CN112376028A - Sn doped Ge2Sb2Te5Thermoelectric film and method for manufacturing the same - Google Patents
Sn doped Ge2Sb2Te5Thermoelectric film and method for manufacturing the same Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses Sn doped Ge2Sb2Te5Thermoelectric thin film and method for preparing the same, with Ge2Sb2Te5And Sn as raw material, and depositing on the substrate to obtain Sn doped Ge by adopting a magnetron sputtering codeposition method2Sb2Te5A thermoelectric thin film. The invention deposits a single layer of Sn doped Ge on a substrate through material design and optimized process parameters2Sb2Te5The thermoelectric film greatly improves the thermoelectric conversion efficiency of the material and can effectively reduce the preparation of the nano Sn doped Ge2Sb2Te5The complexity and the cost of the manufacturing process of the film are favorable for popularization and application.
Description
Technical Field
The invention relates to a thermoelectric film and a preparation method thereof, in particular to a Sn-doped Ge film2Sb2Te5A thermoelectric film and a method for manufacturing the same.
Background
The appearance of novel energy sources such as solar energy, wind energy, tidal energy and the like relieves the energy shortage and environmental pollution, but is far from enough, and the seeking of more novel energy sources is urgent at present. Since seebeck, a german scientist in the 20 th of the 19 th century, discovered the thermoelectric generation effect, thermoelectric materials as novel energy materials for mutual conversion of heat energy and electric energy rapidly become a new research direction in the field of materials science. In recent decades, with the continuous progress of material science, new semiconductor materials and nanotechnology, scientists worldwide are continuously exploring and developing various new thermoelectric materials with use value. The thermoelectric cell is a green environment-friendly energy source which is widely applicable, and mainly converts heat energy and electric energy directly into each other through the thermoelectric effect of thermoelectric materials, thereby realizing thermoelectric power generation.
At present, thermoelectric conversion materials have been applied to national defense and high and new technology fields, such as aviation aircrafts, medical products, automobile cushions and the like; also in electronics, such as cooling of electronic equipment, electronic devices, computers, etc.; also have applications in industries such as automotive freezers, oil detectors, high vacuum cold traps, etc. However, the thermoelectric conversion efficiency of the thermoelectric materials used in the prior art is generally not high, and the specific power that can be provided is also limited. With the development of micro-nano electronic devices, novel micro-nano electromechanical systems and micro integrated systems, the thermoelectric conversion function of thermoelectric materials is utilized to provide uninterrupted energy for systems with lower power consumption, such as micro-nano integrated circuits and the like, so that the development and research of thermoelectric thin film materials are promoted greatly. Due to the nature of thermoelectric materials, the manufacturing cost is high, the conversion efficiency is low, and the thermoelectric device is difficult to be used on a large scale.
Disclosure of Invention
The purpose of the invention is as follows: it is an object of the present invention to provide a Sn doped Ge2Sb2Te5The thermoelectric film has high thermoelectric conversion efficiency and low cost; another object of the present invention is to provide a Sn-doped Ge2Sb2Te5The preparation method of the thermoelectric film has simple preparation process, and the prepared film has high conversion efficiency and is beneficial to large-scale use of thermoelectric devices.
The technical scheme is as follows: the invention provides Sn doped Ge2Sb2Te5Thermoelectric thin film of Ge2Sb2Te5And Sn as raw material, and adopting a magnetron sputtering codeposition method to deposit and obtain a single-layer Sn doped Ge on the substrate2Sb2Te5A thermoelectric thin film; the chemical formula of the film material is Snx(Ge2Sb2Te5)1-xWherein x is more than 0 and less than 0.25.
Preferably, the thickness of the film is 200-400 nm; sn doped Ge at this thickness2Sb2Te5The thermoelectric performance of the thermoelectric film is optimal.
Ge in the prior art2Sb2Te5Is a chalcogenide phase change memory material with larger electric conduction, small energy band gap and larger effective mass, and the invention breakthroughs in selecting Ge2Sb2Te5Preparing thermoelectric material from the material, doping Sn element, and performing magnetron sputtering codeposition to obtain Sn-doped Ge2Sb2Te5The thermoelectric thin film material has high thermoelectric conversion efficiency and low preparation cost.
