CN111509081B - Preparation method of ultrathin oxygen-containing nitrogen-silicon film and application of ultrathin oxygen-containing nitrogen-silicon film in passivation contact battery - Google Patents
Preparation method of ultrathin oxygen-containing nitrogen-silicon film and application of ultrathin oxygen-containing nitrogen-silicon film in passivation contact battery Download PDFInfo
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- 238000002161 passivation Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000001301 oxygen Substances 0.000 title claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 11
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 title abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 54
- 239000010703 silicon Substances 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- VUFABLRZUDLWFG-UHFFFAOYSA-N [Si].[N].[O].[N] Chemical compound [Si].[N].[O].[N] VUFABLRZUDLWFG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 10
- 230000005641 tunneling Effects 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- UBMXAAKAFOKSPA-UHFFFAOYSA-N [N].[O].[Si] Chemical compound [N].[O].[Si] UBMXAAKAFOKSPA-UHFFFAOYSA-N 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005121 nitriding Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract 4
- 239000010410 layer Substances 0.000 claims description 44
- 238000000137 annealing Methods 0.000 claims description 28
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 25
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 10
- 229920005591 polysilicon Polymers 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 7
- 235000013842 nitrous oxide Nutrition 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005240 physical vapour deposition Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000005468 ion implantation Methods 0.000 claims description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 2
- 229940110728 nitrogen / oxygen Drugs 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 claims 1
- 230000035515 penetration Effects 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052796 boron Inorganic materials 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 24
- 235000012431 wafers Nutrition 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- MQSRKJKAOOSCFF-UHFFFAOYSA-N [N].[N].[O] Chemical compound [N].[N].[O] MQSRKJKAOOSCFF-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 3
- 238000006388 chemical passivation reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- CVZVCXJQWMPXMX-UHFFFAOYSA-N [Si].[N].[N]=O Chemical compound [Si].[N].[N]=O CVZVCXJQWMPXMX-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/24—Deposition of silicon only
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Abstract
The invention discloses a preparation method of an ultrathin oxygen-containing nitrogen-silicon film, which comprises the following steps of 1) cleaning the surface of a silicon wafer; 2) In PECVD, NH is introduced 3 Or N 2 Or other nitrogen-containing source but no oxygen source, and turning on the plasma, dissociating the introduced atmosphere, and nitriding the surface of the silicon wafer; the nitrogen concentration on the surface and the depth of the nitrogen-containing layer are regulated by regulating parameters such as temperature, plasma power, pressure, gas flow and the like; 3) Oxidizing the silicon wafer with the surface nitrided, so as to form an oxygen-nitrogen-silicon layer material; 4) Then, carrying out PECVD surface nitridation treatment on the surface oxynitride silicon layer to form an oxynitride silicon layer, wherein the thickness of the oxynitride silicon layer is below 5nm; 5) And preparing a p-type silicon film layer on the surface. The method can enrich the nitrogen element in the surface position and the interface position near the silicon wafer as much as possible, so that the nitrogen-oxygen-nitrogen-silicon interface material layer is used for the p-type tunneling silicon oxide passivation contact structure, the damage of boron to the interface can be reduced, and the passivation effect is improved; the material is also effective for n-type and can reduce the damage of phosphorus to interface layer.
Description
Technical Field
The invention relates to a solar cell manufacturing technology, in particular to a preparation method of a passivation contact structure.
Background
In 2013, german institute of ferhough proposed a crystalline silicon solar cell, whose n-type cell is typically structured as shown in fig. 1, and the cell is called a polysilicon passivation contact technology (poly-Si passivation contact technology). The core of the structure is to passivate the surface of the silicon wafer by adopting an ultrathin silicon oxide layer and doped polysilicon laminated structure.
The passivation mechanism of the tunneling silicon oxide passivation contact structure mainly derives from two aspects: the chemical passivation of the interface silicon oxide layer and the field passivation of the doping atoms. Improving the integrity of the interface silicon oxide is beneficial to improving the chemical passivation effect of the surface.
For the tunneling silicon oxide passivation contact technology, n-type phosphorus doped polysilicon films are adopted for electron collection, and p-type boron doped polysilicon films are adopted for hole collection. The n-type passivation contact technology has good effect and is widely accepted as a next-generation industrial high-efficiency crystalline silicon battery technology.
