CN109904306A - It can be used for GaTe layer material, application and the preparation method of heat to electricity conversion component - Google Patents
It can be used for GaTe layer material, application and the preparation method of heat to electricity conversion component Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 230000005611 electricity Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004065 semiconductor Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- 238000001451 molecular beam epitaxy Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 91
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003708 ampul Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 230000005619 thermoelectricity Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 description 4
- 230000005678 Seebeck effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005680 Thomson effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
This application discloses a kind of GaTe layer material, application and preparation methods that can be used for heat to electricity conversion component, are related to thermoelectric material application field.GaTe layer material is in GaTe thin layer preparation process, and by adulterating certain density electronics or hole, so that GaTe layer material is in the case where N-type and p-type are adulterated, thermoelectric figure of merit reaches maximum value, realizes it to N-type or the heat to electricity conversion of P-type semiconductor.GaTe can be modulated into N or P-type semiconductor, while N-type and P-type semiconductor can all realize higher conversion efficiency of thermoelectric by the electronics of debita spissitudo and the doping in hole by the application, have the performance of good thermoelectricity.So that it is applied to heat to electricity conversion component.GaTe layer material preparation method can be used the mode that a variety of methods such as bridgman technology, common molecular beam epitaxy, chemical vapor deposition are grown, and are by mechanically pulling off and obtain its thin layer, easy to operate, it is easy to accomplish.
Description
Technical field
This application involves thermoelectric material application fields, thin more particularly to a kind of GaTe that can be used for heat to electricity conversion component
Layer material, application and preparation method.
Background technique
With the fast development of global economy, the non-renewable energy resources such as coal, petroleum, natural gas are increasingly deficient, fossil fuel
Burning causes natural environment to deteriorate increasingly.One side human society faces the predicament of lack of energy, on the other hand, natural environment
Deteriorate the sustainable development for also threatening the mankind.For these problems, there are two types of current main solutions: first is that as far as possible
Find safe, nuisanceless, renewable and clean energy resource in ground；Second is that improving energy use efficiency, unnecessary energy loss is reduced.Example
Such as, the energy that half is had in nature and human production life is wasted in the form of waste heat, if can be by this part energy
It is used, the problem of energy shortage can be alleviated to a certain extent, and energy waste and pollution can be greatly reduced
Situation.
Thermoelectric conversion element is the function element that realization thermal energy and the electric energy synthesized with thermoelectric material is mutually converted.This be because
Heat to electricity conversion phenomenon can occur to contact with each other using electronics or hole as different types of semiconductor of principal carrier,
Associated is three kinds of effects: Seebeck effect, Peltier effect and Thomson effect.Seebeck effect is also referred to as the first heat
Electrical effect refers to the heat of the voltage difference between two kinds of substances due to caused by the temperature difference of two kinds of different electric conductors or semiconductor
Electrical phenomena.By Seebeck effect, thermoelectric material can convert thermal energy into electric energy to a certain extent.Ideal thermoelectricity material
Material should have high thermoelectric figure of merit, i.e., high conductivity, low thermal conductivity and higher Seebeck coefficient.Wherein conductivity and
Seebeck coefficient is related with the electronic structure of material itself, and the two is interrelated, and the increase of carrier concentration will lead to conductivity
Increase, but can also cause the reduction of Seebeck coefficient simultaneously.And thermal conductivity then includes electron thermal conductivity and lattice thermal conductivity, electricity
Sub- thermal conductivity is directly proportional with conductivity, and in most of semiconductor, lattice plays a major role for thermotransport.Therefore, these three
Coefficient is interrelated, wants to obtain relatively high conversion efficiency of thermoelectric, it is necessary to reach good balance between these three parameters.
Thermocouple for heat to electricity conversion application generally includes to be electrically connected in a series arrangement and with the hot linked N of parallel way
Type thermoelectric semiconductor and p-type thermoelectric semiconductor.N-type and P in order to realize preferable heat to electricity conversion effect, for thermocouple application
Type thermoelectric semiconductor is as similar as possible in structure and performance, reduce because materials variances and caused by electrical transmission and Heat transmission
It hinders.There is scholar's proposition, if a kind of material can be used, by different doped chemicals to realize N-type and p-type thermoelectric material
Effect, can maximal efficiency realization the material conversion efficiency of thermoelectric, while be avoided that again because materials variances caused by its
He is lost.Therefore it is most important to find a kind of suitable same material with N-type and p-type conversion efficiency of thermoelectric.
