CN103618026A - Micro-nanometer machining device and method of meshed polycrystalline silicon - Google Patents
Micro-nanometer machining device and method of meshed polycrystalline silicon Download PDFInfo
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- CN103618026A CN103618026A CN201310558211.2A CN201310558211A CN103618026A CN 103618026 A CN103618026 A CN 103618026A CN 201310558211 A CN201310558211 A CN 201310558211A CN 103618026 A CN103618026 A CN 103618026A
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- H01—ELECTRIC ELEMENTS
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a micro-nanometer machining device and method of meshed polycrystalline silicon. The effect of an antireflection layer used for preparation of a polycrystalline silicon solar cell at present is poor. According to the micro-nanometer machining device, the output end of each ultrasonic generator controller is connected with the tail portion of an amplitude-change pole in a threaded mode through an energy converter. The head portion of each amplitude-change pole pile is connected with the tail portion of a plane ultrasonic tool head in a threaded mode. The head portion of each plane ultrasonic tool head extends into a reaction observation room. The inner side walls, opposite to the plane ultrasonic tool heads respectively, of the reaction observation room are respectively provided with a sound wave reflecting plate in a fixed mode. A reaction container is arranged in the reaction observation room. The micro-nanometer machining method of the polycrystalline silicon comprises the steps that mixed acidizing fluid is poured into the reaction container, the plane ultrasonic tool heads are driven to form ultrasonic standing waves, a polycrystalline silicon material is placed in the reaction container to conduct preparation, the prepared polycrystalline silicon is placed in a deionizing solution to be washed, and packaging is conducted. By the adoption of the micro-nanometer machining device and method of the meshed polycrystalline silicon, the antireflection effect of the surface of the polycrystalline silicon can be improved, and therefore the photoelectric converting efficiency of the polycrystalline silicon solar cell is improved.
Description
Technical field
The invention belongs to solar energy new energy field, relate to the processing of polysilicon photovoltaic cells plate, be specifically related to a kind of polysilicon micro-nano processing unit (plant) and method of gridding.
Background technology
New forms of energy become one of key areas of 21 century research, and the application and popularization of solar energy has been subject to people's great attention.The energy of the sun is very abundant, is irradiated to tellurian energy equivalence each second in 5,000,000 tons of standard coals, if be converted into electric energy, is approximately 3.8 * 10
19mW, solar energy does not contain hazardous substance, and does not discharge carbon dioxide, is rich in development prospect, is a kind of effective way that the mankind solve current energy crisis.Until the nineties in 20th century, solar energy photovoltaic material also mainly be take monocrystalline silicon as main.The eighties in 20th century, polysilicon was with relatively low cost, high efficiency advantage application rapid development, constantly tie up the market of monocrystalline silicon, from 10% left and right that only accounts for photovoltaic material the latter stage eighties, develop at the beginning of 21 century more than 50%, become topmost solar cell material.Polycrystalline silicon solar cell is current comparatively ripe, the relatively low solar cell technology of cost, diversity due to polysilicon grain orientation, can not be by traditional monocrystalline silicon suede technology of preparing, how the cheap antireflection layer of preparing reliably polycrystalline silicon solar cell is one of key technology of polycrystalline silicon solar cell industrialization.
The manufacturing technology of producing at present polysilicon surface mainly contains following several:
1, laser grooving: can make inverted pyramid structure at polysilicon surface by the method for laser grooving, in 500～900nm spectral region, reflectivity is 4～6% is suitable with surface making double layer antireflection coating.And be 11% at the reflectivity of (100) face monocrystalline silicon chemistry making matte.With laser, make matte than plate double-layer reflection-decreasing rete (ZnS/MgF at shiny surface
2) short circuit current of battery will improve 4% left and right, this is mainly the reason that longwave optical (wavelength is greater than 800nm) oblique fire enters battery.The problem that laser is made matte existence is that in etching, surface causes damage to introduce some impurity simultaneously, remove surface damage layer by chemical treatment.The common short circuit current of solar cell that the method is done is higher, but open circuit voltage is not too high, and main cause is that battery table area increases, and causes that recombination current improves.
