CN112979342A - Thermoelectric material bismuth telluride surface micro-channel adjusting method and surface nickel plating method - Google Patents
Thermoelectric material bismuth telluride surface micro-channel adjusting method and surface nickel plating method Download PDFInfo
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- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5144—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
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Abstract
The invention provides a surface treatment process before electroplating of a bismuth telluride base mother material, which comprises the steps of carrying out surface degreasing treatment on bismuth telluride, then preparing bismuth-based Bi-UN-901 organic complex mother liquor, growing a layer of bismuth-based metal organic framework film (Bi-MOF) on a bismuth telluride base body by selecting an in-situ growth mode, and finally entering a nickel plating process The performance is stable.
Description
Technical Field
The invention belongs to the field of semiconductor device design and manufacture, and particularly relates to a thermoelectric material bismuth telluride surface micro-channel adjusting method and a surface nickel plating method.
Background
The semiconductor thermoelectric material can realize the conversion of electric energy and heat energy, and the prepared semiconductor refrigerating device is mainly applied to the fields of accurate temperature reduction and control, thermoelectric generation, industrial waste heat power generation and the like of electronic devices.
In the packaging process of the semiconductor refrigeration device, the semiconductor bismuth telluride-based thermoelectric material is connected with the metallized ceramic substrate by using a welding or bonding method, so that the diffusion of the solder or the metallized atoms of the ceramic substrate to the bismuth telluride base material is prevented, and the thermoelectric property of the bismuth telluride and the reliability of a connection interface (joint) in high-temperature service are influenced. Therefore, an electroplating method is often used to prepare a nickel diffusion barrier layer on the surface of bismuth telluride.
Before the bismuth telluride base parent material is used for preparing the nickel diffusion blocking layer, surface micro-channel treatment needs to be carried out on the bismuth telluride base parent material, the binding force between the bismuth telluride base parent material and the nickel diffusion blocking layer obtained by different micro-channel adjustment treatment methods is different, and the binding force is an important influence factor for ensuring that the nickel diffusion blocking layer and the bismuth telluride base parent material are firmly bound and do not crack or fall off under long-term cold and hot work of a semiconductor device.
Therefore, in order to improve the bonding force between the bismuth telluride base mother material and the nickel diffusion barrier layer, ensure the stable work of the semiconductor refrigerator and prolong the service life, the development of a method for adjusting the micro-channels on the surface of the bismuth telluride is very necessary.
Disclosure of Invention
The invention aims to provide a bismuth telluride surface micro-channel adjusting method and a surface nickel plating method, which can improve the bonding strength between a thermoelectric material bismuth telluride matrix and a nickel plating layer and reduce the stress residue on the plating layer and the bismuth telluride surface.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for adjusting micro channels on the surface of a thermoelectric material bismuth telluride comprises the following steps,
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding Bi (NO)3)·5H2Mixing O and trifluoroacetic acid in a dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding a 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is a bismuth-based organic metal framework complex mother solution, and the yellow suspension in the suspension contains a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing ligands which are not bonded by ultrasound, repeating the steps, growing a layer of bismuth-based metal organic framework film on the bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property.
The method for adjusting the micro channels on the surface of the thermoelectric material bismuth telluride comprises the following steps,
a. preparation of bismuth-based organometallic framework complex mother liquor
Will be 0.16-02mmol of Bi (NO)3)·5H2Mixing O and 5.5-6 mmol of trifluoroacetic acid in 10-20 ml of dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding 0.05-0.1 mmol of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and 10-20 ml of dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, and then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is bismuth-based organic metal framework complex mother liquor, and yellow suspended matters in the suspension contain a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing ligands which are not bonded by ultrasound, repeating the steps, growing a layer of bismuth-based metal organic framework film on the bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property.
The frequency of ultrasonic treatment in the step a is 20-30 kHz, and the frequency of ultrasonic treatment in the step b is 20-30 kHz.
The bismuth telluride substrate is a thin wafer with the diameter of 30mm and the thickness of 1-2 mm.
And in the step b, the oil removing treatment is to put the bismuth telluride matrix into NaOH solution with the concentration of 30-50 g/L, the oil removing temperature is 50-65 ℃, and the oil removing time is 20-30 min.
