CN1460728A - Velvet zinc oxide transparent conductive film and its preparation method - Google Patents
Velvet zinc oxide transparent conductive film and its preparation method Download PDFInfo
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- CN1460728A CN1460728A CN 03137254 CN03137254A CN1460728A CN 1460728 A CN1460728 A CN 1460728A CN 03137254 CN03137254 CN 03137254 CN 03137254 A CN03137254 A CN 03137254A CN 1460728 A CN1460728 A CN 1460728A
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- Prior art keywords
- transparent conductive
- conductive film
- zinc oxide
- oxide transparent
- film
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 title claims description 25
- 238000000034 method Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000004544 sputter deposition Methods 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000003746 surface roughness Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 45
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000011787 zinc oxide Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- AKVPCIASSWRYTN-UHFFFAOYSA-N zinc oxygen(2-) silicon(4+) Chemical compound [Si+4].[O-2].[Zn+2].[O-2].[O-2] AKVPCIASSWRYTN-UHFFFAOYSA-N 0.000 description 1
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- Manufacturing Of Electric Cables (AREA)
- Non-Insulated Conductors (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to the field of transparent conductive film design technology for solar cell. The film is a zine oxide transparent conductive film with pile face, and its preparation method is magnetic control sputtering method, and the pressure of sputtering gas is 3.0 Pa-15.0 Pa, and the substrate temp. is 20-400 deg.c. Said film has higher textureness and surface roughness, and can increase of absorption of light.
Description
Technical field:
Pile face zinc oxide transparent conductive film and preparation method thereof relates to the photoelectric material technical field that is used for solar cell, specially refers to the transparent conductive film design field that is used for solar cell.
Background technology:
Transparent conductive oxide (transparent conductive oxide, TCO) film mainly comprises In, the oxide compound of Sn, Zn, Cd and composite multi-component sull thereof, common light electrical characteristic such as have that the forbidden band is wide, visible range transmitance height and resistivity are low are usually as thin film solar cell transparency electrode, plane liquid-crystal display (LCD), plasma display (PDP) etc.The matte film is meant the film with certain surfaceness and optical property, and the criterion of matte is the suede degree (Haze) and the surfaceness (δ of matte
RMS), the suede degree is meant when the incident light wavelength is 550nm that (diffuse transmittance is Td) with total transmitance (total transmittance, ratio Tt) for the dispersion transmitance of film.Surfaceness adopts root-mean-square deviation roughness (root mean square roughness, δ
RMS).Oxidic transparent conductive film with matte, the main effect of its suede structure is by to reflection of light, refraction and scattering, the light that incides in the film is distributed to all angles, thereby increases the light path of light in the solar cell absorption layer, increase the absorption of light.
Existing matte fluorine-doped tin dioxide (fluorine-doped SnO in the prior art
2, SnO
2: F) transparent conductive film is made light restricted type amorphous silicon solar cell as the transparent preceding electrode of amorphous silicon film solar battery, has greatly improved the efficiency of conversion of solar cell and obtained application in actual production.But at SnO
2Preparation process in, require depositing temperature to reach more than 450 ℃, so increased cost greatly, limited its application.
Zinc oxide transparent conductive film refers generally to zinc oxide (the available ZnO:X represents) transparent conductive film of pure zinc oxide (ZnO) transparent conductive film and doped element X, and X refers generally to any element among IIIB family, Si and the Sn.As a kind of important TCO film, zinc oxide transparent conductive film not only has the features and applications of general oxidic transparent conductive film, enrich but also have material source, low price, excellent optics and electric property, in hydrogen plasma zone satisfactory stability, be difficult for making advantages such as the active reduction of solar cell material.Present ZnO and ZnO:X transparent conductive film all are light faces, do not embody more excellent characteristic in the solar cell application facet.Through literature search both domestic and external, do not find document about pile face zinc oxide transparent conductive film and preparation method thereof aspect.
Summary of the invention:
The objective of the invention is to, proposed a kind of pile face zinc oxide transparent conductive film, it has stronger optical absorption characteristics than general light face zinc oxide transparent conductive film, and the present invention has also designed the method for preparing the pile face zinc oxide transparent conductive film.
Pile face zinc oxide transparent conductive film proposed by the invention is characterised in that it is a kind of zinc oxide transparent conductive film of matte.
It is characterized in that the suede degree of described pile face zinc oxide transparent conductive film is 3.0%～31.6%.
It is characterized in that the roughness of described pile face zinc oxide transparent conductive film is 10.8nm～50.2nm.
