CN113241399B - High-density thermoelectric thick film device based on pulse laser direct writing technology and manufacturing method thereof - Google Patents
High-density thermoelectric thick film device based on pulse laser direct writing technology and manufacturing method thereof Download PDFInfo
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- CN113241399B CN113241399B CN202110505375.3A CN202110505375A CN113241399B CN 113241399 B CN113241399 B CN 113241399B CN 202110505375 A CN202110505375 A CN 202110505375A CN 113241399 B CN113241399 B CN 113241399B
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Abstract
The invention relates to a design and a manufacturing method of a high-density thermoelectric thick film device based on a pulse laser direct writing technology. Depositing high-length-width-ratio rectangular n-type thermoelectric materials and p-type thermoelectric materials which are alternately arranged on a metallized substrate, respectively patterning a metal electrode and the thermoelectric materials on the substrate by adopting a pulse laser direct writing technology, and preparing a supporting layer and an upper electrode in a specific area to obtain a complete thermoelectric device; the invention applies the ultrafast pulse laser direct writing technology to the thermoelectric thick film device processing for the first time, can realize the processing of a micron-sized thermopile array structure, and effectively improves the integration level and the output performance of the device. By combining the L-shaped structural design of the edge electrode of the device, the thermopiles of the same type can be arranged adjacently in an aligned manner, and the thermopiles of different patterns and the multilayer structure of the electrode have high adaptability through laser direct writing processing, so that in-situ integrated processing is effectively realized; the device integration method has the advantages of strong compatibility of all process links, controllability, high efficiency and large-scale low-cost production potential.
Description
Technical Field
The invention belongs to the technical field of functional micro-device integrated processing, and particularly relates to a design and preparation method of a thermoelectric thick film device based on a pulse laser direct writing technology.
Background
The thermoelectric conversion technology is a new energy technology for directly converting electric energy and heat energy, and has the characteristics of pure solid state, compact structure, no vibration noise, high reliability, environmental protection, no pollution and the like. The thermoelectric material is applied to thermoelectric power generation, rapid refrigeration and the like based on the Seebeck effect and the Peltier effect respectively, and micro-energy collection, low-grade heat energy utilization, accurate temperature control and the like are realized. The thermoelectric device mainly comprises a substrate, a metal electrode, an n-type semiconductor thermoelectric material, a p-type semiconductor thermoelectric material and the like. The thermoelectric thick film device generally has the characteristics of large heat flow density, quick response, small volume, easy flexibility and the like, and the main development direction of the thermoelectric thick film device is high density, miniaturization and modularization.
With the development of microelectronic devices and wearable devices, it is important to provide energy and thermal management through thin-sized thermoelectric thick film devices. The thermoelectric thick film device is a functional electronic device which is composed of multiple layers of heterogeneous film materials and realizes direct conversion between electric energy and heat energy. When application scenarios are miniaturized, it is desirable to achieve greater output power densities, which depend on the fabrication of high density thermopile arrays. When high density, miniaturization and modularization are met, materials of all layers of the thermoelectric thick film device need to be subjected to multiple patterning, the precision requirement is high, the process is complex, and the reliability is poor.
