CN112458541A - Surface treating agent and method for n-type bismuth telluride-based thermoelectric material - Google Patents
Surface treating agent and method for n-type bismuth telluride-based thermoelectric material Download PDFInfo
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Abstract
The invention discloses a surface treating agent for an n-type bismuth telluride-based thermoelectric material, which comprises a roughening liquid and a dedusting liquid; the coarsening liquid comprises the following components in percentage by volume: 5-20% of phosphoric acid, 5-30% of nitric acid, 5-50% of glacial acetic acid, 5-20% of sulfuric acid and the balance of water; the ash removing liquid comprises a solvent and a solute, wherein the solvent comprises the following components in percentage by volume: 5-20% of nitric acid, 5-20% of hydrochloric acid and the balance of water, wherein the solute is potassium bromate and the concentration is 1-10 g/L. When the surface treating agent is used, the roughening solution and the dedusting solution are used in a matched mode, the clean n-type bismuth telluride base wafer is firstly immersed into the roughening solution and then immersed into the dedusting solution, pretreatment can be completed, and then metallization connection is directly carried out in an electroplating or chemical plating mode. The surface treatment agent and the method for the n-type bismuth telluride-based thermoelectric material provided by the invention have the advantages that the n-type bismuth telluride-based wafer has higher surface activity before electroplating, higher coating bonding strength is favorably obtained, the wafer is not physically damaged, and the product percent of pass is improved.
Description
Technical Field
The invention relates to the field of thermoelectric devices, in particular to a surface treatment agent and a surface treatment method for an n-type bismuth telluride-based thermoelectric material.
Background
Energy is one of the power of modern society and economic development, and as non-renewable energy is continuously consumed, new energy technology is widely concerned by people. Among new energy technologies, the thermoelectric technology is more and more emphasized by people as a technology capable of realizing direct interconversion between heat energy and electric energy, and a device manufactured by utilizing the thermoelectric effect of a thermoelectric material has two functions of power generation and refrigeration, and has important application in a plurality of fields such as the electronic industry, the biomedical industry, the space military, the aerospace and the like. At present, the whole thermoelectric device develops towards miniaturization, the manufacturing process of the conventional large-size thermoelectric device cannot meet the manufacturing requirement of the miniature thermoelectric device, particularly, in the aspect of surface treatment, the most critical part of the whole thermoelectric device is the surface metallization process of a thermoelectric material, the quality of coating combination not only influences the interface bonding strength of the device, but also influences contact resistance and contact thermal resistance, and further influences the power generation performance, the refrigeration performance and the reliability of the whole device.
The surface treatment of the traditional n-type bismuth telluride-based wafer is divided into two stages, namely an electroplating pretreatment stage and an electroplating treatment stage. The traditional mode of electroplating pretreatment is sand blasting combined with electric arc spraying nickel, the sand blasting of a physical method can improve the surface roughness of a sheet, the electric arc spraying nickel plays a role of pre-deposition and is convenient for the subsequent electroplating treatment stage, the treatment mode is generally used for manufacturing a conventional thermoelectric device, the thickness of an n-type bismuth telluride-based wafer required by the conventional thermoelectric device exceeds 1mm, and for a miniature thermoelectric device, the thickness of the n-type bismuth telluride-based wafer used by the conventional thermoelectric device is less than 1 mm. By adopting the traditional surface treatment mode, a high-pressure environment can be generated in the sand blasting process, a high-temperature environment is generated in the electric arc spraying process, the n-type bismuth telluride-based wafer is easy to damage, the yield and the production efficiency are reduced, and meanwhile, the production link and the production cost are increased. Therefore, the development of a new surface treatment method for n-type bismuth telluride-based wafers is urgent.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a surface treatment agent and a method for an n-type bismuth telluride-based thermoelectric material aiming at the defects in the prior art, so that an n-type bismuth telluride-based wafer has higher surface activity before electroplating, higher coating bonding strength is favorably obtained, no physical damage is caused to the wafer, and the product percent of pass is improved.
The technical scheme adopted by the invention for solving the problems is as follows:
a surface treatment method of an n-type bismuth telluride-based thermoelectric material comprises the following steps:
preparing a roughening solution of the n-type bismuth telluride-based wafer, wherein the roughening solution comprises 5-20% of phosphoric acid (by volume), 5-30% of nitric acid (by volume), 5-50% of glacial acetic acid (by volume), 5-20% of sulfuric acid (by volume) and the balance of water;
preparing an ash removal solution for the n-type bismuth telluride-based wafer, wherein the ash removal solution comprises 5-20% by volume of nitric acid, 5-20% by volume of hydrochloric acid, 1-10 g/L of potassium bromate and the balance of water;
immersing the clean n-type bismuth telluride-based wafer into a roughening solution for roughening;
then immersing the coarsened n-type bismuth telluride-based wafer into a dedusting liquid for dedusting;
the n-type bismuth telluride-based wafer after ash removal is subjected to surface treatment, and can be directly subjected to metallization connection in an electroplating or chemical plating mode.
