CN101308882A - Preparing method of transparent electricity conductive oxide suede - Google Patents
Preparing method of transparent electricity conductive oxide suede Download PDFInfo
- Publication number
- CN101308882A CN101308882A CNA2008101322609A CN200810132260A CN101308882A CN 101308882 A CN101308882 A CN 101308882A CN A2008101322609 A CNA2008101322609 A CN A2008101322609A CN 200810132260 A CN200810132260 A CN 200810132260A CN 101308882 A CN101308882 A CN 101308882A
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- Prior art keywords
- dry etching
- conductive oxide
- preparation
- matte
- plasma
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000005611 electricity Effects 0.000 title claims description 5
- 238000001312 dry etching Methods 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 27
- 238000005530 etching Methods 0.000 claims description 23
- 239000005357 flat glass Substances 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 9
- 230000005284 excitation Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- 241000720974 Protium Species 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 44
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to a method to fabricate a transparent conductive oxide textured surface, including the following steps: a base plate provided with a transparent conductive oxide film is processed with dry etching so that a textured surface can be developed on the transparent conductive oxide film. The invention also relates to a method to fabricate another transparent conductive oxide textured surface, which includes the step of developing a transparent conductive oxide film on the dry etched base plate. The method introduces dry etching to process the base plate or the TCO film so as to obtain a TCO textured surface which is of high roughness and homogeneity. The TCO textured surface is capable of realizing good optical trap force and improving the efficiency of the battery.
Description
Technical field
The present invention relates to film preparing technology, relate in particular to a kind of transparent conductive oxide (Transparent Conductive Oxide is called for short TCO) matte preparation method.
Background technology
In the thin-film solar cells industry, adopt the TCO film of band matte to do electrode usually, can allow light in battery, form ligh trap, prolong the utilance of the propagation path of light in absorbed layer, and then improve battery efficiency with increase light.Preceding electrode material at the thin-film solar cells conducting film adopts SnO more
2: F or ZnO:B, the material that grows by methods such as magnetron sputterings is SnO
2Or the TCO profile pattern of ZnO is too high.In order to increase the availability of light, form ligh trap at inside battery, to carry out chemical acid etch to the TCO film surface that grows usually, promptly the TCO film is put into acid solution or acid mist carries out etching, so that the TCO film surface forms suede structure.
The roughness of the resulting suede structure of this chemical acid etch is not very high, is difficult to form the ligh trap of function well, just can't obtain higher battery efficiency yet, and unfriendly to environment.In addition, existing matte preparation method comprises that also the homogeneity of the film that this method forms is not high with the method for chemical vapour deposition (CVD) (Chemicalvapor deposition is called for short CVD) method direct growth formation matte.
Summary of the invention
The objective of the invention is to propose a kind of transparent electricity conductive oxide suede preparation method, can prepare the TCO film of good roughness, to realize good ligh trap effect.
For achieving the above object, the invention provides a kind of TCO matte preparation method, comprising: the substrate that has the TCO film is carried out dry etching, on described TCO film, to form matte.
In technique scheme, in the dry etching process, the TCO film surface is handled by plasma, plasma cognition weak bond preferential and the crystal boundary place reacts and etches away crystal boundary, exposes relatively more outstanding crystal grain, thereby form the TCO matte of higher roughness on macroscopic view; And because the stability of plasma atmosphere helps forming uniformity matte preferably; This TCO matte can form good ligh trap effect.
Further, the described operation that has the substrate of TCO film to carry out dry etching to generation is specially: by halogen-containing gas with contain a kind of gas in the gas of protium or plasma that two or more mists produces has the substrate of TCO film to carry out dry etching to generation.
Further, described substrate is flat glass, matte glass that is not etched that has been etched or the matte glass that has been etched.
Further, the etching operation of described flat glass or matte glass is specially: by at least a fluoride gas plasma described flat glass or matte glass are carried out dry etching.
Further, in the dry etching process, also the TCO film is bombarded by high-octane inert gas ion.The bombardment effect of this inert gas ion is a kind of physical action, can make the TCO film the surface lattice damage and cause the activity chemistry point, further quickened the chemical etching speed of plasma.