A method for plating nickel on the surface of thermoelectric material bismuth telluride comprises the following steps,
(1) surface treatment before plating:
putting the bismuth telluride matrix into NaOH solution for chemical degreasing, removing oil stains on the surface of the bismuth telluride matrix, washing with hot water at the temperature of 55-80 ℃ and removing residues on the surface of the bismuth telluride matrix;
(2) and (3) micro-channel adjustment and nickel plating on the surface of the bismuth telluride matrix:
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding Bi (NO)3)·5H2Mixing O and trifluoroacetic acid in a dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding a 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is a bismuth-based organic metal framework complex mother solution, and the yellow suspension in the suspension contains a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing ligands which are not bonded by ultrasound, repeating the steps, growing a layer of bismuth-based metal organic framework film on a bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property;
c. nickel plating
Putting the bismuth telluride matrix with the Bi-MOF film growing on the surface into a nickel plating bath, wherein the nickel plating bath contains 150-300 g/L of NiSO4·7H2O, 30-35 g/L boric acid, 5-10 g/L NaCl, 30-80 g/L sodium sulfate, 0.05-0.1 g/L sodium dodecyl sulfate, electroplating temperature of 15-50 ℃, and cathode current density of 0.8-1.5A/dm2Carrying out nickel plating treatment on the bismuth telluride matrix under the condition that the PH value is 3-4.5;
(3) and (3) post-treatment: and (3) washing the nickel-plated bismuth telluride treated in the step (2) with deionized water to be neutral, drying at the temperature of 100-150 ℃, and taking out to obtain a finished product.
A method for plating nickel on the surface of thermoelectric material bismuth telluride comprises the following steps,
(1) surface treatment before plating:
putting the bismuth telluride matrix into 30-50 g/L NaOH solution for chemical oil removal, wherein the oil removal temperature is 50-65 ℃, the oil removal time is 20-30 min, removing oil stains on the surface of the bismuth telluride matrix, and then washing with hot water at 55-80 ℃ to remove residues on the surface of the bismuth telluride;
(2) and (3) micro-channel adjustment and nickel plating on the surface of the bismuth telluride matrix:
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding 0.16 to 0.2mmol of Bi (NO)3)·5H2Mixing O and 5.5-6 mmol of trifluoroacetic acid in 10-20 ml of dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding 0.05-0.1 mmol of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and 10-20 ml of dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, and then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is bismuth-based organic metal framework complex mother liquor, and yellow suspended matters in the suspension contain a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing ligands which are not bonded by ultrasound, repeating the steps, growing a layer of bismuth-based metal organic framework film on the bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a propertyA stable porous foamy surface structure;
c. nickel plating
Putting the bismuth telluride matrix with the Bi-MOF film growing on the surface into a nickel plating bath, wherein the nickel plating bath contains 150-300 g/L of NiSO4·7H2O, 30-35 g/L boric acid, 5-10 g/L NaCl, 30-80 g/L sodium sulfate, 0.05-0.1 g/L sodium dodecyl sulfate, electroplating temperature of 15-50 ℃, and cathode current density of 0.8-1.5A/dm2Carrying out nickel plating treatment on the bismuth telluride matrix under the condition that the PH value is 3-4.5;
(3) and (3) post-treatment: and (3) washing the nickel-plated bismuth telluride processed in the step (2) with deionized water to be neutral, drying at the temperature of 120 ℃, and taking out to obtain a finished product.
The frequency of ultrasonic treatment in the step a is 20-30 kHz, and the frequency of ultrasonic treatment in the step b is 20-30 kHz.
The bismuth telluride substrate is a thin wafer with the diameter of 30mm and the thickness of 1-2 mm.
The invention discloses a method for adjusting micro channels on the surface of bismuth telluride, which is characterized in that a Bi-UN-901MOF film is grown on the surface of the bismuth telluride, the MOF is a metal organic framework compound, the uniform and adjustable size of channels can be realized due to the planar topological structure of the Bi-UN-901 on the surface of the bismuth telluride, and a specific foamy channel structure is left after the organic structure disappears after high-temperature evaporation.