At present, the film material of the conventional high-density thermopile is usually patterned based on a metal mask method and a photolithography method. However, the metal mask method cannot construct a micron-sized fine structure, and it is difficult to realize a high-density array with low accuracy. The photoresist is usually an organic material, so that the photoresist is difficult to resist high temperature, temperature conditions of various thermoelectric material preparation methods are limited, and the improvement of the performance of the thermoelectric thick-film device is restricted. Meanwhile, the metal mask method and the photolithography method need to replace corresponding mask patterns according to different film materials in the device preparation process, so that the manufacturing cost and difficulty are increased. Therefore, there is a need for new techniques for designing new thermoelectric device structures and developing high-density thermoelectric device integrated manufacturing.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-density thermoelectric thick film device design and preparation method based on a pulse laser direct writing technology. The method adopts the pulse laser direct writing technology to realize high-precision patterning in-situ processing of the high-density thermoelectric material and the electrode material, and develops the integrated processing and integration technology of the thermoelectric thick film device based on the pulse laser direct writing construction of the three-dimensional structure of the heterogeneous film material.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-density thermoelectric thick film device based on a pulse laser direct writing technology comprises the following steps:
(1) depositing bottom electrode and barrier layer material
Sequentially depositing a bottom electrode Cu layer, a barrier layer Ni layer and an Au layer on the pretreated substrate;
(2) depositing high aspect ratio rectangular pattern thermoelectric materials
Sequentially depositing high-aspect-ratio rectangular n-type thermoelectric materials and p-type thermoelectric materials on the metalized substrate obtained in the step (1);
(3) thermoelectric material and bottom electrode pattern structure integrally processed by pulse laser direct writing technology
Placing the sample on which the thermoelectric material is deposited in the step (2) on an ultrafast pulse laser processing platform, processing the thermoelectric material into a thermopile array with a certain size by utilizing pulse laser direct writing, then performing high-precision patterning processing on the bottom electrode according to design, constructing electrical connection on the lower surface of the thermopile array, and realizing in-situ integrated processing of thermopiles with different patterns and electrode multilayer structures;
(4) preparing an upper electrode supporting layer
Coating a layer of ultraviolet photosensitive resin on the surface of the sample obtained in the step (3), aligning and attaching a photoetching plate with a supporting pattern to the sample, curing under the irradiation of ultraviolet light to obtain an upper electrode supporting layer, and realizing the insulating packaging of the thermoelectric material;
(5) depositing a top barrier material and an upper electrode
And (5) depositing an Au layer, a Ni layer and a Cu layer on the surface of the sample obtained in the step (4) in sequence according to the shape of a preset upper electrode, and preparing a patterned upper electrode to obtain the high-density thermoelectric thick film device.
In the step (1), the method for depositing the bottom electrode Cu layer, the barrier layer Ni layer and the Au layer is any one of magnetron sputtering, thermal evaporation, electron beam evaporation or electrochemistry.
When the bottom electrode Cu layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-400 ℃, the sputtering power is 20-200W, and the deposition time is 1-12 h;
when the barrier layer Ni layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-400 ℃, the sputtering power is 10W-100W, and the deposition time is 0.5h-8 h.
And when the Au layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-400 ℃, the sputtering power is 10W-50W, and the deposition time is 10min-1 h.
In the step (2), the n-type thermoelectric material is Bi 2 Te 3 、Bi 2 Te 2.7 Se 0.3 Any one of the p-type thermoelectricityThe material is Sb 2 Te 3 、Bi 0.5 Sb 1.5 Te 3 Either one of them.
In the step (2), the method for depositing the thermoelectric material is any one of magnetron sputtering, thermal evaporation, electron beam evaporation, electrochemical deposition or selective laser melting.
Sputtering Bi by direct current 2 Te 3 (or Bi) 2 Te 2.7 Se 0.3 ) And depositing the n-type thermoelectric material by a double-target co-sputtering method of radio-frequency sputtering Te;
the direct current sputtering pressure is 0.5Pa-3Pa, the substrate temperature is 100 ℃ to 480 ℃, the direct current sputtering power is 5W to 50W, the radio frequency sputtering power is 5W to 50W, and the deposition time is 1h to 24 h.
By sputtering with DC Sb 2 Te 3 (or Bi) 0.5 Sb 1.5 Te 3 ) Depositing the p-type thermoelectric material by a radio-frequency sputtering Te double-target co-sputtering method;
the direct current sputtering pressure is 0.5Pa-3Pa, the substrate temperature is 100 ℃ to 500 ℃, the direct current sputtering power is 5W to 50W, the radio frequency sputtering power is 5W to 50W, and the deposition time is 1h to 24 h.