Further, in the dry etching process, the mode that produces the plasma of active etching ion comprises:
Utilize direct current, intermediate frequency, radio frequency, microwave, direct current+pulse or direct current+RF-wise in reaction chamber, to make the gas molecule ionization, produce plasma; Perhaps
Utilize the remote excitation mode outside reaction chamber, to make the gas molecule ionization, produce plasma, feed reaction chamber by pipeline then.
For achieving the above object, the invention allows for the preparation method of another kind of TCO matte, comprising: the substrate growth TCO film after carrying out dry etching.
In technique scheme, earlier substrate is adopted dry etching, obtain the matte of higher roughness, then at matte surface preparation TCO film, thereby obtain the TCO matte of higher roughness, to form good ligh trap effect.
Further, described substrate is flat glass or matte glass.
Further, the operation that described flat glass or matte glass are carried out dry etching is specially:
By at least a fluoride gas plasma described flat glass or matte glass are carried out dry etching.
Further, in the dry etching process, the mode that produces the plasma of active etching ion comprises:
Utilize direct current, intermediate frequency, radio frequency, microwave, direct current+pulse or direct current+RF-wise in reaction chamber, to make the gas molecule ionization, produce plasma; Perhaps
Utilize the remote excitation mode outside reaction chamber, to make the gas molecule ionization, produce plasma, feed reaction chamber by pipeline then.
Based on technique scheme, the present invention adopts dry etching treatment substrate or TCO film, and to obtain to have higher roughness and the good TCO suede structure of homogeneity, this TCO suede structure can be realized good ligh trap effect and can improve battery efficiency.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 is the schematic flow sheet of the preparation method's of TCO matte of the present invention first embodiment.
Fig. 2 is the schematic flow sheet of the preparation method's of TCO matte of the present invention second embodiment.
Fig. 3 is the schematic flow sheet of the preparation method's of TCO matte of the present invention the 3rd embodiment.
Fig. 4 is the schematic flow sheet of the preparation method's of TCO matte of the present invention the 4th embodiment.
Fig. 5 is the schematic flow sheet of the preparation method's of TCO matte of the present invention the 5th embodiment.
Embodiment
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
The method of using plasma dry etching of the present invention is handled the substrate that has covered the TCO film, make the TCO film have suede structure, by the TCO film handled of contrast and untreated TCO film, the TCO matte presents tangible matte on microstructure, thereby has the roughness that can form ligh trap.
As shown in Figure 1, be the schematic flow sheet of the preparation method's of TCO matte of the present invention first embodiment.In the present embodiment, processed substrate adopts flat glass.At first pass through NF
3, HF, SF
6, SF
2Deng gaseous plasma at least a in the fluoride dry etching is carried out on the flat glass surface, the flat glass substrate after the etching has tangible rough surface.Flat glass substrate after etching generates the TCO film then, and this TCO film can adopt ZAO (ZnO of doped with Al), SnO
2: the F (SnO of doped F
2), ZnO:B materials such as (ZnO of doping B) generates by the CVD method.
The TCO film that generates also possesses certain matte in appearance, and this is because the suede structure that flat glass has after being etched causes.By indentation method test, can find that the TCO film that plates on the flat glass after the etch processes has better adhesive force than the TCO film that directly generates on flat glass.
For obtain to form ligh trap the TCO suede structure of roughness, next the TCO film that generates is carried out dry etching.In the etching processing process, can adopt any HCl, Cl
2, BCl
3Etc. halogen-containing gas or H
2, CH
4Etc. hydrogeneous gas, perhaps above-mentioned two or more similar mist, perhaps two or more inhomogeneity mists.Under plasma environment, carry out the chemical reaction etching by control process parameters, obtain the surface roughness that needs.
In order to increase etching speed, physical etchings and chemical etching can also be combined, utilize high-octane Ar, N
3The TCO film surface is bombarded under the high-density plasma environment Deng inert gas, make the lattice surface damage of TCO film cause activity chemistry point, the chemical etching speed of accelerated particle.This bombardment has further increased the roughness of TCO film.
