CN106205876A - A kind of preparation method of flexible fiber element base transparent conductive material - Google Patents
A kind of preparation method of flexible fiber element base transparent conductive material Download PDFInfo
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- CN106205876A CN106205876A CN201610784630.1A CN201610784630A CN106205876A CN 106205876 A CN106205876 A CN 106205876A CN 201610784630 A CN201610784630 A CN 201610784630A CN 106205876 A CN106205876 A CN 106205876A
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
Abstract
The present invention discloses the preparation method of a kind of flexible fiber element base transparent conductive material, relates to the preparation of conductive cellulose thin film, especially relates to a kind of method using four steps to prepare cellulose membrane conductive material.The preparation method of the transparent conductive material based on cellulosic substrate of a kind of high conductivity, high transmission rate is provided.By magnetron sputtering at cellulose membrane Grown ground floor tin indium oxide (ITO) conductive layer, and then on ground floor ITO, grow second layer silver (Ag) conductive layer, growing third layer ITO conductive layer on second layer Ag conductive layer, annealing obtains " ITO/Ag/ITO/ cellulose " flexible fiber element base transparent conductive material of high conductivity, high transmission rate.
Description
Technical field
The present invention relates to the preparation method of a kind of flexible fiber element base transparent conductive material, especially relate to a kind of employing four
Step prepares flexible fiber element base transparent conductive material.
Background technology
Cellulose has abundance, cheap, biodegradable, recyclability, lightweight, flexing etc. because of it
Advantage has vast potential for future development at electronic applications.Meanwhile, cellulose membrane has good heat stability, chemically stable
Property, the physical and chemical performance such as optical property, mechanical property, be expected to replace the substrate such as plastics, glass preparation a new generation " green " electric
Sub-device, and cause the concern of whole world scientist.Various countries scientist by different preparation methoies by various electronic device structures
It build on the cellulosic substrate of electrically conducting transparent, such as display, transistor, Organic Light Emitting Diode (OLED), lithium battery, solar energy
Battery etc..
At present, the method for cellulose membrane of electrically conducting transparent is prepared mainly in the way of coating.It is mainly with Nanowire
Dimension element thin film is substrate, and nano-silver thread, Graphene, CNT etc., as conductive materials, are coated on substrate.But due to
Nano silver wire easily forms silver oxide with oxygen reaction and loses electric conductivity, it is impossible to ensure electrically conducting transparent cellulose membrane electric conductivity
Stability；Graphene and CNT as conductive materials, also exist poor with the associativity of cellulose membrane, light transmittance is low
Etc. defect, cause preparing transparency cellulose film conductivity, light transmission poor, affect the space of its further application development.So,
Flexible fiber element base transparent conductive material is prepared at present still in the laboratory research stage in the way of coating.
Utilize the method for magnetron sputtering at cellulose membrane Grown monolayer ITO conductive material (seeing Fig. 1), it is achieved
Prepare flexible fiber element base transparent conductive material.The preparation cost of the method is low, efficiency is higher, it is possible to achieve big of conductive film
Prepared by long-pending and volume to volume, be suitable for industrialized production.But, cellulosic substrate grows the light transmittance of monolayer ITO conductive material also
Relatively low, electric conductivity is poor, is mainly affected by following two aspect: on the one hand, the growth temperature of ITO thin film is the highest, ITO
Composed atom the highest in suprabasil extent of migration, the component of thin film is the most uniform, and film quality is the highest, but owing to cellulose is thin
The temperature ratio that film can bear is relatively low, prepares flexible fiber element base transparent conductive material at a lower temperature, ITO thin film
Of poor quality, cause cellulose membrane electric conductivity to decline.
On the other hand, owing to cellulosic substrate material is organic material, and ITO material is inorganic semiconductor material, both
Difference in lattice structure huge.ITO quasiconductor directly grows at the bottom of cellulose base, owing to the two lattice mismatch is very big, by
In the existence of crystal lattice stress, the ito thin film lattice of growth is distorted, and the ITO therefore grown easily produces lattice defect, even
Crack, cause cellulose membrane poorly conductive.Meanwhile, the lattice defect density of the ito thin film of growth is high, prohibits at quasiconductor
Band is formed defect level, visible ray is produced and absorbs, cause the visible light transmittance rate of thin film to decline.
By introducing transparent Ag nanometer interposed layer (seeing Fig. 2) in ito thin film, preparation ITO/Ag/ITO sandwich knot
The transparency conducting layer of structure, electric conductivity good for Ag can be greatly improved the monolithic conductive of ITO/Ag/ITO composite membrane.Meanwhile, by
In Ag, there is good ductility, the stress between lattice can be discharged, reduce the lattice defect concentrations in ito thin film, improve
The electric conductivity of ito thin film and light transmittance, thus prepare the flexible fiber element base transparent conductive material of high conductivity, high transmission rate
Conductive material.
