CN116387400A - Boron diffusion method and device of TOPCON battery - Google Patents
Boron diffusion method and device of TOPCON battery Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 167
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 88
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
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Abstract
The invention relates to the technical field of solar cells, and particularly discloses a boron diffusion method and device of a TOPCON cell. The method comprises the following steps: the method comprises the following steps: the silicon wafer enters a diffusion furnace tube, and sequentially undergoes first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling annealing and the silicon wafer exits the diffusion furnace tube; wherein the temperature of the first deposition is 800-850 ℃; the temperature of the first oxidation, the second oxidation and the third deposition are 5-10 ℃ higher than the temperature of the previous step, and the temperature of the fourth deposition is 10-20 ℃ higher than the temperature of the third deposition; the temperature of the second deposition is the same as the temperature of the first oxidation. The method can improve the open-circuit voltage and the short-circuit current of the TOPCON battery, thereby improving the photoelectric conversion efficiency of the TOPCON battery.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a boron diffusion method and device of a TOPCON cell.
Background
TOPCon cells, i.e., tunnel Oxide Passivated Contact cells, are a type of solar cell based on the selective carrier principle with passivation contact of the tunnel oxide layer, and are one of the most competitive cell types for mass production at present. TOPCon cell fronts are typically formed with P-type emitters using a boron diffusion process.
The application of the selective emitter can improve the open-circuit voltage and short-circuit current of the battery, and further improve the photoelectric conversion efficiency of the battery. The boron-diffused selective emitter (SE, selective Emitter) structure battery is characterized in that the contact area (namely an electrode contact part) between a boron diffusion surface metal grid line and a silicon wafer is heavily doped (P++), and the non-metal contact area between metal electrodes is lightly doped (P+). To achieve this structure, boron-diffused laser direct doping techniques must be used. The boron diffusion laser direct doping technology has two difficult problems, namely, the laser directly contacts the PN junction surface to damage the PN junction surface, and sufficient boron atoms are needed to be pushed by the laser to enable the PN junction surface to be heavily doped corresponding to the printed grid line region, and if the difficult problems are solved, the boron diffusion process is also the key, so that the boron diffusion process is challenged.
Although the boron diffusion process is improved, the purpose of manufacturing the emitter is only achieved, the higher boron surface concentration is not obtained, and more boron atoms cannot be provided due to the diffusion difference of boron in silicon and silicon oxide and impurity segregation phenomenon; in addition, in order to obtain a higher surface concentration, the advancing temperature is high, which is liable to cause problems such as oxygen ring and crystal defects.
Disclosure of Invention
In view of the above problems, the present invention provides a boron diffusion method for a TOPCon battery, which can provide a sufficient boron diffusion source for laser to advance so as to form heavy doping in a corresponding printed grid line region; and a protective film can be formed on the surface of the PN junction, so that the damage of the PN junction caused by laser is avoided. The method is a boron diffusion method suitable for selective emitter laser doping, and can improve the open-circuit voltage and short-circuit current of the TOPCON battery, thereby improving the photoelectric conversion efficiency of the TOPCON battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a boron diffusion method of a TOPCon battery, comprising the steps of: the silicon wafer enters a diffusion furnace tube, and sequentially undergoes first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling annealing and the silicon wafer exits the diffusion furnace tube;
wherein the temperature of the first deposition is 800-850 ℃;
the temperature of the first oxidation, the second oxidation and the third deposition are 5-10 ℃ higher than the temperature of the previous step, and the temperature of the fourth deposition is 10-20 ℃ higher than the temperature of the third deposition;
the temperature of the second deposition is the same as the temperature of the first oxidation.
