CN117038801A - Silicon wafer, processing method thereof and preparation method of solar cell - Google Patents
Silicon wafer, processing method thereof and preparation method of solar cell Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 165
- 239000010703 silicon Substances 0.000 title claims abstract description 165
- 238000003672 processing method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009792 diffusion process Methods 0.000 claims abstract description 167
- 235000012431 wafers Nutrition 0.000 claims abstract description 164
- 230000003647 oxidation Effects 0.000 claims abstract description 152
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 152
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 79
- 230000005641 tunneling Effects 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 62
- 239000007789 gas Substances 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000007517 polishing process Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 47
- 239000010409 thin film Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 3
- 238000002161 passivation Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 40
- 239000010453 quartz Substances 0.000 description 39
- 230000001276 controlling effect Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Formation Of Insulating Films (AREA)
Abstract
The application relates to the technical field of semiconductor preparation processes, and discloses a silicon wafer for preparing a solar cell, a processing method thereof and a preparation method of the solar cell; the processing method of the silicon wafer comprises the following steps: placing the silicon wafers to be processed after the alkali polishing process in a diffusion oxidation furnace in pairs, and attaching the front surfaces of the silicon wafers to be processed to each other; vacuumizing the diffusion oxidation furnace, and controlling the temperature in the furnace to be in a first set temperature range, introducing oxygen into the diffusion oxidation furnace, and forming a tunneling layer on the back surface of the silicon wafer to be processed; vacuumizing the diffusion oxidation furnace and controlling the temperature in the furnace to be in a second set temperature range, and introducing SiH into the diffusion oxidation furnace 4 And forming an amorphous silicon film layer on the surface of the tunneling layer of the silicon wafer to be processed by using the gas. According to the application, the front surfaces of every two silicon wafers are mutually attached, so that a tunneling layer and an amorphous silicon film layer can be formed only on the back surface of the silicon wafer to be processed, and the processing process of the solar cell is simplified.
Description
Technical Field
The application relates to the technical field of production and preparation of solar cells, in particular to a silicon wafer for preparing a solar cell, a processing method of the silicon wafer and a preparation method of the solar cell.
Background
As shown in fig. 1 and 2, fig. 1 is a flowchart of a process for manufacturing a solar cell; fig. 2 is a schematic cross-sectional structure of a TOPCon battery. In the process of manufacturing a solar cell, a silicon wafer is used as a substrate, and a plurality of complicated processing steps are repeatedly performed on the surface of the silicon wafer. As shown in fig. 1 and 2, the tunneling layer and the amorphous silicon thin film on the back surface of the solar cell are formed by sequentially performing etching, boron diffusion, and alkali polishing processes such as BSG removal and back surface polishing on the silicon wafer substrate, and then preparing the silicon wafer substrate on the back surface.
The LPCVD technology is one of the common technological methods for forming tunneling layer and amorphous silicon film on the back of silicon wafer; the method comprises placing silicon wafer in a diffusion oxidation furnace, heating the furnace to a specific temperature, introducing oxygen capable of oxidizing the surface of the silicon wafer to form a tunneling layer, and introducing SiH capable of further forming an amorphous silicon film layer on the tunneling layer 4 And (3) preparing the gas, so as to prepare a silicon wafer with a tunneling layer and an amorphous silicon film layer on the back surface, and preparing the solar cell by using the silicon wafer later.
However, the current process for preparing the tunneling layer and the amorphous silicon thin film layer on the back surface of the silicon wafer is complex, and the preparation production efficiency of the whole solar cell is reduced to a certain extent.
Disclosure of Invention
The application aims to provide a silicon wafer for preparing a solar cell, a processing method thereof and a preparation method of the solar cell, which can simplify the technological process of forming a tunneling layer and an amorphous silicon film layer on the back surface of the silicon wafer in the process of preparing the solar cell to a certain extent, thereby improving the production efficiency of the solar cell.
In order to solve the technical problems, the application provides a silicon wafer processing method for preparing a solar cell, which comprises the following steps:
placing silicon wafers to be processed in pairs in a diffusion oxidation furnace, wherein the front surfaces of each pair of silicon wafers to be processed are mutually attached; the silicon wafer to be processed is a silicon wafer subjected to an alkali polishing process;
vacuumizing the diffusion oxidation furnace, and introducing oxygen into the diffusion oxidation furnace under the condition that the temperature in the furnace is controlled to be in a first set temperature range so as to form a tunneling layer on the back surface of each silicon wafer to be processed;
for the diffusion oxidation furnaceIntroducing SiH into the diffusion oxidation furnace under the conditions of internal vacuumizing and controlling the temperature in the furnace to be in a second set temperature range 4 And the gas is used for forming an amorphous silicon film layer on the surface of the tunneling layer of the silicon wafer to be processed.
Optionally, the process of forming the tunneling layer on the back surface of the silicon wafer to be processed includes:
controlling the temperature of the diffusion oxidation furnace from the first temperature region to the fifth temperature region to be 570-600 ℃ under the condition of vacuumizing in the diffusion oxidation furnace, wherein the temperature of the sixth temperature region is 560-590 ℃ in a constant temperature environment;
continuously introducing oxygen into the diffusion oxidation furnace to oxidize the surface of the silicon wafer to be processed to form a tunneling layer.
