CN115285946B - Ultra-high performance flexible silver selenide film with (201) dominant crystal plane orientation and power generation device - Google Patents
Ultra-high performance flexible silver selenide film with (201) dominant crystal plane orientation and power generation device Download PDFInfo
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- KDSXXMBJKHQCAA-UHFFFAOYSA-N disilver;selenium(2-) Chemical compound [Se-2].[Ag+].[Ag+] KDSXXMBJKHQCAA-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000013078 crystal Substances 0.000 title claims abstract description 44
- 238000010248 power generation Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 230000000149 penetrating effect Effects 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 64
- 229910052709 silver Inorganic materials 0.000 claims description 64
- 239000004332 silver Substances 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 15
- 239000004642 Polyimide Substances 0.000 claims description 14
- 229920001721 polyimide Polymers 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 description 130
- 239000011669 selenium Substances 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000002003 electron diffraction Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- -1 chalcogenide compounds Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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Abstract
The invention relates to an ultra-high performance flexible silver selenide film with (201) dominant crystal plane orientation and a power generation device. The flexible substrate is a flexible film, and Ag 2 Se with a (201) crystal face as a dominant growth crystal face and penetrating columnar crystals is grown on the flexible substrate. The invention prepares the uniform silver selenide film with (201) dominant crystal plane orientation and excellent crystallinity quickly and controllably through the room temperature selenization reaction for the first time, the film power factor and the thermoelectric figure of merit can respectively reach the ultra-high value of 2590 mu W m ‑1K‑2 and 1.2, and the film is used as a thermoelectric arm for the first time to assemble a series of flexible film thermoelectric power generation devices, the power density of the devices reaches the ultra-high performance of 27.6+/-1.95 W.m ‑2 (30K temperature difference) and 124+/-8.78 W.m ‑2 (60K temperature difference) under the room temperature working condition, and the invention has wide commercialized application prospect.
Description
Technical Field
The invention belongs to the field of thermoelectric materials and power generation devices, and particularly relates to an ultra-high-performance flexible silver selenide thin film with (201) dominant crystal plane orientation and a thermoelectric power generation device.
Background
Energy utilization is an inexhaustible motive force for human beings to keep sustainable development. Wearable devices may make humans a part of the internet of things (IoT) and show tremendous commercial promise. However, due to the limited life of the various batteries, continuously powering wearable or embedded devices presents a significant challenge. As an emerging energy harvesting tool, thermoelectric generators (TEGs) are becoming the best choice for achieving this goal, converting heat into electrical energy in a unique manner. Several indices such as zT value, PF (power factor) and MOPD (maximum output power density) of the relevant semiconductor materials or actual power generation devices reflect the influence of different microstructure materials on thermoelectric performance from different aspects. According to the well-known formulas (pf=s 2 σ and zt=s 2σTκ-1), it is desirable to obtain higher S (seebeck coefficient) and σ (electrical conductivity), but at the same time keep the k (thermal conductivity) low. However, it is very difficult to optimize these factors simultaneously in practical applications, because two key factors, S as a molecule and κ as a denominator, tend to change toward the same direction. Worse yet, the seebeck coefficient trend, which is the square term in the formula, is opposite to the carrier mobility, which is another key factor positively affecting σ. Nevertheless, efforts to find new materials and more efficient manufacturing strategies have never stopped.
Over the past few decades, many conventional bulk chalcogenide compounds have been explored to meet the high zT value requirements, such as Bi 2Te3、Bi2Se2、Bi0.5Sb1.5Te3、TiS2 and Sb 2Se2, etc., to accomplish the task of thermoelectric conversion around room temperature, with some compounds such as Bi 2Te3 having been used in commercial products. Considering that the rigid nature of bulk materials limits their further application in F-TEG (flexible thermoelectric generators), thin film chalcogenides offer promise for future artificial intelligence and wearable devices due to their high thermoelectric conversion performance and flexibility. Obviously, the most ideal state for future flexible wearable devices is to operate at room temperature. Group I-VI (especially Ag-Se based) compounds are a promising class of chalcogenides that has recently emerged, showing significant advantages and receiving great attention as flexibility TEGs at room temperature. For example, n-type narrow bandgap semiconductor β -Ag 2 Se (eg= -0.04-0.2 eV) has been considered promising F-TEG due to its excellent room temperature thermoelectric properties and good flexibility, especially Ag 2 Se with a 2:1Ag/Se molar stoichiometric ratio has been demonstrated by several groups to exhibit optimal performance in various Ag-Se ratios.