In the step (3), the thermopile and electrode multilayer structure with different patterns is subjected to in-situ integrated processing by using a pulse laser direct writing technology, and the specific operations are as follows:
fixing the sample on the pulse laser processing platform after depositing the thermoelectric material in the step (2), associating the processing drawing with the sample to be processed by determining the coordinates of three marking points, respectively introducing the processing graphs of the thermoelectric material and the bottom electrode into a computer, wherein the target structure is mainly characterized by a micro-groove, and adopting ultrafast pulse laser with the central wavelength of 343-1064nm and the pulse width of 200fs-500ps to perform single-pulse energy density of 150mJ cm on the thermoelectric material -2 -1810-mJ cm -2 The spot overlapping rate is 10-90%, the line filling space is 5-30 μm, and the removal efficiency is 100 nm/time-3 μm/time; the energy density of the counter bottom electrode in a single pulse is 5000mJ cm -2 -20000mJ cm -2 The spot overlapping rate is 30-90%, the line filling space is 5-30 μm, and the removal efficiency is highThe thickness is 100 nm/time to 2 mu m/time, and finally the in-situ integrated processing of the thermopile with different patterns and the electrode multilayer structure is realized.
In the step (4), the specific preparation method of the upper electrode support layer is as follows:
coating ultraviolet photosensitive resin on the surface of a sample in a yellow light room, spin-coating for 3-15 min under the condition that the rotating speed is 3000-8000 rpm, drying for 5-20 min at 150 ℃, aligning and bonding a photoetching plate with a supporting pattern with the sample, exposing for 1-3 min under ultraviolet light, placing in an acetone solution, and ultrasonically cleaning for 10-90 s to obtain the upper electrode supporting layer, and meanwhile, realizing the insulating packaging of the thermoelectric material.
In the step (5), the method for depositing the top barrier layer Au layer, the Ni layer and the upper electrode Cu layer is any one of magnetron sputtering, thermal evaporation, electron beam evaporation, electrochemical deposition or spraying;
and when the Au layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-400 ℃, the sputtering power is 10W-50W, and the deposition time is 10min-1 h.
When the top barrier layer Ni layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-300 ℃, the sputtering power is 10W-100W, and the deposition time is 0.5h-8 h;
when the upper electrode Cu layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-300 ℃, the sputtering power is 20-200W, and the deposition time is 1-12 h.
The utility model provides a high density thermoelectricity thick film device based on pulse laser directly writes technique which characterized in that, the design of the marginal bottom electrode of thermoelectricity thick film device is "L" type, and the thermopile of the same type can realize the adjacent range of permutation, promotes the laser of the different patterning structure of multilayer material directly to write normal position processing suitability greatly.
The beneficial effects of the invention are as follows:
(1) according to the high-density thermoelectric thick film device, the edge of the bottom electrode is designed to be L-shaped, the n-type and p-type thermopiles in the traditional thermoelectric device are changed to be in checkerboard-type staggered distribution, and the same type thermopiles can be arranged in an aligned and adjacent manner. The structure can deposit a rectangular thermoelectric material with a large area and a high length-width ratio, and is suitable for a material preparation process with a wide temperature range so as to meet the requirements of various material performance optimization strategies such as doping and annealing. Meanwhile, the thermopile and the electrode have simple multilayer structure patterns, have consistency, reduce the processing difficulty and improve the yield of devices.