The invention also provides Sn doped Ge2Sb2Te5The preparation method of the thermoelectric film specifically comprises the following steps:
(1) in a magnetron sputtering system, a Sn target material is placed at a magnetron radio frequency sputtering target position, and Ge is put at a magnetron radio frequency sputtering target position2Sb2Te5Placing the target material on a magnetic control direct current sputtering target position, and closing the chamber door;
(2) vacuumizing the cavity, and introducing inert gas, wherein the gas flow is set to be 20sccm or below;
(3) deposition of Sn doped Ge on a substrate by sputter co-deposition2Sb2Te5A film;
(4) carrying out vacuum annealing on the film obtained by deposition in a vacuum annealing furnace to obtain the Sn doped Ge in an annealed state2Sb2Te5A thermoelectric thin film.
Wherein, the substrates used for deposition are quartz plates and silicon wafers; the purpose of testing the substrates is different, the silicon wafer can be used for testing the phase structure and the section effect of the doped film, and the quartz plate can be used for testing thermoelectric parameters.
In the step (2), the vacuum degree of the magnetron sputtering background is kept at 1.0 multiplied by 10 in the vacuum-pumping stage-4～4.0×10-4And Pa, then introducing inert gas to set the pressure of the magnetron sputtering system at 0.4-1.0 Pa.
In order to optimize the thermoelectric property of the film, in the step (3), the radio frequency sputtering power of the Sn target material is set to be 20-55W, and Ge is set2Sb2Te5Setting the direct-current sputtering power of the target material to be 50-60W; the sputtering time is 30-45 min; furthermore, the radio frequency sputtering power of the Sn target is set to be 40-55W.
And (4) annealing in vacuum at 200-300 ℃ for 20-30 min.
Specifically, the Sn is doped with Ge2Sb2Te5The preparation method of the thermoelectric film comprises the following steps:
A. selecting Sn target material with the purity of 99.99 percent and Ge with the purity of 99.99 percent2Sb2Te5Using Sn target material and Ge as raw materials2Sb2Te5The targets are respectively arranged on station target racks of the sputtering system;
B. pumping the background vacuum degree of the sputtering system to 1.0-4.0 multiplied by 10-4Pa, introducing inert gas, and controlling the pressure of the sputtering system to be 0.4-1 Pa;
C. deposition of Sn doped Ge on silicon chip and quartz substrate by sputtering codeposition method2Sb2Te5A film;
D. will be depositedCarrying out heat treatment on the film at the temperature of 200-300 ℃ to obtain Sn doped Ge2Sb2Te5A thermoelectric thin film.
The key technical links of the invention are respectively the selection design of materials and the control of preparation process conditions, and the two supplement each other. The measurement of thermoelectric material performance is characterized mainly by a dimensionless ZT, wherein ZT is S2σ T/K, where S is the Seebeck coefficient, σ is the electrical conductivity, T is the absolute temperature, and K is the thermal conductivity (T is a certain temperature, and ZT values at different temperatures are different). Generally, the thermoelectric figure of merit of a thermoelectric material is an important criterion for determining whether a thermoelectric material can be effectively applied to a thermoelectric device, and a thermoelectric figure of merit of less than 1 of a thermoelectric material is not favorable for the application of the thermoelectric device, and has a low thermoelectric conversion value. And Ge2Sb2Te5The Sn-doped Ge-doped phase-change memory material is a chalcogenide phase-change memory material, has larger electric conduction, small energy band gap and larger effective mass, is applied to thermoelectric thin film materials in a breakthrough manner, is doped with Sn, is successfully prepared by adopting a magnetron sputtering codeposition method and combining with a preferred preparation process2Sb2Te5The thermoelectric thin film material greatly improves the Seebeck coefficient of the material.
Has the advantages that:
(1) the preparation method of the invention is to form the Sn doped Ge with the nano structure by controlling the thickness of the nano layer to perform the layer prefabrication mode2Sb2Te5The content of Sn doping is adjusted by adjusting and controlling the preparation process parameters of the film, so that a complete and compact film with a nano structure is formed, and the thermoelectric performance of the thermoelectric film is greatly improved.
(2) Compared with the prior art, the invention deposits the single layer Sn doped Ge on the substrate through material design and optimized process parameters2Sb2Te5The thermoelectric film greatly improves the thermoelectric conversion efficiency of the material and can effectively reduce the preparation of the nano Sn doped Ge2Sb2Te5The complexity and the cost of the manufacturing process of the film are favorable for popularization and application.
