CN112186092B - Thermopile power generation device based on super-hydrophilic structure and preparation method thereof - Google Patents
Thermopile power generation device based on super-hydrophilic structure and preparation method thereof Download PDFInfo
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
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Abstract
The invention belongs to the field of manufacturing of micro-nano structures, and discloses a thermopile power generation device based on a super-hydrophilic structure and a preparation method thereof, wherein the power generation device comprises an insulating substrate and a plurality of power generation units positioned on the insulating substrate, each power generation unit comprises a first suspended thermocouple electrode, a second suspended thermocouple electrode and a super-hydrophilic layer, and one ends of the two suspended thermocouple electrodes are respectively positioned on a cold end base of the first thermocouple electrode and a cold end base of the second thermocouple electrode and are connected with a cold end; the other end of the first thermocouple electrode is respectively positioned on the first thermocouple electrode hot end base and the second thermocouple electrode hot end base and is connected with the hot end; the hot end is a suspended super-hydrophilic layer which has a micro-nano structure. According to the invention, the super-hydrophilic structure is used as the hot end to be matched with the thermocouple electrode to form the thermopile power generation device, the formed thermopile power generation device has higher power generation efficiency and stable structure, and the preparation method can realize the preparation of the large-scale thermopile array power generation device.
Description
Technical Field
The invention belongs to the field of manufacturing of micro-nano structures, and particularly relates to a thermopile power generation device based on a super-hydrophilic structure and a preparation method thereof.
Background
With the development of society, people have an increasing demand for energy, especially for electric energy. The current power generation modes mainly comprise wind power generation, thermal power generation, water power generation, solar cell power generation and the like. These methods require a large floor space and have high investment costs.
The thermopile is a thermocouple array device and can convert temperature difference into potential difference, so that current is caused. Therefore, generating a large temperature difference is a key factor for thermopile power generation. At present, the commercial thermopile array mainly adopts the technical means of photoetching electrodes, thermocouples, deposition sensitive layers and the like to realize the infrared detection performance, and is mainly suitable for night vision devices, temperature sensing and other aspects. Due to the lack of a good super-hydrophilic material or the fact that a super-hydrophilic micro-nano structure cannot be prepared in situ directly, the physical temperature difference is not high, and the super-hydrophilic micro-nano structure is difficult to be directly applied to the field of power generation.
In the field of power generation by adopting a micro-nano structure, for single liquid drop power generation, a kinetic energy conversion method and a charge transfer method are adopted at present, and the methods can realize power generation performance to a certain degree but are not enough to meet the normal power consumption requirement. The main reason is that the kinetic energy of a single droplet is limited and multiple droplets are required to simultaneously drop different devices to improve their efficiency. In addition, the charge transfer method has a disadvantage of short service life. Therefore, the finding and the design of the efficient power generation device capable of meeting daily requirements are of great significance.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a thermopile power generation device based on a super-hydrophilic structure and a preparation method thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a thermopile power generating device based on a super-hydrophilic structure, which includes an insulating substrate and a plurality of power generating units located on the insulating substrate, each power generating unit includes a pair of suspended thermocouple electrodes arranged in parallel, the two suspended thermocouple electrodes are respectively denoted as a first suspended thermocouple electrode and a second suspended thermocouple electrode, and one ends of the two suspended thermocouple electrodes are respectively located on a base of a cold end of the first thermocouple electrode and a base of a cold end of the second thermocouple electrode and connected to the cold ends; the other end of the first thermocouple electrode is respectively positioned on the first thermocouple electrode hot end base and the second thermocouple electrode hot end base and is connected with the hot end; the hot end is a suspended super-hydrophilic layer which has a micro-nano structure.
As a further preferred aspect of the present invention, the suspended super-hydrophilic layer is located above the first thermocouple electrode hot end base and the second thermocouple electrode hot end base.
As a further preferred aspect of the present invention, the insulating substrate is a substrate material having an insulating layer deposited on a surface thereof.