Compared with the prior art, the method provided by the invention provides sufficient boron diffusion sources for subsequent laser propulsion through four-time deposition and two-time oxidation of temperature layer-by-layer progression, so that heavy doping is formed in the corresponding printed grid line area; and a protective film is formed on the surface of the PN junction, so that the damage of the PN junction caused by laser is avoided. The junction depth of the finally formed non-metal contact area is shallow, and the sheet resistance is large; and performing laser propulsion on the printed grid line area by the subsequent steps to realize secondary doping, so as to obtain deeper junction depth and smaller sheet resistance and realize good ohmic contact. The temperature of the whole boron diffusion process is not more than 900 ℃, the sheet resistance of the silicon wafer is larger, the laser propulsion effect of the subsequent steps is ensured, and the service life of equipment is prolonged.
The invention carries out oxidation and boron atom deposition on the surface of the silicon wafer through the first deposition, the second deposition and the third deposition; the generation of a boron diffusion dead layer can be reduced through the first oxidation and the second oxidation, and meanwhile, the deep boron source can be pushed into the silicon wafer by heating, so that the effect of 'removing the surface and pushing the inner' can be achieved; providing sufficient boron doping source for subsequent laser heavy doping through fourth deposition, which is beneficial to improving the conversion efficiency of the battery, and meanwhile, borosilicate glass with thicker surface layer can also form a protective layer for the P-N junction; and finally, reducing the thermal internal stress of the silicon wafer caused by high temperature by cooling and annealing, thereby reducing the generation of fragments. Light doping is formed through first deposition, first oxidation, second deposition, second oxidation and third deposition, and preparation is made for laser propulsion in subsequent steps through fourth deposition to achieve secondary doping. The method is a boron diffusion method suitable for selective emitter laser doping, and can improve the open-circuit voltage and short-circuit current of the TOPCON battery, thereby improving the photoelectric conversion efficiency of the TOPCON battery.
Optionally, empty pipe purification is performed before the silicon wafer enters the diffusion furnace tube step, and silicon wafer purification is performed before the silicon wafer starts the first deposition step. Through empty pipe purification, metal ions such as sodium, iron and the like in the diffusion furnace tube can be removed, and the silicon wafer is prevented from being polluted by metal. After the silicon wafer is cleaned in the last texturing process, the risk of pollution of certain metal ions and the like exists in the process of transporting the silicon wafer to the boron diffusion process, and the silicon wafer can be purified through silicon wafer purification.
After the silicon wafer purifying step and before the first deposition step, evacuation, leak detection and stabilization are also required; and after the cooling annealing step and before the silicon wafer exits the diffusion furnace tube step, nitrogen is filled into the diffusion furnace tube.
Optionally, the temperature of the empty pipe purification and the silicon chip purification is 750-800 ℃, the time is 1-5 min, the flow rate of nitrogen is 4500-5500 sccm, and the pressure is 1000-1050 mbar.
Optionally, the flow rate of the boron trichloride purified by the empty pipe is 100-200 sccm, and the flow rate of the boron trichloride purified by the silicon wafer is 50-100 sccm. At high temperature, boron trichloride is thermally decomposed to obtain chlorine, and the chlorine has the effect of removing metal ions such as sodium, iron and the like.
Optionally, the time of the first deposition, the second deposition and the third deposition is 5-10 min, the flow rate of oxygen is 300-500 sccm, the flow rate of nitrogen is 2500-3000 sccm, and the pressure is 80-120 mbar.
Optionally, the flow rate of the first deposited boron trichloride and the flow rate of the second deposited boron trichloride are both 100-200 sccm, and the flow rate of the third deposited boron trichloride is 300-500 sccm.
And oxidizing the surface of the silicon wafer and depositing boron atoms through three times of deposition at different temperatures and at the flow rate of boron trichloride. Wherein the flow of oxygen in the first deposition and the second deposition is excessive compared with the flow of boron trichloride so as to enhance the oxidability and reduce the generation of a diffusion dead layer; the flow rate of the boron trichloride in the third deposition is increased, so that more boron atoms are attached to the surface of the silicon wafer.
Optionally, the time of the first oxidation and the second oxidation is 1-5 min, the flow rate of oxygen is 2000-3000 sccm, the flow rate of nitrogen is 2500-3000 sccm, and the pressure is 80-120 mbar.
Optionally, the first oxidized gas further comprises an inert gas, and the flow ratio of the inert gas to the oxygen is 1:9-11.