Summary of the invention
Present invention aims to existing cellulose membrane Grown monolayer transparent conductive material exist
The problems such as ITO lattice defect concentrations is high, film crack is more, electric conductivity is unstable, light transmittance is low, it is provided that a kind of raising is flexible fine
The preparation method of dimension element base electrically conducting transparent.
The technical scheme is that and utilize Ag to have the advantages such as good electric conductivity, ductility, the thinnest at cellulose
Film Grown ground floor ITO conductive layer, then on ground floor ITO, grow second layer Ag conductive layer, maintain cellulose base good
Good electric conductivity, and then on second layer Ag, grow third layer ITO conductive layer, finally annealing improves the electrical and optical property of composite membrane
Can, thus obtain " ITO/Ag/ITO/ cellulose " flexible fiber element base transparent conductive material of high conductivity and high transmission rate.
The object of the present invention is achieved like this, the preparation side of described a kind of flexible fiber element base transparent conductive material
Method, it is characterised in that comprise the following steps:
1) on cellulose membrane substrate, ground floor tin indium oxide (ITO) conductive layer is grown by magnetron sputtering technique, described
The sputter temperature of magnetron sputtering at 30 ~ 150 DEG C, sputtering power 30 ~ 200W；
2) on ground floor tin indium oxide (ITO) conductive layer, second layer silver (Ag) conductive layer is grown by magnetron sputtering technique,
The sputter temperature of described magnetron sputtering at 30 ~ 150 DEG C, sputtering power 10 ~ 100W；
3) growing third layer ITO conductive layer by magnetron sputtering technique on second layer silver (Ag) conductive layer, described magnetic control spatters
The sputter temperature penetrated is at 30 ~ 150 DEG C, and sputtering power is 30 ~ 200W；
4) laminated film growing into step (3) is annealed, and obtains " the ITO/Ag/ITO/ of high conductivity, high transmission rate
Cellulose " flexible fiber element base transparent conductive material.
Above-mentioned cellulose membrane substrate is nano-cellulose film, regenerated cellulose film or bacteria cellulose film.
Ground floor ITO conductive layer thickness is 50 ~ 500nm.
The thickness of second layer Ag conductive layer is 2 ~ 20nm.
The thickness of third layer ITO conductive layer is 50 ~ 500nm.
The atmosphere of described annealing is at least a kind of selected from vacuum, oxygen atmosphere, argon atmospher, blanket of nitrogen, hydrogen atmosphere or sky
Gas atmosphere, annealing temperature is 30 ~ 150 DEG C, and annealing time is 1 ~ 24h.
Specifically, the present invention comprises the following steps:
1) by magnetron sputtering technique, at cellulose membrane Grown ground floor ITO conductive layer, sputter temperature is 30 ~ 150
DEG C, sputtering power is 30 ~ 200W；
2) on ground floor ITO grow second layer Ag conductive layer, sputter temperature at 30 ~ 150 DEG C, sputtering power 10 ~ 100W；
3) rising high-temperature, grow third layer ITO conductive layer on second layer Ag, sputter temperature is at 30 ~ 150 DEG C, and sputtering power is
30~200W；
4) laminated film of growth is annealed, obtain " ITO/Ag/ITO/ cellulose " flexibility of high conductivity, high transmission rate
Cellulose base transparent conductive material.
Cellulose membrane is preferably nano-cellulose film, regenerated cellulose film, bacteria cellulose film.
Ground floor ITO) conductive layer growth thickness is preferably 50 ~ 500nm.
Second layer Ag conductive layer growth thickness is preferably 2 ~ 20nm.
Third layer ITO conductive layer growth thickness is preferably 50 ~ 500nm.
The atmosphere of described annealing includes vacuum, oxygen atmosphere, argon atmospher, blanket of nitrogen, hydrogen atmosphere, air atmosphere etc., annealing
Temperature is 30 ~ 150 DEG C, and annealing time is 1 ~ 24h.
Compared with the preparation method of existing cellulose membrane Grown monolayer transparent conductive material, the present invention
There is advantage highlighted below:
1) grow nanometer Ag layer at ITO, utilize the good ductility of Ag material, the crystal lattice stress between release ITO, reduce by crystalline substance
The lattice defect of lattice stress generation and film crack, thus improve electric conductivity and light transmittance.
2) due to nanoscale Ag, there is high conductivity, ITO inserts Ag nanometer layer and prepares ITO/Ag/ITO sandwich knot
Structure thin film, can be greatly improved the electric conductivity of laminated film.
3) one layer of Ag of flexible fiber element base transparent conductive material growth, in the case of same conductivity requires, can subtract
Few ITO growth thickness, improves the light transmittance of flexible fiber element base transparent conductive material.
