CN104883806B - A kind of plasma jet device and component and a kind of method of crystal silicon battery surface oxidation and decontamination - Google Patents
A kind of plasma jet device and component and a kind of method of crystal silicon battery surface oxidation and decontamination Download PDFInfo
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- CN104883806B CN104883806B CN201510100653.1A CN201510100653A CN104883806B CN 104883806 B CN104883806 B CN 104883806B CN 201510100653 A CN201510100653 A CN 201510100653A CN 104883806 B CN104883806 B CN 104883806B
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Abstract
The invention discloses a kind of plasma jet device and component and a kind of methods of crystal silicon battery surface oxidation and decontamination comprising the hollow rod-shaped metal outer pipe body (2) of ground connection, which is characterized in that further include：Insulation tube (3), metallic cathode body (4), metal anode body (6), inlet channel (8).The present invention can be in barrier encapsulation glass sodium ion enter silicon chip surface, to which the defective bit for preventing sodium ion from causing in the accumulation on crystal silicon surface crystal silicon surface micrometre-grade causes a large amount of compound of carrier in battery component, the power output of battery component is caused to reduce, meanwhile also for pollutants such as the fingerprints for eliminating cell piece surface.
Description
Technical field
The present invention relates to for material surface deep oxidation and surface clean atmosphere pressure plasma jet flow device and side
Method, the pollutant that deep oxidation and material surface can be especially carried out to silicon chip of solar cell surface, film surface clean
Plasma jet technology and method.
Background technology
Low temperature plasma includes electronics and ion the two important energy carriers, large-scale electronics and ion energy
The excited state particle of amount distribution and high activity makes plasma have metachemistry ability, anti-to cause conventional chemical
The physical change and chemical reaction cannot or being difficult to realize in answering.These features determine that plasma has in numerous areas
Such as film growth, substrate etching, material surface modifying, biological surface modification, cell separation, sterilizing, air purification and from
The stealthy equal extensive use of daughter.
It is well known that the photovoltaic generation based on solar energy is one of 21st century most important utilization of new energy resources, wherein
The photovoltaic generation of crystal silicon solar cell sheet is the mainstream technology of current photovoltaic art.However, these crystal silicon battery components exist
Various atmospheric environments are undergone especially under damp and hot severe environmental conditions, usually will appear so-called work(after a period of time
The problem of potential induction attenuation (PID) of rate output.The EVA glue being primarily due between packaged glass and crystal silicon chip
There is aging, form some microchannels, under the forceful electric power gesture effect of battery component, the sodium ion of packaged glass kind can be along micro-
Channel enters crystal silicon surface, and accumulation of these sodium ions on crystal silicon surface causes the defective bit of crystal silicon surface micrometre-grade, this
A little surface defect positions cause a large amount of compound of carrier in battery component, directly result in the power output drop of battery component
It is low.
To overcome sodium ion to enter crystal silicon surface, on the one hand, researchers set about in terms of the improvement of EVA glue, improve
The impedance operator of EVA glue delays the entrance of sodium ion, but the cost is relatively high, also has longer a distance from practical application；Separately
On the one hand, researchers coat the barrier layer of one layer of densification SiOx on crystal silicon surface, prevent the entrance of sodium ion, for example, using
Plasma enhanced chemical vapor deposition method is grown as presoma on crystal silicon surface using laughing gas (N2O) and silane (SiH4)
The barrier layer of SiOx, but grown SiOx films are not fine and close enough, and actual blocking effect is unsatisfactory；Also have and directly use ozone
Method for oxidation grows the silica of one layer of 2-3nm in crystal silicon surface enhanced, and this method has certain application in production at present,
But still it is faced with thinner thickness, the oxidation depth unfavorable factors such as not enough.
