WO2015027946A1 - Film passif diélectrique, cellule solaire et procédé de préparation associé - Google Patents

Film passif diélectrique, cellule solaire et procédé de préparation associé Download PDF

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Publication number
WO2015027946A1
WO2015027946A1 PCT/CN2014/085612 CN2014085612W WO2015027946A1 WO 2015027946 A1 WO2015027946 A1 WO 2015027946A1 CN 2014085612 W CN2014085612 W CN 2014085612W WO 2015027946 A1 WO2015027946 A1 WO 2015027946A1
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passivation film
silicon
silicon nitride
dielectric passivation
film
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PCT/CN2014/085612
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English (en)
Chinese (zh)
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叶继春
王洪喆
高平奇
潘淼
韩灿
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中国科学院宁波材料技术与工程研究所
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Publication of WO2015027946A1 publication Critical patent/WO2015027946A1/fr

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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
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to the field of solar cell materials, and in particular to a silicon nitride dielectric passivation film containing a doping element for a surface of a silicon-based material, and a silicon-based solar cell including a dielectric passivation film and a method of fabricating the same.
  • Semiconductor materials are the core materials for the preparation of photovoltaic solar cells.
  • the surface of these semiconductor materials (for example, silicon) will have a certain number of surface recombination centers such as dangling bonds. These recombination centers will cause carriers to recombine on the semiconductor surface, reducing The lifetime of the carrier ultimately limits the efficiency of the solar cell. For this reason, people have reduced the number of surface dangling bonds by growing a passivation film on the surface of the silicon material, and reduced the surface sub-composite, thereby achieving surface passivation. This passivation method by reducing the dangling bonds on the surface of the semiconductor material is commonly referred to as chemical passivation.
  • the passivation film usually contains a large amount of fixed charges, which form an electrostatic field at the interface between the film and the silicon, reducing or increasing the surface minority concentration, depending on the electrical properties of the charge and the conductivity type of the substrate, such as the minority of p-type silicon.
  • the passivation film has a negatively charged fixed charge, the recombination of the minority at the interface is inhibited.
  • the way in which the passivation effect is enhanced by establishing an electric field at the surface of the semiconductor is called field effect passivation.
  • a good passivation film generally has both chemical passivation and field effect passivation.
  • A1 forms a high doping on the back surface, thereby forming high and low sections, and has a certain electric field passivation effect.
  • the backside structure of the structure is substantially free of any chemical passivation effect, and the overall passivation effect is low.
  • dielectric films can passivate the unsaturated dangling bonds of the silicon wafer well, so that the battery effect is greatly improved, such as A1 2 0 3 , Si x N y , a-Si, Si0 2 , Ti0 2 and the like.
  • silicon nitride film has been widely used in passivation of crystalline silicon solar cells due to its good optical matching and passivation properties.
  • SiNx grown by PECVD is used for back-passivation of a p-type battery, an inversion layer is formed on the back side of the battery, causing parasitic shunting, resulting in deterioration of battery type performance.
  • the industry generally uses the ALD method to grow a very thin layer of A1 2 0 3 between SiNx and silicon wafers.
  • the A1 2 0 3 brings good chemical passivation effect.
  • the ALD equipment suitable for industrial production is very expensive, nearly 30 million yuan/set, which greatly hinders the application and popularization of the technology in solar cells.
  • crystalline silicon solar cells generally produce photo-induced attenuation under illumination, while crystalline silicon cells with A1 2 0 3 as a passivation layer produce photo-enhancement under illumination, but effective minority lifetimes from annealing
  • the value of the increase to the saturation value takes a long time and is placed in the dark, and this passivation enhancement effect is restored to the state before the illumination.
  • 24 hours a day according to the 12 hours of light in a day, the A1 2 0 3 applied to the silicon solar cell can't be upgraded to one-tenth of the saturated passivation value to decay to the state before the light. It does not play its practical role in the application of conventional solar devices, and its production cost is high.
  • the film's electrical properties and power are controllable without increasing or increasing the lower cost, it has good field effect passivation; it has excellent anti-reflection and passivation properties, and can be under illumination. It can enhance the passivation effect and can be upgraded to saturation passivation value under short-time illumination. This will effectively increase the actual power generation of solar cells, which will surely become a major technological breakthrough in the field of crystalline silicon solar energy. Further promotion of the battery.
  • the passivation film of the present invention was developed based on such a consideration. Summary of the invention
  • An object of the present invention is to provide a silicon nitride dielectric passivation film having element doping on a silicon-based material, and a silicon-based solar cell containing the dielectric passivation film and a method of fabricating the same.
