CN102260853B - Method for depositing silicon membrane for solar cell on basis of magnetic control sputtering technology - Google Patents
Method for depositing silicon membrane for solar cell on basis of magnetic control sputtering technology Download PDFInfo
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- CN102260853B CN102260853B CN 201110188670 CN201110188670A CN102260853B CN 102260853 B CN102260853 B CN 102260853B CN 201110188670 CN201110188670 CN 201110188670 CN 201110188670 A CN201110188670 A CN 201110188670A CN 102260853 B CN102260853 B CN 102260853B
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Abstract
The invention relates to a method for depositing a silicon membrane for a solar cell on the basis of the magnetic control sputtering technology. The prepared silicon membrane is between 0.01 and 5 micrometers, and the equipment used in the method is magnetic control sputtering equipment. The method comprises the following steps of: selecting a base material, and performing pre-cleaning treatment; putting the base material on a fixture frame, and conveying the base material to a vacuum cavity of the magnetic control sputtering equipment; while keeping the linear motion of the fixture frame in the process of preparing the silicon membrane, vacuumizing the integral vacuum cavity; introducing mixed gas of argon and hydrogen continuously under a constant working air pressure; and increasing the target current of a silicon target material to 0.3 to 15 A or increasing the target power of the silicon target material to 100 to 2,000 W, and maintaining electric parameters of the silicon target material to deposit the silicon membrane for 1 to 3 minutes. In the method, toxic and dangerous gas is prevented from being introduced in the preparation process, a process is stable, safe, reliable and high in repeatability, and the prepared silicon membrane is high in deposition rate and compactness.
Description
Technical field
The invention belongs to new energy materials manufacturing technology field, be specifically related to a kind of based on the method for magnetron sputtering technique depositing solar cell with silicon film.
Background technology
Solar energy resources because of its distribution is not subjected to regional limits, reserves are huge and inexhaustible, utilize the advantages such as process noiseless to become a kind of new forms of energy that receive much concern; In various solar cells, silica-based solar cell is because having abundant raw material, nontoxic and cost is low and favored with advantages such as semiconductor technology compatibilities.
At present, battery component technology maturation take monocrystaline silicon solar cell and polysilicon solar cell as representative and efficiency of conversion are high, but energy and high material consumption in the preparation process, cost decline space and efficiency of conversion room for promotion are limited, are unfavorable for big area production.Amorphous silicon thin-film solar cell is because having preparation process silicon raw material and electric energy consumption is few, and cost advantage highlights, and is suitable for the advantages such as industrialization big area production, in recent years industry development speed-raising.At present institute's silicon-based film solar cells of research and develop and producing has that the energy return period is short, high-temperature behavior is good and the characteristics such as the low light level/short wave response is good, and utilize its assembly foundation be incorporated into the power networks the power station and from net the power station dilatation conveniently and operation expense low.
Current, industrial community when preparation silicon-based film solar cells used silicon film all take plasma enhanced chemical vapor deposition (PECVD) as preparation means, the special gas such as three alkane (silane, borine, phosphine) is as main raw material, safety control is very strict and technical process is comparatively complicated in the production process, and not good enough, the hydrogen richness of its structural compactness of prepared amorphous silicon membrane is difficult to accurate control simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of based on the method for magnetron sputtering technique depositing solar cell with silicon film, compared with prior art, the inventive method preparation process gets involved without toxic gas, safe and reliable, process stabilizing, good reproducibility, and the silicon deposited film speed that makes is high, compactness is good.