Compared with the traditional surface treatment process (oil removal, coarsening, activation and nickel electroplating) before bismuth telluride plating, the invention has less process steps for the bismuth telluride surface treatment process, in the invention, a Bi-UN-901MOF film is grown on the bismuth telluride surface, MOF is a metal organic framework compound, the pore canal size can be microscopically regulated and controlled through different organic framework structures, after high-temperature evaporation, the organic structure disappears to leave a specific foam pore canal structure, nickel atoms enter the foam pore canal structure, a reaction layer is formed between the foam pore canal structure and Te atoms in the bismuth telluride, a nickel diffusion barrier layer in the reaction layer and a bismuth telluride base material are mainly linked through Bi-Bi bonds, Bi-Te bonds, Ni-Te bonds and Ni-Ni bonds of Bi and Te in the Bi-UN-901 and Bi and the Bi-Te bonds and the Ni-Te bonds in the bismuth telluride base material, so as to ensure the bonding strength of the nickel diffusion barrier layer and the bismuth telluride, meanwhile, the planar topological structure of Bi-UN-901 on the surface of bismuth telluride can realize uniform pore channels and adjustable size, so that the surface of the obtained nickel diffusion barrier layer is compact and low in porosity, and the foamed organic structure of Bi-UN-901 can effectively absorb stress residue caused by the difference of linear expansion coefficients of the surfaces of nickel and bismuth telluride, thereby finally achieving the purposes of improving the bonding strength of the surfaces of nickel and bismuth telluride and reducing the stress residue.
By adopting the surface treatment process before electroplating of the bismuth telluride base parent metal, the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity of topological structures, tailorability and the like of Bi-MOF can be fully utilized, so that the obtained nickel coating has a smooth surface, a compact structure, low porosity and strong binding force with a matrix, various index requirements of the electroplating process are met, the bismuth telluride can work reliably in a semiconductor refrigerator, and the refrigerator is guaranteed to work stably, have long service life and have stable performance.
Drawings
FIG. 1 is a schematic diagram of a structure obtained by electroplating nickel after surface treatment of bismuth telluride in the prior art.
FIG. 2 is a schematic view of the chemical bond at the junction of the nickel diffusion barrier layer and the bismuth telluride-based base material.
FIG. 3 is a schematic diagram of the structure of an MOF (Metal-Organic-Framework) membrane, wherein Metal atoms are Framework nodes, and Organic complexes are Framework supports.
FIG. 4 is a 1,3,6, 8-tetrakis (4-carboxyphenyl) pyrene organic linker.
FIG. 5 shows Bis6And (4) a metal node.
FIG. 6 shows a Bi-UN-901 Metal-Organic Framework (Metal-Organic-Framework) topology.
FIG. 7 shows the topology of the Bi-UN-901 plane direction.
FIG. 8 is a schematic diagram of the structure of a diffusion barrier layer of bismuth telluride and nickel obtained after the adjustment of micro channels on the surface of bismuth telluride.
FIG. 9 is a schematic view of the chemical bond at the junction between the nickel diffusion barrier layer treated by nickel plating after the adjustment of the micro channels on the surface of bismuth telluride and the bismuth telluride-based base material.
Wherein 1 is the surface of bismuth telluride; and 2 is a nickel diffusion barrier layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
A method for adjusting micro channels on the surface of a thermoelectric material bismuth telluride comprises the following steps,
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding 0.16 to 0.2mmol of Bi (NO)3)·5H2Mixing O and 5.5-6 mmol of trifluoroacetic acid in 10-20 ml of dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding 0.05-0.1 mmol of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and 10-20 ml of dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, and then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is bismuth-based organic metal framework complex mother liquor, and yellow suspended matters in the suspension contain a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing the ligand which is not bonded by ultrasonic,and repeating the steps to grow a layer of bismuth-based metal organic framework film on the bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable properties.