Further optionally, the inert gas includes at least one of argon, helium, or neon.
The generation of a diffusion dead layer can be reduced through the first oxidation and the second oxidation, and meanwhile, the deep boron source is pushed into silicon by heating, so that the technical effect of 'removing the surface and pushing the inside' is achieved. The inert gas is introduced in the first oxidation process, and serves as a protective gas to reduce the oxidation of the silicon wafer, reduce the heat loss, and play a role in air flow circulation to take away volatile matters such as silicon oxide and the like on the surface of the silicon wafer.
Optionally, the fourth deposition time is 20-40 min, the flow rate of oxygen is 4500-5500 sccm, the flow rate of nitrogen is 2500-3000 sccm, the flow rate of boron trichloride is 500-1000 sccm, and the pressure is 80-120 mbar. By further improving the flow of boron trichloride and oxygen, thicker borosilicate glass is formed on the surface of the silicon wafer, sufficient boron atoms are provided for selective emitter laser secondary doping, and the printed grid line area is subjected to heavy doping, so that good ohmic contact is realized; meanwhile, a layer of protective film is formed on the inner surface of the silicon wafer by thicker borosilicate glass, so that damage to PN junctions in the process of selective emitter laser secondary doping is avoided.
Optionally, the temperature of the cooled annealing is 700-750 ℃, the time is 10-20 min, the flow of nitrogen is 5000-8000 sccm, and the pressure is 80-120 mbar.
In combination with the above technical solution, as an embodiment of the present invention, the method includes the following steps:
(1) Silicon wafer enters into diffusion furnace tube
After the temperature in the diffusion furnace tube reaches a preset temperature, placing the silicon wafer into a quartz boat, and feeding the silicon wafer into the diffusion furnace tube;
(2) First deposition
After the temperature in the diffusion furnace tube reaches a preset temperature, introducing boron trichloride, oxygen and nitrogen to oxidize the surface of the silicon wafer and deposit boron atoms;
(3) First oxidation
After the temperature in the diffusion furnace tube is increased by 5-10 ℃ compared with the preset temperature in the step (2), introducing inert gas, oxygen and nitrogen to oxidize the surface of the silicon wafer;
(4) Second deposition
Introducing boron trichloride, oxygen and nitrogen to oxidize the surface of the silicon wafer and depositing boron atoms under the temperature condition of the first oxidation;
(5) Second oxidation
After the temperature in the diffusion furnace tube is increased by 5-10 ℃ compared with the temperature of the second deposition, introducing oxygen and nitrogen to oxidize the surface of the silicon wafer;
(6) Third deposition
After the temperature in the diffusion furnace tube is increased by 5-10 ℃ compared with the temperature of the second oxidation, introducing boron trichloride, oxygen and nitrogen to oxidize the surface of the silicon wafer and deposit boron atoms;
(7) Fourth deposition
After the temperature in the diffusion furnace tube is increased by 10-20 ℃ compared with the temperature of the third deposition, introducing boron trichloride, oxygen and nitrogen to oxidize the surface of the silicon wafer and deposit boron atoms;
(8) Cooling and annealing
Introducing nitrogen, and cooling and annealing;
(9) And the silicon wafer exits the diffusion furnace tube.
Optionally, purging the silicon wafer before the silicon wafer enters the diffusion furnace tube and after the silicon wafer exits the diffusion furnace tube by using high-pressure nitrogen;
the outlet pressure of the high-pressure nitrogen pipeline is 0.1-1.0 MPa.
The invention further provides a boron diffusion device of the TOPCO battery, and a high-pressure nitrogen pipeline is arranged at the position of a diffusion furnace mouth of the boron diffusion device.