Summary of the invention
Aiming to overcome that the above problem or at least being partially solved or extenuate for the application solves the above problems.
According to the one aspect of the application, a kind of GaTe layer material that can be used for heat to electricity conversion component is provided, is
In GaTe thin layer preparation process, by adulterating certain density electronics or hole so that the GaTe layer material in N-type and
In the case that p-type is adulterated, thermoelectric figure of merit reaches maximum value, realizes it to N-type or the heat to electricity conversion of P-type semiconductor.
Optionally, the GaTe layer material is stratiform monocline compound, is by Covalent bonding together in layer, interlayer is logical
It crosses weaker Van der Waals for combine, two-dimension single layer material has similar InSe fold honeycomb.
Optionally, the space group structure of the GaTe layer material is represented by
Optionally, crystal thermal conductivity of GaTe layer material at a temperature of 1200K can reach 1.5W/mK.
Optionally, the GaTe layer material can be changed into P-type semiconductor under the hole doping of debita spissitudo, in turn
1100K at a temperature of realize 0.83 thermoelectric figure of merit.
Optionally, the GaTe layer material debita spissitudo it is electron adulterated under can be changed into N-type semiconductor, in turn
1100K at a temperature of realize 0.87 thermoelectric figure of merit.
According to further aspect of the application, provide a kind of using the GaTe layer material as heat to electricity conversion member device
The application of part.
The application is that the GaTe layer material of preparation is individually used for heat to electricity conversion component；Or
It is to combine the GaTe layer material of preparation and other conventional thermoelectric materials to be used for heat to electricity conversion component.
According to further aspect of the application, a kind of preparation method for the GaTe layer material is provided, including
Following steps,
Step 100, thin layer GaTe is prepared, chemical vapor deposition, common molecular beam epitaxy or bridgman technology are utilized
GaTe monocrystalline, then the method that is by mechanically pulling off are grown thin layer GaTe is prepared；
Step 200, prepare GaTe layer material, the thin layer GaTe that will be obtained in step 100, into predetermined concentration electronics or
Hole doping, so that GaTe layer material is in the case where N-type and p-type are adulterated, thermoelectric figure of merit reaches maximum value, realizes it to N
The heat to electricity conversion of type or P-type semiconductor.
The preparation method, wherein step 100, the step of preparing thin layer GaTe includes:
Step 101, the high-purity tellurium for filling 1:1.2 ratio and gallium crucible are put into the quartz ampoule of argon gas protection, it will
Quartz ampoule is evacuated to 2Kpa；
Step 102, temperature is rapidly heated to 500 degrees Celsius, and is kept for 2 hours；Then it is Celsius temperature to be risen to 850 again
Degree is kept for 2 hours, then Temperature fall obtains GaTe monocrystalline to room temperature；
Step 103, the GaTe that step 102 obtains is crystallized, thin layer GaTe is prepared with the method for mechanical stripping.
The GaTe layer material of the application, by the electronics of debita spissitudo and the doping in hole, GaTe can be modulated into N or
P-type semiconductor, while N-type and P-type semiconductor can all realize higher conversion efficiency of thermoelectric, have the performance of good thermoelectricity.Into
And the GaTe layer material is made to be applied to heat to electricity conversion component.The GaTe layer material preparation method can be used in cloth
A variety of methods such as odd graceful technology, common molecular beam epitaxy, chemical vapor deposition are grown, and the mode being by mechanically pulling off obtains
Its thin layer is obtained, it is easy to operate, it is easy to accomplish.
According to the accompanying drawings to the detailed description of the specific embodiment of the application, those skilled in the art will be more
Above-mentioned and other purposes, the advantages and features of the application are illustrated.
