CN104962998A - Diamond wire cutting-based silicon wafer texturing pretreatment method and silicon wafer texturing method - Google Patents
Diamond wire cutting-based silicon wafer texturing pretreatment method and silicon wafer texturing method Download PDFInfo
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Abstract
The invention provides a diamond wire cutting-based silicon wafer texturing pretreatment method. The method comprises the following steps: a, mixing a hydrofluoric acid solution, a hydrogen dioxide solution, metal salt and water to obtain pretreatment liquid; b, putting a silicon wafer cut by a diamond wire into the pretreatment liquid and performing pretreatment A, until cutting lines on the silicon wafer are basically removed; c, cleaning the silicon wafer subjected to pretreatment A by an acid solution, so as to remove metal particles on the silicon wafer; d, putting the silicon wafer cleaned by the acid solution into the pretreatment liquid and performing pretreatment B, and forming a pretreatment texturing surface with a uniform micro/nano structure on the silicon wafer. The invention also provides a diamond wire cutting-based silicon wafer texturing method.
Description
Technical field
The present invention relates to crystal silicon solar energy battery making herbs into wool field, particularly relate to a kind of silicon wafer wool making technical field based on diamond wire cutting.
Background technology
Diamond wire cutting technique, is also called the cutting of concretion abrasive diamond fretsaw, normally to be anchored at by diamond particles with plating or the resin method of fixing to make in the nickel base alloy layer on Stainless Steel Wire top layer.In cutting process, diamond fretsaw runs up, and directly carries out grinding cutting with certain pressure to silicon materials.Relative to traditional mortar multi-wire saw technology, because having, cutting efficiency is high, cutting processing cost is low and the advantage such as clean environment for diamond wire cutting technique, and is expected to the future thrust becoming the hard and fragile material microtomies such as photovoltaic art sliced crystal silicon.
But, in polysilicon chip surface wool manufacturing, there is a series of problem, cause the application of diamond-cutting technique to be limited.For example diamond-cutting technique easily forms cutting line when cutting on silicon chip, and described cutting line is difficult to when adopting conventional acid caustic solution to carry out making herbs into wool eliminate, namely the silicon chip surface after making herbs into wool still leaves cutting line, thus after making making herbs into wool, the reflectivity of silicon chip can not meet demand of industrial production etc.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind of the making herbs into wool pretreatment process based on diamond cutting silicon chip and the silicon wafer fine hair making method of removing cutting line, thus make silicon chip can substantially remove cutting line at pretreatment stage, thus make the silicon wafer wool making product matte that obtains after making herbs into wool through described pretreated silicon chip even, without cutting line.
The invention provides a kind of making herbs into wool pretreatment process of the silicon chip based on diamond wire cutting, it comprises the steps: that hydrofluoric acid solution, superoxol, metal-salt and additive are mixed to get pretreatment fluid by a; The silicon chip that diamond wire cuts is placed in described pretreatment fluid and carries out pre-treatment A by b, until the basic cutting line removed on silicon chip; C acidic solution cleans the silicon chip through pre-treatment A process, to remove the metallic particles on silicon chip; The silicon chip cleaned with acidic solution is placed in pretreatment fluid and carries out pre-treatment B by d, until form the pre-treatment matte of the even micro-nano structure of tool on described silicon chip.
The volume ratio of hydrofluoric acid solution described in step a and superoxol is 1 ~ 10:5 ~ 40, and in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, and in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%; In described pretreatment fluid, metal-salt is at least one in cupric nitrate, Silver Nitrate, Palladous nitrate, cupric chloride, hydrochloro-auric acid, Platinic chloride, potassiumchromate, single nickel salt, and the volumetric molar concentration of described metal-salt is 1 μm of ol/L ~ 10
5μm ol/L.
Described pretreatment fluid comprises additive further, and described additive is at least one in Virahol, ethanol, propyl carbinol, isopropylcarbinol, ethylene glycol, n-propyl alcohol, ethylene glycol ethyl ether, Diethylene Glycol.
