CN102433545A - Suede-structured ZnO film prepared by alternative growth technology and application thereof - Google Patents
Suede-structured ZnO film prepared by alternative growth technology and application thereof Download PDFInfo
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- CN102433545A CN102433545A CN2011104436957A CN201110443695A CN102433545A CN 102433545 A CN102433545 A CN 102433545A CN 2011104436957 A CN2011104436957 A CN 2011104436957A CN 201110443695 A CN201110443695 A CN 201110443695A CN 102433545 A CN102433545 A CN 102433545A
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Abstract
The invention provides a suede-structured ZnO film prepared by an alternative growth technology. A suede-structured ZnO-TCO (transparent conductive oxide) film is alternatively grown on a glass substrate by a metal organic chemical vapor deposition method based on diethylzinc and water as source materials and hydrogen used for diluting and doping a gas borane B2H6. The steps are as follows: 1) firstly, growing a layer of undoped ZnO film on the glass substrate; 2), then growing a B-doped type ZnO film on the undoped ZnO film; and 3) repeating the steps 1) and 2), so as to obtain a multi-layer overlapping-grown ZnO film. The suede-structured ZnO film has the advantages that the direct growth of the suede-structured ZnO film on the glass substrate can be realized by using an MOCVD (metal oxide chemical vapor deposition) technology; the preparation method has simple process, and is convenient for large-area production and popularization; through the alternative growth technology compatible to the process technology, the light scattering of visible light and neat infrared regions and subsequent deposition of a silicon-based film are facilitated; and the suede-structured ZnO film can be applied to a film solar battery, thereby effectively improving the photoelectric conversion efficiency.
Description
[technical field]
The invention belongs to the transparent conductive oxide film field, its its application of particularly a kind of alternating growth technology preparation matte structure ZnO film.
[background technology]
Transparent conductive oxide (Transparent conductive oxides-TCO) film refers to visible light (average transmittances of λ=380～800nm) high (T>=80%), low-resistivity (ρ≤10
-3Ω cm) sull.The TCO film of broad research and application mainly is the adulterated SnO of F
2: F film, the adulterated In of Sn
2O
3: the adulterated ZnO:Al film of Sn (ITO) film and Al.In the solar cell Application Areas, because ITO and SnO
2Film is reduced blackening easily and causes its deterioration in optical properties in the hydrogen plasma ambient, become the obstacle of application.In recent years, to have a cost low, nontoxic for ZnO film; Be easy to lithography process and in the H plasma environment chemicalstability 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.].
For the Si thin film solar cell, mainly comprise non-crystalline silicon a-Si:H battery, microcrystal silicon μ c-Si:H battery and amorphous/crystallite lamination " micromorph " battery, the sunken light of TCO film (light trapping) effect is particularly important [referring to Arvind 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 realized uneven surface through regulating characteristics such as film grain-size size, grain shape, and its physical and chemical performance helps subsequent thin film deposition (like the Si film).
Magnetron sputtering technique is used the most extensive.But the ZnO film surfacing that magnetron sputtering technique obtains, crystal grain less (30nm-100nm) is difficult to form good scattering of light effect; In addition, obtain the common growth temperature higher (＞200 ℃) that needs of ZnO-TCO of good light electrical property.Yet; MOCVD technology (metal organic chemical vapor deposition technology) can realize low temperature (135-150 ℃) film growth, and crystal grain is big (300nm-500nm), can directly form suede structure [referring to X.L.Chen; X.H.Geng; J.M.Xue, etc.Journal of Crystal Growth, 296 (2006) 43.; Chen Xinliang, Xue Junming, Sun Jian etc., semi-conductor journal, 2007,28 (7): 1072; S.
; U.Kroll; C.Bucher; Etc.Sol.Energy Mater.Sol.Cells 86 (2005) 385 and S.
; L.Feitknecht; R.Schluchter, etc.Sol.Energy Mater.Sol.Cells90 (2006) 2960.], can realize two-forty large area film deposition.
Therefore; Utilize MOCVD technology (metal organic chemical vapor deposition technology) growth matte structure ZnO-TCO film; Can be used as preceding electrode of suede structure and back reflector and be applied to flexible substrate silicon based thin film solar battery, improve cell photoelectric efficiency of conversion and stability.Yet; In order further to improve the optical property of film at visible light and near infrared region; Mainly be to be applied to microcrystal silicon (μ c-Si:H) hull cell and non-crystalline silicon (a-Si:H)/microcrystal silicon (μ c-Si:H) laminate film battery, the ZnO-TCO film performance still need improve and improve.In the ZnO thin film doped process of MOCVD growth boron, the adulterated main influence of B is: 1) suitable B is doped with to be beneficial to and improves the film electric property; 2) B mixes and causes the film grain-size to diminish easily, thereby the suede degree reduces, and the film light scattering power descends; 3) B mixes and will introduce too much free carrier, influences the transmitance of film near infrared region.
