CN105220118B - A kind of Al doping Mg2Si base thermal electric films and preparation method thereof - Google Patents
A kind of Al doping Mg2Si base thermal electric films and preparation method thereof Download PDFInfo
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- CN105220118B CN105220118B CN201510704525.8A CN201510704525A CN105220118B CN 105220118 B CN105220118 B CN 105220118B CN 201510704525 A CN201510704525 A CN 201510704525A CN 105220118 B CN105220118 B CN 105220118B
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Abstract
The invention discloses a kind of Al doping Mg2Si base thermal electric films and preparation method thereof.It is 6.5 × 10 in background vacuum‑4~1.0 × 10‑5 Pa, working gas is high-purity Ar gas, and operating air pressure is under conditions of 0.1~5.0 Pa, carries out double targets circulation sputterings on an insulating substrate using magnetron sputtering deposition method, and a target position puts Mg2Si targets, power supply selects radio-frequency power supply；Another target position puts Al simple substance targets, and power supply selects dc source；First plate Mg2Si layers, Al layers are then plated, then plate Mg2Si layers；By this loop cycle repeatedly, so as to obtain the film with laminated construction, Al doping Mg is finally obtained using vacuum annealing2Si base thermal electric films.The magnetron sputtering method preparation technology of the present invention has that technique is simple, the low advantage of cost, can meet large-scale production needs.
Description
Technical field
The present invention relates to thermoelectricity field of functional materials, more particularly to a kind of Al doping Mg2Si bases thermal electric film and its preparation
Method.
Background technology
It is special with increasingly serious, clean in the urgent need to actively pushing forward and the advocating use regenerative resource of energy crisis
It is not to pay attention to regenerative resource new technology development to be combined with industrialization investment, to reduce the utilization cost of regenerative resource.Heat
Electric material is a kind of can to realize the environmental type functional material that heat energy and electric energy are directly mutually changed；Made with thermoelectric material
Thermoelectric device have small size, light weight, without any mechanical rotation part, work noiseless, service life length, be not present
The advantages of environmental pollution problem, it can be widely applied to the fields such as thermoelectric generator, TEC and sensor.Therefore prepare
High performance thermoelectric material, not only conforms to environmental protection and the requirement of low-carbon economy, while having important scientific meaning and wide
General application prospect.
Currently, due to being limited by pyroelectric material performance, the application of thermo-electric device is also far from reaching substitution mechanical refrigeration
The stage of machine, this turns into the bottleneck of thermo-electric device large-scale application, therefore high performance thermoelectric material is that current international material is ground
Study carefully one of the hot subject in field.The performance of thermoelectric material is main to be characterized by dimensionless figure factor Z T values：ZT=Tσα2/ κ, its
Middle T is absolute temperature, and σ is the electrical conductivity of material, and α is Seebeck coefficients, and κ is thermal conductivity.
Mg2Si thermoelectric materials are a kind of applied to one of thermoelectric material with application prospect of middle warm area, its pyroelectricity
The optimization of energy and the advanced subject that raising is current international thermoelectric material science.Recent study finds that thermoelectric film has
Beneficial to the pyroelecthc properties for improving thermoelectric material, main reason is that：First, Interfacial scattering effect can be formed by the reduction of dimension
So as to reduce the thermal conductivity of material, increase the thermoelectric figure of merit of material, quantum taboo can also be produced when film thickness is in nanometer scale
Close the power factor that effect improves material.2nd, filming can improve its response speed, energy density and small-sized static localization
Ability.In addition, the thermoelectric material of filming has very big advantage in terms of the transformation efficiency and in terms of cost.Therefore it is right
In Mg2The research of Si base thermal electric films has great importance.
At present for Mg2The preparation research of Si thermal electric films only has a small amount of report, and effect is also not satisfactory；Mainly mesh
Preceding simple technology of preparing can not prepare many doping, high performance Mg2Si base thermoelectric film materials.Although complicated technique
The higher Mg of the figure of merit can be prepared2Si base thermal electric films, but its preparation cost is high, complex process can not all meet its industrialization
Demand.And Mg2Si needs the doping of associated materials, can realize the larger raising of thermoelectricity capability；It is the most frequently used at present to mix
Miscellaneous mode is first by the material and Mg of required doping2Si is prepared by mixing into same target, then plates film is made, this mode into
This height, tedious process, time are long, while target is not consistent with the chemical composition of film, poor controllability.Therefore doping how is simplified
Type Mg2The synthesis and preparation process of Si base thermal electric films, realizes Mg2The optimal doping of Si base thermal electric films, obtains Stability Analysis of Structures, property
The superior Mg of energy2The key technology of Si base thermal electric films, is current research emphasis.
