CN102140697A - Method for preparing porous pyramid structure on monocrystalline silicon substrate - Google Patents
Method for preparing porous pyramid structure on monocrystalline silicon substrate Download PDFInfo
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- CN102140697A CN102140697A CN 201010611615 CN201010611615A CN102140697A CN 102140697 A CN102140697 A CN 102140697A CN 201010611615 CN201010611615 CN 201010611615 CN 201010611615 A CN201010611615 A CN 201010611615A CN 102140697 A CN102140697 A CN 102140697A
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Abstract
The invention discloses a method for preparing a porous pyramid structure on a monocrystalline silicon substrate, and belongs to the technical field of semiconductors. The method comprises the following steps of: preparing a pyramid structure on the monocrystalline silicon substrate by the conventional solar cell texturing method; and preparing a nanostructure on the pyramid structure by a plasma immersion ion implantation method so as to form the porous pyramid structure on the surface of the monocrystalline silicon substrate. The porous pyramid structure is prepared on the monocrystalline silicon substrate by a two-step process, the preparation process is simple, and the method is low in cost and wide in industrial prospect; meanwhile, through the porous pyramid structure prepared on the surface of monocrystalline silicon by the method, the reflectivity of the surface of the monocrystalline silicon is reduced.
Description
Technical field
The present invention relates to technical field of semiconductors, the manufacture method of porous pyramid structure on particularly a kind of based single crystal silicon substrate.
Background technology
In bionical field, lotus leaf effect (lotus effect) enjoys people to pay close attention to, and so-called lotus leaf effect is meant that water droplet drops on the phenomenon that can tumble and leave no trace after the very strong plant leaf surface of hydrophobicity such as lotus leaf.As far back as the seventies in 20th century, the someone discovers that the coarse structure of lotus leaf surface micro-meter scale is to cause it to have the key factor of hydrophobicity and self-cleaning function.On this basis, thunder study group in river finds also to exist nanostructure on the mastoid process of lotus leaf surface micrometer structure then, thinks that the hierarchical structure that this micrometer structure combines with nanostructure is the basic reason that causes the lotus leaf surface strong-hydrophobicity.The surface of super-hydrophobicity all has wide practical use in automatically cleaning material, microfluid, the transmission of not damaged liquid, snow defence, a lot of fields such as anti-pollution, anticorrosion, anti-oxidant.
At optics and photoelectric field, how to improve the absorption of material surface, and then the performance of raising optics and photoelectric device is the focus that people study always to light.For example in the photovoltaic field, industrial common employing pyramid suede structure reduces the reflection of monocrystalline silicon surface at present, but the reflectivity of the monocrystalline silicon surface after the pyramid texture is still up to 10%-15% (in the 300nm-1100nm wavelength region), and the reflectivity of short-wave band is higher.Therefore at the new antireflection structure of monocrystalline silicon surface design, the efficiency of conversion that increases shortwave absorption and then raising solar cell just seems very meaningful.
Be used for porous pyramid structure on the single crystal silicon material in photovoltaic field integrated the strong hydrophobic advantage of lotus leaf effect and the characteristics of new antireflection structure antiradar reflectivity; it can reduce reflection of light; and then the efficiency of conversion of raising solar cell, can protect solar battery sheet not to be subjected to outside contamination by strong-hydrophobicity again.American Studies personnel and Chinese research personnel respectively at 2008 and 2009 by having made the porous pyramid structure at monocrystalline silicon surface with the method for indium metal or the auxiliary wet etching of silver, its manufacturing processed mainly comprises following four steps: 1, common monocrystalline substrate is immersed in the mixing solutions of NaOH (or KOH) and IPA (Virahol), utilizes above-mentioned solution that silicon single crystal is carried out anisotropic etching and form traditional pyramid structure; 2, deposition indium or silver metal nanoparticle on the pyramid structure of making; 3, the silicon substrate that will deposit metallic nano-particle is put into HF/H
2O
2Carry out the etching second time in the solution; 4, the silicon substrate behind the twice etching is immersed in KI/I
2(Au is auxiliary) or HNO
3In (Ag is auxiliary) solution, remove sedimentary metallic nano-particle and finally form the grade pyramid structure.But, this processing step complexity that on silicon substrate, prepares the porous pyramid structure, and cost height.