According to the scheme, the clean p-type bismuth telluride-based wafer is washed by water and solvents such as acetone, absolute ethyl alcohol and the like in advance, and dirt or impurities such as grease on the surface are removed.
According to the scheme, the mass percentage concentration of the phosphoric acid is 80-90%; the mass percentage concentration of the nitric acid is 60-70%; the mass percentage concentration of the acetic acid is more than 95 percent; the mass percentage concentration of the sulfuric acid is more than 95%, and the mass percentage concentration of the hydrochloric acid is 30-40%.
Preferably, the n-type bismuth telluride-based wafer roughening solution, the phosphoric acid 10% (volume), the nitric acid 30% (volume), the glacial acetic acid 50% (volume), and the sulfuric acid 10% (volume).
Preferably, the temperature required by coarsening the n-type bismuth telluride-based wafer is 25 ℃, and the coarsening time is 5 min.
Preferably, the n-type bismuth telluride-based wafer ash removing liquid comprises 20% by volume of nitric acid, 20% by volume of hydrochloric acid, 5g/L of potassium bromate and the balance of water.
Preferably, the temperature required by the ash removal of the n-type bismuth telluride-based wafer is 25 ℃, and the ash removal time is 5 min.
Based on the above, the present invention may be modified, replaced or changed in various forms according to the common technical knowledge and means in the field without departing from the basic technical idea of the present invention. For example, the preparation method of the n-type bismuth telluride-based wafer comprises zone melting, powder metallurgy and the like.
In a micro thermoelectric device, the interface bonding strength, the contact resistance and the contact thermal resistance between a thermoelectric material and a metal plating layer influence the service performance and the reliability of the device.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has no physical damage to the n-type bismuth telluride-based wafer, improves the surface roughness and the surface activity of the n-type thermoelectric material, is beneficial to obtaining higher interface bonding strength with a nickel layer, effectively reduces the interface contact resistance and the interface contact thermal resistance, and optimizes the service life, the cycle frequency and the performance of the thermoelectric device;
2. the solution is simple and convenient to prepare and convenient to operate, the n-type bismuth telluride-based wafer contains selenium, the ash removing liquid can remove the enriched selenium remained on the surface of the wafer after coarsening, and the solution can be managed through regular analysis and detection and is suitable for large-scale production.
3. The surface treatment method provided by the invention has no physical damage to the wafer, improves the product percent of pass, and can reduce the production links and flows of electric arc spraying and reduce the production cost.
Drawings
FIG. 1 is a photograph of the surface-pretreated n-type bismuth telluride-based wafer obtained in step 2) of example 1;
FIG. 2 is a photograph of the n-type bismuth telluride-based wafer obtained in step 3) of example 1 after nickel plating and gold plating;
FIG. 3 shows a micro thermoelectric device fabricated in step 4) of example 1.
FIG. 4 shows the surface morphology of the n-type bismuth telluride-based SEM used in step 1) of example 2.
FIG. 5 shows the surface morphology of the n-type bismuth telluride-based SEM after the chemical treatment of the step 2) in the embodiment 2.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
In the following examples, phosphoric acid was used in AR purity at 85%; the nitric acid AR is analyzed and pure, and the concentration is 65-68%; the purity of the glacial acetic acid is 99.7 percent; the mass fraction of concentrated sulfuric acid is 98.3 percent; concentrated hydrochloric acid is AR analytically pure, and the content is 36-38%.
