CN103302910B - A kind of biodegradable flexible conductive base plate and preparation method thereof - Google Patents
A kind of biodegradable flexible conductive base plate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of biodegradable flexible conductive base plate and preparation method thereof.This substrate comprises flexible substrate and the conductive layer of biodegradability, and described flexible substrate material is biodegradable material, and conductive layer is attached to biodegradable flexible substrate surface.This type of substrate not only has conductive capability but also have biodegradability, can be widely used in the preparation of flexible optoelectronic/electronic device, expands the scope of application of photoelectron/electronic device, can reduce the environmental pollution that electronic waste causes simultaneously.
Description
Technical field
The present invention relates to organic optoelectronic/electronic technology field, field of biology and environmental science, be specifically related to a kind of biodegradable flexible conductive base plate and preparation method thereof.
Background technology
Organic optoelectronic/electronic technology is the industry that the scientific and technological content that develops rapidly after microelectric technique is very high.Along with the fast development of organic optoelectronic/electronic technology, the photoelectron/electronic products such as organic solar batteries, sensor, thin film transistor (TFT) are full-fledged all gradually, and they substantially improve the life of people.Meanwhile, photoelectron/electronic technology, in the extensive use of social life every field, also creates growing great market.But, along with the growing of technology also brings a lot of problems.First, the rigid substrates of photoelectron/electronic equipments routine can not meet people to portability, the requirement of portability; Secondly, increasing photoelectron/electronic product causes a large amount of solid pollutions due to its non-biodegradable.Therefore, degradable flexible conductive base plate is studied significant to the range of application and environmental protection of widening photoelectron/electronic technology.
As everyone knows, substrate is as the support zone of photoelectron/electronic device, and its physics, chemical property determine the scope of application of photoelectron/electronic device to a great extent.General conventional substrate mostly is glass, quartz, silicon and plastic base.Quartz base plate and silicon substrate except expensive, the same with glass substrate all exist easily cracked, weight is relatively heavier, carry the shortcoming such as inconvenience, non-degradable; Though plastic supporting base has the advantage such as flexibility, light weight, scarcely degradable or have toxicity, can cause very large harm to environmental and biological materials, the range of application of device is very restricted.And the substrate possessing biodegradability is the key addressed this problem.
Summary of the invention
For prior art, the technical problem to be solved in the present invention how to provide a kind of biodegradable flexible conductive base plate and preparation method thereof.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: a kind of biodegradable flexible conductive base plate, described substrate comprises flexible substrate and conductive layer, and flexible substrate material is biodegradable material, and conductive layer is attached to biodegradable flexible substrate surface.
The acid of the polysaccharides such as described flexible substrate material is string, fibroin albumen, gelatin, PLA, glucose, viral fiber element, PLA, Poly(D,L-lactide-co-glycolide, polyvinyl alcohol, polyvinylpyrrolidone, pla-pcl and the copolymer between them, PHA, shellac, shitosan and hyaluronic acid, polyalcohols and EVA, collagen gel, fibrin gel etc. have in biological degradable material one or more.
Further, the thickness of described flexible substrate is 10 ~ 2000 μm.
Further, the thickness of described conductive layer is less than or equal to 200nm.
Further, described conductive is one or more in Graphene, CNT, metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire, zinc oxide, titanium oxide or polymer electrode material.
Further, described metal simple-substance nano wire is the one in Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires.
