CN105483832A - Crystalline silicon surface oxidation device with anti-potential-induced degradation (PID) effect and method thereof - Google Patents
Crystalline silicon surface oxidation device with anti-potential-induced degradation (PID) effect and method thereof Download PDFInfo
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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- C30B33/005—Oxydation
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Abstract
The invention discloses a crystalline silicon surface oxidation device with anti-potential-induced degradation (PID) effect and a method thereof for carrying out oxidation treatment on the surface of crystalline silicon. The crystalline silicon surface oxidation device with the anti-PID effect is characterized by comprising a hydroxyl generating chamber (2), electrolyte arranged inside the hydroxyl generating chamber (2), an anode body and a cathode body which are immersed into the electrolyte and are respectively connected with the positive electrode and the negative electrode of a power supply as well as an applying device (4), wherein the anode body can decompose water molecules in part of the electrolyte in the hydroxyl generating chamber (2) into hydroxyls and hydrogen free radicals which are mixed into the electrolyte to form mixed solution; and the applying device (4) is communicated with the hydroxyl generating chamber through a first pipeline, a first power device which can transport the mixed solution in the hydroxyl generating chamber (2) onto the applying device (4) is arranged on the first pipeline, and the applying device (4) can apply the mixed solution onto the surface of the crystalline silicon. According to the invention, water is electrolysed, hydroxyls are mixed into the electrolyte to form emulsified liquid, hydroxyl-containing emulsified liquid is directly sprayed onto the upper surface and the lower surface of the crystalline silicon by virtue of the applying device (4), and an oxidation film with a certain thickness is generated on the surface of the crystalline silicon, so that anti-PID effect is realized.
Description
Technical field
The present invention relates to crystal silicon surface oxygenation device and the method thereof of anti-potential induction attenuation effect, belong to electrochemical field, is specifically that crystal silicon solar batteries manufactures field.
Background technology
The photovoltaic generation of crystal silicon solar cell sheet is one of mainstream technology of current photovoltaic art.In recent years, there is a new effect affecting component power decay in the generating of photovoltaic module, i.e. potential induction attenuation (PID) effect of power stage.This attenuation effect is closely related with high-voltage (600V-1000V) conventional in photovoltaic parallel in system, and these high-voltages are applied to cell piece and aluminium frame two ends usually.When crystal silicon battery assembly is experiencing various atmospheric environment especially under damp and hot severe environmental conditions, inevitable generating assembly electric leakage, leakage current will flow through at cell piece, packaged material, backboard and aluminium frame.Under normal circumstances, sodium ion in float glass process packaged glass is under the forceful electric power gesture effect of battery component, crystal silicon surface can be entered into along some microchannels in EVA packaged material, these sodium ions are gathered in again the defective bit on crystal silicon surface usually, thus be degrading the passivation effect of battery surface, cause a large amount of compounds of current carrier in battery component, also result in the decline of battery component packing factor, short-circuit current, the power stage that thus directly results in battery component reduces.
Enter into crystal silicon surface for overcoming sodium ion, on the one hand, investigators set about from the improvement aspect of EVA glue, improve the impedance characteristic of EVA glue, delay entering of sodium ion, but cost are relatively high, also have a longer segment distance from practical application; On the other hand, investigators are on the blocking layer of the fine and close SiOx of crystal silicon surface-coated one deck, stop entering of sodium ion, such as, using plasma strengthens chemical gaseous phase depositing process and utilizes laughing gas (N2O) and silane (SiH4) as the blocking layer of presoma at crystal silicon surface growth SiOx, but to grow SiOx film fine and close not, actual blocking effect is unsatisfactory; Also have and directly adopt high temperature wet or dry method thermal oxidation process, but its process time is longer, and thickness is difficult to accurate control.Conventional Ozone oxidation method on current product line, ozone gas by the higher concentration of high-voltage discharge generation is directly transported to crystal silicon surface, utilize its oxidation capacity in crystal silicon surface growth skim zone of oxidation, it is worth mentioning that, the crystal silicon surface oxidation of current ozone carries out in a nonocclusive open environment, surface oxide layer thickness is thinner on the one hand, only 1-2nm is thick, on the other hand, ozone gas is inevitably emitted in surrounding environment, all can cause certain toxic action to human body and environment.
