CN117107314A - Method and device for horizontal electrochemical deposition of metal - Google Patents

Method and device for horizontal electrochemical deposition of metal Download PDF

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Publication number
CN117107314A
CN117107314A CN202311167437.XA CN202311167437A CN117107314A CN 117107314 A CN117107314 A CN 117107314A CN 202311167437 A CN202311167437 A CN 202311167437A CN 117107314 A CN117107314 A CN 117107314A
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semiconductor device
electrode
metal
conductive
electrolyte
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李中天
姚宇
邓晓帆
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Suzhou Taiyangjing New Energy Co ltd
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Suzhou Taiyangjing New Energy Co ltd
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/12Semiconductors
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/001Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10Electrodes, e.g. composition, counter electrode
    • C25D17/12Shape or form

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Photovoltaic Devices (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The application discloses a method for horizontally and electrochemically depositing metal, which is characterized in that a semiconductor device is horizontally moved, an upper electrode is contacted with the upper surface of the semiconductor device by adopting whole-surface contact or multi-point contact, the surface of the metal to be electrochemically deposited below the semiconductor device is contacted with electrolyte solution, metal ions in the electrolyte solution obtain electrons and deposit on the surface of the metal ions, and the potential difference between the upper electrode and the lower surface of the semiconductor device contacted with the electrolyte solution is realized by photoinduction and external voltage or the combination of the upper electrode and the electrolyte solution. The application also discloses a device for horizontally and electrochemically depositing metal. The method and the device for horizontally and electrochemically depositing metal can implement a reliable and mass-producible metallization process on the surface of the transparent conductive film or the surface of the passivation film of the battery.

Description

Method and device for horizontal electrochemical deposition of metal
The application relates to a method for depositing metal by horizontal electrochemistry and a device thereof, which are filed to the China intellectual property office, wherein the application date is 22 days of 6 months of 2018, the application number is 201810658609.6, and the application name is the divisional application of the application.
Technical Field
The application relates to a method and a device for horizontally electrochemically depositing metal, which are used for electrochemically depositing metal of a transparent conductive film or a passivation film of a solar cell, and belong to the field of solar cell manufacturing.
Background
Semiconductor devices typically use metal as a device electrode to extract or inject charge carriers. Metallization is therefore often an important process step in semiconductor fabrication, as is the case in the fabrication of solar cells. In particular, the metallization of the front-side light-entering surface of a solar cell generally needs to take into account factors such as shading losses, metal conductivity and contact resistance with a semiconductor. The screen printing silver paste is sintered at high temperature to form a metal grid line, which is the most widely used front metallization method of crystalline silicon solar cells at present. The method has simple process and has long been realized for mass production.
With the continuous development of silicon chip and battery technology, the battery manufacturing cost is continuously reduced, and the cost occupied by the metallization process adopting expensive silver paste is continuously increased in the whole battery cost, especially for a double-sided HJT battery with silver grid lines on both front and back sides. Today, the technology of multiple batteries and components tends to be mature, and in order to achieve the aim of low price of the power generation side of the photovoltaic technology, it is imperative to reduce the metallization cost of the batteries. The electrodes may be formed by electroplating metal on the solar cell surface using electrochemical methods. The method can use cheaper nickel, copper and other metals to replace silver partially or completely to realize cost reduction. In this method, metal ions in an electrolyte solution are reduced to metal on the surface of a solar cell by electrons obtained and deposited on the surface thereof. During electrochemical deposition, the electron source at the cell surface may be provided by a photo-induced current of the solar cell, which will be referred to hereinafter as photo-induced plating, or by a current driven by an external power source during plating, which will be referred to hereinafter as current plating. However, the methods of conventional plating, vertical plating, and the like have problems of uneven metal deposition, low yield, low mass production efficiency, and the like.
Patent CN101257059a and patent CN102083717a disclose methods for horizontal electroplating of crystalline silicon solar surfaces in mass production using either light induced electroplating or current electroplating. However, this method still requires a screen-printed aluminum back surface field and may cause damage to the cell surface during horizontal plating. Patent CN105590981a discloses a method in which the surface of the negative electrode does not need to be in contact with any solid, but the difficulty of process control is high. In other similar horizontal plating methods, the upper electrode is in a single point or single row contact, which is difficult to apply in a single-sided cell or a double-sided cell to which a back passivation technique is applied.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide a method and a device for horizontally and electrochemically depositing metal, which can implement a uniform, reliable and mass-producible metallization process on the surface of a transparent conductive film or a passivation film of a battery.
In order to solve the technical problems, the application adopts the following technical scheme:
a method for horizontally and electrochemically depositing metal includes horizontally moving a semiconductor device, contacting an upper electrode with the upper surface of the semiconductor device by whole-surface contact or multipoint contact, contacting the surface of the metal to be electrochemically deposited under the semiconductor device with electrolyte solution, obtaining electrons from metal ions in the electrolyte solution and depositing them on the surface, and applying voltage or a combination of both to realize potential difference between the upper electrode and the lower surface of the semiconductor device contacted with the electrolyte solution by photoinduction.
The method is used for direct electroplating on a transparent conductive film of a HJT cell or a perovskite film cell, or on a passivation film or a transparent conductive film of an HBC cell or other crystalline silicon cell to which TopCon, POLO surface full-face passivation technology is applied.