Optionally, continuously introducing oxygen into the diffusion oxidation furnace, including:
300s-600s of oxygen gas with the concentration of 30000sccm-40000sccm is continuously introduced into the diffusion oxidation furnace.
Optionally, the process of forming the amorphous silicon thin film layer on the surface of the tunneling layer of the silicon wafer to be processed includes:
heating the diffusion oxidation furnace under the condition of vacuumizing the diffusion oxidation furnace, so that the inside of the diffusion oxidation furnace is in a constant temperature environment with the temperature of 580-615 ℃ in a first temperature zone to a sixth temperature zone;
introducing nitrogen into the diffusion oxidation furnace so as to maintain the inside of the diffusion oxidation furnace in a set constant pressure state;
SiH is respectively introduced from the front end and the rear end of the diffusion oxidation furnace 4 And (3) gas so that an amorphous silicon film layer is formed on the surface of the tunneling layer of the silicon wafer to be processed.
Optionally, siH is introduced from the front end and the rear end of the diffusion oxidation furnace respectively 4 A gas, comprising:
introducing 100sccm-300sccm SiH from the front end of the diffusion oxidation furnace 4 Introducing 1300-1700 sccm SiH from the rear end of the diffusion oxidation furnace 4 And (3) gas.
Optionally, siH is introduced from the front end and the rear end of the diffusion oxidation furnace respectively 4 A gas, comprising:
and continuously introducing SiH4 gas with the duration of 1300s-1500s from the front end and the rear end of the diffusion oxidation furnace respectively.
Optionally, after forming an amorphous silicon thin film layer on the surface of the tunneling layer of the silicon wafer to be processed, the method further comprises:
vacuumizing the diffusion oxidation furnace;
introducing 1000sccm-3000sccm SiH from the front end of the diffusion oxidation furnace 4 Introducing 3000sccm-6000sccm SiH from the rear end of the diffusion oxidation furnace 4 A gas to maintain the inside of the diffusion oxidation furnace in a set constant pressure state;
introducing 900-1200 sccm SiH from the front end of the diffusion oxidation furnace for 10-30 s 4 Introducing 1000sccm-3000sccm SiH from the rear end of the diffusion oxidation furnace 4 A gas to purge the interior of the diffusion oxidation furnace;
and after introducing nitrogen into the diffusion oxidation furnace for cleaning, vacuumizing and breaking the inside of the diffusion oxidation furnace in sequence, and taking out the silicon wafer to be processed.
A silicon wafer for producing a solar cell, the surface of the silicon wafer having a tunneling layer and an amorphous silicon thin film layer formed by the silicon wafer processing method for producing a solar cell as described in any one of the above.
Optionally, the thickness of the tunneling layer is 1.0nm-1.5nm; the thickness of the amorphous silicon film layer is 120nm-130nm.
A preparation method of a solar cell comprises the following steps:
sequentially performing texturing, boron diffusion, BSG removal and back polishing by taking a silicon wafer as a substrate;
according to the silicon wafer processing method for preparing the solar cell, a tunneling layer and an amorphous silicon film layer are formed on the back surface of the silicon wafer;
and sequentially carrying out phosphorus doping, PSG removal, surface passivation and metallization processing operations on the silicon wafer after the tunneling layer and the amorphous silicon film layer are processed, so as to obtain the solar cell.
The application provides a silicon wafer for preparing a solar cell, a processing method thereof and a preparation method of the solar cell; the processing method of the silicon wafer for preparing the solar cell comprises the following steps: the silicon wafers to be processed are placed in a diffusion oxidation furnace in pairs, wherein the front surfaces of the silicon wafers to be processed are mutually attached; the silicon wafer to be processed is a silicon wafer subjected to an alkali polishing process; vacuumizing the diffusion oxidation furnace, and introducing oxygen into the diffusion oxidation furnace under the condition that the temperature in the furnace is controlled to be in a first set temperature range so as to form a tunneling layer on the back surface of each silicon wafer to be processed; vacuumizing the diffusion oxidation furnace and controlling the temperature in the furnace to be in a second set temperature range, and introducing SiH into the diffusion oxidation furnace 4 And (3) gas to form an amorphous silicon film layer on the surface of the tunneling layer of the silicon wafer to be processed.
In the application, in the process of forming the tunneling layer and the amorphous silicon film layer on the back surface of the silicon wafer subjected to the alkali polishing process, the front surfaces of every two silicon wafers to be processed are mutually attached, so that when the tunneling layer and the amorphous silicon film layer are generated on the surfaces of the silicon wafers to be processed, the tunneling layer and the amorphous silicon film layer can only be formed on the back surface of the silicon wafer to be processed because of the mutual shielding coverage between the front surfaces of the two silicon wafers to be processed which are mutually attached, thereby avoiding the process of removing the amorphous silicon film layer on the front surface of the silicon wafer to be processed in the subsequent processing process, simplifying the processing process of the solar cell to a certain extent, and being beneficial to improving the processing efficiency of the solar cell.