In etching process, need have the plasma of etching activity in a large number, two kinds of producing methods are arranged, a kind of is to utilize direct current, intermediate frequency, radio frequency, microwave, direct current+pulse or direct current+RF-wise etc. to make the gas molecule ionization in reaction chamber, produces plasma.Another kind is to utilize the remote excitation mode to make the gas molecule ionization outside reaction chamber, produces plasma, feeds reaction chamber by pipeline then; The mode that this remote excitation produces plasma has selectivity, can reduce the damage that ion bombardment brings to film, and it is higher that its metastable atom, living radical etc. have chemically active particle concentration, can effectively carry out chemical etching.
As shown in Figure 2, be the schematic flow sheet of the preparation method's of TCO matte of the present invention second embodiment.Substrate adopts the glass (being matte glass) of band matte in the present embodiment, and the processing procedure of present embodiment is identical with a last embodiment.Earlier matte glass is carried out dry etching, the suede structure after the acquisition etching generates the TCO film then on the matte after this etching, adopt dry etching that the TCO film is carried out etching at last again, obtains the good TCO matte of higher roughness and homogeneity.
As shown in Figure 3, be the schematic flow sheet of the preparation method's of TCO matte of the present invention the 3rd embodiment.Substrate adopts matte glass in the present embodiment, if matte glass has certain roughness, can directly generate the TCO film on matte, by dry etching the TCO film is carried out etching again, obtains the good TCO matte of higher roughness and homogeneity.
In another embodiment, if substrate can directly carry out etching by dry etching to the TCO film so for the glass of band TCO film, obtain to form the TCO matte of the roughness of ligh trap.
Requiring for the roughness of matte is not under the very high situation, can be to direct growth TCO film on the substrate after carrying out dry etching.Therefore this film has possessed the suede structure that can form the roughness of ligh trap because its substrate that adheres to has possessed certain roughness.
As shown in Figure 4, be the schematic flow sheet of the preparation method's of TCO matte of the present invention the 4th embodiment.In the present embodiment, substrate is a flat glass.At first flat glass is carried out dry etching; Flat glass substrate after etching generates the TCO film then.Because the flat glass substrate after the etching has tangible rough surface, so this layer TCO film possesses better adhesive force, and also has the suede structure of the roughness that can form ligh trap on the TCO film.
As shown in Figure 5, be the schematic flow sheet of the preparation method's of TCO matte of the present invention the 5th embodiment.Substrate adopts matte glass in the present embodiment, and its processing mode is identical with a last embodiment, promptly at first matte glass is carried out dry etching; Matte glass substrate after etching generates the TCO film of the suede structure with the roughness that can form ligh trap then.
Should be noted that at last: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the field are to be understood that: still can make amendment or the part technical characterictic is equal to replacement the specific embodiment of the present invention; And not breaking away from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope that the present invention asks for protection.
Claims (10)
1, a kind of preparation method of transparent electricity conductive oxide suede comprises: have the substrate of transparent conductive oxide film to carry out dry etching to generation, to form matte on described transparent conductive oxide film.
2, preparation method according to claim 1, the wherein said operation that has the substrate of transparent conductive oxide film to carry out dry etching to generation is specially: by halogen-containing gas with contain a kind of gas in the gas of protium or plasma that two or more mists produces has the substrate of transparent conductive oxide film to carry out dry etching to generation.
3, preparation method according to claim 1, wherein said substrate is flat glass, matte glass that is not etched that has been etched or the matte glass that has been etched.
4, preparation method according to claim 3, the etching operation of wherein said flat glass or matte glass is specially:
By at least a fluoride gas plasma described flat glass or matte glass are carried out dry etching.
5, preparation method according to claim 1 wherein in the dry etching process, also bombards transparent conductive oxide film by high-octane inert gas ion.
6, preparation method according to claim 1, wherein in the dry etching process, the mode that produces the plasma with etching activity comprises:
Utilize direct current, intermediate frequency, radio frequency, microwave, direct current+pulse or direct current+RF-wise in reaction chamber, to make the gas molecule ionization, produce plasma; Perhaps
Utilize the remote excitation mode outside reaction chamber, to make the gas molecule ionization, produce plasma, feed reaction chamber by pipeline then.