In addition, in crystal-silicon battery slice processing with operating process, operation employee is often casual in cell piece
Surface leaves the pollutants such as fingerprint, these pollutants are difficult to be perceived as before crystal silicon chip coats anti-reflection layer SiNx films, and one
After denier coats anti-reflection layer, fingerprint trace is it is obvious that the serious appearance for affecting cell piece.Sometimes, crystal-silicon battery slice finished product
Also there are some fingerprints on surface.
Invention content
The technical problem to be solved in the present invention is to provide a kind of sodium ions that can be in barrier encapsulation glass from the micro- of EVA glue
Channel enters the device of silicon chip surface.
To solve the above problems, the present invention provides a kind of plasma jet device, including ground connection is hollow metal, rod-shaped
Outer tube body, which is characterized in that further include：
Insulation tube is located in the inner cavity of the outer tube body, and axis is parallel with the axis of the outer tube body；
Metallic cathode body is located in the inner cavity of the glass tube and is connected with the RF output end of radio frequency output device, institute
State cathode be rod-like structure and its axis it is parallel with the axis of the vitreum；
Metal anode body is hollow rod-like structure, its inner wall of the anode bodies is set on the outer wall of the glass tube,
Its outer wall is clamped in the outer tube body inner wall；
Inlet channel is connected to the inner cavity of the glass tube, and the gas outlet of the inlet channel is arranged in the jet stream
The outside of device.
As a further improvement on the present invention, further include the first attachment device and the second attachment device being connected with each other, institute
The one end for stating cathode is clamped in first attachment device, and the outer wall of the outer tube body is clamped in second attachment device
On.
As a further improvement on the present invention, the connection type of first attachment device and the second attachment device is flange
The clamping mode of connection, the cathode, outer tube body and first attachment device, the second attachment device is that centering clamps.
As a further improvement on the present invention, the cathode is tungsten filament.
A kind of plasma jet component, including：
Fluidic device as described in claim 1-4 any of which；
The inlet duct being connected on the inlet channel of the fluidic device；And
Can into the cathode of the fluidic device feed-in radio-frequency power radio-frequency power supply；
The gas sending device can be sent into one or more of argon gas, oxygen into the inlet channel.
A kind of crystal silicon battery process for surface oxidation, it is characterised in that include the following steps：
A1, the axis center position that the negative electrode in the hollow tubular glass tube of fluidic device is adjusted to the glass tube,
The negative electrode is retracted in the glass tube, and the glass tube protrudes from the hollow tubular anode bodies of setting on its external wall
Outside, radio-frequency power supply is adjusted, to the cathode feed-in radio-frequency power；
B1, argon gas and oxygen mix are passed through into the inlet channel being connected to the glass tube cavity by inlet duct
Gas；
C1, fluidic device is evenly being subjected to two-dimentional row with the polysilicon chip surface impregnated in 4% hydrofluoric acid solution
Column scan.
Further, in step A1, radio-frequency power 20MHz.
Further, in mixed gas, the content of oxygen is less than 0.5%.
Further, in step B1, mixed gas flow 10SLM, the wherein flow of oxygen are 20SCCM, in addition, will
The radio-frequency power supply is adjusted to 70W.
A kind of crystal silicon battery surface decontamination method, which is characterized in that include the following steps：
A2, the axis center position that the negative electrode in the hollow tubular glass tube of fluidic device is adjusted to the glass tube,
The negative electrode is retracted in the glass tube, and the glass tube protrudes from the hollow tubular anode bodies of setting on its external wall
Outside, radio-frequency power supply is adjusted, is 13.56MHz to the cathode feed-in radio-frequency power；
B2, argon gas and oxygen mix are passed through into the inlet channel being connected to the glass tube cavity by inlet duct
Gas 8SLM, the wherein flow of oxygen are 10SCCM, while the discharge power radio frequency for adjusting radio-frequency power supply is 100W；
C2, the jet stream of fluidic device is radiated on the stain on crystal silicon battery surface；
D2, it the processed crystal silicon chip of jet stream is put into deionized water rinses；
E2, the crystal silicon chip after rinsing is put into temperature to carry out drying and processing in 110 degree of baking oven.
