CN104934526A - Heteroid flexible thermoelectric conversion device capable of bending and folding - Google Patents
Heteroid flexible thermoelectric conversion device capable of bending and folding Download PDFInfo
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- CN104934526A CN104934526A CN201510319637.1A CN201510319637A CN104934526A CN 104934526 A CN104934526 A CN 104934526A CN 201510319637 A CN201510319637 A CN 201510319637A CN 104934526 A CN104934526 A CN 104934526A
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Abstract
The invention relates to a heteroid flexible thermoelectric conversion device capable of bending and folding. The heteroid flexible thermoelectric conversion device comprises a flexible substrate, a dielectric layer and a heterostructure, which are grown on the flexible substrate in turn. The heterostructure comprises a grapheme layer and a two-dimensional semiconducting crystal layer which are overlapped from the lower to the upper. A first metal electrode is grown at one end of the grapheme layer; a second metal electrode is grown at one end of the two-dimensional semiconducting crystal layer, and the first metal electrode and the second metal electrode are isolated with each other. When the thermoelectric conversion device works, the overlapping layer of the grapheme layer and the two-dimensional semiconducting crystal layer generates temperature gradient under the radiation of an external heat source to cause a seebeck effect to generate open-circuit voltage and perform thermoelectric conversion. Compared with prior art, the heteroid flexible thermoelectric conversion device of the invention is simple and compact in integrated structure, and bendable and foldable. The heteroid flexible thermoelectric conversion device of the invention has super-high seebeck coefficient and thermoelectric value, and can be widely applied to wearable equipment and other flexible electrical application area, and has wide application prospect.
Description
Technical field
The invention belongs to flexible electronic technical field, relate to a kind of flexible folding heterogeneous flexible thermal power conversion device, particularly a kind of heterogeneous flexible thermal power conversion device of the two-dimensional semiconductor crystalline material-Graphene grown on flexible substrates.
Background technology
Due to the miniaturization trend that portable type electronic product is growing, promote the research and development of compact power supply.Thermoelectric generator is as the self-centered energy of one, and heat energy is directly converted to electric energy by Seebeck effect by it, becomes a kind of new and high technology of energy field.On the other hand, due to the miniaturization trend that portable type electronic product is growing, the research and development of compact power supply becomes focus.
Because Graphene is different from the Seebeck coefficient of two-dimensional semiconductor crystalline material, both can be combined and jointly form heterostructure, form thermoelectric conversion element.When contacting infrared source, in device, Graphene is with two-dimensional semiconductor crystalline material because its Seebeck coefficient is different, and both overlapping regions produce temperature gradient, cause Seebeck effect, and producing open circuit voltage, open circuit voltage is proportional to temperature difference linearly simultaneously: Δ V=α (α
two-dimensional semiconductor-α
graphene) Δ T, wherein, α
sfor Seebeck coefficient, also referred to as thermoelectric (al) power.As mentioned above, when external heat source exists, the thermal power transfer that between Graphene and two-dimensional semiconductor crystalline material, the difference of Seebeck coefficient causes then has wide application prospect.
Meanwhile, because Graphene and two-dimensional semiconductor crystalline material have unique two-dimension plane structure, can be connected with modern micro-nano technology technology, the High Density Integration of thermoelectric device can be realized well.On the other hand, bi-material all has extensible, flexible feature, and the heterostructure growth both formed, on any flexible material substrate, can realize the characteristic bending thereupon, fold.To the application of bi-material flexible characteristic, the thermoelectric conversion element of random bending fold can be obtained, the application demand of some special circumstances can be met, more can meet the technical need of portable type electronic product to compact power supply.
But be combined with two-dimensional semiconductor crystalline material by Graphene at present, the technology jointly for the preparation of flexible thermal power conversion device rarely has report.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of flexible thermal power conversion device based on two-dimensional semiconductor material-Graphene heterostructure is provided, in order to improve conversion efficiency of thermoelectric, and improve device integration and portability.
Object of the present invention can be achieved through the following technical solutions:
A kind of flexible folding heterogeneous flexible thermal power conversion device, this heterogeneous flexible thermal power conversion device comprises flexible substrate, grows dielectric layer on flexible substrates and heterostructure successively, described heterostructure comprises graphene layer and the two-dimensional semiconductor crystal layer of overlapping setting from bottom to top, described graphene layer one end grows the first metal electrode, described two-dimensional semiconductor crystal layer one end grows the second metal electrode, and mutually isolated between the first described metal electrode and the second metal electrode;
During work, under the radiation of external heat source, the overlapping region of described graphene layer and two-dimensional semiconductor crystal layer produces temperature gradient, causes Seebeck effect, produces open circuit voltage, and carries out thermoelectricity conversion.
The material of described flexible substrate is the one in ultra-thin glass, high molecular polymer or tinsel.
