CN101714416A - Transparent conductive film and manufacturing method thereof - Google Patents
Transparent conductive film and manufacturing method thereof Download PDFInfo
- Publication number
- CN101714416A CN101714416A CN200910154979A CN200910154979A CN101714416A CN 101714416 A CN101714416 A CN 101714416A CN 200910154979 A CN200910154979 A CN 200910154979A CN 200910154979 A CN200910154979 A CN 200910154979A CN 101714416 A CN101714416 A CN 101714416A
- Authority
- CN
- China
- Prior art keywords
- zno
- znmgo
- target
- film
- substrate
- Prior art date
- 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.)
- Pending
Links
Images
Abstract
The invention discloses a transparent conductive film. A buffering undoped n type ZnO film and a buffering Ga doped n type ZnMgO film are deposited on an organic polymer substrate in turn. The transparent conductive film is prepared by a magnetron sputtering method, the method is simple, the transparent conductive film has excellent electrical properties, and the square resistance is 5 to 10 omega/sq. The transparent conductive film has the advantages of light weight, foldability, insusceptibility to breakage, suitability for large-scale production, convenient transportation, low cost and the like, which can be used for manufacturing flexible light-emitting devices, plastic liquid crystal displays and flexible substrate amorphous silicon solar cells, can be used as an electromagnetic shielding layer, a touch-sensitive covering layer and the like, and can also be used as a transparent heat insulating material for a plastic tunnel.
Description
Technical field
The present invention relates to a kind of nesa coating and preparation method thereof.
Background technology
In recent years, zinc oxide (ZnO) nesa coating has obtained very extensive studies.Zinc-oxide film has advantages such as abundant raw materials, nontoxic, the conductivity can improve film of mixing and stability for indium tin oxide (ITO).As a kind of important optoelectronic information material, the good photoelectric characteristic of zinc oxide transparent conducting film makes it be widely used in fields such as solar cell, LCD, hot mirrors.
The resistance of unadulterated ZnO film is very high, and poor electric conductivity in order to obtain more excellent electric property, can be carried out the doping of ZnO usually, mainly is the III major element.In all doped chemicals, Ga and Zn atomic radius are the most approaching, and the bond distance of Ga-O key and Zn-O key is more approaching, so behind the Ga atom replacement Zn atom, the ZnO distortion of lattice that causes is little, helps mixing of Ga, and compares with Al, and Ga is difficult for oxidation.So Ga is considered to the most promising doped chemical.In ZnO, mix the energy band engineering that Mg can realize ZnO, make it important purposes be arranged at aspects such as multi-heterostructure-layers, quantum well structure, two-dimensional electron gas.
Compare with glass substrate, there are many shortcomings in the organic polymer substrate: thermal resistance is low, and mechanical strength is low, and the thermal coefficient of expansion height is easy to absorb aqueous vapor.In order to overcome these shortcomings, need between nesa coating and polymer substrate, introduce one deck resilient coating.Because the lattice match of ZnO and ZnMgO, so select ZnO as cushioning layer material.
Organic substrate nesa coating not only has the photoelectric characteristic of glass substrate nesa coating, and many distinct advantages are arranged.It can be used as the transparency electrode of collapsible LCD, non-crystal silicon solar cell, also can be used as Pasting formula vehicle glass frost protection film, on transparency electromagnetic wave shield and collapsible reflection heat mirror, also be widely used, provide a kind of new thinking for developing flexible full impregnated funerary objects spare.
Summary of the invention
The purpose of this invention is to provide good nesa coating of a kind of electric property and preparation method thereof.
Nesa coating of the present invention has deposited the ZnO film layer and the ZnMgO rete of cushioning effect successively on substrate, it is characterized in that substrate is an organic polymer, the ZnO film layer that plays cushioning effect is unadulterated n type ZnO film, and the ZnMgO rete is a Ga doped n type ZnMgO film.
Above-mentioned organic polymer can be polyethylene terephthalate (PET), poly-carbonic acid dead drunk (PC), polymethyl methacrylate (PMMA) or PEN (PEN).