The upper electrode is contacted with the upper surface of the semiconductor device by adopting multipoint contact, and the minimum linear distance between any point on the surface of the semiconductor device contacted with the upper electrode and the nearest conductive contact part of the upper electrode is smaller than 60mm.
In the process of electrochemically depositing metal, the upper electrode moves horizontally in synchronization with the semiconductor device.
The semiconductor device is a solar cell, and the light emitting device is used for uniformly illuminating the light receiving surface of the solar cell to generate a potential difference.
The electrolyte solution is provided with a lower electrode which is electrically connected with the positive electrode of the bias power supply, and an upper electrode which is electrically connected with the negative electrode of the bias power supply.
The upper surface of the semiconductor device is provided with a wireless upper electrode, the wireless upper electrode receives electric energy of the wireless transmitting device, the wireless upper electrode comprises an upper layer structure and a lower layer conducting plate, the upper layer structure comprises a wireless electric energy receiving element and a rectifying element, and a negative electrode of the upper layer structure is output to the lower layer conducting plate.
The utility model provides a device of horizontal electrochemical deposition metal, includes the liquid discharge groove, be provided with the electrolyte groove that is used for holding electrolyte in the liquid discharge groove, the lower extreme intercommunication of electrolyte groove has the transfer line, the lower extreme intercommunication of liquid discharge groove has the liquid discharge line, the side of electrolyte groove is equipped with and is used for adjusting electrolyte liquid level's high floodgate, be provided with the bottom electrode in the electrolyte groove, the top of electrolyte groove is provided with the lower conveying gyro wheel that is used for carrying the semiconductor device, the whole or multiple spot contact type top electrode of semiconductor device upper surface with the bottom electrode links to each other.
The connection of the upper electrode and the lower electrode comprises the following three modes, wherein one mode is that the upper electrode is connected with the negative electrode of a bias power supply, and the lower electrode is connected with the positive electrode of the bias power supply; the second is that the upper electrode is directly connected with the lower electrode, and a light-emitting device is arranged above or below the semiconductor device; and the third is that the upper electrode is connected with the negative electrode of the bias power supply, the lower electrode is connected with the positive electrode of the bias power supply, and the light-emitting device is arranged above or below the semiconductor device.
The upper conveying roller is made of conductive materials and sequentially connected in series, the upper conveying roller is used for conveying the electricity taking and guiding device, a conductive electrode plate is arranged on the upper surface of the semiconductor device, the upper surface of the conductive electrode plate is connected with the lower end of a supporting rod, and the upper end of the supporting rod is connected with the lower surface of the electricity taking and guiding device.
The solar cell is electrically connected with the bias power supply through a plurality of rows of conductive brushes, the conductive brushes are positioned above the solar cell, the upper ends of the conductive brushes are electrically connected with the negative electrode of the bias power supply, and the lower ends of the conductive brushes are in contact with the upper surface of the solar cell.
The utility model provides a device of horizontal electrochemical deposition metal, includes drainage groove and bias voltage power supply, be provided with the electrolyte groove that is used for holding electrolyte in the drainage groove, the lower extreme intercommunication of electrolyte groove has the transfer line, the lower extreme intercommunication of drainage groove has the drain line, the side of electrolyte groove is equipped with and is used for adjusting electrolyte liquid level's high floodgate, the top of electrolyte groove is provided with the lower conveying gyro wheel that is used for carrying semiconductor device, semiconductor device's upper surface is provided with wireless upper electrode, wireless upper electrode accepts wireless transmission device's electric energy, wireless upper electrode includes upper structure and lower floor's conducting plate, upper structure includes wireless receiving electric energy component and rectifier element, its negative pole output extremely lower floor's conducting plate.
The application has the beneficial effects that:
1. the method and the device for horizontally and electrochemically depositing the metal provided by the application adopt horizontal electroplating and are suitable for mass production.
2. The application adopts the method of multipoint contact or full contact of the upper electrode, thereby ensuring the uniformity and reliability of the electrochemical deposition metal. The upper roller is avoided, and surface damage or device damage can not be caused in the metal deposition process.
3. The application is suitable for directly electroplating metals such as tin, nickel, copper, silver and the like on a transparent conductive film of a HJT battery, perovskite or other thin film batteries or on a passivation film of a HBC battery and a crystalline silicon battery applying surface whole-surface passivation technologies such as TopCon, POLO and the like, and can be used for generating a metal gate line electrode by combining a graphical mask technology. Compared with the screen printing silver paste process, the method has the advantages of low material cost, realization of finer metal grid lines, improvement of battery efficiency and the like.
Drawings
FIG. 1 is a schematic view of an apparatus for horizontal electrochemical deposition of metal according to embodiment 1 of the present application;
FIG. 2 is a schematic view of an apparatus for horizontal electrochemical deposition of metal according to embodiment 2 of the present application;
FIG. 3 is a schematic view showing an apparatus for horizontal electrochemical deposition of metal according to embodiment 3 of the present application;
fig. 4 is a schematic structural diagram of an apparatus for horizontal electrochemical deposition of metal according to embodiment 4 of the present application.