As a further preferred aspect of the present invention, the power generating unit is a plurality of power generating units, and the power generating units are connected in series through a circuit on the insulating substrate;
preferably, for 2 adjacent power generation units, the first thermocouple electrode cold end base of one power generation unit and the second thermocouple electrode cold end base of the other power generation unit are connected with the same cold end; and for any 1 power generation unit, the first thermocouple electrode hot end base and the second thermocouple electrode hot end base are connected with the same hot end.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned super hydrophilic structure-based thermopile power generating device, characterized by comprising the steps of:
(1) preparing an insulating layer covering the surface of a clean and dry substrate, forming a cold end region graph on the substrate through photoetching treatment in a preset first target region or directly applying a physical mask, and depositing a cold end material and a cold end protective material in the cold end region graph, wherein the cold end protective material is deposited and covered above the cold end material;
(2) then, forming a thermocouple electrode base graphic array on the substrate by photoetching treatment or directly applying a physical mask in a preset second target area, and then depositing an electrode base material in the thermocouple electrode base graphic array to form an electrode base as a thermocouple electrode hot end base and a thermocouple electrode cold end base;
(3) then, forming a first thermocouple electrode pattern on a substrate by photoetching treatment or directly applying a physical mask in a preset third target area, and then depositing a first thermocouple electrode material and a thermocouple protection material in the first thermocouple electrode pattern to form a first thermocouple electrode, wherein the thermocouple protection material is deposited and covered above the first thermocouple electrode material;
(4) then, forming a second thermocouple electrode pattern on the substrate by photoetching treatment or directly applying a physical mask in a preset fourth target area, and then depositing a second thermocouple electrode material and a thermocouple protection material in the second thermocouple electrode pattern to form a second thermocouple electrode, wherein the thermocouple protection material is deposited and covered above the second thermocouple electrode material;
(5) then, forming a supporting structure pattern on the substrate by photoetching treatment or directly applying a physical mask plate in a preset fifth target area, and then depositing a supporting structure material in the supporting structure pattern to form a supporting structure;
(6) then, forming a super-hydrophilic region pattern on the substrate in a preset sixth target region through photoetching or directly applying a physical mask, and depositing a super-hydrophilic seed layer material in the super-hydrophilic region pattern to form a super-hydrophilic structure seed layer; then, growing a super-hydrophilic layer on the super-hydrophilic structure seed layer in situ to obtain a super-hydrophilic structure;
(7) and finally, dissolving and releasing the support structure to form a suspended support structure, thus obtaining the thermopile power generation device based on the super-hydrophilic structure.
As a further preferred aspect of the present invention, in the step (5), the support structure material is a specific solvent-soluble material selected in advance for subsequent release.
As a further preferred aspect of the present invention, in the step (6), the super-hydrophilic seed layer material is selected from zinc oxide, copper, and aluminum, and is preferably copper;
the super-hydrophilic layer is obtained by wet growth or chemical vapor deposition growth, preferably by wet growth.
As a further preferred aspect of the present invention, in the step (1), the cold end material has conductivity;
the insulating layer in the step (1), the thermocouple protection material in the step (3) and the thermocouple protection material in the step (4) are preferably made of the same material and have the same thickness.
As a further preferred aspect of the present invention, in the step (7), the dissolution release is a multi-step dissolution release, and the concentration of the solution used in each step of dissolution release is gradually increased, so that the release stress can be reduced; preferably, the multi-step dissolution release is a three-step dissolution release.
According to a further aspect of the present invention, the present invention provides the use of the above-described thermopile power generating device based on a superhydrophilic structure as a power generating device or a raindrop sensor.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the super-hydrophilic material with the micro-nano structure is introduced to the surface of the thermopile, the temperature difference effect is good, and the power generation efficiency of the device is greatly improved. The thermopile in the prior art is often used for preparing a temperature measuring instrument, and a super-hydrophilic material with a micro-nano structure is not required to be endowed, but the super-hydrophilic structure is used as a hot end to be matched with a thermocouple electrode to form a thermopile power generating device, so that the formed thermopile power generating device has high power generating efficiency and stable structure. When water drops drop on the super-hydrophilic sensitive layer, due to the super-hydrophilic effect of the sensitive layer, the water drops can be rapidly spread within 10ms and rapidly volatilize after being diffused to the maximum area, the temperature of the super-hydrophilic sensitive layer can be rapidly reduced within a short time according to the evaporation heat absorption principle, at the moment, the temperatures of the hot end of the first thermocouple electrode and the hot end of the second thermocouple electrode are both lower than the temperatures of the corresponding cold ends, and according to the Seebeck effect, a potential difference is generated between the cold end of the first thermocouple electrode and the cold end of the second thermocouple electrode. The invention can particularly adopt a plurality of series-connected power generation units, compared with the efficiency of the traditional single-thermocouple and charge transfer method power generation device, the thermopile power generation device based on the super-hydrophilic structure can further amplify weak potential by virtue of the potential series amplification advantage, obtain larger power generation potential, and greatly reduce the design cost of subsequent circuits.
