CN117438492A - Heterojunction solar cell, manufacturing method thereof and photovoltaic module - Google Patents

Heterojunction solar cell, manufacturing method thereof and photovoltaic module Download PDF

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Publication number
CN117438492A
CN117438492A CN202210827213.6A CN202210827213A CN117438492A CN 117438492 A CN117438492 A CN 117438492A CN 202210827213 A CN202210827213 A CN 202210827213A CN 117438492 A CN117438492 A CN 117438492A
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transparent conductive
conductive film
film layer
tco
layer
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姚铮
崔巍
黄常州
吴坚
蒋方丹
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CSI Cells Co Ltd
Jiaxing Canadian Solar Technology Research Institute
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Jiaxing Canadian Solar Technology Research Institute
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Abstract

The invention provides a heterojunction solar cell, a manufacturing method thereof and a photovoltaic module, wherein the heterojunction solar cell comprises an n-type semiconductor substrate, a first intrinsic crystal layer, a second intrinsic crystal layer, an n-type doped crystal layer, a p-type doped crystal layer and a first transparent conductive film layer, wherein the doping concentration of the n-type doped crystal layer is more than or equal to 1e19/cm 3 The first transparent conductive film layer comprises at least two TCO films with gradually increased carrier concentration from inside to outside, wherein the innermost TThe carrier concentration of the CO film is 0.2e20-1.5e20/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the According to the invention, the n-type doped crystal layer with high doping concentration is arranged, so that the carrier concentration requirement in the first transparent conductive film layer can be reduced, and the carrier concentration of the innermost TCO film can be lower than the conventional range, thereby being beneficial to further improvement of optical properties, increasing the expression of Isc and finally improving the conversion efficiency of the solar cell.

Description

Heterojunction solar cell, manufacturing method thereof and photovoltaic module
Technical Field
The invention belongs to the field of photovoltaics, and relates to a heterojunction solar cell, a manufacturing method thereof and a photovoltaic module.
Background
Heterojunction solar cells are attracting attention as next-generation more efficient crystalline silicon solar cells, which combine the characteristics of crystalline silicon cells and silicon-based thin film cells, and have the advantages of short manufacturing process, low process temperature, high conversion efficiency, more generated energy and the like, and because the heterojunction solar cells have small temperature degradation coefficient and double-sided power generation, the annual generated energy can be 15-30% higher than that of common polycrystalline silicon cells under the same area, so that the heterojunction solar cells have great market potential.
The heterojunction solar cell generally comprises a first collector electrode, a first transparent conductive film layer, a first amorphous doped layer, a first intrinsic doped amorphous layer, a monocrystalline silicon substrate, a second intrinsic amorphous layer, a second doped amorphous layer, a second transparent conductive film layer and a second collector electrode which are sequentially arranged from top to bottom. Among them, the electrical and optical properties of a transparent conductive film layer formed of a Transparent Conductive Oxide (TCO) have a great influence on the efficiency of the heterojunction solar cell.
The low-doped transparent conductive film layer has better optical absorption performance, but has poorer conductivity, and can limit the further improvement of the electrical performance of the heterojunction solar cell; the highly doped transparent conductive film layer has better electrical property and high conductivity, but has poorer light transmittance, and can influence the Isc (short-circuit current) of the heterojunction solar cell; therefore, the transparent conductive film layer needs to be structurally designed to achieve the best balance. In addition, the low-doped transparent conductive film layer has poor matching property with the amorphous silicon layer and the electrode slurry, so that the contact resistivity between the transparent conductive film layer and the amorphous silicon layer and between the transparent conductive film layer and the electrode is higher, therefore, in the prior art, the concentration of carriers is generally further improved only at the contact part of the amorphous silicon layer and the electrode, a TCO layer with higher carrier concentration than that in the conventional transparent conductive film layer is formed, and the thickness of the layers is required to be ensured to be smaller, so that the optical absorption is not influenced, and serious Isc loss is caused. For example, CN114242805a discloses a laminated TCO film, in which the first TCO film layer and the third TCO film layer are set as ITO film layers, and the second TCO film layer located between the first and third TCO film layers is set as ICO or IWO film layers, so that the carrier concentration of the second TCO film layer of the intermediate body is reduced, and the mobility is improved, thereby reducing optical loss to some extent.