Summary of the invention
In order to solve problems such as existing metal auxiliary law prepares the porous pyramid structure on monocrystalline substrate complex process, cost height, the invention provides the manufacture method of porous pyramid structure on a kind of based single crystal silicon substrate, described method comprises: prepare pyramid structure with the conventional solar cell etching method on monocrystalline substrate earlier, utilize plasm immersion ion implantation on described pyramid structure, to prepare nanostructure again, thereby form the porous pyramid structure on described monocrystalline substrate surface.
Further, described method specifically comprises:
Monocrystalline substrate is immersed in the mixing solutions of alkalescence and Virahol, described mixing solutions carries out anisotropic etching to described monocrystalline substrate, forms traditional pyramid structure on described monocrystalline substrate surface;
The monocrystalline substrate of described traditional pyramid structure is put into the plasma immersion ion injection device, adjust the processing parameter of described plasma immersion ion injection device, make it to produce plasma body;
Utilize plasm immersion ion implantation,, on described pyramid structure, form nanostructure, on described monocrystalline substrate surface, form the porous pyramid structure by adjusting described processing parameter.
Further, the mass percent of described mixing solutions neutral and alkali material is 0.1%-50%, and the percent by volume of described Virahol is 1%-80%; The soak time of described monocrystalline substrate in described mixing solutions is 10-50 minute.
Further, the characteristic dimension of described traditional pyramid structure is 1-10 μ m.
Further, described processing parameter comprises process gas kind and the throughput ratio of injecting in the described plasma immersion ion injection device chamber, operating pressure in the injecting chamber, be used to produce the power of the radio-frequency power supply of plasma body, the power type of bias voltage, bias voltage, and injection length.
Further, described process gas is mixed by gas with corrasion and the gas with passivation; Described gas with corrasion comprises SF
6, CF
4, CHF
3, C
4F
8, NF
3, SiF
4, C
2F
6, HF, BF
3, PF
3, Cl
2, HCl, SiH
2Cl
2, SiCl
4, BCl
3Or HBr, described gas with passivation comprises O
2, N
2O or N
2Described gas with corrasion is 0.01-100 with the throughput ratio with gas of passivation.
Further, the scope of described operating pressure is 10
-3Pa-1000Pa.
Further, the scope of described bias voltage is-100000～100000V.
Further, described injection length is 0-1000 minute.
Further, described nanostructure is shaped as poroid, needle-like or tree-shaped.
Compared with prior art, the present invention has the following advantages:
Adopt the inventive method to prepare the porous pyramid structure on monocrystalline substrate, only need two step process to finish, manufacturing processed is simple, and cost is low, and wide industrialization prospect is arranged; Simultaneously, utilize the porous pyramid structure of the inventive method, reduced the reflectivity of monocrystalline silicon surface in the monocrystalline silicon surface preparation.
Description of drawings
Fig. 1 is that the embodiment of the invention utilizes plasm immersion ion implantation to prepare the principle schematic of nanostructure on pyramid structure;
Fig. 2 is that the embodiment of the invention prepares porous pyramid structure technological process synoptic diagram on monocrystalline substrate;
Fig. 3 is the manufacture method schema of porous pyramid structure on the based single crystal silicon substrate that provides of the embodiment of the invention;
Fig. 4 is the sem photograph of traditional pyramid structure of embodiment of the invention preparation;
Fig. 5 is the sem photograph of a kind of porous pyramid structure of embodiment of the invention preparation;
Fig. 6 is the sem photograph of the another kind of porous pyramid structure of embodiment of the invention preparation;
Fig. 7 is the pyramid structure of embodiment of the invention preparation and the reflectance curve synoptic diagram of two kinds of porous pyramid structures.