(2) The invention relates to a preparation method of a high-density thermoelectric thick film device, which comprises the steps of firstly depositing a bottom electrode and a barrier layer material, then depositing a rectangular thermoelectric material with a high length-width ratio on the surface of the bottom electrode material, then adopting a pulse laser direct writing technology to realize in-situ integrated processing of different patterned structures of the thermoelectric material and an electrode multilayer material, and then preparing an upper electrode supporting layer, depositing a top barrier layer material and an upper electrode in sequence to prepare a complete thermoelectric device; the invention applies the ultrafast pulse laser direct writing technology to the processing of the thermoelectric thick film device for the first time, because the ultrafast pulse laser has high instantaneous power and small heat affected zone, the micron-scale processing of the multilayer structure of the thermopile and the electrode can be realized by the method of the invention, and by combining the L-shaped structure design of the edge electrode of the device, the thermopile of the same type can realize the adjacent arrangement of the whole column, and the laser direct writing processing of the thermopile with different patterns and the multilayer structure of the electrode has high adaptability, thereby effectively realizing the in-situ fast integrated processing; the device integration method has the advantages of strong compatibility of each process link, controllability, high efficiency and potential of large-scale low-cost production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of a process and structure of a thick thermoelectric film device according to embodiment 1 of the present invention;
FIG. 2 is a schematic diagram showing a process window distribution of laser processing of a thermoelectric material according to example 1 of the present invention;
fig. 3 is a schematic structural view of the thermoelectric material and the bottom electrode after the integrated pattern structure is processed according to embodiment 1 of the present invention;
FIG. 4 is a graph showing the results of testing the power generation performance of the thick thermoelectric film device according to example 1 of the present invention;
FIG. 5a is a graph of the electrode profile produced by the metallization layer fabrication process described in example 1 of the present invention;
FIG. 5b is a diagram of a metallization layer formed by low power sputtering as described in example 2 of the present invention;
FIG. 5c is a diagram of a metallization layer formed by an electrochemical deposition process as described in example 3;
FIG. 6a is a cross-sectional profile of a deposited bismuth telluride thermoelectric material at high power as described in example 1 of the present invention;
FIG. 6b shows the use of Bi according to example 4 of the present invention 2 Te 2.7 Se 0.3 Preparing an n-type ternary thermoelectric material section morphology graph by using a target material;
fig. 6c is a cross-sectional profile of the deposited bismuth telluride thermoelectric material under the low power condition in embodiment 5 of the present invention;
FIG. 7a is a cross-sectional profile of an antimony telluride thermoelectric material deposited as described in example 1 of the present invention;
FIG. 7b is a cross-sectional profile of a columnar-grown p-type antimony telluride thermoelectric material as described in example 6 of the present invention;
FIG. 8a is a schematic diagram of the deposition of thermoelectric material on the L-shaped edge electrodes of the thick-film thermoelectric device according to example 1 of the present invention;
FIG. 8b is a schematic structural diagram of a thick film thermoelectric device with L-shaped edge electrodes according to example 1 of the present invention;
FIG. 8c is a schematic diagram of a checkerboard-like distributed thermopile structure of a conventional device "pi" structure;
FIG. 9a is a schematic structural diagram of a thermoelectric material processed by the pulsed laser direct writing technique adopted in embodiment 1 of the present invention;
fig. 9b is a schematic view of a thermoelectric device integrated by flip chip technology.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a high-density thermoelectric thick film device based on a pulse laser direct writing technology, which comprises the following steps:
(1) depositing bottom electrode and barrier layer material
Respectively placing the aluminum nitride substrate in deionized water, acetone and alcohol solution for ultrasonic cleaning for 5-20 minutes, drying the aluminum nitride substrate by using dry nitrogen, and then carrying out plasma cleaning on the aluminum nitride substrate to obtain a pretreated substrate;
placing the pretreated substrate in a magnetron sputtering vacuum chamber, and after the steps of vacuumizing, heating, pre-sputtering and the like are completed, sequentially depositing a Cu layer, a Ni layer and an Au layer on the substrate; when the bottom electrode Cu layer is deposited, the sputtering pressure is 2Pa, the substrate temperature is 200 ℃, the sputtering power is 120W, and the deposition time is 5 h; when the barrier layer Ni layer is deposited, the sputtering pressure is 2Pa, the substrate temperature is 200 ℃, the sputtering power is 50W, and the deposition time is 1 h; when depositing the Au layer, the sputtering pressure is 2Pa, the substrate temperature is 200 ℃, the sputtering power is 50W, the deposition time is 10min, and the obtained substrate metallization layer has the shape shown in FIG. 5 a.