Theoretical calculation and experimental result show that Al is important n-type doped chemical, wherein You et al. result of study table
It is bright：Mg2Si:Al0.02Thermoelectric material obtains maximum thermoelectric figure of merit under 823KZT=0.47.In addition, Al elements containing in the earth's crust
Amount is only second to O and Si, occupies the 3rd, is content most abundant metallic element in the earth's crust, with cheap advantage.At present,
Al doping Mg2Si base thermal electric films have not yet to see report.
The content of the invention
To solve the above problems, the invention provides a kind of Al doping Mg2Si base thermal electric films and preparation method thereof, it is intended to
Solve existing Al doping Mg2The preparation method technique of Si base thermal electric films is cumbersome, efficiency is low, poor controllability the problem of；And this
Invention can be accurately controlled sputtering power, sputtering time than etc. parameter adjust Al doping, simplify preparation technology, reduce
Cost, can meet large-scale production needs.
Technical scheme is as follows：
A kind of Al doping Mg2The preparation method of Si base thermal electric films, is 6.5 × 10 in background vacuum-4~1.0 × 10-5
Pa, working gas be high-purity Ar gas, the sccm of Ar throughputs 10~50, operating air pressure be 0.1~5.0 Pa under conditions of, use
Magnetron sputtering deposition method carries out double target circulation sputterings on an insulating substrate, and a target position puts Mg2Si targets, power supply selects radio-frequency power supply；
Another target position puts Al simple substance targets, and power supply selects dc source；First plate Mg2Si layers, Al layers are then plated, then plate Mg2Si layers, as
One cycle；By this loop cycle repeatedly, so as to obtain the film with laminated construction, Al doping is finally obtained using vacuum annealing
Mg2Si base thermal electric films.
Cycle period is 1~24 time, Al and Mg2Si sputtering time ratio is 1:4~1:60, total sputtering time and for 0.5
~1.5 h.
Mg2The radio-frequency sputtering power of Si targets is 40~200 W, and the sputtering power of Al simple substance targets is 20~150 W.
After the completion of sputtering, sputtering source is closed, is less than 5.0 × 10 in background vacuum-4It is passed through in Pa vacuum chamber high-purity
Ar gas, turns down evacuating valve, the atmosphere of Ar gas is maintained 1~50 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove
Al doping Mg is made2Si base thermal electric films.
The annealing temperature is 100~500 DEG C, and annealing time is the h of 0.5 h~5.
Described dielectric substrate carries out ultrasonic wave cleaning, ultrasonic wave scavenging period point using acetone, alcohol successively before
Wei not 10~30 min.
Described dielectric substrate is insulating glass, single crystalline Si, quartz, Al2O3In one kind.
Al doping Mg2The thermoelectricity capability of Si base films is better than existing Mg2Si materials, its mechanism is that Al elements have and alkali
The similar property of earth metal, after Al elements are added, easily substitution Mg, load is used as donor doping there is provided conduction electrons
Stream, so as to improve the electrical conductivity and thermoelectricity capability of material；In addition, the quantum effect of film low-dimensional further lifts its thermoelectricity
Performance.
The remarkable advantage of the present invention is：
The present invention improves Mg by Al doping and film low-dimensionalization2The thermoelectricity capability of Si sills；Splashed using the circulation of double targets
Penetrate deposition process and prepare Al doping Mg2Si base thermal electric films, controllability is strong, film has good tack and repeatability, can
Meet large-scale production needs, and can accurately control sputtering power, sputtering time than etc. parameter adjust Al doping,
Preparation technology is simplified, cost is reduced, large-scale production needs can be met.
Brief description of the drawings
Fig. 1 is Al of the present invention doping Mg2The sedimentary schematic diagram of Si base thermal electric films；
The Mg that the Al dopings that Fig. 2 is provided by the embodiment of the present invention 2 are 1.56%2The EDS collection of illustrative plates of Si base thermal electric films.
Embodiment
The present invention provides a kind of Al doping Mg2The preparation method of Si base thermal electric films, to make the purpose of the present invention, technical side
Case and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that specific reality described herein
Example is applied only to explain the present invention, is not intended to limit the present invention.