4) having the characteristic of high migration due to metal Ag, the height that can fill ITO surface after growth ground floor ITO rises and falls
Defect, improves the surface smoothness of thin film, improves the light transmittance of flexible fiber element base transparent conductive material.
Accompanying drawing explanation
Fig. 1 is cellulose membrane Grown monolayer ITO conductive material schematic diagram.
Fig. 2 is the present invention " ITO/Ag/ITO/ cellulose " flexible fiber element base transparent conductive material structural representation.
Fig. 3 is that the embodiment of the present invention is at cellulose membrane Grown " ITO/Ag/ITO " detailed process figure.
Being numbered in figure: 1. substrate；2. ITO conductive layer；3. Ag conductive layer；4. ITO conductive layer.
Detailed description of the invention
Illustrate below by specific embodiment, to be further elucidated with substantive distinguishing features and the marked improvement of the present invention.
Embodiment 1
Seeing accompanying drawing 3, the preparation of flexible fiber element base transparent conductive material uses nano-cellulose as substrate 1, first uses pure N2
Process 3min thoroughly to remove substrate surface dust (process a)；Again by magnetron sputtering technique, in sputter temperature 110 DEG C growth
(process b), sputtering power is 110W to ground floor tin indium oxide (ITO) conductive layer, and thickness is about 300nm；Then ITO source is closed,
Open Ag source, reduce the temperature to 60 DEG C ITO and the cellulose membrane Grown second layer silver (Ag) conductive layer (process c),
Growth thickness is about 10nm, and the nanometer Ag layer at this moment grown has the characteristic of high migration, and the height that can fill ITO surface rises and falls
Defect, makes surfacing；Close Ag source, open ITO source, increase the temperature to 110 DEG C growth third layer ITO conductive layer (process d),
Sputtering power is 110W, and thickness is about 300nm；Last in pure Ar atmosphere, annealing temperature 60 DEG C, annealing time about 12h moves back
Fire, prepares flexible fiber element base transparent conductive material (process f).
Embodiment 2
Seeing accompanying drawing 3, the preparation of flexible fiber element base transparent conductive material uses nano-cellulose as substrate 1, first uses pure N2
Process 3min thoroughly to remove substrate surface dust (process a)；Again by magnetron sputtering technique, in sputter temperature 110 DEG C growth
(process b), sputtering power is 90W to ground floor tin indium oxide (ITO) conductive layer, and thickness is about 250nm；Then close ITO source, beat
Open Ag source, reduce the temperature to 40 DEG C in ITO and the cellulose membrane Grown second layer silver (Ag) conductive layer (process c), life
Long thickness is about 6nm, and the nanometer Ag layer at this moment grown has the characteristic of high migration, and the height that can fill ITO surface rises and falls scarce
Fall into, make surfacing；Closing Ag source, open ITO source, (process d), spatters to increase the temperature to 110 DEG C of growth third layer ITO conductive layer
Penetrating power is 90W, and thickness is about 250nm；Last in pure air atmosphere, annealing temperature 30 DEG C, annealing time about 12h moves back
Fire, prepares flexible fiber element base transparent conductive material (process f).
Embodiment 3
Seeing accompanying drawing 3, the preparation of flexible fiber element base transparent conductive material uses nano-cellulose as substrate 1, first uses pure N2
Process 3min thoroughly to remove substrate surface dust (process a)；Again by magnetron sputtering technique, at 80 DEG C of growth regulations of sputter temperature
(process b), sputtering power is 90W to indium oxide layer stannum (ITO) conductive layer, and thickness is about 200nm；Then close ITO source, open
Ag source, reduces the temperature to 30 DEG C in ITO and the cellulose membrane Grown second layer silver (Ag) conductive layer (process c), growth
Thickness is about 3nm, and the nanometer Ag layer at this moment grown has the characteristic of high migration, and the height that can fill oxygen ITO surface rises and falls scarce
Fall into, make surfacing；Closing Ag source, open ITO source, (process d), spatters to increase the temperature to 80 DEG C of growth third layer ITO conductive layer
Penetrating power is 90W, and thickness is about 200nm；Last in nitrogen atmosphere, annealing temperature 90 DEG C, annealing time is about 6h annealing, system
Obtain flexible fiber element base transparent conductive material (process f).
Claims (6)
1. the preparation method of a flexible fiber element base transparent conductive material, it is characterised in that comprise the following steps:
Cellulose membrane substrate grows ground floor tin indium oxide (ITO) conductive layer, described magnetic by magnetron sputtering technique
Control sputtering sputter temperature at 30 ~ 150 DEG C, sputtering power 30 ~ 200W；
Ground floor tin indium oxide (ITO) conductive layer grows second layer silver (Ag) conductive layer, institute by magnetron sputtering technique
State the sputter temperature of magnetron sputtering at 30 ~ 150 DEG C, sputtering power 10 ~ 100W；
Second layer silver (Ag) conductive layer grows third layer ITO conductive layer, described magnetron sputtering by magnetron sputtering technique
Sputter temperature at 30 ~ 150 DEG C, sputtering power is 30 ~ 200W；
4) laminated film growing into step (3) is annealed, and obtains " the ITO/Ag/ITO/ of high conductivity, high transmission rate
Cellulose " flexible fiber element base transparent conductive material.