Along with the introduction of the microcrystalline technology in the solar cell, the doping concentration of the microcrystalline silicon layer is gradually increased, so that the requirement for the carrier concentration in the TCO layer in direct contact with the microcrystalline silicon layer is reduced, the carrier concentration of the transparent conductive film layer in the prior art can be newly adjusted and optimized, a wider optical window is further obtained under the same electrical contact condition, the optical performance is enhanced, and a new path is provided for developing a novel solar cell with higher efficiency.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a heterojunction solar cell, a manufacturing method thereof and a photovoltaic module, wherein the heterojunction solar cell comprises an n-type semiconductor substrate, a first intrinsic crystal layer, an n-type doped crystal layer, a first transparent conductive film layer, a second intrinsic crystal layer, a p-type doped crystal layer and a second transparent conductive film layer, wherein the doping concentration of the n-type doped crystal layer is greater than or equal to 1e19/cm 3 The first transparent conductive film layer comprises at least two TCO films attached to the surface of the n-type doped crystal layer, wherein the carrier concentration of the innermost TCO film is 0.2e20-1.5e20/cm 3 And less than the carrier concentration of the outermost TCO film; the invention can reduce the carrier concentration requirement in the first transparent conductive film layer by arranging the n-type doped crystal layer with high doping concentration, so that the carrier concentration of the innermost TCO film can be adjusted to be lower than the conventional range, thereby being beneficial to further improvement of optical properties, increasing the performance of the Isc and finally improving the performance of the IscConversion efficiency of solar cells.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a heterojunction solar cell, which comprises an n-type semiconductor substrate, a first intrinsic crystal layer, an n-type doped crystal layer, a first transparent conductive film layer and a first collector electrode, which are sequentially stacked from inside to outside on a first main surface of the n-type semiconductor substrate, and a second intrinsic crystal layer, a p-type doped crystal layer, a second transparent conductive film layer and a second collector electrode, which are sequentially stacked from inside to outside on a second main surface of the n-type semiconductor substrate;
the first transparent conductive film layer comprises at least two TCO films which are sequentially laminated from inside to outside, and the carrier concentration of the TCO films is sequentially increased from inside to outside; the doping concentration of the n-type doped crystal layer is more than or equal to 1e19/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The carrier concentration of the innermost TCO film in the first transparent conductive film layer is 0.2e20-1.5e20/cm 3 。
The invention sets the n-type doped crystal layer to be more than or equal to 1e19/cm 3 The carrier concentration requirement of the transparent conductive film layer in contact with the high doping concentration of (a) can be reduced, and further, when the n-type doped crystal layer is microcrystalline silicon, the doping concentration is preferably 1e20/cm or more 3 The method comprises the steps of carrying out a first treatment on the surface of the The structural integrity of microcrystalline silicon is improved compared with amorphous silicon, so that the effective doping concentration of microcrystalline is greatly improved compared with the carrier concentration of amorphous silicon in the same doping process atmosphere, and the effective doping concentration of a doped crystal layer is further improved by one to two orders of magnitude along with the microcrystallization upgrading of industrial equipment. The doping concentration in the non/microcrystalline silicon layer is increased, so that the work function of the doped crystal layer can be effectively reduced, and the tunneling of the minority carrier thermally excited mode is facilitated; meanwhile, the defect concentration of the doped crystal layer side in the doped crystal layer/TCO contact surface is increased due to the increase of the doping concentration, which is favorable for the tunneling (TAT) of a minority carrier defect auxiliary mode, the two effects are further favorable for the improvement of the contact condition, and the carrier concentration of the TCO film layer can be contacted with the microcrystal on the premise of the same contact resistivityCompared with the amorphous contact requirement, the first transparent conductive film layer is divided into at least two layers of TCO films, the carrier concentration of the innermost TCO film in contact with the n-type doped crystal layer is reduced, the carrier concentration is lower than the carrier concentration range conventional in the prior art, the optical performance can be greatly enhanced on the premise of ensuring the electrical performance, and the device can generate larger Isc by effectively absorbing and utilizing more light energy, so that the final conversion efficiency is improved.
It should be noted that the carrier concentration of the innermost TCO film in the first transparent conductive film layer is 0.2e20-1.5e20/cm 3 For example 0.2e20/cm 3 、0.3e20/cm 3 、0.4e20/cm 3 、0.5e20/cm 3 、0.6e20/cm 3 、0.7e20/cm 3 、0.8e20/cm 3 、0.9e20/cm 3 、1e20/cm 3 、1.1e20/cm 3 、1.2e20/cm 3 、1.3e20/cm 3 、1.4e20/cm 3 Or 1.5e20/cm 3 And the like, but are not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, the first intrinsic crystal layer, the n-type doped crystal layer, the second intrinsic crystal layer and the p-type doped crystal layer are all amorphous semiconductors and/or microcrystalline semiconductors.
As a preferable technical scheme of the invention, the first transparent conductive film layer and the second transparent conductive film layer both comprise indium oxide and/or zinc oxide, and further comprise doped oxide.
Preferably, the doped oxide comprises any one or a combination of at least two of tin oxide, gallium oxide, aluminum oxide, tungsten oxide, titanium oxide, zirconium oxide, or molybdenum oxide, typical but non-limiting examples of which include a combination of tin oxide and gallium oxide, a combination of tin oxide and aluminum oxide, a combination of tin oxide and tungsten oxide, a combination of tin oxide and titanium oxide, a combination of tin oxide and zirconium oxide, a combination of tin oxide and molybdenum oxide, a combination of gallium oxide and aluminum oxide, a combination of gallium oxide and tungsten oxide, a combination of gallium oxide and titanium oxide, a combination of gallium oxide and zirconium oxide, a combination of gallium oxide and molybdenum oxide, a combination of aluminum oxide and tungsten oxide, a combination of aluminum oxide and zirconium oxide, a combination of tungsten oxide and titanium oxide, a combination of tungsten oxide and molybdenum oxide, a combination of titanium oxide and zirconium oxide, a combination of titanium oxide and molybdenum oxide, and a combination of zirconium oxide and molybdenum oxide.
Preferably, the mass ratio of the doped oxide in the first transparent conductive film layer is 0.1 to 3%, preferably 3%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8% or 3%, etc., but not limited to the above-mentioned values, and other non-cited values in the above-mentioned value range are equally applicable.
In the first transparent conductive film layer of the present invention, since the first transparent conductive film layer is provided on the first main surface (light receiving surface) of the battery, the first transparent conductive film layer is preferably formed in a low doping form, that is, the mass of the doped oxide is 3% or less, in order to control the carrier concentration range in the first transparent conductive film layer, because the influence on the optical performance is larger than that of the second transparent conductive film layer.