  • a first aspect of the present invention provides a surface dielectric passivation film suitable for a silicon-based material, the surface dielectric passivation film comprising a silicon nitride dielectric passivation film on a surface of a silicon-based material, and the nitriding
  • the passivation film of the silicon medium contains a doping element selected from the group consisting of: a passivation film of a silicon nitride dielectric film exhibiting a negatively charged doping element, and a passivation film of the silicon nitride dielectric being positively charged. Sex doping element, or a combination thereof;
  • the doping element that renders the silicon nitride dielectric passivation film negatively elective is selected from the group consisting of: phosphorus, arsenic, antimony or a combination thereof; and the passivation film of the silicon nitride dielectric exhibits a positively doping
  • the element is selected from the group consisting of: boron, aluminum, gallium, indium, antimony, zinc, or a combination thereof.
  • the doping element is present in a passivating effective amount.
  • a non-silicon nitride dielectric passivation film or an additional silicon nitride dielectric passivation film is further disposed over the silicon nitride dielectric passivation film (the side away from the silicon substrate).
  • the silicon nitride dielectric passivation film (on the side close to the silicon substrate) further has a non-silicon nitride dielectric passivation film or an additional silicon nitride dielectric passivation film.
  • the non-silicon nitride dielectric passivation film does not change the field passivation effect of the silicon nitride dielectric passivation film on the silicon-based material.
  • the non-silicon nitride dielectric passivation film is a dielectric passivation film containing a component selected from the group consisting of: Si0 2 , Ti0 2 , A1 2 0 3 , a-Si, ITO, c-Si Or a combination thereof.
  • the non-silicon nitride dielectric film further comprises:
  • the doping element that renders the silicon nitride dielectric passivation film negatively charged and/or
  • the passivation film of the silicon nitride dielectric is rendered positively doped.
  • the doping element causes the silicon nitride dielectric passivation film to exhibit a negative charge, and the total content of the doping element is
  • the doping element causes the silicon nitride dielectric passivation film to exhibit positive polarity, and the total content of the doping element is 0.01-50%, more preferably 1-30%, more preferably The ground is 2-20%, based on the total atomic number of the film layer in which the doping element is located in the passivation film of the silicon nitride medium.
  • the total electrical property of the silicon nitride dielectric passivation film is positively charged, and the silicon-based material is n-type or P-type, preferably n-type; or
  • the total electrical property of the silicon nitride dielectric passivation film is negatively charged, and the silicon-based material is P-type or n-type, preferably P-type.
  • the silicon nitride dielectric passivation film is formed by chemical vapor deposition or physical vapor deposition.
  • the non-silicon nitride dielectric passivation film is formed by another method of chemical vapor deposition or physical vapor deposition, and the chemical vapor deposition method comprises: PECVD, APCVD, LPCVD , ALD, etc.
  • the physical vapor deposition method includes: sputtering, evaporation, and the like.
  • the silicon nitride dielectric passivation film is formed by plasma enhanced chemical vapor deposition.
  • the silicon nitride in the passivation film of the silicon nitride dielectric is mainly prepared by a plasma enhanced chemical vapor deposition (PECVD) growth apparatus compatible with existing conventional silicon-based solar cell devices.
  • PECVD plasma enhanced chemical vapor deposition
  • the surface of the silicon-based material has a single layer film or a multilayer composite film, and at least one film is the passivation film of the silicon nitride dielectric, and the single layer or layers
  • the total electrical properties of the composite membrane are either negative or positive.
  • the total electrical properties of the single or multi-layer composite film are positively charged above the surface of the n-type silicon-based material. In another preferred embodiment, the total electrical properties of the layer or multilayer composite film are negatively charged above the surface of the p-type silicon-based material.
  • the multilayer composite film comprises:
  • non-silicon nitride dielectric passivation film layers selected from the group consisting of SiO 2 , Ti 2 2 , A 1 2 0 3 , a-Si, ITO, c-Si, or a combination thereof.
  • each film layer in (b) optionally contains:
  • the doping element that renders the silicon nitride dielectric passivation film negatively charged and/or
  • the passivation film of the silicon nitride dielectric is rendered positively doped.
  • the doping element which renders the silicon nitride dielectric passivation film negatively elective is selected from the group consisting of phosphorus, arsenic, antimony or a combination thereof;
  • the doping element that renders the silicon nitride dielectric passivation film positively electrified is selected from the group consisting of boron, aluminum, gallium, indium, antimony, zinc, or a combination thereof.
  • each of the film layers in (a) is the same or different.
  • each of the film layers in (b) is the same or different.
  • each of the film layers in (b) is on the silicon nitride dielectric passivation film (away from the side of the silicon-based material) or below (on the side close to the silicon-based material).
