CN111996594A - Gallium, hydrogen and nitrogen doped monocrystalline silicon, preparation method thereof and solar cell - Google Patents

Gallium, hydrogen and nitrogen doped monocrystalline silicon, preparation method thereof and solar cell Download PDF

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CN111996594A
CN111996594A CN202010904115.9A CN202010904115A CN111996594A CN 111996594 A CN111996594 A CN 111996594A CN 202010904115 A CN202010904115 A CN 202010904115A CN 111996594 A CN111996594 A CN 111996594A
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hydrogen
nitrogen
gallium
atoms
silicon
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CN111996594B (en
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肖贵云
白枭龙
尚伟泽
何丽珠
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Zhejiang Jinko Solar Co Ltd
Jinko Solar Co Ltd
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Jinko Solar Co Ltd
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    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
    • C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
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    • 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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    • H01L31/00—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
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    • Y02E10/547—Monocrystalline silicon PV cells
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Abstract

The application relates to the field of photovoltaics and provides gallium, hydrogen and nitrogen doped monocrystalline silicon, a preparation method thereof and a solar cell, wherein the hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 multiplied by 105~1×1016atoms/cm3The doping concentration of gallium is 1 × 1015~5×1017atoms/cm3Nitrogen doping concentration of 1X 1012~1×1016atoms/cm3(ii) a The resistivity of the gallium, hydrogen and nitrogen doped monocrystalline silicon is 0.1-10 omega cm. Gallium, hydrogen and nitrogen doped monocrystalline silicon, preparation method thereof and solar cellThe method can effectively prolong the minority carrier lifetime in the monocrystalline silicon, is favorable for improving the passivation effect of the battery, improves the mechanical strength of the silicon wafer and improves the conversion efficiency of the solar battery.

Description

Gallium, hydrogen and nitrogen doped monocrystalline silicon, preparation method thereof and solar cell
Technical Field
The application relates to the technical field of photovoltaic cells, in particular to gallium, hydrogen and nitrogen doped monocrystalline silicon, a preparation method thereof and a solar cell.
Background
Currently, as one of the fastest growing fields in solar photovoltaic utilization, the technical development of crystalline silicon cells is attracting attention, and the improvement of the conversion efficiency of solar cells is a problem to be solved. In the existing monocrystalline silicon production process, the czochralski silicon is easy to have midpoint defects, dislocation defects, metal defects and the like, and the existence of the defects is easy to reduce the minority carrier lifetime of the monocrystalline silicon and reduce the conversion efficiency of the solar cell.
Disclosure of Invention
In view of this, the application provides gallium, hydrogen and nitrogen doped monocrystalline silicon, a preparation method thereof and a solar cell, which can effectively prolong the minority carrier lifetime in the monocrystalline silicon, facilitate the promotion of the cell passivation effect, promote the mechanical strength of a silicon wafer and improve the conversion efficiency of the solar cell.
The application provides gallium, hydrogen and nitrogen doped monocrystalline silicon, wherein the hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 multiplied by 105~1×1016atoms/cm3The doping concentration of gallium is 1 × 1015~5×1017atoms/cm3Nitrogen doping concentration of 1X 1012~1×1016atoms/cm3(ii) a The resistivity of the gallium, hydrogen and nitrogen doped monocrystalline silicon is 0.1-10 omega cm.
The application provides a preparation method of the gallium, hydrogen and nitrogen doped monocrystalline silicon, which comprises the following steps:
putting a polycrystalline silicon raw material and a gallium dopant into a quartz crucible;
placing the quartz crucible in a single crystal furnace, vacuumizing, and melting a polycrystalline silicon raw material under the protection of inert gas to obtain a silicon melt;
after the temperature of the silicon melt is stable, adding a hydrogen source and a nitrogen source into the single crystal furnace, and immersing a seed crystal into the silicon melt to start seeding;
after seeding is finished, shouldering is started to enable the diameter of the crystal to be gradually increased to a preset width, and then equal-diameter growth is carried out;
after the isodiametric growth is finished, entering a final stage, and gradually reducing the diameter of the crystal until the crystal is separated from the silicon melt;
and cooling the grown crystal to room temperature and taking out the crystal, wherein the crystal is gallium, hydrogen and nitrogen doped monocrystalline silicon.