Detailed description of the invention
Some specific embodiments of the application are described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical appended drawing reference denotes same or similar part or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing:
Fig. 1 is according to the schematic of the GaTe layer material that can be used for heat to electricity conversion component of the application one embodiment
Atomic diagram；
Fig. 2 is its Seebeck at a temperature of 300K, 500K, 700K, 900K, 1100K respectively of GaTe layer material shown in Fig. 1
Coefficient with potential trend chart；
Fig. 3 is its conductivity at a temperature of 300K, 500K, 700K, 900K, 1100K respectively of GaTe layer material shown in Fig. 1
With the trend chart of potential；
Fig. 4 be GaTe layer material shown in Fig. 1 respectively at a temperature of 300K, 500K, 700K, 900K, 1100K its power because
Son with potential trend chart；
Fig. 5 is the crystal thermal conductivity variation with temperature tendency chart of GaTe layer material shown in Fig. 1；
Fig. 6 is that its thermoelectricity is excellent at a temperature of 300K, 500K, 700K, 900K, 1100K respectively by GaTe layer material shown in Fig. 1
It is worth the trend chart with potential；
Fig. 7 is the step flow chart for preparing thin layer GaTe according to another embodiment of the application.
Specific embodiment
Fig. 1 is according to the schematic of the GaTe layer material that can be used for heat to electricity conversion component of the application one embodiment
Atomic diagram.
A kind of GaTe layer material that can be used for heat to electricity conversion component is present embodiments provided, is prepared in GaTe thin layer
In the process, by adulterating certain density electronics or hole, so that the GaTe layer material is the case where N-type and p-type are adulterated
Under, thermoelectric figure of merit reaches maximum value, realizes it to N-type or the heat to electricity conversion of P-type semiconductor.More specifically, the GaTe is thin
Layer material is stratiform monocline compound, is by Covalent bonding together in layer, interlayer is combined by weaker Van der Waals for, such as
Shown in Fig. 1, two-dimension single layer material has similar InSe fold honeycomb.The space group structure of the GaTe layer material can
It is expressed as
Since blocky GaTe itself is a kind of monocline stratiform semiconductor material, Ga, Te atom pass through and are covalently keyed in layer,
Interlayer is combined by the weaker Van der Waals for of active force, thus to obtain GaTe thin for the mode for being easy to be by mechanically pulling off
Layer is the GaTe material of two-dimension single layer.The atomic structure of GaTe layer material provided herein is as shown in Figure 1, be space group
ForClass graphene honeycomb pleated structure.And then by GaTe thin layer, pass through the electronics of debita spissitudo and mixing for hole
It is miscellaneous, GaTe can be modulated into N or P-type semiconductor, while N-type and P-type semiconductor can all realize higher conversion efficiency of thermoelectric, had
There is good thermoelectricity to show.
Fig. 2 is its Seebeck at a temperature of 300K, 500K, 700K, 900K, 1100K respectively of GaTe layer material shown in Fig. 1
Coefficient with potential trend chart.In Fig. 2, within the scope of low potential, Seebeck coefficient shows biggish value.And with
Temperature increases, and Seebeck coefficient is substantially reduced.
Fig. 3 is its conductivity at a temperature of 300K, 500K, 700K, 900K, 1100K respectively of GaTe layer material shown in Fig. 1
With the trend chart of potential.In Fig. 3, within the scope of low potential, conductivity is lower, and close to 0, and conductivity becomes with temperature
Change little.
Fig. 4 be GaTe layer material shown in Fig. 1 respectively at a temperature of 300K, 500K, 700K, 900K, 1100K its power because
Son with potential trend chart.In Fig. 4, as the temperature rises, power factor is presented increased trend.And it is highest
Power factor numerical value appears in the lower range of potential.
Fig. 5 is the crystal thermal conductivity variation with temperature tendency chart of GaTe layer material shown in Fig. 1.In Fig. 5, with temperature
Raising, lattice thermal conductivity gradually decreases.
Fig. 6 is that its thermoelectricity is excellent at a temperature of 300K, 500K, 700K, 900K, 1100K respectively by GaTe layer material shown in Fig. 1
It is worth the trend chart with potential.In Fig. 6, as the temperature rises, the thermoelectric figure of merit of GaTe layer material is gradually risen, explanation
Its thermoelectricity capability increases with the rising of temperature.
