CN101844872B - Preparation method of flocking liquid - Google Patents
Preparation method of flocking liquid Download PDFInfo
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- CN101844872B CN101844872B CN2010101725950A CN201010172595A CN101844872B CN 101844872 B CN101844872 B CN 101844872B CN 2010101725950 A CN2010101725950 A CN 2010101725950A CN 201010172595 A CN201010172595 A CN 201010172595A CN 101844872 B CN101844872 B CN 101844872B
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Abstract
The invention belongs to the technical field of chemical industry, and relates to flocking liquid, in particular to flocking liquid applied in a flocking process of a process for manufacturing a solar cell; and meanwhile, the invention also discloses a preparation method for the flocking liquid. In order to solve the problems that etching liquid used in the conventional flocking process for manufacturing the solar cell contains low-boiling-point and easily volatile chemical substances such as isopropanol and the like and the chemical substances cause instability between batches of the flocking process during use and frequently produce a large amount of spotted plates to seriously affect the appearance and power generation efficiency of cell plates, the invention provides the flocking liquid. The flocking liquid comprises alkali capable of reacting with silicon, aqueous solution of silicate and mixture of amyl acid and amyl alcohol, wherein the mass ratio of the amyl acid to the amyl alcohol in the mixture of the amyl acid and the amyl alcohol is 3:1-2:1.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of flocking liquid, particularly a kind of flocking liquid that in the flocking technique of making solar battery process, is applied to, the present invention has simultaneously also introduced the preparation method of flocking liquid.
Background technology
It is polycrystalline and monocrystalline solar cells that world today's silica-based solar cell can be divided into two big camps by the material differentiation.The flocking processing procedure is the first road technology in the solar cell processing procedure, also is very crucial together manufacturing process.Generally speaking the reflectivity for the silica-base material of solar cell is 30-35%, and meaning i.e. 100% solar energy projects silicon substrate surface, and the solar energy of the 30-35% that has an appointment is reflected, and can not effectively utilize the energy of this part sunshine.The main effect of flocking technique is minimum with regard to being that reflectivity with silica-base material drops to, in the hope of the energy that utilizes sunshine to provide to us of maximum range.
Flocking technique can be divided into sour processing procedure and alkali processing procedure by silica-base material at present.For the silicon single crystal silica-base material; Traditional matte technology of main flow is the alkali processing procedure at present; Its content is: utilize the aqueous solution of the Pottasium Hydroxide (or sodium hydroxide) (20%) of high density to remove because the cutting vestige (or being called affected layer) that stays in the cutting process earlier; Generally need to remove the silicon materials of 5-10 μ m left and right thickness, and then utilize the mixed aqueous solution of Pottasium Hydroxide (or sodium hydroxide)+Virahol+water glass to form observable intensive pyramid under microcosmic in etching under 80 ℃ the temperature.Its reflectivity will be reduced to about 14%.That is to say and to have brought back the solar energy of 15-20% through the flocking processing procedure.But the greatest drawback of traditional alkali matte processing procedure is: because a large amount of Virahol that uses; And its lower boiling and volatile chemical property have caused the instability between flocking processing procedure batch; A large amount of so-called piebald sheets appear in Shi Changhui, and have a strong impact on the outward appearance and the generating efficiency of battery sheet.
General, solar battery sheet industry matte piebald can be controlled in about 2% in some big factories, but for those little factories or the still not mature enough producer of technology, the piebald rate is generally at 5-10%.
Summary of the invention
Lower boilings such as Virahol, volatile chemical substance that the flocking liquid that the technical problem that will solve required for the present invention is to use in the flocking technique of existing preparation solar cell contains; These chemical substances in use can cause the instability between flocking technique batch; And the time regular meeting a large amount of piebald sheets appears; Thereby have a strong impact on the outward appearance of battery sheet and the problem of generating efficiency; And a kind of flocking liquid is provided to this problem, and in flocking technique, using flocking liquid of the present invention, can fundamentally solve the problems of the technologies described above at least.
Specifically, the present invention solves the problems of the technologies described above through following technical scheme:
A kind of flocking liquid, comprise can with alkali, silicate, skimmer and the water of pasc reaction, said skimmer is the valeric acid amyl alcohol mixture, the mass ratio of valeric acid and amylalcohol is 3: 1～2: 1 in the valeric acid amyl alcohol mixture.
Say as background technology part of the present invention; The mixed aqueous solution that utilizes Pottasium Hydroxide (or sodium hydroxide)+Virahol+water glass is arranged with silicon chip etching under 80 ℃ temperature in the existing flocking technique; Thereby form observable this step of intensive pyramid under the microcosmic on the silicon substrate surface; In this step, Virahol is a skimmer, is used for the hydrogen that the reaction of Pottasium Hydroxide (or sodium hydroxide) and silicon chip is produced is taken away.Since the boiling point lower (82.6 ℃) of Virahol, therefore, the Virahol highly volatile.