In one possible embodiment, the hydrogen source is a hydrogen-containing gas, the nitrogen source is a nitrogen-containing gas, and the step of adding the hydrogen source and the nitrogen source into the single crystal furnace comprises the following steps:
and mixing the hydrogen-containing gas, the nitrogen-containing gas and the inert gas to form mixed gas, and introducing the mixed gas into the single crystal furnace.
In a possible embodiment, the volume ratio of the hydrogen-containing gas in the mixed gas is 0.1% to 2%, and the volume ratio of the nitrogen-containing gas in the mixed gas is 1% to 20%.
In one possible embodiment, the hydrogen-containing gas comprises at least one of hydrogen, silane, ammonia; and/or the nitrogen-containing gas comprises at least one of nitrogen and ammonia.
In one possible embodiment, the hydrogen source is a polysilicon raw material rich in hydrogen, the nitrogen source is a nitrogen-containing gas, and the specific steps of adding the hydrogen source and the nitrogen source into the single crystal furnace comprise:
and adding the hydrogen-rich polycrystalline silicon raw material into the silicon melt, mixing the nitrogen-containing gas and the inert gas to form mixed gas, and introducing the mixed gas into the single crystal furnace.
In a possible embodiment, the volume ratio of the nitrogen-containing gas in the mixed gas is 1% to 20%; and/or the hydrogen content in the polysilicon raw material rich in hydrogen is more than 6 x 1016atoms/cm3。
In one possible embodiment, the inert gas includes at least one of argon and helium.
The present application also provides a solar cell, the solar cell including: the semiconductor substrate, the doping layer positioned on the front surface of the semiconductor substrate, the front passivation layer and/or the antireflection layer positioned on the upper surface of the doping layer, the front electrode positioned on the upper surface of the front passivation layer and/or the antireflection layer, the back passivation layer positioned on the back surface of the semiconductor substrate and the back electrode positioned on the back surface of the back passivation layer,
wherein the semiconductor substrate comprises gallium, hydrogen and nitrogen doped monocrystalline silicon, and the hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 × 105~1×1016atoms/cm3The doping concentration of gallium is 1 × 1015~5×1017atoms/cm3Nitrogen doping concentration of 1X 1012~1×1016atoms/cm3The resistivity of the gallium, hydrogen and nitrogen doped monocrystalline silicon is 0.1-10 omega cm.
In a possible embodiment, the hydrogen content of the central region of the semiconductor substrate is greater than the hydrogen content of the edge region.
The technical scheme of the application has at least the following beneficial effects:
according to the gallium, hydrogen and nitrogen doped monocrystalline silicon, doped hydrogen atoms can form a complex or precipitate with other impurities and point defects in silicon, the electrical activity of the impurities is removed, and a passivation effect is achieved, so that the activity of the point defects, dislocation defects and metal defects in the gallium doped monocrystalline silicon crystal can be greatly reduced, the slip of dislocations can be pinned by the doped nitrogen atoms, the dislocation defects can be favorably controlled, the minority carrier lifetime in the gallium doped monocrystalline silicon can be effectively prolonged, and the quality of the monocrystalline silicon is improved; in the preparation process, a proper amount of nitrogen source and hydrogen source is added, so that trace hydrogen atoms and nitrogen atoms are fused into the silicon melt to realize the doping of hydrogen and nitrogen elements.
Drawings
For a clearer explanation of the embodiments or technical solutions of the prior art of the present application, the drawings needed for the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1a is a schematic structural diagram of a single crystal furnace according to the present embodiment;
FIG. 1b is a schematic view of another structure of a single crystal furnace according to this embodiment;
fig. 2 is a schematic flow chart of a method for preparing gallium, hydrogen and nitrogen doped monocrystalline silicon according to this embodiment;
fig. 3 is a schematic structural diagram of a solar cell provided in this embodiment.
Detailed Description
For better understanding of the technical solutions of the present application, the following detailed descriptions of the embodiments of the present application are provided with reference to the accompanying drawings.
It should be understood that the embodiments described are only a few embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
According to the gallium, hydrogen and nitrogen doped monocrystalline silicon provided by the embodiment of the application, the doped hydrogen atoms can form a complex or precipitate with other impurities and point defects in silicon, the electrical activity of the impurities is removed, and the passivation effect is achieved, so that the activity of the point defects, dislocation defects and metal defects in the gallium doped monocrystalline silicon crystal can be greatly reduced, the slippage of dislocation can be pinned by the doped nitrogen atoms, the dislocation defects can be favorably controlled, the minority carrier lifetime in the gallium doped monocrystalline silicon can be effectively prolonged, and the quality of the monocrystalline silicon is improved.
The hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 multiplied by 105~1×1016atoms/cm3For example, it may be 1 × 105 atoms/cm3、1×106 atoms/cm3、1×107 atoms/cm3、1×108 atoms/cm3、1×109atoms/cm3、1×1010 atoms/cm3、1×1012 atoms/cm3、1×1013 atoms/cm3、1×1014 atoms/cm3、1×1015 atoms/cm3Or 1X 1016 atoms/cm3And the like, and other values within this range are also possible, and are not limited herein.
The doping concentration of gallium in the single crystal silicon is 1 x 1015~5×1017atoms/cm3For example, it may be 1 × 1015 atoms/cm3、5×1015 atoms/cm3、1×1016 atoms/cm3、2×1016 atoms/cm3、4×1016 atoms/cm3、5×1016 atoms/cm3、1×1017 atoms/cm3、2×1017 atoms/cm3Or 5X 1017atoms/cm3And the like, and other values within this range are also possible, and are not limited herein.
The nitrogen doping concentration in the single crystal silicon is 1X 1012~1×1016atoms/cm3For example, it may be 1 × 1012 atoms/cm3、1×1013 atoms/cm3、1×1014 atoms/cm3、1×1015 atoms/cm3Or 1X 1016atoms/cm3And the like, and other values within this range are also possible, and are not limited herein.
The resistivity of the gallium, hydrogen, and nitrogen-doped single crystal silicon is 0.1 to 10 Ω · cm, and may be, for example, 0.1 Ω · cm, 0.5 Ω · cm, 1.4 Ω · cm, 3.7 Ω · cm, 5.2 Ω · cm, 8.5 Ω · cm, or 10 Ω · cm, or may be other values within this range, and is not limited thereto.
The doping concentration of gallium, hydrogen and nitrogen is controlled within the range, so that the performance requirement of a solar cell can be met by a subsequently manufactured silicon wafer, and the activity of point defects, dislocation defects and metal defects in the gallium-doped monocrystalline silicon crystal can be greatly reduced by the monocrystalline silicon doped with gallium, hydrogen and nitrogen, so that the dislocation defects can be controlled, the mechanical strength of the monocrystalline silicon can be improved, the reject ratio of the silicon wafer in the subsequent production can be reduced, and the preparation cost of the monocrystalline silicon can be reduced.
The embodiment of the application also provides a preparation method of the gallium, hydrogen and nitrogen doped monocrystalline silicon, which adopts a monocrystalline furnace, wherein part of the structure of the monocrystalline furnace is shown in figures 1 a-1 b, and the monocrystalline furnace comprises a furnace body 1, a quartz crucible 2, a heater 3, a water-cooling heat shield 4, a heat-insulating cylinder 5, a guide cylinder 6, a crystal pulling device 7 and a crystal 8. The crystal pulling apparatus 7 is used for pulling the crystal 8.
The single crystal furnace also comprises a connecting piece 10 and a water-cooling heat shield lifting rod 11, wherein the connecting piece 10 is used for connecting the water-cooling heat shield lifting rod 11 with the guide cylinder 6, and the water-cooling heat shield lifting rod 11 is used for lifting the water-cooling heat shield 4.
In one embodiment, the connector 10 includes a lift stop 101, a support rod 102, and a lift buckle 103. Two ends of the supporting rod 102 are respectively connected with the lifting limiting part 101 and the guide cylinder 6, one end of the lifting buckle 103 is fixedly connected with the water-cooling heat shield lifting rod 11, and the other end is clamped on the supporting rod 102. The heater 3 is used to heat the polycrystalline silicon raw material and the gallium dopant in the quartz crucible 2, so that the polycrystalline silicon raw material is melted to form the silicon melt 9. The water-cooling heat shield 4 can reduce the temperature of the surface of the crystal 8, increase the temperature gradient inside the crystal 8 and improve the growth speed of the crystal.