Therefore, how to realize the crystal silicon surface oxidation of high-efficiency environment friendly, and can meet the requirement of anti-PID crystal silicon solar batteries, be the problem that people are concerned about always.
Summary of the invention
The object of this invention is to provide a kind of crystal silicon surface oxygenation device and the method that can improve crystal silicon surface oxidation effect.
For solving the problem, the invention provides a kind of crystal silicon surface oxygenation device of anti-potential induction attenuation effect, for carrying out oxide treatment to crystal silicon surface, it is characterized in that, comprising:
-hydroxyl generation chamber, inside be provided with electrolytic solution and immerse the anode bodies and cathode that are connected with the positive and negative electrode of power supply in described electrolytic solution, respectively, the water-molecule dissociation in part electrolytic solution in hydroxyl generation chamber can be become the free radical of hydroxyl and hydrogen and be mixed in this electrolytic solution to form mixed solution by described anode bodies;
-bringing device, with described hydroxyl generation chamber by the first pipeline communication, described first pipeline is provided with first power set that the mixed solution in described hydroxyl generation chamber can be transported on described bringing device, and described mixed solution can be applied to the surface of described crystal silicon by described bringing device.
As a further improvement on the present invention, described hydroxyl generation chamber is also provided with front end processing device, described front end processing device comprises the fluid reservoir be connected by second pipe with described hydroxyl generation chamber, be provided with ionogen in described fluid reservoir, in described second pipe, be provided with second power set that the electrolytic solution in described fluid reservoir can be delivered in described hydroxyl generation chamber.
As a further improvement on the present invention, described front end processing device also comprises the liquid-inlet pipe be arranged on described fluid reservoir, liquid water in described liquid-inlet pipe and ionogen are driven by the 3rd power set and are delivered in described fluid reservoir, and mix in described fluid reservoir.
As a further improvement on the present invention, described liquid-inlet pipe being connected with the priming apparatus for adding liquid water wherein and adding electrolytical dosing pump, between described priming apparatus and described liquid-inlet pipe, being connected with the under meter for controlling liquid velocity.
As a further improvement on the present invention, the flow of described under meter and the addition of described dosing pump all pass through servocontrol.
As a further improvement on the present invention, described cathode by stainless steel part, titanium part, be coated with in the titanium part group of metal platinum one or more form, described anode bodies is made up of the Ti electrode being coated with function nano compound coating, described function nano compound coating by platinum coating, ruthenium oxide/iridium oxide mixed coating, cobalt oxide/iridium oxide mixed coating,
tantalum oxide/iridium oxide mixed coating,one or more compositions in cobalt oxide/diamond-like carbon/iridium oxide mixed coating.
Belong to the innovation and creation of same design with foregoing invention, a kind of crystal silicon surface oxygenation device of anti-potential induction attenuation effect, it is characterized in that, described bringing device comprises spray header, and liquid can directly be sprayed crystal silicon upper and lower surface by described spray header.
As a further improvement on the present invention, comprise the following steps:
S1, by hydroxyl producer, adopt the method for electrolysis, electrolysis is positioned at the electrolytic solution of hydroxyl generation chamber, obtains the mixed solution containing hydroxyl;
S2, above-mentioned mixed solution is input in applying mechanism;
S3, by above-mentioned applying mechanism, this mixed solution is applied to crystal silicon surface;
S4, on silicon oxide workpiece, grow one deck silicon nitride anti-reflection layer by PECVD device, then this workpiece pros and cons is printed and sintered.
As a further improvement on the present invention, be also provided with before described step S1
Step S0, in hydroxyl generation chamber or in the electrolytic solution inputing in this hydroxyl generation chamber, add ionogen, make this liquid water keep the pH value of setting.