Example 1
A surface treatment method of an n-type bismuth telluride-based thermoelectric material comprises the following steps:
1) a round n-type bismuth telluride-based wafer with the diameter of 30mm and the thickness of 0.5mm is washed by acetone to remove surface pollutants, dehydrated by absolute ethyl alcohol, dried and immersed into a roughening solution (the composition of the roughening solution is 15 percent (volume) of phosphoric acid, 30 percent (volume) of nitric acid, 45 percent (volume) of glacial acetic acid and 20 percent of sulfuric acid), the roughening temperature is 25 ℃, and the roughening time is 5 min;
2) transferring the n-type bismuth telluride-based wafer roughened in the step 1) into an ash removal liquid (the ash removal liquid comprises 15% by volume of nitric acid, 20% by volume of hydrochloric acid, 10g/L of potassium bromate and the balance of water) for ash removal treatment, wherein the ash removal temperature is 25 ℃, and the ash removal time is 10 min;
3) pre-electroplating the n-type bismuth telluride-based wafer subjected to ash removal in the step 2) in electroplating solution with nickel, and then performing chemical nickel plating and gold electroplating, wherein,
specific conditions for nickel electroplating are as follows: 200g/L of nickel sulfate; 45g/L of nickel chloride; boric acid 45g/L, 8000# A semi-bright nickel open-cylinder agent 10mL/L, 8000# B semi-bright nickel supplement 0.8mL/L, low foam wetting agent 1mL/L, pH 4.0, temperature 55 ℃, cathode current density 3A/dm2，3min；
The specific conditions of electroless nickel plating are as follows: 0.095mol/L of nickel sulfate, 0.227mol/L of sodium hypophosphite, 0.135mol/L of succinic acid, 0.179mol/L of malic acid, pH 6, temperature 90 ℃, 40 min;
the specific conditions for gold electroplating are as follows: 15g/L of potassium aurocyanide, 35g/L of citric acid, 55g/L of potassium citrate, 4.5 of pH, 50 ℃ of temperature and 1.3A/dm of cathode current density2，10min；
4) Performing one 4.7 multiplied by 4.9mm process on the nickel-plated and gold-plated n-type bismuth telluride-based wafer obtained in the step 3)2Assembling of micro-thermoelectric devices and testing thereofCold property.
FIG. 1 is a photograph of the surface-pretreated n-type bismuth telluride-based wafer obtained in step 2) of example 1, in which the exposed fresh surface of the material can be seen;
FIG. 2 is a photograph of the n-type bismuth telluride-based wafer obtained in step 3) of example 1 after nickel plating and gold plating;
FIG. 3 is a view showing a micro thermoelectric device manufactured in step 4) of example 1;
table 1 shows the refrigerating performance of the micro thermoelectric device manufactured in step 4) of example 1, and the maximum refrigerating temperature difference can reach 62.8 ℃.
Table 2 shows the refrigeration performance of the micro thermoelectric device fabricated in the conventional manner. The preparation process of the traditional mode is sand blasting, electric arc spraying, nickel electroplating, chemical nickel plating and chemical gold plating, namely, the surface treatment is not carried out by adopting the steps (1) and (2) in the embodiment 1, but a pretreatment mode of sand blasting and electric arc spraying nickel is adopted (the sand blasting adopts 320-mesh spherical glass bead abrasive with the pressure of 0.05MPa, and the electric arc spraying process adopts a nickel wire with the diameter of 1.2mm, the working voltage is 25V, the working current is 90A, the air pressure is 0.65MPa and the spray gun voltage is 9V), and the subsequent treatment processes are consistent.
Comparing table 1 and table 2, it can be seen that the resistance of the device manufactured by the conventional method is increased by 0.38 Ω, mainly due to the contact resistance, and the maximum refrigeration temperature difference is 58 ℃ and is reduced by 4.8 ℃. Therefore, the surface treatment method of the invention effectively reduces the interface contact resistance on the premise of not damaging the integrity of the wafer, which shows that the interface contact performance of the n-type bismuth telluride-based wafer after surface treatment and a subsequent nickel layer is improved.
TABLE 1
TABLE 2
Example 2
A surface treatment method of an n-type bismuth telluride-based thermoelectric material comprises the following steps:
1) a round n-type bismuth telluride-based wafer with the diameter of 30mm and the thickness of 0.5mm is washed by acetone to remove surface pollutants, and then is immersed into a roughening solution (the composition of the roughening solution is 10 percent (volume) of phosphoric acid, 30 percent (volume) of nitric acid, 50 percent (volume) of glacial acetic acid and 10 percent (volume) of sulfuric acid) after being washed by water, the roughening temperature is 25 ℃, and the roughening time is 5 min;
2) transferring the n-type bismuth telluride-based wafer roughened in the step 1) into an ash removal liquid (the ash removal liquid comprises 20% by volume of nitric acid, 20% by volume of hydrochloric acid, 5g/L of potassium bromate and the balance of water) for ash removal treatment, wherein the ash removal temperature is 25 ℃, and the ash removal time is 5 min;
3) pre-electroplating the n-type bismuth telluride-based wafer subjected to ash removal in the step 2) in an electroplating solution for nickel, and then performing chemical nickel plating and gold electroplating (the specific conditions of nickel electroplating, chemical nickel plating and gold electroplating are the same as those in the example 1);
4) performing one 4.7 multiplied by 4.9mm process on the nickel-plated and gold-plated n-type bismuth telluride-based wafer obtained in the step 3)2Assembling the micro thermoelectric device and testing the cooling performance of the micro thermoelectric device.
