CN105274484B - A kind of Sb adulterates Mg2Si base thermal electric films and preparation method thereof - Google Patents
A kind of Sb adulterates Mg2Si base thermal electric films and preparation method thereof Download PDFInfo
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- CN105274484B CN105274484B CN201510704585.XA CN201510704585A CN105274484B CN 105274484 B CN105274484 B CN 105274484B CN 201510704585 A CN201510704585 A CN 201510704585A CN 105274484 B CN105274484 B CN 105274484B
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Abstract
The invention discloses a kind of Sb to adulterate Mg2Si base thermal electric films and preparation method thereof.Double target circulation sputterings are carried out using magnetron sputtering deposition method the film with laminated construction is made, Sb doping Mg is then obtained using vacuum annealing2Si base thermal electric films.The present invention improves Mg using Sb doping and film low-dimensional2The thermoelectricity capability of Si sills, method controllability is strong, can by adjust sputtering power, sputtering time than etc. parameter adjust the doping of Sb elements；Improve the uniformity of doping Sb elements using heat treatment.The present invention has the advantages such as technique is simple, reproducible, utilization rate of raw materials is high, can not only realize that doping is controllable, moreover it is possible to effectively optimizes membrane structure and improves the thermoelectricity capability of film.
Description
Technical field
The invention belongs to thermoelectricity field of functional materials, and in particular to a kind of Sb adulterates Mg2Si bases thermal electric film and its preparation
Method.
Background technology
Thermoelectric material is a kind of environmental type functional material that can be realized heat energy and electric energy and directly mutually change；The temperature difference
Electrical part can realize the mutual conversion between heat energy and electric energy, be the very wide environmental type energy device of the scope of application.Partly to lead
The semiconductor generator and refrigerator of body temperature-difference power generation module manufacture, can be carried out as long as can be generated electricity with the presence of the temperature difference, during power supply
Refrigeration, noiseless, pollution-free during its work, service life can be widely applied to waste-heat power generation, refrigeration for refrigerator etc. more than 10 years
In important base application.It is thus a kind of widely used green energy resource device.Currently, due to being limited by pyroelectric material performance
System, the application of thermo-electric device are also far from reaching the stage for substituting mechanical refrigerator, and this turns into thermo-electric device large-scale application
Bottleneck, therefore high performance thermoelectric material is one of hot subject of current international material research field.The performance of thermoelectric material
Mainly characterized by dimensionless figure factor Z T values：ZT=Tσα2/κ；Wherein T is absolute temperature, and σ is the electrical conductivity of material, and α is
Seebeck coefficients, κ are thermal conductivity.
Recent study finds that thermoelectric film is advantageous to improve the pyroelecthc properties of thermoelectric material, and main cause exists
In：First, Interfacial scattering effect can be formed so as to reduce the thermal conductivity of material, the thermoelectricity for increasing material is excellent by the reduction of dimension
Value, the power factor that quantum confinement effect improves material can also be produced when film thickness is in nanometer scale.2nd, filming can carry
Its high response speed, energy density and the ability of small-sized static localization.In addition, the thermoelectric material of filming is imitated in conversion
In terms of rate and in terms of cost, there is very big advantage.Therefore for Mg2The research of Si base thermal electric films has great importance.
Mg2Si thermoelectric materials are a kind of one of thermoelectric materials with application prospect applied to middle warm area, its pyroelectricity
The optimization of energy and the advanced subject that raising is current international thermoelectric material science.At present for Mg2The preparation of Si thermal electric films is ground
Study carefully only a small amount of report, effect is also not satisfactory；Mainly simple technology of preparing can not prepare more doping, height at present
The Mg of performance2Si base thermoelectric film materials.Although complicated technique can prepare the higher Mg of the figure of merit2Si base thermal electric films, but
It prepares cost height, complex process can not all meet the needs of its industrialization.And Mg2Si needs the doping of associated materials, ability
Enough realize the larger raising of thermoelectricity capability；Doping way the most frequently used at present is first by the material and Mg of required doping2Si is mixed
Conjunction is prepared into same target, then plates and film is made, this mode cost height, tedious process, time length, while the change of target and film
Study point be not consistent, poor controllability.Therefore doping type Mg how is simplified2The synthesis and preparation process of Si base thermal electric films, realize
Mg2The optimal doping of Si base thermal electric films, obtain Stability Analysis of Structures, the Mg of superior performance2The key technology of Si base thermal electric films, it is
Current research emphasis.