Fig. 2 is a flowchart of a method for preparing gallium, hydrogen, and nitrogen doped monocrystalline silicon according to an embodiment of the present disclosure, and as shown in fig. 2, the method includes the following steps:
putting a polycrystalline silicon raw material and a gallium dopant into a quartz crucible;
placing the quartz crucible in a single crystal furnace, vacuumizing, and melting a polycrystalline silicon raw material under the protection of inert gas to obtain a silicon melt;
after the temperature of the silicon melt is stable, adding a hydrogen source and a nitrogen source into the single crystal furnace, and immersing a seed crystal into the silicon melt to start seeding;
after seeding is finished, shouldering is started to enable the diameter of the crystal to be gradually increased to a preset width, and then equal-diameter growth is carried out;
after the isodiametric growth is finished, entering a final stage, and gradually reducing the diameter of the crystal until the crystal is separated from the silicon melt;
and cooling the grown crystal to room temperature, and taking out to obtain the gallium, hydrogen and nitrogen doped monocrystalline silicon.
In the scheme, a nitrogen source and a hydrogen source are added in the seeding process, so that trace hydrogen atoms and nitrogen atoms are fused into silicon melt to realize the doping of hydrogen and nitrogen elements, the activity of point defects, dislocation defects and metal defects in the gallium-doped monocrystalline silicon crystal can be greatly reduced by the doped hydrogen atoms, the slippage of dislocation can be pinned by the doped nitrogen atoms, the dislocation defects can be favorably controlled, the minority carrier lifetime of the gallium-doped monocrystalline can be effectively prolonged, and the quality of the monocrystalline silicon is improved.
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to fig. 2 in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
And (1) putting a polycrystalline silicon raw material and a gallium dopant into a quartz crucible.
In one embodiment, the polysilicon source material may be virgin polysilicon material, the gallium dopant may be gallium metal or a gallium master alloy, the gallium metal may be, for example, liquid gallium, and the resistivity of the gallium master alloy is 0.001 to 0.05 Ω · cm. The amount of gallium dopant added can be formulated according to the concentration of gallium in the finally produced single crystal silicon. Optionally, the doping concentration of gallium is 1 × 10 according to the number of atoms in the single crystal silicon material per cubic centimeter15~5×1017atoms/cm3And then a proper amount of gallium dopant is weighed and added into the quartz crucible.
In other embodiments, gallium-doped polysilicon feedstock may also be employed.
Step (2), placing the quartz crucible in a single crystal furnace for vacuumizing, and melting a polycrystalline silicon raw material under the protection of inert gas to obtain silicon melt;
specifically, the inert gas may be at least one of argon gas and helium gas, for example.
In the process of melting, the temperature in the single crystal furnace is controlled to be 1420-1570 ℃. For example, 1450 ℃, 1480 ℃, 1500 ℃, 1520 ℃, 1540 ℃, 1560 ℃, preferably 1520 ℃, in the single crystal furnace to obtain molten liquid silicon.
And (3) after the temperature of the silicon melt is stable, adding a hydrogen source and a nitrogen source into the single crystal furnace, and immersing a seed crystal into the silicon melt to start seeding.
The stable temperature of the silicon melt is 1420-1480 ℃, at the moment, the temperature of the silicon melt in the quartz crucible is stable, and a hydrogen source and a nitrogen source can be added into the inert gas, so that hydrogen atoms and nitrogen atoms are doped into the silicon melt.
In one embodiment, the hydrogen source is a hydrogen-containing gas, the nitrogen source is a nitrogen-containing gas, and the step of adding the hydrogen source and the nitrogen source into the single crystal furnace comprises:
and mixing the hydrogen-containing gas, the nitrogen-containing gas and the inert gas to form mixed gas, and introducing the mixed gas into the single crystal furnace.
Specifically, the hydrogen-containing gas includes at least one of hydrogen, silane, and ammonia. The nitrogen-containing gas includes at least one of nitrogen gas and ammonia gas. The inert gas includes at least one of argon and helium.
The volume ratio of the hydrogen-containing gas in the mixed gas is controlled to be 0.1% to 2% from the start of the seeding stage, and may be, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, or 2%, or may be other values within this range, which is not limited herein.
The volume ratio of the nitrogen-containing gas in the mixed gas is controlled to be 1% to 20% from the start of the seeding stage, and may be, for example, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, or 20%, or may be other values within this range, which is not limited herein.
In a specific embodiment, the hydrogen-containing gas and the nitrogen-containing gas are combined with the inert gas into the same pipeline before being introduced into the furnace body, and preferably, a gas mixing valve can be arranged on the pipeline, so that the gas mixing is more uniform.