Further, described metal alloy nanowires is copper-iron alloy nano wire, silver ferroalloy nano wire, bule gold nano wire, alfer nano wire, dilval nano wire, ferro-cobalt nano wire, manganeisen nano wire, cadmium ferroalloy nano wire, indium ferroalloy nano wire, tin ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy nano wire, yellow gold nano wire, gold copper nano wire, aluminium copper nano wire, monel nano wire, cobalt-copper alloy nano wire, manganin nano wire, cadmium copper alloy nano wire, yellow gold nano wire, gun-metal nano wire, tungsten-copper alloy nano wire, Mock gold nano wire, electrum nano wire, aluminium silver alloy nanowires, bazar metal nano wire, cobalt silver alloy nanowires, manganese silver alloy nanowires, cadmium silver nano wire, indium silver alloy nanowires, sn-ag alloy nano wire, tungsten silver alloy nanowires, platinum-silver alloys nano wire, aluminium gold alloy nano-wire, nickel billon nano wire, cobalt billon nano wire, manganese billon nano wire, cadmium billon nano wire, indium billon nano wire, Sillim's alloy nano-wire, tungsten billon nano wire, cobalt-nickel alloy nano wire, manganese-nickel nano wire, cadmium-nickel alloy nano wire, indium nickel alloy nano wire, tin-nickel alloy nano wire, tungsten nickel nano wire, platinum-nickel alloy nano wire, cadmium manganese alloy nano wire, indium manganese alloy nano wire, tin manganese alloy nano wire, tungsten manganese alloy nano wire, platinum manganese alloy nano wire, indium cadmium alloy nano wire, tin cadmium alloy nano wire, tungsten cadmium alloy nano wire, platinum cadmium alloy nano wire, tin-indium alloy nano wire, tungsten indium alloy nano wire, platinum indium alloy nano wire, tungsten ashbury metal nano wire, one in platinum ashbury metal nano wire or platinum-tungsten alloys nano wire.
Further, described metal hetero-junction nano wire is copper iron heterojunction nano-wire, silver iron heterojunction nano-wire, gold iron heterojunction nano-wire, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt heterojunction nano-wire, ferromanganese heterojunction nano-wire, cadmium iron heterojunction nano-wire, indium iron heterojunction nano-wire, tin iron heterojunction nano-wire, ferrotungsten heterojunction nano-wire, platinum iron heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, gold copper heterojunction nano-wire, aluminum copper dissimilar junction nanowire, ambrose alloy heterojunction nano-wire, cobalt copper heterojunction nano-wire, copper-manganese heterojunction nano-wire, cadmium copper heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, tin copper heterojunction nano-wire, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold and silver heterojunction nano-wire, aluminium silver heterojunction nano-wire, nickeline heterojunction nano-wire, cobalt silver heterojunction nano-wire, manganese silver heterojunction nano-wire, cadmium silver heterojunction nano-wire, indium silver heterojunction nano-wire, tin silver heterojunction nano-wire, tungsten silver heterojunction nano-wire, platinum silver heterojunction nano-wire, aluminium gold heterojunction nano-wire, nickel gold heterojunction nano-wire, cobalt gold heterojunction nano-wire, manganese gold heterojunction nano-wire, cadmium gold heterojunction nano-wire, indium gold heterojunction nano-wire, Sillim's heterojunction nano-wire, tungsten gold heterojunction nano-wire, cobalt nickel heterojunction nano-wire, manganese nickel heterojunction nano-wire, cadmium nickel heterojunction nano-wire, indium nickel heterojunction nano-wire, tin nickel heterojunction nano-wire, tungsten nickel heterojunction nano-wire, platinum nickel heterojunction nano-wire, cadmium manganese heterojunction nano-wire, indium manganese heterojunction nano-wire, tin manganese heterojunction nano-wire, tungsten manganese heterojunction nano-wire, platinum manganese heterojunction nano-wire, indium cadmium heterojunction nano-wire, tin cadmium heterojunction nano-wire, tungsten cadmium heterojunction nano-wire, platinum cadmium heterojunction nano-wire, tin indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium heterojunction nano-wire, tungsten tin heterojunction nano-wire, one in platinum tin heterojunction nano-wire or platinum tungsten heterojunction nano-wire.
Further, described polymer electrode material is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) or 3,4-polyethylene dioxythiophenes.
The invention also discloses a kind of preparation method of biodegradable flexible conductive base plate described above, comprise the following steps:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. take roller coat, LB film, spin coating, drip painting, spraying, czochralski method, the tape casting, dip-coating, inkjet printing, self assembly or serigraphy mode on the rigid substrates of cleaning, prepare conductive layer;
3. the modes such as roller coat, LB embrane method, blade coating, spin coating, a painting, spraying, czochralski method, the tape casting, dip-coating, inkjet printing, self assembly or serigraphy are adopted to prepare flexible substrate on the electrically conductive;
4. the substrate preparing conductive layer and biodegradable flexible substrate is toasted;
5. conductive layer oven dry bondd and biodegradable flexible substrate, from rigid substrates sur-face peeling, form flexible conductive base plate;
6. the degradation characteristic of flexible conductive base plate, sheet resistance and surface topography is tested.