A kind of Al doping Mg provided by the present invention2The preparation method of Si base thermal electric films, it includes step：Using magnetic control
Sputtering method carries out double target circulation sputterings, wherein, a target position puts Mg2Si targets, power supply selects radio-frequency power supply；Another target position puts Al
Simple substance target, power supply selects dc source；One layer of Mg is first plated on substrate2Si, then plates Al layers one layer thin, then plate one layer
Mg2Si；And so on repeatedly, so as to prepare the film with laminated construction, Al doping is finally obtained using vacuum annealing
Mg2Si base thermal electric films.Al doping Mg2Si base thermal electric film sedimentary schematic diagrames are as shown in Figure 1.
Illustrate the Al doping Mg of the present invention below by some embodiments2The preparation method of Si base thermal electric films.
Embodiment 1
A kind of Al doping Mg2The preparation method of Si base thermal electric films, is concretely comprised the following steps：
1）Ultrasonic wave is carried out respectively to slide with acetone, alcohol cleans 15 min；
2）Double target circulation sputterings are carried out using magnetron sputtering deposition method, wherein, a target position puts Mg2Si targets, power supply is selected and penetrated
Frequency power；Another target position puts Al simple substance targets, and power supply selects dc source；Vacuum is evacuated to 6.5 × 10-4Below Pa, is passed through flow
For 30 sccm high-purity Ar gas as working gas, operating air pressure is 0.5 Pa；One layer of Mg is first plated on substrate2Si, is then plated
Al layers one layer thin, then plate one layer of Mg2Si；Mg2Si target radio-frequency sputterings power is 120 W, and Al targets sputtering power is 30 W；
Cycle period is 12 times, Al and Mg2Si sputtering time ratio is 1:10, total sputtering time and for 0.5h；
3）After the completion of sputtering, sputtering source is closed, 5.0 × 10 are better than in background vacuum-4Height is passed through in Pa vacuum chamber
Pure Ar gas, turns down evacuating valve, the atmosphere of Ar gas is maintained 20 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove
Al doping Mg is made2Si base thermal electric films；Annealing temperature is 400 DEG C, and annealing time is 3h.
Embodiment 2
A kind of Al doping Mg2The preparation method of Si base thermal electric films, is concretely comprised the following steps：
1）Ultrasonic wave is carried out respectively to slide with acetone, alcohol cleans 15 min；
2）Double target circulation sputterings are carried out using magnetron sputtering deposition method, wherein, a target position puts Mg2Si targets, power supply is selected and penetrated
Frequency power；Another target position puts Al simple substance targets, and power supply selects dc source；Vacuum is evacuated to 6.5 × 10-4Below Pa, is passed through flow
For 30 sccm high-purity Ar gas as working gas, operating air pressure is 5.0 Pa；One layer of Mg is first plated on substrate2Si, is then plated
Al layers one layer thin, then plate one layer of Mg2Si；Mg2Si target radio-frequency sputterings power is 120 W, and Al targets sputtering power is 60 W；
Cycle period is 12 times, Al and Mg2Si sputtering time ratio is 1:4, total sputtering time and for 1h；
3）After the completion of sputtering, sputtering source is closed, 5.0 × 10 are better than in background vacuum-4Height is passed through in Pa vacuum chamber
Pure Ar gas, turns down evacuating valve, the atmosphere of Ar gas is maintained 20 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove
Al doping Mg is made2Si base thermal electric films；Annealing temperature is 400 DEG C, and annealing time is 3h.
Embodiment 3
A kind of Al doping Mg2The preparation method of Si base thermal electric films, is concretely comprised the following steps：
1）Ultrasonic wave is carried out respectively to slide with acetone, alcohol cleans 15 min；
2）Double target circulation sputterings are carried out using magnetron sputtering deposition method, wherein, a target position puts Mg2Si targets, power supply is selected and penetrated
Frequency power；Another target position puts Al simple substance targets, and power supply selects dc source；Vacuum is evacuated to 6.5 × 10-4Below Pa, is passed through flow
For 30 sccm high-purity Ar gas as working gas, operating air pressure is 0.1Pa；One layer of Mg is first plated on substrate2Si, is then plated
Al layers one layer thin, then plate one layer of Mg2Si；Mg2Si target radio-frequency sputterings power is 120 W, and Al targets sputtering power is 90 W；
Cycle period is 24 times, Al and Mg2Si sputtering time ratio is 1:60, total sputtering time and for 1.5h；
3）After the completion of sputtering, sputtering source is closed, 5.0 × 10 are better than in background vacuum-4Height is passed through in Pa vacuum chamber
Pure Ar gas, turns down evacuating valve, the atmosphere of Ar gas is maintained 20 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove
Al doping Mg is made2Si base thermal electric films；Annealing temperature is 400 DEG C, and annealing time is 3h.
