CN102174689A - FZO/metal/FZO transparent conductive film and preparation method thereof - Google Patents
FZO/metal/FZO transparent conductive film and preparation method thereof Download PDFInfo
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- CN102174689A CN102174689A CN 201110082032 CN201110082032A CN102174689A CN 102174689 A CN102174689 A CN 102174689A CN 201110082032 CN201110082032 CN 201110082032 CN 201110082032 A CN201110082032 A CN 201110082032A CN 102174689 A CN102174689 A CN 102174689A
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Abstract
The invention discloses a fluorine-doped zinc oxide (FZO)/metal/FZO transparent conductive film. On a substrate, the film comprises an FZO film layer, a metal film layer and the FZO film layer sequentially from bottom to top. The preparation method comprises the following steps of: growing an FZO film by a radio frequency magnetic control sputtering method; and growing a metal film by a direct current magnetic control sputtering method. The method is simple in used equipment and high in controllability; and the prepared film has high optical and electrical properties and high repeatability.
Description
Technical field
The present invention relates to multi-layer film structure transparent conductive film and preparation method thereof, especially FZO/ metal/FZO transparent conductive film and preparation method thereof.
Background technology
Transparent conductive film, has a wide range of applications in the optoelectronic film devices such as photovoltaic cell at plasma display (PDP), liquid-crystal display (LCD), Organic Light Emitting Diode high quality flat-panel monitors such as (OLED) as electrode materials.Transparent conductive film also can be applicable to gas sensor, low radiation coated glass, ir radiation speculum, anti-icing defrost function glass etc. in addition.
The transparent conductive film of Ying Yonging mainly is ITO (In in the market
2O
3: Sn) and FTO (SnO
2: F), but all will use precious metal In in them, In is kind of a scarce resource, causes the production cost of these two kinds of transparent conductive films bigger.Therefore, find a kind of high-performance transparent conductive film that can substitute them to seem very necessary.ZnO is a kind of broad-band gap (3.3 eV) compound semiconductor materials, has aboundresources, and is nontoxic, low price, and advantage such as thermal cycling stability is good is a transparent conductive material of new generation, probably becomes the substitute of ITO.Adulterated ZnO has excellent photoelectric performance, but the transparent conductive film of this unitary film form, and its membrane resistance is bigger, and radiant ratio is higher, and low in the near-infrared band reflection, absorb obviously, these drawbacks limit the application on photoelectric device.Such as with ITO during as the transparency electrode of flat-panel monitor, its electric property has limited exploration on display resolution ratio, and makes reaction times, the consumed power of indicating meter be difficult to descend.
In order further to improve the photoelectric properties of transparent conductive film, there have the investigator to propose medium/medium/metal multilayered structure electrically conducting transparent to be thin.This multilayered structure transparent conductive film has improved its electric property greatly because of the introducing of metal level, and because medium is different with the specific refractory power of metal level, as long as thicknesses of layers control rationally, this multi-layer film structure can improve the transmissivity of film at visible light wave range.The bottom medium layer can increase adhesive force in addition, and surface media can improve stability, the wear resistance of film, also metal level is played a protective role.As seen, the transparent conductive film of this structure gets a good eye value, is expected to break through the bottleneck that the single-layer membrane structure transparent conductive film is run into.
The magnetron sputtering deposition method is to utilize radio frequency (rf) and direct current (dc) power supply at Ar or Ar-O
2Mixed gas produces plasma body, ceramic target or metallic target is bombarded, by processing parameters such as control dividing potential drop, underlayer temperature, target power output, the good reproducibility of growing on various substrates, uniform large area film.Because energy was bigger when plasma sputter arrived substrate, the sticking power of rete and substrate is strengthened.At present, the magnetron sputtering deposition method is one of preparation zno-based transparent conductive film important means, because its energy growing large-area film, so relatively be fit to suitability for industrialized production.
Summary of the invention
The objective of the invention is to prepare FZO/ metal/FZO transparent conductive film with good photoelectric properties and preparation method thereof.
FZO/ metal of the present invention/FZO transparent conductive film is to comprise successively from bottom to top on the substrate mixing fluorine zinc oxide films rete, metal film layer and mixing fluorine zinc oxide films rete.
