CN115064606A - Water vapor annealing equipment for improving passivation effect of polycrystalline silicon layer and water vapor annealing process - Google Patents
Water vapor annealing equipment for improving passivation effect of polycrystalline silicon layer and water vapor annealing process Download PDFInfo
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Abstract
The invention discloses water vapor annealing equipment and a water vapor annealing process for improving the passivation effect of a polycrystalline silicon layer. The water vapor annealing process comprises the steps of carrying out high-temperature crystallization on a silicon wafer, and introducing water vapor for carrying out water vapor annealing treatment. The water vapor annealing equipment and the water vapor annealing process can accurately control the low-proportion water vapor inflow, can ensure that the water vapor is uniformly distributed in the cavity, are suitable for supplementing and increasing the hydrogen content in the polycrystalline silicon, can reduce the oxidization of the polycrystalline silicon layer by the water vapor while improving the water vapor annealing uniformity, are favorable for improving the passivation effect of the polycrystalline silicon layer, and are suitable for preparing high-performance crystalline silicon solar cells.
Description
Technical Field
The invention belongs to the technical field of manufacturing of crystalline silicon solar cells, and relates to water vapor annealing equipment and a water vapor annealing process for improving the passivation effect of a polycrystalline silicon layer.
Background
In the manufacturing process of the crystalline silicon solar cell, amorphous silicon is usually prepared by an LPCVD or PECVD method, and after the deposition of the amorphous silicon is completed, annealing crystallization treatment needs to be performed on the amorphous silicon to form polycrystalline silicon. At present, the methods for annealing amorphous silicon mainly include phosphorus diffusion and high temperature annealing, or directly perform high temperature annealing, but in either method, crystallization needs to be performed under high temperature conditions. Generally, the annealing crystallization temperature of amorphous silicon is 800-. Therefore, how to ensure that the polysilicon layer has a better passivation effect on the premise of effectively forming the polysilicon is a technical problem which needs to be solved urgently at the present stage.
In order to solve the hydrogen escape problem during the high temperature crystallization of amorphous silicon, researchers have proposed introducing water vapor during the annealing process to reduce the hydrogen escape from the amorphous silicon, however, the existing water vapor annealing equipment and the corresponding annealing process still have the following defects: (1) in addition, in order to realize the small-proportion introduction of the water vapor, the conventional method uses a hydrogen-oxygen synthesis mode, and accurately controls the hydrogen inlet amount through small flow under the premise of giving enough oxygen to achieve the low-proportion introduction of the water vapor, but the hydrogen storage, use and safety cost are higher, so that the method is not suitable for large-scale use of enterprises. (2) In the existing water vapor annealing process, water vapor is generally introduced at low temperature for annealing, and then high-temperature crystallization is carried out, so that the advantage of water vapor annealing still cannot be fully exerted, because free hydrogen entering amorphous silicon through water vapor annealing still has a high escape rate at high temperature, hydrogen supplemented by water vapor annealing can escape again in the high-temperature crystallization process, and a good passivation effect is still difficult to obtain, so that the efficiency of the crystalline silicon solar cell is not improved. Therefore, the water vapor annealing equipment which can accurately control the low-proportion water vapor inlet amount and ensure that the water vapor is uniformly distributed in the cavity is obtained, and the equipment has important significance for effectively improving the passivation effect of the polycrystalline silicon layer and improving the efficiency of the polycrystalline silicon solar cell.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the water vapor annealing equipment which can accurately control the low-proportion water vapor inlet amount and ensure that the water vapor is uniformly distributed in the cavity and is used for improving the passivation effect of the polycrystalline silicon layer, and also provides the water vapor annealing process which can effectively form the polycrystalline silicon layer and can obviously improve the passivation effect of the polycrystalline silicon layer.
