CN1507075A - Surface structure of monocrystalline silicon solar cell and its making process - Google Patents

Surface structure of monocrystalline silicon solar cell and its making process Download PDF

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CN1507075A
CN1507075A CNA021552363A CN02155236A CN1507075A CN 1507075 A CN1507075 A CN 1507075A CN A021552363 A CNA021552363 A CN A021552363A CN 02155236 A CN02155236 A CN 02155236A CN 1507075 A CN1507075 A CN 1507075A
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pyramid
solar cell
microns
inverted pyramid
silicon solar
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CN100388511C (en
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莫春东
李仲明
张瑶
何少琪
李海滨
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BEIJING LINUOSANGPU PHOTOVOLTAIC HI-TECH Co Ltd
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BEIJING LINUOSANGPU PHOTOVOLTAIC HI-TECH Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The surface structure of monocrystalline silicon solar cell features that the surface of the cell body has turned pyramids and normal pyramid areas comprising several pyramids arranged alternately. The making process of the surface structure includes the following steps: growing 1000-3000 A thick oxide layer on the surface of silicon chip; photoetching the surface of the silica to form required turned pyramid windows; etching the silicon chip to form turned pyramids; removing residual silica; etching the silicon chip to form randomly normal pyramids in the planes between the turned pyramids. The present invention can lower extremely the reflectivity of the surface of solar cell and raise the short-circuit current of the cell, and the present invention may be used widely in industrial production of monocrystalline silicon solar cell.