  • the total thickness of the surface dielectric passivation film described in (a) is from 1 to 300 nm; (preferably from 10 to 100 nm)
  • the amount is 0. 3-2, preferably 0. 5-2;
  • the silicon-based material has a thickness of from 1 to 1000 ⁇ m, preferably from 20 to 280 ⁇ m;
  • the silicon-based material comprises polycrystalline silicon or single crystal silicon
  • the reflectivity of the silicon-based material having the surface dielectric passivation film is reduced by 0.1% to 10% compared to the control material, the control material It is a silicon-based control material using a conventional single-layer silicon nitride film (undoped) as a passivation layer.
  • the silicon nitride dielectric passivation film has the following illumination enhancement passivation effect:
  • ⁇ i is the minority carrier lifetime of the silicon-based material having the passivation film of the silicon nitride dielectric under steady state under illumination; and ⁇ .
  • the minority life of the steady state is reached under illumination;
  • n i is the photoelectric conversion efficiency of the silicon-based material having the passivation film of the silicon nitride medium under steady state under illumination; and 3 ⁇ 4 is the photoelectric conversion efficiency of the control material under steady state under illumination;
  • control material is a silicon-based control material using a conventional single-layer silicon nitride dielectric film (undoped) as a passivation layer.
  • a second aspect of the invention provides a coated silicon substrate, the coated silicon substrate comprising:
  • the silicon-based material is a silicon-based material having a surface without a film layer or a silicon-based material having a dielectric passivation film on the surface, and the dielectric passivation film may be a non-silicon nitride dielectric passivation film.
  • the silicon-based material comprises a silicon substrate, a silicon substrate.
  • a third aspect of the invention provides a method for preparing a silicon-based material surface dielectric passivation film, the method comprising:
  • the first gas is a silicon germanium or a silicon germanium gas
  • the second gas is ammonia or nitrogen
  • the third gas is a gas containing a doping element, and the third gas is selected from the group consisting of: phosphine, arsine, hydrogen halide, hydrogen halide, phosphorus trifluoride, phosphorus pentafluoride, boron lanthanum , boron trifluoride, trimethyl aluminum (TMA), trimethyl gallium (TMG), trimethyl indium (TMI), diethyl zinc (DeZn), etc. or a combination thereof.
  • the non-silicon nitride dielectric passivation film in the surface dielectric passivation film is prepared by a chemical or physical vapor deposition method.
  • the method further comprises the steps of: depositing one or more silicon nitride dielectric passivation film layers and/or non-silicon nitride dielectric blunt on the surface of the silicon-based material prepared in the previous step. Film layer.
  • the flow volume ratio of the first gas to the third gas is 100: 0.01 to 200, preferably 100: 1-90.
  • the first gas and the second gas have a flow volume ratio of 1: 1 to 12, preferably 1: 2 to 7.
  • the deposition temperature is 150 to 500 °C.
  • the method further comprises the step of: annealing the sample (coated silicon substrate) after forming the passivation film of the silicon nitride dielectric.
  • the apparatus used for the annealing treatment is a conventional annealing furnace or a rapid thermal annealing furnace.
  • the step of annealing is carried out in an atmosphere containing air or a protective gas.
  • the annealing treatment is carried out at 150 to 1000 °C.
  • the annealing treatment is carried out for 0.5 to 120 minutes.
  • a fourth aspect of the invention provides a solar cell comprising the surface dielectric passivation film of the first aspect or the coated silicon substrate of the second aspect. It is to be understood that within the scope of the invention, the various technical features of the invention described above and the technical features specifically described hereinafter (as in the embodiments) may be combined with each other to form a new or preferred embodiment. Due to space limitations, we will not repeat them here. DRAWINGS
  • FIG. 1 is a schematic view showing the field passivation effect of a passivation film of a silicon nitride dielectric with a fixed positive charge on a surface of an n-type silicon substrate;
  • FIG. 2 is a schematic view showing the field passivation effect of a passivation film of a silicon nitride dielectric with a fixed negative charge on a p-type silicon substrate;
  • Figure 3 is a graph showing the change of the minority carrier lifetime in the process of the first embodiment
  • Figure 6 is a graph showing changes in the lifetime of minority carriers in the process of Example 2.
  • Figure 7 is a graph showing the change in lifetime of the minority carrier in the process of Example 3 over time. detailed description
  • the inventors have invented a silicon nitride dielectric passivation film for the surface of a silicon-based material after extensive and intensive research.
  • the silicon nitride dielectric passivation film is doped with one or more doping elements such that the silicon nitride dielectric passivation film has a negative (or positive) electrical property.
  • the dielectric passivation film is negatively charged, and the dielectric passivation film is positively charged after the boron element is doped into the passivation film of the silicon nitride dielectric.