Preferably, the mass ratio of the doped oxide in the second transparent conductive film layer is 8 to 12%, preferably 10%, for example, 8%, 8.2%, 8.4%, 8.6%, 8.8%, 9%, 9.2%, 9.4%, 9.6%, 9.8%, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8% or 12%, etc., but not limited to the above-mentioned values, and other non-cited values in the above-mentioned value ranges are equally applicable.
Preferably, the thickness of each of the first transparent conductive film layer and the second transparent conductive film layer is 50 to 120nm, for example, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, 105nm, 110nm, 115nm, 120nm, or the like, but not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
As a preferable technical scheme of the invention, the carrier concentration of the outermost TCO film in the first transparent conductive film layer is 2e 20-4 e20/cm 3 Preferably 2.5e20 to 3.5e20/cm 3 For example 2e20/cm 3 、2.2e20/cm 3 、2.4e20/cm 3 、2.6e20/cm 3 、2.8e20/cm 3 、3e20/cm 3 、3.2e20/cm 3 、3.4e20/cm 3 、3.6e20/cm 3 、3.8e20/cm 3 Or 4e20/cm 3 And the like, but are not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the carrier concentration of the innermost TCO film in the first transparent conductive film layer is 0.8e20-1.4e20/cm 3 For example 0.8e20/cm 3 、0.9e20/cm 3 、1e20/cm 3 、1.1e20/cm 3 、1.2e20/cm 3 、1.3e20/cm 3 Or 1.4e20/cm 3 And the like, but are not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
In a preferred embodiment of the present invention, the thickness of the innermost TCO film in the first transparent conductive film layer is 30 to 35nm, for example, 30nm, 30.5nm, 31nm, 31.5nm, 32nm, 32.5nm, 33nm, 33.5nm, 34nm, 34.5nm or 35nm, etc., but not limited to the values listed, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the thickness of the outermost TCO film in the first transparent conductive film layer is 35 to 40nm, for example 35nm, 35.5nm, 36nm, 36.5nm, 37nm, 37.5nm, 38nm, 38.5nm, 39nm, 39.5nm or 40nm, etc., but not limited to the values listed, and other values not listed in the above-mentioned value ranges are equally applicable.
As a preferable technical scheme of the invention, the second transparent conductive film layer comprises at least two layers of TCO films which are sequentially laminated from inside to outside.
Preferably, the carrier concentration of the TCO film in the second transparent conductive film layer increases sequentially from inside to outside.
Preferably, the carrier concentration of the innermost TCO film in the second transparent conductive film layer is 0.2e20-1.5e20/cm 3 Preferably 0.3e20 to 0.7e20/cm 3 For example 0.2e20/cm 3 、0.3e20/cm 3 、0.4e20/cm 3 、0.5e20/cm 3 、0.6e20/cm 3 、0.7e20/cm 3 、0.8e20/cm 3 、0.9e20/cm 3 、1e20/cm 3 、1.1e20/cm 3 、1.2e20/cm 3 、1.3e20/cm 3 、1.4e20/cm 3 Or 1.5e20/cm 3 And the like, but are not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the carrier concentration of the outermost TCO film in the second transparent conductive film layer is 2e 20-4 e20/cm 3 Preferably 2.5e20 to 3.5e20/cm 3 For example 2e20/cm 3 、2.2e20/cm 3 、2.4e20/cm 3 、2.6e20/cm 3 、2.8e20/cm 3 、3e20/cm 3 、3.2e20/cm 3 、3.4e20/cm 3 、3.6e20/cm 3 、3.8e20/cm 3 Or 4e20/cm 3 And the like, but are not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the thickness of the innermost TCO film in the second transparent conductive film layer is 30 to 35nm, for example, 30nm, 30.5nm, 31nm, 31.5nm, 32nm, 32.5nm, 33nm, 33.5nm, 34nm, 34.5nm or 35nm, etc., but not limited to the values listed, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the thickness of the outermost TCO film in the second transparent conductive film layer is 35 to 40nm, for example 35nm, 35.5nm, 36nm, 36.5nm, 37nm, 37.5nm, 38nm, 38.5nm, 39nm, 39.5nm or 40nm, but not limited to the listed values, and other non-listed values within the above-mentioned range are equally applicable.
In a second aspect, the present invention provides a method for manufacturing the heterojunction solar cell according to the first aspect, the method comprising the following steps:
(1) Preparing an n-type semiconductor substrate and cleaning and texturing;
(2) Sequentially manufacturing a first intrinsic crystal layer and an n-type doped crystal layer on one side of a first main surface of the n-type semiconductor substrate obtained in the step (1); a second intrinsic crystal layer and a p-type doped crystal layer are sequentially arranged on one side of a second main surface of the n-type semiconductor substrate, so that the doping concentration of the n-type doped crystal layer is more than or equal to 1e19/cm 3 ；
(3) Plating a film on the surface of the n-type doped crystal layer obtained in the step (2) to obtain a first transparent conductive film layer, wherein the first transparent conductive film layer comprises at least two TCO films which are sequentially laminated from inside to outside, and the carrier concentration of the TCO films is sequentially increased from inside to outside; controlling the carrier concentration of the innermost TCO film in the first transparent conductive film layer to be 0.2e20-1.5e20/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Plating a film on the surface of the p-type doped crystal layer obtained in the step (2) to obtain a second transparent conductive film layer;
(4) And (3) printing electrodes on the first transparent conductive film layer and the second transparent conductive film layer respectively to form a first collecting electrode and a second collecting electrode, so as to obtain the heterojunction solar cell.