(2) The thermopile power generation device based on the super-hydrophilic structure fully utilizes the unique property of the super-hydrophilic interface and the characteristic of serial amplification of thermopile potential, integrates the advantages of the super-hydrophilic interface and the super-hydrophilic interface into one device, and realizes an efficient and stable power generation device.
(3) The whole preparation process is simple and environment-friendly. The whole process relates to pattern transfer, film coating, wet growth, suspension structure release and the like, does not have a high-temperature high-pressure process, is completely compatible with the traditional silicon-based IC process, can manufacture thermopile power generation devices in batches, and greatly reduces the production cost.
(4) The invention utilizes the suspended thermocouple electrode, overcomes the difficulty of heat loss caused by direct contact between the thermocouple electrode on the traditional thermopile and the substrate, further improves the temperature difference effect and realizes more excellent power generation efficiency.
(5) The thermopile power generation device based on the super-hydrophilic structure has an excellent liquid drop power generation effect, can be packaged into a raindrop sensor, is applied to the fields of intelligent environment monitoring, unmanned driving and the like, can be used as an energy source of a self-powered device, and realizes stable sensing of an unmanned area.
According to the invention, the super-hydrophilic material with a micro-nano structure is grown in situ, so that a single liquid drop can be rapidly spread after dropping on the surface of the super-hydrophilic material, and then is rapidly self-evaporated, and the repeatability is good. The super-hydrophilic material with the micro-nano structure prepared in situ has a larger specific surface area, and promotes faster diffusion and self-evaporation. The better the super-hydrophilic performance of the super-hydrophilic material is, the more excellent the performance of the obtained thermopile power generating device based on the super-hydrophilic structure is.
The invention adopts a super-hydrophilic interface, and can lead water drops to quickly self-diffuse and self-evaporate to generate temperature difference. When water drops fall on the super-hydrophilic sensitive layer, the drops can spread rapidly due to the super-hydrophilic action of the sensitive layer and can self-volatilize rapidly after being diffused to the maximum area (when in use, the relative humidity of the environment is required to be lower than 100%). According to the principle of evaporation and heat absorption, the temperature of the super-hydrophilic sensitive layer can be reduced, at the moment, the temperatures of the hot end of the first thermocouple electrode and the hot end of the second thermocouple electrode are lower than the temperatures of the corresponding cold ends, and according to the Seebeck effect, a potential difference is generated between the cold ends of the first thermocouple electrode and the cold ends of the second thermocouple electrode. And then the potential differences which are connected in series one by one are superposed in the positive direction, for example, when the number of the thermocouple electrodes reaches a certain number, the voltage exceeding 5V can be detected, so that current is formed, and the function of generating electricity is realized. Based on the action mechanism, the thermopile power generation device based on the super-hydrophilic structure can also be used as a raindrop sensor to be applied to the field of unmanned driving.
In addition, the thermocouple electrode is suspended, so that heat loss can be avoided, namely heat loss is slowed down, the temperature of the cold end and the temperature of the hot end are different, and the voltage is higher.
In conclusion, the thermopile power generation device based on the super-hydrophilic structure has higher power generation efficiency, can be used as a power generation device and a micro power generation device and used as an energy source of a self-powered device, can be used as a raindrop sensor, can be widely applied to raindrop detection, and has certain economic benefits in transportation, intelligent driving and environmental monitoring.
Drawings
Fig. 1 is a bare substrate. Wherein 1 is a substrate.
FIG. 2 illustrates the deposition of an insulating layer substrate. Wherein 2 is an insulating layer.