In another embodiment, the hydrogen source is a polysilicon material rich in hydrogen, the nitrogen source is a nitrogen-containing gas, and the specific steps of adding the hydrogen source and the nitrogen source into the single crystal furnace include:
and adding the hydrogen-rich polycrystalline silicon raw material into the silicon melt, mixing the nitrogen-containing gas and the inert gas to form mixed gas, and introducing the mixed gas into the single crystal furnace.
The hydrogen content in the polysilicon raw material rich in hydrogen is more than 6 x 1016atoms/cm3. It should be noted that when the polysilicon material rich in hydrogen is used, no hydrogen-containing gas is needed to be added in the subsequent seeding, shouldering, equal-diameter growth and ending processes.
The volume ratio of the nitrogen-containing gas in the mixed gas is 1% to 20%, and may be, for example, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 18%, or 20%, or may be other values within this range, which is not limited herein.
In the seeding process, the water flow of the water-cooling heat shield is controlled to be 40-160 slpm, the rotating speed of the quartz crucible is 4-10 r/min, the temperature in the single crystal furnace is 1420-1480 ℃, the pressure in the single crystal furnace is 1000-3000 Pa, the flow of the mixed gas is 50-200 slpm, and the seeding speed is 40-400 mm/h.
Alternatively, the water flow rate of the water-cooled heat shield may be, for example, 40slpm, 60slpm, 80slpm, 100slpm, 120slpm, 140slpm or 160slpm, but may be other values within this range, which is not limited herein.
Alternatively, the rotation speed of the quartz crucible can be, for example, 4r/min, 5r/min, 6r/min, 7r/min, 8r/min, 9r/min or 10r/min, or other values within the range, which is not limited herein.
Alternatively, the temperature in the single crystal furnace may be, for example, 1420 ℃, 1440 ℃, 1460 ℃ or 1480 ℃, but may be other values within this range, and is not limited thereto.
Alternatively, the pressure inside the single crystal furnace may be, for example, 1000Pa, 1500Pa, 2000Pa, 2500Pa, or 3000Pa, but may be other values within this range, and is not limited herein.
Optionally, the flow rate of the mixed gas is 50slpm, 80slpm, 100slpm, 120slpm, 150slpm, 180slpm or 200slpm, but may be other values within this range, which is not limited herein.
Alternatively, the seeding rate may be, for example, 40mm/h, 80mm/h, 100mm/h, 150mm/h, 200mm/h, 250mm/h, 300mm/h, 350mm/h, or 400mm/h, without limitation.
In addition, the temperature and pressure in the furnace, the water flow of the water-cooling heat shield, the flow of the inert gas, the rotating speed of the quartz crucible and the seeding speed range are within the range, so that the seeding success rate is improved.
In this embodiment, as shown in fig. 1a, in the seeding process, the water-cooling heat shield lifting rod 11 lifts the water-cooling heat shield 4 away from the surface of the silicon melt, and the guide cylinder 6 rises along with the water-cooling heat shield lifting rod 11 under the action of the connecting piece 10, so that the distance h between the bottom of the water-cooling heat shield and the surface 91 of the silicon melt is adjusted to a first preset distance. Optionally, the first preset distance is 25-60 mm. The first preset distance is set so that the water-cooling heat shield is far away from the high-temperature silicon melt in the seeding stage, temperature fluctuation is avoided, the temperature of a growth interface is stable, and the seeding success rate is high.
Step (4), after seeding is finished, shouldering is started to enable the diameter of the crystal to be gradually increased to a preset width, and then equal-diameter growth is carried out;
in the shouldering process, the water flow of the water-cooling heat shield is controlled to be 40-160 slpm, the rotating speed of the quartz crucible is 4-10 r/min, the temperature in the single crystal furnace is 1420-1460 ℃, the pressure in the single crystal furnace is 1000-3000 Pa, and the flow of the mixed gas is 50-200 slpm.
The first pulling speed of the crystal is 40-80mm/h, so that the diameter of the crystal is gradually increased to 10-305 mm. Alternatively, the first pulling speed may be, for example, 40mm/h, 55mm/h, 65mm/h, 80mm/h, etc., and the diameter of the crystal is gradually increased to 40mm, 100mm, 150mm, 225mm, 245mm, 285mm, 295mm, 305mm, etc., without limitation. Understandably, the temperature gradient in the crystal is small in the shouldering process, and the growth speed and the pulling speed of the crystal are slow in order to ensure the stability of crystal pulling. In addition, in the whole shouldering process, the temperature in the single crystal furnace can be gradually reduced, and cannot be increased.
