CN102593261A - Silicon substrate nano-structure for solar cell and preparing method thereof - Google Patents
Silicon substrate nano-structure for solar cell and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a silicon substrate nano-structure for a solar cell and a preparing method thereof, and the method includes: cleaning silicon chips; spin-coating and covering single layer polystyrene (PS) spheres on the surface of the silicon chips; etching the PS spheres and reducing the sizes of the PS spheres; depositing a metal film layer on the surface of the silicon chip surface and forming metal mask; removing residual PS spheres on the silicon chip surface and remaining for the left metal masking layer; forming the silicon substrate nano-structure by using a dry etching or wet etching method; treating the silicon chips by heated concentrated acid and removing the residual metal and finishing the preparation of the silicon substrate nano-structure. According to the silicon substrate nano-structure for the solar cell and the preparing method thereof, PS spheres masking and metal film growth are utilized and the dry etching method and the wet etching method are combined so that a preparing method of silicon substrate nano-structure for the solar cell is provided. According to the silicon substrate nano-structure, the reflectivity is low, the light trapping ability is of high efficient, the light absorption of the solar cell is enhanced and the efficiency of the solar cell is improved.
Description
Technical field
The present invention relates to technical field of solar cells, relate in particular to a kind of silicon-based nano structure that is used for solar cell and preparation method thereof.
Background technology
In recent years, the environmental problem of energy scarcity problem and global warming is serious day by day, and human regenerative resource demand to cleaning is unprecedentedly eager.Many advantages such as photovoltaic solar is a kind of important renewable energy, and it is extensive to have the energy, and the region restriction is few, and is safe and reliable.
Use so far from first silicon solar cell in 1954, solar cell has passed through first generation single crystal silicon solar cell, the development of second generation hull cell, and its technology trends is that cost reduces, efficient improves.
The solar cell that existing market is used is main with crystal silicon cell, but the cost height remains the bottleneck of restriction photovoltaic industry development, how to raise the efficiency the focus that becomes solar cell research to reduce cost.
The absorption angle of sunlight is seen that energy loses with the heat energy form greater than the particularly high-octane short wavelength photons of the photon of silicon energy gap greatly from present crystal silicon battery, and the photon of a part of infrared band can not be absorbed through battery.Even at visible waveband, the reflection of silicon face is also bigger, has lost suitable light.If effectively utilize the light of these losses, then can realize significantly improving of battery efficiency.
The present invention utilizes the PS ball to cover and the metal mask layer growth, in conjunction with dry method and wet etching, has prepared a kind of silicon-based nano structure that is applied to solar cell.This nanostructure has ultralow reflectivity and falls into luminous energy power efficiently, is applied on the crystal silicon solar battery, thereby reduces reflection; And the long wavelength threshold system that will be easily sees through battery in vivo; Strengthen light absorption, finally convert photoelectric current into, realize higher battery efficiency.
Summary of the invention
The technical problem that (one) will solve
In view of this; Main purpose of the present invention is to provide a kind of silicon-based nano structure that is used for solar cell and preparation method thereof, and the incident light that exists in the solar cell reflects and the loss problem of transmission to solve, and reaches and reduces reflection; Strengthen light absorption, obtain the purpose of higher battery efficiency.
(2) technical scheme
For achieving the above object, the invention provides a kind of preparation method who is used for the silicon-based nano structure of solar cell, comprising: cleaning silicon chip; Individual layer PS ball on spin coating on the silicon chip surface covers; The PS ball is carried out etching, reduce PS ball size; At silicon chip surface depositing metal films layer, form metal mask; The remaining PS ball of silicon chip surface is removed remaining metal mask layer; Adopt dry etching or wet etching method, form the silicon-based nano structure; And concentrated acid heat treated silicon chip, remove remaining metal, accomplish the preparation of silicon-based nano structure.
In the such scheme, in the step of said cleaning silicon chip, be to use dense H
2SO
4Boiling is cleaned with the hydrogen peroxide solution Hybrid Heating, and then adopts HF solution and washed with de-ionized water respectively, and nitrogen dries up.
In the such scheme, said on silicon chip surface spin coating cover in the step of individual layer PS ball, be that the PS ball is scattered in the ethanol, the spin coating rotating speed is 1000～5000rpm; The PS bulb diameter is 100nm～100 μ m, is covered as the PS ball layer of individual layer solid matter.