The volume ratio of described hydrofluoric acid solution, superoxol and additive is 1 ~ 10:5 ~ 40:1 ~ 20, in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%, and the massfraction of described additive is 60% ~ 98%.
The pretreatment time of the A of pre-treatment described in step b is 1 minute ~ 10 minutes, and pretreated temperature is 10 DEG C ~ 45 DEG C.
The treatment time of the B of pre-treatment described in steps d is 30 seconds ~ 5 minutes, and pretreated temperature is 10 DEG C ~ 45 DEG C.
Acidic solution described in step c is at least one in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, citric acid, carboxylic acid, sulfonic acid,-sulfinic acid, thionothiolic acid, fluorine metaantimmonic acid, fluorine antimony sulfonic acid.
Based on an etching method for the silicon chip of diamond wire cutting, it comprises the steps: that hydrofluoric acid solution, superoxol, metal-salt and additive are mixed to get pretreatment fluid by a; The silicon chip that diamond wire cuts is placed in described pretreatment fluid and carries out pre-treatment A by b, until the basic cutting line removed on silicon chip; C acidic solution cleans the silicon chip through pre-treatment A process, to remove the metallic particles on silicon chip; The silicon chip cleaned with acidic solution is placed in pretreatment fluid and carries out pre-treatment B by d, until form the pre-treatment matte of the even micro-nano structure of tool on described silicon chip; Silicon chip through pre-treatment B is placed in hydrofluoric acid nitric acid Woolen-making liquid and carries out making herbs into wool process by e.
The nitric acid of hydrofluoric acid described in step e Woolen-making liquid is the mixture that hydrofluoric acid solution, salpeter solution and water are mixed to get with the volume ratio of 1 ~ 5:5 ~ 10:5 ~ 15, in described hydrofluoric acid solution, the mass concentration of hydrofluoric acid is 40% ~ 50%, and in described salpeter solution, the mass concentration of nitric acid is 50% ~ 70%; The time of the process of making herbs into wool described in step c is 1 minute ~ 3 minutes, and the temperature of described making herbs into wool process is 5 DEG C ~ 15 DEG C.
Also step f is comprised: the mixing solutions silicon chip after making herbs into wool process being placed in hydrofluoric acid solution, superoxol, silver nitrate solution and Virahol carries out black silicon making herbs into wool after step e; The volume ratio of wherein said hydrofluoric acid solution, superoxol and Virahol is 1 ~ 25:5 ~ 40:1 ~ 30, in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%, and the volumetric molar concentration of described silver nitrate solution is 1 μm of ol/L ~ 10
5μm ol/L.
Compared to prior art, the invention provides a kind of making herbs into wool pretreatment process of silicon chip, the method is before to silicon wafer wool making, by carrying out twice pre-treatment in the same pretreatment fluid being mixed by specific components and ratio and made, and between twice pre-treatment, silicon chip is cleaned, effectively can not only remove the cutting line of silicon chip surface, the pre-treatment matte being beneficial to sequent surface making herbs into wool can also be formed, make this pre-treatment matte be evenly distributed with micro-nano structure, be conducive to follow-up making herbs into wool step.The method technique is simple, cost is low, is applicable to suitability for industrialized production.And the matte of the silicon wafer wool making product obtained by etching method provided by the present invention is even, without stria, the surface albedo of silicon wafer wool making product reduces, fall into light effect good, thus ensure that the solar cell obtained has higher efficiency of conversion, thus after making making herbs into wool, the reflectivity of silicon chip can meet demand of industrial production.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of embodiment 1 through pretreated silicon chip.
Fig. 2 is embodiment 1 another stereoscan photograph through pretreated silicon chip.
Fig. 3 is the stereoscan photograph of the silicon wafer wool making product of embodiment 1 after making herbs into wool.
Fig. 4 is the stereoscan photograph of embodiment 2 through pretreated silicon chip.