Embodiment
In order to understand the present invention in depth, the present invention is described in detail below in conjunction with drawings and the specific embodiments.
Plasma immersion ion injects (Plasma Immersion Ion Implantation, abbreviate PIII as), sometimes being also referred to as plasma body in the semi-conductor industry injects, plasma doping, plasma immersion injects, plasma source is ion implantation, plasma based ion is injected or the like, these several title methods are represented identical a kind of Technology, promptly wait to inject sample and directly be immersed in plasma body, by apply bias voltage (also can be described as " injecting voltage ") to sample, make between sample and the plasma body to form and inject sheath layer electric field, be arranged in and inject sheath layer electric field and under the booster action of electric field, directly be injected into sample from the ion that plasma body enters injection sheath layer electric field.Because the surface at sample forms the sheath layer, so the sample surfaces that exposes to the open air in plasma body will be injected into everywhere simultaneously.
Fig. 1 is that the embodiment of the invention utilizes plasm immersion ion implantation to prepare the principle schematic of nanostructure on pyramid structure.In the plasma immersion ion injection process, can serve as reasons gas with corrasion and have the hybrid technique gas that the gas of passivation is formed according to a certain volume of injecting gas in plasma immersion ion injection device chamber, the gas with corrasion comprises SF
6, CF
4, CHF
3, C
4F
8, NF
3, SiF
4, C
2F
6, HF, BF
3, PF
3, Cl
2, HCl, SiH
2Cl
2, SiCl
4, BCl
3Or HBr, the gas with passivation comprises O
2, N
2O or N
2, preferably can be by multiple gas and multiple gas composition with passivation with corrasion, more preferably can be by a kind of gas and a kind of gas composition, for example by SF with passivation with corrasion
6And O
2The mixed gas of forming is perhaps by CF
4And N
2The mixed gas of forming, is under 0.01～100 condition satisfying mixed gas by the gas with corrasion and gas that has the gas composition of passivation and have a corrasion and the volume ratio with inter gas of passivation, and these gas hybrid modes can be arbitrarily; Gas with corrasion also can be preferably 0.1～10 with the volume ratio with inter gas of passivation.In Fig. 1, mixed gas is blended SF according to a certain volume
6And O
2Under certain process conditions, this mixed gas generation ionization produces some group respectively, for example SF
6And O
2Produce F respectively
*And O
*Group.At this moment, F
*Group is by forming SiF with Si
4, and then to Si formation corrasion; O
*Group forms Si at the etching wall surface
xO
yF
z, the etching wall is produced passivation.Energetic ion bombards effect to silicon chip surface under the effect of injecting voltage simultaneously.Triple role by etching, passivation and ion bombardment like this forms tree-shaped, needle-like or nanostructure such as poroid at silicon chip surface.