In order to solve the technical problems, the invention adopts the following technical scheme:
a water vapor annealing device for improving the passivation effect of a polycrystalline silicon layer comprises a cavity for placing an annealing sample to be treated, wherein the cavity is communicated with a first gas inlet pipeline for inputting process gas and a tail gas discharge pipeline for discharging tail gas, and the cavity is also communicated with a second gas inlet pipeline for inputting water vapor; one end of the second air inlet pipeline is positioned in the cavity, and the other end of the second air inlet pipeline is positioned outside the cavity; a plurality of water vapor spray outlets are arranged on the second air inlet pipeline in the cavity; and a second air inlet pipeline outside the cavity is communicated with a production device for producing water vapor.
As a further improvement of the technical scheme: the production device comprises an air inlet pipe for inputting carrying gas, a closed water tank and an air outlet pipe, the air inlet pipe is inserted into the water in the closed water tank, and the second air inlet pipeline is communicated with the top of the closed water tank through the air outlet pipe; the air inlet pipe is also provided with a first flow control valve for regulating and controlling the flow of the carried gas; the carrier gas is nitrogen.
As a further improvement of the above technical solution: the production device also comprises a heating component for regulating and controlling the temperature of water in the closed water tank; the heating assembly comprises a thermostatic bath; the constant temperature tank comprises a tank body and a temperature regulating medium stored in the tank body, and the closed water tank sleeve is embedded in the temperature regulating medium; the temperature regulating medium is water.
As a further improvement of the technical scheme: an adjusting device for adjusting and controlling the input amount of water vapor is arranged between the second air inlet pipeline and the air outlet pipe; the adjusting device comprises a dilution cavity, and the second air inlet pipeline and the air outlet pipeline are respectively communicated with the dilution cavity; and second auxiliary heating components are arranged around the dilution cavity.
As a further improvement of the above technical solution: the adjusting device further comprises a third air inlet pipeline for inputting dilution air, and the third air inlet pipeline is communicated with the dilution cavity; the diluent gas is nitrogen; and one end of the air inlet of the third air inlet pipeline is provided with a second flow control valve for regulating and controlling the flow of the diluent gas.
As a further improvement of the above technical solution: the second air inlet pipeline inside the cavity is positioned below the annealing sample to be processed in the cavity; and first auxiliary heating assemblies are arranged around the second air inlet pipeline outside the cavity.
As a general technical concept, the present invention also provides a water vapor annealing process for improving a passivation effect of a polycrystalline silicon layer, comprising the steps of:
s1, carrying out high-temperature crystallization on the silicon wafer with the amorphous silicon layer deposited on the surface, and forming a polycrystalline silicon layer on the surface;
and S2, introducing water vapor, and performing water vapor annealing treatment on the silicon wafer with the polysilicon layer formed in the step S1.
As a further improvement of the above technical solution: and (3) processing the silicon wafer with the amorphous silicon layer deposited on the surface by adopting the water vapor annealing equipment.
As a further improvement of the above technical solution: in step S2, the water vapor enters the cavity in a carrying manner; the flow rate of the carried gas in the water vapor annealing process is 10 sccm-50000 sccm; the temperature of the water vapor annealing treatment is 300-900 ℃; the time of the water vapor annealing treatment is 1 min-60 min.
As a further improvement of the above technical solution: in the step S2, in the water vapor annealing process, the temperature of the temperature regulating medium is controlled to be 10-100 ℃, the temperature of the first auxiliary heating assembly and/or the second auxiliary heating assembly is controlled to be 10-100 ℃, and the ratio of the input amount of the carried gas in the gas inlet pipe to the input amount of the diluent gas in the third gas inlet pipe is 1: 0-1: 100.
As a further improvement of the above technical solution: in step S1, the process parameters of the high-temperature crystallization are: the temperature is 600-1200 ℃, the pressure is 100-1000 Pa, the big nitrogen is 100 sccm-10000 sccm, and the time is 500-50000 s.