Fig. 5 is the stereoscan photograph of the silicon wafer wool making product of embodiment 2 after making herbs into wool.
Fig. 6 is the stereoscan photograph of embodiment 3 through pretreated silicon chip
Fig. 7 is the stereoscan photograph of the silicon wafer wool making product of embodiment 3 after making herbs into wool.
Fig. 8 is the stereoscan photograph of the silicon wafer wool making product of embodiment 4-1 after making herbs into wool.
Fig. 9 is the stereoscan photograph of the silicon wafer wool making product of embodiment 4-2 after making herbs into wool.
Figure 10 is the stereoscan photograph of the silicon wafer wool making product of comparative example after making herbs into wool.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, be clearly and completely described the technical scheme in embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of making herbs into wool pretreatment process of the silicon chip based on diamond wire cutting, it comprises the steps:
Hydrofluoric acid solution, superoxol and metal-salt are mixed to get pretreatment fluid by a;
The silicon chip that diamond wire cuts is placed in described pretreatment fluid and carries out pre-treatment A by b, until the basic cutting line removed on silicon chip;
C acidic solution cleans the silicon chip through pre-treatment A process, to remove the metallic particles on silicon chip;
The silicon chip cleaned with acidic solution is placed in pretreatment fluid and carries out pre-treatment B by d, until form the pre-treatment matte of the even micro-nano structure of tool on described silicon chip.
The volume ratio of hydrofluoric acid solution described in step a and superoxol is 1 ~ 10:5 ~ 40, and in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, and in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%.Preferably, the volume ratio of described hydrofluoric acid solution, superoxol and water is 1:5 ~ 20:5 ~ 20.In pretreatment fluid described in step a, metal-salt is at least one in cupric nitrate, Silver Nitrate, Palladous nitrate, cupric chloride, hydrochloro-auric acid, Platinic chloride, potassiumchromate, single nickel salt, and the volumetric molar concentration of described metal-salt is 1 μm of ol/L ~ 10
5μm ol/L.
In a preference, the volume ratio of described hydrofluoric acid solution and superoxol is 1 ~ 5:20 ~ 40.
In another preference, also comprise water in described pretreatment fluid, the volume ratio of described hydrofluoric acid solution, superoxol and water is 1 ~ 10:5 ~ 40:1 ~ 100.
In another preference, in described pretreatment fluid, the volume ratio of hydrofluoric acid solution, superoxol and water is 1 ~ 5:20 ~ 40:5 ~ 20.
In another preference, described pretreatment fluid also comprises additive, and described additive is at least one in Virahol, ethanol, propyl carbinol, isopropylcarbinol, ethylene glycol, n-propyl alcohol, ethylene glycol ethyl ether, Diethylene Glycol.Because this additive is alcoholic solvent or ether solvent, can reduce the surface tension of silicon chip, the Quick uniform being conducive to matte is formed; And it has certain volatility, bubble can be got rid of while its volatilization, thus can assist the even release of bubble in preprocessing process.Now, the volume ratio of described hydrofluoric acid solution, superoxol and additive is 1 ~ 10:5 ~ 40:1 ~ 20.Preferably, the volume ratio of described hydrofluoric acid solution, superoxol and additive is 3 ~ 8:20 ~ 30:1 ~ 10.In described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%, and preferably, in described superoxol, the massfraction of hydrogen peroxide is 25% ~ 48%.The massfraction of described additive is 60% ~ 98%; In described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%.