Compared with prior art, the present invention has following beneficial effect: first, and substrate of the present invention is the thin film-forming method adopting solution to prepare, and preparation technology is simple, and efficiency is high, and cost is low, is applicable to large-scale production; The advantages such as secondly, it is high that the substrate utilizing above-mentioned material to prepare has flatness, and pliability is good, and quality is light, transparent; Again, can control its degradation characteristic by controlling the thickness of substrate and composition and preparation technology, finally, the photoelectron/electronic device prepared on the substrate, owing to having degradability, can effectively reduce the solid pollution that electronic product produces.
Accompanying drawing explanation
Fig. 1 is the structural representation of degradable of the present invention or biocompatible flexible conductive base plate;
Wherein, 1, biodegradable flexible substrate, 2, conductive layer.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Technical scheme of the present invention is to provide a kind of biodegradable flexible conductive base plate and preparation method thereof, and as shown in Figure 1, the structure of flexible conductive base plate comprises biodegradable flexible substrate 1, conductive layer 2.
Flexible substrate 1 in biodegradable flexible conductive base plate of the present invention is biological degradable material, can in vivo or in vitro degrade, toxic action can not be produced to organism or environment, can be absorbed by organism after degraded even in vivo.
Conductive layer 2 in flexible conductive base plate of the present invention requires good electric conductivity, visible light transmissivity is high, comprises one or more in Graphene, CNT, metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire, zinc oxide, titanium oxide, polymer electrode material.
The structure of the biodegradable flexible conductive base plate adopting the present invention to prepare is as follows:
Biodegradable flexible substrate/conductive layer
Embodiment 1
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is fibroin albumen, and conductive layer 2 is CNT, and described conductive layer thickness is 200nm.Whole device architecture is described as:
Fibroin albumen/CNT
Preparation method is as follows:
1. the glass substrate surface utilizing acetone, ethanolic solution and deionized water effects on surface roughness to be less than 1nm carries out ultrasonic cleaning, dries up after cleaning with drying nitrogen.
2. adopt the method for spin coating to prepare carbon nanotube conducting layer, during spin coating, rotating speed is 1000 revolutions per seconds, duration 30s, thickness 200nm, then carries out 130 DEG C of thermal annealings to substrate;
3. be that the silk fibroin protein solution of 10wt% drips painting on the glass substrate by concentration, by base plate heating to 60 DEG C, solution dried.
4. the biodegradable flexible conductive base plate after oven dry is stripped down from nonbreakable glass, cut out substrate, obtain standard size test specimen.
5. test ready-made biodegradable flexible conductive base plate, the surface topography of main test flexible conductive base plate, sheet resistance and degradable characteristic, adopt the surface topography of SEM testing film.
Embodiment 2
As shown in Figure 1, the biodegradable flexible substrate 1 viral fiber element of substrate, conductive layer is nano silver wire, and described conductive layer thickness is 180nm.Whole device architecture is described as:
Viral fiber element/nano silver wire
Preparation flow is similar to embodiment 1.
Embodiment 3
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is gelatin, and conductive layer 2 is nanowires of gold, and the thickness of described conductive layer is 160nm.Whole device architecture is described as:
Gelatin/nanowires of gold
Preparation flow is similar to embodiment 1.
Embodiment 4
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is PLA, and conductive layer 2 is copper nano-wire, and the thickness of described conductive layer is 140nm.Whole device architecture is described as:
PLA/copper nano-wire
Preparation flow is similar to embodiment 1.
Embodiment 5
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is fibroin albumen, and conductive layer 2 is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid), and the thickness of described conductive layer is 120nm.Whole device architecture is described as:
Fibroin albumen/poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid)
Preparation flow is similar to embodiment 1.
