CN112186067A - Preparation method and application of nitrogen-doped silicide film passivation contact structure - Google Patents
Preparation method and application of nitrogen-doped silicide film passivation contact structure Download PDFInfo
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- 229910021332 silicide Inorganic materials 0.000 title claims abstract description 49
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002161 passivation Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 230000005641 tunneling Effects 0.000 claims abstract description 6
- -1 silicide nitride Chemical class 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229920005591 polysilicon Polymers 0.000 abstract description 27
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 229910052581 Si3N4 Inorganic materials 0.000 description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000000137 annealing Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention provides a preparation method and application of a nitrogen-doped silicide film passivation contact structure, which comprises the following steps: firstly growing a silicon oxide layer on the surface of a silicon wafer, then depositing one or more layers of doped silicide nitride films on the surface of the silicon oxide layer, and 780-1100oC, performing high-temperature crystallization treatment to form a tunneling silicon oxide passivation contact structure; the invention adopts the doped nitrogen silicide film to replace the doped polysilicon film, is used for the TOPCon structure, not only can keep the excellent surface passivation performance and contact performance of the TOPCon structure, but also has special advantages which are not possessed by a plurality of polysilicon films.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method and application of a nitrogen-doped silicide thin film passivation contact structure.
Background
The passivation contact is also called selective carrier collection, and is a hot research direction of silicon solar cells in recent years. The passivation contact structure can form obvious energy band bending on the silicon surface, so that one carrier can pass through but the other carrier can not pass through, good carrier collection is formed, and meanwhile, the recombination of the carrier at an interface can be inhibited. Therefore, the passivation contact structure can realize high-efficiency passivation and carrier collection, and eliminate direct contact between silicon and metal, thereby improving the passivation effect and enabling the solar cell to obtain high open-circuit voltage.
The tunnel silicon oxide passivated contact crystalline silicon solar cell is a typical passivated contact cell, also called TOPCon in english, and the typical device structure is shown in fig. 1. It should be noted that other technologies such as POLO, monoPoly, PERPOLY, etc. are based on the silicon oxide/doped polysilicon structure, but the names are different. The TOPCon technology has the advantages of simple structure, good passivation effect, capability of bearing a high-temperature process, compatibility with the existing production line, capability of effectively improving the battery efficiency and the like, and is concerned by the industrial and academic circles.
The main characteristic functional layer of the conventional TOPCon crystal silicon solar cell is composed of two parts: a silicon oxide passivation tunneling layer and a polysilicon carrier collecting layer. Currently, a tunnel silicon oxide passivation structure can achieve very excellent passivation effects. Implicit open circuit voltage (iV)oc) And single-sided saturated dark current (J)0) Is two key indexes for representing passivation effect, wherein iVocThe higher the better, J0The lower the better. In general, the passivation of n-type TOPCon, its iV, is goodoc>730mV,J0<7fA/cm2The contact resistivity of the material can be lower than 20m omega cm2Satisfy the full backThe contact resistivity requirements needed to contact a high efficiency battery.
Currently, large photovoltaic manufacturers have begun investigating the commercialization of TOPCon structures. The TOPCon structure based on doped polysilicon becomes an important next-generation high-efficiency photovoltaic technology and has great application prospect.
The TOPCon technology has two major technical routes in the preparation of doped polysilicon: one is the Low Pressure Chemical Vapor Deposition (LPCVD) route, and the other is the Plasma Enhanced Chemical Vapor Deposition (PECVD) route. Compared with the LPCVD route, the PECVD route can realize high-speed in-situ doped thin film deposition without generating the plating-around, and is considered to be a more suitable technical route for industrial production.
The specific implementation mode of the PECVD technical route is as follows: firstly, preparing a layer of silicon oxide on the surface of a silicon wafer, then depositing a layer of doped amorphous silicon by adopting PECVD (plasma enhanced chemical vapor deposition), and then carrying out high-temperature crystallization treatment to enable the amorphous silicon to form polycrystalline silicon so as to prepare the TOPCon structure.