Compared with the prior art, the invention has the advantages that:
(1) aiming at the defects that the existing water vapor annealing equipment is difficult to accurately control low-proportion water vapor, the water vapor distribution uniformity is poor and the like, the invention creatively provides novel water vapor annealing equipment for improving the passivation effect of a polycrystalline silicon layer, which comprises a cavity for placing an annealing sample to be treated, wherein a first gas inlet pipeline for inputting process gas and a tail gas exhaust pipeline for exhausting tail gas are communicated with the cavity, a second gas inlet pipeline for inputting water vapor is also communicated with the cavity, one end of the second gas inlet pipeline is positioned in the cavity, and the other end of the second gas inlet pipeline is positioned outside the cavity; the second air inlet pipeline inside the cavity is located below the annealing sample to be processed in the cavity, a plurality of water vapor spraying ports are formed in the second air inlet pipeline, and the second air inlet pipeline outside the cavity is communicated with a production device for producing water vapor. In the water vapor annealing equipment, the second gas inlet pipeline for inputting water vapor is additionally arranged in the original annealing equipment, so that the process gas and the water vapor can respectively enter a cavity (generally a quartz furnace tube) for placing an annealing sample to be treated through different channels, the water vapor annealing function is newly added on the basis of not influencing the original function of the annealing equipment, and the entering amount of the water vapor with different proportions can be effectively regulated and controlled; more importantly, the second air inlet pipeline positioned in the cavity is provided with the plurality of water vapor nozzles, so that the entering amount of low-proportion water vapor can be accurately controlled, and the uniform distribution of the low-proportion water vapor in the cavity can be ensured, therefore, the hydrogen content in the polycrystalline silicon layer can be supplemented and increased by utilizing water vapor annealing, the problem of hydrogen escape caused by high temperature is solved, and meanwhile, the defect of thinning of the polycrystalline silicon layer in the water vapor annealing process can be effectively overcome on the basis of effectively improving the passivation effect of the polycrystalline silicon layer. In addition, the water vapor annealing equipment can realize the water vapor annealing function only by slightly improving the existing annealing equipment, and the improvement cost is lower. In addition, compared with the conventional annealing equipment, the solar cell made of the silicon wafer processed by the water vapor annealing equipment has more excellent electrical property, wherein the efficiency of the prepared N-type TOPCon cell is improved by 0.19-0.28 percent, so that the water vapor annealing equipment is suitable for improving the passivation effect of the polycrystalline silicon layer and preparing a high-performance passivated contact cell.
(2) Aiming at the defects that the hydrogen content in the polycrystalline silicon layer is still difficult to improve and the passivation effect of the polycrystalline silicon layer is difficult to effectively improve in the existing water vapor annealing process, the invention creatively provides the water vapor annealing process for improving the passivation effect of the polycrystalline silicon layer. According to the invention, high-temperature crystallization is carried out, an amorphous silicon layer can be effectively converted into polycrystalline silicon, a polycrystalline silicon layer with enough thickness is ensured to be formed, then the crystallized silicon wafer is subjected to water vapor annealing treatment, and the oxidation rate of less water vapor to the surface of the polycrystalline silicon is lower in the low-proportion uniform water vapor introduction process, so that the defect of thickness reduction of the polycrystalline silicon can be effectively improved. The water vapor annealing process is completed in the water vapor annealing equipment, multiple times of entering and exiting of the annealing equipment are not needed, the operation is more convenient, and the time for prolonging the process can be controlled within 1 h. In addition, compared with the conventional hydrogen supplement mode, the annealing process disclosed by the invention has the advantages that low proportion of water vapor is directly introduced, the cost is lower, and the safety is higher. In addition, compared with the conventional water vapor annealing process, the solar cell prepared from the silicon wafer treated by the water body annealing process has more excellent electrical property, wherein the efficiency of the prepared N-type TOPCon cell is improved by 0.14-0.18% by taking the prepared N-type TOPCon cell as an example, and therefore, the water vapor annealing process is suitable for improving the passivation effect of the polycrystalline silicon layer and preparing a high-performance crystalline silicon solar cell.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a schematic structural view of a steam annealing apparatus in embodiment 1 of the present invention.
Fig. 2 is a schematic flow chart of a steam annealing process in embodiment 2 of the present invention.
Fig. 3 is a schematic flow chart of a conventional annealing process.