The preparation method of nesa coating may further comprise the steps:
1) the pure ZnO powder of weighing, compression moulding behind the ball milling then at 1200 ℃ of sintering temperatures, makes pure ZnO ceramic target;
2) pure ZnO, MgO and the Ga of weighing
2O
3Powder, wherein the Ga molar content is 4%, the Mg molar content is 5%, with above-mentioned powder ball milling mix, compression moulding, then at 1200 ℃ of sintering temperatures, make the ZnMgO ceramic target of mixing Ga;
3) adopting radio-frequency magnetron sputter method, is target with pure ZnO ceramic target, the unadulterated n type of deposition one deck ZnO film on the organic polymer substrate, and sputtering condition: the distance between target and the substrate remains 4～6cm, and growth room's vacuum degree is evacuated to 3 * 10 at least
-3Pa, the growth room feeds a kind of or this two kinds the mist in pure argon and the purity oxygen, and control pressure is 0.1～3.0Pa, Ar: O
2=1: 0～0: 1, sputtering power 100W～300W;
4) adopt radio-frequency magnetron sputter method, with the ZnMgO ceramic target of mixing Ga is target, deposit one deck Ga doped n type ZnMgO film on the unadulterated n type ZnO film of step 3) again, sputtering condition: the distance between target and the substrate remains 4～6cm, and growth room's vacuum degree is evacuated to 3 * 10 at least
-3Pa, the growth room feeds a kind of or this two kinds the mist in pure argon and the purity oxygen, and control pressure is 0.1～3.0Pa, Ar: O
2=1: 0～0: 1, sputtering power 100W～300W.
The purity of above-mentioned pure argon is more than 99.99%, and the purity of purity oxygen is more than 99.99%.ZnO, Ga
2O
3Be more than 99.99% with the purity of MgO powder.
The thickness of the thickness of ZnO film layer and ZnMgO rete all can be decided by sedimentation time in the nesa coating.
Advantage of the present invention is:
1) preparation method is simple, can at room temperature grow, nesa coating electric property excellence of the present invention, and square resistance is 5～10 Ω/sq.
2) the ZnO resilient coating of Yin Ruing can reduce the absorption to aqueous vapor so that organic substrate surface is more smooth, reduces because the caused defective of mismatch of substrate and ZnMgO film.
3) nesa coating of the present invention, adopt flexible substrate, have light weight, collapsible, non-friable, be easy to large tracts of land production, be convenient to the transportation and low cost and other advantages, can be applicable to make flexible luminescent device, plastic liquid crystal display and flexible substrate non-crystal silicon solar cell, can be used as transparency electromagnetic wave shield and touch sensitive overlays etc., also can be used as transparent heat-insulated insulation material and be used for hot house.
Description of drawings
Fig. 1 is the transparent conductive film structure schematic diagram.
Fig. 2 is the optical transmission spectrum of film.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing and instantiation.
With reference to Fig. 1, nesa coating of the present invention has deposited the ZnO film layer 2 and the ZnMgO rete 3 of cushioning effect successively on substrate 1, substrate is an organic polymer, and the ZnO film layer that plays cushioning effect is unadulterated n type ZnO film, and the ZnMgO rete is a Ga doped n type ZnMgO film.
Embodiment 1:
The preparation method of nesa coating may further comprise the steps:
The ZnO powder of 1) weighing purity 99.99% is poured load weighted ZnO powder in the ball grinder that agate ball is housed into, and ball milling is 24 hours on ball mill, to a certain extent refinement.Take out oven dry then, add binding agent and grind compression moulding.The idiosome of moulding is put into sintering furnace, and row is plain through low temperature (400 ℃), makes the binding agent volatilization, is warming up to 1200 ℃ of sintering again 4 hours, obtains mixing the ZnMgO ceramic target of Ga.
ZnO, MgO and the Ga of 2) weighing purity 99.99%
2O
3Powder, wherein the molar content of Ga is 4%, the Mg molar content is 5%.With load weighted ZnO, MgO and Ga
2O
3Powder is poured in the ball grinder that agate ball is housed, and ball milling is 24 hours on ball mill, and purpose is to allow evenly also refinement to a certain extent of powder.Take out oven dry then, add binding agent and grind compression moulding.The idiosome of moulding is put into sintering furnace, and row is plain through low temperature (400 ℃), makes the binding agent volatilization, is warming up to 1200 ℃ of sintering again 4 hours, obtains mixing the ZnMgO ceramic target of Ga.