In step b, take metal-salt as Silver Nitrate be example, when adopting other metal-salts, mechanism is consistent.This pretreated mechanism is specially: the first step, the Ag of silicon face
+trapped electron from Si-Si bond, makes Ag
+be reduced to Argent grain, silica changes into silicon-dioxide, and this Argent grain is deposited on the surface of silicon.Second step, H
2o
2silicon below further oxidation silver oxide particle, accelerates the carrying out of the first step reaction, and silicon-dioxide is fallen by HF corrosion dissolution simultaneously, discharges hydrogen.Be equivalent to, silver is catalyzer, H
2o
2for oxygenant, HF is etching agent, and reaction general equation is as follows:
Si+H
2O
2+6HF＝H
2SiF
6+2H
2O+H
2↑ (1)
When pretreatment fluid comprise further comprise alcoholic solvent or ether solvent time, this alcoholic solvent or ether solvent can reduce the surface tension of silicon chip, be conducive to matte Quick uniform formed; And it has certain volatility, bubble can be got rid of while its volatilization, thus can assist the even release of hydrogen gas bubbles in preprocessing process thus pre-treatment is etched and evenly carry out, and be beneficial to the uniform surface of formation.
In stepb, the part that silicon chip is in convex surface is comparatively large with the contact surface of pretreatment fluid, and first corroded, thus make the various piece of silicon chip after excessive erosion, surface is progressively tending towards smooth.Be appreciated that due in stepb, mainly eliminate cutting line and remove affected layer, therefore, now silicon chip surface will comparatively smooth, and simultaneously due to the deposition of metallic particles, the surface that process obtains also is unfavorable for making herbs into wool, must carry out the pre-treatment of second step.
Further, for effectively removing the cutting line of silicon chip surface, the pretreatment time of described pre-treatment A is 1 minute ~ 10 minutes, and pretreated temperature is 10 DEG C ~ 45 DEG C.In the present embodiment, for taking into account treatment effect and processing efficiency, the pretreatment time of described pre-treatment A is 4 minutes ~ 7 minutes, and pretreated temperature is 20 ~ 30 DEG C.
In step c, described acidic solution is used for reacting with the metallic particles of the silicon chip surface through pre-treatment A process, to remove the metallic particles on silicon chip, described acidic solution is at least one in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, citric acid, carboxylic acid, sulfonic acid,-sulfinic acid, thionothiolic acid, fluorine metaantimmonic acid, fluorine antimony sulfonic acid.Be appreciated that the concentration of described acidic solution is can effectively remove described metallic particles, and not damage silicon chip surface be good.In the present embodiment, when described metallic particles is silver, described acidic solution to be concentration be 68% salpeter solution.
In steps d, pre-treatment B for forming the pre-treatment matte of the even micro-nano structure of tool on silicon chip.Because described silicon chip is through the cleaning of step c, surface, substantially without metallic particles, therefore, can be corroded further on silicon chip, form the pre-treatment matte of the even micro-nano structure of tool, be convenient to next step making herbs into wool.The treatment time of described pre-treatment B is 30 seconds ~ 5 minutes, and pretreated temperature is 10 DEG C ~ 45 DEG C.Preferably, the treatment time of described pre-treatment B is 30 seconds ~ 3 minutes, and pretreated temperature is 20 DEG C ~ 30 DEG C.
The invention provides a kind of etching method of the silicon chip based on diamond wire cutting, it comprises the steps:
Hydrofluoric acid solution, superoxol and metal-salt are mixed to get pretreatment fluid by a;
The silicon chip that diamond wire cuts is placed in described pretreatment fluid and carries out pre-treatment A by b, until the basic cutting line removed on silicon chip;
C acidic solution cleans the silicon chip through pre-treatment A process, to remove the metallic particles on silicon chip;
The silicon chip cleaned with acidic solution is placed in pretreatment fluid and carries out pre-treatment B by d, until form the pre-treatment matte of the even micro-nano structure of tool on described silicon chip;
Silicon chip through pre-treatment B is placed in hydrofluoric acid nitric acid Woolen-making liquid and carries out making herbs into wool process by e.
Step a-d is substantially identical with the making herbs into wool pretreatment process of the described silicon chip cut based on diamond wire.