The preparation method of FZO/ metal/FZO transparent conductive film may further comprise the steps:
1) be that 99.99% metallic target is respectively installed on radio frequency target head and the direct current target head mixing fluorine zinc oxide target and purity, the percentage composition of mixing zinc fluoride in the fluorine zinc oxide target is 1%-4%, substrate through cleaning is put on the substrate holder, distance between target and the substrate is 6 ~ 8 cm, and growth room's vacuum tightness is extracted into 1.0 * 10
-3Pa is a protective atmosphere with the argon gas, regulates the pressure 0.1-2.0Pa of growth room, and the fluorine zinc oxide target is mixed in radio-frequency sputtering, deposition FZO thin film layer on substrate, and sputtering power is at 50-200W, and temperature is 20-500 ℃;
2) close radio frequency source, growth room's vacuum tightness is extracted into 3.5 * 10
-4Below the Pa, be protective atmosphere with the argon gas, regulating growth room's pressure is 0.8-2Pa, d.c. sputtering metal level film on the FZO thin film layer, and sputtering power is at 50-200W, and temperature is at 20-500 ℃;
3) close DC source,, obtain FZO/ metal/FZO transparent conductive film with step 1) radio-frequency sputtering FZO thin film layer on the metal level film.
Above-mentioned metal can be Ag, Au, Cu or Al.Said substrate is silicon, sapphire, glass, quartz or flexible substrate (as PET).
In film deposition process, do not destroy the vacuum tightness of growth room, multilayer film is that successive sedimentation forms.
The present invention can prepare the FZO/ metal/FZO transparent conductive film of different thickness combination by control depositing temperature, F content and depositing time.
Advantage of the present invention:
1) multi-layer film structure FZO/ metal/FZO transparent conductive film, because of the introducing of metal level has improved its electric property greatly, and because FZO is different with the specific refractory power of metal, by the reasonable control of thicknesses of layers, FZO/ metal/FZO transparent conductive film is increased in the transmissivity of visible light wave range.
2) in multi-layer film structure FZO/ metal/FZO transparent conductive film, the FZO film of bottom can increase adhesive force, and the FZO on upper strata can improve stability, the wear resistance of film, also metal level is played a protective role.
3) multi-layer film structure FZO/ metal/FZO transparent conductive film can be done thinlyyer than the transparent conductive film of single layer structure, saves material usage, reduces production costs.
4) in multi-layer film structure FZO/ metal/FZO transparent conductive film, if metal level is the Ag film, can make the reflection enhancement of FZO/Ag/FZO transparent conductive film in the near-infrared region, therefore, this transparent conductive film is potential and is used to make ir radiation speculum, low radiation building glass and glass for vehicle window.
5) multi-layer film structure FZO/ metal/FZO transparent conductive film institute use equipment of mentioning of preparation the present invention is magnetron sputtering, and controllability is strong, is suitable for depositing uniform large area film, therefore helps suitability for industrialized production.
Description of drawings
Fig. 1 is the magnetic control sputtering deposition device synoptic diagram that the inventive method adopts, and among the figure: 1 is Ar gas admission passage; 2 is O
2Admission passage; 3 under meters; 4 is surge chamber; 5 is from the dynamic pressure controller; 6 is vacuumometer; 7 is vacuum pump; 8 is inlet pipe; 9 is water coolant; 10 is the S rifle; 11 is steam leak-off valve; 12 is sight glass; 13 is baffle plate; 14 substrate heaters;
Fig. 2 is x ray diffraction (XRD) collection of illustrative plates of FZO/Ag/FZO transparent conductive film;
Fig. 3 is the optical transmission spectrum of FZO/Ag/FZO transparent conductive film.
Embodiment
Below be to further specify the present invention in conjunction with specific examples.
Embodiment 1
1) be that 99.99% metal A g target is respectively installed on radio frequency target head and the direct current target head mixing fluorine zinc oxide target and purity, the percentage composition of mixing zinc fluoride in the fluorine zinc oxide target is 3%, glass substrate through cleaning is put on the substrate holder, distance between target and the substrate is 7 cm, and growth room's vacuum tightness is extracted into 1.0 * 10
-3Pa is a protective atmosphere with the argon gas, regulates the pressure 0.5Pa of growth room, and the fluorine zinc oxide target is mixed in radio-frequency sputtering, and sputtering power is at 100W, and temperature is 25 ℃, the thick FZO thin film layer of deposition 48nm on substrate;
2) close radio frequency source, growth room's vacuum tightness is extracted into 3.5 * 10
-4Pa is a protective atmosphere with the argon gas, and regulating growth room's pressure is 1Pa, and d.c. sputtering Ag layer film on the FZO thin film layer, sputtering power be at 100W, and temperature is at 25 ℃, the thick 8nm of Ag layer film;
3) close DC source,, obtain FZO/ Ag/FZO transparent conductive film with the thick FZO thin film layer of step 1) radio-frequency sputtering 48nm on the Ag layer film.