Drawings
For a clearer description of embodiments of the application or of the prior art, the drawings that are used in the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only some embodiments of the application, and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram for the preparation of solar cells;
fig. 2 is a schematic cross-sectional structure of a TOPCon battery;
fig. 3 is a schematic flow chart of a silicon wafer processing method for preparing a solar cell according to an embodiment of the present application.
Detailed Description
After boron diffusion and subsequent alkali polishing processes are completed on the silicon wafer substrate, in the process of forming a tunneling layer and an amorphous silicon film on the surface of the silicon wafer through an LPCVD process, a double-sided amorphous silicon film is generally formed on the front surface and the back surface of the silicon wafer at the same time; however, as can be seen from the structure diagram shown in fig. 2, the amorphous silicon film on the back surface of the final solar cell needs to be retained, so that the amorphous silicon film on the front surface of the silicon wafer needs to be removed, the process is complicated, and unnecessary material waste is caused to a certain extent.
Therefore, the application provides a technical scheme capable of simplifying the technological process of generating the tunneling layer and the amorphous silicon film on the surface of the silicon wafer.
In order to better understand the aspects of the present application, the present application will be described in further detail with reference to the accompanying drawings and detailed description. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
As shown in fig. 3, fig. 3 is a schematic flow chart of a processing method of a silicon wafer for manufacturing a solar cell according to an embodiment of the present application, where the processing method of the silicon wafer may include:
s11: the silicon wafers to be processed are placed in a diffusion oxidation furnace in pairs, wherein the front surfaces of the silicon wafers to be processed are mutually attached; and the silicon wafer to be processed is the silicon wafer after the alkali polishing process.
It is understood that, for a solar cell, the surface directly receiving solar light is the front surface of the cell, and the surface opposite to the front surface of the cell is the back surface of the cell. For the front surface of the silicon wafer to be processed in this embodiment, that is, the front surface of the battery piece after the silicon wafer to be processed is finally processed to form the battery piece, the back surface of the silicon wafer to be processed corresponds to the back surface of the battery piece. Too much discussion is not made in this embodiment.
In addition, the silicon wafer to be processed in the embodiment is a silicon wafer subjected to an alkali polishing process, that is, a silicon wafer subjected to processes such as texturing, boron diffusion, BSG removal, back polishing and the like, and the above processes are conventional processes in the process of preparing a solar cell, and the process is specifically referred to a conventional process for preparing a solar cell, and will not be discussed in detail in the present application.
As shown in fig. 2, since the silicon wafer to be processed is prepared to form a solar cell, only a tunneling layer and an amorphous silicon thin film layer need be formed on the back surface thereof. Therefore, in this embodiment, in order to simplify the steps of forming the tunneling layer and the amorphous silicon thin film layer to a certain extent, the front surfaces of every two silicon wafers to be processed are relatively bonded, so that the front surfaces of the two silicon wafers to be processed are covered and shielded, thereby isolating the contact between the front surface of the silicon wafer to be processed and the gas in the furnace, and avoiding the generation of the tunneling layer and the amorphous silicon thin film layer on the front surface of the silicon wafer to be processed. Meanwhile, the back surfaces of the silicon wafers to be processed are not in contact with each other but are directly exposed in the internal environment of the diffusion oxidation furnace, so that the generation of the tunneling layer and the amorphous silicon film layer on the back surfaces of the silicon wafers to be processed can be completed on the basis of avoiding the generation of the tunneling layer and the amorphous silicon film layer on the front surfaces of the silicon wafers to be processed, the tunneling layer and the amorphous silicon film layer do not need to be removed from the front surfaces of the silicon wafers to be processed in subsequent procedures, the processing process of forming the tunneling layer and the amorphous silicon film layer on the back surfaces of the silicon wafers to be processed is simplified to a certain extent, the processing flow of the whole solar cell is simplified, and the production efficiency of the cell is improved.
S12: and (3) vacuumizing the diffusion oxidation furnace, and introducing oxygen into the diffusion oxidation furnace under the condition that the temperature in the furnace is controlled to be in a first set temperature range so as to form a tunneling layer on the back surface of each silicon wafer to be processed.
It can be understood that in this embodiment, when the tunneling layer is actually generated on the back surface of the silicon wafer to be processed, two silicon wafers to be processed are attached together for processing; thus, the heat dissipation of the silicon wafer itself is slower than the formation of the tunneling layer by processing both the front and back surfaces of each silicon wafer to be processed, and for this purpose, the process conditions during the actual processing should be appropriately adjusted.
In an alternative embodiment of the present application, the process of forming the tunneling layer on the back surface of each silicon wafer to be processed may include:
s121: under the condition of vacuumizing in the diffusion oxidation furnace, controlling the temperature of the diffusion oxidation furnace from the first temperature region to the fifth temperature region to be 570-600 ℃ and the temperature of the sixth temperature region to be 560-590 ℃ in a constant temperature environment;
s122: oxygen is continuously introduced into the diffusion oxidation furnace so as to oxidize the surface of the silicon wafer to be processed to form a tunneling layer.