And in actually operating, the temperature of the different sites of flocking groove can receive the influence of temperature control precision unavoidably and height is inhomogeneous, also i.e. different sites in the flocking groove, and the volatilization degree of Virahol is not quite similar.If the temperature drift at some position; Then the volatilization of Virahol is just bigger; Thereby will cause the isopropyl alcohol concentration at these positions on the low side, make the silicon substrate etch rate of different sites also inconsistent (being the instability between flocking technique batch), finally form the colored sheet that naked eyes are seen at silicon chip surface.
The boiling point of the valeric acid amyl alcohol mixture that the present invention adopts generally is higher than 200 ℃, therefore, is enough to guarantee in flocking technique, not volatilize.
Each component in the valeric acid amyl alcohol mixture according to the invention all has effect separately simultaneously; Generally speaking; The adding of alcohols material (promptly referring to amylalcohol here) can effectively reduce the diagram of system surface tension; Make that producing hydrogen can not be adsorbed on the silicon chip, the hydrogen deaeration that helps producing is discharged, thereby can play the froth breaking effect.And ability of the valeric acid in the valeric acid amyl alcohol mixture and Pottasium Hydroxide reaction generate valeric acid potassium, and valeric acid potassium is adsorbed on silicon chip surface can effectively strengthen the anisotropy of Pottasium Hydroxide to silicon chip erosion, promptly form little pyramid structure more easily.
In order to make the each component in the valeric acid amyl alcohol mixture can fully play effect separately; The mass ratio of valeric acid and amylalcohol is 3: 1～2: 1 in the valeric acid amyl alcohol mixture; Need be pointed out that further that all isomerss of valeric acid amylalcohol can be used to as valeric acid of the present invention and amylalcohol.
In fact; The effect of the valeric acid amyl alcohol mixture of introducing above; Be enough to solve technical problem to be solved by this invention (a large amount of piebald sheets are arranged, thereby influence the efficiency of conversion of battery sheet), in general; Use flocking liquid according to the invention to prepare solar cell, the transformation efficiency of its battery sheet can promote 0.2-0.5%.But the present invention finds some technique effects that bring other that the valeric acid amyl alcohol mixture can also be indirect, and one of them example is to use flocking fluid power of the present invention enough to simplify the equipment of flocking technique:
Before the present invention, than higher, this is embodied in the flocking groove at least need be equipped with bubbling or groove internal circulation apparatus to flocking technique to the requirement of equipment, to high this two aspect of the stability requirement of bubbling or groove internal circulation apparatus.
For existing flocking technique; The purpose that installs high bubbling of stability or groove internal circulation apparatus additional is exactly the temperature height of different sites in the even flocking groove; So that Virahol can be volatilized at each position uniformly, thereby obtain the lower finished product of piebald rate.
The present invention with the valeric acid amyl alcohol mixture substitute Virahol as skimmer after; Because the valeric acid amyl alcohol mixture has higher boiling point; Do not exist in the easy evaporable problem of skimmer in the process of flocking technique running, the bubbling or the groove internal circulation apparatus that are equipped with in the therefore existing flocking groove just not have necessity of existence yet.
Another example is, uses flocking liquid of the present invention, can simplify traditional flocking technique:
Before the etching of carrying out silicon chip, often need remove the affected layer that cutting stays; Thus; The tradition flocking technique is provided with affected layer technology; Get off like this, silicon substrate will be thinned about 30 μ m, and flocking fluid power of the present invention enough makes the initial etch rate height very of silicon substrate (generally can reach about 3g/m
2Min), this has just played the polishing action of silicon substrate, can reach the technique effect identical with going affected layer technology equally, and the silicon substrate attenuate is general all within 15 μ m.
Therefore, through flocking liquid according to the invention, on the one hand, the affected layer technology of going in the existing flocking technique has not had necessity of setting; On the one hand; The attenuate quantity of silicon substrate can be reduced greatly, and having solved that the fragmentation rate in the technological process promotes after the silica-based film source thinning (is that silicon substrate is being etched back attenuation, insufficient strength; In subsequent handling, break easily) puzzlement, improved the battery bending tablet degree under the thin slice condition; On the one hand, from the angle of environmental protection, because the present invention says that in process of production the waste liquid of generation is 1/3rd (reduce greatly through the attenuate quantity of silicon substrate at least and realize) of traditional technology, so practiced thrift the cost of wastewater treatment greatly.