In the step (3) of the manufacturing method, the second transparent conductive film layer includes at least two TCO films sequentially stacked from inside to outside in the step (3) of the manufacturing method.
Preferably, the carrier concentration of the TCO film in the second transparent conductive film layer is controlled to increase sequentially from inside to outside.
Preferably, the carrier concentration of the innermost TCO film in the second transparent conductive film layer is controlled to be 0.2e20-1.5e20/cm 3 。
According to the manufacturing method, the carrier concentration of the first transparent conductive film layer and the carrier concentration of the second transparent conductive film layer are adjusted by controlling the oxygen atmosphere parameter and/or the pressure parameter.
The step (3) of the manufacturing method is preferably performed in equipment provided with a plurality of targets, and the targets respectively correspond to the TCO film to be manufactured, so that different targets respectively corresponding to each other can be arranged, the product can be sequentially manufactured layer by layer through the targets, and the oxygen atmosphere parameter and/or the pressure parameter are/is adjusted at each target, so that the carrier concentration of the corresponding TCO layer is effectively regulated and controlled.
Preferably, the volume ratio of oxygen to the innermost TCO film in the first transparent conductive film layer is 5 to 8%, for example, 5%, 5.2%, 5.4%, 5.6%, 5.8%, 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8% or 8%, etc., but not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the pressure of the innermost TCO film in the first transparent conductive film layer is 0.6 to 0.9Pa, for example, 0.6Pa, 0.63Pa, 0.66Pa, 0.69Pa, 0.72Pa, 0.75Pa, 0.78Pa, 0.81Pa, 0.84Pa, 0.87Pa, or 0.9Pa, etc., but not limited to the listed values, and other values not listed in the above-mentioned value ranges are equally applicable.
According to the invention, carrier concentration adjustment in the transparent conductive film is realized by adjusting oxygen atmosphere parameters such as oxygen volume ratio and environmental pressure in a film coating process, in the first and second transparent conductive film layers, the oxygen ratio required by the inner TCO film is higher than that required by the outer TCO film, the flow rate is higher, the pressure is higher, the oxygen ratio is in a high oxygen ratio state when the oxygen ratio is more than or equal to 4%, the pressure is in a high pressure state when the pressure is more than or equal to 0.6Pa, and interface passivation between the TCO film prepared in the high pressure state and the doped crystal layer is improved, so that the pressure for preparing the innermost TCO film in the first transparent conductive film layer is set to be 0.6-0.9 Pa, and the improvement of the efficiency of the battery can be further ensured.
Preferably, the volume ratio of oxygen to the outermost TCO film in the first transparent conductive film layer is 2.5 to 4.5%, for example, 2.5%, 2.7%, 2.9%, 3.1%, 3.3%, 3.5%, 3.7%, 3.9%, 4.1%, 4.3%, or 4.5%, etc., but not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
Preferably, the pressure of the outermost TCO film in the first transparent conductive film layer is 0.4 to 0.7Pa, for example, 0.4Pa, 0.43Pa, 0.46Pa, 0.49Pa, 0.52Pa, 0.55Pa, 0.58Pa, 0.61Pa, 0.64Pa, 0.67Pa, or 0.7Pa, etc., but not limited to the listed values, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the volume ratio of oxygen to the innermost TCO film in the second transparent conductive film layer is 6 to 8%, for example 6%, 6.2%, 6.4%, 6.6%, 6.8%, 7%, 7.2%, 7.4%, 7.6%, 7.8% or 8%, etc., but not limited to the values listed, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the pressure of the innermost TCO film in the second transparent conductive film layer is 0.7 to 0.9Pa, for example, 0.7Pa, 0.72Pa, 0.74Pa, 0.76Pa, 0.78Pa, 0.8Pa, 0.82Pa, 0.84Pa, 0.86Pa, 0.88Pa, or 0.9Pa, etc., but not limited to the listed values, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the volume ratio of oxygen to the outermost TCO film in the second transparent conductive film layer is 3 to 5%, for example, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, or 5%, etc., but not limited to the recited values, and other non-recited values within the above-mentioned ranges are equally applicable.
Preferably, the pressure of the outermost TCO film in the second transparent conductive film layer is 0.3 to 0.6Pa, for example, 0.3Pa, 0.33Pa, 0.36Pa, 0.39Pa, 0.42Pa, 0.45Pa, 0.48Pa, 0.51Pa, 0.54Pa, 0.57Pa, or 0.6Pa, etc., but not limited to the listed values, and other values not listed in the above-mentioned value ranges are equally applicable.