X ray diffraction (XRD) collection of illustrative plates of the FZO/Ag/FZO transparent conductive film for preparing is seen Fig. 2; The optical transmission spectrum is seen Fig. 3, and it has excellent electric property and optical property: resistivity is 5.65 * 10
-5Ω cm, face resistance 4.708 Ω/sq, electronic mobility is 17.0 cm2V
-1s
-1, carrier concentration is 6.49 * 10
21Cm
-3, the transmissivity of 500-700nm visible light wave range surpasses 95%, and the visible light average transmittance surpasses 90%.
1) be that 99.99% metal A g target is respectively installed on radio frequency target head and the direct current target head mixing fluorine zinc oxide target and purity, the percentage composition of mixing zinc fluoride in the fluorine zinc oxide target is 2%, glass substrate through cleaning is put on the substrate holder, distance between target and the substrate is 7 cm, and growth room's vacuum tightness is extracted into 1.0 * 10
-3Pa is a protective atmosphere with the argon gas, regulates the pressure 0.8Pa of growth room, and the fluorine zinc oxide target is mixed in radio-frequency sputtering, and sputtering power is at 120W, and temperature is 25 ℃, the thick FZO thin film layer of deposition 68nm on substrate;
2) close radio frequency source, growth room's vacuum tightness is extracted into 3.5 * 10
-4Pa is a protective atmosphere with the argon gas, and regulating growth room's pressure is 1.2Pa, and d.c. sputtering Ag layer film on the FZO thin film layer, sputtering power be at 100W, and temperature is at 25 ℃, the thick 13nm of Ag layer film;
3) close DC source,, obtain the FZO/Ag/FZO transparent conductive film with the thick FZO thin film layer of step 1) radio-frequency sputtering 68nm on the Ag layer film.
The FZO/Ag/FZO transparent conductive film for preparing has electric property and optical property preferably: resistivity is 3.21 * 10
-5Ω cm, face resistance 2.673 Ω/sq, electronic mobility is 20.1 cm2V
-1s
-1, carrier concentration is 9.63 * 10
21Cm
-3, the visible light average transmittance surpasses 70%.
1) be that 99.99% metal A g target is respectively installed on radio frequency target head and the direct current target head mixing fluorine zinc oxide target and purity, the percentage composition of mixing zinc fluoride in the fluorine zinc oxide target is 3%, glass substrate through cleaning is put on the substrate holder, distance between target and the substrate is 7 cm, and growth room's vacuum tightness is extracted into 1.0 * 10
-3Pa is a protective atmosphere with the argon gas, regulates the pressure 0.5Pa of growth room, and the fluorine zinc oxide target is mixed in radio-frequency sputtering, and sputtering power is at 100W, and temperature is 25 ℃, the thick FZO thin film layer of deposition 48nm on substrate;
2) close radio frequency source, growth room's vacuum tightness is extracted into 3.5 * 10
-4Pa is a protective atmosphere with the argon gas, and regulating growth room's pressure is 1.0Pa, and d.c. sputtering Ag layer film on the FZO thin film layer, sputtering power be at 100W, and temperature is at 25 ℃, the thick 16nm of Ag layer film;
3) close DC source,, obtain the FZO/Ag/FZO transparent conductive film with the thick FZO thin film layer of step 1) radio-frequency sputtering 48nm on the Ag layer film.
The FZO/Ag/FZO transparent conductive film for preparing has good electric property and optical property: resistivity is 2.626 * 10
-5Ω cm, face resistance 2.189 Ω/sq, electronic mobility is 20.3 cm2V
-1s
-1, carrier concentration is 1.17 * 10
22Cm
-3, the visible light average transmittance surpasses 75%.
Claims (4)
1. FZO/ metal/FZO transparent conductive film is characterized in that comprising successively from bottom to top on the substrate and mixes fluorine zinc oxide films rete, metal film layer and mix fluorine zinc oxide films rete.
2. prepare the method for the described FZO/ metal of claim 1/FZO transparent conductive film, it is characterized in that may further comprise the steps:
1) be that 99.99% metallic target is respectively installed on radio frequency target head and the direct current target head mixing fluorine zinc oxide target and purity, the percentage composition of mixing zinc fluoride in the fluorine zinc oxide target is 1%-4%, substrate through cleaning is put on the substrate holder, distance between target and the substrate is 6 ~ 8 cm, and growth room's vacuum tightness is extracted into 1.0 * 10
-3Pa is a protective atmosphere with the argon gas, regulates the pressure 0.1-2.0Pa of growth room, and the fluorine zinc oxide target is mixed in radio-frequency sputtering, deposition FZO thin film layer on substrate, and sputtering power is at 50-200W, and temperature is 20-500 ℃;
2) close radio frequency source, growth room's vacuum tightness is extracted into 3.5 * 10
-4Below the Pa, be protective atmosphere with the argon gas, regulating growth room's pressure is 0.8-2Pa, d.c. sputtering metal level film on the FZO thin film layer, and sputtering power is at 50-200W, and temperature is at 20-500 ℃;
3) close DC source,, obtain FZO/ metal/FZO transparent conductive film with step 1) radio-frequency sputtering FZO thin film layer on the metal level film.