The technical solution adopted in the present invention is, a kind of based on the method for magnetron sputtering technique depositing solar cell with silicon film, it is characterized in that, prepared silicon film thickness is 0.01 μ m～5 μ m, and the equipment that uses mainly comprises magnetron sputtering equipment, a plurality of assisted vacuum chambers that the vacuum chamber of this magnetron sputtering equipment comprises at least one working vacuum chamber and is connected to described working vacuum chamber both sides, be provided with high purity solid silicon target material in the described working vacuum chamber, connect whole vacuum chamber and be horizontally disposed with machine frame, be connected with drive unit on the described machine frame;
Specifically may further comprise the steps:
Step 1: the durable flexible polymeric materials of choosing conductive glass, stainless steel substrates or being coated with in advance electrode is base material, and base material is carried out front clean;
Step 2: the front cleaned base material of step 1 is positioned on the machine frame, base material is delivered in the vacuum chamber of magnetron sputtering equipment by drive unit; This machine frame maintenance speed in the silicon film preparation process is the translational motion of 10mm/min～1000mm/min; Whole vacuum chamber is vacuumized, make the base vacuum degree of working vacuum chamber be not more than 6.0 * 10
-3Pa;
Step 3, at substrate surface depositing silicon film
To continue to pass into the mixed gas of argon gas and hydrogen in the working vacuum chamber, wherein, the hydrogen dividing potential drop is 0%～60%, and guarantees that the operating air pressure of working vacuum chamber is 1.0 * 10
-1Pa～9.5 * 10
-1Pa;
After with the speed of 0.01A/min～5A/min the target current of silicon target material being increased to 0.3A～15A, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 1min～30min;
Or, with the speed of 2W/min～500W/min the target power output of silicon target material is increased to 100W～2000W after, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 1min～30min.
In the step 1, the concrete grammar that base material is carried out pretreatment cleaning is: base material is placed the solution that contains clean-out system, and ultrasonic cleaning or mechanical hairbrush clean, the spot of removing substrate surface; Again this matrix is put into deionized water, ultrasonic cleaning or mechanical hairbrush clean, removing residual clean-out system, and hot blast drying.
In the step 2, the distance on the control machine frame between matrix and the silicon target material is 20mm～200mm.
The silicon target material is silicon single crystal target or polysilicon target.
The silicon target material is P type, N-type or I type.
Durable flexible polymeric materials is plastics and resin.
The inventive method is take magnetron sputtering technique as preparation means, take high purity solid silicon target material as the silicon source, come the depositing silicon film by glow discharge-PARTICLE TRANSPORT FROM, matrix keeps kinestate in surface deposition silicon film process, and by accurately controlling the intake of hydrogen, accurately controlled the hydrogen richness in the prepared silicon film, its technique is simple, be convenient to control, improved density and the sedimentation rate of silicon film.On the other hand, comparing the used PECVD equipment of current industrial community mostly is import and involves great expense, the positive and negative electrode layer of silicon-based film solar cells all adopts the sputtering method preparation simultaneously, but the inventive method has obtained the technical progress of industrial applications especially, significantly reduce the investment threshold of industry, the minimizing of simultaneously Production Flow Chart also obviously reduces silicon-based film solar cells assembly cost, can promote the civil nature process of silicon-based film solar cells.
Description of drawings
Fig. 1 is the perspective electron microscopic shape appearance figure of the silicon for solar cell film of the inventive method embodiment 6 preparations;
Fig. 2 is the diffraction pattern analysis chart in silicon film shown in Figure 1 cross section;
Fig. 3 is the High-Resolution Map of silicon film shown in Figure 1 cross section regional area.
Embodiment
The equipment that present embodiment uses mainly comprises magnetron sputtering equipment, a plurality of assisted vacuum chambers that the vacuum chamber of this magnetron sputtering equipment comprises at least one working vacuum chamber and is connected to working vacuum chamber both sides, be provided with high purity solid silicon target material in the working vacuum chamber, connect whole vacuum chamber and be horizontally disposed with machine frame, be connected with drive unit on the machine frame, drive unit is used for driving machine frame and does lasting translational motion along the trend of vacuum chamber in vacuum chamber.
The present invention is a kind of based on the method for magnetron sputtering technique depositing solar cell with silicon film, specifically may further comprise the steps:
Step 1: choose conductive glass as base material, base material is carried out front clean.