  • the negatively charged silicon nitride dielectric passivation film is used on the P-type silicon-based material, or the positively-charged silicon nitride dielectric passivation film is used on the n-type silicon-based material to not only maintain the original solar cell.
  • the present invention has been completed on this basis.
  • chemical passivation means that during the deposition process, the reaction gas can release atomic hydrogen, or other chemical bonds, which saturate the dangling bonds in the silicon wafer, deactivate the defects, and achieve surface passivation and bulk passivation. purpose.
  • electrically passivated refers to a dielectric passivation film having a negative (or positive) electrical property on the surface of a silicon wafer. These charges accumulate on the contact surface of the silicon wafer and the dielectric passivation film, creating a barrier on the surface of the silicon wafer, so that minority carriers (hereinafter referred to as “small children” are not easily transported to the surface for recombination, also known as field blunt Chemical.
  • silicon substrate As used herein, “silicon substrate”, “wafer” are used interchangeably and refer to the substrate material used to prepare the solar cell of the present invention.
  • the silicon-based material refers to a silicon-based material that is in direct contact with a dielectric film (rather than a solar cell host substrate).
  • silicon nitride dielectric passivation film refers to silicon nitride. A dielectric passivation film that is the main component.
  • non-silicon nitride dielectric passivation film means a dielectric passivation film containing a component selected from the group consisting of, but not limited to, Si0 2 , Ti0 2 , A1 2 0 3 , a-Si, ITO, c-Si.
  • passivation film As used herein, "passivation film”, “dielectric passivation film” are used interchangeably and refer to a film used to passivate a silicon substrate. Passivation film
  • the silicon nitride dielectric passivation film of the present invention is mainly a dielectric passivation film made of negative (or positive) electric silicon nitride doped with one or more elements, wherein the silicon nitride medium is blunt
  • the negatively charged elements of the film include, but are not limited to, phosphorus, arsenic, antimony, or a combination thereof, preferably phosphorus.
  • the positively charged elements of the passivation film of the silicon nitride dielectric include, but are not limited to, boron, aluminum, gallium, indium, antimony, zinc, or a combination thereof. Preferred is: boron.
  • the coated silicon substrate of the present invention has a single layer film or a multilayer composite film, and the number of film layers of the multilayer composite film is preferably 1-5 layers.
  • the passivation film is a silicon nitride dielectric passivation film; when the passivation film is a multilayer composite film, the composite film includes at least one layer of the element doped silicon nitride medium according to the present invention.
  • a passivation film such as one or more layers of a silicon nitride dielectric passivation film, which may also include one or more layers of non-silicon nitride dielectric passivation films of other compositions, such as Si0 2 , Ti0 2 , A1 2 0 3 , a-Si, ITO, c-Si and other film layers.
  • each of the silicon nitride dielectric passivation film layer or the non-silicon nitride dielectric passivation film layer may be the same or different, that is, the content of doping elements in each passivation film layer of the silicon nitride dielectric may be the same or different, silicon nitride
  • the dielectric passivation film layer may be doped with an element which makes the silicon nitride dielectric passivation film be negatively charged or an element which makes the silicon nitride dielectric passivation film be positively charged, or may be doped by mixing two elements. miscellaneous. 5-2 ⁇ More preferably, the x/y value is preferably 0.3-3, more preferably 0. 5-2.
  • the Si/N value of the silicon nitride dielectric passivation film may be the same or different.
  • the content of the components in each of the non-silicon nitride dielectric passivation film layers may be the same or different.
  • each non-silicon nitride dielectric passivation film layer may also include a doping element that renders the silicon nitride dielectric passivation film negatively charged and/or renders the silicon nitride dielectric passivation film positively charged. Doping element.
  • the order between the layers can be randomly combined, but it must be ensured that the net charge in all layers is not equal to zero, that is, while the total layer is negative (or positive), the negative (or positive) Sexually has an electrical passivation effect on the surface of the silicon wafer.
  • the superimposed combination structure of each film layer includes, but is not limited to, the following examples:
  • One or more layers of silicon nitride dielectric passivation film are directly attached to the surface of the silicon substrate, and then adhered to the surface of the passivation film of the silicon nitride dielectric.
  • One or more layers of other non-silicon nitride dielectric passivation film are directly attached to the surface of the silicon substrate, and then adhered to the surface of the passivation film of the silicon nitride dielectric.
  • a silicon nitride dielectric passivation film is directly adhered to the surface of the silicon substrate, and a non-silicon nitride dielectric passivation film of other composition is adhered on the surface of the passivation film of the silicon nitride dielectric, and then A passivation film of a silicon nitride dielectric is adhered to the surface of the non-silicon nitride dielectric passivation film, and thus alternately stacked.