The thickness of described ultra-thin glass is within 10um.
Described high molecular polymer is the one in polyimides, PEN or PETG.
Described dielectric layer is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 10-100nm.
The overlapping setting vertical with two-dimensional semiconductor crystal layer of described graphene layer.
The thickness of described graphene layer is 10-20nm, and the thickness of described two-dimensional semiconductor crystal layer is 1-50nm
The material of described two-dimensional semiconductor crystal layer is transition metal two chalcogen compound, and this transition metal two chalcogen compound comprises MoS
2, MoSe
2, WS
2, WSe
2, TiS
2or VSe
2in one.
The thickness of the first described metal electrode is 10-200nm, and the material of the first described metal electrode comprises the one in gold, silver, aluminium or titanium.
The thickness of the second described metal electrode is 10-200nm, and the material of the second described metal electrode comprises the one in gold, silver, aluminium or titanium.
Thermoelectric conversion element of the present invention adopts flexible material to form flexible substrate, grow silica dioxide medium layer, graphene layer and two-dimensional semiconductor crystal layer successively on flexible substrates, wherein, graphene layer and the overlapping setting of two-dimensional semiconductor crystal layer, common formation heterostructure, meanwhile, grows the first metal electrode in graphene layer one end, the second metal electrode is grown in two-dimensional semiconductor crystal layer one end, and without any overlapping between the first metal electrode and the second metal electrode.Because Graphene is different from the Seebeck coefficient of two-dimensional semiconductor crystal, when contacting infrared source, in thermoelectric conversion element, the overlapping region of graphene layer and two-dimensional semiconductor crystal layer produces temperature gradient, causes Seebeck effect, produce open circuit voltage, and carry out thermoelectricity conversion.
In actual fabrication process, at flexible substrate first deposit layer of silicon dioxide dielectric layer, to increase the adhesiveness between Graphene and flexible substrate; Subsequently, can pass through vapour deposition process (CVD) direct growth or obtain Graphene by standard mechanical stripping technology, transfer on silica dioxide medium layer, Graphene can be individual layer or number layer graphene; When graphene layer is prepared two-dimensional semiconductor crystal layer, the synthesis of mechanical stripping method, chemical liquid phase or vapour deposition process can be adopted to prepare two-dimensional semiconductor crystal layer, then be transferred on graphene layer by transfer techniques, or on graphene layer, directly adopt vapour deposition process to grow one deck two-dimensional semiconductor crystal layer; Finally, by magnetically controlled sputter method, electron-beam vapor deposition method or thermal evaporation method, respectively in one end of graphene layer, one end deposit layer of metal barrier film of two-dimensional semiconductor crystal layer, then by stripping technology, make the first metal electrode and the second metal electrode.
Compared with prior art, the present invention has following characteristics:
1) when external heat source exists, between Graphene and two-dimensional semiconductor crystal, Seebeck coefficient is different, produces thermal voltage, and device architecture has Seebeck coefficient and the thermoelectricity value of superelevation, and the thermal power transfer caused has wide application prospect;
2) Graphene adopted and two-dimensional semiconductor crystal all have unique two-dimension plane structure, can be connected mutually, can realize the High Density Integration of thermoelectric device well with the micro-nano technology technology of modern high technology;
3) overall structure is simple, compact, adopt flexible substrate, and Graphene and two-dimensional semiconductor crystal all have extensible, flexible feature, the thermoelectric conversion element made has can the feature of random bending fold, after bending, the electric property of device remains unchanged, and meets the application demand of some special circumstances, more can meet the technical need of portable type electronic product to compact power supply, there is good application prospect.
Accompanying drawing explanation
Fig. 1 is perspective view of the present invention;
Description of symbols in figure:
1-flexible substrate, 2-dielectric layer, 3-graphene layer, 4-two-dimensional semiconductor crystal layer, the 5-the first metal electrode, the 6-the second metal electrode.
Embodiment
Hereafter in conjunction with the execution mode that particular instance illustrates, embodiment herein and various characteristic sum details carry out more complete explanation with reference to the non-limiting example described in detail in diagram in accompanying drawing and following description.Omit the description of well-known parts and treatment technology, in order to avoid the unnecessary embodiment indigestion made herein.When making described structure, well-known traditional handicraft in semiconductor technology can be used.Example used herein is only used to help to understand embodiment herein can effective mode, and the embodiment making those skilled in the art can implement herein further.Thus, example herein should be interpreted as the scope of restriction embodiment herein.