Currently, the bottleneck of Poly-Si passivation contact technology is mainly in the p-type. The p-type passivation contact technology has poor technical indexes and is characterized by poor passivation quality. Generally, J 0s >20fA/cm 2 ，iV oc <680mV (n-type silicon wafer substrate). It is generally believed that the main reasons for the poor p-type passivation contact technology are two: firstly, the boron concentration in the polysilicon is low, and secondly, the interface silicon oxide is easily damaged by the diffusion of boron.
In contrast, the n-type Poly-Si passivation contact technology has much more reliable quality, high technical index and good passivation quality, and can easily realize single-sided saturated dark current J on different devices 0s <8fA/cm 2 Corresponding hidden open circuit voltage iV oc >Excellent index of 730mV (n-type silicon wafer substrate); low p at the same time contact resistivity c <10mΩcm 2 . The mass production verification phase has now begun.
Thus, improving the passivation quality of p-type Poly-Si passivation contact technology is an important issue that currently needs to be overcome. The passivation quality of the p-type Poly-Si passivation contact technology is improved, and the further development of the technology is promoted. Wherein, the improvement of the integrality of the interface silicon oxide is very favorable for improving the passivation effect of the interface.
Disclosure of Invention
Aiming at how to improve the integrity of interface silicon oxide in a p-type Poly-Si passivation contact structure, the invention provides a preparation method for replacing silicon dioxide by adopting an oxygen-nitrogen-silicon material and preparing an oxygen-nitrogen-silicon layer in situ, and the method is suitable for mass production type Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment.
The invention provides a preparation method of an ultrathin nitrogen-oxygen-nitrogen-silicon film, which comprises the following steps of 1) cleaning the surface of a silicon wafer; 2) In PECVD, ammonia (NH) 3 ) Or nitrogen (N) 2 ) Or other nitrogen-containing source but no oxygen source, and turning on the plasma, dissociating the introduced atmosphere, and nitriding the surface of the silicon wafer; the concentration of nitrogen on the surface and the depth of the nitrogen-containing layer can be adjusted by adjusting parameters such as temperature, plasma power, pressure, gas flow and the like; 3) Oxidizing the silicon wafer with the surface nitrided, so as to form an oxygen-nitrogen-silicon layer material; 4) Then, carrying out PECVD surface nitridation treatment on the surface oxynitride silicon layer to form an oxynitride silicon layer, wherein the thickness of the oxynitride silicon layer is below 5nm; 5) A p-type silicon thin film layer (the silicon thin film layer can be amorphous silicon or polycrystalline silicon) is prepared on the surface.
On the other hand, according to the requirements of the technological process or the performance of the device, the step 4) can be omitted, namely, the steps 1), 2), 3) and 5) are sequentially carried out, and the oxygen-nitrogen film is prepared, wherein the thickness of the oxygen-nitrogen film is below 5nm; or omitting the step 2), namely sequentially carrying out the steps 1), 3), 4) and 5), and preparing the nitrogen-oxygen film with the thickness of less than 5nm.
Further, oxygenThe chemical treatment modes can be various, and include: high temperature thermal oxidation treatment (oxygen (O) 2 ) Nitrogen/oxygen (N) 2 /O 2 ) Mixed qi, laughing qi (N) 2 O)), ozone (O) 3 ) Oxidation, plasma assisted oxidation (N) 2 O、CO 2 ) Wet chemical oxidation (hot nitric acid, hot nitric sulfuric acid mixed acid), and the like.
Preferably, laughing gas (N) 2 O) is used as a protective gas for high-temperature thermal oxidation treatment, and the annealing temperature is 400-900 ℃.
Further, in the step 4), the thickness of the oxynitride silicon layer is 1.5nm-3.5nm;
further, the preparation method of the p-type polysilicon in the step 5) includes various conventional preparation methods, such as an LPCVD method, a PECVD method, or a Physical Vapor Deposition (PVD) method, for directly preparing a doped polysilicon layer or a doped amorphous silicon layer, and performing crystallization treatment; or depositing intrinsic polycrystalline silicon or amorphous silicon, and preparing doped polycrystalline silicon by high-temperature diffusion and ion implantation combined with high-temperature annealing, wherein the annealing temperature is more than 800 ℃, and the preferable temperature is 880-1100 ℃.
The invention has the advantages and beneficial effects that: 1) The nitrogen-oxygen-nitrogen-silicon interface material layer is used for the p-type tunneling silicon oxide passivation contact structure, so that the passivation effect can be improved; the material is also effective for n-type and can reduce the damage of phosphorus to interface layer. 2) The invention naturally covers the preparation method of the oxygen-nitrogen-silicon layer.