Illustration of the drawings:
1. a cavity; 2. a first air intake duct; 3. a tail gas discharge pipeline; 4. a second air intake duct; 41. a water vapor outlet; 42. a first auxiliary heating assembly; 51. an air inlet pipe; 52. sealing the water tank; 53. an air outlet pipe; 54. a first flow control valve; 61. a trough body; 62. a temperature regulating medium; 7. a dilution chamber; 71. a second auxiliary heating assembly; 8. a third air intake duct; 81. a second flow control valve; a. and (5) annealing the sample to be treated.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The raw materials and instruments used in the following examples are all commercially available; the equipment and the preparation process are conventional equipment and conventional process unless otherwise specified.
Example 1
As shown in fig. 1, the water vapor annealing device for improving the passivation effect of the polysilicon layer of the embodiment includes a cavity 1 for placing an annealing sample to be processed, the cavity 1 is communicated with a first gas inlet pipeline 2 for inputting process gas and a tail gas exhaust pipeline 3 for exhausting tail gas, the cavity 1 is further communicated with a second gas inlet pipeline 4 for inputting water vapor, one end of the second gas inlet pipeline 4 is located inside the cavity 1, and the other end is located outside the cavity 1; the second air inlet pipe 4 inside the cavity 1 is positioned below the annealing sample to be processed in the cavity 1, a plurality of water vapor spray outlets 41 are formed in the second air inlet pipe 4, and the second air inlet pipe 4 outside the cavity 1 is communicated with a production device for producing water vapor.
In the water vapor annealing equipment, the second gas inlet pipeline for inputting water vapor is additionally arranged in the original annealing equipment, so that the process gas and the water vapor can respectively enter a cavity (generally a quartz furnace tube) for placing an annealing sample to be treated through different channels, the water vapor annealing function is newly added on the basis of not influencing the original function of the annealing equipment, and the entering amount of the water vapor with different proportions can be effectively regulated and controlled; meanwhile, the second air inlet pipeline positioned in the cavity is provided with a plurality of water vapor nozzles, so that the entering amount of low-proportion water vapor can be accurately controlled, and the uniform distribution of the low-proportion water vapor in the cavity can be ensured, thereby supplementing and increasing the hydrogen content in the polycrystalline silicon layer by using water vapor annealing, solving the problem of hydrogen escape caused by high temperature, and simultaneously effectively overcoming the defect of thinning of the polycrystalline silicon layer in the water vapor annealing process on the basis of effectively improving the passivation effect of the polycrystalline silicon layer. In addition, the water vapor annealing equipment can realize the water vapor annealing function only by slightly improving the existing annealing equipment, and the improvement cost is lower. More importantly, in the invention, the second gas inlet pipeline (water vapor transport pipeline) extends into the cavity (quartz furnace tube) to the tail of the tube and is arranged below the annealing sample to be processed (such as a silicon wafer with an amorphous silicon layer deposited on the surface), so that water vapor can be transported to the samples to be processed at different positions in the cavity through the water vapor ejection port arranged on the pipeline, the control of the adding amount of the water vapor is facilitated, the uniformity of water vapor output at different positions in the cavity (quartz furnace tube) can be improved, the water vapor annealing of the annealing sample to be processed is facilitated, and the hydrogen content in the annealing sample to be processed is finally improved.
In this embodiment, the production apparatus in which the second gas inlet pipe 4 outside the cavity 1 is communicated includes a gas inlet pipe 51 for inputting the carrier gas, a closed water tank 52 and a gas outlet pipe 53, the gas inlet pipe is inserted into the water in the closed water tank 52, and the second gas inlet pipe 4 is communicated with the top of the closed water tank 52 through the gas outlet pipe 53; the air inlet pipe 51 is also provided with a first flow control valve 54 for regulating and controlling the flow of the carried gas; the carrier gas was nitrogen. In the invention, by adjusting the opening degree of the first flow control valve 54, the carried gas with different flow rates can be introduced into the water in the closed water tank 52, so that the carried water vapor can further enter the cavity 1 through the air outlet pipe 53 and the second air inlet pipeline 4, and the water vapor entering amount with different proportions can be controlled and the entering of the water vapor with low proportion can be accurately controlled by adjusting the opening degree of the first flow control valve 54.