Reference numerals in the drawings are as follows: 10-an electrolyte tank; 11-an infusion line; 12-height gate; 20-a liquid discharge tank; 21-a liquid discharge pipeline; 30-lower conveying rollers; 40-conducting brushes; 41-wireless transmitting means; 42-wireless upper electrode; 43-upper transfer roller; 44-power and steering device; 45-supporting rods; 46-a conductive electrode plate; a 50-semiconductor device; 60-electrolyte; 70-a lower electrode; 80-a light emitting device; 90-bias power supply.
Detailed Description
The present application will be further described with reference to the accompanying drawings, and the following examples are only for more clearly illustrating the technical aspects of the present application, and are not to be construed as limiting the scope of the present application.
With the high efficiency of solar cells, PERC cells, HJT cells or IBC cells, etc. using surface passivation technology will become the mainstream, and the device for horizontal electrochemical deposition of metals according to the present application can perform a reliable and mass-producible metallization process on the surface of transparent conductive films or passivation films of these cells.
According to the method for horizontally electrochemically depositing metal, disclosed by the application, a semiconductor device is horizontally moved, meanwhile, an upper electrode is in full-face or multi-point contact with the upper surface of the semiconductor device, the surface of the metal to be electrochemically deposited below the semiconductor device is contacted with electrolyte solution, electrons are obtained and deposited on the surface of the metal to be electrochemically deposited, and the electrolyte solution can be in full-face contact with the surface of the metal to be electrochemically deposited (the lower surface of the semiconductor device) through spraying or by means of surface tension. The potential difference between the upper electrode and the lower surface of the semiconductor device in contact with the electrolyte solution is achieved by photoinduction, an applied voltage, or a combination of both.
The method is used for directly electroplating on a transparent conductive film of a HJT battery or a perovskite film battery, and can also be used for directly electroplating on a passivation film or a transparent conductive film of an HBC battery or other crystal silicon batteries with the surface integral passivation technology of TopCon, POLO and the like.
The semiconductor device is a solar cell, and the light emitting device is used for uniformly illuminating the light receiving surface of the solar cell to generate a potential difference.
The electrolyte solution is provided with a lower electrode which is electrically connected with the positive electrode of the bias power supply, and an upper electrode which is electrically connected with the negative electrode of the bias power supply.
The semiconductor device 50 is selected as a solar cell in several embodiments below.
Example 1
As shown in fig. 1, an apparatus for horizontal electrochemical deposition of metal according to the present application uses a plurality of rows of conductive brushes as fixed upper electrodes and performs photoinduced plating metallization on the cathode surface of a semiconductor device. The specific structure comprises a liquid discharge groove 20 and a bias power supply 90, wherein an electrolyte groove 10 for containing electrolyte 60 is arranged in the liquid discharge groove 20, the lower end of the electrolyte groove 10 is communicated with a liquid delivery pipeline 11, and the lower end of the liquid discharge groove 20 is communicated with a liquid discharge pipeline 21. The infusion line 11 is connected to a liquid pump for adjusting the inflow speed of the electrolyte 60 and controlling the solution composition of the electrolyte 60. Electrolyte 60 exiting electrolyte tank 10 flows into drain tank 20 and is circulated or collected through drain conduit 21 thereunder.
The side of the electrolyte tank 10 is provided with a height gate 12 for adjusting the liquid level of the electrolyte 60, so that it can sufficiently contact the surface of the metal to be electrochemically deposited of the semiconductor device 50 by adjusting the liquid level of the electrolyte 60, and the other surface of the semiconductor device 50 is not in contact with the electrolyte 60.
A lower electrode 70 is provided in the electrolyte tank 10, and the lower electrode 70 is made of solid metallic copper as an anode. A plurality of solid metal lower electrodes 70 may be uniformly disposed under the electrolyte tank 10 and connected to the conductive brush 40 (upper electrode) by a wire through a bias power supply 90.
Above the electrolyte tank 10 is provided a lower transfer roller 30 for conveying the semiconductor device 50, and the semiconductor device 50 is supported and transferred by the electrolyte tank 10 under a series of lower transfer rollers 30. The lower transfer roller 30 is provided at both ends with fixing members spaced apart by a distance slightly longer than the width of the metal semiconductor device to be electrochemically deposited for preventing the semiconductor device from being deviated during horizontal movement.
The semiconductor device 50 is electrically connected to the negative pole of the bias power supply 90. A light emitting device 80 is provided above or below the semiconductor device 50, preferably below the semiconductor device 50, and in this embodiment, the light emitting device 80 is located in the electrolyte tank 10. The light emitting device 80 is composed of a plurality of uniformly distributed light sources (e.g., LEDs, etc.) to ensure that the semiconductor device 50 is uniformly illuminated throughout the deposition process. It should be noted here that the position of the light emitting device 80 is not limited to the position shown in the drawings, and the light emitting device 80 and the lower electrode metal 70 are not blocked from each other due to the three-dimensional nature of the actual device.
The semiconductor device 50 is a p-type PERC semiconductor device, the p-type surface of which is a screen printed aluminum electrode, and the n-type surface (the surface of the metal to be electrochemically deposited) is a passivation film. The surface of the passivation film of the metal to be electrochemically deposited is subjected to patterning treatment. In this embodiment, the electrochemical deposition of metallic copper will be performed for the n-type surface of the semiconductor device.