In the such scheme, saidly the PS ball is carried out etching reducing in the step of PS ball size, is to adopt the method for dry etching that the PS ball is carried out etching, and the diameter of PS ball is reduced to 60nm～60 μ m.Said dry etching method is to adopt reactive ion etching (RIE) method.
In the such scheme; Said in the step of silicon chip surface depositing metal films layer formation metal mask; Be to adopt electron beam evaporation or magnetron sputtering not to have the area deposition metal film layer that the PS ball is sheltered at silicon chip surface; The metal that this metal film layer adopts is gold, silver, copper or nickel, and the thickness of this metal film layer is 20nm～200nm.
In the such scheme, in the said step, be to adopt the mode of ultrasonic cleaning to remove the remaining PS ball of silicon chip surface with the remaining PS ball removal of silicon chip surface.
In the such scheme; Said employing dry etching or wet etching method form in the step of silicon-based nano structure; Said dry etching is a reactive ion etching, and said wet etching is for using the corrosion of HF and hydrogen peroxide mixed solution, and etching time is 10 minutes～120 minutes; Said silicon-based nano structure, its degree of depth are 0.3～3 μ m, are shaped as the shape of metal mask.
In the such scheme, said concentrated acid heat treated silicon chip is removed in the step of remaining metal, is to adopt red fuming nitric acid (RFNA) heated wash silicon chip, adopts HF and washed with de-ionized water again, removes remaining metal.
For achieving the above object, the present invention also provides a kind of silicon-based nano structure that is used for solar cell, comprising: silicon substrate combines with nano column array or nanohole array on it; And be formed at nano column array or the nanohole array on this silicon substrate.
In the such scheme, said silicon substrate is a crystal silicon chip, and this crystal silicon chip is P type silicon chip or N type silicon chip.
In the such scheme, said silicon substrate is used to support nano column array or nanohole array on it, simultaneously as solar cell base and emitter region.
In the such scheme, said nano column array or nanohole array, on silicon substrate directly etching prepare, combine for one naturally with silicon substrate.Described nano column array or nanohole array are used for anti-reflection layer and sunken photosphere as solar cell, simultaneously as solar cell base and emitter region.Said nano column array or nanohole array, diameter are 60nm～60 μ m, and the cycle is 100nm～100 μ m, and the degree of depth or length are 0.3 μ m～3 μ m.
(3) beneficial effect
Can find out that from technique scheme the present invention has following beneficial effect:
1, the preparation method who is used for the silicon-based nano structure of solar cell provided by the invention, effectively preparation size is even, the nanostructure of distribution rule; The silicon-based nano structure applications in solar cell, can be increased battery to absorption of incident light and utilization effectively, increased photogenerated current, improve battery conversion efficiency.
2, the preparation method who is used for the silicon-based nano structure of solar cell provided by the invention; Under part and the compatible prerequisite of existing solar cell preparation technology; Innovation structure has been proposed; And provide effective preparation method, to improve the conversion efficiency of crystal silicon solar batteries, reduce the production cost of solar cell.
3, the preparation method who is used for the silicon-based nano structure of solar cell provided by the invention adopts spin coating PS ball to shelter to add corroding method to prepare the silicon-based nano structure, and the technology of employing is comparatively ripe, has the potentiality compatible mutually with existing production technology;
4, the preparation method who is used for the silicon-based nano structure of solar cell provided by the invention; The PS ball that adopts covers the plated metal mask and adds corroding method; Can preparation size controlled, size is consistent, the silicon-based nano structure of distribution rule, has optimizable optics and electrical properties;
5, the preparation method who is used for the silicon-based nano structure of solar cell provided by the invention, the basic full silica-base material that adopts, raw material is sufficient, and cost is lower, and silicon process technology is quite ripe, helps applying of large-scale production.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously with easily understanding becoming the description of embodiment below in conjunction with accompanying drawing, wherein:
Fig. 1 is used for the method flow diagram of the silicon-based nano structure of solar cell for the preparation according to the embodiment of the invention;
Fig. 2 is used for the process chart of each production phase of silicon-based nano structure of solar cell for the preparation according to the embodiment of the invention to Fig. 9.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention.