The doped polysilicon prepared by PECVD is used in the TOPCon structure and has some disadvantages, mainly including: 1) in conventional TOPCon structures, the thickness of the polysilicon film needs to be increased (typically >100nm) in order to achieve the target sheet resistance. At this time, amorphous silicon having an excessively high thickness is very likely to be exfoliated during high-temperature crystallization. The reason for the peeling of the silicon film is not clear, and it is generally considered that the hydrogen content in the amorphous silicon film grown by PECVD is too high, and hydrogen overflows during annealing, thus damaging the adhesion of the silicon film and the silicon oxide at the interface, and causing the silicon film to peel off. Once the film peeling phenomenon occurs, the passivation performance of the TOPCon structure is remarkably reduced, and the TOPCon structure is not suitable for subsequent silk-screen sintering treatment. 2) The polysilicon film is highly optically absorbed, which results in the structure not being used on the front side of the cell. If absorption is reduced by reducing the film thickness, it is easily burned through during the metallization sintering process, destroying passivation properties. 3) The refractive index of polysilicon is consistent with that of crystalline silicon, typically above 3.0, and is difficult to adjust, such a high refractive index being detrimental to front or back antireflection. Therefore, the conventional TOPCon structure based on a polysilicon thin film is not suitable for a double-sided passivated cell because it cannot be applied to a cell front side structure. 4) The polysilicon film has weak barrier capability to phosphorus, boron and other impurity atoms, and has insufficient protective capability to the interface in the processes of high-temperature diffusion and long-term use. It is worth pointing out that the p-type topocon structure based on boron doped polysilicon has poor passivation performance, and one important reason is caused by the high diffusion rate of boron in the polysilicon film. 5) Plasma Enhanced Chemical Vapor Deposition (PECVD) is one of the thin film fabrication techniques commonly used in the industry. However, when the amorphous silicon thin film is prepared by the PECVD method, dust is large, the maintenance period is shortened, and the production cost is increased.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: the preparation method and the application of the nitrogen-doped silicide film passivation contact structure are provided, wherein the silicon film is not easy to peel off, the passivation effect is good, and the production cost is low.
The technical solution of the invention is as follows: a method for preparing a nitrogen-doped silicide film passivation contact structure comprises the following steps: firstly, growing a silicon oxide layer on the surface of a silicon wafer, then depositing one or more layers of doped silicide nitride films on the surface of the silicon oxide layer, and carrying out high-temperature crystallization treatment at 780-1100 ℃ to form a tunneling silicon oxide passivation contact structure.
Preferably, one or more layers of doped amorphous or polycrystalline silicon films are deposited on the surface of the nitrogen silicide film before the high-temperature crystallization treatment.
Preferably, the nitrogen content in the nitrogen silicide thin film is 3at% to 60at%, and the preferred concentration is 5 at% to 20 at%.
Preferably, the thickness of the silicon oxide layer is 1.0 to 3.5 nm.
The nitrogen silicide film is a doped film, and the dopant can be phosphorus, arsenic for providing electrons or boron, aluminum and gallium for providing holes. Preferred are phosphorus or boron.
The invention provides application of a nitrogen-silicide-doped thin film passivation contact structure, which is mainly used for a tunneling silicon oxide passivation contact crystalline silicon solar cell.
The invention adopts the doped nitrogen silicide film to replace the doped polysilicon film, is used for the TOPCon structure, not only can keep the excellent surface passivation performance and contact performance of the TOPCon structure, but also has special advantages which are not possessed by a plurality of polysilicon films.
The invention has the beneficial effects that: the passivated contact structure of the present invention has the following features and advantages.