The prior art reports polycrystalline Ag 2 Se bulk materials obtained by direct reaction of elemental silver and selenium at 1000 ℃ (10 -4 Torr) for 10 hours. In addition, cai and colleagues reported at Nature Communications an Ag 2 Se F-TEG (film thickness of about 10 μm) prepared by hot pressing at 200℃and 24MPa, with a higher power factor of about 987.4 μm W m -1K-2, estimated zT at 300K to be 0.6, and further increased the PF value to 2231.5 μm W m -1K-2 by Cu/AgCuSe incorporation. Almost all of the presently reported selenization strategies inevitably require relatively high temperatures (> 130 ℃ for the phase transition from the alpha phase to the beta phase) or high pressure or vacuum conditions, which are also detrimental to the further commercial popularization of Ag 2 Se materials. In addition, if the film thickness can be further reduced, not only the cost can be reduced, but also the flexibility of the film product can be facilitated.
The subject group applied for the application number 201310090546.6 in 2013, and the invention name is: the invention relates to a chemical method for synthesizing Ag 2 Se semiconductor photoelectric film material in situ at room temperature, which comprises the steps of dissolving simple substance Se powder in aqueous solution of Na 2 S to form orange-yellow solution, then putting a substrate material with a certain thickness of simple substance silver film sputtered on the surface and the solution in the same container, adding the solution, putting the substrate material into the container, ensuring that the substrate material is soaked below the liquid level, reacting at 7-35 ℃ for different time (under different conditions, the reaction time is changed within 1.5 min-3 h) according to actual conditions, and washing the obtained product with deionized water and drying at 80 ℃.
In the application, the applicant regulates and controls the selenizing reaction condition in many aspects through a large number of experiments, realizes the controllable preparation of the uniform silver selenide film with (201) dominant crystal face orientation and excellent crystallinity, takes the film directly as a thermoelectric arm, prepares a series of flexible film thermoelectric power generation devices in situ, has the ultra-high performance of the device power density of 27.6+/-1.95 W.m -2 (30K temperature difference) and 124+/-8.78 W.m -2 (30K temperature difference) under the room temperature working condition, and has wide commercialized application prospect.
The invention comprises the following steps:
the technical problems to be solved by the invention are as follows: aiming at the defects of the prior art, the ultra-high performance flexible silver selenide film and a power generation device with (201) dominant crystal plane orientation are provided.
The invention adopts the technical scheme that:
The ultra-high performance flexible silver selenide film with the (201) dominant crystal plane orientation is provided, the flexible film is formed by growing Ag 2 Se with the (201) dominant crystal plane and columnar crystal penetrating through a flexible substrate.
According to the scheme, the thickness of the flexible silver selenide film is 600-1400nm, the surface is uniform, and the crystallinity is excellent.
The method for synthesizing the ultra-high-performance flexible silver selenide film with the (201) dominant crystal face orientation based on the silver simple substance film in situ large-area control is provided, simple substance Se powder is dissolved in an aqueous solution of Na2S to form a dark red solution, then the simple substance silver film with the silver thickness of 250-450 nm is immersed in the solution, and the ultra-high-performance flexible silver selenide film with the (201) dominant crystal face orientation is synthesized through reaction.
According to the scheme, the simple substance silver film adopts a flexible substrate.
In the scheme, the film forming method of the silver simple substance film is a direct current magnetron sputtering or silver mirror reaction wet chemical method.
In the above scheme, the substrate material is flexible PI (polyimide).
In the above scheme, the Se source is excessive.
In the scheme, the molar ratio of Se/S in the sodium sulfide/Se powder aqueous solution is 1:1-2:1.
In the scheme, the reaction temperature is selected within the range of 20-40 ℃; the reaction time is 15 seconds to 60 seconds.
According to the scheme, after the reaction is finished, the silver selenide film sample is cleaned by deionized water and naturally dried, and the obtained silver selenide film sample is gray black.
The application of the ultra-high performance flexible silver selenide film with the (201) dominant crystal plane orientation as a thermoelectric power generation device is provided.