Drawings
FIG. 1 is a view of as-deposited Sn-Ge2Sb2Te5The thermoelectric thin film is formed schematically.
FIG. 2 is an annealed Sn-Ge film2Sb2Te5The thermoelectric thin film is formed schematically.
FIG. 3 is Sn-Ge2Sb2Te5Thermoelectric thin film XRD patterns.
FIG. 4 is Sn-Ge2Sb2Te5Cross-sectional SEM pictures of the thermoelectric thin films.
FIG. 5 is Sn-Ge2Sb2Te5Surface topography SEM pictures of thermoelectric films.
FIG. 6 is Ag-Ge2Sb2Te5XRD pattern of thermoelectric thin film.
FIG. 7 is Ag-Ge2Sb2Te5Surface topography SEM pictures of thermoelectric films.
Detailed Description
The present invention will be described in further detail with reference to examples and comparative examples.
The starting materials and reagents used in the following examples and comparative examples are commercially available.
Example 1:
preparation of Sn doped Ge in this example2Sb2Te5A thermoelectric thin film.
Plating film by adopting a magnetron sputtering mode, and plating Sn and Ge with the purity of 99.99 percent2Sb2Te5The target material is arranged on a sputtering target position of a magnetron sputtering chamber, a silicon wafer and a quartz glass sheet are used as substrates, and a single-layer Sn doped Ge is obtained by deposition on a substrate2Sb2Te5A thermoelectric thin film.
The preparation method specifically comprises the following steps:
(1) selecting Sn target material with the purity of 99.99 percent and Ge with the purity of 99.99 percent2Sb2Te5Using a target material as a raw material, and then using a Sn target material and Ge as raw materials2Sb2Te5The target materials are respectively arranged on a station target material rack of the sputtering system, a chamber door is closed, and an air release valve is closed; namely, placing the Sn target material at a magnetron radio frequency sputtering target position, and placing Ge at the target position2Sb2Te5The target material is placed on a magnetic control direct current sputtering target position.
(2) Vacuumizing, wherein the background vacuum degree of a sputtering system is pumped to 1.0 multiplied by 10-4Pa, introducing argon gas with the flow rate of 20sccm, and controlling the pressure of the sputtering system at 0.4 Pa;
(3) adjusting Ge by adopting a magnetron sputtering codeposition method2Sb2Te5The power of the target is 60W, the power of the Sn target is respectively set to be 20W, 30W, 40W, 50W and 55W, and Sn doped Ge is deposited on a silicon wafer and a quartz substrate2Sb2Te5Depositing the film for 45min to obtain the Sn-doped Ge in the deposition state2Sb2Te5A thermoelectric thin film.
Sn-doped Ge2Sb2Te5The film thickness was about 300nm and the film deposition rate was measured to be about 6.65 nm/min.
(4) Carrying out heat treatment on the co-deposited film, wherein the heat treatment temperature is 280 ℃, the annealing time is 30min, and finally obtaining Sn doped Ge2Sb2Te5A thermoelectric thin film.
This example is implemented by selecting an elemental target Sn target and a compound target Ge2Sb2Te5Target as a starting material, Sn-doped Ge was co-deposited on the substrate 12Sb2Te5 A film 2, as shown in FIG. 1; then annealing the thin film as shown in FIG. 2; finally forming Sn doped Ge2Sb2Te5In the thermoelectric thin film 3, Sn was prepared when the Sn target power was 20W0.05(Ge2Sb2Te5)0.95A thermoelectric thin film; when the power of the Sn target is 30W, Sn is prepared0.11(Ge2Sb2Te5)0.89A thermoelectric thin film; when the power of the Sn target is 40W, Sn is prepared0.14(Ge2Sb2Te5)0.86A thermoelectric thin film; when the power of the Sn target is 50W, Sn is prepared0.17(Ge2Sb2Te5)0.83A thermoelectric thin film; when the power of the Sn target is 55W, Sn is prepared0.23(Ge2Sb2Te5)0.77A thermoelectric thin film.
