CN117646261B - Limited domain electrodeposition method of metal grid line structure for photovoltaic power generation - Google Patents
Limited domain electrodeposition method of metal grid line structure for photovoltaic power generation Download PDFInfo
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- 238000010248 power generation Methods 0.000 title claims abstract description 17
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract description 79
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- 238000009713 electroplating Methods 0.000 claims description 20
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention discloses a finite field electrodeposition method of a metal grid line structure for photovoltaic power generation, which comprises the following steps: 1. soft etching and forming of polydimethylsiloxane PDMS core mould with grid line pattern; 2. self-assembling a molecular layer on the surface of the PDMS core mold; 3. the PDMS core mould is chemically combined with the interface of the substrate to be electroplated; 4. a metal grid line structure is electrodeposited in a limited area; 5. and demolding the metal grid line structure. According to the invention, the ordered self-assembled molecular layer is formed on the surface of the PDMS core mold by utilizing the self-adsorption reaction of mercaptan, and the ordered self-assembled molecular layer is reacted with the metal seed layer on the surface of the substrate to be electroplated to realize chemical combination, so that the PDMS core mold is tightly attached to the substrate to be electroplated, patterning and metallization are realized in the electrodeposition process, the process flow is effectively shortened, the preparation cost is reduced, the metal electrode with the patterned low-line-width grid line can be electroplated on the surface of the battery substrate safely and environmentally friendly, and the method is suitable for various photovoltaic cells.
Description
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to a finite field electrodeposition method of a metal grid line structure for photovoltaic power generation.
Background
The metallization link is an important procedure for producing photovoltaic cells in the photovoltaic field, and is mainly used for manufacturing electrode grid lines of the cells, and high-efficiency ohmic contact is formed by tightly combining electrodes and cell pieces so as to realize current output. At present, silver paste screen printing is a metallization processMass production routes of the main stream. However, this process is difficult to produce with line widths < 20The low line width structure of the silver paste also restricts the industrialization acceleration of the solar cell. Copper electroplating has significant development advantages as a revolutionary approach to completely silver-free plating. Electrode copper grid lines are prepared on the surface of the substrate by electroplating, and compared with the traditional silver paste silk screen printing, the method can remarkably reduce the metallization cost. In addition, the copper grid line prepared by electroplating has better conductivity, better plasticity and narrower line width. Therefore, copper electroplating is expected to replace a screen printing method with high silver consumption, and cost reduction, synergy and large-scale production of various photovoltaic cells are realized.
The process flow of the photovoltaic copper electroplating mainly comprises four links of metal seed layer deposition, patterning, electroplating and post-treatment: firstly, preparing a metal seed layer on the surface of a battery substrate for conducting treatment so as to improve the adhesiveness between the substrate and a subsequent grid line electrode; secondly, preparing a grid line pattern on the surface of the seed layer by a photoetching technology, wherein the grid line pattern is used as a core link for determining the width of the grid line, and the imaging directly influences the conversion efficiency of the electroplating battery; and finally, filling the grid line micro cavity by electroplating, preparing a copper grid line structure on the surface of the battery substrate, and removing the photoresist and the seed layer by etching after the electroplating is finished to prepare a finished product.
However, the existing copper electroplating process in the photovoltaic field has the following problems: (1) The photoetching technology adopted by the current patterning method not only needs expensive photoetching machine equipment, but also needs complex processes such as photoresist homogenizing, pre-baking, exposure, post-baking and the like; (2) In the post-treatment process, the photoresist structure needs to be removed by adopting corrosive liquid, and the generated waste liquid can cause environmental pollution. These disadvantages have limited to a certain extent the wide application of electroplated copper in the photovoltaic field. Therefore, a novel method is explored to electroplate the grid line structure on the surface of the battery substrate with short flow, low cost, high precision and no pollution, and the method has important significance for cost reduction, synergy and industrialization process in the photovoltaic field.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a limited-area electrodeposition method of a metal grid line structure for photovoltaic power generation aiming at the defects of the prior art. According to the method, the self-assembled molecular layer is formed on the surface of the PDMS core mold through the thiol and reacts with the metal seed layer on the surface of the substrate to be electroplated to realize chemical combination, so that the PDMS core mold is tightly attached to the substrate to be electroplated, patterning and metallization are realized simultaneously in the electrodeposition process, the forming precision of a metal grid line structure is improved, the process flow is effectively shortened, the preparation cost is reduced, the generation of toxic waste liquid is reduced, and the problems of complex process, high equipment requirement, high cost, environmental pollution and the like of the electroplating grid line structure in the current photovoltaic field are solved.