The flexible thin film thermoelectric power generation device is prepared by directly taking the high-orientation flexible silver selenide thermoelectric thin film penetrated by the synthesized columnar crystal as a thermoelectric arm.
According to the scheme, the method comprises the steps of placing the silver selenide films prepared in the above manner into a thermal evaporator, depositing gold electrodes at two ends of each silver selenide film by using a mask plate, and directly taking the gold electrodes as thermoelectric arms to manufacture the power generation device.
According to the scheme, a plurality of silver selenide films, such as 4 silver selenide films, are connected in series to form the silver selenide single-arm thermoelectric power generation device. For example, 4 silver selenide films are placed side by side up and down, after gold electrodes are deposited at two ends, silver paste is used for series connection, one end is used as a cold end, and the other end is used as a hot end, so that the power generation device is assembled.
According to the invention, through regulating and controlling the thickness, se content, se/S molar ratio and the like of an initial silver simple substance film and further selecting a flexible substrate, the selenizing reaction is carried out simultaneously from the upper interface and the lower interface of the simple substance Ag film, and the gray black flexible silver selenide film with the thickness of 600-1400 nanometers, the orientation of a dominant crystal face of (201), the uniform surface and excellent crystallinity is controllably prepared through the room-temperature selenizing reaction. And the reaction is rapid, the silver selenide film with firm combination is obtained, the reaction time is short, and the commercialized use is convenient.
The invention prepares the uniform silver selenide film with (201) dominant crystal plane orientation and excellent crystallinity quickly and controllably through the room temperature selenization reaction for the first time, the film power factor and the thermoelectric figure of merit can respectively reach the ultra-high value of 2590 mu W m -1K-2 and 1.2, and the film is used as a thermoelectric arm for the first time to assemble a series of flexible film thermoelectric power generation devices, and the device power density reaches the ultra-high performance of 27.6+/-1.95 W.m -2 (30K temperature difference) and 124+/-8.78 W.m -2 (60K temperature difference) under the room temperature working condition. The method is simple to operate, and complex processes such as high temperature, high pressure, forging and forming are not needed. Low cost and low energy consumption, and has wide industrial application prospect. Overcomes the defects that the prior selenization strategy for preparing the Ag 2 Se thermoelectric material needs relatively high temperature (> 130 ℃ and the phase transition temperature from alpha phase to beta phase), has long reaction time and needs high pressure or vacuum condition, and solves the problems of poor crystal crystallinity and orientation and low thermoelectric performance.
The invention has the advantages that:
1. the silver selenide film has obvious (201) dominant crystal face orientation, uniform surface and excellent crystallinity, and compared with the film without (201) dominant crystal face orientation, the thermoelectric performance (ZT value and PF value) is greatly improved, and the optimized film power factor (PF value) and thermoelectric figure of merit (zT) can respectively reach ultra-high values of 2590 mu Wm -1K-2 and 1.2.
2. The method can be used for in-situ control synthesis of the ultrahigh-performance flexible silver selenide film with obvious (201) dominant crystal face orientation, and can well control the morphology, size, thickness and crystal phase of the Ag 2 Se film material to obtain the crystal film with high orientation columnar crystal penetration.
The macro geometry of the in-situ prepared film is controllable, so that the manufacture of large-size devices can be realized, and the device performance repeatability is high;
The synthesis can be controlled in situ in a large area; the reaction is rapid, the reaction can be completed within 1 minute of the room-temperature aqueous solution, the operation is simple, and the silver selenide film with firm combination can be obtained; is suitable for the needs of industrial application, and is green and environment-friendly.
3. Based on the flexible silver selenide film which is directly used as a series of flexible film thermoelectric power generation devices assembled by thermoelectric arms, the power density of the device is greatly improved compared with that of a thermoelectric device prepared by silver selenide without (201) dominant crystal face orientation under the room temperature working condition, and the power density of the device is optimized to achieve the ultra-high performance of 27.6+/-1.95 W.m -2 (30K temperature difference) and 124+/-8.78 W.m -2 (30K temperature difference).