FIG. 4 shows the surface morphology of the n-type bismuth telluride-based SEM used in step 1) of example 2, in which significant cutting traces are visible;
FIG. 5 shows the surface morphology of the chemically treated n-type bismuth telluride-based SEM material obtained in step 2) of example 2, showing that the cutting traces disappear and the material is exposed on the fresh surface;
table 3 shows the refrigerating performance of the micro thermoelectric device manufactured in step 4) of example 1, with a maximum refrigerating temperature difference of 62 ℃.
TABLE 3
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (6)
1. A surface treating agent of an n-type bismuth telluride-based material is characterized by comprising a roughening liquid and an ash removing liquid; the coarsening liquid comprises the following components in percentage by volume: 5-20% of phosphoric acid, 5-30% of nitric acid, 5-50% of acetic acid, 5-20% of sulfuric acid and the balance of water;
the ash removing liquid comprises a solvent and a solute; wherein, the solvent comprises the following components in percentage by volume: 5-20% of nitric acid, 5-20% of hydrochloric acid and the balance of water; the solute is potassium bromate, and the concentration is 1-10 g/L.
2. The surface treatment agent of an n-type bismuth telluride-based material as claimed in claim 1, wherein the mass percentage concentration of the phosphoric acid is 80-90%; the mass percentage concentration of the nitric acid is 60-70%; the mass percentage concentration of the acetic acid is more than 95 percent; the mass percentage concentration of the sulfuric acid is more than 95%, and the mass percentage concentration of the hydrochloric acid is 30-40%.
3. The surface treatment agent of an n-type bismuth telluride-based material as claimed in claim 1, wherein the composition of the roughening liquid comprises, in volume percent: 10-20% of phosphoric acid, 20-30% of nitric acid, 40-50% of glacial acetic acid, 10-20% of sulfuric acid and the balance of water;
the ash removing liquid comprises a solvent and a solute; wherein, the solvent comprises the following components in percentage by volume: 15-20% of nitric acid, 15-20% of hydrochloric acid and the balance of water; the solute is potassium bromate, and the concentration is 5-10 g/L.
4. A surface treatment method of an n-type bismuth telluride-based material is characterized in that the surface treatment agent of claim 1 is adopted to pretreat an n-type bismuth telluride-based wafer, firstly, the clean n-type bismuth telluride-based wafer is immersed into a roughening solution and then immersed into an ash removal solution to finish the pretreatment, and then, the metallization connection is directly carried out in an electroplating or chemical plating mode.
5. The surface treatment method of an n-type bismuth telluride-based material as claimed in claim 4, wherein the n-type bismuth telluride-based wafer is immersed in a roughening solution at a temperature of 25 to 30 ℃ for a roughening time of 1 to 10 min.
6. The surface treatment method of an n-type bismuth telluride-based material as claimed in claim 4, wherein the n-type bismuth telluride-based wafer treated with the roughening solution is immersed in the ash removing solution at a temperature of 25-30 ℃ for 1-10 min.
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| CN202011238922.8A CN112458541B (en) | 2020-11-09 | 2020-11-09 | Surface treating agent and method for n-type bismuth telluride-based thermoelectric material |
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| CN101701348A (en) * | 2009-06-26 | 2010-05-05 | 上海申和热磁电子有限公司 | Coarsening solution for electroplating pretreatment on surface of semiconductor N\P type cooling wafer and related electroplating pretreatment process |
| TW201607087A (en) * | 2014-08-04 | 2016-02-16 | 中國鋼鐵股份有限公司 | Method of roughening surface of thermoelectric material |
| CN107227475A (en) * | 2017-05-22 | 2017-10-03 | 广东省稀有金属研究所 | A kind of surface treatment method of bismuth telluride-base thermoelectric material chip |
| CN107723767A (en) * | 2017-09-29 | 2018-02-23 | 广东先导稀材股份有限公司 | The surface treatment method of tellurium bismuthino chip |
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| TW201607087A (en) * | 2014-08-04 | 2016-02-16 | 中國鋼鐵股份有限公司 | Method of roughening surface of thermoelectric material |
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| CN114561257A (en) * | 2021-11-15 | 2022-05-31 | 杭州大和热磁电子有限公司 | Surface treating agent for bismuth telluride and using method thereof |
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