Therefore; Based on above analysis; Be the have excellent photoelectric performance of realization ZnO-TCO film at visible light and near infrared region, and have good light scattering characteristic, the present invention proposes to utilize the method for MOCVD alternating growth multilayer ZnO film and application thereof; It is applicable to Si thin film solar cell application, especially laminated film solar battery.This method helps to realize the photoelectric properties balance, and film has good light scattering characteristic.
[summary of the invention]
The objective of the invention is to above-mentioned technical Analysis, a kind of alternating growth technology preparation matte structure ZnO film and application thereof are provided, the ZnO-TCO film that this method growth obtains has the low-temperature epitaxy characteristic; And it is good to have suede structure and visible light and near infrared light zone optical transmittance and scattering of light scattering property, and than traditional coating technique, the multicycle growth has higher suede degree and visible light and near infrared region height and sees through; And keep certain electric property; It is high that square resistance Rs～10 ohm, this film are applied in the thin film solar cell photoelectric transformation efficiency, and process compatible; Simple to operate, easy to implement in production practice, be convenient to big area and promote.
Technical scheme of the present invention:
A kind of alternating growth technology preparation matte structure ZnO film is that 99.995% zinc ethyl and water are source material with purity, with diluted in hydrogen impurity gas borine B
2H
6, adopting the Metalorganic Chemical Vapor Deposition matte structure ZnO-TCO film of on glass substrate, alternately growing, step is following:
1) growth one deck non-blended ZnO film on glass substrate at first, film thickness is 30-1000nm;
2) then at above-mentioned non-blended ZnO film growth B doped ZnO film, film thickness is 30-1000nm;
3) repeat above-mentioned 1) and 2) step, thereby obtaining the ZnO film that multilayer overlaps and grows, film thickness is 1000-2500nm.
Borine B in the said doping gas mixture
2H
6Concentration of volume percent be 1.0%.
The processing parameter of said Metalorganic Chemical Vapor Deposition: underlayer temperature is 125-180 ℃, and the plated film reaction gas pressure is 50-200Pa.
A kind of application of said alternating growth technology preparation matte structure ZnO film; Be used for pin type " non-crystalline silicon " thin film solar cell or " non-crystalline silicon/microcrystal silicon " laminated film solar battery; The structure of pin type " non-crystalline silicon " thin film solar cell is " a glass/ matte structure ZnO film/pin a-Si:H hull cell/ZnO/Al ", and the structure of " non-crystalline silicon/microcrystal silicon " laminated film solar battery is " a glass/ matte structure ZnO film/pin a-Si:H hull cell/pin μ c-Si:H hull cell/ZnO/Al ".
Advantage of the present invention is: the MOCVD technology can realize direct growth matte structure ZnO film on the glass substrate, and this preparing method's technology is simple, is convenient to big area and produces popularization; Through the compatible alternating growth technology of Technology, help realizing visible light and near infrared region scattering of light and follow-up silica-base film deposition; Be applied to thin film solar cell, can effectively improve the photoelectric transformation efficiency of solar cell.
[description of drawings]
Fig. 1 is this alternating growth matte structure ZnO film structural representation.
Fig. 2 be conventional constant growth and alternating growth matte structure ZnO film afm image relatively, among the figure: (a) conventional constant doping growth, (b) alternating growth-1 cycle alternately, (c) alternating growth-10 cycle alternately.
Fig. 3 is conventional constant growth and alternating growth matte structure ZnO film transmittance curve comparison diagram.
Fig. 4 is that this alternating growth matte structure ZnO film is applied to roof liner structure pin type non-crystalline silicon (a-Si:H) thin-film solar cell structure synoptic diagram.
Fig. 5 is that this alternating growth matte structure ZnO film is applied to roof liner structure pin type non-crystalline silicon/microcrystal silicon (a-Si:H/ μ c-Si:H) laminated film solar battery structural representation.
[embodiment]
The present invention proposes a kind of MOCVD of utilization technology alternating growth multilayer ZnO film and is applied to the method for thin film solar cell.