  • the multilayer composite film is a silicon nitride dielectric passivation film directly in contact with the silicon substrate, the multilayer composite film also has a good chemical passivation effect; if the multilayer composite film is passivated by a non-silicon nitride medium The film is directly in contact with the silicon substrate, and the chemical passivation effect is directly related to the chemical properties of the non-silicon nitride dielectric passivation film layer.
  • a non-silicon nitride dielectric passivation film layer having excellent chemical passivation effect includes: Si0 2 , A1 2 0 3 , a-Si, and the like.
  • each film layer may be the same or different, and the total film thickness is between 1 and 300 nm, preferably 10 to 100 nm.
  • the total thickness of the passivation film is less than 1 nm, high passivation effect may not be exhibited.
  • the preparation cost may be too high.
  • the usual passivation of silicon nitride film is mainly determined by chemical passivation, and since it is positively charged, it has a certain electrical effect.
  • the silicon nitride film has a large fixed positive charge, it is generally considered to be unsuitable as a passivation film corresponding to the p-type silicon substrate, and the p-region in the n-type or p-type silicon substrate.
  • a conventional silicon nitride passivation film is reinforced by doping a certain amount of doping elements in a conventional silicon nitride passivation film to make the silicon nitride passivation film negative (or positive).
  • Electrical passivation so that a silicon nitride film, which is usually mainly chemically passivated, can be used as a passivation film for a p-type silicon substrate, and a p-region in an n-type or p-type silicon substrate, and also has Light enhances the passivation effect.
  • a negatively-charged silicon nitride passivation film on the surface of a p-type silicon substrate incorporating a certain amount of phosphorus
  • a positively-charged silicon nitride passivation film on the surface of the n-type silicon substrate can make the silicon nitride as a passivation layer also enhance the passivation of p-type and n-type silicon.
  • the negative charge of the surface of the silicon substrate or the positive charge of the surface of the n-type silicon substrate thereby repelling minority carriers to the surface to aggregate, reducing surface recombination, thereby further enhancing surface passivation.
  • the total content of the doping element is generally from 0.01 to 50%, more preferably from 1 to 30%, and most preferably from 2 to 20%, based on the total atomic number of the film layer in which the doping element is present in the passivation film of the silicon nitride dielectric.
  • the silicon nitride dielectric passivation film of the present invention can be applied to an n-type or p-type silicon substrate by controlling the amount of the doping element;
  • the silicon nitride dielectric passivation film of the present invention can be applied to a p-type or n-type silicon substrate by controlling the amount of the doping element.
  • the doping element is a positively charged element
  • the silicon substrate is n-type; when the doping element is a negatively charged element, and the silicon substrate is p-type.
  • the passivation film of the silicon nitride medium with element doping has the effect of light enhancement passivation under illumination, the surface recombination is related to the surface minority concentration, the lower the surface minority concentration, the smaller the surface recombination degree, and the better the passivation effect.
  • the minority carriers are electrons (negatively charged).
  • the band is bent, and the passive substrate is fixed on the silicon substrate and the negative charge.
  • the contact area of the layer forms a barrier to the movement of electrons from the silicon substrate to the interface, preventing it from moving toward the surface.
  • the amount of negatively charged negative charge in the passivation film layer is increased, and the hindrance effect is more obvious.
  • the concentration of the minority particles accumulated on the surface of the silicon substrate is lower, and the surface recombination degree is smaller, thereby making the photo-enhanced surface blunt.
  • the role of the role It can be seen from the figure that the passivation of the silicon nitride passivation layer also enhances the passivation of the n-type and p-type silicon substrates.
  • ⁇ i is the minority carrier lifetime of the silicon-based material having the passivation film of the silicon nitride dielectric under steady state under illumination; and ⁇ .
  • the minority life of the steady state is reached under illumination;
  • n i is the photoelectric conversion efficiency of the silicon-based material having the passivation film of the silicon nitride medium under steady state under illumination; and 3 ⁇ 4 is the photoelectric conversion efficiency of the control material under steady state under illumination;
  • the control material is a silicon-based control material using a conventional single-layer silicon nitride dielectric film (undoped) as a passivation layer.
  • the coated silicon substrate of the present invention has the following anti-reflection effect: a reduction of 0.1% to 10% compared to a conventional silicon-based control material in which a single-layer silicon nitride film (undoped) is used as a passivation layer.
  • the effective minority carrier lifetime of silicon wafers passivated by silicon nitride film takes less than one hour from the value after annealing to the saturation value (ie, the passivation saturation value), and does not currently contain any doping elements.
  • the saturation value ie, the passivation saturation value
  • the passivation effect is enhanced.
  • the time to reach the saturation passivation value is significantly shortened, and the practical performance is stronger.