To describe the fabrication method of the present invention in more detail, the present invention shows a preferred fabrication method of the heterojunction solar cell by the following steps:
(1) Preparing an n-type monocrystalline silicon wafer with resistivity of 0.5-3 omega cm, thickness of 150-200 mu m and size of 156.75cm as an n-type semiconductor substrate; firstly, removing an oxide layer on the surface of the n-type semiconductor substrate by using a 5% HF solution, and then forming shallower pyramid structures on the two side surfaces of the n-type semiconductor substrate by using KOH and/or NaOH or adopting a tetramethyl ammonium hydroxide (TMAH) alcohol adding method;
(2) SiH is then added to 4 (silane) gas is introduced into the vacuum chamber, and a first intrinsic crystal layer is formed on the whole area of the first main surface of the n-type semiconductor substrate by PECVD, and SiH is then introduced 4 Gas, H 2 Gas and PH 3 (phosphine) gas is introduced into a vacuum chamber, and an n-type doped crystal layer is formed on the first intrinsic crystal layer through PECVD; the n-type semiconductor substrate is then flipped over, palletized, and SiH is then applied 4 Introducing a gas into the vacuum chamber and forming a second intrinsic crystal layer on the whole region of the second main surface of the substrate by PECVD, and then SiH 4 Gas, H 2 Gas and B 2 H 6 Introducing diborane gas into a vacuum chamber, and forming a p-type doped crystal layer on the second intrinsic crystal layer by PECVD to obtain a first matrix;
(3) Placing the first substrate obtained in the step (2) in PVD (physical vapor deposition) mass production equipment such as Reactive Plasma Deposition (RPD) or magnetron sputtering, wherein the PVD mass production equipment has at least 2 non-pollution coating targets, and different targets are arranged on the targets; the first substrate is loaded on a carrier plate, the carrier plate is of a hollowed-out flat plate design, and a convex edge with the thickness of about 0.6-0.8 mm exists at the edge of the hollowed-out part so as to support the first substrate and expose a region capable of being coated with a film; bombarding phases in the target material by using certain energy, and simultaneously introducing argon, oxygen and hydrogen to enable the first substrate to sequentially undergo different target positions for coating and obtain a required film design;
namely, forming at least two TCO films sequentially laminated from inside to outside on the surface of the n-type doped crystal layer in the step (2) to obtain a first transparent conductive film layer; forming a second transparent conductive film layer on the surface of the p-type doped crystal layer in the step (2); simultaneously, adjusting oxygen atmosphere parameters and/or pressure parameters under different target positions, wherein the volume ratio of oxygen for manufacturing the innermost TCO film in the first transparent conductive film layer is 5-8%, and the ambient pressure is 0.6-0.9 Pa, so that the carrier concentration of the innermost TCO film in the first transparent conductive film layer is 0.2e20%1.5e20/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Similarly, adjusting oxygen atmosphere parameters and/or pressure parameters to control carrier concentration in each TCO film layer to be adjusted to a required concentration range, and enabling the carrier concentration of the TCO film in the first transparent conductive film layer to be sequentially increased from inside to outside to obtain a second substrate;
(4) Printing a layer of low-temperature conductive silver paste on the first transparent conductive film layer and the second transparent conductive film layer of the second substrate obtained in the step (3) by using a screen printing method, and then sintering at a low temperature of 150-300 ℃ to respectively form a first collecting electrode and a second collecting electrode with good ohmic contact, so as to obtain the heterojunction solar cell.
In a third aspect, the present invention provides a photovoltaic module, where the photovoltaic module includes the heterojunction solar cell of the first aspect or includes the heterojunction solar cell obtained by the manufacturing method of the second aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the invention, the n-type doped crystal layer with high doping concentration is arranged, so that the carrier concentration requirement in the first transparent conductive film layer is reduced, the carrier concentration of the innermost TCO film is adjusted to be lower than the range conventionally used in the prior art, the further improvement of optical properties is facilitated, the performance of Isc is increased, and meanwhile, the coating film under a high-pressure process is beneficial to the improvement of interface passivation between the innermost TCO film and the doped crystal layer, so that the conversion efficiency of the heterojunction solar cell obtained by the invention is effectively improved by the improvement.
Drawings
Fig. 1 is a schematic structural diagram of a heterojunction solar cell according to embodiment 1 of the present invention;
fig. 2 is a schematic structural diagram of a heterojunction solar cell according to embodiment 2 of the present invention;
fig. 3 is a schematic structural view of a heterojunction solar cell obtained in comparative example 3 of the present invention;