A method for plating nickel on the surface of thermoelectric material bismuth telluride comprises the following steps,
(1) surface treatment before plating:
putting the bismuth telluride matrix into 30-50 g/L NaOH solution for chemical oil removal, wherein the oil removal temperature is 50-65 ℃, the oil removal time is 20-30 min, removing oil stains on the surface of the bismuth telluride matrix, and then washing with hot water at 55-80 ℃ to remove residues on the surface of the bismuth telluride matrix;
(2) and (3) micro-channel adjustment and nickel plating on the surface of the bismuth telluride matrix:
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding 0.16 to 0.2mmol of Bi (NO)3)·5H2Mixing O and 5.5-6 mmol of trifluoroacetic acid in 10-20 ml of dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding 0.05-0.1 mmol of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and 10-20 ml of dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, and then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is bismuth-based organic metal framework complex mother liquor, and yellow suspended matters in the suspension contain a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing the ligand which is not bonded by ultrasonic, repeating the steps, and growing a layer of bismuth-based metal organic on the bismuth telluride matrixThe framework film is characterized in that the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable properties.
c. Nickel plating
Putting the bismuth telluride matrix with the Bi-MOF film growing on the surface into a nickel plating bath, wherein the nickel plating bath contains 150-300 g/L of NiSO4·7H2O, 30-35 g/L boric acid, 5-10 g/L NaCl, 30-80 g/L sodium sulfate, 0.05-0.1 g/L sodium dodecyl sulfate, electroplating temperature of 15-50 ℃, and cathode current density of 0.8-1.5A/dm2Carrying out nickel plating treatment on the bismuth telluride matrix under the condition that the PH value is 3-4.5;
(3) and (3) post-treatment: and (3) washing the nickel-plated bismuth telluride treated in the step (2) with deionized water to be neutral, drying at the temperature of 100-150 ℃, and taking out to obtain a finished product.
The frequency of ultrasonic treatment in the step a is 20-30 kHz, and the frequency of ultrasonic treatment in the step b is 20-30 kHz.
The reagents used in the invention are all analytical pure reagents.
Example 1
The process for plating the nickel on the thermoelectric material bismuth telluride of the refrigerating plate in the semiconductor refrigerating device comprises a surface treatment process before plating, a nickel plating process and a post-treatment process. In the embodiment, the thermoelectric material needing nickel plating adopts a bismuth telluride sheet with the diameter of 30mm, and the surface electroplating process of the material requires to obtain a plating layer with strong bonding force, smooth surface and low porosity.
Surface treatment process before plating: firstly, performing surface degreasing treatment on the bismuth telluride matrix. And (2) putting the bismuth telluride matrix into a NaOH solution with the concentration of 45g/L, carrying out chemical degreasing at the degreasing temperature of 50 ℃ for 25min, removing oil stains on the surface of the bismuth telluride, and then washing with hot water at the temperature of 65 ℃ to flush out residual degreasing liquid on the surface.
Then, a bismuth-based organic complex mother liquor (Bi-UN-901) was prepared. Adding 0.2mmol of Bi (NO)3)·5H2O is mixed with 5.5mmol of trifluoroacetic acid (TFA) in 15ml of Dimethylformamide (DMF) to form a MOF metal salt solution, which is heated at 100 ℃ for 1h and then cooledCool to room temperature 25 ℃. Adding 40ml of 1,3,6, 8-tetra-p-benzoic acid with the concentration of 0.1mmol/l and 15ml of dimethylformamide solution (DMF) into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution at 25kHz for 10min, and preserving the heat in an oven at 100 ℃ for 8h to obtain a yellow suspension, wherein the yellow suspension in the liquid contains a Bi-UN-901 metal organic framework topological structure, and the obtained yellow suspension is a bismuth-based organic metal framework complex mother liquor (Bi-UN-901).