2, chemical cutting: using mask (Si
3n
4or SiO
2) isotropic etch, corrosive liquid can be acid etching solution, also can be NaOH or potassium hydroxide solution that concentration is higher, and the method cannot form the formed that cone-shaped structure of anisotropic etch.It is reported, the formed matte of the method has obvious antireflective effect to 700～1030 microns of spectral regions.But mask layer generally will form at higher temperature, causes polycrystalline silicon material hydraulic performance decline, lower to quality especially polycrystalline material, minority carrier life time shortens.Apply this technique at 225cm
2polysilicon on the conversion efficiency of the battery of doing reach 16.4%.The mask layer also method of available silk screen printing forms.
3, reactive ion etching (RIE): the method is a kind of without mask corrosion technique, and formed matte reflectivity is low especially, can be less than 2% at the reflectivity of 450～1000 microns of spectral regions., from the angle of optics, be only a kind of desirable method, but the problem existing is that silicon face damage is serious, declining appears in the open circuit voltage of battery and fill factor, curve factor, complex process.
4, make antireflection film layer: for efficient solar battery, the most frequently used and effective method is evaporation ZnS/MgF
2double layer antireflection coating, its optimum thickness depends on the thickness of oxide layer and the feature of battery surface below, and for example, surface is shiny surface or matte, and antireflective technique also has evaporation Ta
2o
5, PECVD deposits Si
3n
3deng.ZnO conducting film also can be used as anti-reflection material.But this kind of technical matters complexity, when being applied to suitability for industrialized production, cost is very high, is unfavorable for wide popularization and application.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of polysilicon micro-nano processing method of gridding is provided, the method utilizes ultrasonic and acting in conjunction acid corrosion liquid to process polysilicon surface, optimize polysilicon surface micro-structural, improve polysilicon surface anti-reflection effect, thereby improve polysilicon photovoltaic cells electricity conversion.Another object of the present invention is to provide the device that the method is used.
Polysilicon micro-nano processing unit (plant) of the present invention comprises control device, plane excusing from death generating means and reaction unit.
Described control device comprises a plurality of supersonic generator controllers and video camera, and the input of each supersonic generator controller and video camera are all connected with computer.The camera orientating reaction device of video camera.
Described plane excusing from death generating means comprises transducer, ultrasonic transformer, plane ultrasonic tool heads; The output of each supersonic generator controller is connected with the afterbody of a transducer, and the head of each transducer is connected with the tailing screw flight of a ultrasonic transformer, and the head of each ultrasonic transformer is connected with the tailing screw flight of a plane ultrasonic tool heads.
Described reaction unit comprises reaction observation ward, sound wave baffle-board and reaction vessel; Described reaction observation ward is transparent closed container, and the head of each plane ultrasonic tool heads all stretches in reaction observation ward; The reaction observation ward madial wall place relative with each plane ultrasonic tool heads is fixedly installed respectively a sound wave baffle-board.Described reaction vessel is arranged in reaction observation ward, and is arranged between plane ultrasonic tool heads and sound wave baffle-board.
The distance of described sound wave baffle-board and plane ultrasonic tool heads is
, wherein, n is the number of plane ultrasonic tool heads, value is 2～4,
for ultrasonic wavelength in liquid;
, wherein,
for ultrasonic speed in liquid,
for the supersonic frequency of using, span is 40KHz～1MHz, and ultrasonic power is 500～1000W.
The head of described plane ultrasonic tool heads is square column type.
Polysilicon micro-nano processing method of the present invention, step is as follows:
Step 1. by the pure hydrofluoric acid solution of analysis, analyze pure salpeter solution and deionized water is deployed into mix acid liquor, the volume ratio that to analyze pure hydrofluoric acid solution in mix acid liquor be 0.1～0.9:1 with the volume ratio of analyzing pure salpeter solution, analyze pure hydrofluoric acid solution and deionized water is 0.1～0.4:1, and mix acid liquor is injected to reaction vessel.