3. the preparation method of FZO/ metal according to claim 2/FZO transparent conductive film is characterized in that said metal is Ag, Au, Cu, Al.
4. the preparation method of FZO/ metal according to claim 2/FZO transparent conductive film is characterized in that substrate is silicon, sapphire, glass, quartz or flexible substrate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102426876A (en) * | 2011-11-18 | 2012-04-25 | 安徽康蓝光电股份有限公司 | H doped FZO transparent conductive film and preparation method thereof |
| CN103402280A (en) * | 2013-07-23 | 2013-11-20 | 蒋昊 | Automatic demisting glass and preparation method of automatic demisting glass |
| US20140363932A1 (en) * | 2013-06-10 | 2014-12-11 | Samsung Electronics Co., Ltd. | Zinc target including fluorine, method of fabricating zinc nitride thin film by using the same, and method of fabricating thin film transistor by using the same |
| CN104766894A (en) * | 2015-04-08 | 2015-07-08 | 合肥工业大学 | Method for improving photoelectric property of dielectric/metal/dielectric electrodes |
| CN104867674A (en) * | 2015-04-15 | 2015-08-26 | 赫得纳米科技(昆山)有限公司 | Method for preparing metalized thin film of novel thin-film capacitor |
| CN105039911A (en) * | 2015-08-14 | 2015-11-11 | 陕西师范大学 | Transparent conducting thin film and manufacturing method thereof |
| CN106282925A (en) * | 2016-09-27 | 2017-01-04 | 南京航空航天大学 | A kind of TCO/TiW transparent conductive film and preparation method thereof |
| CN108074991A (en) * | 2017-12-06 | 2018-05-25 | 中国航发北京航空材料研究院 | A kind of composite transparent conductive film |
| CN113889296A (en) * | 2021-09-30 | 2022-01-04 | 中国航发北京航空材料研究院 | Low-resistance, high-light-transmission and low-loss composite film layer and preparation method thereof |
| CN115094378A (en) * | 2022-06-13 | 2022-09-23 | 桂林电子科技大学 | Multilayer composite ITO film |
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| CN102426876A (en) * | 2011-11-18 | 2012-04-25 | 安徽康蓝光电股份有限公司 | H doped FZO transparent conductive film and preparation method thereof |
| US20140363932A1 (en) * | 2013-06-10 | 2014-12-11 | Samsung Electronics Co., Ltd. | Zinc target including fluorine, method of fabricating zinc nitride thin film by using the same, and method of fabricating thin film transistor by using the same |
| CN103402280A (en) * | 2013-07-23 | 2013-11-20 | 蒋昊 | Automatic demisting glass and preparation method of automatic demisting glass |
| CN104766894A (en) * | 2015-04-08 | 2015-07-08 | 合肥工业大学 | Method for improving photoelectric property of dielectric/metal/dielectric electrodes |
| CN104867674A (en) * | 2015-04-15 | 2015-08-26 | 赫得纳米科技(昆山)有限公司 | Method for preparing metalized thin film of novel thin-film capacitor |
| CN105039911B (en) * | 2015-08-14 | 2019-01-22 | 陕西师范大学 | A kind of transparent conductive film and preparation method thereof |
| CN105039911A (en) * | 2015-08-14 | 2015-11-11 | 陕西师范大学 | Transparent conducting thin film and manufacturing method thereof |
| CN106282925A (en) * | 2016-09-27 | 2017-01-04 | 南京航空航天大学 | A kind of TCO/TiW transparent conductive film and preparation method thereof |
| CN106282925B (en) * | 2016-09-27 | 2018-08-07 | 南京航空航天大学 | A kind of TCO/TiW transparent conductive films and preparation method thereof |
| CN108074991A (en) * | 2017-12-06 | 2018-05-25 | 中国航发北京航空材料研究院 | A kind of composite transparent conductive film |
| CN113889296A (en) * | 2021-09-30 | 2022-01-04 | 中国航发北京航空材料研究院 | Low-resistance, high-light-transmission and low-loss composite film layer and preparation method thereof |
| CN115094378A (en) * | 2022-06-13 | 2022-09-23 | 桂林电子科技大学 | Multilayer composite ITO film |
| CN115094378B (en) * | 2022-06-13 | 2023-11-03 | 桂林电子科技大学 | Multilayer composite ITO film |
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Application publication date: 20110907 |