FIG. 3 is a lithographic cold side pattern. Where 3-1 is the exposed portion of the photoresist.
FIG. 4 is a post development cold end pattern. Wherein 3-2 is a photoresist remaining portion.
FIG. 5 is a deposition of cold end material. Wherein 4-1 is a cold junction layer material.
FIG. 6 is a cold end graph after stripping. Wherein 4-2 is a cold side layer pattern.
FIG. 7 is a lithographic electrode pattern. Wherein 3-3 is the exposed portion of the photoresist.
Fig. 8 is a developed electrode pattern. Wherein 3-4 are photoresist reserved parts.
Fig. 9 is a deposition of electrode material. Wherein 5-1 is an electrode material.
Fig. 10 is a pattern of electrodes after lift-off. Wherein 5-2 is the electrode pattern.
FIG. 11 is a diagram of a lithographic thermocouple electrode. Wherein 3-5 is photoresist.
Fig. 12 shows the pattern of the thermocouple electrodes after exposure (the depth of exposure can be controlled using photolithographic diffraction techniques). Where 3-6 are the exposed portions of the photoresist.
Fig. 13 is a developed thermocouple electrode pattern.
Fig. 14 is a deposited thermocouple electrode pattern. Wherein 6-1 is thermocouple electrode material.
FIG. 15 is a graph of a thermocouple electrode after stripping. Wherein 6-2 is a thermocouple electrode.
FIG. 16 is a lithographic support structure pattern. Where 3-7 are the exposed portions of the photoresist.
FIG. 17 is a developed support structure pattern. Wherein 3-8 are photoresist reserved parts.
FIG. 18 is a deposition support structure. Wherein 7-1 is a support structure material.
FIG. 19 is the support structure after peeling. Wherein 7-2 is a support structure.
Fig. 20 is a photolithographic super hydrophilic seed layer pattern. Where 3-9 are the exposed portions of the photoresist.
FIG. 21 shows a super hydrophilic seed layer pattern after development. Wherein 3-10 are photoresist reserved parts.
FIG. 22 is a deposition of a superhydrophilic seed layer. Wherein 8-1 is a super-hydrophilic seed layer material.
FIG. 23 shows a super hydrophilic seed layer after lift-off. Wherein 8-2 is a super-hydrophilic seed layer.
FIG. 24 is a solution process for growing superhydrophilic structures. Wherein 9 is a super-hydrophilic micro-nano composite structure.
Fig. 25 is a cross-sectional view of the device after dissolution of the support structure.
Fig. 26 is a top view of the device.
Fig. 27 is an isometric view of a device unit. Wherein, 5-1-1 is a second thermocouple electrode cold end base (i.e., thermocouple electrode II cold end base), 5-1-2 is a first thermocouple electrode cold end base (i.e., thermocouple electrode I cold end base), 5-1-3 is a first thermocouple electrode hot end base (i.e., thermocouple electrode I hot end base), 5-1-4 is a second thermocouple electrode hot end base (i.e., thermocouple electrode II hot end base), 6-1-1 is a first thermocouple electrode (i.e., thermocouple electrode I), and 6-1-2 is a second thermocouple electrode (i.e., thermocouple electrode II).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In general, the thermopile power generating device based on the super-hydrophilic structure mainly comprises an insulating substrate, electrodes and a thermocouple unit array. The thermocouple unit consists of a first thermocouple electrode (namely, a thermocouple electrode I), a second thermocouple electrode (namely, a thermocouple electrode II), an electrode base and a super-hydrophilic sensitive layer. Specifically speaking, as shown in fig. 26 and 27, the device includes a substrate, a substrate surface insulating layer, a thermocouple array interconnection circuit, a first thermocouple electrode cold end base (i.e., thermocouple electrode I cold end base), a first suspended thermocouple electrode (i.e., suspended thermocouple electrode I), a first thermocouple electrode hot end base (i.e., thermocouple electrode I hot end base), a second thermocouple electrode cold end base (i.e., thermocouple electrode II cold end base), a second suspended thermocouple electrode (i.e., suspended thermocouple electrode II), a second thermocouple electrode hot end base (i.e., thermocouple electrode II hot end base), and a suspended super-hydrophilic layer; the unit in the thermocouple array is that a suspension thermocouple electrode I is erected on a cold end base of the thermocouple electrode I and a hot end base of the thermocouple electrode I; and similarly, the suspension thermocouple electrode II is erected on the cold end base of the thermocouple electrode II and the hot end base of the thermocouple electrode II. The suspension super-hydrophilic layer is arranged above and connected with the hot end of the thermocouple electrode I and the hot end of the thermocouple electrode II to form a suspension super-hydrophilic layer structure similar to a cantilever beam.