In order to solve the technical problems, the invention adopts the following technical scheme: the finite field electrodeposition method of the metal grid line structure for photovoltaic power generation is characterized by comprising the following steps of:
step one, soft etching and forming of a polydimethylsiloxane PDMS mandrel with a grid line pattern: uniformly mixing PDMS prepolymer and a Dow Corning 184 curing agent according to the volume ratio of 10:1, pouring the mixture on an original template with a grating line pattern, removing bubbles in vacuum drying equipment, putting the mixture into an oven for curing and forming, cooling to room temperature, and demolding to obtain a PDMS core mold with the grating line pattern;
step two, self-assembling a molecular layer on the surface of the PDMS core mold: immersing the surface of the PDMS core mould prepared in the first step into a mercaptan solution and standing at room temperature, and forming an ordered self-assembled molecular layer on the surface of the PDMS core mould through self-adsorption reaction of the mercaptan molecular layer to prepare the PDMS core mould with the self-assembled molecular layer;
step three, chemically combining the PDMS core mold with the interface of the substrate to be electroplated: standing and attaching the PDMS core mould with the self-assembled molecular layer and the substrate to be electroplated with the surface metal seed layer at room temperature, and reacting the mercapto functional group in the self-assembled molecular layer with the surface metal seed layer of the substrate to be electroplated to form a chemical bond at the interface to prepare a PDMS core mould and substrate to be electroplated assembly;
step four, a metal grid line structure is electrodeposited in a limited area: immersing the PDMS core mould and the substrate assembly to be electroplated prepared in the step three as a cathode into electroplating liquid for finite field electrodeposition, immersing the PDMS core mould and the substrate assembly to be electroplated into deionized water after the micro cavity of the PDMS core mould is fully cast by metal ions to form a deposition structure, and carrying out ultrasonic cleaning and drying;
step five, demolding the metal grid line structure: and (3) removing the self-assembled molecular layer in the PDMS core mould, and taking out the dried deposition structure in the step four from the PDMS core mould micro-cavity by adopting a manual demoulding mode to obtain the metal grid line structure.
The finite field electrodeposition method of the metal grid line structure for photovoltaic power generation is characterized in that the time for placing at the room temperature in the second step is 10-60 min; the thickness of the self-assembled molecular layer is 0.7 nm-5 nm.
The finite field electrodeposition method of the metal grid line structure for photovoltaic power generation is characterized in that standing and attaching time at room temperature in the third step is 10-50 hours, and a surface metal seed layer of a substrate to be electroplated is copper, nickel, gold or copper-nickel alloy. In the process path of photovoltaic plating, a metal seed layer needs to be deposited on the surface of a silicon wafer substrate due to poor conductivity of the silicon wafer substrate, wherein copper is the most used seed layer metal, nickel and copper-nickel alloy are selected to avoid the problem that copper is easy to oxidize, and a gold seed layer needs to be adopted when an ultra-high depth-to-diameter ratio or a more special structure is needed.
The finite field electrodeposition method of the metal grid line structure for photovoltaic power generation is characterized in that the electroplating solution in the fourth step is a single metal solution containing copper or nickel elements or a multi-metal solution containing copper and nickel elements simultaneously, the finite field electrodeposition is direct current deposition or pulse electrodeposition, and the current density is 1A/dm 2 ~10A/dm 2 . The effect of electrodeposition is optimal in the current density range, the problems that the electrodeposition rate is too slow and the electrodeposition efficiency is low due to low current density are avoided, meanwhile, the electrodeposition rate is too fast due to high current density are avoided, and the metal grid line structure prepared by deposition is easy to have forming defects such as pinholes, pits and the like.
The finite field electrodeposition method of the metal grid line structure for photovoltaic power generation is characterized in that the self-assembled molecular layer removing method in the fifth step is ultraviolet irradiation, plasma cleaning or ultrasonic cleaning.
The finite field electrodeposition method of a metal grid line structure for photovoltaic power generation is characterized in that the grid line width of the metal grid line structure in the fifth step is not more than 100。
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the ordered self-assembled molecular layer is formed on the surface of the PDMS core mold by utilizing the self-adsorption reaction of mercaptan, and chemical combination is realized by the self-assembled molecular layer and the metal seed layer on the surface of the substrate to be electroplated, so that the PDMS core mold is tightly attached to the substrate to be electroplated, patterning and metallization are realized in the electrodeposition process, a metal grid line structure is obtained, the process flow is effectively shortened, the preparation cost is reduced, the metal electrode with the patterned low-line-width grid line can be electroplated on the surface of the battery substrate safely and environmentally-friendly, and the method is suitable for various photovoltaic cells.