In this embodiment, the production apparatus further includes a heating element for regulating and controlling the temperature of water in the closed water tank 52; the heating component comprises a constant temperature groove; the thermostatic bath comprises a bath body 61 and a temperature regulating medium 62 stored in the bath body 61, and the closed water tank 52 is nested in the temperature regulating medium 62; the temperature regulating medium 62 is water. In the invention, the sealed water tank 52 is embedded in the temperature regulating medium of the thermostatic bath, so that the water in the sealed water tank 52 can be ensured to be always kept in a constant temperature state, the adverse effect caused by external temperature change can be reduced, the evaporation rate of the water in the sealed water tank 52 can be controlled, and the accurate control of the low-proportion water vapor inlet amount can be realized.
In this embodiment, an adjusting device for adjusting and controlling the input amount of water vapor is further disposed between the second air inlet pipe 4 and the air outlet pipe 53; the adjusting device comprises a dilution cavity 7, and the second air inlet pipeline 4 and the air outlet pipe 53 are respectively communicated with the dilution cavity 7; and second auxiliary heating components 71 such as an insulating layer and a heating belt are arranged around the dilution cavity 7. In the invention, the adjusting device for adjusting and controlling the water vapor input quantity is arranged between the second air inlet pipeline 4 and the air outlet pipe 53, so that the impact of high-proportion water vapor entering the cavity 1 on the temperature in the cavity 1 can be effectively relieved, and the low-proportion water vapor is more favorably added, thereby being more favorable for obtaining a polycrystalline silicon layer with larger thickness. Meanwhile, the second auxiliary heating assemblies 71 (such as a heat insulation layer, a heating belt and the like) are arranged around the diluting cavity 7, so that the temperature in the diluting cavity 7 can be maintained in a proper range (such as 10-100 ℃), the condensation phenomenon of water vapor in the transportation process can be avoided, the harmful damage of the condensed water entering the cavity 1 to the cavity 1 can be relieved, the addition amount of the water vapor can be controlled, and the accurate control of the low-proportion water vapor can be realized.
In this embodiment, the adjusting device further includes a third gas inlet pipe 8 for inputting a diluent gas, and the third gas inlet pipe 8 is communicated with the dilution cavity 7; the diluent gas is nitrogen; one end of the air inlet of the third air inlet pipeline 8 is provided with a second flow control valve 81 for regulating and controlling the flow of the diluent gas. In the invention, the dilution cavity 7 is communicated with the third gas inlet pipeline 8 for inputting the dilution gas, and the dilution gas with different flow rates can be introduced into the dilution cavity 7 by adjusting the opening degree of the second flow control valve 81, so that the water vapor inlet amount with different proportions can be controlled more favorably and the water vapor inlet amount with low proportion can be controlled more accurately by adjusting the opening degrees of the two valves through the effective matching with the first flow control valve 54 and the dilution cavity 7.
In this embodiment, the second air inlet duct 4 outside the cavity 1 is provided with first auxiliary heating assemblies 42 around, such as an insulating layer, a heating belt, and the like. According to the invention, the first auxiliary heating assemblies 42 (such as the heat-insulating layer, the heating belt and the like) are arranged around the second air inlet pipeline 4 outside the cavity 1, so that the temperature in the second air inlet pipeline 4 outside the cavity can be maintained within a proper range (such as 10-100 ℃), and the condensation phenomenon on the inner wall of the pipeline in the water vapor transportation process can be avoided, thereby being beneficial to relieving bad damage to the cavity 1 caused by the entering of condensed water into the cavity 1, being beneficial to controlling the adding amount of water vapor and realizing the accurate control of low-proportion water vapor.