The nitric acid of hydrofluoric acid described in step e Woolen-making liquid is the mixture that hydrofluoric acid solution, salpeter solution and water are mixed to get with the volume ratio of 1 ~ 5:5 ~ 10:5 ~ 15, in described hydrofluoric acid solution, the mass concentration of hydrofluoric acid is 40 ~ 50%, and in described salpeter solution, the mass concentration of nitric acid is 50 ~ 70%; The time of the process of making herbs into wool described in step c is 1 minute ~ 3 minutes, and the temperature of described making herbs into wool process is 5 ~ 15 DEG C.
In step e, the reaction mechanism of this making herbs into wool process is that silicon face is oxidized by nitric acid generation silicon-dioxide, and silicon-dioxide is by hydrofluoric acid dissolution subsequently, thus forms uneven and uniform matte, realizes surface-texturing, i.e. making herbs into wool.Reaction equation is as follows:
4HNO
3+Si＝SiO
2+4NO
2↑+2H
2O (2)
SiO
2+6HF＝H
2SiF
6+2H
2O (3)
Described hydrofluoric acid nitric acid Woolen-making liquid is the mixture that hydrofluoric acid solution, salpeter solution and water are mixed to get with the volume ratio of 1 ~ 5:5 ~ 10:5 ~ 15.In described hydrofluoric acid solution, the mass concentration of hydrofluoric acid is 40% ~ 50%, and in described salpeter solution, the mass concentration of nitric acid is 50% ~ 70%.The time of described making herbs into wool process is 30 seconds ~ 3 minutes.The temperature of described making herbs into wool process is 5 DEG C ~ 15 DEG C.After making herbs into wool process, silicon chip clear water can be rinsed.
Preferably, the mixture that described hydrofluoric acid nitric acid Woolen-making liquid is 40wt% hydrofluoric acid solution, 68wt% salpeter solution and water are mixed to get with the volume ratio of 3:8:9, the time of described making herbs into wool process is 80 seconds, and the temperature of described making herbs into wool process is 8 DEG C.
In order to form the matte that reflectivity is lower, be conducive to battery efficiency lifting further,, described etching method comprises step f further after step e: the mixing solutions silicon chip after making herbs into wool process being placed in hydrofluoric acid solution, superoxol, silver nitrate solution and Virahol carries out black silicon making herbs into wool; The volume ratio of wherein said hydrofluoric acid solution, superoxol and Virahol is 1 ~ 25:5 ~ 40:1 ~ 30, in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%, and the volumetric molar concentration of described silver nitrate solution is 1 μm of ol/L ~ 10
5μm ol/L.
Compared to prior art, the invention provides a kind of making herbs into wool pretreatment process of silicon chip, the method is before to silicon wafer wool making, by carrying out twice pre-treatment in the same pretreatment fluid being mixed by specific components and ratio and made, and between twice pre-treatment, silicon chip is cleaned, effectively can not only remove the cutting line of silicon chip surface, the pre-treatment matte being beneficial to sequent surface making herbs into wool can also be formed, make this pre-treatment matte be evenly distributed with micro-nano structure, be conducive to follow-up making herbs into wool step.The method technique is simple, cost is low, is applicable to suitability for industrialized production.And the matte of the silicon wafer wool making product obtained by etching method provided by the present invention is even, without stria, the surface albedo of silicon wafer wool making product reduces, fall into light effect good, thus ensure that the solar cell obtained has higher efficiency of conversion, thus after making making herbs into wool, the reflectivity of silicon chip can meet demand of industrial production.
Below in conjunction with specific embodiment, the making herbs into wool pretreatment process of the silicon chip based on diamond cutting of the present invention and etching method are described.
Embodiment 1
40wt% hydrofluoric acid solution, 30wt% superoxol and water are mixed with the volume ratio of 3:24:5, and adds Silver Nitrate and obtain pretreatment fluid.In described pretreatment fluid, silver nitrate concentration is 80 μm of ol/L.