It will be appreciated that the diffusion oxidation furnace is generally of a columnar structure and is divided into six temperature zones in sequence along the length direction of the diffusion oxidation furnace, and the heating temperature of each temperature zone can be independently controlled and regulated.
In the actual processing process, the temperature of the first temperature region to the fifth temperature region in the diffusion oxidation furnace can be heated and raised to 540-605 ℃; and then the quartz boat bearing the silicon wafers to be processed is sent into a diffusion oxidation furnace, and meanwhile, nitrogen is also filled into the diffusion oxidation furnace, so that the contact between the silicon wafers to be processed and air is isolated, and the purpose of protecting the silicon wafers to be processed is achieved. After the air in the diffusion oxidation furnace is completely exhausted, the diffusion oxidation furnace can be closed, and the diffusion oxidation furnace is vacuumized.
When the pressure in the diffusion oxidation furnace reaches about 0mtorr, each temperature zone in the diffusion oxidation furnace can be heated and raised until the temperature in the furnace reaches a constant temperature state that the temperature from the first temperature zone to the fifth temperature zone is 570-600 ℃ and the temperature of the sixth temperature zone is 560-590 ℃; specifically, the temperatures of the first to fifth temperature regions may specifically be 570 ℃, 580 ℃, 590 ℃, 600 ℃; the temperature of the sixth temperature zone may be 560 ℃, 570 ℃, 580 ℃, 590 ℃.
In the process of heating and raising the temperature of each temperature zone in the diffusion oxidation furnace, leak detection should also be carried out in the diffusion oxidation furnace, and if the vacuum leak rate in the diffusion oxidation furnace is less than 20mTorr/min, the explanation meets the requirements.
In order to ensure the stability of the constant temperature state in the furnace, the oxygen may be introduced into the diffusion oxidation furnace after the internal constant temperature state of the diffusion oxidation furnace is stably maintained for 400 to 600 seconds.
In the process of introducing oxygen into the diffusion oxidation furnace, 300-600s of oxygen with a depth of 30000-40000 sccm can be continuously introduced into the diffusion oxidation furnace.
Specifically, the duration of oxygen gas is 300s, 350s, 400s, 450s, 500s, 550s and 600s; the flow rate of the oxygen gas introduced into the diffusion oxidation furnace may be 30000sccm, 31000sccm, 32000sccm, 33000sccm, 34000sccm, 35000sccm, 36000sccm, 37000sccm, 38000sccm, 39000sccm, 40000sccm.
On the basis of completing the oxygen introduction, the temperature in the furnace should be further maintained in the above constant temperature state and the pressure in the furnace should be maintained at the pressure of normal atmospheric pressure for at least 500 seconds, so as to ensure the sufficient oxidation of the back surface of the silicon wafer to be processed.
Compared with the processing technology of generating tunneling layers on the two sides of the silicon wafer, the temperature of each temperature zone in the diffusion oxidation furnace in the embodiment is set to be relatively lower, and the duration of oxidizing the back of the silicon wafer to be processed is longer; therefore, the tunneling layer finally formed on the back surface of the silicon wafer to be processed in the embodiment is thinner and denser, so that the silicon wafer to be processed is not easy to spread in a subsequent phosphorus diffusion process. The thickness of the tunneling layer formed in this embodiment may fluctuate between about 1.0nm and about 1.5nm, and the range of the fluctuation is relatively small, so that it can be seen that the thickness of the tunneling layer formed in this embodiment is not too thick, and the uniformity of the thickness is ensured.
S13: vacuumizing and controlling the diffusion oxidation furnaceUnder the condition that the temperature in the furnace is in a second set temperature range, introducing SiH into the diffusion oxidation furnace 4 And (3) gas to form an amorphous silicon film layer on the surface of the tunneling layer of the silicon wafer to be processed.
On the basis of finishing the processing of the tunneling layer on the back surface of the silicon wafer to be processed, an amorphous silicon film layer needs to be further formed on the surface of the tunneling layer.
It is known that amorphous silicon thin films are composed of a number of crystal grains of different sizes and having different crystal plane orientations, with inter-crystal interfaces existing between the crystal grains. The conversion efficiency of the solar cell is greatly reduced because of the presence of recombination centers at the grain boundaries due to dangling bonds, impurities and defects.
In the embodiment, in the process of growing an amorphous silicon film layer on the back surface of a silicon wafer to be processed by an LPCVD (low pressure chemical vapor deposition) method, two silicon wafers to be processed are attached together, so that each silicon wafer to be processed is not easy to cool in the cooling process, the deposition and diffusion time of each silicon wafer to be processed is longer, the transition and growth time of the amorphous silicon film layer is prolonged, the grain boundaries among grains are reduced, and the composite centers generated by dangling bonds, impurities and defects are reduced; but will thus also make the amorphous silicon thin film layer denser and less uniform in thickness.