Description

Surface texture of monocrystaline silicon solar cell and preparation method thereof
Technical field
The present invention relates to a kind of surface structure of solar cell and preparation method thereof, particularly about surface texture of a kind of monocrystaline silicon solar cell that can reduce the solar cell surface reflectivity and preparation method thereof.
Background technology
In the making of solar cell, the reflection loss that reduces battery surface is crucial.In monocrystaline silicon solar cell, the surperficial pyramid structure of general employing, so that light is repeatedly reflected, this structure not only can reduce the reflection of light loss, prolong light path, increase the output of photo-generated carrier, and the pyramid structure on surface can increase the area of pn knot, thereby increase collection rate, improve the short circuit current of battery photo-generated carrier.
The pyramid structure of monocrystalline silicon surface is to utilize the anisotropy of silicon to carry out directional etching to be made, and in general, the density of interplanar covalent bond is high more, and this crystal face is difficult more to be corroded.Because the covalent bond density of " 100 " crystal face is lower than " 111 " crystal face, so " 100 " crystal face is faster than the corrosion rate of " 111 " crystal face.For monocrystalline silicon, select suitable etching condition, the corrosion rate of " 100 " crystal face can be faster more than tens of times than the corrosion rate of " 111 " crystal face.Therefore the anisotropic etch characteristic of the silicon chip of " 100 " crystal face can cause forming on the surface pyramid of " 111 " crystal face.
Make pyramidal method at present and mainly contain two kinds, a kind of is the positive pyramid of making at random 5 (as shown in Figure 1), and another kind is to make inverted pyramid 4 (as shown in Figure 2).
Just pyramidal at random making adopts the mode of chemical corrosion to carry out, the concentration of control reactant liquor, factor such as temperature and reaction time can form the positive tetragonal pyramid (positive pyramid) that differs in size at monocrystalline silicon surface, promptly forms the silicon face (as shown in Figure 1) of matte shape.This manufacture method is widely used in the production of monocrystaline silicon solar cell, and its technology is fairly simple, and cost is low, but because the differing in size of positive tetragonal pyramid, its uniformity is restricted.In addition, when adopting surface passivation in battery is made, the surface passivation at positive tetragonal pyramid top is destroyed easily, influences passivation effect.
The making of inverted pyramid adopts the mode of photoetching and chemical corrosion combination to carry out.After the monocrystalline silicon piece oxidation, carry out photoetching, promptly carve window of the same size, corrode then, form inverted pyramid of the same size (as shown in Figure 2) on the surface of silica.In the manufacturing process of inverted pyramid,, can control the size of distance between inverted pyramid base and inverted pyramid according to designed figure.The surface inverted pyramid structure is to reducing reflection loss, and the effect of protection surface passivation layer is conspicuous, but owing to need carry out photoetching, the technology more complicated, the making of inverted pyramid generally only is used for the laboratory.In addition because the restriction of photoetching process, generally have between inverted pyramid 2~4 microns interplanar every, this interplanar every the surface reflectivity loss be inevitable.
Summary of the invention
At the problems referred to above; it is more consistent to the purpose of this invention is to provide a kind of pyramid size that both can keep; and the protection surface passivation layer, can further reduce reflectivity again, avoid surface texture of the monocrystaline silicon solar cell of reflection loss between inverted pyramid and preparation method thereof.
For achieving the above object, the present invention is by the following technical solutions: a kind of surface texture of monocrystaline silicon solar cell, it comprises battery body, it is characterized in that: the surface at described battery body is provided with inverted pyramid, and the interplanar between the described inverted pyramid is every being provided with the positive pyramid district that some positive pyramids are formed.
The base size of described inverted pyramid is 8~20 microns, and the degree of depth of inverted pyramid is 5.6~14 microns, and the width in described positive pyramid district is 2~8 microns, and just pyramidal size is 2~8 microns.
Size when described inverted pyramid base is 10~15 microns, and the degree of depth of inverted pyramid is 7~10 microns, and the width in described positive pyramid district is 2~4 microns, and is better when just pyramidal size is 2~4 microns.
The manufacture method on a kind of monocrystaline silicon solar cell surface is characterized in that it may further comprise the steps:
(1) generating thickness at silicon chip surface is the oxide layer of 1000~3000 dusts;
(2) carry out photoetching on the surface of silica, form required turned pyramid windows;
(3) silicon chip is corroded, form inverted pyramid;
(4) remove residual oxide layer;
(5) silicon chip is corroded, the interplanar between the inverted pyramid every on form positive pyramid at random.
Wherein in the step (1), generating oxidated layer thickness on the described silicon chip is 1000~2000 Ai Shigengjia.
Wherein in the step (3), the corrosive liquid of corrosion of silicon is the aqueous solution of potassium hydroxide, isopropyl alcohol, and concentration of potassium hydroxide is 5~10%, and isopropyl alcohol concentration is 10~20%, and reaction temperature is 75~90 ℃, and etching time is 10~20 minutes.
Described concentration of potassium hydroxide is 6~8%, and described isopropyl alcohol concentration is 14~18%, and reaction temperature is 80~90 ℃, and 12~18 minutes reaction time is better.
Wherein in the step (5), the corrosive liquid of corrosion of silicon is the aqueous solution of NaOH, isopropyl alcohol, and naoh concentration is 0.5~5%, and isopropyl alcohol concentration is 3~10%, and reaction temperature is 75~90 ℃, and etching time is 10~30 minutes.
Described naoh concentration is 0.5~2%, and described isopropyl alcohol concentration is 5~10%, and reaction temperature is 80~90 ℃, etching time be 10~20 minutes better.