Growing a bismuth-based metal organic framework film (Bi-MOF) in situ on a bismuth telluride matrix. Heating deoiled bismuth telluride matrix at 180 deg.C, and preparing bismuth-based organic metal skeleton complex mother liquor [ Bi (S) ]2CNC4H8)3]2Dropwise adding the bismuth telluride on a high-temperature matrix, and quickly volatilizing the dropwise added mother liquor in a high-temperature environment to obtain Bi in the ligand3+Ions and Bi in bismuth telluride matrix3+、Te2-Forming Bi-Bi and Bi-Te chemical bonds respectively, and removing the ligand which is not bonded by 25kHz ultrasonic; then, mother liquor is repeatedly dripped and ligand which is not bonded is removed by ultrasound, so that a layer of bismuth-based metal organic framework film (Bi-MOF) grows on the bismuth telluride matrix, the Bi-MOF film contains an organic framework with a specific pore structure (topological structure), the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property, and the nickel plating process is carried out. FIG. 3 is a schematic diagram of the structure of an MOF (Metal-Organic-Framework) membrane, wherein Metal atoms are Framework nodes, and Organic complexes are Framework supports. FIG. 4 is a diagram of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene organic linker Bis6A metal node; FIG. 5 shows Bis6A metal node;
FIG. 6 shows a Bi-UN-901 Metal-Organic Framework (Metal-Organic-Framework) topology; FIG. 7 shows the topology of the Bi-UN-901 plane direction.
A nickel plating process: putting the bismuth telluride matrix with the Bi-MOF film growing on the surface which is well treated into a nickel plating bath, wherein the nickel plating bath contains nickel sulfate (NiSO) with the concentration of 250g/L4·7H2O), 35g/L boric acid (H)3BO3) 10g/L NaCl, 80g/L sodium sulfate (Na)2SO4) 0.1g/LSodium dodecyl sulfate (C)12H25SO4Na) at a plating temperature of 35 ℃ and a cathode current density of 0.8A/dm2And carrying out nickel plating treatment on the bismuth telluride under the pH value of 3.8, and then carrying out a post-treatment process.
And a post-treatment process: and (3) washing the bismuth telluride treated in the nickel plating process with deionized water to be neutral, drying at the temperature of 120 ℃, and taking out to obtain a finished product.
FIG. 1 is a schematic diagram of a structure obtained by electroplating nickel after surface treatment of bismuth telluride in the prior art. Wherein, 1 is the surface of bismuth telluride, 2 is the nickel-electroplating diffusion barrier layer; it can be seen from fig. 1 that the bismuth telluride surface roughness obtained by the ordinary surface treatment is not uniform. FIG. 2 is a schematic view of chemical bonds at the junction of the nickel diffusion barrier layer and the bismuth telluride base material, and it can be seen that the nickel diffusion barrier layer and the bismuth telluride base material are linked mainly through Ni-Te bonds and Ni-Ni bonds, and the porosity is not uniform.
In example 1, structures of a bismuth telluride and nickel diffusion barrier layer obtained by nickel plating after adjustment of microchannels on a bismuth telluride surface are shown in fig. 8 and 9, where in fig. 8, 1 is a bismuth telluride surface with uniform surface roughness and adjustable porosity obtained after adjustment of microchannels on a bismuth telluride surface; 2, electroplating nickel on the surface of the bismuth telluride after the micro-channel adjustment to obtain a nickel diffusion barrier layer; FIG. 9 is a schematic view showing the chemical bonds at the junction of the nickel diffusion barrier layer and the bismuth telluride matrix, in which nickel is filled in the porous foam-like structure left by the organic skeleton after high-temperature carbonization, and the nickel diffusion barrier layer and the bismuth telluride matrix are linked mainly by Bi-Bi bonds, Bi-Te bonds, and Ni-Te bonds, Ni-Ni bonds of Bi in Bi-UN-901 and Bi and Te in the bismuth telluride matrix.
Examples 2 to 15
Examples 2 to 15 the specific operation steps are the same as in example 1, except that the parameters of the surface treatment before plating in step (1) are shown in table 1, the mother liquid for preparing the bismuth-based organometallic framework complex in step (2) a is shown in table 2, and the parameters of the in-situ growth of the Bi-BOF film on the bismuth telluride substrate in step (2) b, the nickel plating and the post-treatment in step (3) are shown in table 3.