Compared with the prior art, the high-pressure nitrogen pipeline is arranged at the position of the diffusion furnace mouth of the boron diffusion device to form the air curtain, so that the furnace tube is isolated by high-pressure nitrogen when the door is opened, the possibility of being polluted when the door is opened in the furnace tube is reduced, the cleanliness in the furnace tube is increased, and the diffusion quality is improved. Meanwhile, as the silicon wafers in the same groove can be adhered in the high-temperature diffusion process, at present, conventional diffusion equipment needs to purge the silicon wafers in a loading and unloading area by using compressed air when unloading the diffused silicon wafers, so as to blow the silicon wafers adhered in the same groove open, thereby avoiding the phenomena of wafer falling and fragments caused by adhesion of the silicon wafers when a robot arm unloads the wafers, but the compressed air has impurities such as water and oil and is easy to cause the pollution of the silicon wafers. According to the invention, the high-pressure nitrogen pipeline is arranged at the diffusion furnace mouth of the boron diffusion device, and the high-pressure nitrogen is used for purging the silicon wafer, so that the conditions of wafer connection and fragments during automatic unloading of the silicon wafer caused by adhesion of the silicon wafer in the same groove can be avoided, and meanwhile, the cleaning of the silicon wafer is ensured.
The boron diffusion device of the TOPCO battery further comprises a diffusion furnace tube, a quartz boat, an air inlet mechanism and an exhaust mechanism; the first end of the diffusion furnace tube is provided with a furnace mouth, and the second end of the diffusion furnace tube is provided with the air inlet mechanism and the air exhaust mechanism; the quartz boat is arranged in the diffusion furnace tube and used for loading silicon wafers.
Optionally, before the silicon wafer enters the diffusion furnace tube and after the silicon wafer exits the diffusion furnace tube, the high-pressure nitrogen pipeline is opened to purge the silicon wafer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the boron surface concentration of a silicon wafer as a function of the depth of the silicon wafer after the boron diffusion process treatment of example 3 and comparative example 2;
wherein, curve 1 represents the change of boron surface concentration of the silicon wafer with the depth of the silicon wafer after the boron diffusion process treatment of example 3, and curve 2 represents the change of boron surface concentration of the silicon wafer with the depth of the silicon wafer after the boron diffusion process treatment of comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
The front surface of the traditional TOPCO battery uses silver-aluminum paste to improve contact resistance, aluminum and silicon react well, but aluminum metal is active so as to form aluminum puncture, and the penetration depth is deep. To address this problem, the boron diffusion process typically increases the diffusion temperature to further push the junction deeper and reduce surface recombination in the non-metallic region. Based on this, the entire high-temperature diffusion process is relatively long, so that this is why the current requirements for boron diffusion equipment are very high.
Aiming at the problems, the corresponding printed grid line area can be heavily doped, so that good ohmic contact is realized, the non-electrode grid line area is lightly doped, and the recombination of a diffusion layer can be reduced, so that the output current and voltage of the solar cell are increased through optimizing an emitter, and the photoelectric conversion efficiency is increased. To achieve this structure, a boron diffusion laser direct doping technique must be used, followed by a laser doping process. The boron diffusion laser direct doping technology has two difficult problems, namely, the direct contact with the PN junction surface can cause damage to the PN junction surface, and sufficient boron atoms are needed to be pushed by the PN junction surface to enable the PN junction surface to be correspondingly doped with the printed grid line region, so that the boron diffusion technology has a challenge if the difficult problems are solved and the key is also in the boron diffusion process.
The boron diffusion principle is that gaseous boron trichloride is carried into a high-temperature quartz tube by nitrogen, and reacts with oxygen at high temperature to generate granular boron oxide; the boron atoms are formed by carrying and depositing nitrogen on the surface of the silicon wafer and reacting with silicon, and the specific chemical reaction process is as follows:
4BCl 3 +3O 2 →2B 2 O 3 +6Cl 2
2B 2 O 3 +3Si→3SiO 2 +4B
the boron diffusion method of the TOPCON battery provided by the invention comprises the following steps of: the silicon wafer enters a diffusion furnace tube, and the silicon wafer exits the diffusion furnace tube after first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling and annealing;
wherein the temperature of the first deposition is 800-850 ℃;
the temperature of the first oxidation, the second oxidation and the third deposition are 5-10 ℃ higher than the temperature of the previous step, and the temperature of the fourth deposition is 10-20 ℃ higher than the temperature of the third deposition;
the temperature of the second deposition is the same as the temperature of the first oxidation.