2. According to the invention, the self-assembled molecular layer formed on the surface of the PDMS core mold by the thiol is tightly combined with the substrate to be electroplated, so that the domain limiting effect is realized, the electrodeposition is performed in a specific area on the surface of the substrate to be electroplated, the domain limiting electrodeposition is realized, and the forming precision of the metal grid line structure is improved.
3. According to the invention, the PDMS core mould prepared by adopting a soft etching technology is used for replacing the existing photoresist core mould, and the metal grid line structure is prepared on the surface of the battery substrate by electrodeposition, so that the damage of the demoulding process to the microstructure of the core mould can be reduced due to the excellent elasticity and toughness of the PDMS core mould, and the core mould can be reused after being cleaned, thereby reducing the preparation cost of the core mould, overcoming the problems of high equipment cost, complex process and the like of the photoetching technology, and obviously reducing the cost of the electroplated metal grid line structure.
4. According to the invention, after the conventional methods of removing the thiol self-assembled molecular layer, such as ultraviolet irradiation, plasma cleaning and ultrasonic cleaning, are adopted, the deposited structure is manually demoulded and taken out, and the metal grid line structure is obtained after cleaning and drying, so that the photoresist microstructure is not required to be removed through post-etching treatment, the generation of toxic waste liquid is reduced, the process flow is effectively shortened, the production efficiency is improved, and the problems of environmental pollution and complex photoresist removing process in the post-treatment of the prior art are solved.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic illustration of a polydimethylsiloxane PDMS mandrel soft etch forming with a gate line pattern in accordance with the present invention.
FIG. 2 is a schematic diagram of the chemical bonding of PDMS core to the interface of the substrate to be electroplated according to the present invention.
FIG. 3 is a schematic diagram of a metal gate line structure and stripping of the present invention.
Fig. 4 is a topography of a copper gate line structure prepared in example 1 of the present invention.
Fig. 5 is a topography of a copper gate line structure prepared in example 2 of the present invention.
Fig. 6 is a morphology diagram of a copper-nickel alloy grid line structure prepared in example 3 of the present invention.
Reference numerals illustrate:
1-an original template; 2-PDMS mixtures;
3-PDMS core mold; 4-self-assembling a molecular layer;
5-a substrate to be electroplated having a surface metal seed layer; 6-depositing a structure;
7-metal gate line structure.
Detailed Description
As shown in fig. 1 to 3, the finite field electrodeposition process of the present invention includes: (1) soft etching and forming of PDMS core mould with grid line pattern: pouring the PDMS mixture 2 on an original template 1 with a grating pattern, completely filling the original template 1 in a grating channel, removing bubbles, curing and forming, and demolding to obtain a PDMS core mold 3 with the grating pattern; (2) self-assembled molecular layer on PDMS core surface: immersing the surface of the PDMS core model 3 into a mercaptan solution for standing treatment, and forming an ordered self-assembled molecular layer 4 on the surface of the PDMS core model 3; (3) chemical bonding of PDMS core mold and substrate interface to be electroplated: the PDMS core mould 3 with the self-assembled molecular layer 4 is closely combined with the substrate 5 to be electroplated with the surface metal seed layer after standing and attaching, so as to prepare a PDMS core mould and substrate combination to be electroplated; (4) a confined electro-deposition metal gate line structure: electro-deposition is carried out by taking a PDMS core mold and a substrate assembly to be electroplated as a cathode, and the micro cavity of the PDMS core mold 3 is fully cast by metal ions to form a deposition structure 6; and (5) demolding the metal grid line structure: and removing the self-assembled molecular layer in the PDMS core, taking the deposition structure 6 out of the micro cavity of the PDMS core 3, and performing post-treatment to obtain the metal grid line structure 7.