As a further improvement on the present invention, in described step S3, described applying mode is spray, the mixed solution containing hydroxyl radical free radical is sprayed the upper and lower surface of crystal silicon.
As a further improvement on the present invention, in described step S0, the pH value of setting is between 1.0-6.0.
As a further improvement on the present invention, in described step S4, the cathode of electrolysis by stainless steel part, titanium part, be coated with in the titanium part group of metal platinum one or more form, the anode bodies of electrolysis is made up of the Ti electrode being coated with function nano compound coating, described function nano compound coating by platinum coating, ruthenium oxide/iridium oxide mixed coating, cobalt oxide/iridium oxide mixed coating,
tantalum oxide/iridium oxide mixed coating,one or more compositions in cobalt oxide/diamond-like carbon/iridium oxide mixed coating.
Beneficial effect of the present invention is, the present invention passes through brine electrolysis, hydroxyl is dissolved in electrolytic solution and forms emulsion, pass through bringing device, emulsion containing hydroxyl is directly sprayed the upper and lower surface of crystal silicon, after making crystal silicon Surface Creation certain silicon oxide film, thus play anti-PID effect, solve the problem run in prior art.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
Wherein: 2-hydroxyl generation chamber; 4-bringing device; 6-front end processing device; 8-fluid reservoir; 10-dosing pump; 12-under meter; 14-spray header.
Embodiment
Below the specific embodiment of the present invention is described in further detail.
As shown in Figure 1, the present invention includes:
-hydroxyl generation chamber 2, inside be provided with electrolytic solution and immerse the anode bodies and cathode that are connected with the positive and negative electrode of power supply in described electrolytic solution, respectively, the water-molecule dissociation in part electrolytic solution in hydroxyl generation chamber 2 can be become the free radical of hydroxyl and hydrogen and be mixed in this electrolytic solution to form mixed solution by described anode bodies;
-bringing device 4, with described hydroxyl generation chamber 2 by the first pipeline communication, described first pipeline is provided with first power set that the mixed solution in described hydroxyl generation chamber 2 can be transported on described bringing device 4, and described mixed solution can be applied to the upper and lower surface of described crystal silicon by described bringing device 4.
As a further improvement on the present invention, described hydroxyl generation chamber 2 is also provided with front end processing device 6, described front end processing device 6 comprises the fluid reservoir 8 be connected by second pipe with described hydroxyl generation chamber 2, be provided with ionogen in described fluid reservoir 8, in described second pipe, be provided with second power set that the electrolytic solution in described fluid reservoir 8 can be delivered in described hydroxyl generation chamber 2.
As a further improvement on the present invention, described front end processing device 6 also comprises the liquid-inlet pipe be arranged on described fluid reservoir 8, liquid water in described liquid-inlet pipe and ionogen are driven by the 3rd power set and are delivered in described fluid reservoir 8, and mix in described fluid reservoir 8.
As a further improvement on the present invention, described liquid-inlet pipe being connected with the priming apparatus for adding liquid water wherein and adding electrolytical dosing pump 10, between described priming apparatus and described liquid-inlet pipe, being connected with the under meter 12 for controlling liquid velocity.
As a further improvement on the present invention, the flow of described under meter 12 and the addition of described dosing pump 10 all pass through servocontrol.
As a further improvement on the present invention, described negative electrode by stainless steel part, titanium part, be coated with in the titanium part group of metal platinum one or more form, described anode bodies is made up of the Ti electrode being coated with function nano compound coating, described function nano compound coating by platinum coating, ruthenium oxide/iridium oxide mixed coating, cobalt oxide/iridium oxide mixed coating,
tantalum oxide/iridium oxide mixed coating,one or more compositions in cobalt oxide/diamond-like carbon/iridium oxide mixed coating.