The concrete grammar that base material is carried out pretreatment cleaning is: base material is placed the solution that contains clean-out system, ultrasonic cleaning, the spot of removing substrate surface; Again this matrix is put into deionized water, mechanical hairbrush cleans, removing residual clean-out system, and hot blast drying.
Step 2: the front cleaned base material of step 1 is positioned on the machine frame, and the distance on the control machine frame between matrix and the silicon target material is 200mm.
Base material is delivered in the vacuum chamber of magnetron sputtering equipment by drive unit; This machine frame maintenance speed in the silicon film preparation process is the translational motion of 1000mm/min; Whole vacuum chamber is vacuumized, make the base vacuum degree of working vacuum chamber be not more than 6.0 * 10
-3Pa.The silicon target material is selected the p type single crystal silicon target.
Step 3, at substrate surface depositing silicon film
To continue to pass into the mixed gas of argon gas and hydrogen in the working vacuum chamber, wherein, the hydrogen dividing potential drop is 30%, and guarantees that the operating air pressure of working vacuum chamber is 9.5 * 10
-1Pa;
Adopt the direct-current power supply pattern, with the speed of 2A/min the target current of silicon target material is increased to 10A after, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 1min.
The silicon film thickness of present embodiment preparation is 0.355 μ m, and sedimentation rate is about 355nm/min.
Embodiment 2
The equipment that present embodiment uses is with embodiment 1.
The present invention is a kind of based on the method for magnetron sputtering technique depositing solar cell with silicon film, specifically may further comprise the steps:
Step 1: choosing durable flexible polymeric materials is base material, and specifically selecting the plastics that are coated with in advance electrode is base material, and base material is carried out front clean.
The concrete grammar that base material is carried out pretreatment cleaning is: base material is placed the solution that contains clean-out system, ultrasonic cleaning, the spot of removing substrate surface; Again this matrix is put into deionized water, ultrasonic cleaning, removing residual clean-out system, and hot blast drying.
Step 2: the front cleaned base material of step 1 is positioned on the machine frame, and the distance on the control machine frame between matrix and the silicon target material is 100mm.Base material is delivered in the vacuum chamber of magnetron sputtering equipment by drive unit; This machine frame maintenance speed in the silicon film preparation process is the translational motion of 500mm/min; Whole vacuum chamber is vacuumized, make the base vacuum degree of working vacuum chamber be not more than 6.0 * 10
-3Pa.The silicon target material is selected I type (being eigenmode) silicon single crystal target.
Step 3, at substrate surface depositing silicon film
To continue to pass into argon gas in the working vacuum chamber, this moment, the hydrogen dividing potential drop was 0%, and guaranteed that the operating air pressure of working vacuum chamber is 6.5 * 10
-1Pa;
Adopt the direct-current power supply pattern, with the speed of 0.01A/min the target current of silicon target material is increased to 0.3A after, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 20min.
The silicon film thickness of present embodiment preparation is 0.012 μ m, and sedimentation rate is about 0.6nm/min.
Embodiment 3
The equipment that present embodiment uses is with embodiment 1.
The present invention is a kind of based on the method for magnetron sputtering technique depositing solar cell with silicon film, specifically may further comprise the steps:
Step 1: choose conductive glass as base material, base material is carried out front clean.
The concrete grammar that base material is carried out pretreatment cleaning is: base material is placed the solution that contains clean-out system, and mechanical hairbrush cleans, the spot of removing substrate surface; Again this matrix is put into deionized water, ultrasonic cleaning, removing residual clean-out system, and hot blast drying.
Step 2: the front cleaned base material of step 1 is positioned on the machine frame, and the distance on the control machine frame between matrix and the silicon target material is 110mm.Base material is delivered in the vacuum chamber of magnetron sputtering equipment by drive unit; This machine frame maintenance speed in the silicon film preparation process is the translational motion of 400mm/min; Whole vacuum chamber is vacuumized, make the base vacuum degree of working vacuum chamber be not more than 6.0 * 10
-3Pa.The silicon target material is selected I type polysilicon target.