(2) Depositing high aspect ratio rectangular pattern thermoelectric materials
Sequentially depositing strip-shaped n-type thermoelectric materials Bi on the surface of the bottom electrode obtained in the step (1) by adopting a method of double-target co-sputtering of direct-current magnetron sputtering and radio-frequency sputtering Te 2 Te 3 And p-type thermoelectric material Sb 2 Te 3 (ii) a The conditions for depositing the n-type thermoelectric material are controlled as follows: the direct-current sputtering pressure is 3Pa, the substrate temperature is 400 ℃, the direct-current sputtering power is 30W, the radio-frequency sputtering power is 25W, the deposition time is 5h, and the shape of the obtained material is shown in figure 6 a; the conditions for depositing the p-type thermoelectric material are controlled as follows: the DC sputtering pressure is 3Pa, the substrate temperature is 400 ℃, and the DC sputtering power is 25WThe radio frequency sputtering power is 25W, the deposition time is 6h, and the shape of the obtained material is shown in figure 7 a;
(3) integrated processing thermoelectric material and bottom electrode pattern structure by ultrafast laser direct writing technology
Placing the sample on which the thermoelectric material is deposited in the step (2) on an ultrafast pulse laser processing platform, associating a processing drawing with the sample to be processed by determining coordinates of three marking points, introducing a processing graph of the thermoelectric material and a bottom electrode into a computer, wherein a target structure is mainly characterized by a microgroove, and adopting ultrafast laser with the central wavelength of 343nm and the pulse width of 290fs to carry out single-pulse energy density on the thermoelectric material of 328mJ cm -2 The spot overlapping rate is 80%, the line filling space is 15 μm, and the removal efficiency is 1.5 μm/time; the energy density of a counter bottom electrode in a single pulse is 11000mJ cm -2 The spot overlapping rate is 80%, the line filling pitch is 15 μm, the removal efficiency is 2 μm/time, and finally the integrated pattern structure of the thermoelectric material and the bottom electrode is processed, as shown in fig. 3;
(4) preparing an upper electrode supporting layer
Coating ultraviolet photosensitive resin on the surface of a sample in a yellow light room, spin-coating for 5min under the condition of 8000rpm of rotation speed, drying for 10min at 150 ℃, aligning and attaching a photoetching plate with a supporting pattern and the sample, exposing the photoetching plate under ultraviolet light for 1min, and placing the photoetching plate in an acetone solution for ultrasonic cleaning for 30s to obtain the upper electrode supporting layer, and meanwhile, realizing the insulating packaging of the thermoelectric material;
(5) depositing a top barrier material and an upper electrode
Sequentially depositing a top barrier layer Ni layer and an upper electrode Cu layer on the surface of the sample obtained in the step (4) by adopting a magnetron sputtering process to obtain the high-density thermoelectric thick film device;
when the top barrier layer Ni layer is deposited, the sputtering pressure is 2Pa, the substrate temperature is 200 ℃, the sputtering power is 50W, and the deposition time is 1 h; and when the upper electrode Cu layer is deposited, the sputtering pressure is 2Pa, the substrate temperature is 200 ℃, the sputtering power is 120W, and the deposition time is 5 h.
The thermoelectric film thickness measuring device of the embodimentThe thermopile density of the part is 496 pairs/cm 2 The bottom electrode at the edge of the device adopts an L-shaped design, and the structure is shown in figure 1. As can be seen in fig. 1f, the geometry of the n-type and p-type thermopiles is 240 μm, arranged adjacent to the same type of thermopile in the x-direction. The processing of the thermopile with the above size is realized by adopting a pulsed laser direct writing technology after depositing a high-aspect-ratio rectangular thermoelectric material as shown in FIG. 1 b; patterning the exposed bottom electrode to form an "L" shape at its edge, as shown in FIG. 1 c; and respectively spin-coating an upper electrode supporting layer, and preparing an upper electrode to obtain the complete thermoelectric device.
As shown in fig. 2, the window distribution of the laser processing thermoelectric material process in the embodiment is shown, and it can be seen from the figure that the dashed frame is a target parameter area, the thermoelectric material in the embodiment can realize continuous micro-groove construction by the window parameter processing, and the micro-groove has smooth bottom, clear edge, and high pattern precision.
As shown in fig. 3, which is a schematic structural diagram of the material processed by the step (2) of processing the integrated pattern structure of the thermoelectric material and the bottom electrode, it can be seen from the diagram that, based on the parameters of the process window, the thermoelectric material is successfully prepared into a square thermopile under the pulsed laser direct writing processing, and the bottom electrode is also successfully patterned, so as to ensure the structural characteristics of the thermoelectric arms of the device in electrical series connection.