Drawings
FIG. 1 is a physical diagram of a gray black silver selenide film obtained through a room temperature in-situ selenization reaction;
FIG. 2, X-ray powder diffraction pattern of a silver selenide film obtained by a reaction of depositing a 150nm silver film in comparative example 1;
FIGS. 3-4, and cross-sectional morphology diagrams of the scanning electron microscope of the silver selenide film obtained in comparative example 1;
FIG. 5, maximum output power plot of silver selenide film obtained in comparative example 1;
FIG. 6 is a graph of maximum output power density of silver selenide film obtained in comparative example 1;
FIG. 7, X-ray powder diffraction pattern of a silver selenide film obtained by the reaction of example 1 to deposit a 250nm silver film;
FIGS. 8 to 9 are scanning electron microscope images of silver selenide films obtained in example 1;
FIG. 10 is a maximum output power plot of a silver selenide film obtained in example 1;
FIG. 11 is a graph of maximum output power density of silver selenide film obtained in example 1;
FIG. 12, X-ray powder diffraction pattern of a silver selenide film resulting from the reaction of example 2 to deposit a 350nm silver film;
FIGS. 13 to 14, and a cross-sectional morphology of a scanning electron microscope of a silver selenide film obtained in example 2;
FIG. 15, example 2, shows a cross-sectional coaxial transmission back-scattered electron diffraction image of a silver selenide film;
FIG. 16 is a maximum output power plot of a silver selenide film obtained in example 2;
FIG. 17 is a graph of maximum output power density of silver selenide film obtained in example 2;
FIG. 18, example 3, X-ray powder diffraction pattern of silver selenide film resulting from a 450nm silver film deposition reaction;
FIGS. 19-20, and example 3 are scanning electron microscope images of silver selenide films;
FIG. 21 is a maximum output power plot of a silver selenide film obtained in example 3;
FIG. 22 shows maximum output power density graphs of silver selenide thin films obtained in example 3.
FIG. 23 SEM-EDS of solid powder residue after natural drying of Se/Na 2 S aqueous solution reacted with Ag (corresponding to P-1000);
Fig. 24, a diagram of a silver selenide single-arm thermoelectric generator device.
The specific embodiment is as follows:
The invention synthesizes the high-orientation flexible silver selenide thermoelectric film and the power generation device which penetrate through columnar crystals based on the silver simple substance film in-situ large-area control. Through regulating and controlling parameters such as initial silver simple substance film thickness, substrate type, se content, reaction time and the like, the selenization reaction can be carried out simultaneously from the upper interface and the lower interface of the simple substance Ag film, a gray black flexible silver selenide film with the thickness of 600-1400 nanometers, the orientation of (201) dominant crystal faces, uniform surface and excellent crystallinity is rapidly and controllably prepared on a PI (polyimide) substrate through the room temperature selenization reaction, and a series of flexible film thermoelectric power generation devices are prepared in situ.
Further depositing gold electrodes at two ends of each silver selenide film by using a mask plate, directly serving as 4 thermoelectric arms, placing the 4 silver selenide films up and down side by side, connecting the four silver selenide films in series by using silver paste, and then forming a silver selenide single-arm thermoelectric power generation device by using one end as a cold end and one end as a hot end. And the effective length of the silver selenide thermoelectric arm was controlled to be 14mm. And controlling the temperature difference at two ends of the device, and evaluating the actual output performance of the device.
Example 1
(1) Preparation of elemental silver films
A thin film of approximately 250nm silver was deposited on a Polyimide (PI) substrate by means of direct current magnetron sputtering at a sputtering current of 40mA and a sputtering vacuum of 4X 10 -3 mbar, the thickness of the sputtered silver film being controlled by film thickness monitoring. In the sputtering process, a mask is used for controlling the size and the like of the deposited silver film, and finally, the elemental silver film deposited on the surface of the PI substrate is in 4 rectangles which are arranged in parallel. Wherein each rectangle is 16mm long and 5mm wide, and the interval between the rectangles is 5mm.
