CN106299123B - A method of being patterned with machine electrode PEDOT:PSS - Google Patents
A method of being patterned with machine electrode PEDOT:PSS Download PDFInfo
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- CN106299123B CN106299123B CN201610887107.1A CN201610887107A CN106299123B CN 106299123 B CN106299123 B CN 106299123B CN 201610887107 A CN201610887107 A CN 201610887107A CN 106299123 B CN106299123 B CN 106299123B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/80—Constructional details
- H10K10/82—Electrodes
Abstract
The invention belongs to organic electrode fields, and in particular to a method of it is patterned with machine electrode PEDOT:PSS.The spin coating electron beam resist in substrate, with electron beam exposure method by the electron beam resist pattern layers in substrate after drying, PEDOT:PSS is deposited in the substrate with patterned electron beam lithography glue-line, it is impregnated after drying with organic solvent under certain temperature and removes electron beam resist, the patterned organic electrode PEDOT:PSS in substrate is obtained after being rinsed with a large amount of deionized waters, realization is patterned with machine electrode PEDOT:PSS.Method provided by the invention makes the patterned precision of organic electrode PEDOT:PSS reach 10nm, photoresist residual defects and reactive ion etching damage problem are got rid of simultaneously, for one new approaches of patterning path exploration of organic electrode, while extensive basis has been established for the large-scale application of organic electrode.
Description
Technical field
The present invention principally falls into organic electrode field, and in particular to a kind of side for being patterned with machine electrode PEDOT:PSS
Method.
Background technique
The resource of the earth is limited, and wherein metal electrode resource is even more fewer and fewer.But as excellent electronics produces
Product, which are widely used, to be rooted in the hearts of the people, and the metal electrode demand of semicon industry is growing day by day, and the shortage of final metal electrode must
The further development of electronic product can so be restricted.Simultaneously now electronic product just towards flexible, transparent, wearable trend development,
Metal electrode obviously can not carry on a shoulder pole this important task.For metal electrode because of its good thermal conductivity, excessively high molten boiling point makes deposited metal
When electrode, metallic vapour is easily burnt sample.The mixture of the PEDOT and PSS of different proportion have different work functions simultaneously, right
Different metal electrode is answered, so can replace a variety of metals rather than wherein a certain metal electrode.And organic electrode
PEDOT:PSS by feat of conduction it is strong, flexible, transparent performance is so cause extensive research, but its patterning techniques
All restrict its development always.
The patterning techniques of existing organic electrode PEDOT:PSS are mainly real by traditional mask plate photoetching process
It is existing.Its cardinal principle are as follows: heating, then spin coating after organic electrode PEDOT:PSS is spun in a clean substrate first
After photoresist, uv-exposure instrument is used with the help of mask plate, is exposed corresponding figure, is used reactive ion after developing fixing
Etching (RIE) etches the PEDOT:PSS film being exposed, and finally removes remaining photoresist using glue-dispenser.This pattern
Change technology is confined to complicated technique first: needing to be fabricated separately mask plate and uses reactive ion etching (RIE), if made
Got on rear spin coating PEDOT:PSS, then temperature needed for existing ultraviolet photoresist can not endure dry PEDOT:PSS is toasted；
If secondly, contact of the channel material with organic electrode is channel upper, organic electrode is under, then technical staff is difficult very
The technique for precisely getting hold of reactive ion etching (RIE), will necessarily etch substrate or leave organic electrode PEDOT:PSS and lead
Immediately below electric channel, and organic electrode, because photoresist can not be thoroughly removed there are residue problem, the photoresist of insulation increases
Electrodes；If finally, organic electrode is upper, conducting channel is under, then reactive ion etching (RIE) can also etch
To conducting channel material, or it still can leave photoetching glue residua.The precision of the technique of this photoetching is also limited to the essence of photoresist
About 1 μm of degree, source is higher than the precision of other Patternized techniques.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of method for being patterned with machine electrode PEDOT:PSS, make precision can be with
Reach 10nm, while getting rid of photoresist residual defects and reactive ion etching (RIE) damage problem.This is patterned with electromechanics
Pole PEDOT:PSS technology is one new approaches of patterning path exploration of organic electrode, while being the extensive of organic electrode
Using having established extensive basis.