TABLE 1
| Examples | NaOH | Oil removal temperature | Oil removal time | Temperature of water washing | |
| Unit of | g/L | | min | ℃ | |
| 2 | 42 | 55 | 30 | 55 | |
| 3 | 50 | 55 | 30 | 55 | |
| 4 | 48 | 65 | 25 | 65 | |
| 3 | 32 | 60 | 25 | 60 | |
| 6 | 36 | 50 | 30 | 80 | |
| 7 | 40 | 60 | 20 | 70 | |
| 8 | 38 | 65 | 20 | 70 | |
| 9 | 30 | 50 | 25 | 75 | |
| 10 | 35 | 50 | 30 | 65 | |
| 11 | 44 | 55 | 20 | 60 | |
| 12 | 37 | 60 | 25 | 80 | |
| 13 | 45 | 65 | 20 | 70 | |
| 14 | 50 | 55 | 20 | 55 | |
| 15 | 35 | 60 | 30 | 65 |
TABLE 2
TABLE 3
| Examples | Heating of bismuth telluride matrix | Ultrasonic frequency | NiSO4·7H2O | Boric acid | NaCl | Sodium sulfate | Sodium dodecyl sulfate | Temperature of plating | Cathode current density | pH | Drying temperature |
| Unit of | ℃ | kHz | g/L | g/L | g/L | g/L | g/L | ℃ | A/dm2 | / | |
| 2 | 120 | 20 | 300 | 30 | 9 | 50 | 0.0.5 | 30 | 0.9 | 3.5 | 120 |
| 3 | 170 | 30 | 280 | 35 | 5 | 65 | 0.1 | 20 | 1.2 | 3.2 | 110 |
| 4 | 150 | 30 | 300 | 32 | 6 | 45 | 0.06 | 45 | 1.1 | 4 | 100 |
| 5 | 130 | 30 | 150 | 33 | 8 | 30 | 0.09 | 30 | 1.5 | 4.3 | 140 |
| 6 | 140 | 25 | 180 | 30 | 7 | 70 | 0.08 | 15 | 1.1 | 4.2 | 150 |
| 7 | 160 | 25 | 220 | 32 | 9 | 50 | 0.08 | 20 | 0.8 | 4.5 | 120 |
| 8 | 180 | 20 | 200 | 31 | 10 | 60 | 0.07 | 50 | 1.3 | 3.5 | 130 |
| 9 | 190 | 30 | 240 | 30 | 5 | 55 | 0.08 | 25 | 0.9 | 3.4 | 140 |
| 10 | 200 | 25 | 260 | 35 | 7 | 40 | 0.1 | 35 | 1 | 3.6 | 100 |
| 11 | 120 | 25 | 300 | 34 | 8 | 35 | 0.05 | 40 | 1.5 | 3.1 | 150 |
| 12 | 160 | 25 | 280 | 33 | 6 | 75 | 0.09 | 15 | 1.4 | 3.7 | 120 |
| 13 | 130 | 30 | 170 | 35 | 10 | 70 | 0.08 | 50 | 1.2 | 3.9 | 130 |
| 14 | 150 | 20 | 160 | 32 | 5 | 60 | 0.1 | 45 | 1 | 3 | 150 |
| 15 | 140 | 30 | 190 | 30 | 6 | 50 | 0.06 | 35 | 0.9 | 3.3 | 140 |
Compared with the traditional surface treatment process (oil removal, coarsening, activation and nickel electroplating) before bismuth telluride plating, the invention has less process steps for the bismuth telluride surface treatment process, in the invention, a Bi-UN-901MOF film is grown on the bismuth telluride surface, MOF is a metal organic framework compound, the pore canal size can be microscopically regulated and controlled through different organic framework structures, after high-temperature evaporation, the organic structure disappears to leave a specific foam pore canal structure, nickel atoms enter the foam pore canal structure, a reaction layer is formed between the foam pore canal structure and Te atoms in the bismuth telluride, a nickel diffusion barrier layer in the reaction layer and a bismuth telluride base material are mainly linked through Bi-Bi bonds, Bi-Te bonds, Ni-Te bonds and Ni-Ni bonds of Bi and Te in the Bi-UN-901 and Bi and the Bi-Te bonds and the Ni-Te bonds in the bismuth telluride base material, so as to ensure the bonding strength of the nickel diffusion barrier layer and the bismuth telluride, meanwhile, the planar topological structure of Bi-UN-901 on the surface of bismuth telluride can realize uniform pore channels and adjustable size, so that the surface of the obtained nickel diffusion barrier layer is compact and low in porosity, and the foamed organic structure of Bi-UN-901 can effectively absorb stress residue caused by the difference of linear expansion coefficients of the surfaces of nickel and bismuth telluride, thereby finally achieving the purposes of improving the bonding strength of the surfaces of nickel and bismuth telluride and reducing the stress residue.