  • the coated silicon substrate and solar cell of the present invention can be formed by conventional chemical vapor deposition (including PECVD, APCVP, LPCVD, ALD, etc.) or physical vapor deposition (including sputtering, evaporation, etc.).
  • the deposition of silicon nitride in the surface dielectric passivation film can be carried out using a chemical vapor deposition growth apparatus compatible with conventional conventional silicon-based solar cell devices.
  • the invention is preferably prepared by plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition
  • a preferred method of preparation is: forming a dielectric passivation film on the surface of a silicon-based material by performing a PECVD reaction on a mixed gas containing a first gas, a second gas, and a third gas, wherein the first gas is silicon germanium (Si3 ⁇ 4) Or a silicon germanium (3 ⁇ 4 ⁇ 4) gas, the second gas is ammonia (NH 3 ), the third gas is a gas containing a doping element, and the third gas includes but is not limited to: phosphine, arsine, helium Hydrogen, hydrogen, Phosphorus trifluoride, phosphorus pentafluoride, boron lanthanum, boron trifluoride, trimethyl aluminum (TMA), trimethyl gallium (TMG), trimethyl indium (TMI), diethyl zinc (DeZn), Or a combination of the above gases.
  • the thickness of the silicon substrate is preferably from 1 to 1000 ⁇ m, more preferably from 20 to 280 ⁇ m.
  • Silicon substrates include, but are not limited to, polycrystalline silicon, monocrystalline.
  • the silicon nitride dielectric passivation film of the present invention may be attached to the front side and/or the back side of the solar cell silicon material of the present invention, and the silicon nitride dielectric passivation film is applicable to p-type and n-type solar cells.
  • the surface of the silicon substrate on which the sunlight is incident on the solar light of the solar cell is referred to as a light receiving surface (ie, the front surface), and the surface opposite to the light receiving surface, that is, the surface of the silicon substrate on the non-sunlight incident side is referred to as a reverse side or a back surface.
  • the third gas includes, but is not limited to: phosphine, arsine, hydrogen halide, germanium Hydrogen, phosphorus trifluoride, phosphorus pentafluoride, etc.; preferably phosphine.
  • the third gas includes but is not limited to: boron lanthanum, boron trifluoride, trimethyl aluminum (TMA), trimethyl gallium (TMG), trimethyl indium (TMI), diethylzinc (DeZn), preferably boron bismuth.
  • the flow volume ratio of silicon germanium or silicon germanium gas to ammonia gas is 1 : 1-12, preferably 1 : 2-7. 100: 0.01-200, preferably 100: 1-90, of a silicon germanium gas and a third gas such as phosphonium or boron germanium.
  • a silicon germanium gas and a third gas such as phosphonium or boron germanium.
  • the silicon substrate it is preferred to subject the silicon substrate to an annealing treatment after forming the dielectric passivation film.
  • the equipment used for the annealing treatment is a conventional annealing furnace or a rapid thermal annealing furnace.
  • the annealing treatment in the present invention means heat treatment of a silicon substrate. This annealing treatment is preferably carried out in an atmosphere containing air or a protective gas.
  • the annealing treatment preferably heats the silicon substrate at 150 to 1000 ° C, more preferably at 350 to 750 ° C.
  • the annealing treatment is performed at a temperature of less than 150 ° C, the annealing effect may not be obtained; when the annealing treatment temperature exceeds 1000 ° C, the passivation film of the surface is destroyed (hydrogen detachment in the film), possibly Causes its characteristics to decline.
  • the annealing treatment is preferably carried out for 0.5 to 120 minutes because the time is too short, and the annealing effect may not be obtained; if the time is too long, the passivation film of the surface is destroyed (hydrogen detachment in the film), which may cause a decrease in characteristics thereof. .
  • the atmosphere of the protective gas is preferably used, and specific examples thereof include at least one selected from the group consisting of nitrogen gas and argon gas.
  • the characteristics of the formed solar cell can be further improved by the above annealing treatment.
  • the present invention includes the following main advantages:
  • the surface dielectric passivation film of the present invention has excellent passivation properties for solar cells
  • coated silicon substrate and the solar cell of the present invention have a light-enhanced passivation effect
  • the coated silicon substrate and the solar cell of the present invention can reach the saturation passivation value in less than one hour under illumination, thereby improving the practicability of the passivation film of the silicon nitride medium;
  • coated silicon substrate and solar cell of the present invention have excellent antireflection properties
  • the p-type and n-type polished single crystal silicon wafers used in the examples of the present invention were purchased from Hefei Kejing Material Technology Co., Ltd.
  • the steps of cleaning, drying, etc. before use of the silicon wafer are carried out by a conventional method.
  • the coated silicon substrate and the preparation of the solar cell were all prepared by a known PECVD method.