The invention provides a brand new boron diffusion process concept, which can provide a sufficient boron diffusion source for laser to advance so as to form heavy doping in the corresponding printed grid line area; and a protective film can be formed on the surface of the PN junction, so that the damage of the PN junction caused by laser is avoided. The method is a boron diffusion method suitable for selective emitter laser doping, and can improve the open-circuit voltage and short-circuit current of the TOPCON battery, thereby improving the photoelectric conversion efficiency of the TOPCON battery.
Furthermore, the inventors found that diffusion furnace port contamination during production had an impact on TOPCon cell performance. In order to avoid the fluctuation of the battery performance caused by the pollution of the diffusion furnace mouth, the TOPCON battery production needs to be stopped, after the silicon wafer in the furnace tube is discharged out of the tube, the furnace tube is thoroughly cooled, and then the tube mouth is manually cleaned, so that the waste of productivity is caused. In order to solve the problems, the invention also provides a boron diffusion device, wherein a high-pressure nitrogen pipeline is arranged at the position of a diffusion furnace mouth of the boron diffusion device to form an air curtain, so that a furnace tube is isolated by high-pressure nitrogen when the furnace tube is opened, pollution in the furnace tube when the furnace tube is opened is reduced, cleanliness in the furnace tube is increased, and diffusion quality is improved; meanwhile, the silicon wafers in the same groove have the adhesion phenomenon in the high-temperature diffusion process, at present, when the diffused silicon wafers are unloaded by conventional diffusion equipment, compressed air is required to be used for blowing each boat of silicon wafers in a loading and unloading area, so that the silicon wafers adhered in the same groove are blown away, the phenomenon that the adhered silicon wafers are simultaneously sucked up to cause wafer falling and fragments when a robot arm unloads the wafers is avoided, but the compressed air has the phenomenon of containing water, oil and other impurities, and the silicon wafers can be polluted. Therefore, when the silicon wafer is finished with the process outlet pipe, the device sweeps the silicon wafer by process nitrogen, so that the phenomenon that the silicon wafer is stuck in the same groove to cause connection and fragments during automatic unloading of the silicon wafer can be avoided, and meanwhile, the silicon wafer can be ensured to be clean and not polluted.
Example 1
1000 TOPCon cells were prepared according to the following procedure, including texturing, boron diffusion, laser doping, oxidation, wet texturing, tunnel oxidation and polysilicon, annealing, wet processing, plating, screen printing, sintering and implantation. The process flow is a conventional process flow.
In the boron diffusion process, the embodiment provides a boron diffusion method of a TOPCO battery, which comprises the following steps: the silicon wafer enters a diffusion furnace tube, is pumped out, is subjected to leak detection, is stabilized, and is subjected to first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling and annealing, nitrogen filling and exits the diffusion furnace tube. Wherein the technological parameters of each step are shown in Table 1, and the specific operation of each step is as follows:
(1) Silicon wafer enters into diffusion furnace tube
And after the temperature in the diffusion furnace tube reaches 750 ℃, placing the silicon wafer into a quartz boat, and feeding the silicon wafer into the diffusion furnace tube. Wherein the pressure in the diffusion furnace tube is 1030mbar.
(2) Evacuating and evacuating
And (5) raising the temperature in the diffusion furnace tube to 800 ℃ and carrying out vacuumizing treatment.
(3) Leak detection
And (3) carrying out leak detection on the diffusion furnace tube at the temperature of the step (2), wherein the pressure in the diffusion furnace tube is 1030mbar.
(4) Stabilization
And (3) introducing oxygen into the diffusion furnace tube at the temperature of the step (3) for stabilizing for 5min. Wherein the flow rate of oxygen is 2000sccm, and the pressure in the diffusion furnace tube is 100mbar.