In sum, the technique effect that this technique means of valeric acid amyl alcohol mixture material substitution Virahol that the present invention takes is brought all can make the cost of flocking technique decline to a great extent, and generally speaking, flocking production priming cost will reduce more than 35%.This, acquires a special sense under the situation of expensive for present solar cell silica-base material shortage.
Except the valeric acid amyl alcohol mixture; Other component in the flocking liquid also can produce corresponding effect; In fact, the overall technique effect of flocking liquid needs the mutual cooperation of various components to bring into play preferably, therefore; For the beneficial effect that makes flocking liquid of the present invention can be given full play to, need the ratio of each component in the flocking liquid reasonably be provided with.
For the present invention, the mass percent of said alkali is 5%-15%:
The principle of etching is to utilize the anisotropy of silicon substrate; Alkali lye when concentration is low in different directions etch rate can differ 100 times; If alkali number is crossed conference and slackened anisotropy, promptly etch rate is very nearly the same in different directions, does not so just reach the effect of etching.Certainly the lower words of concentration of lye are the requirements that do not reach etch amount.It is suitable that the mass percent concentration of alkali is set to 5%-15%, and the present invention finds that such concentration can guarantee the anisotropic while of silicon substrate, keeps certain etch amount.
For the present invention, the mass percent of silicate is 20%-30%:
An amount of silicate plays the effect of a buffered soln, because etched process can produce silicate, and can be in the etching later stage because the enrichment meeting of silicate ion has a strong impact on etch rate if add under the original state into silicate.It is suitable that the mass percent concentration of silicate is set to 20%-30%; When the present invention finds that such concentration can be brought into play the silicate shock absorption, can not cause the etching later stage to have a strong impact on the consequence of etch rate owing to the enrichment of silicate ion at least.
For the present invention, the mass percent of valeric acid amyl alcohol mixture is 5%-15%:
The present invention finds that the valeric acid amyl alcohol mixture has been added not only can be increased cost but also can consume more alkali lye; Add to have lacked not have and reduce the capillary effect of flocking liquid (also being the froth breaking effect), the mass percent of valeric acid amyl alcohol mixture is set to 5%-15% and has taken all factors into consideration above-mentioned two kinds of factors.
The silica-base material that is used to prepare solar cell through flocking liquid processing according to the invention; Generally have some significant advantages; For example stability high (the film clips rate is generally 0%), the investment low (owing to need not set up utility appliance such as bubbling or groove internal circulation apparatus, the low 30-50% of cost of investment of the existing flocking apparatus of therefore general cost of investment) of flocking apparatus, the waste liquid generation between the matte good uniformity of silica-base material (can the silica-base material surface seeing thin and close little pyramid with microscope), flocking technique batch is few or the like.
For those skilled in the art are convenient to embodiment of the present invention, the present invention also provides a kind of method for preparing flocking liquid, and this method comprises:
A, with water and can add in the reaction kettle with the alkali of pasc reaction, stir and promote its dissolving, obtain alkali lye, and make the temperature of alkali lye remain on 50 ℃-80 ℃;
B, in the alkali lye of a step preparation, add the valeric acid amyl alcohol mixture, obtain first mixed solution, and make the temperature of first mixed solution remain on 50 ℃-80 ℃;
C, in first mixed solution, add silicate, obtain second mixed solution, and make the temperature of second mixed solution remain on 50 ℃-80 ℃;
D, in second mixed solution, add entry, and make the temperature of solution remain on 50 ℃-80 ℃,, promptly obtain flocking liquid with postcooling.
Consider the solubleness of silicate, silicate according to the invention refers to water glass or potassium silicate, preferred water glass.
Various components in the flocking liquid according to the invention are generally mixed under 50 ℃-80 ℃ condition, and such temperature setting can make the fully dissolving mutually of various components, lays the foundation thereby bring into play beneficial effect for flocking liquid.
Embodiment
Embodiment
The described flocking liquid of present embodiment comprises that mass percent is that 10% electronic-grade Pottasium Hydroxide, mass percent are that 25% water glass, mass percent are 10% valeric acid amyl alcohol mixture (wherein the mass ratio of valeric acid and amylalcohol is 2.5: 1); All the other are pure water, and valeric acid and amylalcohol be the AR for being produced by Shanghai reagent three factories all.