The preparation method of a kind of flexible fiber element base transparent conductive material the most as claimed in claim 1, it is characterised in that fiber
Element film-substrate is nano-cellulose film, regenerated cellulose film or bacteria cellulose film.
The preparation method of a kind of flexible fiber element base transparent conductive material the most as claimed in claim 1, it is characterised in that first
Layer ITO conductive layer thickness is 50 ~ 500nm.
The preparation method of a kind of flexible fiber element base transparent conductive material the most as claimed in claim 1, it is characterised in that second
The thickness of layer Ag conductive layer is 2 ~ 20nm.
The preparation method of a kind of flexible fiber element base transparent conductive material the most as claimed in claim 1, it is characterised in that the 3rd
The thickness of layer ITO conductive layer is 50 ~ 500nm.
The preparation method of a kind of flexible fiber element base transparent conductive material the most as claimed in claim 1, it is characterised in that step
(3) atmosphere of the annealing described in is at least a kind of selected from vacuum, oxygen atmosphere, argon atmospher, blanket of nitrogen, hydrogen atmosphere or air gas
Atmosphere, annealing temperature is 30 ~ 150 DEG C, and annealing time is 1 ~ 24h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107170831A (en) * | 2017-06-14 | 2017-09-15 | 华南理工大学 | A kind of nanometer paper substrate film transistor and preparation method thereof |
| CN108362199A (en) * | 2017-01-26 | 2018-08-03 | 华邦电子股份有限公司 | Straining and sensing device and its manufacturing method |
| CN112908517A (en) * | 2021-01-19 | 2021-06-04 | 大正(江苏)微纳科技有限公司 | Transparent conductive film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257135A (en) * | 1999-12-23 | 2000-06-21 | 复旦大学 | Metal indium-stannic oxide compound transparent electricity conductive film and preparation process thereof |
| CN103777417A (en) * | 2007-04-20 | 2014-05-07 | 凯博瑞奥斯技术公司 | Composite transparent conductors and methods of forming the same |
| CN104201280A (en) * | 2014-08-04 | 2014-12-10 | 北京科技大学 | Preparation methods of nanometer piezoelectric film and nanometer composite piezoelectric generator |
| CN104979037A (en) * | 2015-05-14 | 2015-10-14 | 上海电力学院 | Transparent conducting thin film with enhanced thermal stability and preparation method and application thereof |
-
2016
- 2016-08-31 CN CN201610784630.1A patent/CN106205876A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257135A (en) * | 1999-12-23 | 2000-06-21 | 复旦大学 | Metal indium-stannic oxide compound transparent electricity conductive film and preparation process thereof |
| CN103777417A (en) * | 2007-04-20 | 2014-05-07 | 凯博瑞奥斯技术公司 | Composite transparent conductors and methods of forming the same |
| CN104201280A (en) * | 2014-08-04 | 2014-12-10 | 北京科技大学 | Preparation methods of nanometer piezoelectric film and nanometer composite piezoelectric generator |
| CN104979037A (en) * | 2015-05-14 | 2015-10-14 | 上海电力学院 | Transparent conducting thin film with enhanced thermal stability and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| M. BENDER，ET AL: "Dependence of film composition and thicknesses on optical and electrical properties of ITO–metal–ITO multilayers", 《THIN SOLID FILMS》 * |
| YANG JIAZHI，ET AL: "Preparation of High Quality Indium Tin Oxide Film on a Microbial Cellulose Membrane Using Radio Frequency Magnetron Sputtering", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
| 李扬，等: "氧化铟锡/银/氧化铟锡多层膜作为阳极的柔性有机电致发光器件", 《科学通报》 * |
| 王孝丽，等: "ITO/Ag / ITO 透明导电膜性能研究进展", 《山东建筑大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108362199A (en) * | 2017-01-26 | 2018-08-03 | 华邦电子股份有限公司 | Straining and sensing device and its manufacturing method |
| CN107170831A (en) * | 2017-06-14 | 2017-09-15 | 华南理工大学 | A kind of nanometer paper substrate film transistor and preparation method thereof |
| CN112908517A (en) * | 2021-01-19 | 2021-06-04 | 大正(江苏)微纳科技有限公司 | Transparent conductive film and preparation method thereof |
| CN112908517B (en) * | 2021-01-19 | 2022-08-05 | 大正(江苏)微纳科技有限公司 | Transparent conductive film and preparation method thereof |
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