in the figure: 1-n type semiconductor substrate, 21-first intrinsic crystal layer, 22-second intrinsic crystal layer, 31-n type doped crystal layer, 32-p type doped crystal layer, 41-first transparent conductive film layer, 411-first TCO film, 412-second TCO film, 42-second transparent conductive film layer, 421-third TCO film, 422-fourth TCO film, 51-first collector, 52 second collector.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a heterojunction solar cell, whose schematic structural diagram is shown in fig. 1, wherein the heterojunction solar cell comprises an n-type semiconductor substrate 1, a first intrinsic crystal layer 21, an n-type doped crystal layer 31, a first transparent conductive film layer 41 and a first collector electrode 51, which are sequentially stacked from inside to outside on a first main surface of the n-type semiconductor substrate 1, and a second intrinsic crystal layer 22, a p-type doped crystal layer 32, a second transparent conductive film layer 42 and a second collector electrode 52, which are sequentially stacked from inside to outside on a second main surface of the n-type semiconductor substrate 1;
the first and second intrinsic crystal layers 21 and 22, the n-type doped crystal layer 31 and the p-type doped crystal layer 32 are microcrystalline semiconductor materials; the thicknesses of the first intrinsic crystal layer 21 and the second intrinsic crystal layer 22 are 5+/-2 nm and 7+/-2 nm respectively; the thicknesses of the n-type doped crystal layer 31 and the p-type doped crystal layer 32 are respectively 7+ -2 nm and 9+ -2 nm, and the doping concentrations are respectively 3+ -1 e20/cm 3 4+ -1 e20/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The first collector 51 and the second collector 52 are both silver;
the first transparent conductive film layer 41 is ITO, the mass ratio of doped oxide SnO is 3%, the thickness is 70nm, the first transparent conductive film layer 41 includes a first TCO film 411 and a second TCO film 412 which are sequentially stacked from inside to outside, the first TCO film 411 is the innermost TCO film, and is in direct contact with the n-type doped crystal layer 31; the carrier concentration of the first TCO film 411 is 0.8e20-1.4e20/cm 3 The thickness is 33nm; the second TCO film 412 is the outermost TCO film, and has a carrier concentration of 2.5e20-3.5e20/cm 3 The thickness is 37nm;
the second transparent conductive film layer 42 is ITO, the mass ratio of doped oxide SnO is 10%, the thickness is 75nm, the carrier concentration of the second transparent conductive film layer 42 is 2.5-3.5e20/cm 3 。
Example 2
The present embodiment provides a heterojunction solar cell, whose schematic structural diagram is shown in fig. 2, wherein the heterojunction solar cell comprises an n-type semiconductor substrate 1, a first intrinsic crystal layer 21, an n-type doped crystal layer 31, a first transparent conductive film layer 41 and a first collector electrode 51, which are sequentially stacked from inside to outside on a first main surface of the n-type semiconductor substrate 1, and a second intrinsic crystal layer 22, a p-type doped crystal layer 32, a second transparent conductive film layer 42 and a second collector electrode 52, which are sequentially stacked from inside to outside on a second main surface of the n-type semiconductor substrate 1;
the first and second intrinsic crystal layers 21 and 22, the n-type doped crystal layer 31 and the p-type doped crystal layer 32 are microcrystalline semiconductor materials; the thicknesses of the first intrinsic crystal layer 21 and the second intrinsic crystal layer 22 are 5+/-2 nm and 7+/-2 nm respectively; the thicknesses of the n-type doped crystal layer 31 and the p-type doped crystal layer 32 are respectively 7+ -2 nm and 9+ -2 nm, and the doping concentrations are respectively 3+ -1 e20/cm 3 4+ -1 e20/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The first collector 51 and the second collector 52 are both silver;
the first transparent conductive film layer 41 is ITO, the mass ratio of doped oxide SnO is 3%, the thickness is 70nm, the first transparent conductive film layer 41 includes a first TCO film 411 and a second TCO film 412 which are sequentially stacked from inside to outside, and the first TCO film 411 is the innermost TCO film and is in direct contact with the n-type doped crystal layer 31; the carrier concentration of the first TCO film 411 is 0.8e20-1.4e20/cm 3 The thickness is 33nm; the second TCO film 412 is the outermost TCO film, and has a carrier concentration of 2.5e20-3.5e20/cm 3 The thickness is 37nm;
the second transparent conductive film layer 42 is ITO, the mass ratio of doped oxide SnO is 10%, the thickness is 75nm, the second transparent conductive film layer 42 comprises a third TCO film 421 and a fourth TCO film 422 which are sequentially laminated from inside to outside, the third TCO film 421 isAn innermost TCO film and in direct contact with the p-doped crystalline layer 32; the carrier concentration of the third TCO film 421 is 0.3e20-0.7e20/cm 3 The thickness is 35nm; the fourth TCO film 422 is the outermost TCO film, and the carrier concentration is 2.5e20-3.5e20/cm 3 The thickness was 40nm.
Example 3
The embodiment provides a heterojunction solar cell, wherein the doping concentration of the n-type doped crystal layer is 3+ -1 e20/cm 3 Adjusted to 3+/-1 e19/cm 3 Other conditions were the same as in example 1.
Example 4
The embodiment provides a heterojunction solar cell, wherein the n-type doped crystal layer and the p-type doped crystal layer are adjusted from microcrystalline semiconductor material to amorphous semiconductor material, and the doping concentration of the n-type doped crystal layer is 3+ -1 e20/cm 3 Adjust to 3+ -1 e19/cm 3 The doping concentration of the p-type doped crystal layer is changed from 4+/-1 e20/cm 3 Adjust to 4+/-1 e19/cm 3 Other conditions were the same as in example 1.
Comparative example 1
The present comparative example provides a heterojunction solar cell in which the carrier concentration of the first TCO film is in the range of 0.8e20 to 1.4e20/cm 3 Is regulated to be 1.8e20-2.4e20/cm 3 Other conditions were the same as in example 1.
Comparative example 2
The present comparative example provides a heterojunction solar cell in which the carrier concentration of the first TCO film is in the range of 0.8e20 to 1.4e20/cm 3 Is regulated to be 1.8e20-2.4e20/cm 3 Other conditions were the same as in example 4.