For this reason, in another alternative embodiment of the present application, in order to improve the thickness uniformity of the amorphous silicon thin film layer as much as possible, forming the amorphous silicon thin film layer on the surface of the tunneling layer of the silicon wafer to be processed may include:
s131: heating the diffusion oxidation furnace under the condition of vacuumizing the diffusion oxidation furnace, so that the inside of the diffusion oxidation furnace is in a constant temperature environment with the temperature of 580-615 ℃ in a first temperature zone to a sixth temperature zone;
s132: introducing nitrogen into the diffusion oxidation furnace to maintain the inside of the diffusion oxidation furnace in a set constant pressure state;
s133: siH is respectively introduced from the front end and the rear end of the diffusion oxidation furnace 4 And (3) gas so as to form an amorphous silicon film layer on the surface of the tunneling layer of the silicon wafer to be processed.
It can be understood that after the growth of the tunneling layer is completed on the back surface of the silicon wafer to be processed, a large amount of oxygen is necessarily filled in the diffusion oxidation furnace; for this reason, before further growing to form the amorphous silicon thin film layer, it is necessary to evacuate the diffusion oxidation furnace and then empty the oxygen in the diffusion oxidation furnace.
In addition, the ambient temperature required for the growth of the amorphous silicon thin film layer is higher, and for this reason, after the diffusion oxidation furnace is evacuated, it is necessary to further raise the temperature in the diffusion oxidation furnace until the temperature of each temperature zone in the diffusion oxidation furnace is raised to 580-615 ℃. In order to ensure the stability of the constant temperature environment in the diffusion oxidation furnace, the constant temperature environment in the diffusion oxidation furnace can be considered to be stable after the constant temperature environment is stably maintained for a period of 200s to 400 s. Meanwhile, the diffusion oxidation furnace should be subjected to vacuum leak detection, and if the vacuum leak rate is smaller than 10mTorr/min, the requirements are considered to be met. After that, a certain amount of SiH is introduced into the diffusion oxidation furnace 4 The gas makes the inside of the diffusion oxidation furnace reach a constant pressure state with the gas pressure of 300 mtorr.
After the diffusion oxidation furnace reaches a constant temperature and constant pressure state, siH can be introduced into the diffusion oxidation furnace 4 And (3) gas. For a diffusion oxidation furnace, it includes a front end vent at the furnace mouth position and a rear end vent at the furnace bottom position. Introducing SiH into the diffusion oxidation furnace 4 During the gas process, siH can be simultaneously introduced into the diffusion oxidation furnace by utilizing the front end vent and the rear end vent 4 And (3) gas.
Alternatively, 100sccm to 300sccm of SiH4 gas may be introduced from the front end of the diffusion oxidation furnace, and 1300sccm to 1700sccm of SiH4 gas may be introduced from the rear end of the diffusion oxidation furnace.
Specifically, the flow rate of the SiH4 gas introduced from the front end of the diffusion oxidation furnace may be 100sccm, 150sccm, 200sccm, 250sccm, or 300sccm.
In addition, the duration of the aeration of the SiH4 gas continuously introduced from the front end and the rear end of the diffusion oxidation furnace, respectively, may be 1300s to 1500s.
Specifically, the duration of the SiH4 gas introduction into the diffusion oxidation furnace may be 1300s, 1350s, 1400s, 1450s, 1500s, or the like.
Compared with the production process of simultaneously growing the amorphous silicon film layers on the two sides of the silicon wafer, in the production process of only carrying out single-sided growth on the back side of the silicon wafer to be processed, the temperature setting of each temperature in the diffusion oxidation furnace is relatively higher, the deposition and diffusion time is shorter, namely the thickness of the finally-generated amorphous silicon film layer is relatively thinner, and the amorphous silicon film layer is more loose; thereby making phosphorus doping more advantageous in the subsequent phosphorus diffusion process. In this embodiment, the thickness of the amorphous silicon thin film layer formed on the back surface of the silicon wafer to be processed by growth may be 120nm to 130nm.
Simultaneously carrying out single-sided amorphous silicon film layer growth, and introducing SiH into a diffusion oxidation furnace 4 The gas pressure of the gas can be lower, the uniformity of the gas in the furnace is better, and the thickness uniformity of the amorphous silicon film layer is ensured. In addition, siH is introduced from the front end of the diffusion oxidation furnace 4 The SiH is introduced into the process of the double-sided growth of the amorphous silicon film layer by the gas flow 4 The flow rate of the gas is lower, and the black edge of the silicon wafer to be processed in the diffusion oxidation furnace, which is closer to the furnace mouth, can be eliminated.
It will be appreciated that after the amorphous silicon thin film layer has been grown on the tunneling layer on the back side of the silicon wafer to be processed, it is also required to exit from the diffusion oxidation oven. To this end, in another alternative embodiment of the present application, after the growth of the amorphous silicon thin film layer is completed, it may further include:
vacuumizing the diffusion oxidation furnace;
introducing 1000sccm-3000sccm SiH from the front end of the diffusion oxidation furnace 4 Introducing 3000sccm-6000sccm SiH from the rear end of the diffusion oxidation furnace 4 A gas to maintain the inside of the diffusion oxidation furnace in a set constant pressure state;
continuously introducing 900-1200 sccm SiH from the front end of the diffusion oxidation furnace for 10-30 s 4 Introducing 1000sccm-3000sccm SiH from the rear end of the diffusion oxidation furnace 4 A gas to purge the inside of the diffusion oxidation furnace;
and after introducing nitrogen into the diffusion oxidation furnace for cleaning, vacuumizing and breaking the inside of the diffusion oxidation furnace in sequence, and taking out the silicon wafer to be processed.