The electrolyte solution 60 may contain one or more acid groups (e.g., sulfate, nitrate, etc.), plating metal ions (here copper ions), water, and one or more additives, among others. The electrolyte solution is preferably prepared by dissolving 150.0-250.0 g/L of copper sulfate, 45.0-110.0 g/L of sulfuric acid, 0.5g/L of zinc powder, 1.0-2.0 g/L of active carbon and a proper amount of brightening additive into water. The electrolyte solution composition may be monitored and adjusted during electrochemical deposition of metal using a plating solution monitoring system.
The semiconductor device 50 is electrically connected to the bias power supply 90 through a plurality of rows of conductive brushes 40, the adjacent conductive brushes are spaced apart by preferably not more than 60mm, the conductive brushes 40 serve as upper electrodes, the conductive brushes 40 are located above the semiconductor device 50, the upper ends of the conductive brushes 40 are electrically connected to the negative electrode of the bias power supply 90, and the lower ends of the conductive brushes 40 are in contact with the upper surface of the semiconductor device 50, so that the minimum distance between any point of the upper surface of the solar cell 50 and the nearest conductive brush is less than 30mm. In the electrochemical deposition of metal using light-induced plating, a bias voltage is applied by a bias voltage power supply 90 to control the plating rate.
In this embodiment, the potential difference is realized by photoinduction. In the electrochemical deposition of metal, the semiconductor device 50 develops a potential difference across the light emitting device 80 after it is illuminated. The surface of the P-type electrode connected with the upper electrode is a positive electrode, and electrons flow into the battery through the positive electrode. The lower electrode metal connected with the electrolyte loses electrons and is oxidized into metal ions to enter the electrolyte solution. The surface of the N-type metal to be electrochemically deposited is the negative electrode, and the metal ions in the electrolyte solution 60 in contact therewith acquire electrons from the surface, reduce to metal and deposit on the surface.
In this embodiment, the electrochemical deposition rate may be controlled by varying the bias power supply 90. Here, it is preferable to use white LED light having an energy density of 0.05W/cm2 and control the current density of the plating area to 3.5A/dm by an external power source 2 . After 5 minutes of irradiation (control of the irradiation time was achieved by adjusting the transfer rate of the lower transfer roller), a copper layer was deposited on the cathode surface of the semiconductor device 50 to a thickness of about 4 μm.
Example 2
As shown in fig. 2, an apparatus for horizontal electrochemical deposition of metal according to the present application uses a schematic view of the wireless upper electrode for full-face contact and for galvanic metallization on the surface of a semiconductor device. The specific structure comprises a liquid discharge groove 20 and a bias power supply 90, wherein an electrolyte groove 10 for containing electrolyte 60 is arranged in the liquid discharge groove 20, the lower end of the electrolyte groove 10 is communicated with a liquid delivery pipeline 11, and the lower end of the liquid discharge groove 20 is communicated with a liquid discharge pipeline 21. The infusion line 11 is connected to a liquid pump for adjusting the inflow speed of the electrolyte 60 and controlling the solution composition of the electrolyte 60. Electrolyte 60 exiting electrolyte tank 10 flows into drain tank 20 and is circulated or collected through drain conduit 21 thereunder.
The side of the electrolyte tank 10 is provided with a height gate 12 for adjusting the liquid level of the electrolyte 60, so that it can sufficiently contact the surface of the metal to be electrochemically deposited of the semiconductor device 50 by adjusting the liquid level of the electrolyte 60, and the other surface of the semiconductor device 50 is not in contact with the electrolyte 60.
A lower electrode 70 is arranged in the electrolyte tank 10, and the lower electrode 70 is solid metallic silver as an anode. A plurality of lower electrodes 70 are uniformly disposed under the electrolyte tank 10 and connected to a bias power supply 90 by wires.
Above the electrolyte tank 10 is provided a lower transfer roller 30 for conveying the semiconductor device 50, and the semiconductor device 50 is supported and transferred by the electrolyte tank 10 under a series of lower transfer rollers 30. The lower transfer roller 30 is provided at both ends with fixing members spaced apart by a distance slightly longer than the width of the metal semiconductor device to be electrochemically deposited for preventing the semiconductor device from being deviated during horizontal movement.
The semiconductor device 50 is a HJT battery, the surface of the transparent conductive film of p-type doped amorphous silicon is the surface of the metal to be chemically deposited and is contacted with the electrolyte solution 60, and the surface of the transparent conductive film of n-type doped amorphous silicon is contacted with the wireless upper electrode 42. In this embodiment, the electrochemical deposition of metallic silver will be performed for the n-type surface of the semiconductor device.
The electrolyte solution 60 may contain one or more acid groups (e.g., sulfate, nitrate, etc.), plating metal ions (here, silver ions), water, and one or more additives, among others. The electrolyte solution is preferably prepared by dissolving 40-80g/L of silver nitrate, 200-300g/L of sodium thiosulfate, 50-100g/L of potassium metabisulfite, 10-50g/L of citric acid, 20-50g/L of potassium iodide and 5-10g/L of thiocarbonyl compound in water. The electrolyte solution composition may be monitored and adjusted during electrochemical deposition of metal using a plating solution monitoring system.