Drawings
Fig. 1 is a schematic view of a typical structure of a current n-type battery.
Detailed Description
The specific operation and principles of the present invention will be further described with reference to the following detailed description.
The invention provides a method for preparing an ultrathin oxygen-containing nitrogen-silicon film in situ, taking a nitrogen-oxygen-nitrogen-containing film as an example, adopting a nitrogen-oxygen-nitrogen-silicon interface material is beneficial to improving the passivation quality of p-type Poly-Si passivation contact, and the basic principle is as follows: 1) Compared with silicon oxide, the boron in the nitrogen-oxygen-nitrogen-silicon layer has low diffusion rate and low solid solubility, so that the damage of the boron to the interface nitrogen-oxygen-nitrogen-silicon layer is effectively reduced, the integrity of the nitrogen-oxygen-nitrogen-silicon layer is improved, and the chemical passivation effect is maintained; 2) The energy band structure of the nitrogen-oxygen-nitrogen-silicon layer is close to that of silicon nitride, the valence band step is smaller, the hole transmission is facilitated, the hole transmission efficiency and the hole selectivity are improved, and therefore passivation quality is improved; while also facilitating a reduction in contact resistivity. Therefore, the invention adopts the oxynitride to replace silicon oxide, inhibits the damage of boron to the interface tunneling layer, improves the integrity of the interface tunneling layer, and improves passivation quality compared with the conventional silicon oxide interface layer by adopting the p-type Poly-Si passivation contact technology of the oxynitride interface layer; secondly, nitrogen oxygen nitrogen silicon is used as an interface layer, so that the contact resistivity of the p-type Poly-Si passivation contact structure can be reduced; the nitrogen oxide nitrogen silicon is denser than silicon oxide, has higher thickness and can bear higher annealing treatment; and finally, the nitrogen-oxygen-nitrogen-silicon material has reliable performance, simple preparation method, is suitable for in-situ preparation of PECVD equipment, has good industrialized application prospect, and is not only suitable for p-type Poly-Si passivation contact technology, but also can be used for n-type Poly-Si passivation contact technology.
In the preparation process, the key is to form the nitrogen-oxygen-nitrogen-silicon film material with gradient distribution of components. The distribution of the components of the oxynitride silicon material is as follows: the nitrogen is mainly concentrated at the near-surface layer and the near-silicon interface, and the concentration distribution of main elements of the film material from the surface to the silicon substrate shows the rule of nitrogen-oxygen-nitrogen. Therefore, the invention firstly uses PECVD to carry out nitriding treatment on the surface of the silicon wafer; surface oxidation treatment is required after surface nitridation to form silicon oxynitride; and finally, repeatedly carrying out surface nitridation treatment to form the nitrogen-oxygen-nitrogen-silicon layer. This treatment has the advantage of enriching nitrogen as much as possible in the surface sites and near-silicon interface sites. The components of the nitrogen-oxygen-nitrogen-silicon film are characterized in that the nitrogen is enriched in the two positions as far as possible: the nitrogen concentration is in high-low-high distribution from the nitrogen-oxygen-nitrogen silicon to the silicon direction, namely the nitrogen impurity concentration at the near-silicon surface layer and the film surface is high, the middle is lower, the nitrogen content of the high concentration area is not lower than 30at%, and the nitrogen content of the low concentration area is not lower than 8at%; in addition, the nitrogen is permeated into one side of the nitrogen-oxygen-nitrogen film/silicon interface, the depth is usually not more than 5nm, the concentration gradually decreases from the interface to the inside of the silicon wafer, and the near-surface concentration is not less than 1at%, thereby being beneficial to improving the blocking effect of the material on boron element.
The substrates used in the following examples were all n-type monocrystalline silicon wafers 170 μm thick, were double-sided chemically polished, and had a resistivity of 3Ω·cm, and the passivation structures used were double-sided p-type tunneling silicon oxide passivation structures.