Embodiment 1:
A kind of alternating growth technology preparation matte structure ZnO film is that 99.995% zinc ethyl and water are source material with purity, with borine B
2H
6Be impurity gas, with diluted in hydrogen impurity gas borine B
2H
6, impurity gas borine B
2H
6Concentration of volume percent in gas mixture is 1.0%, adopts Metalorganic Chemical Vapor Deposition (MOCVD) matte structure ZnO-TCO film of on glass substrate, alternately growing, and step is following:
1) non-blended ZnO film of at first on glass substrate, growing, underlayer temperature is 155 ℃, and the plated film reaction gas pressure is 130Pa, and film thickness is 1000nm;
2) then at above-mentioned non-blended ZnO film growth one deck B doped ZnO film, underlayer temperature is 155 ℃, and the plated film reaction gas pressure is 130Pa, and film thickness is 1000nm;
3) repeat above-mentioned 1) and 2) step, thereby obtaining the ZnO film that 1 cycle alternative overlaps and grows, film thickness is 2000nm.
The alternating growth matte structure ZnO film structure that obtains on this glass substrate is as shown in Figure 1.
Fig. 2 is that conventional constant growth and alternating growth matte structure ZnO film afm image compare, and among the figure: (a) conventional constant doping growth, (b) alternating growth-1 cycle are alternately.Show among the figure: the matte structure ZnO film roughness RMS of conventional growth is 41.9nm, and alternating growth be the matte structure ZnO film roughness RMS in 1 cycle is 52.0nm.
Conventional constant growth and alternating growth alternating growth are that the matte structure ZnO film transmittance curve in 1 cycle compares; As shown in Figure 3; Show among the figure: the ZnO film of alternating growth all has higher transmittance at visible light and near infrared region, and the film light scattering power improves.
This glass substrate alternating growth matte structure ZnO film is used for pin type " non-crystalline silicon " thin film solar cell; The structure of pin type " non-crystalline silicon " thin film solar cell is " a glass/ matte structure ZnO film/pin a-Si:H hull cell/ZnO/Al ", and as shown in Figure 4, alternating growth is coated with the glass/ZnO film; Thereafter p grows; I, three layers of a-Si:H film of n are coated with ZnO and Al layer at last.
Embodiment 2:
A kind of preparation method of glass substrate matte structure ZnO film is that 99.995% zinc ethyl and water are source material with purity, with borine B
2H
6Be impurity gas, with diluted in hydrogen impurity gas borine B
2H
6, impurity gas borine B
2H
6Concentration of volume percent in gas mixture is 1.0%, adopts Metalorganic Chemical Vapor Deposition (MOCVD) matte structure ZnO-TCO film of on glass substrate, alternately growing, and step is following:
1) non-blended ZnO film of at first on glass substrate, growing, underlayer temperature is 155 ℃, and the plated film reaction gas pressure is 130Pa, and film thickness is 100nm;
2) then at above-mentioned non-blended ZnO film growth one deck B doped ZnO film, underlayer temperature is 155 ℃, and the plated film reaction gas pressure is 130Pa, and film thickness is 100nm;
3) repeat above-mentioned 1) and 2) step, thereby the ZnO film that 10 cycle alternative overlap and grow, film thickness 2000nm obtained.
The alternating growth matte structure ZnO film structure that obtains on this glass substrate is as shown in Figure 1.
Fig. 2 is that conventional constant growth and alternating growth matte structure ZnO film afm image compare; Among the figure: (a) conventional constant doping growth, (c) alternating growth-10 cycle are alternately; Show among the figure: alternating growth is that the ZnO film in 10 cycles presents the suede structure characteristic; Roughness RMS is 48.5nm, and the roughness of the ZnO film of conventional growth is big.
Conventional constant growth and 10 cycle alternating growth matte structure ZnO film transmittance curves compare, and as shown in Figure 3, show among the figure: the ZnO film of alternating growth all has higher transmittance at visible light and near infrared region, and the film light scattering power improves.
This glass substrate alternating growth matte structure ZnO film is used for pin type " non-crystalline silicon/microcrystal silicon " laminated film solar battery, and the structure of " non-crystalline silicon/microcrystal silicon " laminated film solar battery is " glass/ matte structure ZnO film/pin a-Si:H hull cell/pin μ c-Si:H hull cell/ZnO/Al ", and is as shown in Figure 5; The MOCVD alternating growth is coated with ZnO film, the p that grows thereafter, i; Three layers of a-Si:H film of n and p; I, three layers of μ c-Si:H of n film is coated with ZnO and Al layer at last.