The upper surface of the semiconductor device 50 is provided with a wireless upper electrode 42, the wireless upper electrode 42 receives electric power of the wireless transmitting device 41, the wireless upper electrode 42 includes an upper layer structure including a wireless electric power receiving element and a rectifying element, and a lower layer conductive plate to which a negative electrode thereof is output. The lower conductive plate is made of conductive polymer such as conductive fiber and conductive nylon plate or conductive material such as expanded graphite with the characteristics of softness, compression rebound resilience and the like, and is in multi-point or whole-surface contact with the non-electrochemical plating surface of the semiconductor device 50. The positive electrode output of the upper portion of the wireless upper electrode 42 is connected to the electrolyte solution via a plurality of inert conductors or replaceable metal conductors containing plating metal and is uniformly distributed around the semiconductor device 50. During electrochemical deposition of metal, the surface of the n-type metal to be electrochemically deposited of the semiconductor device 50, which is connected to the negative electrode of the wireless upper electrode 42, is the cathode, and the metal ions in the electrolyte solution 60 in contact therewith acquire electrons from the surface, are reduced to metal, and are deposited on the surface.
In this embodiment, the electrochemical deposition efficiency can be controlled by controlling the output current of the upper electrode 42. It is preferable to control the current in the plating area to 5A/dm 2 The deposition was performed for 10 minutes, and the average thickness of silver deposited on the surface of the transparent conductive film of p-type doped amorphous silicon of the semiconductor device 50 was about 10 μm.
Example 3
As shown in fig. 3, an apparatus for horizontal electrochemical deposition of metal according to the present application uses a movable upper electrode for full-face contact and performs galvanic metallization on the surface of a semiconductor device. The specific structure comprises a liquid discharge groove 20 and a bias power supply 90, wherein an electrolyte groove 10 for containing electrolyte 60 is arranged in the liquid discharge groove 20, the lower end of the electrolyte groove 10 is communicated with a liquid delivery pipeline 11, and the lower end of the liquid discharge groove 20 is communicated with a liquid discharge pipeline 21. The infusion line 11 is connected to a liquid pump for adjusting the inflow speed of the electrolyte 60 and controlling the solution composition of the electrolyte 60. Electrolyte 60 exiting electrolyte tank 10 flows into drain tank 20 and is circulated or collected through drain conduit 21 thereunder.
The side of the electrolyte tank 10 is provided with a height gate 12 for adjusting the liquid level of the electrolyte 60, so that it can sufficiently contact the surface of the metal to be electrochemically deposited of the semiconductor device 50 by adjusting the liquid level of the electrolyte 60, and the other surface of the semiconductor device 50 is not in contact with the electrolyte 60.
Above the electrolyte tank 10 is provided a lower transfer roller 30 for conveying the semiconductor device 50, and the semiconductor device 50 is supported and transferred by the electrolyte tank 10 under a series of lower transfer rollers 30. The lower transfer roller 30 is provided at both ends with fixing members spaced apart by a distance slightly longer than the width of the metal semiconductor device to be electrochemically deposited for preventing the semiconductor device from being deviated during horizontal movement.
The semiconductor device 50 is an HBC solar cell, and the front surface thereof is a transparent passivation film. In this embodiment, the copper of the inter-digitated metal electrode is electrochemically deposited for the back side of the patterned masking HBC semiconductor device 50.
The electrolyte solution 60 may contain one or more acid groups (e.g., sulfate, nitrate, etc.), plating metal ions (here copper ions), water, and one or more additives, among others. The electrolyte solution is preferably prepared by dissolving 150.0-250.0 g/L of copper sulfate, 45.0-110.0 g/L of sulfuric acid, 0.5g/L of zinc powder, 1.0-2.0 g/L of active carbon and a proper amount of brightening additive into water. The electrolyte solution composition may be monitored and adjusted during electrochemical deposition of metal using a plating solution monitoring system.
An upper transfer roller 43 for transferring the power and guide means 44, preferably a conductive block of metal, is provided above the lower transfer roller 30, a conductive electrode plate 46 as an upper electrode is provided on the upper surface of the semiconductor device 50, the upper surface of the conductive electrode plate 46 is connected to the lower end of a support rod 45, the upper end of the support rod 45 is connected to the lower surface of the power and guide means 44 and the upper transfer roller 43 made of a conductive material is connected to a bias power supply 90 (or in other embodiments using only photoinduced plating, the power and guide means 44 and the lower electrode 70 are directly conducted, two fixing members are provided at both ends of the upper transfer roller 43 at a distance slightly wider than the width of the power and guide means 44, for ensuring that the power take-off and guide means 44 does not deviate from a predetermined trajectory during transport, the power take-off and guide means 44, preferably a copper ingot, is used as a conductive device and simultaneously moves the support rod 45 and the conductive electrode plate 46 along with the semiconductor device 50 during electrochemical deposition of metal, the support rod 45 is made of a conductive material or comprises a conductive part for connecting the power take-off and guide means 44 and the conductive electrode plate 46, and the support rod 45 comprises a gas spring or the like, so that the pressure applied by the conductive electrode plate 46 to the semiconductor device 50 is adjustable, the conductive electrode plate 46 is a single-layer metal plate or a light polymer plate with a metal foil coated on the surface, the conductive electrode plate 46 can also be a double-layer conductive plate, namely a thin metal plate on the upper layer, a conductive fiber on the lower layer, conductive polymers such as conductive nylon plates, or conductive materials such as expanded graphite, which have the characteristics of softness, compression resilience and the like. The conductive electrode plate 46 is preferably a lightweight polymer plate with an aluminum foil covered surface. The shape of the conductive electrode plate 46 should be the same as the shape of the semiconductor device 50 to which the metal is to be chemically deposited and have a size equal to or slightly smaller than the size of the semiconductor device 50. During the whole deposition process, the conductive electrode plate 46 covers the non-deposition metal surface of the semiconductor device 50 and moves along with the non-deposition metal surface, the contact surface pressure of the conductive electrode plate can be regulated through the support rods 45, and the conductive electrode plate and the support rods can form good whole-surface contact while avoiding damaging the semiconductor device 50.