Following mask body introduction is the method steps (the following percentage ratio of mentioning is mass percent) of the said flocking liquid of preparation present embodiment down:
1. the Pottasium Hydroxide with 20% industrial pure water and 10% electronic-grade adds in the reaction kettle, and middling speed (800-2500r/min) stirs and promotes its dissolving, and through the heating spacer temperature of solution is remained on 70 ℃.Churning time was controlled at 25 minutes;
2. after treating that Pottasium Hydroxide dissolves fully, the ratio in 10% adds the valeric acid amyl alcohol mixture by amount, and middling speed (800-3000r/min) stirs and promotes its dissolving, and through the heating spacer temperature of solution is remained on 70 ℃.Churning time was controlled at 50 minutes;
3. the water glass (30% solid content) that adds electronic-grade in 25% ratio, middling speed (800-2500r/min) stir and promote its dissolving, and through the heating spacer temperature of solution are remained on 70 ℃.Churning time was controlled at 50 minutes;
4. the hot pure water (temperature is 70 ℃) that adds remaining proportion at last, middling speed (800-2500r/min) stir, and through the heating spacer temperature of solution are remained on 70 ℃, and churning time was controlled at 50 minutes, was cooled to 30 ℃ of after-filtration subsequently, and packing gets final product.
During use, only need silicon substrate is put into the etching groove that fills flocking liquid, the temperature of etching groove is 80 ℃, thereby arrives intensive pyramid at the silicon substrate surface observation under the microcosmic, and etching 30 minutes can be accomplished the flocking processing procedure.
After the silicon substrate of handling with above-mentioned flocking liquid was finally processed the battery sheet, its cell photoelectric efficiency of conversion generally reached 16.8-17%, and the battery angularity is generally 0.95-1.25mm.
For the ease of beneficial effect of the present invention is described, enumerate a method steps of accomplishing the flocking processing procedure with prior art at present:
Utilizing mass percent concentration earlier is that the aqueous solution of 20% Pottasium Hydroxide is removed because the cutting vestige (or being called affected layer) that stays in the cutting process; Remove the silicon materials of 8 μ m thickness; And then (wherein the mass percent concentration of Pottasium Hydroxide is 3%, and the mass percent concentration of Virahol is 0.5%, and the mass percent concentration of water glass is 1% to utilize the mixed aqueous solution of Pottasium Hydroxide+Virahol+water glass; All the other are water) etching 30 minutes under 80 ℃ temperature; Equally, under the microcosmic, arrive intensive pyramid at the silicon substrate surface observation.
After the silicon substrate of handling with the mixed aqueous solution of above-mentioned Pottasium Hydroxide+Virahol+water glass was finally processed the battery sheet, its cell photoelectric efficiency of conversion was generally 16.0-16.5%, and the battery angularity is generally 1.4-1.6mm
Table 1 is the performance comparison table of the said silicon substrate of handling respectively with the mixed aqueous solution of flocking liquid and Pottasium Hydroxide+Virahol+water glass of embodiment.
Table 1
Claims (1)
1. a method for preparing flocking liquid is characterized in that, comprises the steps:
(1) Pottasium Hydroxide with 20% industrial pure water and 10% electronic-grade adds in the reaction kettle, and middling speed 800-2500r/min stirs and promotes its dissolving, and through the heating spacer temperature of solution is remained on 70 ℃; Churning time was controlled at 25 minutes;
(2) treat that Pottasium Hydroxide dissolves fully after, the ratio in 10% adds the valeric acid amyl alcohol mixture by amount, middling speed 800-3000r/min stirs and promotes its dissolving, and through the heating spacer temperature of solution is remained on 70 ℃; Churning time was controlled at 50 minutes;
(3) add 30% solid content water glass of electronic-grade in 25% ratio, middling speed 800-2500r/min stirs and promotes its dissolving, and through the heating spacer temperature of solution is remained on 70 ℃; Churning time was controlled at 50 minutes;
(4) temperature that adds remaining proportion at last is 70 ℃ of hot pure water, and middling speed 800-2500r/min stirs, and through the heating spacer temperature of solution is remained on 70 ℃, and churning time was controlled at 50 minutes, was cooled to 30 ℃ of after-filtration subsequently, and packing gets final product;
During use, only need silicon substrate is put into the etching groove that fills flocking liquid, the temperature of etching groove is 80 ℃, thereby arrives intensive pyramid at the silicon substrate surface observation under the microcosmic, and etching 30 minutes can be accomplished the flocking processing procedure.
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| CN2010101725950A CN101844872B (en) | 2010-05-07 | 2010-05-07 | Preparation method of flocking liquid |
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| CN2010101725950A CN101844872B (en) | 2010-05-07 | 2010-05-07 | Preparation method of flocking liquid |
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| CN101844872B true CN101844872B (en) | 2012-05-02 |
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| AU2005297901B2 (en) * | 2004-10-28 | 2008-11-27 | Mimasu Semiconductor Industry Co., Ltd. | Process for producing semiconductor substrate, semiconductor substrate for solar application and etching solution |
| CN101323955B (en) * | 2008-02-27 | 2010-11-03 | 苏州苏电微电子信息化学品研发中心有限公司 | Wool-making agent for monocrystalline silicon solar cell surface treatment and manufacturing method thereof |
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