By adopting the surface treatment process before bismuth telluride electroplating, the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity of topological structure, tailorability and the like of Bi-MOF can be fully utilized, so that the obtained coating has the advantages of smooth surface, compact structure, low porosity and strong bonding force with a substrate, and meets various index requirements of the electroplating process, so that the bismuth telluride can reliably work in a semiconductor refrigerator, and the refrigerator can work stably, has long service life and stable performance.
Claims (9)
1. A thermoelectric material bismuth telluride surface micro-channel adjusting method is characterized in that: comprises the following steps of (a) carrying out,
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding Bi (NO)3)·5H2Mixing O and trifluoroacetic acid in a dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding a 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is a bismuth-based organic metal framework complex mother solution, and the yellow suspension in the suspension contains a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing ligands which are not bonded by ultrasound, repeating the steps, growing a layer of bismuth-based metal organic framework film on the bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property.
2. The method for adjusting the micro-channels on the surface of the thermoelectric material bismuth telluride as set forth in claim 1, wherein: comprises the following steps of (a) carrying out,
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding 0.16 to 0.2mmol of Bi (NO)3)·5H2Mixing O and 5.5-6 mmol of trifluoroacetic acid in 10-20 ml of dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding 0.05-0.1 mmol of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and 10-20 ml of dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, and then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is bismuth-based organic metal framework complex mother liquor, and yellow suspended matters in the suspension contain a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Separately forming Bi-Bi and Bi-Te chemical bonds, removing non-bonded ligands by ultrasonic treatment, and repeating the above stepsGrowing a layer of bismuth-based metal organic framework film on a bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property.
3. The method for adjusting the micro-channels on the surface of the thermoelectric material bismuth telluride as set forth in claim 1, wherein: the frequency of ultrasonic treatment in the step a is 20-30 kHz, and the frequency of ultrasonic treatment in the step b is 20-30 kHz.
4. The method for adjusting the micro-channels on the surface of the thermoelectric material bismuth telluride as set forth in claim 1, wherein: the bismuth telluride substrate is a thin wafer with the diameter of 30mm and the thickness of 1-2 mm.
5. The method for adjusting the micro-channels on the surface of the thermoelectric material bismuth telluride as set forth in claim 1, wherein: and in the step b, the oil removing treatment is to put the bismuth telluride matrix into NaOH solution with the concentration of 30-50 g/L, the oil removing temperature is 50-65 ℃, and the oil removing time is 20-30 min.
6. A method for plating nickel on the surface of thermoelectric material bismuth telluride is characterized in that: comprises the following steps of (a) carrying out,
(1) surface treatment before plating:
putting the bismuth telluride matrix into NaOH solution for chemical degreasing, removing oil stains on the surface of the bismuth telluride matrix, washing with hot water at the temperature of 55-80 ℃ and removing residues on the surface of the bismuth telluride matrix;
(2) and (3) micro-channel adjustment and nickel plating on the surface of the bismuth telluride matrix:
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding Bi (NO)3)·5H2Mixing O and trifluoroacetic acid in a dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding a 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, and carrying out ultrasonic treatment on the obtained light yellow solutionThen, keeping the temperature in an oven at 100-150 ℃ for 8-10 hours to obtain yellow suspension, wherein the yellow suspension is the mother liquor of the bismuth-based organic metal framework complex, and the yellow suspension in the suspension contains a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing ligands which are not bonded by ultrasound, repeating the steps, growing a layer of bismuth-based metal organic framework film on a bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property;
c. nickel plating
Putting the bismuth telluride matrix with the Bi-MOF film growing on the surface into a nickel plating bath, wherein the nickel plating bath contains 150-300 g/L of NiSO4·7H2O, 30-35 g/L boric acid, 5-10 g/L NaCl, 30-80 g/L sodium sulfate, 0.05-0.1 g/L sodium dodecyl sulfate, electroplating temperature of 15-50 ℃, and cathode current density of 0.8-1.5A/dm2Carrying out nickel plating treatment on the bismuth telluride matrix under the condition that the PH value is 3-4.5;
(3) and (3) post-treatment: and (3) washing the nickel-plated bismuth telluride treated in the step (2) with deionized water to be neutral, drying at the temperature of 100-150 ℃, and taking out to obtain a finished product.
