CN101882632B - Glass substrate matte structure ZnO film and application - Google Patents
Glass substrate matte structure ZnO film and application Download PDFInfo
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- CN101882632B CN101882632B CN2010102021112A CN201010202111A CN101882632B CN 101882632 B CN101882632 B CN 101882632B CN 2010102021112 A CN2010102021112 A CN 2010102021112A CN 201010202111 A CN201010202111 A CN 201010202111A CN 101882632 B CN101882632 B CN 101882632B
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Abstract
The invention relates to a glass substrate matte structure ZnO film, which is prepared through a magnetron sputtering technology, and adopts glass as a substrate, Zn-Al alloy target and O2 as raw materials and adopts Al as a doping agent. The magnetron sputtering is carried out under the vacuum condition. A matte structure ZnO film is directly grown on a glass substrate, the thickness of the film is 900 to 1500 nm, the film structure is of a glass/matte ZnO film, and the film is applied to the pin-typed a-Si film solar battery or a-Si/uc-Si laminated film solar battery. The glass substrate matte structure ZnO film has the advantage that: the magnetron sputtering technology is utilized, so the film plating temperature is relatively low, the growth speed is fast, and the large-area growth can be realized; the matte is free from being made through a following wet-method etching technology, and the matte structure ZnO-TCO film with rough surface can be obtained through the direct growth, so the light scattering effect can be increased; and the glass substrate matte structure ZnO film is applied to the pin-typed a-Si film solar battery, so the photoelectric conversion efficiency is high.
Description
[technical field]
The invention belongs to solar cell transparent conductive oxide film field, particularly a kind of glass substrate matte structure ZnO film and application.
[background technology]
Transparent conductive oxide (Transparent conductive oxides-TCO) film refers to visible light (the mean transmissivity height of λ=380～780nm) (T 〉=80%), low-resistivity (ρ≤10
-3Ω cm) sull.The TCO film of broad research and application mainly is the SnO that F mixes
2: F film, the In that Sn mixes
2O
3: the ZnO:Al film that Sn (ITO) film and Al mix.In the solar cell application, because ITO and SnO
2Film is reduced blackening easily and causes its deterioration in optical properties in the H plasma ambient, become the obstacle in the application.In recent years, it is low that ZnO film has a cost, nontoxic, be easy to lithography process and in the H plasma environment chemical stability good, in the Si thin film solar cell, obtained applications well research [referring to J.Meier, S.Dubail, R.Platz, etc.Solar Energy Materials and Solar Cells, 49 (1997) 35.].
(mainly comprise amorphous silicon (a-Si:H) battery for the Si thin film solar cell, microcrystal silicon (μ c-Si:H) battery and amorphous/crystallite lamination " micromorph " battery), sunken light (lighttrapping) effect of TCO film is particularly important [referring to A.V.Shah to device performance, J.Meier, E.Vallat-Sauvain, etc.Thin Solid Films, 403-404 (2002) 179. and A.V.Shah, H.Schade, M.Vanecek, etc.Progress in Photovoltaics, 12 (2004) 113.], promptly improve light scattering ability, increase the light path of incident light.The application of light trapping structure can effectively strengthen the optical absorption of intrinsic layer (active layer), improves short-circuit current density, thereby improves battery efficiency.Usually electrode and back reflector can realize falling into light action before the suede structure.Suede structure can be by regulating film crystallite dimension size, and features such as grain shape realize rough surface, and its physical and chemical performance helps subsequent thin film deposition (as the Si film).