Example 1
The embodiment comprises the following steps:
step one, soft etching and forming of a polydimethylsiloxane PDMS mandrel with a grid line pattern: the PDMS mixture formed by uniformly stirring and mixing 2mL of PDMS prepolymer and 0.2mL of Dow Corning 184 curing agent in a slurry cup is poured into a slurry cup with a grating pattern and a line width of 20Filling the hard original template in the grid line channel of the original template completely, placing the original template in a vacuum drying oven, vacuumizing for 30min to remove bubbles, taking out, placing the original template in the oven, heating at 100 ℃ for curing and forming for 30min, taking out, cooling to room temperature, and demolding to obtain the product with 20%>PDMS core mold of line width pattern;
step two, self-assembling a molecular layer on the surface of the PDMS core mold: immersing the surface of the PDMS core mould prepared in the first step into a mercaptan solution and standing for 10min at room temperature, wherein mercaptan molecules are adsorbed on the surface of the PDMS core mould and are automatically arranged into a regular structure in order to obtain a self-assembled molecular layer with the thickness of 0.7nm on the surface of the PDMS core mould through self-adsorption reaction of the mercaptan molecular layer, so that the PDMS core mould with the self-assembled molecular layer is prepared;
step three, chemically combining the PDMS core mold with the interface of the substrate to be electroplated: standing and attaching the PDMS core mould with the self-assembled molecular layer prepared in the second step and a substrate to be electroplated with a surface copper seed layer for 10 hours at room temperature, wherein the PDMS core mould is prepared by self-assembled molecular layer with mercapto (SH) functional groupsReacts with the copper seed layer on the surface of the substrate to be electroplated to form a chemical bond, namely a strong Cu-S bond, at the interface, and the methoxysilane (Si-O-CH 3 ) The method comprises the steps of hydrolyzing to form a siloxane (Si-O-Si) network with stable chemical property and corrosion resistance, wherein the siloxane network and the Si-O-Si network cooperate to enable the PDMS core mould to be tightly combined with a substrate to be electroplated with a surface copper seed layer, so that a PDMS core mould and substrate to be electroplated combination is prepared;
step four, a limited-area electrodeposited copper grid line structure: immersing the PDMS core module and the substrate to be electroplated which are prepared in the third step into an electroplating solution as a cathode, immersing a copper sheet with the mass purity of more than 99% into the electroplating solution as an anode, and then performing direct current deposition at room temperature with the current density of 1A/dm 2 Immersing the PDMS core mould micro-cavity into deionized water for ultrasonic cleaning and drying after the PDMS core mould micro-cavity is fully cast by copper ions to form a copper deposition structure; the electroplating solution comprises the following components: 90g/L of copper sulfate, 150g/L of sulfuric acid, 4mg/L of gelatin, 35mg/L of copper chloride and 3mg/L of polyethylene glycol;
step five, demolding the metal grid line structure: removing the self-assembled molecular layer in the PDMS core mold by Ar plasma cleaning, ultrasonically cleaning with ethanol and water by adopting a manual demolding mode, and taking out the dried copper deposition structure in the fourth step from the PDMS core mold micro-cavity to obtain the grid line with the line width of 20Is provided.
Fig. 4 is a morphology diagram of the copper gate line structure prepared in this embodiment, and as can be seen from fig. 4, the copper gate line structure prepared by deposition in this embodiment is complete and defect-free, which illustrates that the method of the present invention can accurately prepare the copper gate line structure in a short process at low cost.
Example 2
This embodiment differs from embodiment 1 in that: step one, a hard original template with a grid line pattern and a line width of 100 mu m is adopted;
step two, standing for 60min at room temperature; the thickness of the self-assembled molecular layer is 5nm;
thirdly, the electroplated matrix is provided with a surface nickel seed layer, is kept stand and attached for 50 hours at room temperature, and forms Ni-S chemical bonds at the interface through reaction;
the current density of the direct current deposition in the fourth step is 10A/dm 2 ；
In the fifth step, naBH is adopted 4 Ultrasonic cleaning is carried out in ethanol water mixed solution to remove self-assembled molecular layers in the PDMS core mould, and the grid line width is 100Is provided.
Fig. 5 is a morphology diagram of the copper gate line structure prepared in this embodiment, and as can be seen from fig. 5, the copper gate line structure prepared by deposition in this embodiment is complete and defect-free, which illustrates that the method of the present invention can accurately prepare the copper gate line structure in a short process at low cost.
Example 3
This embodiment differs from embodiment 1 in that: in step one, a semiconductor device having a gate line pattern with a line width of 60~90/>A hard original template of (a);
step two, standing for 40min at room temperature; the thickness of the self-assembled molecular layer is 2nm;
step three, the electroplated substrate is provided with a surface gold seed layer, is kept stand and attached for 30 hours at room temperature, and forms Au-S chemical bonds at the interface through reaction;
in the fourth step, copper sheets and nickel sheets with the area ratio of 3:1 are adopted as anodes, an electrochemical workstation is adopted to carry out pulse electrodeposition at room temperature, and the current density is 5A/dm 2 The electroplating solution comprises the following components: 250g/L of copper sulfate, 40g/L of nickel sulfate, 30g/L of sodium chloride, 0.5g/L of sodium dodecyl sulfate, 35g/L of boric acid and 5g/L of saccharin, adjusting the pH value of the electroplating solution to 4.0 by dilute sulfuric acid, and ending the electrodeposition process after copper ions and nickel ions are fully deposited and cover the cavity of the PDMS core mold;
in the fifth step, ultraviolet irradiation is adopted to irradiate the PDMS core mouldIs removed to obtain the gate line with the line width of 60~90/>Is a copper-nickel alloy grid line structure.