Example 1
The preparation method of the embodiment comprises the following steps: 1) The wafer was cut to a size of 4cm by 4cm and subjected to standard RCA cleaning. 2) The silicon wafer is put into PECVD for plasma nitridation treatment, NH is used 3 The treatment was carried out in an atmosphere at a power of 10W for 200 seconds on both sides. 3) The sample is put into a tubular annealing furnace, laughing gas is used as protective gas, and annealing treatment is carried out for 20 minutes at 700 ℃. 4) Placing the sample in PECVD, still with NH 3 The treatment was carried out in an atmosphere, and plasma surface treatment was carried out at a power of 10W for a treatment time of 60 seconds. 5) And then depositing boron doped amorphous silicon films on two sides of the silicon wafer by PECVD, wherein the thickness of the formed nitrogen-oxygen-nitrogen layer is 2nm. 6) The sample was placed in a tube annealing furnace for annealing at 820-920 ℃ for 30 minutes. 7) And analyzing and testing passivation performance.
Example two
The preparation method of the embodiment comprises the following steps: 1) The wafer was cut to a size of 4cm by 4cm and subjected to standard RCA cleaning. 2) The silicon wafer is put into PECVD for plasma nitridation treatment, NH is used 3 The treatment was carried out in an atmosphere at a power of 10W for 200 seconds on both sides. 3) And (3) placing the sample into a tubular annealing furnace, and carrying out annealing treatment at 700 ℃ for 20 minutes by taking laughing gas as a protective gas, wherein the thickness of the formed nitrogen-oxygen film is 2nm. 4) And then depositing boron doped amorphous silicon films on two sides of the silicon wafer by PECVD. 5) The sample was placed in a tube annealing furnace for annealing at 820-920 ℃ for 30 minutes. 6) And analyzing and testing passivation performance.
Example III
The preparation method of the embodiment comprises the following steps: 1) The wafer was cut to a size of 4cm by 4cm and subjected to standard RCA cleaning. 2) The sample is put into a tubular annealing furnace, laughing gas is used as protective gas, and annealing treatment is carried out for 20 minutes at 700 ℃.3) The silicon wafer is put into PECVD for plasma nitridation treatment, NH is used 3 The treatment was conducted in an atmosphere at a power of 10W for 200 seconds, and the thickness of the oxygen-nitrogen thin film was 2nm. 4) And then depositing boron doped amorphous silicon films on two sides of the silicon wafer by PECVD. 5) The sample was placed in a tube annealing furnace for annealing at 820-920 ℃ for 30 minutes. 6) And analyzing and testing passivation performance.
Examples four to eight
Examples four to eight differ from example one in that the thickness of the formed oxynitride layer was 1.5nm, 2.5nm, 3.5nm, 4nm, 5nm, respectively, the annealing temperature was 920℃and the remainder was the same as example one. The obtained samples were subjected to performance test, and the results are shown in table 2.
Comparative example one:
1) The wafer was cut to a size of 4cm by 4cm and subjected to standard RCA cleaning. 2) The silicon wafer is put into hot nitric acid for treatment for 10 minutes to form a surface oxide layer. 3) And then depositing boron doped amorphous silicon films on two sides of the silicon wafer by PECVD. 4) The sample was placed in a tube annealing furnace for annealing at 820-920 ℃ for 30 minutes. 5) And analyzing and testing passivation performance.
Comparative example two:
1) The wafer was cut to a size of 4cm by 4cm and subjected to standard RCA cleaning. 2) Placing the silicon wafer into PECVD for plasma oxidation treatment, and using CO 2 The surface oxide layer was formed by treating both sides with a power of 10W for 200 seconds for gas. 3) And then depositing boron doped amorphous silicon films on two sides of the silicon wafer by PECVD. 4) The sample was placed in a tube annealing furnace for annealing at 820-920 ℃ for 30 minutes. 5) And analyzing and testing passivation performance.
The test results of each example and comparative example are shown in table 1:
TABLE 1 passivation effect of different samples (hidden open circuit voltage iV oc ) Comparison
| Annealing temperature | Example 1 | Example two | Example III | Comparative example one | Comparative example two |
| 800℃ | iV oc ＝615mV | iV oc ＝623mV | iV oc ＝611mV | iV oc ＝628mV | iV oc ＝612mV |
| 840℃ | iV oc ＝697mV | iV oc ＝706mV | iV oc ＝701mV | iV oc ＝673mV | iV oc ＝664mV |
| 880℃ | iV oc ＝716mV | iV oc ＝708mV | iV oc ＝703mV | iV oc ＝652mV | iV oc ＝678mV |
| 920℃ | iV oc ＝726mV | iV oc ＝717mV | iV oc ＝712mV | iV oc ＝612mV | iV oc ＝662mV |
By comparing passivation effects of different samples, the performance of the nitrogen-oxygen-nitrogen-silicon interface material for the p-type tunneling silicon oxide passivation contact structure is optimal at the optimal annealing temperature of 800-920 ℃, the passivation effect of the battery can be improved by comparing the passivation effect of different samples with the passivation effect of the oxygen-nitrogen-silicon layer material.