The present invention is owing to adopt above design, it has the following advantages: 1, the present invention since the interplanar between the solar cell surface inverted pyramid every on be provided with positive pyramid district, therefore both can have the more consistent advantage of inverted pyramid size, can avoid effectively again that interplanar has improved the short circuit current of battery every the reflection loss that causes between inverted pyramid.2, the present invention since between inverted pyramid many very little positive pyramids of formation in the very narrow zone, so it has not only reduced reflection loss to greatest extent, and it is minimum that positive pyramid is dropped to the influence of passivation layer, has improved the open circuit voltage of battery.3, the present invention is because the mode that adopts inverted pyramid to combine with positive pyramid, therefore the interplanar between the inverted pyramid is not afraid of reflection loss every can suitably relaxing, and then the formation technological requirement of inverted pyramid is reduced, use common mask aligner just can process, promote the making of inverted pyramid from the laboratory, to walk out, moved towards industrialization.4, manufacture method of the present invention is to utilize the corrosion rate fast principle of " 100 " crystal face than " 111 " crystal face, after battery forms inverted pyramid of the same size by photoetching corrosion, remove oxide layer, with the whole corrosive liquid of putting into of silicon chip, because the corrosion rate of " 100 " crystal face can be faster more than tens of times than " 111 " crystal face, therefore can the interplanar between the inverted pyramid every on form positive pyramid district soon at random, but on established inverted pyramid surface, can not form positive pyramid, this slight corrosiveness to " 111 " crystal face, only form hair side, and the formation of this hair side can further reduce reflection loss.
The invention will be further described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is positive at random pyramid (matte) structural representation in surface in the prior art
Fig. 2 is a surperficial inverted pyramid structure schematic diagram in the prior art
Fig. 3 is that silicon face of the present invention generates the silica schematic diagram
Fig. 4 is that photoetching technique of the present invention forms the turned pyramid windows schematic diagram
Fig. 5 is that schematic diagram after the inverted pyramid is corroded in the present invention
Fig. 6 is that the present invention removes schematic diagram behind the silica
Fig. 7 be the present invention corrode form behind the positive pyramid just, inverted pyramid integrated structure schematic diagram
Embodiment
Monocrystaline silicon solar cell of the present invention be just be provided with on the battery body surface, inverted pyramid structure combining form, promptly the interplanar between the inverted pyramid is every being provided with the positive pyramid district that is made up of some positive pyramids.
The surface texture of positive pyramid of the present invention and inverted pyramid combination, can adopt following manufacture method to form: as shown in Figure 3, at first generating thickness on monocrystalline silicon silicon chip 1 is the oxide layer 2 of 1000~3000 dusts, adopt photoetching technique to form window 3 (as shown in Figure 4) then on silicon chip 1 surface, window 3 is corroded, in window 3, form inverted pyramid 4 (as shown in Figure 5), removes remaining oxide layer 2 after, just can be in silicon chip 1 surface formation inverted pyramid 4 (as shown in Figure 6).After again silicon chip being carried out the corrosion second time, utilize on the silicon chip 1 interplanar between the inverted pyramid every (i.e. " 100 " crystal face) the fast principle of corrosion rate than inverted pyramid surface (i.e. " 111 " crystal face), the interplanar between the inverted pyramid 5 every on form the positive pyramid district (as shown in Figure 7) that forms by some very little positive pyramids, thereby formed the surface texture that inverted pyramid 4 of the present invention combines with pyramid 5 just.
In above-mentioned manufacturing process, corrosion is very crucial, and corrosion window adopts potassium hydroxide, the aqueous solution of isopropyl alcohol.Concentration of potassium hydroxide is controlled at 5~10%, and isopropyl alcohol concentration is controlled at 10~20%, and reaction temperature is controlled at 75~90 ℃, and etching time was controlled at 10~20 minutes.
Above-mentioned concentration of potassium hydroxide is controlled at 6~8%, and isopropyl alcohol concentration is controlled at 14~18%, and reaction temperature is controlled at 80~90 ℃, etching time be controlled at 12~18 minutes better.
It is also very crucial to corrode just pyramidal process, and NaOH, the aqueous solution of isopropyl alcohol are adopted in corrosion.Naoh concentration is controlled at 0.5~5%, and isopropyl alcohol concentration is controlled at 3~10%, and reaction temperature is controlled at 75~90 ℃, and etching time was controlled at 10~30 minutes.
Above-mentioned naoh concentration is controlled at 0.5~2%, and isopropyl alcohol concentration is controlled at 5~10%, and reaction temperature is controlled at 80~90 ℃, etching time be controlled at 10~20 minutes better.
For several embodiment, further specify the present invention below.
Embodiment one
Shown in Fig. 3~7, generating thickness on silicon chip 1 is the oxide layer 2 of 1100 dusts, forming length of side a by photoetching is 10 microns, at interval b is 3 microns a window 3, is 6.5% with concentration of potassium hydroxide then, and isopropyl alcohol concentration is that 15% the aqueous solution corrodes, reaction temperature is 85 ℃, in 16 minutes reaction time, removing oxide layer 2 back formation base a then is 10 microns, and b is 3 microns a inverted pyramid 4 at interval.Be 2% with NaOH again, isopropyl alcohol concentration is that 10% the aqueous solution corrodes, and reaction temperature is 90 ℃, 12 minutes reaction time, the some positive pyramid 5 that can be formed at random.
Embodiment two
Generating thickness on silicon chip 1 is the oxide layer 2 of 1300 dusts, window by photoetching formation, with concentration of potassium hydroxide is 7%, isopropyl alcohol concentration is that 16% the aqueous solution corrodes, reaction temperature is 85 ℃, in 14 minutes reaction time, removing oxide layer 2 back formation base a then is 12 microns, and b is 2 microns a inverted pyramid 4 at interval.Be 1.5% with naoh concentration again, isopropyl alcohol concentration is that 6% the aqueous solution corrodes, and reaction temperature is 15 minutes 85C reaction time, the some positive pyramid 5 that can be formed at random.
Embodiment three
Generating thickness on silicon chip 1 is the oxide layer 2 of 1500 dusts, forming length of side a by photoetching is 14 microns, b is 3 microns a window 3 at interval, with concentration of potassium hydroxide is 7.5%, isopropyl alcohol concentration is that 13% the aqueous solution corrodes, and reaction temperature is 88 ℃, 15 minutes reaction time, removing oxide layer 2 back formation base a then is 14 microns, and b is 3 microns a inverted pyramid 4 at interval.Be 1% with naoh concentration again, isopropyl alcohol concentration is that 5% the aqueous solution corrodes, and reaction temperature is 82 ℃, 20 minutes reaction time, the some positive pyramid 5 that can be formed at random.
In the various embodiments described above, the base a of inverted pyramid 4 can be controlled between 8~20 microns, and inverted pyramid 4 degree of depth h can be controlled between 5.6~14 microns.And between 2~8 microns of the width b in positive pyramid district (just the interplanar between the inverted pyramid 4 every) controls, the big or small c of positive pyramid 5 is controlled between 2~8 microns.
Above-mentionedly align, in the control of inverted pyramid 5,4 sizes, when inverted pyramid base a is 10~15 microns, inverted pyramid degree of depth h is 7~10 microns, the width b in positive pyramid district is 2~4 microns, and is better when just pyramidal big or small c is 2~4 microns.