In the growth process of the amorphous silicon film layer, hydrogen is generated besides the amorphous silicon film layer formed on the back surface of the silicon wafer to be processed; after the growth of the amorphous silicon film layer is completed, the diffusion oxidation furnace is vacuumized, and hydrogen in the diffusion oxidation furnace can be discharged. Based on this, the SiH is again introduced 4 The gas pressure in the diffusion oxidation furnace is restored to a constant pressure state of about 300 mtorr. On the basis, siH is continuously introduced into the diffusion oxidation furnace 4 And (3) gas so as to purge the diffusion oxidation furnace.
In this embodiment, the diffusion oxidation furnace is evacuated and SiH is again introduced 4 The purging of the gas takes into account the SiH in the diffusion oxidation furnace while the furnace is being evacuated 4 The gas may still continue to react to grow and deposit an amorphous silicon film layer on the silicon wafer to be processed, namely, hydrogen is generated again in the diffusion oxidation furnace. For this reason, in this embodiment, after the diffusion oxidizing furnace is evacuated, siH is again introduced 4 The gas is used for purging the diffusion oxidation furnace, so that the hydrogen is completely removed.
On the basis, after nitrogen and the like are introduced into the diffusion oxidation furnace for cleaning and various gases in the furnace are thoroughly exhausted, the vacuum is pumped again and broken, and the silicon wafer to be processed with the tunneling layer and the amorphous silicon oxide layer can be taken out. Of course, the process of taking out the silicon wafer to be processed should be completed under the protection of nitrogen, which belongs to the conventional operation and is not described in detail in this embodiment.
After the growth of the tunneling layer and the amorphous silicon thin film layer is completed, the silicon wafer to be processed in this embodiment may continue to start the subsequent processing procedures such as phosphorus diffusion until the solar cell is formed by final processing, which will not be discussed in detail in this embodiment.
In summary, in the process of forming the tunneling layer and the amorphous silicon thin film layer on the back surface of the silicon wafer after the alkaline polishing process, the front surfaces of every two silicon wafers to be processed are mutually attached, so that when the tunneling layer and the amorphous silicon thin film layer are generated on the surfaces of the silicon wafers to be processed, the tunneling layer and the amorphous silicon thin film layer can only be formed on the back surface of the silicon wafer to be processed due to mutual shielding coverage between the front surfaces of the two silicon wafers to be processed, the process of removing the amorphous silicon thin film layer on the front surface of the silicon wafer to be processed in the subsequent processing process is omitted, the processing process of the solar cell is simplified to a certain extent, and the processing efficiency of the solar cell is improved.
Based on the above discussion, in another embodiment of the present application, a process for forming a tunneling layer and an amorphous silicon thin film layer on a silicon wafer for fabricating a solar cell sheet may include:
1) The front side of the silicon wafer is horizontally arranged in a quartz boat by leaning against the front side, and the temperature of a 1-6 temperature zone of a quartz furnace tube (i.e. a diffusion oxidation furnace) is set to be 540-605 ℃.
2) Pushing a quartz boat filled with silicon chips into a quartz furnace tube, and keeping the temperature of a 1-6 temperature zone of the quartz furnace tube to be the same as 1); and introducing 1000-6000 sccm of protective nitrogen into the quartz furnace tube.
3) Vacuumizing: and closing a nitrogen gas inlet valve, and controlling the inside of the quartz furnace tube to be under the pressure of 0 mtorr.
4) Heating: setting the temperature of a 1-5 temperature zone of a quartz furnace tube to 570-600 ℃ and the temperature of a temperature zone 6 to 560-590 ℃; the duration is 600s-800s, and different heating rates can be set according to different temperature areas.
5) Leak detection: the duration is 10s-30s, the temperature of a 1-6 temperature zone of the quartz furnace tube is equal to 4), and the vacuum leak rate is set to 20mTorr/min;
6) Constant temperature: the duration is 400s-600s, and the temperature of 1-6 temperature areas of the quartz furnace tube is kept to be equal to 4).
7) Oxidizing: maintaining the temperature of a 1-6 temperature zone of the quartz furnace tube to be the same as 4) for 300-600 s; and introducing 30000sccm to 40000sccm of oxygen to restore the pressure in the quartz furnace tube to normal pressure.
8) Constant temperature: the duration time is not less than 500s, the temperature of a 1-6 temperature zone of the quartz furnace tube is kept to be equal to 4), and the pressure is normal pressure.
9) Vacuumizing: the duration is 150s-200s, the temperature of 1-6 temperature areas of the quartz furnace tube is controlled to be 580-615 ℃, and the pressure in the quartz furnace tube is controlled to be 0 mtorr.
10 Heating up: the duration is 400s-500s, and the temperature of 1-6 temperature areas of the quartz furnace tube is kept to be 9).
11 Constant temperature): the duration is 200s-400s, and the temperature of 1-6 temperature areas of the quartz furnace tube is kept to be 9).