As shown in fig. 4, which is a schematic diagram illustrating the detection of the power generation performance of the high-density thick thermoelectric film device in this embodiment, it can be seen from the diagram that as the temperature difference between two ends of the device increases, the output power of the device gradually increases, and under the condition of 80K temperature difference, the output power reaches 0.0375mW, and the output power density reaches 0.15mW cm -2 (ii) a Along with the rise of temperature difference, the output voltage is also improved in a certain linear way, which shows that the internal electricity connection of the thermoelectric device is reliable, and higher output voltage can be realized under large temperature difference, and the voltage reaches more than 45 mV.
Example 2
Example 2 differs from example 1 only in the preparation conditions of the substrate metallization layer, the deposition conditions adopted are Cu 30W, 1.5Pa, 200 ℃, the deposition time is 12h, the power is lower, and the film layer is more dense, as shown in fig. 5 b.
Example 3
Example 3 differs from example 1 only in that the substrate metallization layer is prepared by electrochemical deposition, and the obtained metallization layer is dense and thick, as shown in fig. 5 c.
Example 4
Example 4 differs from example 1 only in the deposition conditions of the thermoelectric material, which are Bi 2 Te 2.7 Se 0.3 The DC sputtering is carried out for 20W, the Te radio frequency sputtering is carried out for 30W, the pressure is 1.5Pa, the temperature is 300 ℃, the deposition is carried out for 3h, the growth is shown as a column shape, and the growth speed is higher, as shown in figure 6 b.
Example 5
Example 5 differs from example 1 only in the deposition conditions of the thermoelectric material, which are Bi 2 Te 3 DC sputtering 10W, Te radio frequency sputtering 8W, 3Pa, 400 ℃, deposition for 10h, the growth of which is shown as a layered structure, the film layer is dense, but the growth speed is slower, as shown in FIG. 6 c.
Example 6
Example 6 is different from example 1 only in the deposition conditions of the thermoelectric material, which are Sb 2 Te 3 The DC sputtering is carried out for 28W, the Te radio frequency sputtering is carried out for 40W, 3Pa and 450 ℃, the deposition is carried out for 5h, the growth is shown as a column shape, and the growth speed is higher, as shown in figure 7 b.
Example 7
Example 7 differs from example 1 only in the processing conditions for the laser direct writing, and the use of an ultrafast laser with a center wavelength of 343nm and a pulse width of 290fs for the pyroelectric material at a single pulse energy density of 690mJ cm -2 The spot overlapping rate is 80%, the line filling space is 15 μm, and the removal efficiency is about 2 μm/time; the energy density of the counter bottom electrode in a single pulse is 5545mJ cm -2 The spot overlapping rate is 90%, the line filling space is 15 μm, and the removal efficiency is 0.8 μm/time.
The invention provides an L-shaped bottom electrode edge structure design, which can realize adjacent arrangement of thermopiles of the same kind in a certain direction, and changes the checkerboard distribution that the thermopiles of the traditional pi-shaped device cannot be arranged adjacently, thereby realizing the deposition of a rectangular thermoelectric pattern with high length-width ratio, and reducing the requirement of patterning precision in the material preparation process, as shown in fig. 8a and 8 b. Meanwhile, the structure is highly matched with the method for processing the micro thermoelectric device by the pulse laser direct writing technology, and the integrated processing of the bottom electrode and the thermoelectric material can be realized. Fig. 8c is a thermopile distribution mode of a conventional micro thermoelectric device, which has a high requirement on patterning precision in a material preparation process, a metal mask method cannot realize small-size thermopile pattern preparation, a photolithography method cannot be compatible with various thermoelectric material preparation processes, and development of the micro thermoelectric device is greatly limited. The L-shaped edge electrode structure provided by the invention successfully reduces the requirements of the material preparation process, is compatible with various preparation means including magnetron sputtering, thermal evaporation, electron beam deposition, electrochemical deposition and the like, and has obvious application value.