(5) First deposition
And (3) introducing boron trichloride, oxygen and nitrogen at the temperature of the step (4) to oxidize the surface of the silicon wafer and deposit boron atoms. Wherein the deposition time was 5min, the flow rate of oxygen gas was 300sccm, the flow rate of nitrogen gas was 2500sccm, the flow rate of boron trichloride was 100sccm, and the pressure was 80mbar.
(6) First oxidation
And (3) after the temperature in the diffusion furnace tube is increased to 805 ℃, introducing inert gas, oxygen and nitrogen to oxidize the surface of the silicon wafer. Wherein the time of oxidation is 1min, the flow rate of oxygen is 2000sccm, the flow rate of inert gas is 200sccm, the flow rate of nitrogen is 2500sccm, and the pressure is 80mbar.
(7) Second deposition
And (3) introducing boron trichloride, oxygen and nitrogen at the temperature of the step (6) to oxidize the surface of the silicon wafer and deposit boron atoms. Wherein the deposition time was 5min, the flow rate of oxygen gas was 300sccm, the flow rate of nitrogen gas was 2500sccm, the flow rate of boron trichloride was 100sccm, and the pressure was 80mbar.
(8) Second oxidation
After the temperature in the diffusion furnace tube is increased to 810 ℃, oxygen and nitrogen are introduced to oxidize the surface of the silicon wafer. Wherein the time of oxidation is 1min, the flow rate of oxygen is 2000sccm, the flow rate of nitrogen is 2500sccm, and the pressure is 80mbar.
(9) Third deposition
And (3) after the temperature in the diffusion furnace tube is increased to 815 ℃, introducing boron trichloride, oxygen and nitrogen to oxidize the surface of the silicon wafer and deposit boron atoms. Wherein the deposition time was 5min, the flow rate of oxygen gas was 300sccm, the flow rate of nitrogen gas was 2500sccm, the flow rate of boron trichloride was 300sccm, and the pressure was 80mbar.
(10) Fourth deposition
And (3) after the temperature in the diffusion furnace tube is increased to 825 ℃, introducing boron trichloride, oxygen and nitrogen to oxidize the surface of the silicon wafer and depositing boron atoms. Wherein the deposition time was 20min, the flow rate of oxygen was 4500sccm, the flow rate of nitrogen was 2500sccm, the flow rate of boron trichloride was 500sccm, and the pressure was 80mbar.
(11) Cooling and annealing
And (5) reducing the temperature in the diffusion furnace tube to 700 ℃ and carrying out annealing treatment for 10min. Wherein the flow rate of nitrogen is 2500sccm and the pressure is 80mbar.
(12) Nitrogen filling
And (3) performing nitrogen charging treatment at the temperature of the step (11). Wherein the flow rate of nitrogen is 2500sccm and the pressure is 1030mbar.
(13) And (5) the silicon wafer is withdrawn from the diffusion furnace tube.
TABLE 1
Example 2
1000 TOPCon cells were prepared following the procedure in example 1.
In the boron diffusion process, the embodiment provides a boron diffusion method of a TOPCO battery, which comprises the following steps: the silicon wafer enters a diffusion furnace tube, is pumped out, is subjected to leak detection, is stabilized, and is subjected to first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling and annealing, nitrogen filling and exits the diffusion furnace tube. The process parameters of each step are shown in Table 2.
TABLE 2
Example 3
1000 TOPCon cells were prepared following the procedure in example 1.
In the boron diffusion process, the embodiment provides a boron diffusion method of a TOPCO battery, which comprises the following steps: the silicon wafer enters a diffusion furnace tube, is pumped out, is subjected to leak detection, is stabilized, and is subjected to first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling and annealing, nitrogen filling and exits the diffusion furnace tube. The process parameters of each step are shown in Table 3.
TABLE 3 Table 3
Example 4
1000 TOPCon cells were prepared following the procedure in example 1.
In the boron diffusion process, the embodiment provides a boron diffusion method of a TOPCO battery, which comprises the following steps: empty pipe purification, silicon wafer entering a diffusion furnace tube, silicon wafer purification, evacuation, leak detection, stabilization, first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling annealing, nitrogen charging and silicon wafer exiting the diffusion furnace tube. The process parameters of each step are shown in Table 4.