The diameter range of the crystal can be designed and controlled according to the size requirement of the cell piece on the silicon wafer, and is not limited herein.
In the shouldering process, the distance h between the bottom of the water-cooling heat shield and the surface of the silicon melt can be reduced, and the heat absorption capacity of the water-cooling heat shield on the crystal rod is improved.
Optionally, in the process of constant-diameter growth, the water flow of the water-cooling heat shield is controlled to be 40-160 slpm, the rotating speed of the quartz crucible is 4-10 r/min, the temperature in the single crystal furnace is 1420-1460 ℃, the pressure in the single crystal furnace is 1000-3000 Pa, and the flow of the mixed gas is 50-200 slpm.
The second pulling speed of the crystal is 70-140 mm/h, for example, 70mm/h, 80mm/h, 90mm/h, 100mm/h, 110mm/h, 120mm/h, 130mm/h or 140mm/h, etc., which is not limited herein. Understandably, in the equal-diameter growth stage, the crystal begins to enter the water-cooling heat shield area or completely enters the water-cooling heat shield area, the water-cooling heat shield can quickly absorb the heat of the crystal, so that the temperature gradient of the crystal bar is increased, and in the stage, in order to ensure the growth efficiency, the crystal growth speed is increased, and the crystal pulling speed can be increased.
As shown in fig. 1b, in the process of isodiametric growth, the water-cooling heat shield lifting rod 11 descends towards the direction close to the surface of the silicon melt to the water-cooling heat shield 4, the guide cylinder 6 also descends along with the water-cooling heat shield lifting rod until the flanging of the guide cylinder 6 is abutted to the heat-insulating cylinder 5, and the water-cooling heat shield 4 continues to descend towards the direction close to the surface of the silicon melt, so that the distance h between the bottom of the water-cooling heat shield 4 and the surface 91 of the silicon melt is adjusted to a second preset distance. Optionally, the second preset distance is 10-40 mm. At the moment, the water-cooling heat shield 4 descends relative to the guide cylinder 6, so that the distance between the bottom of the water-cooling heat shield 4 and the surface of the silicon melt is further reduced, the heat absorption capacity of the water-cooling heat shield on the crystal rod is improved, and the variable-temperature gradient crystal pulling is realized.
In this embodiment, the height difference between the first preset distance and the second preset distance is 15-50 mm.
And (5) after the equal-diameter growth is finished, entering a final stage, and gradually reducing the diameter of the crystal until the crystal is separated from the silicon melt.
In the process, the water flow of the water-cooling heat shield is controlled to be 40-160 slpm, the rotating speed of the quartz crucible is 4-10 r/min, the temperature in the single crystal furnace is 1420-1460 ℃, the pressure in the single crystal furnace is 1000-3000 Pa, and the flow of the mixed gas is 50-200 slpm.
The third pulling speed of the crystals is 70 to 130mm/h, and may be, for example, 75mm/h, 85mm/h, 95mm/h, 100mm/h, 115mm/h or 120 mm/h; in the final stage, the temperature in the single crystal furnace is rapidly raised.
And (6) cooling the grown crystal to room temperature, and taking out the crystal to obtain the gallium, hydrogen and nitrogen doped monocrystalline silicon.
The hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 multiplied by 105~1×1016atoms/cm3The doping concentration of gallium is 1 × 1015~5×1017atoms/cm3Nitrogen doping concentration of 1X 1012~1×1016atoms/cm3(ii) a The resistivity of the gallium, hydrogen and nitrogen doped monocrystalline silicon is 0.1-10 omega cm.
Embodiments of the present application further provide a solar cell, which can be formed by using the gallium, hydrogen, and nitrogen doped monocrystalline silicon.
The solar cell comprises a semiconductor substrate, a doping layer positioned on the front surface of the semiconductor substrate, a front passivation layer and/or an antireflection layer positioned on the upper surface of the doping layer, a front electrode positioned on the upper surface of the front passivation layer and/or the antireflection layer, a back passivation layer positioned on the back surface of the semiconductor substrate and a back electrode positioned on the back surface of the back passivation layer.