Embodiment 6
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is polyvinyl alcohol, conductive layer 2 is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) and nano silver wire mixed conducting membrane, and the thickness of described conductive layer is 100nm.Whole device architecture is described as:
Polyvinyl alcohol/poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid): nano silver wire
Preparation flow is similar to embodiment 1.
Embodiment 7
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is shitosan, and conductive layer 2 is nanowires of gold, and the thickness of described conductive layer is 80nm.Whole device architecture is described as:
Shitosan/nanowires of gold
Preparation flow is similar to embodiment 1.
Embodiment 8
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is fibroin albumen, and conductive layer 2 is Graphene and nano silver wire mixed conducting membrane, and the thickness of described conductive layer is 60nm.Whole device architecture is described as:
Fibroin albumen/Graphene: nano silver wire
Preparation flow is similar to embodiment 1.
Embodiment 9
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is PLA, and conductive layer is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) and Graphene mixed conducting membrane, and the thickness of described conductive layer is 40nm.Whole device architecture is described as:
PLA/poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid): Graphene
Preparation flow is similar to embodiment 1.
Embodiment 10
As shown in Figure 1, the biodegradable flexible substrate 1 of substrate is gelatin, and conductive layer 2 is Graphene, and the thickness of described conductive layer is 10nm.Whole device architecture is described as:
Gelatin/Graphene
Preparation flow is similar to embodiment 1.
Claims (6)
1. a biodegradable flexible conductive base plate, is characterized in that: described substrate comprises biodegradable flexible substrate and conductive layer, and flexible substrate material is Biodegradable material, and conductive layer is attached to biodegradable flexible substrate surface; Described flexible substrate material is string, fibroin albumen, gelatin, PLA, glucose, viral fiber element, PLA, Poly(D,L-lactide-co-glycolide, polyvinyl alcohol, polyvinylpyrrolidone, pla-pcl and the copolymer between them, PHA, shellac, polysaccharide, polyalcohols acid and EVA thereof, collagen gel, one or more in fibrin gel; Described conductive is one or more in Graphene, CNT, metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire, zinc oxide, titanium oxide or polymer electrode material; Described flexible substrate thickness is 10 ~ 2000 μm; The thickness of described conductive layer is less than or equal to 200nm.
2. biodegradable flexible conductive base plate according to claim 1, is characterized in that: described metal simple-substance nano wire is the one in Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires.
3. biodegradable flexible conductive base plate according to claim 1, is characterized in that: described metal alloy nanowires is copper-iron alloy nano wire, silver ferroalloy nano wire, bule gold nano wire, alfer nano wire, dilval nano wire, ferro-cobalt nano wire, manganeisen nano wire, cadmium ferroalloy nano wire, indium ferroalloy nano wire, tin ferroalloy nano wire, ferro-tungsten nano wire, pt-fe alloy nano wire, yellow gold nano wire, gold copper nano wire, aluminium copper nano wire, monel nano wire, cobalt-copper alloy nano wire, manganin nano wire, cadmium copper alloy nano wire, yellow gold nano wire, gun-metal nano wire, tungsten-copper alloy nano wire, Mock gold nano wire, electrum nano wire, aluminium silver alloy nanowires, bazar metal nano wire, cobalt silver alloy nanowires, manganese silver alloy nanowires, cadmium silver nano wire, indium silver alloy nanowires, sn-ag alloy nano wire, tungsten silver alloy nanowires, platinum-silver alloys nano wire, aluminium gold alloy nano-wire, nickel billon nano wire, cobalt billon nano wire, manganese billon nano wire, cadmium billon nano wire, indium billon nano wire, Sillim's alloy nano-wire, tungsten billon nano wire, cobalt-nickel alloy nano wire, manganese-nickel nano wire, cadmium-nickel alloy nano wire, indium nickel alloy nano wire, tin-nickel alloy nano wire, tungsten nickel nano wire, platinum-nickel alloy nano wire, cadmium manganese alloy nano wire, indium manganese alloy nano wire, tin manganese alloy nano wire, tungsten manganese alloy nano wire, platinum manganese alloy nano wire, indium cadmium alloy nano wire, tin cadmium alloy nano wire, tungsten cadmium alloy nano wire, platinum cadmium alloy nano wire, tin-indium alloy nano wire, tungsten indium alloy nano wire, platinum indium alloy nano wire, tungsten ashbury metal nano wire, one in platinum ashbury metal nano wire or platinum-tungsten alloys nano wire.