The beneficial effects of the present invention are, the sodium ion that the present invention can be in barrier encapsulation glass enters silicon chip surface, from
And the defective bit for preventing sodium ion from causing crystal silicon surface micrometre-grade in the accumulation on crystal silicon surface causes carrier in battery component
It is a large amount of compound, cause the power output of battery component to reduce, meanwhile, also for pollutions such as the fingerprints for eliminating cell piece surface
Object.
Description of the drawings
Fig. 1 is the structural schematic diagram of the present invention；
Wherein：2- outer tube bodies；3- glass tubes；4- metallic cathode bodies；6- metal anode bodies；8- inlet channels；10- first connects
Connection device；The second attachment devices of 12-.
Specific implementation mode
The specific implementation mode of the present invention is described in further detail below in conjunction with the accompanying drawings.
As shown in Figure 1, the present invention includes the hollow rod-shaped metal outer pipe body 2 of ground connection, which is characterized in that further include：
Insulation tube 3 is located in the inner cavity of the outer tube body 2, and axis is parallel with the axis of the outer tube body 2；
Metallic cathode body 4 is located in the inner cavity of the glass tube 3 and is connected with the RF output end of radio frequency output device,
The metallic cathode body 4 is rod-like structure and its axis is parallel with the axis of the vitreum；
Metal anode body 6, is hollow rod-like structure, its inner wall of the metal anode body 6 is set in the glass tube 3
On outer wall, outer wall is clamped in 2 inner wall of outer tube body；
Inlet channel 8 is connected to the inner cavity of the glass tube 3, and the gas outlet of the inlet channel 8 is arranged described
The outside of fluidic device.
As a further improvement on the present invention, further include the first attachment device 10 and the second attachment device being connected with each other
12, one end of the metallic cathode body 4 is clamped in first attachment device 10, and the outer wall of the outer tube body 2 is clamped in institute
It states in the second attachment device 12.
As a further improvement on the present invention, the connection type of first attachment device, 10 and second attachment device 12 is
Flanged joint, the metallic cathode body 4, outer tube body 2 and first attachment device 10, the second attachment device 12 clamping mode
It is that centering clamps.
As a further improvement on the present invention, the metallic cathode body 4 is tungsten filament.
As a further improvement on the present invention, the length 1-4mm of the metallic cathode body 4, discharge end use taper knot
Structure, cone angle radius of curvature are 0.5mm-3mm, and cone point is retracted grounding ports 3mm-10mm, the internal diameter of the glass tube 3
For 6mm, the grounding ports about 3mm-10mm is protruded.
A kind of plasma jet component, including：
Fluidic device as described in claim 1-5 any of which；
The inlet duct being connected on the inlet channel 8 of the fluidic device；And
Can into the metallic cathode body 4 of the fluidic device feed-in radio-frequency power radio-frequency power supply；
The gas sending device can be sent into one or more of argon gas, oxygen into the inlet channel 8.
A kind of crystal silicon battery process for surface oxidation, it is characterised in that include the following steps：
A1, the axis center position that the negative electrode in the hollow tubular glass tube 3 of fluidic device is adjusted to the glass tube 3
It sets, the negative electrode is retracted in the glass tube 3, and the glass tube 3 protrudes from the hollow tubular gold of setting on its external wall
Belong to outside anode bodies 6, radio-frequency power supply is adjusted, to 4 feed-in radio-frequency power of the metallic cathode body；
B1, argon gas is passed through into the inlet channel 8 being connected to 3 inner cavity of glass tube by inlet duct and oxygen is mixed
Close gas；
C1, fluidic device is evenly being subjected to two-dimentional row with the polysilicon chip surface impregnated in 4% hydrofluoric acid solution
Column scan.
Further, in step A1, radio-frequency power 20Hz.
Further, in mixed gas, the content of oxygen is less than 0.5%.