12 Leak detection: the duration is 20s-50s, the temperature of 1-6 temperature areas of the quartz furnace tube is kept to be 9), and the vacuum leakage rate is set to be 10mTorr/min;
13 Constant pressure: maintaining the temperature of 1-6 temperature areas of the quartz furnace tube at 9) for 10s-30s, and introducing SiH with the flow rate of 100sccm-300sccm from the front end of the quartz furnace tube 4 The back end is introduced with SiH with the flow rate of 1300sccm-1700sccm 4 The inside of the quartz furnace tube is under a pressure of 300 mtorr.
14 Diffusion/deposition): the duration is 1300s-1500s, the temperature of 1-6 temperature areas of the quartz furnace tube is kept at 9), the internal pressure of the quartz furnace tube is kept at 9), and SiH with the flow rate of 100sccm-300sccm is introduced from the front end of the quartz furnace tube 4 The back end is introduced with SiH with the flow rate of 1300sccm-1700sccm 4 ；
15 Vacuum pumping: the duration is 45s-70s, the temperature of 1-6 temperature areas of the quartz furnace tube is kept to be equal to 1), and the pressure in the quartz furnace tube is controlled to be 0 mtorr; then the SiH with the flow rate of 1000sccm-3000sccm is introduced from the front end of the quartz furnace tube 4 The rear end is introduced with SiH with the flow rate of 3000sccm-6000sccm 4 The internal pressure of the quartz furnace tube is enabled to be 300 mtorr;
16 Purge): maintaining the temperature of 1-6 temperature areas of the quartz furnace tube at 1) and maintaining the internal pressure of the quartz furnace tube at 300mtorr for 10s-30s, and introducing SiH with the flow rate of 900-1200 sccm from the front end of the quartz furnace tube 4 Rear end is led toSiH with an inflow of 1000sccm to 3000sccm 4 ；
17 Cleaning: keeping the temperature of a 1-6 temperature zone of the quartz furnace tube at the same temperature as 1) for 6s-13s, introducing nitrogen with the flow rate of 900-1200 sccm, and introducing the nitrogen to drive away the incompletely deposited precursor;
18 Vacuum pumping: the duration time is 55s-70s, and the temperature of 1-6 temperature areas of the quartz furnace tube is kept to be equal to 1);
19 Vacuum breaking/boat out): the duration is 80s-140s, the temperature of 1-6 temperature areas of the quartz furnace tube is kept to be equal to 1), the inside of the quartz furnace tube is controlled to be under normal pressure, and nitrogen with the pressure of 20000sccm-40000sccm is introduced as protection; and when the pressure in the quartz furnace tube is close to the atmospheric pressure, pulling the quartz boat filled with the silicon wafers out of the quartz furnace tube.
The application also provides an embodiment of a silicon wafer for preparing a solar cell, wherein the surface of the silicon wafer is provided with a tunneling layer and an amorphous silicon film layer which are formed by growth according to the silicon wafer processing method for preparing the solar cell.
Optionally, the thickness of the tunneling layer is 1.0nm-1.5nm; the thickness of the amorphous silicon film layer is 120nm-130nm;
specifically, the thickness of the tunneling layer may be 1.0nm, 1.1nm, 1.2nm, 1.3nm, 1.4nm, 1.5nm. The thickness of the amorphous silicon thin film layer may be 120nm, 122nm, 124nm, 126nm, 128nm, 130nm.
The application also provides an embodiment of a preparation method of the solar cell, which can comprise the following steps:
s21: sequentially performing texturing, boron diffusion, BSG removal and back polishing by taking a silicon wafer as a substrate;
s22: according to the silicon wafer processing method for preparing the solar cell, a tunneling layer and an amorphous silicon film layer are formed on the back surface of the silicon wafer;
s23: and sequentially carrying out phosphorus doping, PSG removal, surface passivation and metallization processing operations on the silicon wafer after the tunneling layer and the amorphous silicon film layer are processed, so as to obtain the solar cell.
It is understood that, in the method for manufacturing a solar cell in this embodiment, step S21 is each operation step of boron diffusion and before boron diffusion, which are involved before the growth of the tunneling layer, in the conventional process for manufacturing a solar cell, and step S23 is related to phosphorus diffusion and a subsequent series of process steps, which are involved after the completion of the amorphous silicon thin film layer on the back of the solar cell, in the process for manufacturing a solar cell, and for both step S21 and step S23, similar process steps in the conventional solar cell at present can be referred to, and detailed descriptions thereof are omitted.
The key point of the embodiment is that the preparation process of the tunneling layer and the amorphous silicon film layer of the silicon wafer is simplified, so that the preparation process of the whole solar cell is simplified, the production efficiency of the solar cell is improved, and the wide application of the solar cell is facilitated.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements is inherent to. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. In addition, the parts of the above technical solutions provided in the embodiments of the present application, which are consistent with the implementation principles of the corresponding technical solutions in the prior art, are not described in detail, so that redundant descriptions are avoided.