Being applied to the ZnO-TCO film of Si thin film solar cell and assembly thereof, mainly is magnetron sputtering (magnetron sputtering-MS) and metal-organic chemical vapor deposition equipment (metal organic chemicalvapor deposition-MOCVD) technology in the world.Utilize magnetron sputtering method to prepare the thin film solar cell ZnO film, adopt Al to mix usually and obtain low resistivity (～10
-4Ω cm) mirror surface structure; For being applied to front electrodes of solar cells better, ZnO film after the sputter must take wet etching could form suede structure [referring to O.Kluth, B.Rech, L.Houben, etc.Thin Solid Films 351 (1999) 247.], in the hope of obtaining the good light scattering power.Yet during the modulation suede structure, wet etching plays a crucial role, and has certain risk and cause waste of material (corrosion rear film thickness reduces) when large tracts of land corrosion ZnO film forms suede structure.But MOCVD technology direct growth go out suede structure ZnO film [referring to X.L.Chen, X.H.Geng, J.M.Xue, etc.Journal of Crystal Growth, 296 (2006) 43. and S.
, U.Kroll, C.Bucher, etc.Sol.Energy Mater.Sol.Cells 86 (2005) 385.], thin film growth process is the thermal decomposition process of no particle bombardment, depositing temperature low relatively (～423K).But comparatively speaking, the photoelectric characteristic of the film of magnetron sputtering growth and stability are better.
The present invention regulates technology according to the characteristics of magnetron sputtering technique growth ZnO-TCO film by optimizing, and promptly regulates underlayer temperature, sputtering pressure, O
2Flow, parameters such as sputtering power provide a kind of magnetron sputtering technique direct growth of utilizing to obtain coarse matte structure ZnO film (promptly need not follow-up wet etching technique making herbs into wool), and are applied to the method that silicon-based thin film solar cell is used.Above-mentioned technical characterictic is different from the method that current other magnetron sputterings obtain matte structure ZnO film.
[summary of the invention]
The objective of the invention is at above-mentioned technical Analysis, a kind of coating temperature is low relatively, growth rate is fast, light scattering property is strong glass substrate matte structure ZnO film and application are provided.
Technical scheme of the present invention:
A kind of glass substrate matte structure ZnO film utilizes magnetron sputtering technique preparation, is substrate with glass, and underlayer temperature is (200～280) ℃, with Zn-Al alloy target and O
2Be raw material, wherein Zn component purity is 99.99%, and the weight percent content of dopant Al component is (0.5～3.0) %, and background vacuum pressure is 8 * 10
-5Pa, sputtering pressure are (2.5～7.5) mTorr, and wherein oxygen flow is 2～30sccm, direct growth matte structure ZnO film on glass substrate, and film thickness (900～1500) nm, membrane structure is the glass/ textured ZnO membrane.
Magnetic control sputtering film plating device is adopted in a kind of preparation of glass substrate matte structure ZnO film as described, and this device is made of sputtering chamber and print chamber for hermetically-sealed construction, is provided with slide valve between sputtering chamber and the print chamber and controls its break-make; Sputter indoor set having heaters, substrate, plasma detection resources, an ion source and two controlled sputtering sources, the plasma detection resources is composed controller (PEM) with the plasma emission outside the container and is connected, an ion source is connected with container three power supplys outward respectively with two controlled sputtering sources, and sputtering chamber is provided with two vacuum orifices; Print is indoor to be provided with the laminar print frame of placing print, and the print frame switches by lowering or hoisting gear, and the print on the print frame is sent on the substrate in the sputtering chamber by pull bar, and the print chamber is provided with a vacuum orifice.
A kind of moral of glass substrate matte structure ZnO film is as described used, and is applied to pin type a-Si thin film solar cell or a-Si/uc-Si laminated film solar battery.
Advantage of the present invention and effect: 1) utilize magnetron sputtering technique, coating temperature is low relatively, and growth rate is fast, helps large area deposition; 2) magnetron sputtering technique provided by the invention need not follow-up wet etching technique making herbs into wool, but direct growth obtains the matte structure ZnO-TCO film of rough surface, helps increasing the light scattering effect; 3) be applied to pin type a-Si thin film solar cell (battery structure glass/ZnO/pin a-Si/ZnO/Al), obtain 7.6% photoelectric conversion efficiency.