(2) Preparation of silver selenide film and evaluation of thermoelectric Performance
0.6G of Na 2S·9H2 O was weighed out and added to 20mL of deionized water at 25℃under normal pressure to dissolve, then 0.2g of Se powder was added thereto and stirred to dissolve, thereby obtaining a dark red solution. The elemental silver film prepared above was then immersed in the solution and reacted for about 20 seconds to completely convert the elemental silver to silver selenide. And after the cleaning is finished, the cleaning is carried out by deionized water, and the cleaning is naturally dried. In the reaction process, the simultaneous progress of the selenization reaction from the upper and lower interfaces of the simple substance Ag film can be observed and monitored, and the obtained silver selenide film sample is gray black, as shown in figure 1. Fig. 7 is an XRD pattern of the resulting sample with PDF card number: 71-2410, the test result shows that the prepared film material is highly matched with beta-phase silver selenide, and shows stronger (201) crystal face orientation; fig. 8 and 9 are SEM images of the obtained sample, and the test result shows that the thickness of the sample is 600nm, the silver selenide film material is formed by interweaving micron-sized large grains, the film has better compactness when being observed from a microscopic level, and the grains have rich interfaces. The silver selenide film is columnar penetrating crystal through the cross section coaxial transmission back scattering electron diffraction characterization. And marking the SEM-EDS pattern of the solid powder residue after naturally drying the Se/Na2S aqueous solution reacted with Ag by sample XRD to obtain the silver in the silver simple substance film, wherein the silver is completely converted and the reaction is complete.
The silver selenide film material prepared by measurement has a Seebeck coefficient of-129 mu V/K, an electrical conductivity of 1440S/cm, a thermal conductivity of 0.74W/(m.K), a power factor of 2400 mu W/(m.K) and a thermoelectric figure of merit of about 0.97.
(2) Silver selenide single-arm thermoelectric generator device assembly and performance evaluation
The silver selenide thin films prepared above are placed into a thermal evaporator, gold electrodes are deposited at the two ends of each silver selenide by using a mask plate, and the effective length of a silver selenide thermoelectric arm is controlled to be 14mm. The 4 silver selenide thermoelectric arms were connected in series using room temperature cured silver paste to assemble a silver selenide single-arm thermoelectric generator device, as shown in fig. 24. And controlling the temperature difference at two ends of the device, and evaluating the actual output performance of the device. The temperature of the cold end is controlled to be 25 ℃, the temperature of the hot end is controlled to be raised from 35 ℃ to 85 ℃, and the temperature interval is 10 ℃. The output of the devices was measured using a digital source table, as shown in fig. 10 and 11, at a temperature difference of 10 ℃ to 60 ℃ with corresponding maximum output powers of 19.6, 118, 313, 580.7, 925 and 1346.8nW, respectively, and corresponding maximum output power densities of 1.66, 10.05, 26.56, 49.28, 78.5 and 114.29W/m 2, respectively.
Example 2
(1) Preparation of elemental silver films
A silver film of about 350nm was deposited on a Polyimide (PI) substrate by means of DC magnetron sputtering at a sputtering current of 40mA and a sputtering vacuum of 4X 10 -3 mbar, and the thickness of the sputtered silver film was controlled by film thickness monitoring. In the sputtering process, a mask is used for controlling the size and the like of the deposited silver film, and finally, the elemental silver film deposited on the surface of the PI substrate is in 4 rectangles which are arranged in parallel. Wherein each rectangle is 16mm long and 5mm wide, and the interval between the rectangles is 5mm.
(2) Preparation of silver selenide film and evaluation of thermoelectric Performance
0.6G of Na 2S·9H2 O was weighed out and added to 20mL of deionized water at 25℃under normal pressure to dissolve, then 0.2g of Se powder was added thereto and stirred to dissolve, thereby obtaining a dark red solution. The elemental silver film prepared above was then immersed in the solution and reacted for about 30 seconds to completely convert the elemental silver to silver selenide. And after the cleaning is finished, the cleaning is carried out by deionized water, and the cleaning is naturally dried. The silver selenide film sample was gray black. Fig. 12 is an XRD pattern of the resulting sample with PDF card number: 71-2410, the test result shows that the prepared film material is highly matched with beta-phase silver selenide, and shows stronger (201) crystal face orientation; fig. 13 and 14 are SEM images of the obtained sample, and the test result shows that the thickness of the sample is 1000nm, the silver selenide film material is formed by interweaving micron-sized large grains, and the film has better compactness when being observed from a microscopic level, and has rich interfaces between the grains. Fig. 15 is a cross-sectional on-axis transmission back-scattered electron diffraction band contrast image of the resulting sample, and it can be seen that the silver selenide film is a columnar through-crystal. And (3) carrying out sample XRD and characterization on an SEM-EDS (electron microscope-electron microscope) map (shown in figure 23) of the solid powder residue after naturally drying an Se/Na 2 S aqueous solution reacted with Ag (corresponding to P-1000), so as to obtain the silver in the silver simple substance film, wherein the silver is completely converted and the reaction is complete.