The present invention is achieved by the following technical solutions:
A method of it being patterned with machine electrode PEDOT:PSS, the described method comprises the following steps:
(1) the spin coating electron beam resist in substrate obtains the electron beam lithography glue-line in substrate after drying；
(2) the electron beam resist pattern layers in the substrate are obtained with patterned with electron beam exposure method
The substrate of electron beam lithography glue-line；
(3) PEDOT:PSS is deposited in the substrate with patterned electron beam lithography glue-line, is done under certain temperature
It is dry to obtain intermediary；
(4) intermediary is impregnated with organic solvent and remove electron beam resist, obtain after being rinsed with a large amount of deionized waters
Patterned organic electrode PEDOT:PSS in substrate, realization are patterned with machine electrode PEDOT:PSS.
Further, the electron beam resist is polymethyl methacrylate or polymethyl methacrylate and methyl-prop
The mixed ester of e pioic acid methyl ester;The molecular weight of the polymethyl methacrylate is 495K or 950k.
Further, dry for 5-30min dry at 120 DEG C -220 DEG C under certain temperature in step (3), this temperature and
Time guarantees PEDOT:PSS invariance, and the PEDOT:PSS after drying finally can be not soluble in water.
Further, patterned precision is 0.01 micron to 100 microns in the step (2).
Further, the step (4) is impregnated with organic solvent and impregnates 0.5- for 50 DEG C of -100 DEG C of temperature in acetone
12h。
Further, in step (3) PEDOT:PSS deposition method be spin-coating method, spin coating liquid used be PEDOT:PSS with it is different
The mixed solution of propyl alcohol 1:1 by volume.
Further, the condition of drying described in step (1) are as follows: keep 1-2min at a temperature of 170 DEG C -190 DEG C.
Further, the substrate is the smooth substrate of arbitrary surfaces.
Substrate can for cleaning after silica, be deposited with single layer molybdenum disulfide silica, flexible and transparent PET or
PEI etc..
Further, dry for 15-30min dry at a temperature of 180 DEG C under certain temperature in the step (3).
Advantageous effects of the invention:
(1) method provided by the invention gets rid of the use of mask plate and reactive ion etching (RIE), solves photoetching glue residua
It is damaged with plasma resonance；
(2) present invention uses electron beam lithography, improves patterned precision；
(3) it is prepared by the present invention be patterned with machine electrode instead of metal electrode realize low cost green be patterned with electromechanics
There is the irreplaceable effect of metal electrode in pole especially for the electrode preparation of New Two Dimensional material.
Detailed description of the invention
Fig. 1, the present invention are patterned with the flow diagram of machine electrode PEDOT:PSS；
The patterned SEM figure of PEDOT:PSS in Fig. 2, the embodiment of the present invention 1；
The patterned SEM figure of Fig. 3,2 PEDOT:PSS of the embodiment of the present invention；
The structural schematic diagram of crystal of molybdenum disulfide pipe in Fig. 4, the embodiment of the present invention 3；
The current -voltage curve of crystal of molybdenum disulfide pipe in Fig. 5, the embodiment of the present invention 3；
In figure: 1, PEDOT:PSS organic electrode, 2, molybdenum disulfide nano sheet, 3, silica substrate, 4, electron beam
Photoresist.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
The present invention can also be understood completely in description.