Theoretical calculation and experimental result show that Sb is important n-type doped chemical, and Sb elements are identical with Si electronegativity, from
Sub- radius is close, easily substitutes Si positions, as donor doping, there is provided conduction electrons is as carrier, so as to improve the electricity of material
Conductance and thermoelectricity capability；In addition, the quantum effect of film low-dimensional further lifts its thermoelectricity capability.At present, Sb adulterates Mg2Si
Base thermal electric film has not yet to see report.
The content of the invention
To solve the above problems, the invention provides a kind of Sb to adulterate Mg2Si base thermal electric films and preparation method thereof, it is intended to
Solves existing Sb doping Mg2The problem of Si base thermal electric film preparation method techniques are cumbersome, efficiency is low, poor controllability, has work
The advantages such as skill is simple, reproducible, utilization rate of raw materials is high, it can not only realize that doping is controllable, moreover it is possible to effectively optimization film knot
Structure and the thermoelectricity capability for improving film.
Technical scheme is as follows：
A kind of Sb adulterates Mg2The preparation method of Si base thermal electric films, double target circulations are carried out using magnetron sputtering deposition method and splashed
Penetrate, wherein, a target position puts Mg2Si targets, power supply select radio-frequency power supply；Another target position puts Sb targets, and power supply selects dc source；To exhausted
Edge substrate carries out organic solvent ultrasonic wave cleaning；Background vacuum is better than 6.5 × 10-4Pa, working gas are high-purity Ar gas, work
It is 0.1~5.0 Pa to make air pressure；One layer of Mg is first plated on substrate2Si, one layer of Sb is then plated, then plate one layer of Mg2Si；And so on
Repeatedly, the film with laminated construction is made, Sb doping Mg is finally obtained using vacuum annealing2Si base thermal electric films.
Sb elements are splashed to by Mg using the method for double targets circulation sputtering several times2Doping, circulation are realized in Si film layers
Cycle is 1~24 time, Sb and Mg2Si sputtering time ratio is 1:4~1:60, total sputtering time and be 0.5~1.5 h.
Mg2Si target radio-frequency sputterings power is 40~200 W, and Sb targets sputtering power is 20~150 W.
After the completion of sputtering, sputtering source is closed, is better 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
Obtain Sb doping Mg2Si base thermal electric films.
Annealing temperature is 100~500 DEG C, and annealing time is the h of 0.5 h~5.
Described organic solvent is followed successively by acetone, alcohol, and ultrasonic wave scavenging period is 10~30 min.
Described dielectric substrate is insulating glass, single crystalline Si, quartz, Al2O3In one kind.
The remarkable advantage of the present invention is：
The present invention obtains p-type Mg using Sb doping2Si sills simultaneously further improve its pyroelectricity by film low-dimensionalization
Energy；Sb doping Mg is prepared using sputter-deposition technology2Si base thermal electric films, controllability is strong, film has good tack and
It repeatability, can meet to mass produce needs, and the parameters such as sputtering power, sputtering time ratio can be accurately controlled to adjust Sb
Doping, using heat treatment come improve doping Sb elements uniformity, simplify preparation technology, reduce cost, can meet
Large-scale production needs.Sb adulterates Mg2The thermoelectricity capability of Si base films is better than existing Mg2Si materials, its mechanism be Sb elements and
Si electronegativity is identical, and ionic radius is close, easily substitutes Si positions, as donor doping, there is provided conduction electrons as carrier, from
And improve the electrical conductivity and thermoelectricity capability of material；In addition, the quantum effect of film low-dimensional further lifts its thermoelectricity capability.
Brief description of the drawings
Fig. 1 is that Sb of the present invention adulterates Mg2The sedimentary schematic diagram of Si base thermal electric films.
Embodiment
The present invention provides a kind of Sb 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 is it should be appreciated that described herein specific real
Example is applied only to explain the present invention, is not intended to limit the present invention.
A kind of Sb 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 select radio-frequency power supply；Another target position puts Sb
Simple substance target, power supply select dc source.One layer of Mg is first plated on substrate2Si, then plates one layer thin of Sb layers, then plates one layer
Mg2Si；And so on repeatedly, so as to which the film with laminated construction be prepared, Sb doping is finally obtained using vacuum annealing
Mg2Si base thermal electric films.Sb adulterates Mg2Si base thermal electric film sedimentary schematic diagrames are as shown in Figure 1.
Illustrate that the Sb of the present invention adulterates Mg below by some embodiments2The preparation method of Si base thermal electric films.
