and surface attachments are removed, and is convenient for Be2Ti3The deposition of film, the power of magnetron sputtering chip bench

For 40w, air pressure 0.4pa, using DC voltage;

Start to sputter, using on-line heating, vacuum heat-preserving destressing, the distance between sputtering target material and glass substrate surface

For 5cm, magnetron sputtering chip bench revolving speed is 25rmin, power 40w, air pressure 0.4pa, using radio-frequency power supply;

Heating mode is to dry to cabin, while being vacuumized, in the incipient stage of sputtering by cabin superfluous water

Divide extraction, starts the heating of magnetron sputtering chip bench after required vacuum degree to be achieved, magnetron sputtering chip bench temperature is preparatory

50 DEG C are warming up to, 10 minutes is kept the temperature, stablizes subsequent temperature of continuing rising to temperature, keep the temperature 10 minutes after being warming up to 200 DEG C repeatedly, after stablizing

Start to sputter, sputtering time 5min, Be2Ti3The average thickness of film is 2.4 μm, vacuum cool-down destressing.

Under doping condition, Bi is improved by doping various concentration Ge element2Te3Film performance significantly improves.

It is increased substantially as seen from Figure 1 by this technique built up membrane performance.

Those of ordinary skill in the art will understand that the embodiments described herein, which is to help reader, understands this hair

Bright implementation method, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.Ability

The those of ordinary skill in domain disclosed the technical disclosures can make its various for not departing from essence of the invention according to the present invention

Its various specific variations and combinations, these variations and combinations are still within the scope of the present invention.

图1
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