[description of drawings]
Fig. 1 is the magnetic control sputtering film plating device structural representation.
Among the figure: 1. sputtering chamber print chambers 2. 3. slide valves, 4. heaters 5. substrates 6. plasma detection resources 7. ion source 8-I, 8-II. controlled sputtering source 9. plasma emission are composed controller (PEM) 10-I, 10-II, 10-III. power supply 11-I, 11-II. vacuum orifice 12. prints 13. print framves 14. lowering or hoisting gears 15. pull bars 16. vacuum orifices
Fig. 2 is this matte structure ZnO film structural representation.
Fig. 3 is the SEM image of this matte structure ZnO film.
Fig. 4 is applied to roof liner structure pin type a-Si thin-film solar cell structure schematic diagram for this matte structure ZnO film.
Fig. 5 is applied to roof liner structure pin type a-Si/uc-Si thin-film solar cell structure schematic diagram for this matte structure ZnO film.
[embodiment]
The present invention proposes a kind of method of utilizing the magnetron sputtering technique direct growth to obtain matte structure ZnO film and solar cell application.
Magnetic control sputtering film plating device is adopted in a kind of preparation of glass substrate matte structure ZnO film, and this device is made of sputtering chamber 1 and print chamber 2 for hermetically-sealed construction, is provided with slide valve 3 its break-makes of control between sputtering chamber 1 and the print chamber 2; Device having heaters 4 in the sputtering chamber 1, substrate 5, plasma emission source 6, ion source 7 and two controlled sputtering source 8-I, 8-II, plasma emission source 6 is composed controller (PEM--15) 9 with the plasma emission outside the container and is connected, an ion source 7 is connected with container three power supply 10-I, 10-II, 10-III outward respectively with two controlled sputtering source 8-I, 8-II, and sputtering chamber 1 is provided with two vacuum orifice 11-I, 11-II; Be provided with the laminar print frame 13 of placing print 12 in the print chamber 2, print frame 13 switches by lowering or hoisting gear 14, and the print 12 on the print frame 13 is sent on the substrate 5 in the sputtering chamber 1 by pull bar 15, and print chamber 2 is provided with a vacuum orifice 16.
Following examples all prepare on above-mentioned magnetic control sputtering film plating device.
Embodiment 1:
1, utilizes above-mentioned magnetic control sputtering device, by high-purity Zn-Al alloy target (component purity: 99.99%, wherein the weight percent content of dopant Al component is 2.0%) and O
2As raw material, low temperature direct growth matte structure ZnO film on glass substrate, underlayer temperature is 250 ℃, background vacuum pressure is 8 * 10
-5Pa, sputtering pressure are 4.5mTorr, and wherein oxygen flow is 8.5sccm, the film thickness 1000nm that test obtains, square resistance～8 Ω, visible region mean transmissivity～85%, roughness of film RMS～65nm.The membrane structure that growth obtains is the glass/ textured ZnO membrane.Fig. 2 is this matte structure ZnO film structural representation.
Fig. 3 is the SEM image of this matte structure ZnO film, shows that this film has coarse surface texture, presents " crater " shape, characteristic size 300-1000nm.
2, suede structure glass/ZnO film is applied to pin type a-Si thin film solar cell.As shown in Figure 4, be coated with textured ZnO membrane on the glass substrate, the p that grows thereafter, i, three layers of a-Si film of n are coated with the ZnO/Al composite film at last, and above-mentioned feature constitutes the solar cell device.Through the I-E characteristic test, obtained 7.6% photoelectric conversion efficiency.