As shown in fig. 3, in one embodiment, the solar cell is a solar cell having a PERC structure, which includes:
the semiconductor substrate 100, the semiconductor substrate 100 comprising the gallium, hydrogen, and nitrogen doped monocrystalline silicon substrate described above, may be sliced from the prepared monocrystalline silicon rod described above to form a silicon wafer, which may be used as a semiconductor substrate. Wherein the hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 x 105~1×1016atoms/cm3The doping concentration of gallium is 1 × 1015~5×1017atoms/cm3Nitrogen doping concentration of 1X 1012~1×1016atoms/cm3The resistivity of the gallium, hydrogen and nitrogen doped monocrystalline silicon is 0.1-10 omega cm.
During the preparation process of the cell, the silicon wafer is subjected to a high temperature treatment (such as a high temperature annealing treatment), hydrogen atoms in the silicon wafer can escape at a high temperature, and in some embodiments, hydrogen in the edge region of the silicon wafer is easier to escape than hydrogen in the center region of the silicon wafer, so that the hydrogen content in the center region of the semiconductor substrate is greater than that in the edge region. To some extent, the escaped hydrogen atoms contribute to defect passivation of the semiconductor substrate, thereby improving the conversion efficiency of the cell.
In some embodiments, the inside of the semiconductor substrate 100 may form an H-P bond, an H-Ga bond, or an H-N bond for fixing the hydrogen atoms from excessive escape during the fabrication of the solar cell.
In the present embodiment, the semiconductor substrate 100 includes a front surface and a back surface which are oppositely disposed, and the hydrogen content in the semiconductor substrate 100 is unevenly distributed, for example, the hydrogen content in the center region of the semiconductor substrate 100 is greater than the hydrogen content in the edge region thereof. It is understood that the edge region may refer to a region located at a depth, e.g., within 10nm, within the surface (e.g., front, back, and/or side) of the substrate. The central region may refer to a specific partial region or the entire region other than the edge region.
The doped layer 13 on the front surface of the semiconductor substrate 100 may be doped with, for example, phosphorus by diffusion to form an N-type doped layer. Preferably, the doped layer 13 includes a lightly doped region 131 having a first doping concentration and a heavily doped region 132 having a second doping concentration, and a selective emitter structure is formed between the heavily doped region 131 and the lightly doped region 132, wherein the phosphorus concentration in the lightly doped region 131 is less than the phosphorus concentration in the heavily doped region. The selective emitter can reduce the contact resistance between the silicon wafer and the electrode, reduce the recombination of current carriers, improve the surface passivation effect and prolong the minority carrier lifetime.
A front passivation and/or antireflective layer 12 on the top surface of doped layer 13;
a front electrode 111 disposed on the upper surface of the front passivation layer and/or the anti-reflection layer 12, wherein the front electrode 111 penetrates the front passivation layer and/or the anti-reflection layer 12 and the heavily doped region 131 of the doped layer 13 to form an ohmic contact;
a backside passivation layer 14 on the backside of the semiconductor substrate 100.
A back electrode 15 located on the back side of the back passivation layer 8, wherein the back passivation layer 14 is provided with an opening through which at least a portion of the back electrode 15 is brought into electrical contact with the semiconductor substrate 100.
In the embodiment of the present invention, the specific types of the front passivation layer and/or the antireflective layer 12 and the back passivation layer 14 are not limited, and for example, the front passivation layer and/or the antireflective layer may be any one or a combination of a plurality of silicon nitride layers, silicon oxynitride layers, and aluminum oxide/silicon nitride stacked structures, which can generate a good passivation effect on a silicon substrate, and is helpful for improving the conversion efficiency of a battery.
In the embodiment of the present invention, the specific material of the front electrode 111 and the back electrode 15 is not limited. For example, the front electrode 111 is a silver electrode or a silver/aluminum electrode, and the back electrode 15 is a silver electrode.
The specific type of doped layer 13 is not limited in the embodiment of the present invention, and for example, doped layer 13 is an N-type polysilicon layer. The front passivation layer and/or the antireflective layer 12 and the back passivation layer 14 are not limited to specific types in the embodiments of the present invention, and may be, for example, a silicon nitride layer, a silicon oxynitride layer, an aluminum oxide/silicon nitride stacked structure, or the like.
In the embodiment of the invention, the conductive paste can be printed on the surface of the semiconductor substrate by adopting a screen printing technology, and the conductive paste is sintered and dried to form the grid-line-shaped electrode structure. And the formed grid line electrode is electrically connected with the semiconductor substrate through the heavily doped region of the doped layer. The conductive paste includes, but is not limited to, silver paste and/or aluminum paste, etc.