It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then graphicly only the assembly relevant with the present invention is shown but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
Embodiment 1:
As shown in Figure 1, a kind of flexible folding heterogeneous flexible thermal power conversion device, this heterogeneous flexible thermal power conversion device comprises flexible substrate 1, grows dielectric layer 2 in flexible substrate 1 and heterostructure successively, heterostructure comprises graphene layer 3 and the two-dimensional semiconductor crystal layer 4 of overlapping setting from bottom to top, graphene layer 3 one end grows the first metal electrode 5, two-dimensional semiconductor crystal layer 4 one end grows the second metal electrode 6, and mutually isolated between the first metal electrode 5 and the second metal electrode 6; During work, under the radiation of external heat source, graphene layer 3 produces temperature gradient with the overlapping region of two-dimensional semiconductor crystal layer 4, causes Seebeck effect, produces open circuit voltage, and carries out thermoelectricity conversion.
Wherein, the material of flexible substrate 1 is PETG, and dielectric layer 2 is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 100nm.
In heterostructure, graphene layer 3 overlapping setting vertical with two-dimensional semiconductor crystal layer 4, the thickness of graphene layer 3 is 20nm, and the thickness of two-dimensional semiconductor crystal layer 4 is 10nm, and the material of two-dimensional semiconductor crystal layer 4 is MoS
2.
In actual fabrication process, at flexible substrate 1 first deposit layer of silicon dioxide dielectric layer, to increase the adhesiveness between Graphene and flexible substrate 1; Graphene layer 3 is by vapour deposition process (CVD) direct growth silica dioxide medium layer, and wherein, the Graphene in graphene layer 3 is single-layer graphene; Subsequently, graphene layer 3 directly adopt vapour deposition process grow one deck two-dimensional semiconductor crystal layer 4; Finally, by magnetically controlled sputter method respectively in one end of graphene layer 3, one end deposit layer of metal barrier film of two-dimensional semiconductor crystal layer 4, then by stripping technology, make the first metal electrode 5 and the second metal electrode 6.
In the present embodiment, the thickness of the first metal electrode 5 and the second metal electrode 6 is 200nm, and material is titanium.
Embodiment 2:
In the present embodiment, the material of flexible substrate 1 is PEN, and dielectric layer 2 is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 80nm; The thickness of graphene layer 3 is 15nm, and the thickness of two-dimensional semiconductor crystal layer 4 is 50nm, and the material of two-dimensional semiconductor crystal layer 4 is MoSe
2.
During preparation, graphene layer 3 is obtained by standard mechanical stripping technology, transfer on silica dioxide medium layer, Graphene in graphene layer 3 is multi-layer graphene, subsequently, adopt mechanical stripping legal system for two-dimensional semiconductor crystal layer 4, be transferred on graphene layer 3 by transfer techniques, finally, by electron-beam vapor deposition method respectively in one end of graphene layer 3, one end deposit layer of metal barrier film of two-dimensional semiconductor crystal layer 4, then by stripping technology, the first metal electrode 5 and the second metal electrode 6 is made.
In the present embodiment, the thickness of the first metal electrode 5 and the second metal electrode 6 is 100nm, and material is aluminium.All the other are with embodiment 1.
Embodiment 3:
In the present embodiment, the material of flexible substrate 1 is polyimides, and dielectric layer 2 is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 60nm; The thickness of graphene layer 3 is 16nm, and the thickness of two-dimensional semiconductor crystal layer 4 is 32nm, and the material of two-dimensional semiconductor crystal layer 4 is WS
2.
During preparation, graphene layer 3 is obtained by standard mechanical stripping technology, transfer on silica dioxide medium layer, Graphene in graphene layer 3 is multi-layer graphene, subsequently, chemical liquid phase synthetic method is adopted to prepare two-dimensional semiconductor crystal layer 4, be transferred on graphene layer 3 by transfer techniques, finally, by thermal evaporation method respectively in one end of graphene layer 3, one end deposit layer of metal barrier film of two-dimensional semiconductor crystal layer 4, then by stripping technology, the first metal electrode 5 and the second metal electrode 6 is made.
In the present embodiment, the thickness of the first metal electrode 5 and the second metal electrode 6 is 80nm, and material is silver.All the other are with embodiment 1.
Embodiment 4:
In the present embodiment, the material of flexible substrate 1 is tinsel, and dielectric layer 2 is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 30nm; The thickness of graphene layer 3 is 12nm, and the thickness of two-dimensional semiconductor crystal layer 4 is 6nm, and the material of two-dimensional semiconductor crystal layer 4 is WSe
2.
During preparation, graphene layer 3 is obtained by standard mechanical stripping technology, transfer on silica dioxide medium layer, Graphene in graphene layer 3 is multi-layer graphene, subsequently, vapour deposition process is adopted to prepare two-dimensional semiconductor crystal layer 4, be transferred on graphene layer 3 by transfer techniques, finally, by magnetically controlled sputter method respectively in one end of graphene layer 3, one end deposit layer of metal barrier film of two-dimensional semiconductor crystal layer 4, then by stripping technology, the first metal electrode 5 and the second metal electrode 6 is made.