It is characterized in that: the pressure of sputter gas is 3.0Pa～15.0Pa; Underlayer temperature is 20 ℃～400 ℃.
Experiment showed, that pile face zinc oxide transparent conductive film proposed by the invention has higher suede degree and surfaceness, can increase the absorption of light; This preparation method can prepare the pile face zinc oxide transparent conductive film of higher suede degree and surfaceness, has reached its intended purposes.
Description of drawings:
Fig. 1 is total transmitance (Tt) and suede degree (Haze) figure of film at visible region;
Fig. 2 is atomic force microscope (Atomic Force Microscopy, AFM) figure of embodiment 1;
Fig. 3 is the AFM figure of embodiment 2;
Fig. 4 is the AFM figure of embodiment 3;
Fig. 5 is the AFM figure of embodiment 4.
Embodiment:
The present invention adopts magnetically controlled sputter method to prepare the pile face zinc oxide transparent conductive film, and magnetron sputtering is existing the application in the preparation of zinc oxide transparent conductive film.
Embodiment 1:
As starting material, adopt high-purity argon gas as sputter gas with zinc oxide (ZnO) ceramic target, controlling argon pressure by piezo electric valve (can regulate argon pressure) is 9.0Pa, and substrate is a sheet glass, and underlayer temperature is 400 ℃.Operation steps: 1) the substrate sheet glass that will be used to prepare film carries out clean; 2) sheet glass being placed on the base vacuum degree is 2.0 * 10
-3In the vacuum chamber of the coating equipment of Pa; 3) begin to carry out sputter, sputtering time is 4 minutes, sputtering voltage 330V.
The result obtains Textured ZnO Transparent Conductive Thin Film, and its suede degree is 17.6%, and the total transmitance of visible region is 74.13%, calculates its root-mean-square deviation roughness δ
RMSBe 33.0nm, the surface topography of film as shown in Figure 2.
Embodiment 2:
Raw material adopts zinc oxide aluminum (94wt%ZnO+6wt%Al
2O
3) ceramic target, adopt high-purity argon gas as sputter gas, controlling argon pressure by piezo electric valve is 15.0Pa, and substrate is a sheet glass, and underlayer temperature is 250 ℃.Operation steps is the same with embodiment 1.
The result obtains textured ZnO: the Al transparent conductive film, and its suede degree is 31.6%, the total transmitance of visible region is 77.63%, calculates root-mean-square deviation roughness δ
RMSBe 50.2nm, the surface topography of film as shown in Figure 3.
Embodiment 3:
Raw material adopts zinc oxide silicon (96wt%ZnO+4wt%SiO
2) ceramic target, adopt high-purity argon gas as sputter gas, controlling argon pressure by piezo electric valve is 8.0Pa, and substrate is a sheet glass, and underlayer temperature is 150 ℃.Operation steps is the same with embodiment 1.
The result obtains textured ZnO: the Si transparent conductive film, and its suede degree is 8.3%, the total transmitance of visible region is 82.27%, calculates root-mean-square deviation roughness δ
RMSBe 22.8nm, the surface topography of film as shown in Figure 4.Embodiment 4:
Raw material adopts zinc-tin oxide (99wt%ZnO+1wt%SnO
2) ceramic target, adopt high-purity argon gas as sputter gas, controlling argon pressure by piezo electric valve is 3.0Pa, and substrate is a sheet glass, and underlayer temperature is 20 ℃.Operation steps is the same with embodiment 1.
The result obtains textured ZnO: the Sn transparent conductive film, and its suede degree is 3.0%, the total transmitance of visible region is 86.93%, calculates root-mean-square deviation roughness δ
RMSBe 10.8nm, the surface topography of film as shown in Figure 5.
Among the preparation method of the present invention, base vacuum degree and voltage all are conventional parameters of preparation zinc oxide transparent conductive film.
Employing has the amorphous silicon solar cell of the ZnO electrically conducting transparent series thin film of suede degree, comparing with the amorphous silicon solar cell of the ZnO series thin film that should use up face, has higher photoelectric transformation efficiency.In the application of amorphous silicon solar cell, under the prerequisite of certain suede degree, requirement has the total transmitance of higher visible light, and the comprehensive action of the two can make solar cell that the absorption of visible light is reached maximum, and the embodiment prepared film has satisfied such requirement.