Embodiment 1：
Double target circulation sputterings are carried out using magnetron sputtering deposition method, wherein, a target position puts Mg2Si targets, power supply select radio frequency
Power supply；Another target position puts Sb simple substance targets, and power supply selects dc source.One layer of Mg is first plated on substrate2Si, then plate one layer thin
Sb layers, then plate one layer of Mg2Si；And so on repeatedly, so as to which the film with laminated construction be prepared, finally moved back using vacuum
Fire obtains Sb doping Mg2Si base thermal electric films.It is clear that sputtering carries out ultrasonic wave with organic solvents such as acetone, alcohol to slide before
Wash each 15 min；Vacuum is evacuated to 3.5 × 10-4Below Pa, high-purity Ar gas that flow is 30 sccm is passed through as working gas,
Operating air pressure is 0.5 Pa；Mg2Si target radio-frequency sputterings power is 120 W, and Sb targets sputtering power is 30 W；Cycle period is
12 times, Sb and Mg2Si sputtering time ratio is 1:10, total sputtering time and be 1h.After the completion of sputtering, sputtering source is closed,
Background vacuum is better than 3.0 × 10-4High-purity Ar gas is passed through in Pa vacuum chamber, turns down evacuating valve, maintains the atmosphere of Ar gas
In 20 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove Sb doping Mg is made2Si base thermal electric films；Annealing temperature is
400 DEG C, annealing time 3h.
Embodiment 2：
Double target circulation sputterings are carried out using magnetron sputtering deposition method, wherein, a target position puts Mg2Si targets, power supply select radio frequency
Power supply；Another target position puts Sb simple substance targets, and power supply selects dc source.One layer of Mg is first plated on substrate2Si, then plate one layer thin
Sb layers, then plate one layer of Mg2Si；And so on repeatedly, so as to which the film with laminated construction be prepared, finally moved back using vacuum
Fire obtains Sb doping Mg2Si base thermal electric films.It is clear that sputtering carries out ultrasonic wave with organic solvents such as acetone, alcohol to slide before
Wash each 15 min；Vacuum is evacuated to 3.5 × 10-4Below Pa, high-purity Ar gas that flow is 30 sccm is passed through as working gas,
Operating air pressure is 0.5 Pa；Mg2Si target radio-frequency sputterings power is 120 W, and Sb targets sputtering power is 60 W；Cycle period is
12 times, Sb and Mg2Si sputtering time ratio is 1:10, total sputtering time and be 1h.After the completion of sputtering, sputtering source is closed,
Background vacuum is better than 3.0 × 10-4High-purity Ar gas is passed through in Pa vacuum chamber, turns down evacuating valve, maintains the atmosphere of Ar gas
In 20 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove Sb doping Mg is made2Si base thermal electric films；Annealing temperature is
400 DEG C, annealing time 3h.
Embodiment 3：
Double target circulation sputterings are carried out using magnetron sputtering deposition method, wherein, a target position puts Mg2Si targets, power supply select radio frequency
Power supply；Another target position puts Sb simple substance targets, and power supply selects dc source.One layer of Mg is first plated on substrate2Si, then plate one layer thin
Sb layers, then plate one layer of Mg2Si；And so on repeatedly, so as to which the film with laminated construction be prepared, finally moved back using vacuum
Fire obtains Sb doping Mg2Si base thermal electric films.It is clear that sputtering carries out ultrasonic wave with organic solvents such as acetone, alcohol to slide before
Wash each 15 min；Vacuum is evacuated to 3.5 × 10-4Below Pa, high-purity Ar gas that flow is 30 sccm is passed through as working gas,
Operating air pressure is 0.5 Pa；Mg2Si target radio-frequency sputterings power is 120 W, and Sb targets sputtering power is 90 W；Cycle period is
12 times, Sb and Mg2Si sputtering time ratio is 1:10, total sputtering time and be 1h.After the completion of sputtering, sputtering source is closed,
Background vacuum is better than 3.0 × 10-4High-purity Ar gas is passed through in Pa vacuum chamber, turns down evacuating valve, maintains the atmosphere of Ar gas
In 20 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove Sb doping Mg is made2Si base thermal electric films；Annealing temperature is
400 DEG C, annealing time 3h.
The Mg prepared under the different Sb targets sputtering powers of table 12The constituent analysis of Si base thermal electric films
The Mg of the different Sb dopings at room temperature of table 22The electronic transport performance of Si base thermal electric films
From experimental data as can be seen that Sb doped chemicals are fully diffused into Mg2In Si base films, and suitable Sb dopings
To Mg2The thermoelectricity capability important of Si base films；Experiment shows to carry out double target circulations using magnetron sputtered deposition technology
Sputtering prepares doping type Mg2Si base thermal electric films are truly feasible.