Referring to Fig. 2 and Fig. 3, the embodiment of the invention provides the manufacture method of porous pyramid structure on a kind of based single crystal silicon substrate, specifically comprises the steps:
Step 101: monocrystalline substrate is immersed in the mixing solutions of NaOH/KOH and IPA (Virahol), utilizes mixing solutions that monocrystalline substrate is carried out anisotropic etching, form traditional pyramid structure at silicon face;
Wherein, the mass percent of NaOH or KOH can be 0.1%-50% in the mixing solutions, preferably can be 1%-10%, and the percent by volume of IPA can be 1%-80%, preferably can be 10%-40%; Soak time can be 10-50 minute, preferably can be 20-40 minute; By the first time etching of mixing solutions, can form traditional pyramid structure that characteristic dimension is 1-10 μ m at silicon face, as shown in Figure 4 to monocrystalline substrate; In actual applications, can be by adjusting the mass percent of NaOH or KOH, the percent by volume of IPA, and parameter such as soak time is controlled the size of pyramid structure and the pyramidal gradient etc.;
Step 102: have the monocrystalline substrate of pyramid structure to put into the plasma immersion ion injection device surface length, adjust the processing parameter of plasma immersion ion injection device, make it to reach the working conditions that can produce plasma body; Mixed gas is the discharge generation plasma body under the effect of radio-frequency power supply, plasma body pyramid structure to silicon face under the effect of grid bias power supply is carried out selective etch, i.e. etching for the second time, finally form the pyramid structure of micron number magnitude at silicon chip surface, and on pyramid structure, form nanostructure, promptly form the porous pyramid structure;
The processing parameter of plasma immersion ion injection device can comprise the process gas kind and the throughput ratio of injecting chamber, operating pressure, mixed gas moiety, proportion of composing and concentration, be used to produce the power of the radio-frequency power supply of plasma body, the power type of bias voltage, bias voltage, and injection length or the like; The operating pressure scope of injecting chamber can be 10
-3Pa～1000Pa is preferably 0.01Pa～100Pa; The bias voltage that applies can be-100000～100000V, is preferably-50000～50000V; Injection length can be 0-1000 minute, is preferably 0-100 minute;
In actual applications, gas pressure intensity when kind that can be by adjusting process gas, the throughput ratio of process gas, work in the chamber, be used to impel geseous discharge to produce the size of the radio-frequency power supply power of plasma body, the parameters such as size, injection length that are used for the auxiliary bias voltage that injects are controlled the shape and the size of nanostructure; That nanostructure can be is tree-shaped, needle-like or poroid etc., and the size of nanostructure can be tens nanometers to several microns, as shown in Figure 5 and Figure 6.
Fig. 7 is the reflectance curve synoptic diagram of the porous pyramid structure silicon face of employing embodiment of the invention preparation.As seen from Figure 7, in the scope of wavelength 300-1000nm, the average reflectance of tree-shaped (curve c) and needle-like (curve d) hierarchical organization is respectively 3.3% and 1.4%, well below the average reflectance (curve b) 13.3% of traditional pyramid structure.As a comparison, (curve is a) up to 31.9% for the average reflectance of original dull and stereotyped silicon chip surface.Porous pyramid structure on the single crystal silicon material of this antiradar reflectivity can be used for multiple optics and photoelectric field, can be used for area of solar cell as it, can have the potential quality that improves conversion efficiency of solar cell by reducing reflection, can prevent the pollution of external environment by superpower hydrophobicity again solar cell.
Above-described specific embodiment further describes purpose of the present invention, technical scheme and beneficial effect.Will be appreciated that above said content is the specific embodiment of the present invention only, is not limited to the present invention.All within essence of the present invention and ultimate principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the manufacture method of porous pyramid structure on the based single crystal silicon substrate, it is characterized in that, described method comprises: prepare pyramid structure with the conventional solar cell etching method on monocrystalline substrate earlier, utilize plasm immersion ion implantation on described pyramid structure, to prepare nanostructure again, thereby form the porous pyramid structure on described monocrystalline substrate surface.
2. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 1, and described method specifically comprises:
Monocrystalline substrate is immersed in the mixing solutions of alkalescence and Virahol, described mixing solutions carries out anisotropic etching to described monocrystalline substrate, forms traditional pyramid structure on described monocrystalline substrate surface;
The monocrystalline substrate of described traditional pyramid structure is put into the plasma immersion ion injection device, adjust the processing parameter of described plasma immersion ion injection device, make it to produce plasma body;
Utilize plasm immersion ion implantation,, on described pyramid structure, form nanostructure, on described monocrystalline substrate surface, form the porous pyramid structure by adjusting described processing parameter.
3. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 2, and the mass percent of described mixing solutions neutral and alkali material is 0.1%-50%, and the percent by volume of described Virahol is 1%-80%; The soak time of described monocrystalline substrate in described mixing solutions is 10-50 minute.
4. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 3, and the characteristic dimension of described traditional pyramid structure is 1-10 μ m.
5. the manufacture method of porous pyramid structure on the based single crystal silicon substrate as claimed in claim 2, it is characterized in that, described processing parameter comprises process gas kind and the throughput ratio of injecting in the described plasma immersion ion injection device chamber, operating pressure in the injecting chamber, be used to produce the power of the radio-frequency power supply of plasma body, the power type of bias voltage, bias voltage, and injection length.
6. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 5, and described process gas is mixed by gas with corrasion and the gas with passivation; Described gas with corrasion comprises SF
6, CF
4, CHF
3, C
4F
8, NF
3, SiF
4, C
2F
6, HF, BF
3, PF
3, Cl
2, HCl, SiH
2Cl
2, SiCl
4, BCl
3Or HBr, described gas with passivation comprises O
2, N
2O or N
2Described gas with corrasion is 0.01-100 with the throughput ratio with gas of passivation.
7. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 5, and the scope of described operating pressure is 10
-3Pa-1000Pa.
8. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 5, and the scope of described bias voltage is-100000～100000V.
9. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 5, and described injection length is 0-1000 minute.
10. the manufacture method of porous pyramid structure is characterized in that on the based single crystal silicon substrate as claimed in claim 1 or 2, and being shaped as of described nanostructure is poroid, needle-like or tree-shaped.
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| CN103500775A (en) * | 2013-09-25 | 2014-01-08 | 泰州德通电气有限公司 | Process for conducting alkali treatment after felting on crystalline silicon plasma |
| CN103500769A (en) * | 2013-09-11 | 2014-01-08 | 北京工业大学 | Super-hydrophobic pyramid-silicon nanowire compound light trapping structure and preparation method thereof |
| CN103647000A (en) * | 2013-12-20 | 2014-03-19 | 天威新能源控股有限公司 | Surface texturing technology for crystalline silicon solar cell |
| CN103806105A (en) * | 2012-11-02 | 2014-05-21 | 无锡尚德太阳能电力有限公司 | Coating source diffusion method capable of improving diffusion property |
| CN103924306A (en) * | 2014-04-25 | 2014-07-16 | 南开大学 | Texture surface making method for silicon heterojunction solar cells |
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Cited By (9)
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|---|---|---|---|---|
| CN103806105A (en) * | 2012-11-02 | 2014-05-21 | 无锡尚德太阳能电力有限公司 | Coating source diffusion method capable of improving diffusion property |
| CN103500769A (en) * | 2013-09-11 | 2014-01-08 | 北京工业大学 | Super-hydrophobic pyramid-silicon nanowire compound light trapping structure and preparation method thereof |
| CN103500769B (en) * | 2013-09-11 | 2017-02-01 | 北京工业大学 | Super-hydrophobic pyramid-silicon nanowire compound light trapping structure and preparation method thereof |
| CN103500775A (en) * | 2013-09-25 | 2014-01-08 | 泰州德通电气有限公司 | Process for conducting alkali treatment after felting on crystalline silicon plasma |
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| CN103647000B (en) * | 2013-12-20 | 2016-08-24 | 天威新能源控股有限公司 | A kind of crystal-silicon solar cell Surface Texture metallization processes |
| CN103924306A (en) * | 2014-04-25 | 2014-07-16 | 南开大学 | Texture surface making method for silicon heterojunction solar cells |
| CN103924306B (en) * | 2014-04-25 | 2016-05-25 | 南开大学 | A kind of etching method of silicon heterojunction solar battery |
| CN104576831A (en) * | 2014-12-31 | 2015-04-29 | 江苏顺风光电科技有限公司 | Monocrystalline silicon wafer alcohol-free texturing process and texturing additive |
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Application publication date: 20110803 |