Fig. 6 is a morphology diagram of a copper-nickel alloy gate line structure prepared in this embodiment, and as can be seen from fig. 6, the copper-nickel alloy structure prepared by deposition in this embodiment is complete and defect-free, which illustrates that the method of the present invention completely replicates the microstructure of the original template and implements deposition of copper-nickel alloy electrodes, and can expand the metal electrodes deposited in a limited area to a wider material field to meet different application requirements.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (6)
1. The finite field electrodeposition method of the metal grid line structure for photovoltaic power generation is characterized by comprising the following steps of:
step one, soft etching and forming of a polydimethylsiloxane PDMS mandrel with a grid line pattern: uniformly mixing PDMS prepolymer and a Dow Corning 184 curing agent according to the volume ratio of 10:1, pouring the mixture on an original template with a grating line pattern, removing bubbles in vacuum drying equipment, putting the mixture into an oven for curing and forming, cooling to room temperature, and demolding to obtain a PDMS core mold with the grating line pattern;
step two, self-assembling a molecular layer on the surface of the PDMS core mold: immersing the surface of the PDMS core mould prepared in the first step into a mercaptan solution and standing at room temperature, and forming an ordered self-assembled molecular layer on the surface of the PDMS core mould through self-adsorption reaction of the mercaptan molecular layer to prepare the PDMS core mould with the self-assembled molecular layer;
step three, chemically combining the PDMS core mold with the interface of the substrate to be electroplated: standing and attaching the PDMS core mould with the self-assembled molecular layer and the substrate to be electroplated with the surface metal seed layer at room temperature, and reacting the mercapto functional group in the self-assembled molecular layer with the surface metal seed layer of the substrate to be electroplated to form a chemical bond at the interface to prepare a PDMS core mould and substrate to be electroplated assembly;
step four, a metal grid line structure is electrodeposited in a limited area: immersing the PDMS core mould and the substrate assembly to be electroplated prepared in the step three as a cathode into electroplating liquid for finite field electrodeposition, immersing the PDMS core mould and the substrate assembly to be electroplated into deionized water after the micro cavity of the PDMS core mould is fully cast by metal ions to form a deposition structure, and carrying out ultrasonic cleaning and drying;
step five, demolding the metal grid line structure: and (3) removing the self-assembled molecular layer in the PDMS core mould, and taking out the dried deposition structure in the step four from the PDMS core mould micro-cavity by adopting a manual demoulding mode to obtain the metal grid line structure.
2. The method for limiting the electrodeposition of a metal grid line structure for photovoltaic power generation according to claim 1, wherein the time for the placement at room temperature in the second step is 10-60 min; the thickness of the self-assembled molecular layer is 0.7 nm-5 nm.
3. The method for limiting electro-deposition of a metal grid line structure for photovoltaic power generation according to claim 1, wherein the time for standing and attaching at room temperature in the third step is 10-50 h, and the surface metal seed layer of the substrate to be electroplated is copper, nickel, gold or copper-nickel alloy.
4. The method for limiting electrodeposition of a metal grid line structure for photovoltaic power generation according to claim 1, wherein in the fourth step, the plating solution is a single metal solution containing copper or nickel or a multi-metal solution containing copper and nickel simultaneously, the limiting electrodeposition is direct current deposition or pulse electrodeposition, and the current density is 1A/dm 2 ~10A/dm 2 。
5. The method for finite field electrodeposition of a metal grid line structure for photovoltaic power generation according to claim 1, wherein the method for removing the self-assembled molecular layer in the fifth step is ultraviolet irradiation, plasma cleaning or ultrasonic cleaning.
6. The method for finite field electrodeposition of a metal gate line structure for photovoltaic power generation according to claim 1, wherein the gate line width of the metal gate line structure in the fifth step is not more than 100。
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| US8294025B2 (en) * | 2002-06-08 | 2012-10-23 | Solarity, Llc | Lateral collection photovoltaics |
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