  • the equipment uses PECVD growth equipment compatible with existing conventional silicon-based solar cell equipment.
  • the annealing treatment is carried out using a conventional annealing furnace or a rapid thermal annealing furnace.
  • the minority life test method namely the microwave photoconductive attenuation method, is tested in accordance with ASTM International Standard -1535.
  • the reflectance of the samples was measured using a HELIOS LAB-RE reflectance tester from AudioDev GmbH.
  • the CV (capacitor voltage) test of the sample was performed using Keithley's Keithley Model 4200-SCS Semiconductor Parameter Analyzer.
  • a phosphorus-doped silicon nitride film with a thickness of about 70 nm is deposited on the surface of sample A by using a PECVD apparatus.
  • the percentage of phosphorus atoms in the silicon nitride film is about 3%, and the deposition temperature is 250 ° C.
  • the volumetric flow ratio to 33 ⁇ 4 is 5:100, the flow ratio of SiH ⁇ N3 ⁇ 4 is 1 : 2, and the reaction chamber pressure is 30Pa;
  • a non-phosphorus-doped silicon nitride film having a thickness of about 70 nm is deposited on the surface of the sample B at a deposition temperature of 250 ° C, a flow ratio of Si to N 3 ⁇ 4 of 1: 2, and a reaction chamber pressure of 30 Pa;
  • the sample was made into a MIS (Metal-Insulator-Semiconductor) device, and the samples before and after the illumination were subjected to CV test.
  • the test results are shown in Fig. 4.
  • the annealed sample can rapidly rise to a saturation value after a short time (less than 60 min) illumination, unlike the photoinduced attenuation when an undoped silicon nitride passivation film is used ( LID) phenomenon.
  • LID photoinduced attenuation when an undoped silicon nitride passivation film is used
  • the lifetime of the silicon wafer needs to be increased from the value after annealing to the saturation value of about 80 hours.
  • the passivation film of the present invention shows better practical value.
  • the sample A has a significantly lower reflectance than the sample B (note: these are polished silicon wafers), while the battery efficiency after saturation is increased by 0.63%, thus indicating a phosphorus-doped silicon nitride medium.
  • the passivation film has anti-reflection effect, which can effectively achieve lower surface reflection, so that more sunlight can enter the solar cell for photoelectric conversion.
  • the first illumination After the first illumination, it rises to the saturated passivation value for a short time. After the dark room is left for a period of time, the second illumination is performed. After the dark room is left for a period of time, the third illumination is performed, and the sample A can be raised to a saturated blunt in a short time. The value shows that Sample A has better stability.
  • a boron-doped silicon nitride film with a thickness of about 90 nm is deposited on the surface of the sample C by a PECVD apparatus.
  • the percentage of boron atoms in the silicon nitride film is about 10%, and the deposition temperature is 320 ° C, 8 2
  • the volumetric flow ratio to 513 ⁇ 4 is 20:100, the ratio of flow to 51 is 1:3, and the pressure in the reaction chamber is 50 Pa.
  • a layer of boron-doped silicon nitride film with a thickness of about 90 nm is deposited on the surface of sample D.
  • the temperature is 320 ° C
  • the reaction chamber pressure is 50 Pa;
  • the C sample is irradiated with a xenon lamp (0.5 suns), and the minority carrier life test is performed every 1 to 10 minutes. After the sample has a small sub-lifetime to reach a saturation value, the sample is placed in the dark room for a period of time, and the measurement is performed. The life of the youngest.
  • the sample was made into a MIS (Metal-Insulator-Semiconductor) device, and the samples before and after the illumination were subjected to CV test, and the test results are shown in Fig. 5.
  • MIS Metal-Insulator-Semiconductor
  • the annealed sample C can rapidly rise to a saturation value after a short time (less than 60 min) illumination, unlike the photoinduced attenuation when an undoped silicon nitride passivation film is used ( LID) phenomenon.
  • LID photoinduced attenuation when an undoped silicon nitride passivation film is used
  • sample C has a significantly lower reflectance than the sample D, and the battery efficiency after saturation is increased by 0.29%, thus indicating that the boron-doped silicon nitride dielectric passivation film has an anti-reflection effect. Effectively achieve lower surface reflections, allowing more sunlight to enter the solar cell for photoelectric conversion.
  • the first illumination After the first illumination, it rises to the saturated passivation value for a short time. After the dark room is left for a period of time, the second illumination is performed. After the dark room is left for a period of time, the third illumination is performed, and the sample C can be raised to a saturated blunt in a short time. The value of the sample shows that the sample C has better stability.