The prepared Sn-Ge is shown in figure 32Sb2Te5Thermoelectric power generationThin film XRD pattern, FIG. 4 is Sn-Ge2Sb2Te5SEM image of the cross section of the thermoelectric film, it can be seen from FIG. 3 that Sn element is doped into Ge2Sb2Te5In the structure, a single-phase solid solution is formed, and FIG. 4 shows Sn-Ge2Sb2Te5Scanning cross-sectional view of the thermoelectric thin film with a cross-sectional thickness of 300nm, and Sn-Ge in FIG. 52Sb2Te5The surface topography of the thermoelectric film has good compactness of the film layer.
As shown in table 1 below, in order to obtain the thermoelectric properties of the prepared thin film, the Sn sputtering powers of 20W, 30W, 40W, 50W and 55W are respectively shown in the table, and the measured temperature is measured under 723k, it can be seen that the seebeck coefficient is increased with the increase of the Sn doping power, the resistivity is reduced, the thermal conductivity is also reduced, and the power factor and the thermoelectric figure of merit are improved.
TABLE 1
Comparative example:
this comparative example prepares Ag doped Ge2Sb2Te5A thermoelectric thin film.
The method specifically comprises the following steps:
(1) selecting an Ag target material with the purity of 99.99 percent and Ge with the purity of 99.99 percent2Sb2Te5Using target material as raw material, then using Ag target material and Ge2Sb2Te5The target materials are respectively arranged on a station target material rack of the sputtering system, a chamber door is closed, and an air release valve is closed;
(2) vacuumizing, wherein the background vacuum degree of a sputtering system is pumped to 1.0 multiplied by 10-4Pa, introducing argon gas with the flow rate of 20sccm, and controlling the pressure of the sputtering system at 0.4 Pa;
(3) adjusting Ge by adopting a magnetron sputtering codeposition method2Sb2Te5The target power is 60W, the Ag target power is respectively set to 6W, 8W, 10W and 12W, and the Ag-doped Ge is deposited on a silicon wafer and a quartz substrate2Sb2Te5Film, depositionThe time is 50min, and the deposited Ag doped Ge is obtained2Sb2Te5A thermoelectric thin film; the thickness of the film was about 280nm, and the deposition rate of the film was 5.6nm/min in terms of conversion.
(4) Carrying out heat treatment on the co-deposited film, wherein the heat treatment temperature is 250 ℃, and the annealing time is 25min, so as to obtain Ag doped Ge2Sb2Te5A thermoelectric thin film.
This example is carried out by selecting an elemental target Ag target and a compound target Ge2Sb2Te5Target as raw material, co-depositing Ag-doped Ge on substrate2Sb2Te5Film of Ag-Ge prepared as shown in FIG. 62Sb2Te5XRD pattern of the thermoelectric film, FIG. 7 is Ag-Ge2Sb2Te5A surface topography map of the thermoelectric film; from FIG. 6, it can be seen that when Ag is doped into Ge2Sb2Te5In the crystal structure, secondary phases are separated out, and the thermoelectric performance of the crystal is influenced; as can be seen from FIG. 7, Ag is doped with Ge2Sb2Te5The quality of the thermoelectric film is poor, the surface defects and cavities are increased, and the surface compactness of the film layer is reduced.
The thermoelectric properties of the prepared film are shown in the following table 2, in which the Ag sputtering power is 6W, 8W, 10W, 12W, and the measured temperature is measured at 723 k; it can be seen that Ag is doped with Ge2Sb2Te5The hot spot figure of merit of the thermoelectric film is significantly lower than that of Sn-doped Ge2Sb2Te5A thermoelectric thin film; moreover, as the doping power continues to increase, the thermoelectric performance thereof decreases.
TABLE 2
It can be seen that the Ag-doped thermoelectric film has poor quality, cannot be used in thermoelectric devices, and has poor thermoelectric performance; whereas the prior art thermoelectric films had a hotspot figure of merit of at most about 0.5-0.7, relative to the thermoelectric films and Ag-doped Ge films commonly used in the prior art2Sb2Te5Thermoelectric thin film, the present invention innovatively employs Sn-doped Ge2Sb2Te5The thermoelectric film obtained by the method can greatly improve the Seebeck coefficient of the material, the thermoelectric performance of the film material is excellent, the preparation method is simple, the multilayer film does not need to be plated, and the cost is low.
Example 2:
preparation of Sn doped Ge in this example2Sb2Te5A thermoelectric thin film.
The process of this example is substantially the same as that of example 1, except that Sn is prepared by adjusting the deposition time with the Sn doping power set at 50W0.17(Ge2Sb2Te5)0.83The thickness of the thermoelectric film is 205nm and 388nm respectively; in the step (4), the annealing temperature is 210 ℃, and the annealing time is 25 min.