Example 2
A water vapor annealing process for improving the passivation effect of a polysilicon layer, which is implemented by using the water vapor annealing apparatus in embodiment 1 to process a silicon wafer with a polysilicon layer deposited on the surface, and the process flow diagram is shown in fig. 2, and includes the following steps:
s1, placing the silicon wafer with the amorphous silicon layer (thickness of 100nm) deposited on the surface in a quartz boat, sending the quartz boat into a cavity 1 (quartz furnace tube), and sequentially carrying out boat feeding, constant temperature, oxidation, diffusion and deep diffusion (namely high-temperature crystallization) on the silicon wafer with the amorphous silicon layer deposited on the surface, wherein the process parameters of each step are shown in Table 1, so that a polycrystalline silicon layer is formed on the surface of the silicon wafer.
And S2, after the deep diffusion is finished, cooling the cavity 1, wherein the process parameters are shown in Table 1, directly cooling to 650 ℃, introducing water vapor into the cavity 1 in a carrying mode, wherein the carrying gas is nitrogen, the flow rate is 200sccm, and carrying out water vapor annealing treatment on the silicon wafer with the polycrystalline silicon layer formed in the step S1 for 15 min. Meanwhile, the temperature of the temperature adjusting medium 62 is controlled to be 90 ℃ in the water vapor annealing process, the temperatures of the first auxiliary heating assembly 42 and the second auxiliary heating assembly 71 are controlled to be 90 ℃, and the gas (water vapor N) carried in the gas inlet pipe 51 is controlled 2 2) with the dilution gas (water vapour N) in the third gas inlet line 8 2 The ratio of the input quantities of-1) is 1: 9.
S3, after the water vapor annealing treatment is finished, continuing to perform N 2 Cleaning and taking out the silicon wafer, wherein the process parameters are shown in the table 1, and the silicon wafer is processed.
TABLE 1 Process parameters of the vapor phosphorus diffusion annealing Process
In Table 1, water vapor N 2 The gas-phase reaction chamber-1 is a diluent gas, specifically nitrogen, and enters the chamber-1 (quartz furnace tube) after being diluted by a dilution chamber-7 through a third gas inlet pipe 8 of the annealing equipment; water vapor N 2 2, carrying gas, specifically nitrogen, which enters the cavity 1 (quartz furnace tube) after being diluted by the closed water tank 52 and the dilution chamber 7 through the second gas inlet pipeline 4 of the annealing equipment; large N 2 Nitrogen gas for cleaning, phosphorus source nitrogen and O 2 All enter the cavity 1 (quartz furnace tube) through a first gas inlet pipeline 2 of the annealing equipment. In addition, tail gas generated in the water vapor annealing treatment process is discharged through a tail gas discharge pipeline 3.
Comparative example 1
A phosphorus diffusion annealing process adopts conventional annealing equipment to treat a silicon wafer with an amorphous silicon layer deposited on the surface, and the process flow schematic diagram is shown in figure 3, and comprises the following steps:
placing the silicon wafer with the amorphous silicon layer deposited on the surface in a quartz boat, sending the quartz boat into a cavity 1 (quartz furnace tube), and sequentially carrying out boat feeding, constant temperature, oxidation, diffusion, deep diffusion (namely high-temperature crystallization), cooling and N treatment on the silicon wafer with the amorphous silicon layer deposited on the surface 2 And cleaning and taking out the silicon wafer, wherein the process parameters of each step are shown in the table 2, and the silicon wafer is processed.
TABLE 2 Process parameters of conventional phosphorus diffusion annealing Process
The annealed wafers of example 2 and comparative example 1 were used to fabricate N-type TOPCon cells, and the results of the electrical property tests are shown in table 3.
TABLE 3 Electrical Performance data of N-type TOPCon cells prepared from wafers treated by different annealing processes
| VOC(mV) | Jsc(mA/cm 2 ) | FF(％) | Eta(％) | |
| Conventional annealing 1 (comparative example 1) | 701 | 40.66 | 83.4 | 23.77％ |
| Conventional annealing 2 (comparative example 1) | 699 | 40.71 | 83.3 | 23.70％ |
| Water vapor annealing 1 (example 2) | 705 | 40.60 | 83.7 | 23.96％ |
| Water vapor annealing 2 (example 2) | 706 | 40.53 | 83.8 | 23.98％ |
As can be seen from Table 3, compared with the conventional annealing treatment method, the N-type TOPCon battery prepared from the silicon wafer treated by the water vapor annealing equipment has more excellent electrical property, wherein the efficiency of the N-type TOPCon battery prepared by the invention is improved by 0.19-0.28%.