In the present embodiment, the thickness of the first metal electrode 5 and the second metal electrode 6 is 50nm, and material is aluminium.All the other are with embodiment 1.
Embodiment 5:
In the present embodiment, the material of flexible substrate 1 is ultra-thin glass, and the thickness of this ultra-thin glass is 10 μm, and dielectric layer 2 is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 10nm; The thickness of graphene layer 3 is 10nm, and the thickness of two-dimensional semiconductor crystal layer 4 is 1nm, and the material of two-dimensional semiconductor crystal layer 4 is TiS
2.
In the present embodiment, the thickness of the first metal electrode 5 and the second metal electrode 6 is 10nm, and material is gold.All the other are with embodiment 1.
Embodiment 6:
In the present embodiment, the material of flexible substrate 1 is ultra-thin glass, and the thickness of this ultra-thin glass is 6 μm, and dielectric layer 2 is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 15nm; The thickness of graphene layer 3 is 15nm, and the thickness of two-dimensional semiconductor crystal layer 4 is 10nm, and the material of two-dimensional semiconductor crystal layer 4 is VSe
2.
In the present embodiment, the thickness of the first metal electrode 5 and the second metal electrode 6 is 20nm, and material is gold.All the other are with embodiment 1.
The above is only preferred embodiment of the present invention, not does any type of restriction to the present invention.Although the present invention discloses as above with preferred embodiments, but and be not used to limit the present invention.Any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when method described above and technology contents can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from the technology of the present invention incidence of criminal offenses, the any simple modification done above example according to technical spirit of the present invention, equivalent variations and modification, still belong in the scope of technical solution of the present invention.
Claims (10)
1. a flexible folding heterogeneous flexible thermal power conversion device, it is characterized in that, this heterogeneous flexible thermal power conversion device comprises flexible substrate, grows dielectric layer on flexible substrates and heterostructure successively, described heterostructure comprises graphene layer and the two-dimensional semiconductor crystal layer of overlapping setting from bottom to top, described graphene layer one end grows the first metal electrode, described two-dimensional semiconductor crystal layer one end grows the second metal electrode, and mutually isolated between the first described metal electrode and the second metal electrode;
During work, under the radiation of external heat source, the overlapping region of described graphene layer and two-dimensional semiconductor crystal layer produces temperature gradient, causes Seebeck effect, produces open circuit voltage, and carries out thermoelectricity conversion.
2. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 1, it is characterized in that, the material of described flexible substrate is the one in ultra-thin glass, high molecular polymer or tinsel.
3. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 2, it is characterized in that, the thickness of described ultra-thin glass is within 10um.
4. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 2, it is characterized in that, described high molecular polymer is the one in polyimides, PEN or PETG.
5. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 1, it is characterized in that, described dielectric layer is silica dioxide medium layer, and the thickness of this silica dioxide medium layer is 10-100nm.
6. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 1, is characterized in that, the overlapping setting vertical with two-dimensional semiconductor crystal layer of described graphene layer.
7. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 1 or 6, is characterized in that, the thickness of described graphene layer is 10-20nm, and the thickness of described two-dimensional semiconductor crystal layer is 1-50nm.
8. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 7, it is characterized in that, the material of described two-dimensional semiconductor crystal layer is transition metal two chalcogen compound, and this transition metal two chalcogen compound comprises MoS
2, MoSe
2, WS
2, WSe
2, TiS
2or VSe
2in one.
9. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 1, it is characterized in that, the thickness of the first described metal electrode is 10-200nm, and the material of the first described metal electrode comprises the one in gold, silver, aluminium or titanium.
10. a kind of flexible folding heterogeneous flexible thermal power conversion device according to claim 1, it is characterized in that, the thickness of the second described metal electrode is 10-200nm, and the material of the second described metal electrode comprises the one in gold, silver, aluminium or titanium.
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| CN107293634A (en) * | 2017-06-14 | 2017-10-24 | 上海萃励电子科技有限公司 | A kind of preparation method of novel flexible thermoelectric element |
| CN108878636A (en) * | 2018-06-26 | 2018-11-23 | 上海电力学院 | A method of two-dimentional thermo-electric device is prepared based on two telluride molybdenums |
| CN113782665A (en) * | 2021-09-16 | 2021-12-10 | 河北工业大学 | WSe2/MoS2Preparation method of composite thermoelectric material |
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| CN113782665A (en) * | 2021-09-16 | 2021-12-10 | 河北工业大学 | WSe2/MoS2Preparation method of composite thermoelectric material |
| CN113782665B (en) * | 2021-09-16 | 2023-06-16 | 河北工业大学 | WSe (Wireless sensor package) 2 /MoS 2 Preparation method of composite thermoelectric material |
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