In other embodiments, both the front side and/or the back side of the semiconductor substrate may form an electrode structure.
It should be noted that, in the embodiment of the present invention, the thickness of each layer structure in the solar cell is not limited, and can be adjusted and controlled by a person skilled in the art according to actual situations.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. The gallium, hydrogen and nitrogen doped monocrystalline silicon is characterized in that the hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 multiplied by 105~1×1016atoms/cm3The doping concentration of gallium is 1 × 1015~5×1017atoms/cm3Nitrogen doping concentration of 1X 1012~1×1016atoms/cm3(ii) a The resistivity of the gallium, hydrogen and nitrogen doped monocrystalline silicon is 0.1-10 omega cm.
2. A method of preparing gallium, hydrogen, and nitrogen doped single crystal silicon as claimed in claim 1, comprising the steps of:
putting a polycrystalline silicon raw material and a gallium dopant into a quartz crucible;
placing the quartz crucible in a single crystal furnace, vacuumizing, and melting a polycrystalline silicon raw material under the protection of inert gas to obtain a silicon melt;
after the temperature of the silicon melt is stable, adding a hydrogen source and a nitrogen source into the single crystal furnace, and immersing a seed crystal into the silicon melt to start seeding;
after seeding is finished, shouldering is started to enable the diameter of the crystal to be gradually increased to a preset width, and then equal-diameter growth is carried out;
after the isodiametric growth is finished, entering a final stage, and gradually reducing the diameter of the crystal until the crystal is separated from the silicon melt;
and cooling the grown crystal to room temperature and taking out the crystal, wherein the crystal is gallium, hydrogen and nitrogen doped monocrystalline silicon.
3. The method of claim 2, wherein the hydrogen source is a hydrogen-containing gas and the nitrogen source is a nitrogen-containing gas, and the step of adding the hydrogen source and the nitrogen source into the single crystal furnace comprises:
and mixing the hydrogen-containing gas, the nitrogen-containing gas and the inert gas to form mixed gas, and introducing the mixed gas into the single crystal furnace.
4. The method of claim 3, wherein the hydrogen-containing gas is present in the mixed gas in a volume ratio of 0.1% to 2%, and the nitrogen-containing gas is present in the mixed gas in a volume ratio of 1% to 20%.
5. The method of claim 3 or 4, wherein the hydrogen-containing gas comprises at least one of hydrogen, silane, ammonia; and/or the nitrogen-containing gas comprises at least one of nitrogen and ammonia.
6. The method of claim 2, wherein the hydrogen source is a hydrogen-rich polysilicon feedstock and the nitrogen source is a nitrogen-containing gas, and the step of adding the hydrogen source and the nitrogen source to the single crystal furnace comprises:
and adding the hydrogen-rich polycrystalline silicon raw material into the silicon melt, mixing the nitrogen-containing gas and the inert gas to form mixed gas, and introducing the mixed gas into the single crystal furnace.
7. The method of claim 6, wherein the nitrogen-containing gas is present in the mixed gas in a volume ratio of 1% to 20%; and/or the presence of a gas in the gas,
the hydrogen content in the polysilicon raw material rich in hydrogen is more than 6 x 1016atoms/cm3。
8. The method of claim 3 or 6, wherein the inert gas comprises at least one of argon, helium.
9. A solar cell, comprising: the semiconductor substrate, the doping layer positioned on the front surface of the semiconductor substrate, the front passivation layer and/or the antireflection layer positioned on the upper surface of the doping layer, the front electrode positioned on the upper surface of the front passivation layer and/or the antireflection layer, the back passivation layer positioned on the back surface of the semiconductor substrate and the back electrode positioned on the back surface of the back passivation layer,
wherein the semiconductor substrate comprises gallium, hydrogen and nitrogen doped monocrystalline silicon, and the hydrogen doping concentration in the gallium, hydrogen and nitrogen doped monocrystalline silicon is 1 × 105~1×1016atoms/cm3The doping concentration of gallium is 1 × 1015~5×1017atoms/cm3Nitrogen doping concentration of 1X 1012~1×1016atoms/cm3The resistivity of the gallium, hydrogen and nitrogen doped monocrystalline silicon is 0.1-10 omega cm.
10. The solar cell according to claim 9, wherein a hydrogen content of the central region of the semiconductor substrate is greater than a hydrogen content of the edge region.
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