  • (2) is deposited by a PECVD apparatus in a thickness of about lOnm E SiO 2 layer surface of the sample, and then grown to a thickness of 65nm boron-doped silicon nitride film, a silicon nitride film in a percentage of about 12% boron atom
  • the deposition temperature is 300 ° C
  • the volume flow ratio of B3 ⁇ 4 to SiH 4 is 15 : 100
  • the flow ratio of 33 ⁇ 4 to 3 is 2: 3
  • the pressure in the reaction chamber is 40 Pa
  • the thickness of the surface of sample F is about 10 nm.
  • SiOJl a 65nm thick boron-doped silicon nitride film is deposited at a deposition temperature of 300 ° C, a volume flow ratio of B 2 ft to Si 3 ⁇ 4 is 15 : 100, and a reaction chamber pressure of 40 Pa;
  • the annealed sample can rapidly rise to a saturation value after a short time (less than 60 min) illumination, unlike the photoinduced attenuation when an undoped silicon nitride passivation film is used ( LID) phenomenon.
  • LID photoinduced attenuation when an undoped silicon nitride passivation film is used
  • the lifetime of the silicon wafer needs to be increased from the value after annealing to the saturation value of about 80 hours.
  • the passivation film of the present invention shows better practical value.
  • the sample E has a significantly lower reflectance than the sample F, and the battery efficiency after saturation under illumination is increased by 0.41%, thus indicating multilayer passivation of a boron-doped silicon nitride dielectric passivation film.
  • the film has anti-reflection effect, which can effectively achieve lower surface reflection, enabling more sunlight to enter the solar cell for photoelectric conversion.
  • Example 4 After the first illumination, it rises to the saturated passivation value for a short time. After the dark room is left for a period of time, the second illumination is performed. After the dark chamber is left for a period of time, the third illumination is performed. The sample E can be raised to a saturated blunt in a short time. The value of the sample E shows that the sample E has better stability.
  • Example 4
  • a phosphorus-doped silicon nitride film with a thickness of about 50 nm is deposited on the surface of the sample G by a PECVD apparatus.
  • the percentage of phosphorus atoms in the silicon nitride film is about 5%, and the deposition temperature is 300 ° C.
  • the volumetric flow ratio to 51 is 10:100, the flow ratio of Si to N3 ⁇ 4 is 2:3, and the pressure in the reaction chamber is 30Pa;
  • An aluminum oxide film having a thickness of about 35 nm is deposited on the surface of the sample H by an ALD apparatus;
  • sample G is annealed at 300 ° C for 10 min in a nitrogen atmosphere to measure the life of the minority carrier
  • the annealed sample G can quickly rise to a saturation value after a short time (less than 60 min) illumination, and the sample H takes a longer time to reach saturation (greater than 60 min).
  • the efficiency of the sample G and the sample H is higher than that of the non-passivation film on the back side, and the degree of improvement is basically the same, indicating that the phosphorus-doped silicon nitride can passivate the p-type silicon surface well, which is almost identical to that of the aluminum oxide. effect.

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Abstract

L'invention concerne un film passif diélectrique de surface convenant à des matériaux à base de silicium. Le film passif diélectrique est un film passif diélectrique à nitrure de silicium situé sur la surface du matériau à base de silicium, le film passif contenant des éléments dopants sélectionnés dans le groupe comprenant : des éléments dopants donnant de l'électronégativité au film passif diélectrique à nitrure de silicium, des éléments dopants donnant de l'électropositivité au film passif diélectrique à nitrure de silicium, ou des combinaisons des deux. D'une part le film passif diélectrique de surface est contrôlable en ce qui concerne la quantité d'électricité et la propriété électrique, et il est excellent pour l'effet de passivation de champ, et d'autre part il peut renforcer l'effet de passivation au moyen d'un éclairage, de sorte que l'on peut atteindre une valeur de passivation saturée au moyen d'un éclairage dans une courte période de temps. L'invention concerne en outre un substrat en silicium revêtu d'un film et une cellule solaire contenant le film passif diélectrique de surface, ainsi qu'un procédé de préparation associé.
PCT/CN2014/085612 2013-08-30 2014-08-29 Film passif diélectrique, cellule solaire et procédé de préparation associé WO2015027946A1 (fr)

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CN105470347A (zh) * 2015-12-22 2016-04-06 浙江晶科能源有限公司 一种perc电池的制作方法
CN108417481B (zh) * 2018-03-22 2021-02-23 京东方科技集团股份有限公司 氮化硅介电层的处理方法、薄膜晶体管和显示装置
CN110596917B (zh) * 2019-09-18 2023-04-07 深圳先进技术研究院 一种太赫兹波光控调制器及其制备方法
CN113782638A (zh) * 2021-09-09 2021-12-10 海宁正泰新能源科技有限公司 一种电池背钝化结构及其制作方法、太阳能电池

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