Example 3
A steam annealing process for improving the passivation effect of a polycrystalline silicon layer is characterized in that high-temperature crystallization is carried out firstly, and then steam annealing is carried out, which is basically the same as the steam annealing process in the embodiment 2, and the difference is that: the temperature of the water vapor annealing was 600 ℃.
Comparative example 2
A water vapor annealing process, substantially the same as the water vapor annealing process of example 3, except that: in comparative example 2, the water vapor annealing treatment was performed first, and then the high temperature crystallization treatment was performed.
The annealed wafers of example 3 and comparative example 2 were used to fabricate N-type TOPCon cells, and the results of the electrical property tests are shown in table 4.
TABLE 4 Electrical Performance data of N-type TOPCon cells prepared from silicon wafers treated by different annealing processes
| VOC(mV) | Jsc(mA/cm 2 ) | FF(％) | Eta(％) | |
| Annealing followed by crystallization 1 (comparative example 2) | 702 | 40.55 | 83.6 | 23.80％ |
| Annealing followed by crystallization 2 (comparative example 2) | 704 | 40.50 | 83.4 | 23.78％ |
| Crystallization followed by annealing 1 (example 3) | 706 | 40.61 | 83.5 | 23.94％ |
| Crystallization followed by annealing 2 (example 3) | 706 | 40.66 | 83.6 | 23.96％ |
As can be seen from table 4, compared with the conventional method (water vapor annealing at high temperature), the N-type TOPCon battery prepared from the silicon wafer processed by the water vapor annealing method (high temperature crystallization followed by water vapor annealing) has more excellent electrical properties, wherein the efficiency of the N-type TOPCon battery prepared by the method is improved by 0.14% -0.18%.
From the above results, it can be seen that in the water vapor annealing method of the present invention, high temperature crystallization is performed, so that an amorphous silicon layer can be effectively converted into polycrystalline silicon, a polycrystalline silicon layer with sufficient thickness is ensured to be formed, and then water vapor annealing treatment is performed on the crystallized silicon wafer, and the oxidation rate of less water vapor on the surface of the polycrystalline silicon is lower in the process of uniformly introducing water vapor at a low ratio, so that the defect of reducing the thickness of the polycrystalline silicon can be effectively improved, and meanwhile, the hydrogen content in the polycrystalline silicon layer can be supplemented and increased through the water vapor annealing treatment, so that the passivation effect of the polycrystalline silicon layer can be significantly improved, and the problem of hydrogen escape caused by high temperature is overcome. The water vapor annealing process is completed in the water vapor annealing equipment, multiple times of entering and exiting of the annealing equipment are not needed, the operation is more convenient, and the time for prolonging the process can be controlled within 1 h. In addition, compared with the conventional hydrogen supplement mode, the annealing process disclosed by the invention directly introduces low proportion of water vapor, so that the cost is lower and the safety is higher. In addition, compared with the conventional water vapor annealing process, the solar cell prepared from the silicon wafer treated by the water body annealing process has more excellent electrical property. Therefore, the water vapor annealing process is suitable for improving the passivation effect of the polycrystalline silicon layer and preparing a high-performance passivated contact battery.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A steam annealing device for improving the passivation effect of a polycrystalline silicon layer comprises a cavity (1) for placing an annealing sample to be treated, wherein the cavity (1) is communicated with a first gas inlet pipeline (2) for inputting process gas and a tail gas discharge pipeline (3) for discharging tail gas, and the steam annealing device is characterized in that the cavity (1) is also communicated with a second gas inlet pipeline (4) for inputting steam; one end of the second air inlet pipeline (4) is positioned inside the cavity (1), and the other end of the second air inlet pipeline is positioned outside the cavity (1); a plurality of water vapor spray outlets (41) are arranged on the second air inlet pipeline (4) in the cavity (1); and a second air inlet pipeline (4) outside the cavity (1) is communicated with a production device for producing water vapor.