The film prepared in this example was subjected to morphology characterization and performance testing, and the results were the same as those of Sn prepared in example 10.17(Ge2Sb2Te5)0.83The thermoelectric film test results are consistent.
Example 3:
preparation of Sn doped Ge in this example2Sb2Te5A thermoelectric thin film.
The preparation process of this example is substantially the same as that of example 1, wherein the doping power of Sn is set to 50W, and Sn is prepared0.17(Ge2Sb2Te5)0.83A thermoelectric thin film with a thickness of 300 nm;
the difference lies in that: in the step (4), the annealing temperatures are respectively set to be 180 ℃, 200 ℃, 250 ℃, 300 ℃ and 320 ℃, and the annealing time is 30 min.
The five groups of prepared thermoelectric films are subjected to thermoelectric performance test, and the results are shown in the following table 3, so that the films with the annealing temperature of 200-300 ℃ have excellent thermoelectric performance; the thin film prepared at the annealing temperature of 180 ℃ and 320 ℃ has poor thermoelectric performance.
TABLE 3
Example 4:
preparation of Sn doped Ge in this example2Sb2Te5A thermoelectric thin film.
The process of this example is substantially the same as that of example 1, except that the doping power of Sn is set to 60W, and Sn is prepared0.25(Ge2Sb2Te5)0.75A thermoelectric thin film with a thickness of 300 nm; the test results are shown in table 4 below.
TABLE 4
Claims (8)
1. Sn doped Ge2Sb2Te5A thermoelectric film, characterized by: with Ge2Sb2Te5And Sn as raw material, and depositing on the substrate to obtain Sn doped Ge by adopting a magnetron sputtering codeposition method2Sb2Te5A thermoelectric thin film; the chemical formula of the film material is Snx(Ge2Sb2Te5)1-xWherein x is more than 0 and less than 0.25.
2. The Sn-doped Ge2Sb2Te5 thermoelectric thin film of claim 1, wherein: the thickness of the film is 200 to 400 nm.
3. Sn doped Ge2Sb2Te5The preparation method of the thermoelectric film is characterized by comprising the following steps:
(1) in a magnetron sputtering system, a Sn target material is placed at a magnetron radio frequency sputtering target position, and Ge is put at a magnetron radio frequency sputtering target position2Sb2Te5Placing the target material on a magnetic control direct current sputtering target position, and closing the chamber door;
(2) vacuumizing the cavity, and then introducing inert gas;
(3) deposition of Sn doped Ge on a substrate by sputter co-deposition2Sb2Te5A film;
(4) carrying out vacuum annealing on the film obtained by deposition in a vacuum annealing furnace to obtain the Sn doped Ge in an annealed state2Sb2Te5A thermoelectric thin film.
4. The Sn doped Ge of claim 32Sb2Te5The preparation method of the thermoelectric film is characterized by comprising the following steps: in the step (3), the radio frequency sputtering power of the Sn target is set to be 20-55W, and Ge is set2Sb2Te5The direct-current sputtering power of the target is set to be 50-60W; the sputtering time is 30-45 min.
5. The Sn doped Ge of claim 32Sb2Te5The preparation method of the thermoelectric film is characterized by comprising the following steps: in the step (4), the annealing temperature is 200-300 ℃, and the annealing time is 20-30 min.
6. The Sn doped Ge of claim 42Sb2Te5The preparation method of the thermoelectric film is characterized by comprising the following steps: the radio frequency sputtering power of the Sn target is set to be 40-55W.
7. The Sn doped Ge of claim 32Sb2Te5The preparation method of the thermoelectric film is characterized by comprising the following steps: in the step (2), the vacuum degree of the magnetron sputtering background is kept at 1.0 multiplied by 10 in the vacuum-pumping stage-4～4.0×10-4And Pa, then introducing inert gas to set the pressure of the magnetron sputtering system at 0.4-1.0 Pa.
8. The Sn doped Ge of claim 32Sb2Te5The preparation method of the thermoelectric film is characterized by comprising the following steps: the substrate is a quartz wafer or a silicon wafer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6365009B1 (en) * | 1997-06-17 | 2002-04-02 | Anelva Corporation | Combined RF-DC magnetron sputtering method |
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