7, a kind of preparation method of transparent electricity conductive oxide suede comprises: the transparent conductive oxide film of growing on the substrate after carrying out dry etching.
8, preparation method according to claim 7, wherein said substrate is flat glass or matte glass.
9, according to claim preparation method according to claim 8, wherein the operation that described flat glass or matte glass are carried out dry etching is specially:
By at least a fluoride gas plasma described flat glass or matte glass are carried out dry etching.
10, preparation method according to claim 7, wherein in the dry etching process, the mode that produces the plasma of active etching ion comprises:
Utilize direct current, intermediate frequency, radio frequency, microwave, direct current+pulse or direct current+RF-wise in reaction chamber, to make the gas molecule ionization, produce plasma; Perhaps
Utilize the remote excitation mode outside reaction chamber, to make the gas molecule ionization, produce plasma, feed reaction chamber by pipeline then.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101322609A CN101308882A (en) | 2008-07-22 | 2008-07-22 | Preparing method of transparent electricity conductive oxide suede |
| PCT/CN2008/073441 WO2010009598A1 (en) | 2008-07-22 | 2008-12-10 | Transparent conductive oxide pile preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101322609A CN101308882A (en) | 2008-07-22 | 2008-07-22 | Preparing method of transparent electricity conductive oxide suede |
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| Publication Number | Publication Date |
|---|---|
| CN101308882A true CN101308882A (en) | 2008-11-19 |
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ID=40125192
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|---|---|---|---|
| CNA2008101322609A Pending CN101308882A (en) | 2008-07-22 | 2008-07-22 | Preparing method of transparent electricity conductive oxide suede |
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| WO (1) | WO2010009598A1 (en) |
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| WO2010009598A1 (en) * | 2008-07-22 | 2010-01-28 | 东莞宏威数码机械有限公司 | Transparent conductive oxide pile preparing method |
| CN102044593A (en) * | 2009-10-19 | 2011-05-04 | 杜邦太阳能有限公司 | Process of manufacturing TCO substrate with light trapping feature and device thereof |
| CN102097502A (en) * | 2009-12-09 | 2011-06-15 | 英属开曼群岛商精曜有限公司 | Thin film solar cell and manufacturing method thereof |
| 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 |
| CN102074613B (en) * | 2009-11-20 | 2012-08-22 | 中芯国际集成电路制造(上海)有限公司 | Method for manufacturing solar cell |
| CN101792270B (en) * | 2009-02-02 | 2012-11-21 | 信义光伏产业(安徽)控股有限公司 | Transparent electropane and manufacturing method thereof |
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| JP4115071B2 (en) * | 2000-03-29 | 2008-07-09 | 三洋電機株式会社 | Photovoltaic device |
| FR2832706B1 (en) * | 2001-11-28 | 2004-07-23 | Saint Gobain | TRANSPARENT SUBSTRATE HAVING AN ELECTRODE |
| CN100568555C (en) * | 2006-09-05 | 2009-12-09 | 武汉迪源光电科技有限公司 | Coarsening electrode is used for high-brightness packed LED chip and vertical LED chip |
| CN101308882A (en) * | 2008-07-22 | 2008-11-19 | 东莞宏威数码机械有限公司 | Preparing method of transparent electricity conductive oxide suede |
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2008
- 2008-07-22 CN CNA2008101322609A patent/CN101308882A/en active Pending
- 2008-12-10 WO PCT/CN2008/073441 patent/WO2010009598A1/en active Application Filing
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| WO2010009598A1 (en) * | 2008-07-22 | 2010-01-28 | 东莞宏威数码机械有限公司 | Transparent conductive oxide pile preparing method |
| CN101792270B (en) * | 2009-02-02 | 2012-11-21 | 信义光伏产业(安徽)控股有限公司 | Transparent electropane and manufacturing method thereof |
| CN102044593A (en) * | 2009-10-19 | 2011-05-04 | 杜邦太阳能有限公司 | Process of manufacturing TCO substrate with light trapping feature and device thereof |
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|---|---|
| WO2010009598A1 (en) | 2010-01-28 |
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