As shown in Figure 1, Fig. 1 shows the method flow diagram that is used for the silicon-based nano structure of solar cell according to the preparation of the embodiment of the invention, and this method specifically may further comprise the steps:
In step 101, at first silicon chip 201 is cleaned.Wherein silicon substrate can be a p type silicon chip, also can n type silicon chip; Preferably, adopt P type silicon substrate.
Step 101 is used dense H
2SO
4Boiling is cleaned with the hydrogen peroxide solution Hybrid Heating, uses HF solution and washed with de-ionized water then respectively, and nitrogen dries up; Preferably, H
2SO
4With the hydrogen peroxide solution ratio be 5: 1, the concentration of HF solution is 15%.
In step 102,, as shown in Figure 2 at the individual layer PS ball 202 that surperficial spin coating one deck of silicon substrate 201 is closely arranged.Preferably, the PS bulb diameter in the step 102 is 100nm～100 μ m, is scattered in the ethanol, and the spin coating rotating speed is 1000～5000rpm.For example in specific embodiment, adopting diameter is the PS ball of 1 μ m, is scattered in the ethanolic solution, uses sol evenning machine to carry out spin coating, and rotating speed is 3000rpm.
In step 103, the silicon chip 201 of the described PS of the being coated with ball 202 of Fig. 2 is carried out dry etching, the size of PS ball is reduced, form gapped PS ball and distribute 203, as shown in Figure 3.Preferably, the dry etching in the step 103 is a reactive ion etching, and the PS bulb diameter after the etching is 60nm～60 μ m.For example in specific embodiment, the silicon substrate that is coated with individual layer PS ball is put into RIE etching machine carry out etching, adopt CHF
3/ O
2Atmosphere, diameter is 600nm after the etching.
In step 104,, as shown in Figure 4 to the silicon chip 201 surface deposition metallic films 204 of PS ball distribution 203 are arranged among Fig. 3.Preferably, the metal of the metal film layer in the step 104 can be metals such as gold, silver, copper, nickel.The technology of metal film layer deposition includes but not limited to electron beam evaporation, magnetron sputtering etc.Through step 104, the metallic film layer thickness of formation is 20nm～200nm.For example in specific embodiment, can adopt the e-book evaporator of Microelectronics Institute of the Chinese Academy of Sciences to carry out the deposition of metallic film, plated metal is a silver, thickness is 50nm.
In step 105, the silicon chip 201 of the metal film layer 204 of having grown is removed PS ball 203, it is as shown in Figure 5 to form the metal mask layer; Preferably, the removal PS ball of step 105 adopts the ultrasonic cleaning method.
In step 106, on the silicon substrate that metal mask layer 204 is arranged 201, carry out dry etching, to form nano-pore structure, as shown in Figure 6; Preferably, step 106 adopts the RIE lithographic method.Etching depth is 0.3～3 μ m.In step 106, on the silicon substrate that metal mask layer 204 is arranged 201, carry out wet etching, to form the nano-pillar structure, as shown in Figure 8; Preferably, step 106 is adopted HF and hydrogen peroxide mixed solution corrosion, and the ratio of mixing is 5: 1.Etching time is 5 minutes～60 minutes.
In step 107,, remove remaining metal level 204, like Fig. 7 and shown in Figure 9, to obtain being applied to the silicon-based nano structure of new high-efficiency solar cell in that Fig. 6 or etching shown in Figure 8 or the silicon substrate 201 that corrodes are cleaned.Preferably, step 107 is removed metal, for red fuming nitric acid (RFNA) heated wash silicon chip, uses HF and washed with de-ionized water again.
It is pointed out that above-mentionedly to be merely the simple clear schematic example of describing the principle of the invention about step 101 to the specific embodiment mode of step 107, is not that the present invention is done any pro forma restriction, the step that more especially can realize through existing technology.
With reference to Fig. 9, this silicon-based nano structure that is used for solar cell provided by the invention comprises once more: silicon substrate combines with nano column array or nanohole array on it; And be formed at nano column array or the nanohole array on this silicon substrate.
Wherein, said silicon substrate is a crystal silicon chip, and this crystal silicon chip is P type silicon chip or N type silicon chip.Said silicon substrate is used to support nano column array or nanohole array on it, simultaneously as solar cell base and emitter region.