The semiconductor device 50 is electrically connected to the negative pole of the bias power supply 90. A light emitting device 80 is provided above or below the semiconductor device 50, preferably below the semiconductor device 50, and in this embodiment, the light emitting device 80 is located in the electrolyte tank 10. The light emitting device 80 is composed of a plurality of uniformly distributed light sources (e.g., LEDs, etc.) to ensure that the semiconductor device 50 is uniformly illuminated throughout the deposition process. It should be noted here that the position of the light emitting device 80 is not limited to the position shown in the drawings, and the light emitting device 80 and the lower electrode metal 70 are not blocked from each other due to the three-dimensional nature of the actual device.
In this embodiment, the lower electrode 70 is connected to the positive electrode of the bias power supply 90, and the upper electrode communicates the negative electrode of the bias power supply 90 with the semiconductor device 50. In this embodiment, the potential difference is achieved by applying an electric field from a bias power supply. Under the action of the bias power supply, the surface of the metal to be electrochemically deposited of the semiconductor device 50 is the cathode, and the metal ions in the electrolyte solution 60 in contact therewith acquire electrons from the surface, reduce to metal and deposit on the surface.
In this embodiment, the electrochemical deposition efficiency may be controlled by controlling the output current voltage of the bias power supply 90. The deposition is preferably performed at a current of 10A/dm2 for 10 minutes in the electroplating area, and the average thickness of the deposited copper on the semiconductor device 50 is about 20 microns.
Example 4
As shown in fig. 4, an apparatus for horizontal electrochemical deposition of metal according to the present application uses a movable upper electrode for full-face contact and light-induced plating and galvanic plating metallization on the surface of a semiconductor device. The specific structure comprises a liquid discharge groove 20 and a bias power supply 90, wherein an electrolyte groove 10 for containing electrolyte 60 is arranged in the liquid discharge groove 20, the lower end of the electrolyte groove 10 is communicated with a liquid delivery pipeline 11, and the lower end of the liquid discharge groove 20 is communicated with a liquid discharge pipeline 21. The infusion line 11 is connected to a liquid pump for adjusting the inflow speed of the electrolyte 60 and controlling the solution composition of the electrolyte 60. Electrolyte 60 exiting electrolyte tank 10 flows into drain tank 20 and is circulated or collected through drain conduit 21 thereunder.
The side of the electrolyte tank 10 is provided with a height gate 12 for adjusting the liquid level of the electrolyte 60, so that it can sufficiently contact the surface of the metal to be electrochemically deposited of the semiconductor device 50 by adjusting the liquid level of the electrolyte 60, and the other surface of the semiconductor device 50 is not in contact with the electrolyte 60.
Above the electrolyte tank 10 is provided a lower transfer roller 30 for conveying the semiconductor device 50, and the semiconductor device 50 is supported and transferred by the electrolyte tank 10 under a series of lower transfer rollers 30. The lower transfer roller 30 is provided at both ends with fixing members spaced apart by a distance slightly longer than the width of the metal semiconductor device to be electrochemically deposited for preventing the semiconductor device from being deviated during horizontal movement.
The semiconductor device 50 is a HJT semiconductor device. In this embodiment, a photoinduced electroplating method is used to deposit a copper electrode on the surface of the transparent conductive film on the n-type doped amorphous silicon, then the HJT semiconductor device 50 is turned over, and then a current is used to deposit a copper electrode on the surface of the transparent conductive film on the P-type doped amorphous silicon.
The electrolyte solution 60 may contain one or more acid groups (e.g., sulfate, nitrate, etc.), plating metal ions (here copper ions), water, and one or more additives, among others. The electrolyte solution is preferably prepared by dissolving 150.0-250.0 g/L of copper sulfate, 45.0-110.0 g/L of sulfuric acid, 0.5g/L of zinc powder, 1.0-2.0 g/L of active carbon and a proper amount of brightening additive into water. The electrolyte solution composition may be monitored and adjusted during electrochemical deposition of metal using a plating solution monitoring system.