Comparative example 3
The present comparative example provides a heterojunction solar cell, the structure of which is schematically shown in fig. 3, the heterojunction solar cell comprises an n-type semiconductor substrate 1, a first intrinsic crystal layer 21, an n-type doped crystal layer 31, a first transparent conductive film layer 41 and a first collector electrode 51 which are sequentially stacked from inside to outside on a first main surface of the n-type semiconductor substrate 1, and a second intrinsic crystal layer 22, a p-type doped crystal layer 32, a second transparent conductive film layer 42 and a second collector electrode 52 which are sequentially stacked from inside to outside on a second main surface of the n-type semiconductor substrate 1;
the first and second intrinsic crystal layers 21 and 22, the n-type doped crystal layer 31 and the p-type doped crystal layer 32 are microcrystalline semiconductor materials; the thicknesses of the first intrinsic crystal layer 21 and the second intrinsic crystal layer 22 are 5+/-2 nm and 7+/-2 nm respectively; the thicknesses of the n-type doped crystal layer 31 and the p-type doped crystal layer 32 are respectively 7+ -2 nm and 9+ -2 nm, and the doping concentrations are respectively 3+ -1 e20/cm 3 4+ -1 e20/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The first collector 51 and the second collector 52 are both silver;
the first transparent conductive film layer 41 is ITO, the mass ratio of doped oxide SnO is 3%, the thickness is 70nm, the carrier concentration of the first transparent conductive film layer 41 is 2.5e20-3.5e20/cm 3 ；
The second transparent conductive film layer 42 is ITO, the mass ratio of doped oxide SnO is 10%, the thickness is 75nm, the carrier concentration of the second transparent conductive film layer 42 is 2.5-3.5e20/cm 3 。
Heterojunction solar cells obtained in examples and comparative examples were tested and the results are shown in table 1.
TABLE 1
Note that: the (BL) in Table 1 shows the amounts of change in each of the examples and comparative examples shown in parentheses on the basis of the values obtained in comparative example 3.
As can be seen from Table 1, comparing example 1 with comparative example 3, example 1 resulted in a first transparent conductorThe film layer is divided into a first TCO film at the innermost side and a second TCO film at the outermost side, and the carrier concentration of the first TCO film is reduced to 0.8e20-1.4e20/cm 3 Carrier concentrations 2.5e20 to 3.5e20/cm lower than those of the first transparent conductive film layer in comparative example 3 3 Further optical gain can be effectively obtained, so that Isc is increased, meanwhile, due to the introduction of a high-pressure process, the interface passivation of the first TCO film and the n-type doped crystal layer is improved, FF and Voc are improved, and the efficiency of the battery obtained in the final embodiment 1 is 0.05% higher than that of the battery obtained in the comparative embodiment 3;
comparing example 1 with comparative example 1, it was found that in the case of the same structure, although the carrier concentration of the first TCO film in comparative example 1 was still lower than that of the second TCO film, the absolute concentration value was 1.8e20 to 2.4e20/cm 3 The carrier concentration difference between the film and the second TCO film is reduced compared with the embodiment 1, so that the optical gain is smaller than that of the embodiment 1 compared with the embodiment 3, the FF is slightly improved by only 5mA, and the Eff is 0.03% compared with the embodiment 3;
comparing example 1 with example 3, it was found that in the case of the same structure, the n-type doped crystal layer in example 3 is of a conventional doping concentration, so that the concentration requirement of the carriers in the first transparent conductive film layer cannot be reduced, and at this time, the carrier concentration of the first TCO film is reduced, resulting in an increase in contact resistivity between the first transparent conductive film layer and the n-type doped crystal layer, and a significant increase in Rs, which is reduced by 0.2% compared with the efficiency of example 1;
comparing example 2 with example 1 and comparative example 3, it was found that example 2 further reduced the carrier concentration of the third TCO film to 0.3e20 to 0.7e20/cm while the second transparent conductive film layer was composed of the innermost third TCO film and the outermost fourth TCO film 3 Therefore, the overall optical performance of the device is further enhanced, and the interface passivation between the third TCO film and the p-type doped crystal layer is optimized, so that various performances and efficiency are further improved, and compared with comparative example 3, the efficiency obtained in example 2 is increased by 0.08%;
comparing example 4 with comparative example 2, it was found that when the doped crystalline layer is an amorphous doped layer, the reduction in doping concentration of the first TCO film still has a gain effect on the optical Isc, while there is a loss of electrical FF, the combined effect is that the optical gain is greater than the electrical loss, so that an improvement of 0.05% in efficiency of example 4 is obtained compared to comparative example 2.
From the analysis and comparison, the n-type doped crystal layer with high doping concentration can reduce the carrier concentration requirement in the conductive transparent conductive film layer, so that the carrier concentration of the innermost TCO film can be adjusted to be lower than the conventional range, the further improvement of the optical property is facilitated, the performance of the Isc is increased, and the conversion efficiency of the solar cell is finally improved.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Furthermore, any combination of the various embodiments of the invention is possible, as long as it does not violate the idea of the invention on the second main face, which is also to be regarded as the disclosure of the invention.

Claims (10)

1. The heterojunction solar cell is characterized by comprising an n-type semiconductor substrate, a first intrinsic crystal layer, an n-type doped crystal layer, a first transparent conductive film layer and a first collector electrode, which are sequentially stacked from inside to outside on a first main surface of the n-type semiconductor substrate, and a second intrinsic crystal layer, a p-type doped crystal layer, a second transparent conductive film layer and a second collector electrode, which are sequentially stacked from inside to outside on a second main surface of the n-type semiconductor substrate;
the first transparent conductive film layer comprises at least two TCO films which are sequentially laminated from inside to outside, and the carrier concentration of the TCO films is sequentially increased from inside to outside; the doping concentration of the n-type doped crystal layer is more than or equal to 1e19/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The carrier concentration of the innermost TCO film in the first transparent conductive film layer is 0.2e20-1.5e20/cm 3 。
2. The heterojunction solar cell of claim 1, wherein the first intrinsic crystalline layer, the n-type doped crystalline layer, the second intrinsic crystalline layer, and the p-type doped crystalline layer are all amorphous semiconductors and/or microcrystalline semiconductors.