Step 3, at substrate surface depositing silicon film
To continue to pass into argon gas in the working vacuum chamber, this moment, the hydrogen dividing potential drop was 0%, and guaranteed that the operating air pressure of working vacuum chamber is 4.0 * 10
-1Pa;
Adopt the radio-frequency power supply supply model, with the speed of 2W/min the target power output of silicon target material is increased to 100W after, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 20min.
The silicon film thickness of present embodiment preparation is 0.01 μ m, and sedimentation rate is about 0.5nm/min.
Embodiment 4
The equipment that present embodiment uses is with embodiment 1.
The present invention is a kind of based on the method for magnetron sputtering technique depositing solar cell with silicon film, specifically may further comprise the steps:
Step 1: choosing durable flexible polymeric materials is base material, and specifically selecting the resin that is coated with in advance electrode is base material, and base material is carried out front clean.
The concrete grammar that base material is carried out pretreatment cleaning is: base material is placed the solution that contains clean-out system, ultrasonic cleaning, the spot of removing substrate surface; Again this matrix is put into deionized water, mechanical hairbrush cleans, removing residual clean-out system, and hot blast drying.
Step 2: the front cleaned base material of step 1 is positioned on the machine frame, and the distance on the control machine frame between matrix and the silicon target material is 30mm.Base material is delivered in the vacuum chamber of magnetron sputtering equipment by drive unit; This machine frame maintenance speed in the silicon film preparation process is the 10mm/min translational motion; Whole vacuum chamber is vacuumized, make the base vacuum degree of working vacuum chamber be not more than 6.0 * 10
-3Pa.The silicon target material is selected the n type single crystal silicon target.
Step 3, at substrate surface depositing silicon film
To continue to pass into the mixed gas of argon gas and hydrogen in the working vacuum chamber, wherein, the hydrogen dividing potential drop is 50%, and guarantees that the operating air pressure of working vacuum chamber is 1.2 * 10
-1Pa;
Adopt the radio-frequency power supply supply model, with the speed of 500W/min the target power output of silicon target material is increased to 2000W after, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 30min.
The silicon film thickness of present embodiment preparation is 1.5 μ m, and sedimentation rate is about 50nm/min.
As shown in Figure 1, the Cross Section Morphology of silicon film is fine and close, does not see the defectives such as hole, and film is combined well with matrix simultaneously.As shown in Figure 2, for carrying out the electron diffraction pattern analysis chart in the silicon film cross section to Fig. 1, but see that this moment, though silicon film wholely was non-crystalline state, S in the film
i(111) diffraction ring of crystal face is faintly visible, illustrates that the part includes nano-silicon crystal grain in the silicon film, and the ordering degree of Siliciumatom is higher in the film, this also indirect proof the compactness of silicon film better.Cross section regional area to the silicon film of Fig. 1 carries out the analysis of high resolution photo, as shown in Figure 3, though can find out the microtexture Atom long-range lack of alignment of silicon film, but still arrange closely, can see the Cluster Structures of Siliciumatom simultaneously.
As shown in the table, be the process characteristic comparison of the inventive method and the standby silicon for solar cell film of existing PECVD legal system:
As can be seen from the above table, the inventive method gets involved without toxic gas, and process stabilizing is convenient to control, and is safe and reliable, and the silicon deposited film speed that makes is high, compactness is good.