An upper transfer roller 43 for transferring the electricity/guiding means 44, preferably a metal conductive block, is disposed above the lower transfer roller 30, a conductive electrode plate 46 as an upper electrode and a support rod 45 connected thereto are disposed on the upper surface of the solar cell 50, and the upper end of the support rod 45 is connected to the conductive block 44 and connected to a bias power supply 90 through the upper transfer roller 43 made of a conductive material. Two fixing elements, which are slightly wider than the width of the power take-off and guide device 44, are provided at both ends of the upper transfer roller 43 for ensuring that the power take-off and guide device 44 does not deviate from a predetermined track during transfer. The power take-off and guide device 44, preferably a copper ingot, serves as a conductive device and simultaneously moves the support rod 45 and the conductive electrode plate 46 in synchronism with the semiconductor device 50 during electrochemical deposition of metal. The supporting rod 45 is made of conductive material or contains conductive components and is used for connecting the electricity taking and guiding device 44 and the conductive electrode plate 46. While the support rods 45 contain gas springs or the like therein so that the pressure applied by the conductive electrode plates 46 to the semiconductor device 50 can be adjusted. The conductive electrode plate 46 is preferably of a double layer design, the upper aluminum metal plate ensures uniform current transmission across the cross-section, and the lower layer is a conductive polymer such as conductive fiber, conductive nylon plate, or a conductive material such as expanded graphite having the characteristics of softness and compression resilience to provide the necessary conductivity without damaging the wafer surface. Preferably, the upper layer of the conductive electrode plate 46 is an aluminum plate and the lower layer is expanded graphite. The shape of the conductive electrode plate 46 should be the same as the shape of the semiconductor device 50 to which the metal is to be chemically deposited and have a size equal to or slightly smaller than the size of the semiconductor device 50. During the whole deposition process, the conductive electrode plate 46 covers the non-deposition metal surface of the semiconductor device 50 and moves along with the non-deposition metal surface, the contact surface pressure of the conductive electrode plate can be regulated through the support rods 45, and the conductive electrode plate and the support rods can form good whole-surface contact while avoiding damaging the semiconductor device 50.
The lower electrode 70 (anode) is solid metallic copper. A plurality of solid metal lower electrodes 70 may be uniformly placed under the electrolyte tank 10 and connected to the upper electrodes by wires through a bias power supply 90.
During the photoinduced plating, the surface of the transparent conductive film on the n-type doped amorphous silicon of the semiconductor device 50 is in contact with the electrolyte solution 60 and moves from one end of the electrolyte tank 10 to the other end under the conveyance of the lower conveyance roller 30. In this process, the conductive electrode plate 46 is covered on the surface of the transparent conductive film on the p-type doped amorphous silicon of the semiconductor device 50 and moves in synchronization therewith. The light emitting device 80 is preferably placed under the electrolyte tank. The electrochemical deposition rate is controlled by varying the bias voltage power supply 90. Here, it is preferable to use a white LED light having an energy density of 0.05W/cm2 and control the current density of the plating area to 5A/dm by an external power source 2 . After 5 minutes of irradiation, a copper layer was deposited to a thickness of about 5 μm on the surface of the transparent conductive film on the n-type doped amorphous silicon of the semiconductor device 50.
The semiconductor device 50 is then flipped over so that the surface of the transparent conductive film on the p-type doped amorphous silicon is in contact with the electrolyte solution 60 and moved from one end of the electrolyte tank 10 to the other end by the transfer of the lower transfer roller 30. In this process, the conductive electrode plate 46 covers the metal electrode deposited on the n-type doped amorphous silicon side of the semiconductor device 50. At this time, the light emitting device 80 is in an off state. The electroplating potential difference is achieved by applying an electric field to the bias voltage supply 90, and the electrochemical deposition efficiency can be controlled by controlling the output current voltage of the bias voltage supply 90. Here, it is preferable to control the current in the plating area to 2.5A/dm 2 Deposition was performed for 10 minutes, and the average thickness of copper deposited on the surface of the transparent conductive film on the p-type doped amorphous silicon of the semiconductor device 50 was about 5 μm.
The foregoing is merely a preferred embodiment of the present application and it will be apparent to those skilled in the art that numerous modifications and variations can be made without departing from the principles of the application, and such modifications and variations are to be regarded as being within the scope of the application.

Claims (12)

1. A method of horizontal electrochemical deposition of metal, characterized by:
the semiconductor device is moved horizontally,
the upper electrode is brought into contact with the upper surface of the semiconductor device by full-face contact or multipoint contact,
contacting the surface of the metal to be electrochemically deposited under the semiconductor device with an electrolyte solution, so that metal ions in the electrolyte solution obtain electrons and deposit on the surface,
the potential difference between the upper electrode and the lower surface of the semiconductor device in contact with the electrolyte solution is achieved by photoinduction, an applied voltage, or a combination of both.
2. A method of horizontal electrochemical deposition of metal according to claim 1, wherein: the method is used for direct electroplating on a transparent conductive film of a HJT cell or perovskite thin film cell, or for direct electroplating on a passivation film or transparent conductive film of an HBC cell or other crystalline silicon cell to which a surface full-face passivation technique is applied.
3. A method of horizontal electrochemical deposition of metal according to claim 1, wherein: the upper electrode is contacted with the upper surface of the semiconductor device by adopting multipoint contact, and the minimum linear distance between any point on the surface of the semiconductor device contacted with the upper electrode and the nearest conductive contact part of the upper electrode is smaller than 60mm.
4. A method of horizontal electrochemical deposition of metal according to claim 1, wherein: in the process of electrochemically depositing metal, the upper electrode keeps synchronous horizontal movement along with the semiconductor device, so that the upper electrode and the semiconductor device keep contact connection and electrical connection in the process of synchronous horizontal movement, or the upper electrode is in friction contact with the upper surface of the semiconductor device, or induced current is generated on the upper surface of the semiconductor device through an electromagnetic induction principle.
5. An apparatus for horizontal electrochemical deposition of metal, characterized by: the device comprises an electrolyte tank (10), wherein a lower electrode (70) is arranged in the electrolyte tank (10), a lower conveying roller (30) for conveying a semiconductor device (50) is arranged above the electrolyte tank (10), the whole surface of the upper surface of the semiconductor device (50) or multiple points of the upper surface of the semiconductor device are contacted with an upper electrode, and the upper electrode is connected with the lower electrode (70).