The invention provides a method for processing a micro thermoelectric device by adopting a pulse laser direct writing technology, a process window suitable for direct writing processing is obtained by analyzing the effect of ultrafast pulse laser and a thermoelectric material, the non-patterned thermoelectric material and an electrode material are integrally processed based on the window, the processing precision and reliability are improved (as shown in figure 9 a), and the integration level of the device is improved at the same time. As shown in fig. 9b, the thin film type thermoelectric device prepared by the flip chip bonding integration process, compared with fig. 9b, the "L" shaped edge electrode structure design of the present invention can achieve efficient material removal by virtue of high overlapping property of the thermopile and the electrode pattern, the material prepared by the pulse laser direct writing technology has a clear structure and higher precision, and in embodiment 1, the filling density is 496 pairs/cm 2 Fill factor 55.30%; the device filling density which can be realized by the flip chip technology at present is 22 pairs/cm 2 The fill factor was 15.96%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A preparation method of a high-density thermoelectric thick film device based on a pulse laser direct writing technology is characterized by comprising the following steps:
(1) depositing bottom electrode and barrier layer material
Depositing a bottom electrode Cu layer, a barrier layer Ni layer and an Au layer on a clean substrate in sequence in a large area to obtain a metalized substrate material;
(2) depositing high aspect ratio rectangular pattern thermoelectric materials
Sequentially depositing high-aspect-ratio rectangular n-type thermoelectric materials and p-type thermoelectric materials on the metalized substrate obtained in the step (1);
(3) thermoelectric material and bottom electrode pattern structure integrally processed by pulse laser direct writing technology
Placing the sample deposited with the thermoelectric material in the step (2) on an ultrafast pulse laser processing platform, processing the thermoelectric material into a thermopile array by using a pulse laser direct writing technology, then performing high-precision patterning processing on the bottom electrode according to design, constructing electrical connection on the lower surface of the thermopile array, and realizing in-situ integrated processing of thermopiles with different patterns and electrode multilayer structures;
the method comprises the following steps of utilizing a pulse laser direct writing technology to carry out in-situ integrated processing on thermopiles with different patterns and an electrode multilayer structure, and specifically operating the following steps:
fixing the sample on the pulse laser processing platform after depositing the thermoelectric material in the step (2), associating the processing drawing with the sample to be processed by determining the coordinates of three marking points, respectively introducing the processing graphs of the thermoelectric material and the bottom electrode into a computer, wherein the target structure is mainly characterized by a micro-groove, and adopting ultrafast pulse laser with the central wavelength of 343-1064nm and the pulse width of 200fs-500ps to perform single-pulse energy density of 150mJ cm on the thermoelectric material -2 -1810-mJ cm -2 The spot overlapping rate is 10-90%, the line filling space is 5-30 μm, and the removal efficiency is 100 nm/time-3 μm/time; the energy density of the counter bottom electrode in a single pulse is 5000mJ cm -2 -20000mJ cm -2 The overlapping rate of light spots is 30-90%, and the filling distance of lines is 5 μmProcessing under the condition of 30 mu m below zero, wherein the removal efficiency is 100 nm/time to 2 mu m/time, and finally, in-situ integrated processing of the thermopiles with different patterns and the electrode multilayer structure is realized;
(4) preparing an upper electrode supporting layer
Coating a layer of ultraviolet photosensitive resin on the surface of the sample obtained in the step (3), aligning and attaching a photoetching plate with a supporting pattern to the sample, and curing under ultraviolet irradiation to obtain an upper electrode supporting layer and realize the insulating packaging of the thermoelectric material;
(5) depositing a top barrier material and an upper electrode
And (5) sequentially depositing a top barrier layer Au layer, a top barrier layer Ni layer and an upper electrode Cu layer on the surface of the sample obtained in the step (4) according to the shape of a preset upper electrode, and preparing a patterned upper electrode to obtain the high-density thermoelectric thick film device.
2. The method for preparing a high-density thermoelectric thick film device based on the pulsed laser direct writing technology according to claim 1, wherein in the step (1), the method for depositing the bottom electrode Cu layer and the barrier layer Ni layer and Au layer is any one of magnetron sputtering, thermal evaporation, electron beam evaporation or electrochemistry.