Step 2. drives plane ultrasonic tool heads by computer program, in mix acid liquor, form ultrasonic standing wave, the tranquil formation after stable ultrasonic standing wave grid of liquid level of acid solution to be mixed, will put into reaction vessel through clean pretreated polycrystalline silicon material and be prepared, and the time is 1～10 minute.
Step 3. is placed in deionization solution by the silicon chip through step 2 preparation and cleans 1～2 minute, and the surperficial acid solution of removing silicon chip is residual.
Step 4., by the good silicon chip of surface cleaning, encapsulates, and completes silicon wafer to manufacture.
Beneficial effect of the present invention:
1, the head of midplane Ultrasonic probe of the present invention is square column type, standing wave grid that can formation rule;
2, the present invention utilizes the ion of ultrasonic control random motion to form structure comparatively uniformly in silicon face corrosion reaction, optimizes polysilicon surface micro-structural, improves polysilicon surface anti-reflection effect, thereby improves polysilicon photovoltaic cells electricity conversion;
3, the motion of hyperacoustic existence aggravation effects of ion, carries out reaction comparatively rapidly;
4, adopt ultrasonic unit low with respect to laser ablation cost.
Accompanying drawing explanation
Fig. 1 is system configuration schematic diagram of the present invention;
The front view that Fig. 2-1 is midplane Ultrasonic probe of the present invention;
Fig. 2-2 are the vertical view of Fig. 2-1;
Fig. 3 is reaction mechanism figure of the present invention;
Fig. 4 is the polycrystalline silicon suede micro-structural without 10 micro-meter scales are observed under Electronic Speculum after Ultrasonic test;
Fig. 5 is for adopting the inventive method to carry out the polycrystalline silicon suede micro-structural that after quadrature Ultrasonic test, 10 micro-meter scales are observed under Electronic Speculum;
Fig. 6 is for adopting the inventive method to carry out the polycrystalline silicon suede micro-structural that after quadrature Ultrasonic test, 50 micro-meter scales are observed under Electronic Speculum.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
As shown in Figure 1, a kind of polysilicon micro-nano processing unit (plant) of gridding comprises control device, plane excusing from death generating means and reaction unit.
Control device comprises that the input of supersonic generator controller 1 and 2, two supersonic generator controllers 1 of video camera and video camera 2 are all connected with computer 3.The camera orientating reaction device of video camera 2.
As shown in Fig. 1,2-1 and 2-2, plane excusing from death generating means comprises transducer 4, ultrasonic transformer 5, plane ultrasonic tool heads 6; The output of each supersonic generator controller 1 is connected with the afterbody of a transducer 4, and the head of each transducer 4 is connected with the tailing screw flight of a ultrasonic transformer 5, and the head of each ultrasonic transformer 5 is connected with the tailing screw flight of a plane ultrasonic tool heads 6.
Reaction unit comprises reaction observation ward 7, sound wave baffle-board 8 and reaction vessel 9; Reaction observation ward 7 be transparent closed container, and the head of two plane ultrasonic tool heads 6 all stretches into and reacts in observation ward 7, and two plane ultrasonic tool heads 6 along continuous straight runs vertically arrange, and the head of plane ultrasonic tool heads 6 is square column type; The reaction observation ward 7 madial wall place relative with each plane ultrasonic tool heads 6 is fixedly installed respectively a sound wave baffle-board 8.Reaction vessel 9 is arranged in reaction observation ward 7, and is arranged between plane ultrasonic tool heads 6 and sound wave baffle-board 8.
The number n=2 of plane ultrasonic tool heads, ultrasonic speed in liquid
get 1500m/s, computer program control plane Ultrasonic probe 6 produces ultrasonic, supersonic frequency
for 40KHz, power is 750W; According to
and
can be calculated, sound wave baffle-board 8 is 37.5mm with the distance of corresponding flat Ultrasonic probe 6.
A kind of step of polysilicon micro-nano processing method of gridding is as follows:
Step 1. by the pure hydrofluoric acid solution of analysis, analyze pure salpeter solution and deionized water is allocated in proportion, form mix acid liquor and inject reaction vessel 5.