The innovation and creation of same design are belonged to foregoing invention, a kind of crystal silicon surface oxygenation device of anti-potential induction attenuation effect, it is characterized in that, described bringing device 4 comprises spray header 14, and mixed solution directly can be sprayed the upper and lower surface of crystal silicon by described spray header 14.
As a further improvement on the present invention, comprise the following steps:
S1, by hydroxyl producer, adopt the method for electrolysis, electrolysis is positioned at the electrolytic solution of hydroxyl generation chamber 2, obtains the mixed solution containing hydroxyl;
S2, above-mentioned mixed solution is input in bringing device;
S3, by above-mentioned bringing device, this mixed solution is applied to crystal silicon surface;
S4, on silicon oxide workpiece, grow one deck silicon nitride anti-reflection layer by PECVD device, then this workpiece pros and cons is printed and sintered.
As a further improvement on the present invention, be also provided with before described step S1
Step S0, in hydroxyl generation chamber 2 or in the electrolytic solution inputing in this hydroxyl generation chamber 2, add ionogen, make this liquid water keep the pH value of setting.
As a further improvement on the present invention, in described step S3, described applying mode is spray, this mixed solution is sprayed the upper and lower surface of crystal silicon.
As a further improvement on the present invention, in described step S0, the pH value of setting is between 1.0-6.0.
As a further improvement on the present invention, in described step S4, the cathode of electrolysis by stainless steel part, titanium part, be coated with in the titanium part group of metal platinum one or more form, the cathode of electrolysis is made up of the Ti electrode being coated with function nano compound coating, described function nano compound coating by platinum coating, ruthenium oxide/iridium oxide mixed coating, cobalt oxide/iridium oxide mixed coating,
tantalum oxide/iridium oxide mixed coating,one or more compositions in cobalt oxide/diamond-like carbon/iridium oxide mixed coating.
It is of the present invention that to have principle of work as follows:
(1) by liquid-adding device and dosing pump 10 respectively to adding liquid water and eletrolytes in feed-pipe, and be delivered in fluid reservoir 8;
(2) carry out being mixed to get electrolytic solution at fluid reservoir 8, and control the PH of fluid reservoir 8 electrolyte inside in real time, make this pH value between 1.0-6.0, electrical conductivity of water is 100-3000uS/cm.Control method is the multiple servo mode comprising PLC, the aquifer yield of difference adjust flux meter 12, dosing pump 10 and ionogen addition;
(3) electrolysis cathode by stainless steel part, titanium part, be coated with in the titanium part group of metal platinum one or more form, cathode is made up of the Ti electrode being coated with function nano compound coating.Anodic-cathodic vibrational power flow is many group slice-types or reticular pattern, and interelectrode distance can be determined according to size of current, is generally between 1-10mm.Anode coating materials'use platinum coating, ruthenium oxide/iridium oxide mixed coating, cobalt oxide/iridium oxide mixed coating,
tantalum oxide/iridium oxide mixed coating,one or more compositions in cobalt oxide/diamond-like carbon/iridium oxide mixed coating.
(4) brine electrolysis product one of them be hydroxyl, its formation soluble in water contains the emulsion of hydroxyl;
This emulsion is evacuated to spray header 14 place by (5) first power set, is sprayed at the upper and lower surface of crystal silicon through spray header 14, and form zone of oxidation, its thickness is between 3-10nm, and thickness and the output rating according to spray time or electrolysis decide.
Embodiment 1:
User opens the water inlet switch of priming apparatus, according to water yield size, in fluid reservoir 8, injects a certain amount of electrolytic solution, and is injected into hydroxyl and frees in room after mixing.PH value during PLC circuit is interior by hydroxyl generation chamber 2 and specific conductivity control liquid volume added and add electrolytical amount.In the preferred embodiment, pH value is between 1.0-6.0, and electrical conductivity of water is 100-3000uS/cm.When pure water is injected in hydroxyl generation chamber 2, opening driver power switch, electrode reaction occurs thereupon, electrode reaction can produce a large amount of hydroxyls and the free radical of hydrogen, these hydroxyl radical free radicals through Pipeline transport to spray header 14, and having spray header 14 to be ejected into two surfaces up and down of solar battery sheet, the crystal silicon generation oxidizing reaction on the hydroxyl radical free radical that the emulsion ejected exists and cell piece surface, generates fine and close zone of oxidation.Compact construction of the present invention is exquisite, and the oxidation capacity of hydroxyl radical free radical is strong, in production process, and ozone free dissipation problem.