Remove silicon chip surface greasy dirt and the zone of oxidation of diamond wire cutting with the hydrofluoric acid solution of 10wt%, then silicon chip is placed in pretreatment fluid and carries out pre-treatment A process, pretreated temperature is 25 DEG C, and the pretreated time is 5 minutes.Use deionized water rinsing subsequently 2 minutes, nitric acid dousing removes surperficial Argent grain in 2 minutes, deionized water rinsing 2 minutes.
Repeat that above-mentioned silicon chip is put into pretreatment fluid and carry out pre-treatment B process, pretreated temperature is 25 DEG C, and the pretreated time is 1 minute.Use deionized water rinsing subsequently 2 minutes.
40wt% hydrofluoric acid solution, 68wt% salpeter solution and water are mixed to get hydrofluoric acid nitric acid Woolen-making liquid with the volume ratio of 3:8:9.Hydrofluoric acid nitric acid Woolen-making liquid will be placed in through pretreated silicon chip and carry out making herbs into wool process.The time of described making herbs into wool process is 2 minutes, and the temperature of described making herbs into wool process is 8 DEG C.Last deionized water rinsing 2 minutes, obtains silicon wafer wool making product.Fig. 1 and Fig. 2 is that the surperficial SEM of different amplification after silicon chip pre-treatment schemes, and Fig. 3 is the surperficial SEM figure after silicon wafer wool making.
Embodiment 2
The making herbs into wool pretreatment process of embodiment 2 is basic identical with etching method with the making herbs into wool pretreatment process of embodiment 1 with etching method, difference is that pretreatment fluid is mixed to get with the volume ratio of 5:18 by 40wt% hydrofluoric acid solution and 30wt% superoxol, in pretreatment fluid, silver nitrate concentration is 3 μm of ol/L, pre-treatment A process time is 10 minutes, and the pre-treatment B process reaction time is 3 minutes.Fig. 4 is that the pretreated surperficial SEM of silicon chip schemes, and Fig. 5 is the surperficial SEM figure after silicon wafer wool making.
Embodiment 3
The making herbs into wool pretreatment process of embodiment 3 is basic identical with etching method with the making herbs into wool pretreatment process of embodiment 1 with etching method, difference is pretreatment fluid concentration and pre-treatment B process time, 50wt% hydrofluoric acid solution, 30wt% superoxol and 89% Virahol mix with the volume ratio of 1:20:3, in pretreatment fluid, metal-salt is cupric nitrate, the concentration of described copper nitrate solution is 1000 μm of ol/L, pre-treatment A process time is 9 minutes, and pretreatment temperature is 40 DEG C; The pre-treatment B process reaction time is 40 seconds, and treatment temp is 30 DEG C.The pre-treatment A process reaction time is identical with embodiment 1 with temperature.Fig. 6 is that the pretreated surperficial SEM of silicon chip schemes, and Fig. 7 is the surperficial SEM figure after silicon wafer wool making.
Embodiment 4-1
The etching method of embodiment 4-1 is basic identical with the etching method of embodiment 1, difference is pretreatment fluid concentration, pre-treatment A and pre-treatment B process time, in pretreatment fluid, 40wt% hydrofluoric acid solution, 30wt% superoxol and 98% alcohol mix with the volume ratio of 1:4:2, in pretreatment fluid, silver nitrate concentration is 96 μm of ol/L, pre-treatment A process time is 8 minutes, and pre-treatment B process time is 30 seconds.The surperficial SEM figure of the silicon chip after this etching method making herbs into wool of Fig. 8.
Embodiment 4-2
The etching method of embodiment 4-1 is basic identical with the etching method of embodiment 1, and difference is pretreatment fluid concentration, pre-treatment A and pre-treatment B process time, and includes black silicon making herbs into wool process.The mixing solutions of configuration hydrofluoric acid solution, superoxol, silver nitrate solution and Virahol, wherein the volume ratio of hydrofluoric acid solution, superoxol and Virahol is 15:20:28, and the volumetric molar concentration of silver nitrate solution is 120 μm of ol/L.Silicon chip after making herbs into wool process is placed in above-mentioned solution and carries out black silicon making herbs into wool process.Fig. 9 be with the making herbs into wool of black silicon etching method after the surperficial SEM figure of silicon chip.