The thermocouples can be arranged in series to form a thermocouple array on the surface of the substrate and spread around the center, so that the super-hydrophilic layer can form a concentrated area in the middle (as shown in fig. 26) so as to improve the temperature difference caused by the subsequent super-hydrophilic self-diffusion. Between the thermocouples connected in series, the adjacent thermocouples are connected through a circuit, and in order to ensure the consistency of voltage drop, the cold junction base of the thermocouple electrode I and the cold junction base of the thermocouple electrode II of the adjacent thermocouple need to be connected with each other.
Example 1
The method comprises the following steps:
1) cleaning of
The method comprises the steps of taking a silicon wafer as a substrate material, ultrasonically cleaning the substrate for 30min by adopting acetone, alcohol and deionized water, drying the substrate on a hot plate at 100 ℃ after drying by adopting nitrogen for later use.
2) Plated insulating layer
And sputtering a silicon nitride insulating layer on the surface of the substrate by adopting magnetron sputtering, wherein the sputtering thickness is 100 nm. The insulating layer can be used for insulating the subsequent electrode from the substrate.
3) Preparing cold end zone patterns
And preparing a cold end region graph by adopting photoetching steps of gluing, prebaking, exposing, developing and the like.
4) Cold end plating material
And depositing a cold end material on the surface of the substrate by adopting magnetron sputtering, wherein the cold end material comprises a cold end material body and a corresponding protective layer, and obtaining the cold end of the thermocouple by adopting a solution method stripping mode. The cold end material is Ag, the thickness is 100nm, the protective layer can be alumina, and the thickness is 100 nm.
5) Preparing electrode base pattern
And preparing a thermocouple electrode base graphic array by adopting a photoetching technology.
6) Electrode plating base
And depositing an electrode base material on the surface of the substrate by adopting a magnetron sputtering technology, and obtaining the electrode base by adopting a stripping mode. The electrode base material may be Au.
7) Preparation of thermocouple electrode I Pattern
And preparing a thermocouple electrode I pattern by adopting a photoetching technology. The method comprises the steps of spin-coating photoresist, prebaking, placing a mask, exposing, postbaking, developing and the like.
8) Plated thermocouple electrode I
Depositing a thermocouple electrode I material nickel-chromium on the surface of the substrate by magnetron sputtering, wherein the thickness is 100nm, and obtaining the thermocouple electrode I by adopting a stripping mode.
9) Plating thermocouple electrode insulating layer
And directly depositing insulating layer silicon nitride on the substrate by adopting a magnetron sputtering technology, wherein the thickness of the insulating layer silicon nitride is 100nm and the insulating layer silicon nitride is used for protecting the electrode thermocouple electrode I.
10) Preparation of thermocouple electrode II Pattern
And preparing a thermocouple electrode II pattern by adopting a photoetching technology. The method comprises the steps of spin-coating photoresist, prebaking, placing a mask, exposing, postbaking, developing and the like.
11) Plated thermocouple electrode II
And depositing a thermocouple electrode II material nickel silicon on the surface of the substrate by adopting a magnetron sputtering technology, wherein the thickness is 100nm, and obtaining the thermocouple electrode II by adopting a stripping mode.
12) Plated insulating layer
And directly depositing insulating layer silicon nitride on the substrate by adopting a magnetron sputtering technology, wherein the thickness of the insulating layer silicon nitride is 100nm, and the insulating layer silicon nitride is used for protecting the electrode thermocouple electrode II.
13) Preparation of suspended support Structure patterns
And preparing a suspended support structure pattern by adopting a photoetching technology.