Further, in step B1, mixed gas flow 10000SLM, the wherein flow of oxygen are 20SCCM, in addition,
The radio-frequency power supply is adjusted to 70W.
A kind of crystal silicon battery surface decontamination method, which is characterized in that include the following steps：
A2, the axis center position that the negative electrode in the hollow tubular glass tube 3 of fluidic device is adjusted to the glass tube 3
It sets, the negative electrode is retracted in the glass tube 3, and the glass tube 3 protrudes from the hollow tubular gold of setting on its external wall
Belong to outside anode bodies 6, adjust radio-frequency power supply, is 13.56MHz to 4 feed-in radio-frequency power of the metallic cathode body；
B2, argon gas is passed through into the inlet channel 8 being connected to 3 inner cavity of glass tube by inlet duct and oxygen is mixed
Gas 8SLM is closed, the wherein flow of oxygen is 10SCCM, while the discharge power radio frequency for adjusting radio-frequency power supply is 100W；
C2, the jet stream of fluidic device is radiated on the stain on crystal silicon battery surface；
D2, it the processed crystal silicon chip of jet stream is put into deionized water rinses；
E2, the crystal silicon chip after rinsing is put into temperature to carry out drying and processing in 110 degree of baking oven.
The concrete principle of the present invention is as follows：It is passed through the mixed gas of argon gas and oxygen into insulation tube 3, starts radio frequency output
Device and to the certain radio-frequency power of 4 feed-in of metallic cathode body, dielectric impedance nearby occurs for the metallic cathode body 4 in glass tube 3
Electric discharge forms plasma in plasma excitation region, and plasma plume brightness is sprayed with air-flow inside insulation tube 3,
Form include electronics, ion, oxygen atom free radical, ozone and ultraviolet light isoreactivity substance plasma jet, and penetrate
Frequency power, air-flow and electrode material are related, and plumage brightness length longest can reach 40mm.
Polysilicon chip is placed in below generated plasma jet or hand-held device acts on plasma jet
To polysilicon region, i.e. by depth after the active oxygen atom and ozone molecule interaction in polysilicon surface and plasma
Oxidation.If by the fingerprint region on plasma jet zone of action polysilicon chip surface, active group and purple in pdp body
The pollutant of outside line and fingerprint region chemically reacts, the long-chain or weak bond of some organic matters, which are effectively interrupted or aoxidized, to be divided
Solution, some remaining inorganic impurities can use weak acid or weak lye short rinse to fall.
The present invention can be in barrier encapsulation glass sodium ion enter silicon chip surface, to prevent sodium ion on crystal silicon surface
Accumulation cause the defective bit of crystal silicon surface micrometre-grade and cause a large amount of compound of carrier in battery component, lead to battery component
Power output reduce, meanwhile, also for pollutants such as the fingerprints for eliminating cell piece surface.
Here insulation tube 3 selects quartz glass tube, is acted on for dielectric barrier discharge.
The present invention can select a variety of different radio-frequency power supply frequencies, and frequency range can be between 1.2MHz-13.56MHz
It is selected.Radio-frequency power supply discharge power is between 10W-200W.
Cathode body electrode uses thickness for the tungsten filament of 1-4mm, and the discharge end of electrode uses pyramidal fashion, cone angle radius of curvature
For 0.5mm-3mm, cone point is retracted grounding ports about 3mm-10mm, and 3 medium of glass tube that internal diameter thickness is 6mm protrudes ground connection
Hand-held or stationary nozzle mode downward may be used in port about 3mm-10mm, plasma jet device.
Used excited gas can be the mixed gas of helium or argon gas and oxygen, gas flow in the above scheme
Change to that 20SLM is even more from 1SLM according to experimental conditions, the flow of oxygen is less than the 0.5% of total gas couette.
Oxygen is electronegative gas, is easy to dissociate by the electron collision with high energy in the plasma, is generated
Therefore certain density negative oxygen ion mixes the oxygen of too high amount, need the input of higher radio frequency could excite generate etc. from
Daughter, from the point of view of the present embodiment, under conditions of maintaining lower-wattage, the flow for being passed through oxygen is unsuitable excessively high.