More specifically, crystal thermal conductivity of GaTe layer material at a temperature of 1200K can reach referring to Fig. 5
1.5W/mK。
More specifically, in the present embodiment, the GaTe layer material is under the hole doping of debita spissitudo referring to Fig. 6
Can be changed into P-type semiconductor, so 1100K at a temperature of realize 0.83 thermoelectric figure of merit.
More specifically, referring to Fig. 6, in the present embodiment, the GaTe layer material debita spissitudo it is electron adulterated under
Can be changed into N-type semiconductor, so 1100K at a temperature of realize 0.87 thermoelectric figure of merit.
Present invention also provides a kind of using the GaTe layer material as the application of heat to electricity conversion component.It is preferred that
Ground, application of the GaTe layer material as thermocouple.
The application, which can be, is individually used for heat to electricity conversion component for the GaTe layer material of preparation.Alternatively,
The application, which can also be to combine the GaTe layer material of preparation and other conventional thermoelectric materials, is used for thermoelectricity turn
Change component.
The GaTe layer material of the application, by the electronics of debita spissitudo and the doping in hole, GaTe can be modulated into N or
P-type semiconductor, while N-type and P-type semiconductor can all realize higher conversion efficiency of thermoelectric, have the performance of good thermoelectricity.Into
And the GaTe layer material is made to be applied to heat to electricity conversion component.
Present invention also provides a kind of preparation methods for the GaTe layer material, include the following steps,
Step 100, thin layer GaTe is prepared, chemical vapor deposition, common molecular beam epitaxy or bridgman technology are utilized
GaTe monocrystalline, then the method that is by mechanically pulling off are grown thin layer GaTe is prepared；
Step 200, prepare GaTe layer material, the thin layer GaTe that will be obtained in step 100, into predetermined concentration electronics or
Hole doping, so that GaTe layer material is in the case where N-type and p-type are adulterated, thermoelectric figure of merit reaches maximum value, realizes it to N
The heat to electricity conversion of type or P-type semiconductor.
In the present embodiment, the GaTe layer material preparation method can be used bridgman technology, common molecular beam epitaxy,
The mode that a variety of methods such as chemical vapor deposition are grown, and are by mechanically pulling off obtains its thin layer, easy to operate, is easy to real
It is existing.
Fig. 7 is the step flow chart for preparing thin layer GaTe according to another embodiment of the application.The preparation method,
Wherein, step 100, the step of preparing thin layer GaTe include:
Step 101, the high-purity tellurium for filling 1:1.2 ratio and gallium crucible are put into the quartz ampoule of argon gas protection, it will
Quartz ampoule is evacuated to 2Kpa；
Step 102, temperature is rapidly heated to 500 degrees Celsius, and is kept for 2 hours；Then it is Celsius temperature to be risen to 850 again
Degree is kept for 2 hours, then Temperature fall obtains GaTe monocrystalline to room temperature；
Step 103, the GaTe that step 102 obtains is crystallized, thin layer GaTe is prepared with the method for mechanical stripping.
According to above-mentioned preparation method provided by the present application, by this GaTe layer material the case where N appropriate, p-type are adulterated
Under, it realizes the maximum value of thermoelectric figure of merit, can be used for heat to electricity conversion component, realize effective conversion between thermal energy and electric energy.It should
The thermoelectric figure of merit of material theoretically can reach 0.8 or more, lattice thermal conductivity 1100K at a temperature of can reach 1.5W/mK, it is low
In most of thermoelectric materials, it is highly suitable for heat to electricity conversion component.
The preferable specific embodiment of the above, only the application, but the protection scope of the application is not limited thereto,
Within the technical scope of the present application, any changes or substitutions that can be easily thought of by anyone skilled in the art,
Should all it cover within the scope of protection of this application.Therefore, the protection scope of the application should be with scope of protection of the claims
Subject to.