Further, the magnetron sputtering deposition parameter can also be set as follows：Background vacuum is better than 6.5 × 10-4
The sccm of Pa, Ar throughput 10~50, operating air pressure are 0.1~5.0 Pa；Mg2Si target radio-frequency sputterings power is 40~200 W,
Sb targets sputtering power is 20~150 W.Cycle period is 1~24 time, Sb and Mg2Si sputtering time ratio is 1:4~1:
60, total sputtering time and be 0.5~1.5 h.
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, can meet to mass produce needs.
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 (7)
1. a kind of Sb adulterates Mg2Si base thermal electric films, it is characterised in that：The preparation method of the film is：Using magnetron sputtering
Sedimentation carries out double target circulation sputterings, wherein, a target position puts Mg2Si targets, power supply select radio-frequency power supply；Another target position puts Sb
Target, power supply select dc source；Organic solvent ultrasonic wave cleaning is carried out to dielectric substrate；Background vacuum is better than 6.5 × 10-4
Pa, working gas are high-purity Ar gas, and operating air pressure is 0.1~5.0 Pa；One layer of Mg is first plated on substrate2Si, then plate
One layer of Sb, then plate one layer of Mg2Si ；And so on repeatedly, the film with laminated construction is made, is finally obtained using vacuum annealing
Obtain Sb doping Mg2Si base thermal electric films.
A kind of 2. Sb doping Mg according to claim 12Si base thermal electric films, it is characterised in that circulated using double targets
Sb elements are splashed to Mg by the method for sputtering several times2Doping is realized in Si film layers, cycle period is 1~24 time, Sb
And Mg2Si sputtering time ratio is 1:4~1:60, total sputtering time and be 0.5~1.5 h.
A kind of 3. Sb doping Mg according to claim 12Si base thermal electric films, it is characterised in that Mg2Si target radio frequencies
Sputtering power is 40~200 W, and Sb targets sputtering power is 20~150 W.
A kind of 4. Sb doping Mg according to claim 12Si base thermal electric films, it is characterised in that after the completion of sputtering,
Sputtering source is closed, is better than 5.0 × 10 in background vacuum-4 High-purity Ar gas is passed through in Pa vacuum chamber, turns down evacuating valve,
The atmosphere of Ar gas is set to maintain 1~50 Pa；Vacuum annealing is carried out in the case where sample is not come out of the stove and obtains Sb doping
Mg2Si base thermal electric films.
A kind of 5. Sb doping Mg according to claim 42Si base thermal electric films, it is characterised in that annealing temperature 100
~500 DEG C, annealing time is the h of 0.5h~5.
A kind of 6. Sb doping Mg according to claim 12Si base thermal electric films, it is characterised in that described is organic molten
Agent is followed successively by acetone, alcohol, and ultrasonic wave scavenging period is 10~30 min.
A kind of 7. Sb doping Mg according to claim 12Si base thermal electric films, it is characterised in that described insulation lining
Bottom is insulating glass, single crystalline Si, quartz, Al2O3In one kind.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101589480A (en) * | 2006-12-20 | 2009-11-25 | 昭和Kde株式会社 | Thermo-electric converting materials, process for producing the same, and thermo-electric converting element |
| CN101798680A (en) * | 2010-04-15 | 2010-08-11 | 贵州大学 | Magnetron sputtering preparation process for Mg2Si thin film made of environment-friendly semiconductor material |
| CN102251216A (en) * | 2011-07-19 | 2011-11-23 | 电子科技大学 | Method for preparing tungsten-doped vanadium oxide film |
| WO2014007225A1 (en) * | 2012-07-06 | 2014-01-09 | 国立大学法人九州工業大学 | Method for producing thermoelectric conversion material |
| CN103572243A (en) * | 2013-11-15 | 2014-02-12 | 深圳大学 | Zinc antimonide-based thermoelectric film and preparation method thereof |
-
2015
- 2015-10-27 CN CN201510704585.XA patent/CN105274484B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101589480A (en) * | 2006-12-20 | 2009-11-25 | 昭和Kde株式会社 | Thermo-electric converting materials, process for producing the same, and thermo-electric converting element |
| CN101798680A (en) * | 2010-04-15 | 2010-08-11 | 贵州大学 | Magnetron sputtering preparation process for Mg2Si thin film made of environment-friendly semiconductor material |
| CN102251216A (en) * | 2011-07-19 | 2011-11-23 | 电子科技大学 | Method for preparing tungsten-doped vanadium oxide film |
| WO2014007225A1 (en) * | 2012-07-06 | 2014-01-09 | 国立大学法人九州工業大学 | Method for producing thermoelectric conversion material |
| CN103572243A (en) * | 2013-11-15 | 2014-02-12 | 深圳大学 | Zinc antimonide-based thermoelectric film and preparation method thereof |
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