2. The steam annealing equipment for improving the passivation effect of the polycrystalline silicon layer according to claim 1, wherein the production device comprises an air inlet pipe (51) for inputting carrying gas, a closed water tank (52) and an air outlet pipe (53), the air inlet pipe is inserted into the water in the closed water tank (52), and the second air inlet pipeline (4) is communicated with the top of the closed water tank (52) through the air outlet pipe (53); the air inlet pipe (51) is also provided with a first flow control valve (54) for regulating and controlling the flow of the carried gas; the carrier gas is nitrogen.
3. The steam annealing device for improving the passivation effect of the polycrystalline silicon layer according to claim 2, wherein the production apparatus further comprises a heating assembly for regulating and controlling the temperature of water in the closed water tank (52); the heating assembly comprises a thermostatic bath; the thermostatic bath comprises a bath body (61) and a temperature regulating medium (62) stored in the bath body (61), and the closed water tank (52) is embedded in the temperature regulating medium (62); the temperature regulating medium (62) is water.
4. The steam annealing equipment for improving the passivation effect of the polycrystalline silicon layer according to claim 3, wherein a regulating device for regulating and controlling the steam input is further arranged between the second air inlet pipeline (4) and the air outlet pipeline (53); the adjusting device comprises a dilution cavity (7), and the second air inlet pipeline (4) and the air outlet pipeline (53) are respectively communicated with the dilution cavity (7); a second auxiliary heating assembly (71) is arranged around the dilution cavity (7);
the adjusting device further comprises a third air inlet pipeline (8) used for inputting dilution air, and the third air inlet pipeline (8) is communicated with the dilution cavity (7); the diluent gas is nitrogen; and one end of the air inlet of the third air inlet pipeline (8) is provided with a second flow control valve (81) for regulating and controlling the flow of the diluent gas.
5. The water vapor annealing device for improving the passivation effect of the polycrystalline silicon layer according to any one of claims 2 to 4, wherein the second air inlet pipeline (4) inside the cavity (1) is positioned below an annealing sample to be processed in the cavity (1); and first auxiliary heating components (42) are arranged around the second air inlet pipeline (4) outside the cavity (1).
6. A water vapor annealing process for improving the passivation effect of a polycrystalline silicon layer is characterized by comprising the following steps:
s1, carrying out high-temperature crystallization on the silicon wafer with the amorphous silicon layer deposited on the surface, and forming a polycrystalline silicon layer on the surface;
and S2, introducing water vapor, and performing water vapor annealing treatment on the silicon wafer with the polysilicon layer formed in the step S1.
7. The water vapor annealing process according to claim 6, wherein the silicon wafer with the amorphous silicon layer deposited on the surface is processed by the water vapor annealing equipment according to any one of claims 1 to 5.
8. The water vapor annealing process according to claim 7, wherein in step S2, the water vapor enters the cavity (1) in an entrained manner; the flow rate of the carried gas in the water vapor annealing process is 10 sccm-50000 sccm; the temperature of the water vapor annealing treatment is 300-900 ℃; the time of the water vapor annealing treatment is 1 min-60 min.
9. The water vapor annealing process according to claim 8, wherein in the step S2, in the water vapor annealing process, the temperature of the temperature adjusting medium (62) is controlled to be 10-100 ℃, the temperature of the first auxiliary heating assembly (42) and/or the second auxiliary heating assembly (71) is controlled to be 10-100 ℃, and the ratio of the input amount of the carrier gas in the gas inlet pipe (51) to the input amount of the diluent gas in the third gas inlet pipe (8) is 1: 0-1: 100.
10. The water vapor annealing process according to any one of claims 7 to 9, wherein in step S1, the process parameters of the high-temperature crystallization are as follows: the temperature is 600-1200 ℃, the pressure is 100-1000 Pa, the big nitrogen is 100-10000 sccm, and the time is 500-50000 s.
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