3. The method for preparing the high-density thermoelectric thick film device based on the pulse laser direct writing technology according to claim 2, wherein when the bottom electrode Cu layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100 ℃ -400 ℃, the sputtering power is 20-200W, and the deposition time is 1-12 h;
when the barrier layer Ni layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-400 ℃, the sputtering power is 10W-100W, and the deposition time is 0.5h-8 h;
and when the Au layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-400 ℃, the sputtering power is 10W-50W, and the deposition time is 10min-1 h.
4. The method for preparing a high-density thermoelectric thick film device based on the pulse laser direct writing technology according to claim 1, characterized by comprising the steps ofIn the step (2), the n-type thermoelectric material is Bi 2 Te 3 、Bi 2 Te 2.7 Se 0.3 Any one of the p-type thermoelectric materials is Sb 2 Te 3 、Bi 0.5 Sb 1.5 Te 3 Either one of them.
5. The method for preparing a high-density thermoelectric thick film device based on the pulsed laser direct writing technology according to claim 1, wherein in the step (2), the method for depositing the thermoelectric material is any one of magnetron sputtering, thermal evaporation, electron beam evaporation, electrochemical deposition or selective laser melting method.
6. The method for preparing the high-density thermoelectric thick film device based on the pulse laser direct writing technology according to claim 4, characterized in that direct current sputtering of Bi is adopted 2 Te 3 Or Bi 2 Te 2.7 Se 0.3 Depositing the n-type thermoelectric material by a radio-frequency sputtering Te double-target co-sputtering method; the direct current sputtering pressure is 0.5Pa-3Pa, the substrate temperature is 100 ℃ to 480 ℃, the direct current sputtering power is 5W to 50W, the radio frequency sputtering power is 5W to 50W, and the deposition time is 1h to 24 h;
by sputtering with DC Sb 2 Te 3 Or Bi 0.5 Sb 1.5 Te 3 Depositing the p-type thermoelectric material by a radio-frequency sputtering Te double-target co-sputtering method; the direct current sputtering pressure is 0.5Pa-3Pa, the substrate temperature is 100 ℃ to 500 ℃, the direct current sputtering power is 5W to 50W, the radio frequency sputtering power is 5W to 50W, and the deposition time is 1h to 24 h.
7. The method for preparing a high-density thermoelectric thick film device based on the pulse laser direct writing technology according to claim 1, wherein in the step (4), the specific preparation method of the upper electrode supporting layer is as follows:
coating ultraviolet photosensitive resin on the surface of a sample in a yellow light room, spin-coating for 3-15 min under the condition that the rotating speed is 3000-8000 rpm, drying for 5-20 min at 150 ℃, aligning and bonding a photoetching plate with a supporting pattern with the sample, exposing for 1-3 min under ultraviolet light, placing in an acetone solution, and ultrasonically cleaning for 10-90 s to obtain the upper electrode supporting layer, and meanwhile, realizing the insulating packaging of the thermoelectric material.
8. The method for preparing a high-density thermoelectric thick film device based on the pulsed laser direct writing technology according to claim 1, wherein in the step (5), the method for depositing the top barrier layer Au layer, the Ni layer and the upper electrode Cu layer is any one of magnetron sputtering, thermal evaporation, electron beam evaporation, electrochemical deposition or spraying;
when the Au layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-400 ℃, the sputtering power is 10W-50W, and the deposition time is 10min-1 h;
when the top barrier layer Ni layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-300 ℃, the sputtering power is 10W-100W, and the deposition time is 0.5h-8 h;
when the upper electrode Cu layer is deposited, the sputtering pressure is 1Pa-5Pa, the substrate temperature is 100-300 ℃, the sputtering power is 20-200W, and the deposition time is 1-12 h.
9. The high-density thermoelectric thick film device obtained by the preparation method of the high-density thermoelectric thick film device based on the pulse laser direct writing technology according to claim 1, wherein the edge bottom electrode of the thermoelectric thick film device is designed to be L-shaped, and the same type of thermopiles can realize the arrangement and adjacent arrangement, so that the laser direct writing in-situ processing adaptability of different patterned structures of a multilayer material is improved.
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