14) Plating support structure
The method comprises the steps of directly depositing a support structure material silicon dioxide on a substrate by adopting a magnetron sputtering technology for subsequently supporting a super-hydrophilic seed layer, and simultaneously obtaining a support layer by adopting a stripping technology, wherein the thickness of the support layer is the same as the height of a thermocouple electrode relative to the surface of the substrate.
15) Photoetching super hydrophilic area pattern
And preparing a super-hydrophilic area pattern by gluing, pre-baking, exposing and developing.
16) Seed layer plated with super-hydrophilic structure
And depositing a super-hydrophilic seed layer material on the surface of the substrate by adopting a magnetron sputtering technology, and obtaining the super-hydrophilic structural seed layer by adopting a stripping mode. The super hydrophilic seed layer material may be Al.
17) Growing super-hydrophilic structures
And directly preparing the super-hydrophilic structure above the super-hydrophilic structure seed layer by adopting a wet solution method in-situ growth mode. The growth liquid of the super-hydrophilic micro-nano composite structure is sodium hydroxide.
18) Support structure release
Three gradient dissolving solutions of HF acid (such as 5%, 10% and 20% by mass respectively) are prepared, and the support layer structure is gradually dissolved by utilizing gradually increasing solution concentrations to reduce release stress. Of course, the type of solvent used for releasing the support structure can be adjusted according to the specific support structure material, as long as the solvent used can dissolve the corresponding support structure material without affecting other structures of the device (i.e., the support structure material and the solvent used in the releasing step can be pre-selected and adjusted simultaneously).
The overall parameters are shown in the following table:
table 1 process parameters used in example 1
| Base material | Silicon |
| Base insulating layer material | Silicon nitride |
| Thickness of base insulating layer (nm) | 100 |
| Cold end material | Ag |
| Cold end material thickness (nm) | 100 |
| Cold end material protective layer material | Alumina oxide |
| Cold end protective material thickness (nm) | 100 |
| Electrode base material | Gold (Au) |
| Thickness of electrode base material (nm) | 250 |
| Thermocouple electrode material I | Nickel-chromium |
| Thermocouple electrode material I thickness (nm) | 100 |
| Thermocouple electrode material II | Nickel silicon |
| Thickness (nm) of thermocouple electrode material II | 100 |
| Thermocouple protective material | Silicon nitride |
| Thickness of thermocouple protective material | 100 |
| Support layer material | Silicon dioxide |
| Dissolving agent | HF |
| Super-hydrophilic seed layer material | Al |
| Super hydrophilic seed layer thickness (nm) | 100 |
| Super-hydrophilic micro-nano composite structure growth liquid | Sodium hydroxide |
Example 2
The specific operating steps and parameters are the same as in example 1, except for the process parameters in Table 2.
Table 2 process parameters used in example 2
Example 3
The specific operating steps and parameters are the same as in example 1, except for the process parameters in Table 3.
Table 3 process parameters used in example 3
In the above embodiment, the patterns prepared in steps 3), 5), 7), 10), 13) and 15) may be prepared by photolithography or by directly applying a physical mask, the physical mask is selected when the size is greater than 100 μm, photolithography is preferentially selected when the size is less than 10 μm, electron beam lithography is selected when the size is less than 500nm, and other ranges are preferred according to the lower cost. The thickness of the insulating material in the steps 2), 9) and 12) depends on the requirement of the insulating degree, and the three materials are consistent in thickness (the thickness can be 300nm for example). In addition to the above embodiments, the super-hydrophilic seed layer in step 16) may also be made of other materials capable of growing a super-hydrophilic layer by using a subsequent solution method, and the super-hydrophilic material in-situ grown in step 17) is mainly grown by wet growth or chemical vapor deposition. In the above embodiments, reference may be made to the related prior art for details (for example, specific ratio of the growth liquid for the super-hydrophilic micro-nano composite structure). In addition to the above embodiments, the thermocouple electrode material combination can refer to the prior art, and in particular, a thermocouple electrode material with good seebeck effect can be used.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (13)
1. A thermopile power generation device based on a super-hydrophilic structure is characterized by comprising an insulating substrate and a plurality of power generation units positioned on the insulating substrate, wherein each power generation unit comprises a pair of suspended thermocouple electrodes which are arranged in parallel, the two suspended thermocouple electrodes are respectively marked as a first suspended thermocouple electrode and a second suspended thermocouple electrode, and one ends of the two suspended thermocouple electrodes are respectively positioned on a cold end base of the first thermocouple electrode and a cold end base of the second thermocouple electrode and are connected with a cold end; the other end of the first thermocouple electrode is respectively positioned on the first thermocouple electrode hot end base and the second thermocouple electrode hot end base and is connected with the hot end; the hot end is a suspended super-hydrophilic layer which has a micro-nano structure.