6. An apparatus for horizontal electrochemical deposition of metal according to claim 5, wherein: the connection of the upper electrode and the lower electrode (70) comprises the following three modes, wherein one mode is that the upper electrode is connected with the negative electrode of a bias power supply (90), and the lower electrode (70) is connected with the positive electrode of the bias power supply (90); the second is that the upper electrode is directly connected with the lower electrode (70), and a light-emitting device (80) is arranged above or below the semiconductor device (50); and thirdly, the upper electrode is connected with the negative electrode of the bias power supply (90), the lower electrode (70) is connected with the positive electrode of the bias power supply (90), and the light emitting device (80) is arranged above or below the semiconductor device (50).
7. An apparatus for horizontal electrochemical deposition of metal according to claim 5 or 6, wherein: the upper conveying roller (43) capable of synchronously running is arranged above the lower conveying roller (30), the upper conveying roller (43) is made of conductive materials and sequentially connected in series through wires, the upper conveying roller (43) is used for conveying an electricity taking and guiding device (44), a conductive electrode plate (46) is arranged on the upper surface of a semiconductor device (50), the lower end of a supporting rod (45) is connected to the upper surface of the conductive electrode plate (46), and the upper end of the supporting rod (45) is connected with the lower surface of the electricity taking and guiding device (44).
8. The apparatus for horizontal electrochemical deposition of metal according to claim 7, comprising any one or a combination of two or more of the following:
(1) Two fixing elements which are slightly wider than the width of the power taking and guiding device 44 are arranged at two ends of the upper conveying roller 43 and are used for ensuring that the power taking and guiding device 44 does not deviate from a preset track in the conveying process;
(2) The supporting rod 45 contains a gas spring, so that the pressure applied by the conductive electrode plate 46 to the semiconductor device 50 can be adjusted;
(3) The conductive electrode plate 46 is a single-layer metal plate or a light polymer plate coated with metal foil on the surface;
(4) The conductive electrode plate 46 is a double-layer conductive plate, the upper layer is a thin metal plate, and the lower layer is conductive polymer or expanded graphite;
(5) The shape of the conductive electrode plate 46 is the same as that of the semiconductor device 50 to be subjected to electroless deposition of metal, and the size is equal to or slightly smaller than that of the semiconductor device 50;
(6) The rollers 30 are provided with fixing elements at both ends thereof, and the distance between the two fixing elements is slightly longer than the width of the metal semiconductor device to be electrochemically deposited, so as to avoid the semiconductor device from deviating during the horizontal movement.
9. An apparatus for horizontal electrochemical deposition of metal according to claim 5 or 6, wherein: the electrolyte tank is characterized by further comprising a liquid discharge groove (20), an electrolyte tank (10) for containing electrolyte (60) is arranged in the liquid discharge groove (20), the lower end of the electrolyte tank (10) is communicated with a liquid conveying pipeline (11), the lower end of the liquid discharge groove (20) is communicated with a liquid discharge pipeline (21), and a height gate (12) for adjusting the liquid level height of the electrolyte (60) is arranged on the side face of the electrolyte tank (10).
10. An apparatus for horizontal electrochemical deposition of metal according to claim 5 or 6, wherein: the solar cell (50) is electrically connected with the bias power supply (90) through a plurality of rows of conductive brushes (40), the conductive brushes (40) are positioned above the solar cell (50), the upper ends of the conductive brushes (40) are electrically connected with the negative electrode of the bias power supply (90), and the lower ends of the conductive brushes (40) are in contact with the upper surface of the solar cell (50).
11. An apparatus for horizontal electrochemical deposition of metal, the lower surface of a semiconductor device (50) being in contact with an electrolyte solution 60, characterized in that: the wireless power supply device comprises a wireless transmitting device (41) and a wireless upper electrode (42), wherein the wireless upper electrode (42) is arranged on the upper surface of the semiconductor device (50), the wireless upper electrode (42) receives electric energy of the wireless transmitting device (41), the wireless upper electrode (42) comprises an upper structure and a lower conductive plate, the upper structure comprises a wireless power receiving element and a rectifying element, and the negative electrode of the rectifying element is output to the lower conductive plate; the wireless transmitting device (41) transmits current to the wireless receiving electric energy element through an electromagnetic induction principle, the rectifying element is used for converting alternating current output by the wireless receiving electric energy element into direct current, and the positive electrode of the rectifying element is connected to the lower electrode (70) in the electroplating liquid.
12. The device for horizontal electrochemical deposition of metal according to claim 11, further comprising a drain tank (20), wherein an electrolyte tank (10) for containing electrolyte (60) is arranged in the drain tank (20), a transfusion pipeline (11) is communicated with the lower end of the electrolyte tank (10), a drain pipeline (21) is communicated with the lower end of the drain tank (20), a height gate (12) for adjusting the liquid level of the electrolyte (60) is arranged on the side surface of the electrolyte tank (10), and a lower conveying roller (30) for conveying the semiconductor device (50) is arranged above the electrolyte tank (10).
CN202311167437.XA 2018-06-22 2018-06-22 Method and device for horizontal electrochemical deposition of metal Pending CN117107314A (en)

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