4. biodegradable flexible conductive base plate according to claim 1, is characterized in that: described metal hetero-junction nano wire is copper iron heterojunction nano-wire, silver iron heterojunction nano-wire, gold iron heterojunction nano-wire, ferro-aluminum heterojunction nano-wire, ferronickel heterojunction nano-wire, ferro-cobalt heterojunction nano-wire, ferromanganese heterojunction nano-wire, cadmium iron heterojunction nano-wire, indium iron heterojunction nano-wire, tin iron heterojunction nano-wire, ferrotungsten heterojunction nano-wire, platinum iron heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, gold copper heterojunction nano-wire, aluminum copper dissimilar junction nanowire, ambrose alloy heterojunction nano-wire, cobalt copper heterojunction nano-wire, copper-manganese heterojunction nano-wire, cadmium copper heterojunction nano-wire, silver-bearing copper heterojunction nano-wire, tin copper heterojunction nano-wire, tungsten copper heterojunction nano-wire, platinoid heterojunction nano-wire, gold and silver heterojunction nano-wire, aluminium silver heterojunction nano-wire, nickeline heterojunction nano-wire, cobalt silver heterojunction nano-wire, manganese silver heterojunction nano-wire, cadmium silver heterojunction nano-wire, indium silver heterojunction nano-wire, tin silver heterojunction nano-wire, tungsten silver heterojunction nano-wire, platinum silver heterojunction nano-wire, aluminium gold heterojunction nano-wire, nickel gold heterojunction nano-wire, cobalt gold heterojunction nano-wire, manganese gold heterojunction nano-wire, cadmium gold heterojunction nano-wire, indium gold heterojunction nano-wire, Sillim's heterojunction nano-wire, tungsten gold heterojunction nano-wire, cobalt nickel heterojunction nano-wire, manganese nickel heterojunction nano-wire, cadmium nickel heterojunction nano-wire, indium nickel heterojunction nano-wire, tin nickel heterojunction nano-wire, tungsten nickel heterojunction nano-wire, platinum nickel heterojunction nano-wire, cadmium manganese heterojunction nano-wire, indium manganese heterojunction nano-wire, tin manganese heterojunction nano-wire, tungsten manganese heterojunction nano-wire, platinum manganese heterojunction nano-wire, indium cadmium heterojunction nano-wire, tin cadmium heterojunction nano-wire, tungsten cadmium heterojunction nano-wire, platinum cadmium heterojunction nano-wire, tin indium heterojunction nano-wire, tungsten indium heterojunction nano-wire, platinum indium heterojunction nano-wire, tungsten tin heterojunction nano-wire, one in platinum tin heterojunction nano-wire or platinum tungsten heterojunction nano-wire.
5. biodegradable flexible conductive base plate according to claim 1, is characterized in that: described polymer electrode material is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) or 3,4-polyethylene dioxythiophenes.
6. a preparation method for the biodegradable flexible conductive base plate according to any one of claim 1-5, is characterized in that, comprise the following steps:
1. the rigid substrates that effects on surface roughness is less than 1nm cleans, and dries up after cleaning with drying nitrogen;
2. roller coat, LB embrane method, blade coating, spin coating, a painting, spraying, czochralski method, the tape casting, dip-coating, inkjet printing, self assembly or serigraphy is taked to prepare conductive layer on the rigid substrates of cleaning;
3. roller coat, LB embrane method, blade coating, spin coating, a painting, spraying, czochralski method, the tape casting, dip-coating, inkjet printing, self assembly or serigraphy is adopted to prepare flexible substrate on the electrically conductive;
4. the rigid substrates preparing conductive layer and degradable flexible substrate is toasted;
5. conductive layer oven dry bondd and degradable flexible substrate, from rigid substrates sur-face peeling, form flexible conductive base plate;
6. the degradation characteristic of flexible conductive base plate, sheet resistance and surface topography is tested.
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