3) the PC substrate is fixed on the sample tray after cleaning, puts into the reaction vacuum chamber.Pure ZnO ceramic target is contained on the target frame, embeds then on the target head of magnetic control sputtering device.The distance of regulating substrate and target is 6cm, and baffle plate is placed between substrate and the target.Growth room's vacuum degree is evacuated to 3 * 10
-3Pa, growth room feed pure argon, and control pressure is 1.0Pa, begin sputter at the power of 200W, and sputtering time is 10min, obtains the unadulterated n type ZnO film of the about 25nm of thickness.
4) take off pure ZnO ceramic target, the ZnMgO ceramic target that will mix Ga is contained on the target frame, embeds then on the target head of magnetic control sputtering device.Distance between target and the substrate remains 6cm, and baffle plate is placed between substrate and the target.Growth room's vacuum degree is evacuated to 3 * 10
-3Pa, growth room feed pure argon, and control pressure is 0.14Pa, begin sputter at the power of 300W, and sputtering time is 60min, obtains the n type ZnMgO film of mixing Ga that thickness is about 800nm.
All magnetron sputtering deposition processes are all at room temperature carried out.The square resistance of the nesa coating that this example makes is 6 Ω/sq, and average transmittance is higher than 80% in the visible region, and the optical transmission spectrum of film as shown in Figure 2.Device flexible 120 ° and property retention are stable.
Embodiment 2:
Preparation process is with embodiment 1, and different is: substrate is PET, and the thickness of unadulterated n type ZnO film is 50nm, and the thickness of mixing the n type ZnMgO rete of Ga is 700nm.When preparing unadulterated n type ZnO film, the growth room feeds pure argon and purity oxygen, Ar: O
2=9: 1.The square resistance of the nesa coating that this example makes is 5 Ω/sq, and average transmittance is higher than 85% in the visible region, and device flexible 90 ° and property retention are stable.
Embodiment 3:
Preparation process is with embodiment 1, and different is: substrate is PMMA, and the thickness of unadulterated n type ZnO film is 75nm, and the thickness of mixing the n type ZnMgO rete of Ga is 600nm.When preparing unadulterated n type ZnO film, the growth room feeds pure argon and purity oxygen, Ar: O
2=6: 4.The square resistance of the nesa coating that this example makes is 10 Ω/sq, and average transmittance is higher than 80% in the visible region, and device flexible 85 ° and property retention are stable.
Claims (5)
1. nesa coating, it is characterized in that on substrate (1), having deposited successively the ZnO film layer (2) and the ZnMgO rete (3) of cushioning effect, substrate is an organic polymer, and the ZnO film layer that plays cushioning effect is unadulterated n type ZnO film, and the ZnMgO rete is a n type ZnMgO film of mixing Ga.
2. nesa coating according to claim 1 is characterized in that organic polymer is that polyethylene terephthalate, poly-carbonic acid are dead drunk, polymethyl methacrylate or PEN.
3. the method for preparing the described nesa coating of claim 1 is characterized in that may further comprise the steps:
1) the pure ZnO powder of weighing, compression moulding behind the ball milling then at 1200 ℃ of sintering temperatures, makes pure ZnO ceramic target;
2) pure ZnO, MgO and the Ga of weighing
2O
3Powder, wherein the Ga molar content is 4%, the Mg molar content is 5%, with above-mentioned powder ball milling mix, compression moulding, then at 1200 ℃ of sintering temperatures, make the ZnMgO ceramic target of mixing Ga;
3) adopting radio-frequency magnetron sputter method, is target with pure ZnO ceramic target, the unadulterated n type of deposition one deck ZnO film on the organic polymer substrate, and sputtering condition: the distance between target and the substrate remains 4～6cm, and growth room's vacuum degree is evacuated to 3 * 10 at least
-3Pa, the growth room feeds a kind of or this two kinds the mist in pure argon and the purity oxygen, and control pressure is 0.1～3.0Pa, Ar: O
2=1: 0～0: 1, sputtering power 100W～300W;
4) adopt radio-frequency magnetron sputter method, with the ZnMgO ceramic target of mixing Ga is target, deposit one deck Ga doped n type ZnMgO film on the unadulterated n type ZnO film of step 3) again, sputtering condition: the distance between target and the substrate remains 4～6cm, and growth room's vacuum degree is evacuated to 3 * 10 at least
-3Pa, the growth room feeds a kind of or this two kinds the mist in pure argon and the purity oxygen, and control pressure is 0.1～3.0Pa, Ar: O
2=1: 0～0: 1, sputtering power 100W～300W.