Claims (10)
1. a kind of GaTe layer material that can be used for heat to electricity conversion component, which is characterized in that be in GaTe thin layer preparation process
In, by adulterating certain density electronics or hole, so that the GaTe layer material is in the case where N-type and p-type are adulterated, it is hot
The electric figure of merit reaches maximum value, realizes it to N-type or the heat to electricity conversion of P-type semiconductor.
2. GaTe layer material according to claim 1, which is characterized in that it is stratiform monocline compound, is logical in layer
Covalent bonding together is crossed, interlayer is combined by weaker Van der Waals for, and two-dimension single layer material has similar InSe fold honeycomb
Structure.
3. GaTe layer material according to claim 2, which is characterized in that its space group structure is represented by P6m2.
4. GaTe layer material according to claim 1 or 2, which is characterized in that crystal thermal conductivity at a temperature of 1200K
It can reach 1.5W/mK.
5. GaTe layer material according to claim 1 or 2, which is characterized in that can under the hole doping of debita spissitudo
Be changed into P-type semiconductor, so 1100K at a temperature of realize 0.83 thermoelectric figure of merit.
6. GaTe layer material according to claim 1 or 2, which is characterized in that debita spissitudo it is electron adulterated under can
Be changed into N-type semiconductor, so 1100K at a temperature of realize 0.87 thermoelectric figure of merit.
7. a kind of using GaTe layer material of any of claims 1-6 as the application of heat to electricity conversion component.
8. application according to claim 7, which is characterized in that be that the GaTe layer material of preparation is individually used for heat
Electric conversion component；Or
It is to combine the GaTe layer material of preparation and other conventional thermoelectric materials to be used for heat to electricity conversion component.
9. a kind of preparation method for GaTe layer material of any of claims 1-6, which is characterized in that including
Following steps,
Step 100, thin layer GaTe is prepared, is grown using chemical vapor deposition, common molecular beam epitaxy or bridgman technology
Thin layer GaTe is prepared in GaTe monocrystalline, then the method that is by mechanically pulling off；
Step 200, GaTe layer material, the thin layer GaTe that will be obtained in step 100, electronics or hole into predetermined concentration are prepared
Doping, so that GaTe layer material is in the case where N-type and p-type are adulterated, thermoelectric figure of merit reaches maximum value, realizes it to N-type or P
The heat to electricity conversion of type semiconductor.
10. preparation method according to claim 9, which is characterized in that step 100, the step of preparing thin layer GaTe includes:
Step 101, the high-purity tellurium for filling 1:1.2 ratio and gallium crucible are put into the quartz ampoule of argon gas protection, it will be quartzy
Pipe is evacuated to 2Kpa；
Step 102, temperature is rapidly heated to 500 degrees Celsius, and is kept for 2 hours；Then temperature is risen to 850 degrees Celsius again,
It is kept for 2 hours, then Temperature fall obtains GaTe monocrystalline to room temperature；
Step 103, the GaTe that step 102 obtains is crystallized, thin layer GaTe is prepared with the method for mechanical stripping.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013094598A1 (en) * | 2011-12-20 | 2013-06-27 | 独立行政法人科学技術振興機構 | Process for manufacturing thermoelectric material, thermoelectric material and thermoelectric transducer |
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-
2019
- 2019-03-01 CN CN201910157331.9A patent/CN109904306B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013094598A1 (en) * | 2011-12-20 | 2013-06-27 | 独立行政法人科学技術振興機構 | Process for manufacturing thermoelectric material, thermoelectric material and thermoelectric transducer |
| CN107706297A (en) * | 2017-10-16 | 2018-02-16 | 超晶科技（北京）有限公司 | A kind of thermoelectric conversion element based on β type telluride silicon materials and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| A.A. AL-GHAMDI: "Thermoelectric Power (TEP) of Layered Chalcogenides GaTe Crystals", 《JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY》 * |
| BHAGWATI PRASAD BAHUGUNA, ET AL.: "Hybrid functional calculations of electronic and thermoelectric properties of GaS, GaSe, and GaTe monolayers", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 * |
| JING-YUN BI, ET AL.: "Thermoelectric properties of two-dimensional hexagonal indium–VA", 《CHIN. PHYS. B》 * |
| 陈仁文: "《新型环境能量采集技术》", 31 July 2011 * |
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