2. The super hydrophilic structure based thermopile power generating device according to claim 1, wherein said suspended super hydrophilic layer is located above said first thermocouple electrode hot end base and said second thermocouple electrode hot end base.
3. The super hydrophilic structure based thermopile power generating device according to claim 1, wherein said insulating substrate is a substrate material with an insulating layer deposited on the surface.
4. The super hydrophilic structure based thermopile power generating device according to claim 1, wherein said power generating unit is a plurality of power generating units connected in series by a circuit on said insulating substrate;
for 2 adjacent power generation units, a first thermocouple electrode cold end base of one power generation unit and a second thermocouple electrode cold end base of the other power generation unit are connected with the same cold end; and for any 1 power generation unit, the first thermocouple electrode hot end base and the second thermocouple electrode hot end base are connected with the same hot end.
5. Method for preparing a thermopile power generating device based on a superhydrophilic structure according to any of claims 1-4, characterized in that it comprises the following steps:
(1) preparing an insulating layer covering the surface of a clean and dry substrate, forming a cold end region graph on the substrate through photoetching treatment in a preset first target region or directly applying a physical mask, and depositing a cold end material and a cold end protective material in the cold end region graph, wherein the cold end protective material is deposited and covered above the cold end material;
(2) then, forming a thermocouple electrode base graphic array on the substrate by photoetching treatment or directly applying a physical mask in a preset second target area, and then depositing an electrode base material in the thermocouple electrode base graphic array to form an electrode base as a thermocouple electrode hot end base and a thermocouple electrode cold end base;
(3) then, forming a first thermocouple electrode pattern on a substrate by photoetching treatment or directly applying a physical mask in a preset third target area, and then depositing a first thermocouple electrode material and a thermocouple protection material in the first thermocouple electrode pattern to form a first thermocouple electrode, wherein the thermocouple protection material is deposited and covered above the first thermocouple electrode material;
(4) then, forming a second thermocouple electrode pattern on the substrate by photoetching treatment or directly applying a physical mask in a preset fourth target area, and then depositing a second thermocouple electrode material and a thermocouple protection material in the second thermocouple electrode pattern to form a second thermocouple electrode, wherein the thermocouple protection material is deposited and covered above the second thermocouple electrode material;
(5) then, forming a supporting structure pattern on the substrate by photoetching treatment or directly applying a physical mask plate in a preset fifth target area, and then depositing a supporting structure material in the supporting structure pattern to form a supporting structure;
(6) then, forming a super-hydrophilic region pattern on the substrate in a preset sixth target region through photoetching or directly applying a physical mask, and depositing a super-hydrophilic seed layer material in the super-hydrophilic region pattern to form a super-hydrophilic structure seed layer; then, growing a super-hydrophilic layer on the super-hydrophilic structure seed layer in situ to obtain a super-hydrophilic structure;
(7) and finally, dissolving and releasing the support structure to form a suspended support structure, thus obtaining the thermopile power generation device based on the super-hydrophilic structure.
6. The method of claim 5, wherein in step (5), the support structure material is a specific solvent-soluble material that is pre-selected for subsequent release.
7. The method of claim 5, wherein in the step (6), the super-hydrophilic seed layer material is selected from zinc oxide, copper, aluminum;
the super-hydrophilic layer is obtained by wet growth or chemical vapor deposition growth.
8. The method of claim 7, wherein in step (6), the super-hydrophilic seed layer material is copper.
9. The method of claim 7, wherein in step (6), the super-hydrophilic layer is formed by wet growth.
10. The method of claim 5 wherein in step (1) said cold end material is electrically conductive;
the insulating layer in the step (1), the thermocouple protection material in the step (3) and the thermocouple protection material in the step (4) are made of the same material and have the same thickness.