The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
Claims (10)
1. The processing method of the silicon wafer for preparing the solar cell slice is characterized by comprising the following steps of:
placing silicon wafers to be processed in pairs in a diffusion oxidation furnace, wherein the front surfaces of each pair of silicon wafers to be processed are mutually attached; the silicon wafer to be processed is a silicon wafer subjected to an alkali polishing process;
vacuumizing the diffusion oxidation furnace, and introducing oxygen into the diffusion oxidation furnace under the condition that the temperature in the furnace is controlled to be in a first set temperature range so as to form a tunneling layer on the back surface of each silicon wafer to be processed;
vacuumizing the diffusion oxidation furnace and controlling the temperature in the furnace to be in a second set temperature range, and introducing SiH into the diffusion oxidation furnace 4 And the gas is used for forming an amorphous silicon film layer on the surface of the tunneling layer of the silicon wafer to be processed.
2. The method for processing a silicon wafer for manufacturing a solar cell according to claim 1, wherein the process of forming the tunneling layer on the back surface of the silicon wafer to be processed comprises:
controlling the temperature of the diffusion oxidation furnace from the first temperature region to the fifth temperature region to be 570-600 ℃ under the condition of vacuumizing in the diffusion oxidation furnace, wherein the temperature of the sixth temperature region is 560-590 ℃ in a constant temperature environment;
continuously introducing oxygen into the diffusion oxidation furnace to oxidize the surface of the silicon wafer to be processed to form a tunneling layer.
3. The method for processing a silicon wafer for manufacturing a solar cell according to claim 2, wherein continuously introducing oxygen into the interior of the diffusion oxidation furnace comprises:
300s-600s of oxygen gas with the concentration of 30000sccm-40000sccm is continuously introduced into the diffusion oxidation furnace.
4. The method for processing a silicon wafer for manufacturing a solar cell according to claim 1, wherein the process of forming an amorphous silicon thin film layer on the surface of the tunneling layer of the silicon wafer to be processed comprises:
heating the diffusion oxidation furnace under the condition of vacuumizing the diffusion oxidation furnace, so that the inside of the diffusion oxidation furnace is in a constant temperature environment with the temperature of 580-615 ℃ in a first temperature zone to a sixth temperature zone;
introducing nitrogen into the diffusion oxidation furnace so as to maintain the inside of the diffusion oxidation furnace in a set constant pressure state;
SiH is respectively introduced from the front end and the rear end of the diffusion oxidation furnace 4 And (3) gas so that an amorphous silicon film layer is formed on the surface of the tunneling layer of the silicon wafer to be processed.
5. The method for processing a silicon wafer for manufacturing a solar cell according to claim 4, wherein SiH is introduced from the front end and the rear end of the diffusion oxidation furnace, respectively 4 A gas, comprising:
introducing 100sccm-300sccm SiH from the front end of the diffusion oxidation furnace 4 Introducing 1300-1700 sccm SiH from the rear end of the diffusion oxidation furnace 4 And (3) gas.
6. The method for processing a silicon wafer for manufacturing a solar cell according to claim 4, wherein SiH is introduced from the front end and the rear end of the diffusion oxidation furnace, respectively 4 A gas, comprising:
and continuously introducing SiH4 gas with the duration of 1300s-1500s from the front end and the rear end of the diffusion oxidation furnace respectively.
7. The method for processing a silicon wafer for manufacturing a solar cell according to any one of claims 1 to 6, further comprising, after forming an amorphous silicon thin film layer on the surface of the tunneling layer of the silicon wafer to be processed:
vacuumizing the diffusion oxidation furnace;
from the diffusion ofThe front end of the oxidation furnace is filled with 1000sccm-3000sccm SiH 4 Introducing 3000sccm-6000sccm SiH from the rear end of the diffusion oxidation furnace 4 A gas to maintain the inside of the diffusion oxidation furnace in a set constant pressure state;
introducing 900-1200 sccm SiH from the front end of the diffusion oxidation furnace for 10-30 s 4 Introducing 1000sccm-3000sccm SiH from the rear end of the diffusion oxidation furnace 4 A gas to purge the interior of the diffusion oxidation furnace;
and after introducing nitrogen into the diffusion oxidation furnace for cleaning, vacuumizing and breaking the inside of the diffusion oxidation furnace in sequence, and taking out the silicon wafer to be processed.
8. A silicon wafer for producing a solar cell, characterized in that the surface of the silicon wafer has a tunneling layer and an amorphous silicon thin film layer formed by the silicon wafer processing method for producing a solar cell according to any one of claims 1 to 7.
9. The silicon wafer for producing a solar cell according to claim 8, wherein the thickness of the tunneling layer is 1.0nm to 1.5nm; the thickness of the amorphous silicon film layer is 120nm-130nm.
10. The preparation method of the solar cell is characterized by comprising the following steps:
sequentially performing texturing, boron diffusion, BSG removal and back polishing by taking a silicon wafer as a substrate;
a silicon wafer processing method for producing a solar cell according to any one of claims 1 to 7, forming a tunneling layer and an amorphous silicon thin film layer on the back surface of the silicon wafer;
and sequentially carrying out phosphorus doping, PSG removal, surface passivation and metallization processing operations on the silicon wafer after the tunneling layer and the amorphous silicon film layer are processed, so as to obtain the solar cell.
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