7. The method for plating nickel on the surface of the thermoelectric material bismuth telluride as claimed in claim 6, wherein the method comprises the following steps: comprises the following steps of (a) carrying out,
(1) surface treatment before plating:
putting the bismuth telluride matrix into 30-50 g/L NaOH solution for chemical oil removal, wherein the oil removal temperature is 50-65 ℃, the oil removal time is 20-30 min, removing oil stains on the surface of the bismuth telluride matrix, and then washing with hot water at 55-80 ℃ to remove residues on the surface of the bismuth telluride;
(2) and (3) micro-channel adjustment and nickel plating on the surface of the bismuth telluride matrix:
a. preparation of bismuth-based organometallic framework complex mother liquor
Adding 0.16 to 0.2mmol of Bi (NO)3)·5H2Mixing O and 5.5-6 mmol of trifluoroacetic acid in 10-20 ml of dimethylformamide solution to form an MOF metal salt solution, heating the MOF metal salt solution at 100-150 ℃ for 1-1.5 h, cooling to room temperature, adding 0.05-0.1 mmol of 1,3,6, 8-tetra (4-carboxyphenyl) pyrene and 10-20 ml of dimethylformamide solution into the cooled MOF metal salt solution to obtain a light yellow solution, carrying out ultrasonic treatment on the obtained light yellow solution for 10-20 min, and then carrying out heat preservation in an oven at 100-150 ℃ for 8-10 h to obtain a yellow suspension, wherein the yellow suspension is bismuth-based organic metal framework complex mother liquor, and yellow suspended matters in the suspension contain a Bi-UN-901 metal organic framework topological structure;
b. in-situ growth of bismuth-based metal-organic framework film on bismuth telluride substrate
Heating the deoiled bismuth telluride matrix to 120-200 ℃, dropwise adding the prepared organic metal skeleton complex mother liquor on the bismuth telluride matrix in the heating process, volatilizing the dropwise added Bi-UN-901, and volatilizing Bi in the ligand3+With Bi in a bismuth telluride matrix3+、Te2-Respectively forming Bi-Bi and Bi-Te chemical bonds, then removing ligands which are not bonded by ultrasound, repeating the steps, growing a layer of bismuth-based metal organic framework film on a bismuth telluride matrix, wherein the Bi-MOF film contains an organic framework with a topological structure, and the organic framework is carbonized at high temperature to leave a porous foam surface structure with stable property;
c. nickel plating
Putting the bismuth telluride matrix with the Bi-MOF film growing on the surface into a nickel plating bath, wherein the nickel plating bath contains 150-300 g/L of NiSO4·7H2O, 30-35 g/L boric acid, 5-10 g/L NaCl, 30-80 g/L sodium sulfate, 0.05-0.1 g/L sodium dodecyl sulfate, electroplating temperature of 15-50 ℃, and cathode current density of 0.8-1.5A/dm2Carrying out nickel plating treatment on the bismuth telluride matrix under the condition that the PH value is 3-4.5;
(3) and (3) post-treatment: and (3) washing the nickel-plated bismuth telluride processed in the step (2) with deionized water to be neutral, drying at the temperature of 120 ℃, and taking out to obtain a finished product.
8. The method for plating nickel on the surface of the thermoelectric material bismuth telluride as claimed in claim 6, wherein the method comprises the following steps: the frequency of ultrasonic treatment in the step a is 20-30 kHz, and the frequency of ultrasonic treatment in the step b is 20-30 kHz.
9. The method for plating nickel on the surface of the thermoelectric material bismuth telluride as claimed in claim 7, wherein the method comprises the following steps: the bismuth telluride substrate is a thin wafer with the diameter of 30mm and the thickness of 1-2 mm.
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