Said nano column array or nanohole array, on silicon substrate directly etching prepare, combine for one naturally with silicon substrate.Described nano column array or nanohole array are used for anti-reflection layer and sunken photosphere as solar cell, simultaneously as solar cell base and emitter region.Said nano column array or nanohole array, diameter are 60nm～60 μ m, and the cycle is 100nm～100 μ m, and the degree of depth or length are 0.3 μ m～3 μ m.
Silicon-based nano structure that is used for new and effective solar cell provided by the invention and preparation method thereof; Under part and the compatible prerequisite of existing solar cell preparation technology; Proposed innovation structure,, reduced the production cost of solar cell to improve the conversion efficiency of crystal silicon solar batteries; Thereby move towards practicability, the creation of value.The present invention has above-mentioned many advantages and practical value, has large improvement technically, and has produced handy and practical effect, thereby be suitable for practicality more.
Though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention.Those of ordinary skills obviously can know; In not breaking away from technical scheme scope of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be the content that does not break away from technical scheme of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (15)
1. a preparation method who is used for the silicon-based nano structure of solar cell is characterized in that, comprising:
Cleaning silicon chip;
Individual layer PS ball on spin coating on the silicon chip surface covers;
The PS ball is carried out etching, reduce PS ball size;
At silicon chip surface depositing metal films layer, form metal mask;
The remaining PS ball of silicon chip surface is removed remaining metal mask layer;
Adopt dry etching or wet etching method, form the silicon-based nano structure; And
Concentrated acid heat treated silicon chip is removed remaining metal, accomplishes the preparation of silicon-based nano structure.
2. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 1 is characterized in that, in the step of said cleaning silicon chip, is to use dense H
2SO
4Boiling is cleaned with the hydrogen peroxide solution Hybrid Heating, and then adopts HF solution and washed with de-ionized water respectively, and nitrogen dries up.
3. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 1 is characterized in that, said on silicon chip surface spin coating cover in the step of individual layer PS ball, be that the PS ball is scattered in the ethanol, the spin coating rotating speed is 1000～5000rpm; The PS bulb diameter is 100nm～100 μ m, is covered as the PS ball layer of individual layer solid matter.
4. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 1; It is characterized in that; Saidly the PS ball is carried out etching reducing in the step of PS ball size, is to adopt the method for dry etching that the PS ball is carried out etching, and the diameter of PS ball is reduced to 60nm～60 μ m.
5. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 4 is characterized in that, said dry etching method is to adopt reactive ion etching method.
6. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 1; It is characterized in that; Said in the step of silicon chip surface depositing metal films layer formation metal mask; Be to adopt electron beam evaporation or magnetron sputtering not to have the area deposition metal film layer that the PS ball is sheltered at silicon chip surface, the metal that this metal film layer adopts is gold, silver, copper or nickel, and the thickness of this metal film layer is 20nm～200nm.
7. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 1 is characterized in that, in the said step with the remaining PS ball removal of silicon chip surface, is to adopt the mode of ultrasonic cleaning to remove the remaining PS ball of silicon chip surface.
8. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 1; It is characterized in that; Said employing dry etching or wet etching method form in the step of silicon-based nano structure; Said dry etching is a reactive ion etching, and said wet etching is for using the corrosion of HF and hydrogen peroxide mixed solution, and etching time is 10 minutes～120 minutes; Said silicon-based nano structure, its degree of depth are 0.3～3 μ m, are shaped as the shape of metal mask.
9. the preparation method who is used for the silicon-based nano structure of solar cell according to claim 1; It is characterized in that said concentrated acid heat treated silicon chip is removed in the step of remaining metal, is to adopt red fuming nitric acid (RFNA) heated wash silicon chip; Adopt HF and washed with de-ionized water again, remove remaining metal.
10. a silicon-based nano structure that is used for solar cell is characterized in that, comprising:
Silicon substrate combines with nano column array or nanohole array on it; And
Be formed at nano column array or nanohole array on this silicon substrate.
11. silicon-based nano structure according to claim 10 is characterized in that, said silicon substrate is a crystal silicon chip, and this crystal silicon chip is P type silicon chip or N type silicon chip.
12. silicon-based nano structure according to claim 10 is characterized in that, said silicon substrate is used to support nano column array or nanohole array on it, simultaneously as solar cell base and emitter region.
13. silicon-based nano structure according to claim 10 is characterized in that, said nano column array or nanohole array, on silicon substrate directly etching prepare, combine for one naturally with silicon substrate.