4. the preparation method of nesa coating according to claim 3, the purity that it is characterized in that pure argon is more than 99.99%, the purity of purity oxygen is more than 99.99%.
5. the preparation method of nesa coating according to claim 3 is characterized in that ZnO, Ga
2O
3Be more than 99.99% with the purity of MgO powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910154979A CN101714416A (en) | 2009-12-07 | 2009-12-07 | Transparent conductive film and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910154979A CN101714416A (en) | 2009-12-07 | 2009-12-07 | Transparent conductive film and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101714416A true CN101714416A (en) | 2010-05-26 |
Family
ID=42417942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910154979A Pending CN101714416A (en) | 2009-12-07 | 2009-12-07 | Transparent conductive film and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101714416A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352484A (en) * | 2011-09-13 | 2012-02-15 | 山东理工大学 | Method for preparing titanium-doped zinc oxide transparent conductive film on polyethylene terephthalate (PET) flexible substrate |
| CN107195694A (en) * | 2016-03-10 | 2017-09-22 | 盐城金合盛光电科技有限公司 | Silicon substrate heterojunction solar cell and preparation method thereof |
-
2009
- 2009-12-07 CN CN200910154979A patent/CN101714416A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352484A (en) * | 2011-09-13 | 2012-02-15 | 山东理工大学 | Method for preparing titanium-doped zinc oxide transparent conductive film on polyethylene terephthalate (PET) flexible substrate |
| CN107195694A (en) * | 2016-03-10 | 2017-09-22 | 盐城金合盛光电科技有限公司 | Silicon substrate heterojunction solar cell and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jang et al. | Comparison study of ZnO-based quaternary TCO materials for photovoltaic application | |
| CN101697289A (en) | Transparent conducting film and preparation method thereof | |
| CN101609729B (en) | Manufacture method of multilayer transparent electricity conductive film | |
| EP2407575B1 (en) | Transparent conductive film and transparent conductive film laminate, processes for production of same, and silicon thin film solar cell | |
| CN102747334B (en) | Zinc-oxide-based transparent conductive film and preparation method thereof | |
| CN101851745B (en) | Indium zinc gallium oxide (IZGO) sputtering target for transparent conductive film and manufacturing method | |
| Farahamndjou | The study of electro-optical properties of nanocomposite ITO thin films prepared by e-beam evaporation | |
| Fang et al. | Electrical and optical properties of nitrogen doped SnO2 thin films deposited on flexible substrates by magnetron sputtering | |
| Tutsch et al. | The sputter deposition of broadband transparent and highly conductive cerium and hydrogen co‐doped indium oxide and its transfer to silicon heterojunction solar cells | |
| CN101831701A (en) | Method for growing n-type transparent conducting ZnO crystal thin film by F doping | |
| Chen et al. | Fabrication of transparent conducting ATO films using the ATO sintered targets by pulsed laser deposition | |
| CN102931285A (en) | Method for preparing niobium-doped titanium dioxide transparent conducting film | |
| CN103617831B (en) | Preparing aluminum-doped zinc oxide transparent conducting films of a kind of high mobility and preparation method thereof | |
| CN1287003C (en) | Method for preparing transparent conducting film made from multi-element oxides with antimony being doped into | |
| Peng et al. | Excellent properties of Ga‐doped ZnO film as an alternative transparent electrode for thin‐film solar cells | |
| Wu et al. | Highly performance of flexible transparent conductive Cu-based ZnO multilayer thin films via BS barrier layer | |
| CN101714416A (en) | Transparent conductive film and manufacturing method thereof | |
| EP2690192B1 (en) | Multi-elements-doped zinc oxide film, manufacturing method and application thereof | |
| CN101718882A (en) | Bendable transparent high conductive near-infrared reflective film and preparation method thereof | |
| CN102899624A (en) | Preparation method of transparent conductive oxide composite film material | |
| JP2012158825A (en) | Zinc oxide-based transparent conductive film-forming material and method for producing the same, target using the same, method for forming zinc oxide-based transparent conductive film, and transparent conductive substrate | |
| CN101280414A (en) | ZnO: Bi photoemissive thin film and preparation thereof | |
| TW201337014A (en) | Preparation method for magnesium zinc oxide sputtering target blended with group IIIA element | |
| CN102465272B (en) | Multielement composite transparent conductive film and preparation method and application thereof | |
| Čampa et al. | Optical and electrical properties of gallium doped indium tin oxide optimized for low deposition temperature applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100526 |