Comparative example:
The making herbs into wool pretreatment process of comparative example 1 is identical with etching method with the making herbs into wool pretreatment process of embodiment 1 with etching method, difference is, preprocessing process A, B merges into a step process, and the volume ratio 1:20:5 of 40wt% hydrofluoric acid solution, 30wt% superoxol and 98% Virahol, in pretreatment fluid, silver nitrate concentration is 96 μm of ol/L, and pretreatment time is 5 minutes.Surperficial SEM after silicon wafer wool making is shown in Figure 10.
Refer to Fig. 1, the silicon chip in embodiment 1 after pre-treatment, surface cutting line is removed substantially, substantially without surperficial bright rays, and the silicon chip in comparative example after pre-treatment, its surface cutting line is many and comparatively obvious, thus causes having comparatively multi-surface bright rays.Further, as can be seen from Figure 2, pretreated silicon chip surface is equally distributed nano pore structure; As can be seen from Figure 3, after the making herbs into wool of hydrofluoric acid salpeter solution, the nano pore structure of silicon chip surface disappears, and the silicon wafer wool making product obtained are worm's ovum formula structure and are evenly distributed.Refer to Fig. 4-7, pre-treatment silicon chip and sour making herbs into wool silicon chip present identical changing trend.Further, refer to Fig. 8-9, carry out black silicon making herbs into wool process to the silicon chip after the making herbs into wool of hydrofluoric acid salpeter solution, silicon chip surface equally distributed worm's ovum formula structure disappears, and presents uniform vesicular structure.In a word, refer to Fig. 1-9, silicon chip surface all exists without cutting line, that is, by making herbs into wool pretreatment process provided by the invention, surface cutting line can substantially be removed, and the pre-treatment matte with even micro-nano structure can be obtained, thus after making herbs into wool, obtain comparatively even, and without the silicon wafer wool making product of bright rays; Then still there is obvious diamond wire cutting bright rays in the silicon chip that comparative example obtains.
Further, under 350nm ~ 1150nm wave band, reflectance test is carried out to the surface of the silicon wafer wool making product that embodiment 1-4 and comparative example finally obtain.Silicon wafer wool making product are prepared into solar cell respectively, carry out the test of battery efficiency.In the present invention, the reflectivity of silicon wafer wool making product adopts the HELIOS LAB-RE type reflectance test instrument of AudioDev GmbH to record, and cell conversion efficiency test adopts the SoliA type solar cell volt-ampere characteristic test macro of U.S. NewportOriel to record.
Test result is as shown in table 1:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4-1 | Embodiment 4-2 | Comparative example 1 | |
| Reflectivity (%) | 23.39 | 23.16 | 24.12 | 23.52 | 16.08 | 28.69 |
| Battery conversion efficiency (%) | 18.05 | 17.93 | 18.02 | 17.98 | 18.24 | 17.69 |
From table 1, adopt this etching method to obtain the reflectance reduction of silicon wafer wool making product, the efficiency of conversion of the solar cell of preparation increases.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1., based on a making herbs into wool pretreatment process for the silicon chip of diamond wire cutting, it comprises the steps:
Hydrofluoric acid solution, superoxol and metal-salt are mixed to get pretreatment fluid by a;
The silicon chip that diamond wire cuts is placed in described pretreatment fluid and carries out pre-treatment A by b, until the basic cutting line removed on silicon chip;
C acidic solution cleans the silicon chip through pre-treatment A process, to remove the metallic particles on silicon chip;
The silicon chip cleaned with acidic solution is placed in pretreatment fluid and carries out pre-treatment B by d, and described silicon chip is formed the pre-treatment matte of the even micro-nano structure of tool.