The silver selenide film material prepared by measurement has a Seebeck coefficient of-134 mu V/K, an electrical conductivity of 1440S/cm, a thermal conductivity of 0.66W/(m.K), a power factor of 2590 mu W/(m.K) and a thermoelectric figure of merit of about 1.2 at 300K.
(3) Silver selenide single-arm thermoelectric generator device assembly and performance evaluation
The silver selenide thin films prepared above are placed into a thermal evaporator, gold electrodes are deposited at the two ends of each silver selenide by using a mask plate, and the effective length of a silver selenide thermoelectric arm is controlled to be 14mm. And 4 silver selenide thermoelectric arms are connected in series by utilizing silver paste solidified at room temperature, so that the silver selenide single-arm thermoelectric generator device is assembled. And controlling the temperature difference at two ends of the device, and evaluating the actual output performance of the device. The temperature of the cold end is controlled to be 25 ℃, the temperature of the hot end is controlled to be raised from 35 ℃ to 85 ℃, and the temperature interval is 10 ℃. The output of the devices was measured using a digital source table, as shown in fig. 16 and 17, at a temperature difference of 10 ℃ to 60 ℃, the corresponding maximum output powers were 36.6, 241, 576, 1120, 1790 and 2580nW, respectively, and the corresponding maximum output power densities were 1.75, 11.5, 27.6, 53.5, 85.6 and 124W/m 2, respectively.
Example 3
(1) Preparation of elemental silver films
A silver film of about 450nm was deposited on a Polyimide (PI) substrate by means of DC magnetron sputtering at a sputtering current of 40mA and a sputtering vacuum of 4X 10 -3 mbar, and the thickness of the sputtered silver film was controlled by film thickness monitoring. In the sputtering process, a mask is used for controlling the size and the like of the deposited silver film, and finally, the elemental silver film deposited on the surface of the PI substrate is in 4 rectangles which are arranged in parallel. Wherein each rectangle is 16mm long and 5mm wide, and the interval between the rectangles is 5mm.
(2) Preparation of silver selenide film and evaluation of thermoelectric Performance
0.6G Na2S.9H2O is weighed and added into 20mL deionized water to be dissolved under the conditions of 25 ℃ and normal pressure, then 0.2g Se powder is added into the solution, and the solution is stirred to be dissolved, so that a dark red solution is obtained. The elemental silver film prepared above was then immersed in the solution and reacted for about 40 seconds to completely convert the elemental silver to silver selenide. And after the cleaning is finished, the cleaning is carried out by deionized water, and the cleaning is naturally dried. The silver selenide film sample was gray black. Fig. 18 is an XRD pattern of the resulting sample with PDF card number: 71-2410, the test result shows that the prepared film material is highly matched with beta-phase silver selenide, and shows stronger (201) crystal face orientation; fig. 19 and 20 are SEM images of the obtained sample, and the test result shows that the thickness of the sample is 1400nm, the silver selenide film material is formed by interweaving micron-sized large grains, the film has better compactness when being observed from a microscopic level, and the grains have rich interfaces. The silver selenide film is columnar penetrating crystal through the cross section coaxial transmission back scattering electron diffraction characterization. And (3) carrying out sample XRD and SEM-EDS spectrum characterization on solid powder residues after naturally drying Se/Na2S aqueous solution reacted with Ag to obtain the silver in the silver simple substance film, wherein the silver is completely converted and the reaction is complete.
The silver selenide film material prepared by measurement has a Seebeck coefficient of-138 mu V/K, an electrical conductivity of 1230S/cm, a thermal conductivity of 0.76W/(m.K), a power factor of 2340 mu W/(m.K) and a thermoelectric figure of merit of about 0.92 at 300K.