What by accompanying drawing 1 as seen, two solid lines were represented is total transmitance (Tt) and the suede degree (Haze) of embodiment one prepared film at visible region.What the dotted line of three kinds of forms was represented is the total transmitance of visible region (Tt) and the suede degree (Haze) of embodiment two, embodiment three and embodiment four prepared films.Has the usefulness same with embodiment one.Accompanying drawing 2～5 is the atomic force microscope figure of embodiment one, embodiment two, embodiment three and embodiment four prepared film, and as can be seen from the figure, transparent conductive film proposed by the invention has higher surfaceness.
Claims (4)
1, the pile face zinc oxide transparent conductive film is characterized in that, it is a kind of zinc oxide transparent conductive film of matte.
2, pile face zinc oxide transparent conductive film as claimed in claim 1 is characterized in that, the suede degree of described pile face zinc oxide transparent conductive film is 3.0%～31.6%.
3, pile face zinc oxide transparent conductive film as claimed in claim 1 is characterized in that, the roughness of described pile face zinc oxide transparent conductive film is 10.8nm～50.2nm.
4, the preparation method of pile face zinc oxide transparent conductive film as claimed in claim 1 is a magnetically controlled sputter method, it is characterized in that: the pressure of sputter gas is 3.0Pa～15.0Pa; Underlayer temperature is 20 ℃～400 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137254 CN1272465C (en) | 2003-06-03 | 2003-06-03 | Velvet zinc oxide transparent conductive film and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137254 CN1272465C (en) | 2003-06-03 | 2003-06-03 | Velvet zinc oxide transparent conductive film and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1460728A true CN1460728A (en) | 2003-12-10 |
| CN1272465C CN1272465C (en) | 2006-08-30 |
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| CN 03137254 Expired - Fee Related CN1272465C (en) | 2003-06-03 | 2003-06-03 | Velvet zinc oxide transparent conductive film and its preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102348827A (en) * | 2009-03-13 | 2012-02-08 | 住友金属矿山株式会社 | Transparent conductive film and transparent conductive film laminate, processes for production of same, and silicon thin film solar cell |
| CN102368513A (en) * | 2011-11-11 | 2012-03-07 | 保定天威集团有限公司 | Preparation method of double-structure suede transparent conducting oxide thin film of thin film cell |
| CN103081028A (en) * | 2010-08-30 | 2013-05-01 | 住友金属矿山株式会社 | Multilayer transparent electroconductive film and method for manufacturing same, as well as thin-film solar cell and method for manufacturing same |
| CN101661808B (en) * | 2009-09-15 | 2013-08-14 | 中国科学院上海硅酸盐研究所 | Multi-doping zinc-oxide-base wide-bandgap conducting material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105438634B (en) * | 2014-09-18 | 2018-05-04 | 旭硝子株式会社 | Glass plate laminate and its packing method |
-
2003
- 2003-06-03 CN CN 03137254 patent/CN1272465C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102348827A (en) * | 2009-03-13 | 2012-02-08 | 住友金属矿山株式会社 | Transparent conductive film and transparent conductive film laminate, processes for production of same, and silicon thin film solar cell |
| CN102348827B (en) * | 2009-03-13 | 2015-04-29 | 住友金属矿山株式会社 | Transparent conductive film and transparent conductive film laminate, processes for production of same, and silicon thin film solar cell |
| CN101661808B (en) * | 2009-09-15 | 2013-08-14 | 中国科学院上海硅酸盐研究所 | Multi-doping zinc-oxide-base wide-bandgap conducting material and preparation method thereof |
| CN103081028A (en) * | 2010-08-30 | 2013-05-01 | 住友金属矿山株式会社 | Multilayer transparent electroconductive film and method for manufacturing same, as well as thin-film solar cell and method for manufacturing same |
| TWI514600B (en) * | 2010-08-30 | 2015-12-21 | Sumitomo Metal Mining Co | A transparent conductive film laminate, a method for manufacturing the same, and a thin film solar cell and a method for manufacturing the same |
| KR101819775B1 (en) * | 2010-08-30 | 2018-01-17 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Multilayer transparent electroconductive film and method for manufacturing same, as well as thin-film solar cell and method for manufacturing same |
| CN102368513A (en) * | 2011-11-11 | 2012-03-07 | 保定天威集团有限公司 | Preparation method of double-structure suede transparent conducting oxide thin film of thin film cell |
| CN102368513B (en) * | 2011-11-11 | 2013-03-27 | 保定天威集团有限公司 | Preparation method of double-structure suede transparent conducting oxide thin film of thin film cell |
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| CN1272465C (en) | 2006-08-30 |
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Granted publication date: 20060830 Termination date: 20120603 |