Claims (9)

1, a kind of surface texture of monocrystaline silicon solar cell, it comprises battery body, it is characterized in that: the spaced surface at described battery body is provided with inverted pyramid, and the interplanar between the described inverted pyramid is every being provided with the positive pyramid district that is made up of some positive pyramids.
2, the surface texture of monocrystaline silicon solar cell as claimed in claim 1, it is characterized in that: the size on described inverted pyramid base is 8~20 microns, the degree of depth of inverted pyramid is 5.6~14 microns, and the width in described positive pyramid district is 2~8 microns, and just pyramidal size is 2~8 microns.
3, as the surface texture of claim 2 described monocrystaline silicon solar cells, it is characterized in that: the size on described inverted pyramid base is 10~15 microns, the degree of depth of inverted pyramid is 7~10 microns, and the width in described positive pyramid district is 2~4 microns, and just pyramidal size is 2~4 microns.
4, the manufacture method on a kind of monocrystaline silicon solar cell surface is characterized in that it may further comprise the steps:
(1) generating thickness at silicon chip surface is the oxide layer of 1000~3000 dusts;
(2) carry out photoetching on the surface of silica, form required turned pyramid windows;
(3) silicon chip is corroded, form inverted pyramid;
(4) remove residual oxide layer;
(5) silicon chip is corroded, the interplanar between the inverted pyramid every on form positive pyramid at random.
5, the manufacture method on monocrystaline silicon solar cell as claimed in claim 4 surface is characterized in that: wherein the oxidated layer thickness that generates of the described silicon chip surface in the step (1) is 1000~2000 dusts.
6, the manufacture method on monocrystaline silicon solar cell as claimed in claim 4 surface, it is characterized in that: wherein the corrosive liquid of corrosion of silicon is the aqueous solution of potassium hydroxide, isopropyl alcohol in the step (3), concentration of potassium hydroxide is 5~10%, isopropyl alcohol concentration is 10~20%, reaction temperature is 75~90 ℃, and etching time is 10~20 minutes.
7, the manufacture method on monocrystaline silicon solar cell as claimed in claim 6 surface, it is characterized in that: described concentration of potassium hydroxide is 6~8%, and described isopropyl alcohol concentration is 14~18%, and reaction temperature is 80~90 ℃, and the reaction time is 12~18 minutes.
8, the manufacture method on monocrystaline silicon solar cell as claimed in claim 4 surface, it is characterized in that: wherein the corrosive liquid of corrosion of silicon is the aqueous solution of NaOH, isopropyl alcohol in the step (5), naoh concentration is 0.5~5%, isopropyl alcohol concentration is 3~10%, reaction temperature is 75~90 ℃, and etching time is 10~30 minutes.
9, the manufacture method on monocrystaline silicon solar cell as claimed in claim 8 surface, it is characterized in that: described naoh concentration is 0.5~2%, and described isopropyl alcohol concentration is 5~10%, and reaction temperature is 80~90 ℃, and etching time is 10~20 minutes.
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CN110137274A (en) * 2019-05-24 2019-08-16 通威太阳能(安徽)有限公司 A kind of p-type high-efficiency battery and preparation method thereof of passivation on double surfaces contact
CN111180538A (en) * 2019-12-31 2020-05-19 中威新能源(成都)有限公司 Monocrystalline silicon piece with pyramid superposition structure and preparation method
CN114551614A (en) * 2020-11-24 2022-05-27 苏州阿特斯阳光电力科技有限公司 Silicon wafer composite suede manufacturing method and silicon wafer manufactured by same
CN115224147A (en) * 2021-04-20 2022-10-21 中国科学院半导体研究所 Light trapping structure suitable for InAs/GaAsSb quantum dot solar cell and preparation method thereof

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