This ZnO film surface presents the suede structure characteristic, and roughness RMS is 40-120nm.
Claims (4)
1. alternating growth technology preparation matte structure ZnO film is characterized in that: with purity is that 99.995% zinc ethyl and water are source material, with diluted in hydrogen impurity gas borine B
2H
6, adopting the Metalorganic Chemical Vapor Deposition matte structure ZnO-TCO film of on glass substrate, alternately growing, step is following:
1) growth one deck non-blended ZnO film on glass substrate at first, film thickness is 30-1000nm;
2) then at above-mentioned non-blended ZnO film growth B doped ZnO film, film thickness is 30-1000nm;
3) repeat above-mentioned 1) and 2) step, thereby obtaining the ZnO film that multilayer overlaps and grows, film thickness is 1000-2500nm.
2. according to the said alternating growth technology of claim 1 preparation matte structure ZnO film, it is characterized in that: borine B in the said doping gas mixture
2H
6Concentration of volume percent be 1.0%.
3. according to the said alternating growth technology of claim 1 preparation matte structure ZnO film, it is characterized in that: the processing parameter of said Metalorganic Chemical Vapor Deposition: underlayer temperature is 125-180 ℃, and the plated film reaction gas pressure is 50-200Pa.
4. application of alternating growth technology preparation matte structure ZnO film according to claim 1; It is characterized in that: be used for pin type " non-crystalline silicon " thin film solar cell or " non-crystalline silicon/microcrystal silicon " laminated film solar battery; The structure of pin type " non-crystalline silicon " thin film solar cell is " a glass/ matte structure ZnO film/pina-Si:H hull cell/ZnO/Al ", and the structure of " non-crystalline silicon/microcrystal silicon " laminated film solar battery is " a glass/ matte structure ZnO film/pin a-Si:H hull cell/pin μ c-Si:H hull cell/ZnO/Al ".
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140314396A1 (en) * | 2013-04-22 | 2014-10-23 | Chih-Ming Hsu | Electrothermal element |
| CN104928648A (en) * | 2015-07-10 | 2015-09-23 | 南开大学 | Zinc oxide photo-anode film and preparation method and application thereof |
| CN105449013A (en) * | 2014-09-19 | 2016-03-30 | 株式会社东芝 | Photoelectric conversion device, and solar cell |
| CN107527959A (en) * | 2016-12-21 | 2017-12-29 | 蚌埠玻璃工业设计研究院 | A kind of multilayer carries the AZO films of matte |
Citations (1)
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| CN102168256A (en) * | 2011-03-21 | 2011-08-31 | 南开大学 | ZnO:B film grown by utilizing MOCVD (Metal Organic Chemical Vapor Deposition) gradient doping technology and application |
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2011
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Patent Citations (1)
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| CN102168256A (en) * | 2011-03-21 | 2011-08-31 | 南开大学 | ZnO:B film grown by utilizing MOCVD (Metal Organic Chemical Vapor Deposition) gradient doping technology and application |
Non-Patent Citations (2)
| Title |
|---|
| BAOSHENG SANG ET AL.: "Growth of Boron-doped ZnO thin films by atomic layer deposition", 《SOLAR ENERGY MATERIALS AND SOLAR CELLS》 * |
| 陈新亮等: "ZnO-TCO薄膜及其在太阳电池中的应用", 《材料导报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140314396A1 (en) * | 2013-04-22 | 2014-10-23 | Chih-Ming Hsu | Electrothermal element |
| CN105449013A (en) * | 2014-09-19 | 2016-03-30 | 株式会社东芝 | Photoelectric conversion device, and solar cell |
| US9985146B2 (en) | 2014-09-19 | 2018-05-29 | Kabushiki Kaisha Toshiba | Photoelectric conversion device, and solar cell |
| CN104928648A (en) * | 2015-07-10 | 2015-09-23 | 南开大学 | Zinc oxide photo-anode film and preparation method and application thereof |
| CN104928648B (en) * | 2015-07-10 | 2018-04-27 | 南开大学 | A kind of zinc oxide photo-anode film and its preparation method and application |
| CN107527959A (en) * | 2016-12-21 | 2017-12-29 | 蚌埠玻璃工业设计研究院 | A kind of multilayer carries the AZO films of matte |
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Application publication date: 20120502 |