1. The doped polysilicon film is replaced by the doped silicide film, so that the doped silicide film is not easy to peel off in the high-temperature annealing process, and the excellent surface passivation performance of the TOPCon structure is maintained. N-type TOPCon based on phosphorus-nitrogen doped silicide film with highest iVocCan be higher than 740mV, corresponding to a single side J0Can be lower than 3fA/cm2(ii) a P-type TOPCon based on boron-nitrogen-doped silicide film with highest iVocCan be higher than 720mV, corresponding to a single side J0Can be lower than 8fA/cm2. Meanwhile, the contact resistivity of the TOPCon structure based on the phosphorus-doped nitrogen silicide film can be lower than 20m omega cm2。
2. The resistivity of the silicon nitride film increases significantly after nitrogen doping. To overcome this problem, one or more doped silicon nitride films with lower resistivity may be formed over the silicon nitride film. The film with low resistivity can be a doped nitrogen silicon film with low nitrogen content or a doped polysilicon film. Therefore, the structure not only retains the advantages of the silicon nitride film, but also overcomes the defect of higher resistivity.
3. It is worth pointing out that compared with the polysilicon film, the nitrogen silicide film has larger band gap, which is beneficial to reducing interface state and film internal recombination, and is beneficial to enlarging the quasi-Fermi energy level difference of the silicon substrate. Therefore, the TOPCon is made of the nitrogen silicide film, which is beneficial to improving the passivation effect.
4. The absorption of the nitrogen silicide film is between the silicon nitride and the polysilicon, and the absorption coefficient is obviously smaller than that of the polysilicon film. Meanwhile, the refractive index of the nitride silicide film is between that of silicon nitride and that of polysilicon and lower than that of the polysilicon film; and the refractive index can be adjusted by the composition of the film. The specific absorption coefficient and refractive index depend mainly on the atomic ratio of nitrogen to silicon in the actual film. The TOPCon structure adopting the nitrogen silicide film has the advantages that the optical absorption is remarkably reduced, and the refractive index is more suitable for surface antireflection, so that the TOPCon based on the nitrogen silicide film is favorable for being used as a window layer of a battery, the absorption is reduced, the antireflection effect is improved, and the TOPCon structure has the potential for double-sided TOPCon batteries.
5. The nitrogen silicide film has strong blocking capability to impurity atoms, and is favorable for protecting the structure of the interface silicon oxide layer. Research shows that the p-type TOPCon structure based on the boron-doped silicon nitride film has excellent passivation performance or benefits from the barrier effect of the silicon nitride film on boron and the protective effect on silicon oxide at the interface. In addition, the nitrogen silicide film has strong diffusion blocking capacity to potassium ions, calcium ions, sodium ions and the like, is favorable for protecting an interface structure and improves the stability of a device.
6. When the PECVD is adopted for preparing the silicon nitride film, the dust in the cavity is obviously lower than the condition of preparing the polysilicon film. Therefore, when the silicon nitride film is prepared, the maintenance period of the PECVD chamber is obviously increased, and the production cost is favorably reduced. This phenomenon is due to the advantages of the silicon nitride film such as high strength and strong adhesion. The properties of the nitrogen silicide film adopted by the invention are between those of nitride and polysilicon, and the nitrogen silicide film prepared by PECVD is used for replacing the polysilicon film, so that the dust of a PECVD reaction chamber can be reduced to a certain extent, the maintenance period is prolonged, and the production cost is reduced.
Drawings
Figure 1 is a prior art topocon device structure.
Fig. 2 is an optical microscope photograph showing the peeling of the polysilicon thin film.
FIG. 3 is an optical micrograph of a silicon nitride film without a rupture disk.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The n-type silicon wafer used by the invention is a solar-grade Czochralski monocrystalline silicon wafer with the thickness of 180 mu m, the double surfaces are polished by acid, and the resistivity is 0.5-3.0 omega cm.