TABLE 4 Table 4
Example 5
1000 TOPCon cells were prepared following the procedure in example 1.
In the boron diffusion process, the embodiment provides a boron diffusion method of a TOPCO battery, which comprises the following steps: the silicon wafer enters a diffusion furnace tube, is pumped out, is subjected to leak detection, is stabilized, and is subjected to first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling and annealing, nitrogen filling and exits the diffusion furnace tube. Wherein the process parameters of each step are the same as in example 3.
Unlike example 3, the boron diffusion process was performed in the boron diffusion device of the TOPCon cell provided by the present invention, and before the silicon wafer entered the diffusion furnace tube and after the silicon wafer exited the diffusion furnace tube, a high-pressure nitrogen line was opened at the position of the diffusion furnace mouth, and the silicon wafer was purged with high-pressure nitrogen gas, the outlet pressure of the high-pressure nitrogen line being 0.5MPa.
Example 6
1000 TOPCon cells were prepared following the procedure in example 1.
In the boron diffusion process, the embodiment provides a boron diffusion method of a TOPCO battery, which comprises the following steps: empty pipe purification, silicon wafer entering a diffusion furnace tube, silicon wafer purification, evacuation, leak detection, stabilization, first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling annealing, nitrogen charging and silicon wafer exiting the diffusion furnace tube. Wherein the process parameters of each step are the same as in example 4.
Unlike example 4, the boron diffusion process was performed in the boron diffusion device of the TOPCon cell provided by the present invention, and before the silicon wafer entered the diffusion furnace tube and after the silicon wafer exited the diffusion furnace tube, a high-pressure nitrogen line was opened at the position of the diffusion furnace mouth, and the silicon wafer was purged with high-pressure nitrogen gas, the outlet pressure of the high-pressure nitrogen line being 0.5MPa.
Comparative example 1
1000 TOPCon cells were prepared following the procedure in example 1.
In the boron diffusion process, the comparative example provides a boron diffusion method of a TOPCO battery, which comprises the following steps: the silicon wafer enters a diffusion furnace tube, is pumped out, is subjected to leak detection, is stabilized, is subjected to first deposition, is subjected to first oxidation, is subjected to second deposition, is subjected to third deposition, is subjected to cooling and annealing, is filled with nitrogen, and is withdrawn from the diffusion furnace tube. The process parameters of each step are shown in Table 5.
TABLE 5
Comparative example 2
1000 TOPCon cells were prepared following the procedure in example 1.
In the boron diffusion process, the embodiment provides a boron diffusion method of a TOPCO battery, which comprises the following steps: the silicon wafer enters a diffusion furnace tube, is pumped out, is subjected to leak detection, is stabilized, and is subjected to first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling and annealing, nitrogen filling and exits the diffusion furnace tube. The process parameters of each step are shown in Table 6.
TABLE 6
20 silicon wafers treated in the boron diffusion process of example 3 and comparative example 2 are respectively taken, the boron surface concentrations corresponding to different depths are detected, and the average value of the test results is shown in figure 1. As can be seen from the analysis of FIG. 1, the surface of the silicon wafer treated by the boron diffusion method provided in example 3 has a higher boron surface concentration within a thickness of 0.4. Mu.m.
20 silicon wafers after the boron diffusion process treatment and the laser doping process treatment of the example 3 and the comparative example 2 are respectively taken, the sheet resistances are detected, and the average value of the test results is shown in Table 7. As can be seen from the analysis in Table 7, the silicon wafer treated by the boron diffusion method provided in example 3 has higher sheet resistance, and the region doped by laser has more sheet resistance drop, which indicates that the boron diffusion method provided in example 3 realizes better secondary doping after laser propulsion.