Experimental result：
Table 1 is the Mg for preparing under different Al targets sputtering powers2The constituent analysis of Si base thermal electric films, Fig. 2 is Al dopings
For 1.56% Mg2The EDS collection of illustrative plates of Si base thermal electric films, table 2 is the Mg of different Al dopings2The electronic transport of Si base thermal electric films
Energy；From experimental data as can be seen that Al doped chemicals are fully diffused into Mg2In Si base films, and suitable Al dopings pair
Mg2The thermoelectricity capability important of Si base films；Experiment shows that carrying out double target circulations using magnetron sputtered deposition technology splashes
Penetrate and prepare doping type Mg2Si base thermal electric films are truly feasible.
The Mg prepared under the difference Al target sputtering powers of table 12The constituent analysis of Si base thermal electric films
The Mg of the difference Al dopings of table 22The electronic transport performance of Si base thermal electric films
In summary, the present invention carries out double target circulation sputterings by using magnetron sputtered deposition technology and prepares doping type
Mg2Si base thermal electric films, controllability is strong, and film has good tack and repeatability, and can be accurately controlled sputtering work(
Rate, sputtering time than etc. parameter adjust the doping of element；And suitable annealing treating process can be obviously improved doping type
Mg2The performance of Si base thermal electric films；Preparation technology is simplified, large-scale production needs can be met.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (6)
- The Mg 1. a kind of Al adulterates2The preparation method of Si base thermal electric films, it is characterised in that：Using magnetron sputtering deposition method in insulation Double target circulation sputterings are carried out on substrate, wherein, a target position puts Mg2Si targets, power supply selects radio-frequency power supply；Another target position puts Al simple substance Target, power supply selects dc source；First plate Mg2Si layers, Al layers are then plated, then plate Mg2Si layers, as a cycle；Followed by this cycle Ring is multiple, so as to obtain the film with laminated construction；After the completion of sputtering, sputtering source is closed, is less than 5.0 in background vacuum ×10-4High-purity Ar gas is passed through in Pa vacuum chamber, evacuating valve is turned down, the atmosphere of Ar gas is maintained 1~50 Pa；In sample Vacuum annealing is carried out in the case of not coming out of the stove Al doping Mg is made2Si base thermal electric films；The annealing temperature is 100~500 DEG C, Annealing time is the h of 0.5 h~5.
- 2. according to the method described in claim 1, it is characterised in that：Double targets circulate the condition sputtered：Background vacuum is 6.5 ×10-4~1.0 × 10-5Pa, working gas is high-purity Ar gas, and the sccm of Ar throughputs 10~50, operating air pressure is 0.1~5.0 Pa。
- 3. according to the method described in claim 1, it is characterised in that：Cycle period is 1~24 time, Al and Mg2Si sputtering time Than for 1:4~1:60, total sputtering time and for 0.5~1.5 h.
- 4. according to the method described in claim 1, it is characterised in that：Mg2The radio-frequency sputtering power of Si targets is 40~200 W, and Al is mono- The sputtering power of matter target is 20~150 W.
- 5. according to the method described in claim 1, it is characterised in that：Described dielectric substrate uses acetone, wine successively before The row ultrasonic wave that progresses greatly is cleaned, and ultrasonic wave scavenging period is respectively 10~30 min.
- 6. according to the method described in claim 1, it is characterised in that：Described dielectric substrate is insulating glass, single crystalline Si, stone English, Al2O3In one kind.
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| US8031441B2 (en) * | 2007-05-11 | 2011-10-04 | Headway Technologies, Inc. | CPP device with an enhanced dR/R ratio |
| CN100499194C (en) * | 2007-12-13 | 2009-06-10 | 浙江大学 | Rare earth doping Mg2Si based thermoelectric material |
| KR20130006452A (en) * | 2010-03-17 | 2013-01-16 | 소와 케이디이 가부시키가이샤 | PRODUCTION APPARATUS AND METHOD FOR PRODUCING Mg2Si1 - xSnx POLYCRYSTALS |
| CN101798680B (en) * | 2010-04-15 | 2012-07-04 | 贵州大学 | Magnetron sputtering preparation process for Mg2Si thin film made of environment-friendly semiconductor material |
| CN102263198A (en) * | 2010-05-26 | 2011-11-30 | 苏州汉申温差电科技有限公司 | Method for preparing thermoelectric material in low-dimension structure |
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