Embodiment 2:
1, utilizes above-mentioned magnetic control sputtering system, by high-purity Zn-Al alloy target (component purity: 99.99%, wherein the weight percent content of dopant Al component is 1.0%) and O
2As raw material, low temperature direct growth matte structure ZnO film on glass substrate, underlayer temperature～280 ℃, background vacuum pressure is 8 * 10
-5Pa, sputtering pressure～4.0mTorr, wherein oxygen flow is 8.0sccm, the film thickness that test obtains is 1200nm, roughness of film RMS～70nm, square resistance～5 Ω, visible light and near infrared region mean transmissivity～85%.The membrane structure that growth obtains is: the glass/ textured ZnO membrane.Fig. 2 is this matte structure ZnO film structural representation.
2, this kind suede structure glass/ textured ZnO membrane is applied to pin type a-Si/uc-Si laminated film solar battery.Fig. 5 is for being applied to a-Si/uc-Si thin film solar cell battery structure schematic diagram.Be coated with textured ZnO membrane on the glass substrate, grow in succession pin a-Si film and pin uc-Si film (amounting to 6 layers of Si film) then are coated with the ZnO/Al film, and above-mentioned feature constitutes the solar cell device.
Claims (3)
1. one kind is the matte structure ZnO film of substrate with glass, it is characterized in that: utilizing the magnetron sputtering technique preparation, is substrate with glass, and underlayer temperature is 200～280 ℃, with Zn-Al alloy target and O
2Be raw material, wherein Zn component purity is 99.99%, and the weight percent content of dopant Al component is 0.5%～3.0%, and background vacuum pressure is 8 * 10
-5Pa, sputtering pressure are 2.5～7.5mTorr, and wherein oxygen flow is 2～30sccm, direct growth matte structure ZnO film on glass substrate, and film thickness 900～1500nm, membrane structure are glass/textured ZnO membrane.
One kind as claimed in claim 1 be the preparation of the matte structure ZnO film of substrate with glass, it is characterized in that: adopt magnetic control sputtering film plating device, this device is made of sputtering chamber and print chamber for hermetically-sealed construction, is provided with slide valve between sputtering chamber and the print chamber and controls its break-make; Sputter indoor set having heaters, substrate, plasma detection resources, an ion source and two controlled sputtering sources, the plasma detection resources is composed controller (PEM) with the plasma emission outside the container and is connected, an ion source is connected with container three power supplys outward respectively with two controlled sputtering sources, and sputtering chamber is provided with two vacuum orifices; Print is indoor to be provided with the laminar print frame of placing print, and the print frame switches by lowering or hoisting gear, and the print on the print frame is sent on the substrate in the sputtering chamber by pull bar, and the print chamber is provided with a vacuum orifice.
One kind as claimed in claim 1 be the application of the matte structure ZnO film of substrate with glass, it is characterized in that: be applied to pin type a-Si thin film solar cell or a-Si/uc-Si laminated film solar battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102021112A CN101882632B (en) | 2010-06-18 | 2010-06-18 | Glass substrate matte structure ZnO film and application |
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| CN2010102021112A CN101882632B (en) | 2010-06-18 | 2010-06-18 | Glass substrate matte structure ZnO film and application |
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| CN101882632B true CN101882632B (en) | 2011-09-07 |
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| CN102242345B (en) * | 2011-06-29 | 2013-07-10 | 南开大学 | Direct preparation method of textured zinc oxide transparent electroconductive film |
| CN102280529A (en) * | 2011-08-05 | 2011-12-14 | 保定天威集团有限公司 | Transparent conductive film with high Haze value and preparation method thereof |
| CN104022164B (en) * | 2014-06-17 | 2016-07-06 | 浙江大学 | A kind of ZnO:Al matte thin film being applied to amorphous Si solaode |
| US10103282B2 (en) | 2016-09-16 | 2018-10-16 | Nano And Advanced Materials Institute Limited | Direct texture transparent conductive oxide served as electrode or intermediate layer for photovoltaic and display applications |
| CN112599644B (en) * | 2020-11-26 | 2022-09-30 | 佛山汉狮建材科技有限公司 | Light energy plate for electric curtain and preparation method thereof |
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