TABLE 7
The battery performance and yield of TOPCON batteries finally prepared in examples 1 to 6 and comparative examples 1 to 2 were measured, 100 sheets were taken for each example/comparative example, the measuring equipment was a photovoltaic simulation tester, the measuring conditions were production environments (indoor cleanliness: ISO standard grade 7; ambient temperature: 23.+ -. 3 ℃ C., relative humidity: 30% -50% (no condensation)), and the average values of the measuring results are shown in Table 8. From the analysis of table 8, it is seen that the TOPCon cells prepared by examples 1 to 6 exhibited more excellent photoelectric conversion efficiency.
TABLE 8
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A boron diffusion method of a TOPCon battery, comprising the steps of: the silicon wafer enters a diffusion furnace tube, and sequentially undergoes first deposition, first oxidation, second deposition, second oxidation, third deposition, fourth deposition, cooling annealing and the silicon wafer exits the diffusion furnace tube;
wherein the temperature of the first deposition is 800-850 ℃;
the temperature of the first oxidation, the second oxidation and the third deposition are 5-10 ℃ higher than the temperature of the previous step, and the temperature of the fourth deposition is 10-20 ℃ higher than the temperature of the third deposition;
the temperature of the second deposition is the same as the temperature of the first oxidation.
2. The method of boron diffusion in a TOPCon cell of claim 1, wherein the silicon wafer is empty pipe cleaned prior to entering the diffusion furnace step, and wherein the silicon wafer is cleaned prior to beginning the first deposition step.
3. The boron diffusion method of the TOPCon battery as claimed in claim 2, wherein the temperature of the empty pipe purification and the silicon wafer purification is 750-800 ℃, the time is 1-5 min, the flow rate of nitrogen is 4500-5500 sccm, and the pressure is 1000-1050 mbar; and/or
The flow of the boron trichloride purified by the empty pipe is 100-200 sccm, and the flow of the boron trichloride purified by the silicon chip is 50-100 sccm.
4. The method of boron diffusion in a TOPCon cell of claim 1, wherein the first, second and third depositions are each for 5-10 min, the flow rate of oxygen is 300-500 sccm, the flow rate of nitrogen is 2500-3000 sccm, and the pressure is 80-120 mbar; and/or
The flow rates of the first deposited boron trichloride and the second deposited boron trichloride are respectively 100-200 sccm, and the flow rate of the third deposited boron trichloride is 300-500 sccm.
5. The boron diffusion method of the TOPCon battery according to claim 1, wherein the time of the first oxidation and the second oxidation is 1-5 min, the flow rate of oxygen is 2000-3000 sccm, the flow rate of nitrogen is 2500-3000 sccm, and the pressure is 80-120 mbar; and/or
The first oxidized gas also comprises inert gas, and the flow ratio of the inert gas to the oxygen is 1:9-11.
6. The method of boron diffusion in a TOPCon cell of claim 1, wherein the fourth deposition time is 20-40 min, the flow rate of oxygen is 4500-5500 sccm, the flow rate of nitrogen is 2500-3000 sccm, the flow rate of boron trichloride is 500-1000 sccm, and the pressure is 80-120 mbar.
7. The boron diffusion method of a TOPCON cell according to claim 1, wherein the reduced temperature anneal is at a temperature of 700-750 ℃ for 10-20 minutes, the flow of nitrogen is 5000-8000 sccm, and the pressure is 80-120 mbar.
8. The method of boron diffusion of a TOPCon cell of claim 1, wherein the silicon wafer is purged with high pressure nitrogen before entering the diffusion furnace tube and after exiting the diffusion furnace tube;
the outlet pressure of the high-pressure nitrogen pipeline is 0.1-1.0 MPa.
9. The boron diffusion device of the TOPCO battery is characterized in that a high-pressure nitrogen pipeline is arranged at the position of a diffusion furnace mouth of the boron diffusion device.
10. The method of using a boron diffusion device of a TOPCon cell of claim 9, wherein the high pressure nitrogen line is opened to purge the silicon wafer before the silicon wafer enters the diffusion furnace tube and after the silicon wafer exits the diffusion furnace tube.
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