The present invention mainly improves the structure of battery anti-reflection layer, between traditional single or multiple lift silicon nitride and crystalline silicon substrate, adopt the method for hydroxyl oxidize to prepare the silicon dioxide layer of one deck densification, the thickness of this layer is between 2-8nm, other techniques are consistent with traditional technology, can not cause the decline of battery efficiency.This silicon dioxide layer can stop the accumulation of sodium ion on PN junction surface in glass, thus greatly reduces the surface recombination probability of current carrier, improves the ability of the anti-PID of assembly.Compared with ozonation technology, this invention not only can realize the two-sided oxidation of crystal silicon, and without the dissipation problem of ozone, greatly reduces the harm to environment and human body.
The present invention has good anti-PID effect, the assembly made of battery 85 DEG C, carry out the PID test of 96 hours under 85%RH ,-1000V condition after, its power attenuation amplitude is within 0.8%, be better than existing technique far away and prepare the situation of cell piece making assembly decay more than 50%, be also better than the processing method adopting ozone oxidation.
In the present invention, because hydroxyl radical free radical has enough Strong oxdiative abilities, the oxidation capacity of hydroxyl radical free radical is 2.8eV, far away higher than the ability (1.8eV) of ozone oxidation, thus hydroxyl radical free radical can the reaction rapidly of crystal silicon surface generate one deck densification and there is the silicon oxide layer of very strong passivation effect, the silicon oxide layer thickness formed was controlled by the watt level on hydroxyl producer or the emulsion spray time to silicon chip surface, fine and close oxide thin layer layer can meet the requirement of anti-PID, does not affect the anti-reflection effect of cell piece.And the silicon oxide layer adopting the technique of hydroxyl oxidize to obtain, has lower surface density of states, improves the passivation effect of silicon oxide, thus improve the photoelectric transformation efficiency of solar battery sheet.In addition, the oxidation on crystal silicon surface, mainly by the chemical oxidation effect of hydroxyl and silicon face, not to the material dissipation of human body and bad environmental in whole process, substantially increases the practicality of technique, for large-scale industrial production provides effective way.
The solar cell chip module obtained by device of the present invention and preparation method, 85 DEG C, after the PID test of carrying out 96 hours under 85%RH ,-1000V condition, its power attenuation amplitude is within 0.8%, be better than existing technique far away and prepare the situation of cell piece making assembly decay more than 50%, be also better than the processing method adopting ozone oxidation.
Above embodiment is only the present invention's a kind of embodiment wherein, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a crystal silicon surface oxygenation device for anti-potential induction attenuation effect, for carrying out oxide treatment to crystal silicon surface, is characterized in that, comprising:
-hydroxyl generation chamber (2), inside be provided with electrolytic solution and immerse the anode bodies and cathode that are connected with the positive and negative electrode of power supply in described electrolytic solution, respectively, the water-molecule dissociation in part electrolytic solution in hydroxyl generation chamber (2) can be become the free radical of hydroxyl and hydrogen and be mixed in this electrolytic solution to form mixed solution by described anode bodies;
-bringing device (4), with described hydroxyl generation chamber (2) by the first pipeline communication, described first pipeline is provided with first power set that the mixed solution in described hydroxyl generation chamber (2) can be transported on described bringing device (4), and described mixed solution can be applied to the surface of described crystal silicon by described bringing device (4).