Claims (6)
- One kind based on the magnetron sputtering technique depositing solar cell with the method for silicon film, it is characterized in that, prepared silicon film thickness is 0.01 μ m～5 μ m, and the equipment that uses mainly comprises magnetron sputtering equipment, a plurality of assisted vacuum chambers that the vacuum chamber of this magnetron sputtering equipment comprises at least one working vacuum chamber and is connected to described working vacuum chamber both sides, be provided with high purity solid silicon target material in the described working vacuum chamber, connect whole vacuum chamber and be horizontally disposed with machine frame, be connected with drive unit on the described machine frame;Specifically may further comprise the steps:Step 1: the durable flexible polymeric materials of choosing conductive glass, stainless steel substrates or being coated with in advance electrode is base material, and base material is carried out front clean;Step 2: the front cleaned base material of step 1 is positioned on the machine frame, base material is delivered in the vacuum chamber of magnetron sputtering equipment by drive unit; This machine frame maintenance speed in the silicon film preparation process is the translational motion of 10mm/min～1000mm/min; Whole vacuum chamber is vacuumized, make the base vacuum degree of working vacuum chamber be not more than 6.0 * 10 -3Pa;Step 3, at substrate surface depositing silicon filmTo continue to pass into the mixed gas of argon gas and hydrogen in the working vacuum chamber, wherein, the hydrogen dividing potential drop is 0%～60%, and guarantees that the operating air pressure of working vacuum chamber is 1.0 * 10 -1Pa～9.5 * 10 -1Pa;After with the speed of 0.01A/min～5A/min the target current of silicon target material being increased to 0.3A～15A, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 1min～30min;Or, with the speed of 2W/min～500W/min the target power output of silicon target material is increased to 100W～2000W after, keep the electrical parameter of silicon target material to carry out the deposition of silicon film, depositing time is 1min～30min.
- 2. described based on the method for magnetron sputtering technique depositing solar cell with silicon film according to claim 1, it is characterized in that, in the step 1, the concrete grammar that base material is carried out pretreatment cleaning is: base material is placed the solution that contains clean-out system, ultrasonic cleaning or mechanical hairbrush clean, the spot of removing substrate surface; Again this matrix is put into deionized water, ultrasonic cleaning or mechanical hairbrush clean, removing residual clean-out system, and hot blast drying.
- 3. it is characterized in that based on the method for magnetron sputtering technique depositing solar cell with silicon film that according to claim 1 is described in the step 2, the distance on the control machine frame between matrix and the silicon target material is 20mm～200mm.
- 4. according to claim 1 or 2 or 3 described methods based on magnetron sputtering technique depositing solar cell usefulness silicon film, it is characterized in that described silicon target material is silicon single crystal target or polysilicon target.
- 5. according to claim or 2 or 3 described methods based on magnetron sputtering technique depositing solar cell usefulness silicon film, it is characterized in that described silicon target material is P type, N-type or I type.
- 6. according to claim 1 or 2 or 3 described methods based on magnetron sputtering technique depositing solar cell usefulness silicon film, it is characterized in that described durable flexible polymeric materials is plastics and resin.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2732757Y (en) * | 2004-07-15 | 2005-10-12 | 北京清华阳光能源开发有限责任公司 | Continuous coating device for coating capable of selectively absorbing solar spectrum |
| CN101834233A (en) * | 2010-04-01 | 2010-09-15 | 河北大学 | Method for rapidly depositing hydrogenated amorphous silicon solar battery thin film at low temperature |
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2011
- 2011-07-07 CN CN 201110188670 patent/CN102260853B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2732757Y (en) * | 2004-07-15 | 2005-10-12 | 北京清华阳光能源开发有限责任公司 | Continuous coating device for coating capable of selectively absorbing solar spectrum |
| CN101834233A (en) * | 2010-04-01 | 2010-09-15 | 河北大学 | Method for rapidly depositing hydrogenated amorphous silicon solar battery thin film at low temperature |
Non-Patent Citations (1)
| Title |
|---|
| 郭伟.基于磁控溅射技术的掺氢硅薄膜制备及其结构性能研究.《中国优秀硕士学位论文全文数据库基础科学辑》.2010,(第11期),第16、21、33页. * |
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