Any in can be in the following ways of allotment mix acid liquor:
(1) 0.1L analyzes pure hydrofluoric acid solution, 1L analyzes pure salpeter solution and 1L deionized water mixes;
(2) 0.9L analyzes pure hydrofluoric acid solution, 1L analyzes pure salpeter solution and 2.25L deionized water mixes;
(3) 0.5L analyzes pure hydrofluoric acid solution, 1L analyzes pure salpeter solution and 2.5L deionized water.
Step 2. drives plane ultrasonic tool heads 6 by computer program, in mix acid liquor, form ultrasonic standing wave, the tranquil formation after stable quadrature ultrasonic standing wave grid of liquid level of acid solution to be mixed, will put into reaction vessel 9 through clean pretreated polycrystalline silicon material and be prepared, and preparation time is 4 minutes.
Step 3. is placed in deionization solution by the silicon chip through step 2 preparation and cleans 2 minutes, and the surperficial acid solution of removing silicon chip is residual.
Step 4., by the good silicon chip of surface cleaning, encapsulates, and completes silicon wafer to manufacture.
The specific works process of the polysilicon micro-nano processing unit (plant) of this gridding is:
Open computer 3, appropriate mix acid liquor is injected to reaction vessel 9, then open supersonic generator controller 1, adjust computer program, make two plane ultrasonic tool heads 6 send two groups of mutually perpendicular standing waves, wait while forming stable standing wave grid on the liquid level of mix acid liquor, the silicon chip of getting suitable size is positioned in mix acid liquor, in course of reaction, can pass through the intensity of video camera 2 observing responses, then control the time that reacts completely and finish.
Reaction observation ward 9 is closed container, avoids the carrying out of airborne sound wave and Air Flow interference test.
As shown in Figure 3, the reaction mechanism of the polysilicon micro-nano processing method of this gridding is as follows:
When acid corrosion legal system is made polysilicon surface suede structure, be mainly the participation of fluorine ion, fluorine ion belongs to nano particle, and generally, fluorine ion is random collision in water, does free movement.Ultrasonic wave is the longitudinal mechanical wave of a kind of high frequency, and mechanical wave is described the available Newton's second law of effect of nano particle, micron ion bubble:
for effects of ion suffered power in two-dimensional quadrature ultrasonic field,
for the speed of ion in ultrasonic field, arrow represents velocity attitude, utilize the stationary field of two groups of plane excusing from death generating meanss generation quadratures of quadrature, fluorine ion will partly be controlled by sound field distribution form and chemical action environment under the effect of sound field standing wave, thereby the microcorrosion Working position that changes fluorine ion, completes the texture structure to polysilicon surface.
If Fig. 4,5 and 6 is comparison of test results:
To be silicon chip analyzing pure hydrofluoric acid solution (HF) to Fig. 4: analyze pure salpeter solution (HNO3): when the volume ratio of deionized water (H2O) is 2:15:5 through 4 minutes without supersonic test, and the polycrystalline silicon suede micro-structural that 10 micro-meter scales are observed under Electronic Speculum.
Fig. 5 is that silicon chip is being analyzed pure hydrofluoric acid solution (HF): analyze pure salpeter solution (HNO
3): deionized water (H
2when volume ratio O) is 2:15:5 through 4 minutes quadrature Ultrasonic tests, and the polycrystalline silicon suede micro-structural that 10 micro-meter scales are observed under Electronic Speculum.
Fig. 6 is that silicon chip is being analyzed pure hydrofluoric acid solution (HF): analyze pure salpeter solution (HNO
3): deionized water (H
2when volume ratio O) is 2:15:5 through 4 minutes quadrature Ultrasonic tests, and the polycrystalline silicon suede micro-structural that 50 micro-meter scales are observed under Electronic Speculum.
The quadrature Ultrasonic test of the polysilicon micro-nano processing method of visible this gridding of employing, the micro-structural forming at silicon face is comparatively even, can improve polysilicon surface anti-reflection effect, thereby improves polysilicon photovoltaic cells electricity conversion.