2. the crystal silicon surface oxygenation device of a kind of anti-potential induction attenuation effect according to claim 1, it is characterized in that, described hydroxyl generation chamber (2) is also provided with front end processing device (6), described front end processing device (6) comprises the fluid reservoir (8) be connected by second pipe with described hydroxyl generation chamber (2), described fluid reservoir is provided with ionogen in (8), is provided with second power set that the electrolytic solution in described fluid reservoir (8) can be delivered in described hydroxyl generation chamber (2) in described second pipe.
3. the crystal silicon surface oxygenation device of a kind of anti-potential induction attenuation effect according to claim 2, it is characterized in that, described front end processing device (6) also comprises the liquid-inlet pipe be arranged on described fluid reservoir (8), liquid water in described liquid-inlet pipe and ionogen are driven by the 3rd power set and are delivered in described fluid reservoir (8), and mix in described fluid reservoir (8).
4. the crystal silicon surface oxygenation device of a kind of anti-potential induction attenuation effect according to claim 3, it is characterized in that, described liquid-inlet pipe being connected with the priming apparatus for adding liquid water wherein and adding electrolytical dosing pump (12), between described priming apparatus and described liquid-inlet pipe, being connected with the under meter (12) for controlling liquid velocity.
5. the crystal silicon surface oxygenation device of a kind of anti-potential induction attenuation effect according to claim 4, it is characterized in that, described cathode by stainless steel part, titanium part, be coated with in the titanium part group of metal platinum one or more form, described anode bodies is made up of the Ti electrode being coated with function nano compound coating, and described function nano compound coating is made up of one or more in platinum coating, ruthenium oxide/iridium oxide mixed coating, cobalt oxide/iridium oxide mixed coating, tantalum oxide/iridium oxide mixed coating, cobalt oxide/diamond-like carbon/iridium oxide mixed coating.
6. the crystal silicon surface oxygenation device of a kind of anti-potential induction attenuation effect according to claim 5, it is characterized in that, described bringing device (4) comprises spray header (14), and mixed solution directly can be sprayed the upper and lower surface of crystal silicon by described spray header (14).
7. a crystal silicon process for surface oxidation for anti-potential induction attenuation effect, is characterized in that, comprise the following steps:
S1, by hydroxyl producer, adopt the method for electrolysis, electrolysis is positioned at the electrolytic solution of hydroxyl generation chamber, obtains the mixed solution containing hydroxyl;
S2, above-mentioned mixed solution is input in applying mechanism;
S3, by above-mentioned applying mechanism, this mixed solution is applied to crystal silicon surface;
S4, on silicon oxide workpiece, grow one deck silicon nitride anti-reflection layer by PECVD device, then this workpiece pros and cons is printed and sintered.
8. the crystal silicon process for surface oxidation of a kind of anti-potential induction attenuation effect according to claim 7, is characterized in that, be also provided with before described step S1
Step S0, in hydroxyl generation chamber or in the electrolytic solution inputing in this hydroxyl generation chamber, add ionogen, make this liquid water keep the pH value of setting.
9. the crystal silicon surface oxidation method of a kind of anti-potential induction attenuation effect according to claim 8, it is characterized in that, in described step S0, the pH value of setting is between 1.0-6.0.
10. the crystal silicon surface oxidation method of a kind of anti-potential induction attenuation effect according to claim 9, it is characterized in that, in described step S1, the cathode of electrolysis is by stainless steel part, titanium part, be coated with one or more compositions in the titanium part group of metal platinum, the anode bodies of electrolysis is made up of the Ti electrode being coated with function nano compound coating, described function nano compound coating is by platinum coating, ruthenium oxide/iridium oxide mixed coating, cobalt oxide/iridium oxide mixed coating, tantalum oxide/iridium oxide mixed coating, one or more compositions in cobalt oxide/diamond-like carbon/iridium oxide mixed coating.
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| CN104064622A (en) * | 2013-03-21 | 2014-09-24 | 晶科能源有限公司 | Solar energy battery resisting potential-induced attenuation and manufacture method thereof |
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