(2) Silver selenide single-arm thermoelectric generator device assembly and performance evaluation
The silver selenide thin films prepared above are placed into a thermal evaporator, gold electrodes are deposited at the two ends of each silver selenide by using a mask plate, and the effective length of a silver selenide thermoelectric arm is controlled to be 14mm. And 4 silver selenide thermoelectric arms are connected in series by utilizing silver paste solidified at room temperature, so that the silver selenide single-arm thermoelectric generator device is assembled. And controlling the temperature difference at two ends of the device, and evaluating the actual output performance of the device. The temperature of the cold end is controlled to be 25 ℃, the temperature of the hot end is controlled to be raised from 35 ℃ to 85 ℃, and the temperature interval is 10 ℃. The output of the device was measured using a digital source meter, as shown in fig. 21 and 22, under the temperature difference of 10 ℃ to 60 ℃, the corresponding maximum output powers were 41.8, 268.4, 706.7, 1308.4, 2060 and 2927nW, respectively, and the corresponding maximum output power densities were 1.40,9.01, 23.74, 43.95, 69.20 and 98.32W/m 2, respectively.
At the same time, we studied different initial silver film thicknesses, and other different conditions, and found that: the process reaction conditions of the invention have important influence on the successful synthesis of the target product.
For example, the initial silver film thickness affects the crystal plane orientation of the target product: preparing an elemental silver film by the method of the reference example, wherein the initial thickness of the silver film is 150nm; 0.6g of Na 2S·9H2 O was weighed out and added to 20mL of deionized water at 25℃under normal pressure to dissolve, then 0.2g of Se powder was added thereto and stirred to dissolve, thereby obtaining a dark red solution. Then immersing the prepared simple substance silver film into the solution, and completely converting the simple substance silver into silver selenide after the reaction. After the reaction is finished, the mixture is washed by deionized water and naturally dried. The silver selenide film sample was gray black. Fig. 2 is an XRD pattern of the obtained sample, and PDF card number thereof is: 71-2410, the test result shows that the prepared film material is highly matched with beta-phase silver selenide, and shows stronger (121) crystal face orientation; fig. 3 and 4 are SEM images of the obtained samples, and the test results show that the thickness of the samples is 550nm. The silver selenide film material has a seebeck coefficient of-138 mu V/K, an electrical conductivity of 856S/cm, a thermal conductivity of 1.13W/(m.K), a power factor of 1630 mu W/(m.K) and a thermoelectric figure of merit of about 0.43. The properties of the silver selenide film materials synthesized in examples 1-3 are significantly inferior.
Claims (9)
1. An ultra-high performance flexible silver selenide film having (201) a dominant crystal plane orientation, characterized by: the preparation method is characterized in that the flexible substrate is provided with Ag 2 Se with a (201) crystal face as a dominant growth crystal face and penetrating columnar crystals, and the preparation method comprises the following steps: dissolving simple substance Se powder in an aqueous solution of Na 2 S to form a dark red solution, wherein: the molar ratio of Se/S in the sodium sulfide/Se powder aqueous solution is 1:1-2:1, immersing an elemental silver film with the silver thickness of 250-450 nm into the solution, and reacting to synthesize the ultra-high performance flexible silver selenide film with the (201) dominant crystal plane orientation.
2. The silver selenide film of claim 1, wherein: the thickness of the flexible silver selenide film is 600-1400nm, the surface is uniform, and the crystallinity is excellent.
3. The method for synthesizing the ultra-high performance flexible silver selenide film with (201) dominant crystal plane orientation according to claim 1 based on the silver simple substance film, which is characterized in that: dissolving simple substance Se powder in an aqueous solution of Na 2 S to form a dark red solution, wherein: the molar ratio of Se/S in the sodium sulfide/Se powder aqueous solution is 1:1-2:1, immersing an elemental silver film with the silver thickness of 250-450 nm into the solution, and reacting to synthesize the ultra-high performance flexible silver selenide film with the (201) dominant crystal plane orientation.
4. A method according to claim 3, characterized in that: the simple substance silver film adopts a flexible substrate, and the film forming method of the simple substance silver film is a direct current magnetron sputtering or silver mirror reaction wet chemical method.
5. A method according to claim 3, characterized in that: the substrate material is flexible PI polyimide.
6. A method according to claim 3, characterized in that: the Se source is in excess.
7. A method according to claim 3, characterized in that: the reaction temperature is selected within the range of 20-40 ℃; the reaction time is 15 seconds to 60 seconds.
8. Use of the ultra-high performance flexible silver selenide film of claim 1 as a thermoelectric power generation device.
9. The ultra-high performance flexible silver selenide thermoelectric film of claim 1 directly used as a flexible film thermoelectric power generation device prepared by thermoelectric legs.
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