In addition, the firing voltage due to helium is relatively low, it can first be passed through helium and carry out (pre-) ignition discharge, then be gradually added argon
Gas and oxygen, close helium, and plasma jet is just transitioned into the discharge mode of argon gas and oxygen.
Explanation downwards is done further to the present invention with reference to embodiment.
In the first embodiment of the invention, the metal tungsten wire as metallic cathode body 4 is adjusted to the axis center of glass tube 3
Position, needle point are retracted the place of 6 end 5mm of metal anode body, and insulation tube 3 protrudes the place of metal anode body 65mm, radio frequency electrical
The discharge frequency in source is 2.0MHz, and it is 10SLM to be passed through argon gas stream flow, wherein the oxygen of doping 20SCCM flows, discharge power
It is set in 70W.With hand-held, by plasma jet evenly with the 156mm* impregnated in 4% hydrofluoric acid solution
156mm polysilicon chips surface carries out two-dimentional rank scanning, and jet stream end is remote apart from polysilicon surface 3mm, processing time total about 1
Minute.Hydrophilic characteristic is presented through contact angle test in polysilicon surface, and contact angle changes from about 70 degree of contact angle before processing
To only 10 degree or so.Wellability variation before and after the processing shows that polysilicon surface realizes deep oxidation.Take 5 156mm*
The polysilicon chip sample of 156mm has carried out simple chemical cleaning to polysilicon chip and has handled before any plasma treatment.As a result
Show that the carrier lifetime of polysilicon chip has 2-3 times of raising compared to before processing.The test of high-resolution transmission electron microscope
As a result also indicate that the oxidation depth of polysilicon surface in 8nm or so.
In another embodiment of the present invention, the metal tungsten wire as metallic cathode body 4 is adjusted to the axis of glass tube 3
Center, described in the geometrical relationship example as above of tungsten tip, metal anode body 6 and glass tube 3.The discharge frequency of radio-frequency power supply is
13.56MHz, it is 8SLM to be passed through argon flow amount, wherein the oxygen of doping 10SCCM flows, discharge power radio frequency is 100W.With hand
Hold the finger-print region that plasma jet is irradiated polycrystalline silicon battery plate sample surfaces by mode, about 5-8 seconds processing time.It will processing
The cell piece sample crossed, which is put into deionized water, to be rinsed about 10 seconds.After taking-up, it is put into the baking oven that temperature is 110 degree and carries out 5 points
The drying and processing of clock.From metallographic microscope observation indicate that, fingerprint clearance rate has reached 80% or more, and it is remaining that treated
Fingerprint trace is rinsed with deionized water.The photoelectric conversion efficiency of solar battery sheet after finger prints processing has no decline.
The above example only one such embodiment of the present invention, the description thereof is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for those of ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection model of the present invention
It encloses.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of plasma jet device includes the hollow rod-shaped metal outer pipe body (2) of ground connection, which is characterized in that further include：
Glass tube (3) is located in the inner cavity of the outer tube body (2), and axis is parallel with the axis of the outer tube body (2)；
Metallic cathode body (4) is located in the inner cavity of the glass tube (3) and is connected with the RF output end of radio frequency output device,
The cathode (4) is rod-like structure and its axis is parallel with the axis of the glass tube (3)；
Metal anode body (6), is hollow rod-like structure, and described its inner wall of anode bodies (6) is set in the outer of the glass tube (3)
On wall, outer wall is clamped in the outer tube body (2) inner wall；
The end of the needle point opposite anode body of the cathode is retracted in the glass tube；
Inlet channel (8) is connected to the inner cavity of the glass tube (3), and the gas outlet of the inlet channel (8) is arranged in institute
State the outside of fluidic device.