In the method step 2, will put into the time prepared by reaction vessel and can select the scope of 1～10 minute through cleaning pretreated polycrystalline silicon material; In step 3, silicon chip being placed in to deionization solution scavenging period can select in the scope of 1～2 minute.
Claims (3)
1. a polysilicon micro-nano processing unit (plant) for gridding, comprises control device, plane excusing from death generating means and reaction unit, it is characterized in that:
Described control device comprises a plurality of supersonic generator controllers and video camera, and the input of each supersonic generator controller and video camera are all connected with computer; The camera orientating reaction device of video camera;
Described plane excusing from death generating means comprises transducer, ultrasonic transformer, plane ultrasonic tool heads; The output of each supersonic generator controller is connected with the afterbody of a transducer, and the head of each transducer is connected with the tailing screw flight of a ultrasonic transformer, and the head of each ultrasonic transformer is connected with the tailing screw flight of a plane ultrasonic tool heads;
Described reaction unit comprises reaction observation ward, sound wave baffle-board and reaction vessel; Described reaction observation ward is transparent closed container, and the head of each plane ultrasonic tool heads all stretches in reaction observation ward; The reaction observation ward madial wall place relative with each plane ultrasonic tool heads is fixedly installed respectively a sound wave baffle-board; Described reaction vessel is arranged in reaction observation ward, and is arranged between plane ultrasonic tool heads and sound wave baffle-board;
The distance of described sound wave baffle-board and plane ultrasonic tool heads is
, wherein, n is the number of plane ultrasonic tool heads, value is 2～4,
for ultrasonic wavelength in liquid;
, wherein,
for ultrasonic speed in liquid,
for the supersonic frequency of using, span is 40KHz～1MHz, and ultrasonic power is 500～1000W.
2. the polysilicon micro-nano processing unit (plant) of a kind of gridding according to claim 1, is characterized in that: the head of described plane ultrasonic tool heads is square column type.
3. a polysilicon micro-nano processing method for gridding, is characterized in that: the step of the method is as follows:
Step 1. by the pure hydrofluoric acid solution of analysis, analyze pure salpeter solution and deionized water is made into mix acid liquor, the volume ratio that to analyze pure hydrofluoric acid solution in mix acid liquor be 0.1～0.9:1 with the volume ratio of analyzing pure salpeter solution, analyze pure hydrofluoric acid solution and deionized water is 0.1～0.4:1, and mix acid liquor is injected to reaction vessel;
Step 2. drives plane ultrasonic tool heads by computer program, in mix acid liquor, form ultrasonic standing wave, the tranquil formation after stable ultrasonic standing wave grid of liquid level of acid solution to be mixed, will put into reaction vessel through clean pretreated polycrystalline silicon material and be prepared, 1～10 minute time;
Step 3. is placed in deionization solution by the silicon chip through step 2 preparation and cleans 1～2 minute, and the surperficial acid solution of removing silicon chip is residual;
Step 4., by the good silicon chip of surface cleaning, encapsulates, and completes silicon wafer to manufacture.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439083A (en) * | 2015-11-17 | 2016-03-30 | 杭州电子科技大学 | Method for making silicon micro-nano structure array based on ultrasonic standing wave field |
| CN105932096A (en) * | 2016-05-16 | 2016-09-07 | 杭州电子科技大学 | Polysilicon surface light trapping microstructure processing method |
| CN107146829A (en) * | 2017-05-27 | 2017-09-08 | 江西赛维Ldk太阳能高科技有限公司 | The making herbs into wool preprocess method of Buddha's warrior attendant wire cutting polysilicon chip and application |
| CN107840096A (en) * | 2017-08-04 | 2018-03-27 | 杭州电子科技大学 | The micro stable transport device of micro-nano stickiness powder and method |
| CN114348957A (en) * | 2021-12-31 | 2022-04-15 | 杭州电子科技大学 | Equipment for preparing silicon nanostructure by combining alternating electric field with ultrasound |
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| CN114348957A (en) * | 2021-12-31 | 2022-04-15 | 杭州电子科技大学 | Equipment for preparing silicon nanostructure by combining alternating electric field with ultrasound |
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