TABLE 2
As is clear from tables 1 and 2, the passivation effect is optimal when the thickness of the SiON layer is 1.5-3.5 nm.
For the nitrogen-oxygen-nitrogen-silicon film, dilute HF acid is adopted to corrode the film, the characteristics of slow corrosion rate at two ends and fast corrosion rate in the middle are presented, and the introduction of nitrogen is fully shown to be beneficial to the increase of the corrosion resistance of the film.
The materials, reagents and experimental equipment related to the embodiment of the invention are all commercial products conforming to the field of solar cell element preparation unless specified.
While the invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that modifications and variations may be made without departing from the spirit and scope of the invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (7)
1. The preparation method of the ultrathin nitrogen-oxygen-nitrogen-silicon film is characterized by comprising the following steps of:
1) Cleaning the surface of the silicon wafer; 2) In PECVD, NH is introduced 3 Or N 2 Or other nitrogen-containing source but no oxygen source, and turning on the plasma, dissociating the introduced atmosphere, and nitriding the surface of the silicon wafer; regulating the nitrogen concentration on the surface and the depth of the nitrogen-containing layer by regulating temperature, plasma power, pressure and gas flow parameters; 3) Oxidizing the silicon wafer with the surface nitrided, so as to form an oxygen-nitrogen-silicon layer material; 4) Then, carrying out PECVD surface nitriding treatment on the surface oxynitride silicon layer to form an oxynitride silicon layer, wherein the thickness of the oxynitride silicon layer is below 5nm, the nitrogen concentration is distributed in a high-low-high mode from the oxynitride silicon to the silicon direction, namely the nitrogen impurity concentration at the near-silicon surface layer and the film surface is high, the nitrogen content in the middle is lower, the nitrogen content in the high-concentration area is not lower than 30at%, the nitrogen content in the low-concentration area is not lower than 8at%, the oxynitride silicon film/silicon interface is formed, the penetration of nitrogen is formed at one side of the silicon, the depth is not more than 5nm, the concentration gradually decreases from the interface to the inside of the silicon wafer, the near-surface concentration is not lower than 1at%, and the oxynitride silicon layer is used as a tunneling layer in a passivation contact cell; 5) And preparing a p-type silicon film layer on the surface.
2. The method for preparing an ultrathin nitrogen-oxygen-nitrogen-silicon film according to claim 1, wherein the oxidation treatment mode in the step 3) at least comprises one of the following modes: oxygen or nitrogen/oxygen mixed gas or laughing gas is adopted for high-temperature thermal oxidation treatment, ozone oxidation is adopted, laughing gas and carbon dioxide are adopted for plasma auxiliary oxidation, and hot nitric acid sulfuric acid mixed acid are adopted for wet chemical oxidation.
3. The method for preparing an ultrathin nitrogen-oxygen-nitrogen-silicon film according to claim 1, wherein the oxidation treatment mode of the step 3) is to use laughing gas as shielding gas for high-temperature thermal oxidation treatment, and the annealing temperature is 400-900 ℃.
4. The method for preparing an ultrathin nitrogen-oxygen-nitrogen-silicon film according to claim 1, wherein the thickness of the nitrogen-oxygen-nitrogen-silicon layer in the step 4) is 1.5nm-3.5nm.
5. The method for preparing an ultrathin nitrogen-oxygen-nitrogen-silicon film according to claim 1, wherein the preparation method of the p-type polysilicon layer in the step 5) is as follows: directly preparing a doped polysilicon layer or a doped amorphous silicon layer by an LPCVD method, a PECVD method or different physical vapor deposition methods; or depositing intrinsic polycrystalline silicon or amorphous silicon, and further preparing doped polycrystalline silicon by high-temperature diffusion and ion implantation combined with high-temperature annealing, wherein the annealing temperature is required to be above 800 ℃.
6. The method for preparing an ultrathin SiN film according to claim 5, wherein the annealing temperature is 880-1100 ℃ when combined with high-temperature annealing.
7. Use of the preparation method according to claim 1 for the preparation of a passivated contact structure in a passivated contact cell.
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