2. a kind of plasma jet device according to claim 1, which is characterized in that further include that first be connected with each other connects
One end of connection device (10) and the second attachment device (12), the cathode (4) is clamped on first attachment device (10),
The outer wall of the outer tube body (2) is clamped on second attachment device (12).
3. a kind of plasma jet device according to claim 2, which is characterized in that first attachment device (10) and
The connection type of second attachment device (12) is flanged joint, and the cathode (4), outer tube body (2) connect dress with described first
Set (10), the clamping mode of the second attachment device (12) is that centering clamps.
4. a kind of plasma jet device according to claim 3, which is characterized in that the cathode (4) is tungsten filament.
5. a kind of plasma jet component, including：
Fluidic device as described in claim 1-4 any of which；
The inlet duct being connected on the inlet channel (8) of the fluidic device；And it can be to the cathode of the fluidic device
The radio-frequency power supply of feed-in radio-frequency power in body (4)；
The inlet duct can be sent into one or more of argon gas, oxygen into the inlet channel (8).
6. a kind of crystal silicon battery process for surface oxidation using the plasma jet device described in claim 1-4 any one,
Characterized by the following steps：
A1, the axis center position that the negative electrode in the hollow tubular glass tube of fluidic device is adjusted to the glass tube, it is described
Negative electrode is retracted in the glass tube, and the glass tube protrudes from outside the hollow tubular anode bodies of setting on its external wall, institute
The end for stating the needle point opposite anode body of negative electrode is retracted in the glass tube, is adjusted radio-frequency power supply, is penetrated to cathode feed-in
Frequency power；
B1, argon gas and oxygen mixture are passed through into the inlet channel being connected to the glass tube cavity by inlet duct
Body；
C1, fluidic device is evenly swept carrying out two-dimentional ranks with the polysilicon chip surface impregnated in 4% hydrofluoric acid solution
It retouches.
7. crystal silicon battery process for surface oxidation according to claim 6, which is characterized in that in step A1, radio-frequency power is
20MHz。
8. crystal silicon battery process for surface oxidation according to claim 7, which is characterized in that in the mixed gas, oxygen
Content be less than 0.5%.
9. crystal silicon battery process for surface oxidation according to claim 8, which is characterized in that in step B1, mixed gas stream
Amount is 10000SCCM, and wherein the flow of oxygen is 20SCCM.
10. a kind of crystal silicon battery surface decontamination method using the plasma jet device described in claim 1-4 any one,
It is characterized by comprising the following steps：
A2, the axis center position that the negative electrode in the hollow tubular glass tube of fluidic device is adjusted to the glass tube, it is described
Negative electrode is retracted in the glass tube, and the glass tube protrudes from outside the hollow tubular anode bodies of setting on its external wall, institute
The end for stating the needle point opposite anode body of negative electrode is retracted in the glass tube, is adjusted radio-frequency power supply, is penetrated to cathode feed-in
Frequency power is 13.56MHz；
B2, argon gas and oxygen mixture are passed through into the inlet channel being connected to the glass tube cavity by inlet duct
Body, the wherein content of oxygen are less than 0.5%, while the discharge power radio frequency for adjusting radio-frequency power supply is 100W；
C2, the jet stream of fluidic device is radiated on the stain on crystal silicon battery surface；
D2, it the processed crystal silicon chip of jet stream is put into deionized water rinses；
E2, the crystal silicon chip after rinsing is put into temperature to carry out drying and processing in 110 degree of baking oven.
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| CN108321251B (en) * | 2018-01-19 | 2019-11-08 | 河海大学常州校区 | A kind of method that atmospheric pressure plasma discharge jet stream prepares black silicon |
| US11543872B2 (en) | 2019-07-02 | 2023-01-03 | Microsoft Technology Licensing, Llc | Dynamically adjusting device operating voltage based on device performance |
| CN111081819B (en) * | 2019-12-31 | 2021-06-08 | 通威太阳能（合肥）有限公司 | Damage-preventing cutting method and device for solar cell |
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