3. The heterojunction solar cell of claim 1 or 2, wherein the first transparent conductive film layer and the second transparent conductive film layer each comprise indium oxide and/or zinc oxide, further comprising a doped oxide;
preferably, the doped oxide comprises any one or a combination of at least two of tin oxide, gallium oxide, aluminum oxide, tungsten oxide, titanium oxide, zirconium oxide or molybdenum oxide;
preferably, the mass ratio of the doped oxide in the first transparent conductive film layer is 0.1-3%, preferably 3%;
preferably, the mass ratio of the doped oxide in the second transparent conductive film layer is 8-12%, preferably 10%;
preferably, the thickness of the first transparent conductive film layer and the second transparent conductive film layer is 50-120 nm.
4. According to any of claims 1-3The heterojunction solar cell of one of the preceding claims, wherein the carrier concentration of the outermost TCO film in the first transparent conductive film layer is 2e 20-4 e20/cm 3 Preferably 2.5e20 to 3.5e20/cm 3 ；
Preferably, the carrier concentration of the innermost TCO film in the first transparent conductive film layer is 0.8e20-1.4e20/cm 3 。
5. The heterojunction solar cell of any one of claims 1 to 4, wherein the thickness of the innermost TCO film in the first transparent conductive film layer is 30 to 35nm;
preferably, the thickness of the outermost TCO film in the first transparent conductive film layer is 35-40 nm.
6. The heterojunction solar cell of any one of claims 1-5, wherein the second transparent conductive film layer comprises at least two TCO films laminated in sequence from inside to outside;
preferably, the carrier concentration of the TCO film in the second transparent conductive film layer increases sequentially from inside to outside;
preferably, the carrier concentration of the innermost TCO film in the second transparent conductive film layer is 0.2e20-1.5e20/cm 3 Preferably 0.3e20 to 0.7e20/cm 3 ；
Preferably, the carrier concentration of the outermost TCO film in the second transparent conductive film layer is 2e 20-4 e20/cm 3 Preferably 2.5e20 to 3.5e20/cm 3 ；
Preferably, the thickness of the innermost TCO film in the second transparent conductive film layer is 30-35 nm;
preferably, the thickness of the outermost TCO film in the second transparent conductive film layer is 35-40 nm.
7. A method of fabricating a heterojunction solar cell as claimed in any one of claims 1 to 6, comprising the steps of:
(1) Preparing an n-type semiconductor substrate and cleaning and texturing;
(2) Sequentially manufacturing a first intrinsic crystal layer and an n-type doped crystal layer on one side of a first main surface of the n-type semiconductor substrate obtained in the step (1); a second intrinsic crystal layer and a p-type doped crystal layer are sequentially arranged on one side of a second main surface of the n-type semiconductor substrate, so that the doping concentration of the n-type doped crystal layer is more than or equal to 1e19/cm 3 ；
(3) Plating a film on the surface of the n-type doped crystal layer obtained in the step (2) to obtain a first transparent conductive film layer, wherein the first transparent conductive film layer comprises at least two TCO films which are sequentially laminated from inside to outside, and the carrier concentration of the TCO films is sequentially increased from inside to outside; controlling the carrier concentration of the innermost TCO film in the first transparent conductive film layer to be 0.2e20-1.5e20/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Plating a film on the surface of the p-type doped crystal layer obtained in the step (2) to obtain a second transparent conductive film layer;
(4) And (3) printing electrodes on the first transparent conductive film layer and the second transparent conductive film layer respectively to form a first collecting electrode and a second collecting electrode, so as to obtain the heterojunction solar cell.
8. The method according to claim 7, wherein in the step (3), the second transparent conductive film layer includes at least two TCO films sequentially stacked from inside to outside;
preferably, the carrier concentration of the TCO film in the second transparent conductive film layer is controlled to increase from inside to outside;
preferably, the carrier concentration of the innermost TCO film in the second transparent conductive film layer is controlled to be 0.2e20-1.5e20/cm 3 。
9. The manufacturing method according to claim 8, wherein the manufacturing method realizes adjustment of carrier concentrations of the first transparent conductive film layer and the second transparent conductive film layer by controlling an oxygen atmosphere parameter and/or a pressure parameter;
preferably, the volume ratio of oxygen for preparing the innermost TCO film in the first transparent conductive film layer is 5-8%;
preferably, the pressure of the innermost TCO film in the first transparent conductive film layer is 0.6Pa to 0.9Pa;
preferably, the volume ratio of oxygen for preparing the outermost TCO film in the first transparent conductive film layer is 2.5-4.5%;
preferably, the pressure of the outermost TCO film in the first transparent conductive film layer is 0.4-0.7 Pa;
preferably, the volume ratio of oxygen for preparing the innermost TCO film in the second transparent conductive film layer is 6-8%;
preferably, the pressure of the innermost TCO film in the second transparent conductive film layer is 0.7Pa to 0.9Pa;
preferably, the volume ratio of oxygen for preparing the outermost TCO film in the second transparent conductive film layer is 3-5%;
preferably, the pressure of the outermost TCO film in the second transparent conductive film layer is made to be 0.3-0.6 Pa.
10. A photovoltaic module comprising the heterojunction solar cell of any one of claims 1-6 or comprising the heterojunction solar cell obtained by the manufacturing method of any one of claims 7-9.
CN202210827213.6A 2022-07-13 2022-07-13 Heterojunction solar cell, manufacturing method thereof and photovoltaic module Pending CN117438492A (en)

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