The preparation method of the passivation piece comprises the following steps: treating the silicon wafer in hot nitric acid at 90 ℃ for 30min to form a surface silicon oxide layer; then putting the film into a PECVD chamber, and depositing phosphorus (or boron) doped amorphous nitrogen silicide films with different components by taking silane, phosphine (or diborane) and ammonia gas as reaction gases; then placing the mixture into a tubular annealing furnace for high-temperature treatment at 900 ℃ for 30min at 800-; finally, the passivation performance and the contact performance are tested.
EXAMPLE 1 passivation Effect and contact Properties of phosphorus-doped Nitrogen silicide films
The nitrogen silicide film doped with phosphorus is prepared by respectively adopting different mixing ratios of silane and ammonia gas, and the following passivation and contact performances are obtained by annealing at 820 ℃ and subsequent hydrogenation treatment.
Example 2 passivation Effect and contact Properties of boron-doped Nitrogen silicide films
The boron-doped nitrogen silicide film is prepared by respectively adopting different mixing ratios of silane and ammonia gas, and the following passivation and contact performances are obtained by annealing at 880 ℃ and subsequent hydrogenation treatment.
Example 3 use of phosphorus-doped nitrogen silicide thin films for solar cells
The structure of the cell is still as shown in fig. 1, firstly, boron diffusion treatment is carried out on the front surface of an n-type silicon wafer to form a p + emitter;preparing an oxide layer on the back; respectively depositing a layer of phosphorus-doped amorphous silicon film and a layer of phosphorus-doped nitrogen silicide film with the thickness of 100nm by adopting a PECVD method, and annealing the films at 820 ℃ for 30 min; followed by preparation of front surface Al2O3/SiNxA passivation layer; front and rear electrodes are prepared. And finally, testing the battery efficiency by adopting Newport Oriel and SoliA.
EXAMPLE 4 anti-reflection of phosphorus-doped Nitrogen silicide films
And respectively adopting different mixing ratios of silane and ammonia gas to prepare a phosphorus-doped nitrogen silicide film on a quartz substrate, carrying out annealing at 880 ℃ and subsequent hydrogenation treatment, and testing antireflection, transmittance and absorptivity.
EXAMPLE 5 refractive index of phosphorus-doped silicide nitride film
Preparing a phosphorus-doped nitrogen silicide film on a mirror-polished substrate by respectively adopting different mixing ratios of silane and ammonia gas, carrying out 880 ℃ annealing and subsequent hydrogenation treatment, and testing the refractive index.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (6)
1. Nitrogen-doped silicide film passivation jointThe preparation method of the contact structure is characterized by comprising the following steps: the method comprises the following steps: firstly growing a silicon oxide layer on the surface of a silicon wafer, then depositing one or more layers of doped silicide nitride films on the surface of the silicon oxide layer, and 780-1100oAnd C, performing high-temperature crystallization treatment to form a tunneling silicon oxide passivation contact structure.
2. The method for preparing the passivation contact structure of the doped nitrogen silicide film according to claim 1, wherein: and before high-temperature crystallization treatment, depositing one or more layers of doped amorphous or polycrystalline silicon films on the surface of the nitrogen silicide film.
3. The method for preparing the passivation contact structure of the doped nitrogen silicide film according to claim 1, wherein: the nitrogen content in the nitrogen silicide film is 3at percent to 60at percent.
4. The method for preparing the passivation contact structure of the doped nitrogen silicide film according to claim 1, wherein: the thickness of the silicon oxide layer is 1.0-3.5 nm.
5. The method for preparing the passivation contact structure of the doped nitrogen silicide film according to claim 1, wherein: the nitrogen silicide film is a doped film, and the dopant can be phosphorus, arsenic for providing electrons or boron, aluminum and gallium for providing holes.
6. Use of the doped nitrogen silicide thin film passivated contact structure recited in any one of claims 1-5, wherein: the method is used for passivating the contact crystalline silicon solar cell by the tunneling silicon oxide.
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