11. The method according to claim 5, wherein in the step (7), the dissolution release is performed in a plurality of steps, and the concentration of the solution used in each step of dissolution release is gradually increased, so that the release stress can be reduced.
12. The method of claim 11, wherein the multi-step dissolution release is a three-step dissolution release.
13. Use of a super hydrophilic structure based thermopile power generating device according to any of claims 1-4 as a power generating device or as a raindrop sensor.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3836871B1 (en) * | 2006-05-30 | 2006-10-25 | 光保 相良 | Power generation module |
| CN101071842A (en) * | 2006-05-09 | 2007-11-14 | 中国科学院电子学研究所 | Self-test micromechanical thermoelectric pile bioreaction heat detector and its preparing method |
| JP2010112688A (en) * | 2008-11-06 | 2010-05-20 | Yoshihiro Furubayashi | Cooling device for thermoelectric conversion power generation |
| CN102009941A (en) * | 2010-10-09 | 2011-04-13 | 北京大学 | Micro-nano fluid system and preparation method thereof |
| CN103698020A (en) * | 2013-12-02 | 2014-04-02 | 中北大学 | Thermopile infrared gas detector taking composite film as infrared absorption layer, and processing method of detector |
| JP2016153367A (en) * | 2015-02-13 | 2016-08-25 | 株式会社Ｎｅｘｔコロイド分散凝集技術研究所 | Carbon nanotube dispersion, manufacturing method therefor, carbon nanotube-containing thermoelectric transducer and manufacturing method therefor |
| WO2019130187A1 (en) * | 2017-12-27 | 2019-07-04 | 3M Innovative Properties Company | Flexible thermoelectric device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817256B (en) * | 2010-04-30 | 2011-08-10 | 华中科技大学 | Jet-printing head based on double-carbon nanotube microbubble generator and preparation method thereof |
| US8736011B2 (en) * | 2010-12-03 | 2014-05-27 | Alphabet Energy, Inc. | Low thermal conductivity matrices with embedded nanostructures and methods thereof |
| CN102829880B (en) * | 2012-08-23 | 2014-04-16 | 江苏物联网研究发展中心 | High-performance MEMS (Micro Electro Mechanical System) thermopile infrared detector based on black silicon and preparation method thereof |
| CN105841396B (en) * | 2016-04-01 | 2018-01-02 | 华中科技大学 | A kind of cold, heat and electricity triple supply composite energy supply system based on the recovery of waste heat depth |
-
2020
- 2020-09-10 CN CN202010946073.5A patent/CN112186092B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071842A (en) * | 2006-05-09 | 2007-11-14 | 中国科学院电子学研究所 | Self-test micromechanical thermoelectric pile bioreaction heat detector and its preparing method |
| JP3836871B1 (en) * | 2006-05-30 | 2006-10-25 | 光保 相良 | Power generation module |
| JP2010112688A (en) * | 2008-11-06 | 2010-05-20 | Yoshihiro Furubayashi | Cooling device for thermoelectric conversion power generation |
| CN102009941A (en) * | 2010-10-09 | 2011-04-13 | 北京大学 | Micro-nano fluid system and preparation method thereof |
| CN103698020A (en) * | 2013-12-02 | 2014-04-02 | 中北大学 | Thermopile infrared gas detector taking composite film as infrared absorption layer, and processing method of detector |
| JP2016153367A (en) * | 2015-02-13 | 2016-08-25 | 株式会社Ｎｅｘｔコロイド分散凝集技術研究所 | Carbon nanotube dispersion, manufacturing method therefor, carbon nanotube-containing thermoelectric transducer and manufacturing method therefor |
| WO2019130187A1 (en) * | 2017-12-27 | 2019-07-04 | 3M Innovative Properties Company | Flexible thermoelectric device |
| CN111542934A (en) * | 2017-12-27 | 2020-08-14 | 3M创新有限公司 | Flexible thermoelectric device |
Non-Patent Citations (1)
| Title |
|---|
| Design and fabrication of a thermoelectric nanowire characterization platform and nanowire assembly by utilizing dielectrophoresis;Zhi Wang等;《Sensors and Actuators A: Physical》;20121231;第188卷;全文 * |
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