2. a making herbs into wool pretreatment process as claimed in claim 1, it is characterized in that, the volume ratio of hydrofluoric acid solution described in step a and superoxol is 1 ~ 10:5 ~ 40, in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, and in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%; In described pretreatment fluid, metal-salt is at least one in cupric nitrate, Silver Nitrate, Palladous nitrate, cupric chloride, hydrochloro-auric acid, Platinic chloride, potassiumchromate, single nickel salt, and the volumetric molar concentration of described metal-salt is 1 μm of ol/L ~ 10
5μm ol/L.
3. a making herbs into wool pretreatment process as claimed in claim 2, it is characterized in that, described pretreatment fluid comprises additive further, and described additive is at least one in Virahol, ethanol, propyl carbinol, isopropylcarbinol, ethylene glycol, n-propyl alcohol, ethylene glycol ethyl ether, Diethylene Glycol.
4. a making herbs into wool pretreatment process as claimed in claim 3, the volume ratio of described hydrofluoric acid solution, superoxol and additive is 1 ~ 10:5 ~ 40:1 ~ 20, in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%, and the massfraction of described additive is 60% ~ 98%.
5. a making herbs into wool pretreatment process as claimed in claim 1, is characterized in that, the pretreatment time of the A of pre-treatment described in step b is 1 minute ~ 10 minutes, and pretreated temperature is 10 DEG C ~ 45 DEG C.
6. a making herbs into wool pretreatment process as claimed in claim 1, is characterized in that, the treatment time of the B of pre-treatment described in steps d is 30 seconds ~ 5 minutes, and pretreated temperature is 10 DEG C ~ 45 DEG C.
7. a making herbs into wool pretreatment process as claimed in claim 1, it is characterized in that, acidic solution described in step c is at least one in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, citric acid, carboxylic acid, sulfonic acid,-sulfinic acid, thionothiolic acid, fluorine metaantimmonic acid, fluorine antimony sulfonic acid.
8., based on an etching method for the silicon chip of diamond wire cutting, it comprises the steps:
Hydrofluoric acid solution, superoxol, metal-salt and additive are mixed to get pretreatment fluid by a;
The silicon chip that diamond wire cuts is placed in described pretreatment fluid and carries out pre-treatment A by b, until the basic cutting line removed on silicon chip;
C acidic solution cleans the silicon chip through pre-treatment A process, to remove the metallic particles on silicon chip;
The silicon chip cleaned with acidic solution is placed in pretreatment fluid and carries out pre-treatment B by d, until form the pre-treatment matte of the even micro-nano structure of tool on described silicon chip;
Silicon chip through pre-treatment B is placed in hydrofluoric acid nitric acid Woolen-making liquid and carries out making herbs into wool process by e.
9. an etching method as claimed in claim 8, it is characterized in that, the nitric acid of hydrofluoric acid described in step e Woolen-making liquid is the mixture that hydrofluoric acid solution, salpeter solution and water are mixed to get with the volume ratio of 1 ~ 5:5 ~ 10:5 ~ 15, in described hydrofluoric acid solution, the mass concentration of hydrofluoric acid is 40% ~ 50%, and in described salpeter solution, the mass concentration of nitric acid is 50% ~ 70%; The time of the process of making herbs into wool described in step c is 1 minute ~ 3 minutes, and the temperature of described making herbs into wool process is 5 DEG C ~ 15 DEG C.
10. an etching method as claimed in claim 8, is characterized in that, also comprises step f after step e: the mixing solutions silicon chip after making herbs into wool process being placed in hydrofluoric acid solution, superoxol, silver nitrate solution and Virahol carries out black silicon making herbs into wool; The volume ratio of wherein said hydrofluoric acid solution, superoxol and Virahol is 1 ~ 25:5 ~ 40:1 ~ 30, in described hydrofluoric acid solution, the massfraction of hydrofluoric acid is 40% ~ 50%, in described superoxol, the massfraction of hydrogen peroxide is 20% ~ 55%, and the volumetric molar concentration of described silver nitrate solution is 1 μm of ol/L ~ 10
5μm ol/L.
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