14. silicon-based nano structure according to claim 10 is characterized in that, described nano column array or nanohole array are used for anti-reflection layer and sunken photosphere as solar cell, simultaneously as solar cell base and emitter region.
15. silicon-based nano structure according to claim 10 is characterized in that, said nano column array or nanohole array, diameter are 60nm～60 μ m, and the cycle is 100nm～100 μ m, and the degree of depth or length are 0.3 μ m～3 μ m.
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| CN102931277A (en) * | 2012-10-29 | 2013-02-13 | 沈鸿烈 | Method for preparing black silicon by Ni assisted chemical etching method |
| CN102956774A (en) * | 2012-11-05 | 2013-03-06 | 中国科学院半导体研究所 | Method for fabricating nanoscale column array GaN-based normal-structured light emitting diode |
| CN103066173A (en) * | 2012-12-12 | 2013-04-24 | 华灿光电股份有限公司 | Light-emitting diode (LED) chip and preparation method thereof |
| CN103641059A (en) * | 2013-12-30 | 2014-03-19 | 中国人民解放军国防科学技术大学 | Silicon-pillared metal film nano-structure array and preparation method thereof |
| CN103872182A (en) * | 2014-03-31 | 2014-06-18 | 陕西师范大学 | Method for preparing nanowire crystalline silicon solar cell having transverse transport characteristic |
| CN104505408A (en) * | 2014-12-17 | 2015-04-08 | 上海师范大学 | Crystalline silicon nanopore array material and preparation method thereof |
| CN106794985A (en) * | 2014-06-11 | 2017-05-31 | 韩国标准科学研究院 | The large area manufacture method of the GaAs conductor nano tube/linear arrays of vertical alignment |
| CN106809798A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of silicon-based nanometer column array |
| CN107180748A (en) * | 2017-07-07 | 2017-09-19 | 成都海威华芯科技有限公司 | A kind of deep hole cleaning method of SiC wafers |
| CN107745477A (en) * | 2017-12-03 | 2018-03-02 | 无锡市恒利弘实业有限公司 | A kind of method and its application of metal-surface nano injection molding |
| CN108895690A (en) * | 2018-07-05 | 2018-11-27 | 南京大学 | A kind of silicon-based semiconductor-metal nanometer composite material and preparation method thereof |
| CN115692189A (en) * | 2022-11-04 | 2023-02-03 | 广东工业大学 | Gallium nitride nanowire array and processing method thereof |
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| CN102931277B (en) * | 2012-10-29 | 2015-09-30 | 沈鸿烈 | A kind of Ni assistant chemical etch prepares the method for black silicon |
| CN102956774A (en) * | 2012-11-05 | 2013-03-06 | 中国科学院半导体研究所 | Method for fabricating nanoscale column array GaN-based normal-structured light emitting diode |
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| CN103641059B (en) * | 2013-12-30 | 2016-03-30 | 中国人民解放军国防科学技术大学 | Metal film nano-structure array that silicon post supports and preparation method thereof |
| CN103641059A (en) * | 2013-12-30 | 2014-03-19 | 中国人民解放军国防科学技术大学 | Silicon-pillared metal film nano-structure array and preparation method thereof |
| CN103872182A (en) * | 2014-03-31 | 2014-06-18 | 陕西师范大学 | Method for preparing nanowire crystalline silicon solar cell having transverse transport characteristic |
| CN106794985A (en) * | 2014-06-11 | 2017-05-31 | 韩国标准科学研究院 | The large area manufacture method of the GaAs conductor nano tube/linear arrays of vertical alignment |
| CN106794985B (en) * | 2014-06-11 | 2019-03-12 | 韩国标准科学研究院 | The large area manufacturing method of the GaAs conductor nano tube/linear array of vertical alignment |
| CN104505408A (en) * | 2014-12-17 | 2015-04-08 | 上海师范大学 | Crystalline silicon nanopore array material and preparation method thereof |
| CN106809798A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of silicon-based nanometer column array |
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| CN107180748A (en) * | 2017-07-07 | 2017-09-19 | 成都海威华芯科技有限公司 | A kind of deep hole cleaning method of SiC wafers |
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| CN115692189A (en) * | 2022-11-04 | 2023-02-03 | 广东工业大学 | Gallium nitride nanowire array and processing method thereof |
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Application publication date: 20120718 |