Embodiment 1
Pattern PEDOT:PSS organic electrode flow chart as shown in Figure 1,
(1) it cleans silica substrate: the silica substrate of 2.5*2.5cm is successively put into acetone, ethyl alcohol, deionization
Water takes out, is dried with nitrogen in each solution after each ultrasonic cleaning in 10 minutes；
(2) the spin coating PMMA glue (950K) under 3000 rpms, one minute parameter, rear 180 DEG C of drying；
(3) electron beam lithography prepares " comb " shape figure, wherein the width of " comb " branch is 50 nanometers, it is vertical with " comb " branch
" comb " dry width be about 80 nanometers, such as Fig. 2, developing fixing is dried with nitrogen；
(4) spin coating PEDOT:PSS organic electrode, 180 DEG C baking 15-30 minutes, are finally putting into acetone soln on hot plate
Impregnate 12h；
Embodiment 2
(1) it cleans silica substrate: the silica substrate of 2.5*2.5cm is successively put into acetone, ethyl alcohol, deionization
Water takes out, is dried with nitrogen in each solution after each ultrasonic cleaning in 10 minutes.；
(2) the spin coating PMMA glue (495K) under 3000 rpms, one minute parameter, rear 180 DEG C of drying；
(3) electron beam lithography prepares PEDOT:PSS striped, and wherein width of fringe is about 10 microns, such as Fig. 3, development
Fixing is dried with nitrogen；
(4) spin coating PEDOT:PSS organic electrode, 180 DEG C baking 15-30 minutes, are finally putting into acetone soln on hot plate
Impregnate 12h；
Embodiment 3
It can be previously deposited single layer molybdenum disulfide in substrate, then carry out patterning PEDOT:PSS organic electrode, be prepared
The crystal of molybdenum disulfide pipe structural schematic diagram of crystal of molybdenum disulfide pipe, this method preparation is as shown in Figure 4.Specific step is as follows:
(1) it cleans silica substrate: the silica substrate of 2.5*2.5cm is successively put into acetone, ethyl alcohol, deionization
Water takes out, is dried with nitrogen in each solution after each ultrasonic cleaning in 10 minutes.；
(2) chemical vapor deposition growth single layer molybdenum disulfide is prepared using sulphur powder and molybdenum trioxide as reactant at 860 DEG C
Silica surface is deposited to, single layer molybdenum disulfide is equilateral triangle, and wherein side length is about 100 microns；
(3) the spin coating PMMA glue (495K) under 3000 rpms, one minute parameter, rear 180 DEG C of drying；
(4) figure required for electron beam lithography exposes；
(5) spin coating PEDOT:PSS organic electrode, 180 DEG C baking 15-30 minutes, are finally putting into acetone soln on hot plate
Impregnate 12h.
The current -voltage curve of crystal of molybdenum disulfide pipe being prepared is measured as shown in figure 5, when measurement, one of them
Electrode ground connection, another electrode apply voltage.
Claims (8)
1. a kind of method for being patterned with machine electrode PEDOT:PSS, which is characterized in that the described method comprises the following steps:
(1) the spin coating electron beam resist in substrate obtains the electron beam lithography glue-line in substrate after drying；
(2) the electron beam resist pattern layers in the substrate are obtained with patterned electronics with electron beam exposure method
The substrate of beam photoresist layer；
(3) it is deposited in the substrate with patterned electron beam lithography glue-line
PEDOT:PSS, dry 5-30min obtains intermediary at 120 DEG C -220 DEG C；
(4) intermediary is impregnated with organic solvent and remove electron beam resist, obtain after being rinsed with a large amount of deionized waters in substrate
Upper patterned organic electrode PEDOT:PSS, realization are patterned with machine electrode PEDOT:PSS.
2. a kind of method for being patterned with machine electrode PEDOT:PSS as described in claim 1, which is characterized in that the electron beam
Photoresist is the mixed ester of polymethyl methacrylate or polymethyl methacrylate and methyl methacrylate；The poly- methyl
The molecular weight of methyl acrylate is 495K or 950k.
3. a kind of method for being patterned with machine electrode PEDOT:PSS as described in claim 1-2 is any, which is characterized in that described
Patterned precision is 0.01 micron to 100 microns in step (2).
4. a kind of method for being patterned with machine electrode PEDOT:PSS as described in claim 1-2 is any, which is characterized in that described
Step (4) organic solvent impregnates to be changed to 50 DEG C of -100 DEG C of temperature in acetone and impregnate 0.5-12h.
5. a kind of method for being patterned with machine electrode PEDOT:PSS as described in claim 1-2 is any, which is characterized in that step
(3) PEDOT:PSS deposition method is spin-coating method in, and spin coating liquid used is the mixing of PEDOT:PSS and isopropanol 1:1 by volume
Solution.
6. a kind of method for being patterned with machine electrode PEDOT:PSS as described in claim 1-2 is any, which is characterized in that step
(1) condition of drying described in are as follows: keep 1-2min at a temperature of 170 DEG C -190 DEG C.
7. a kind of method for being patterned with machine electrode PEDOT:PSS as described in claim 1-2 is any, which is characterized in that described
The smooth substrate of substrate arbitrary surfaces all may be used.
8. a kind of method for being patterned with machine electrode PEDOT:PSS as described in claim 1-2 is any, which is characterized in that described
It is dry for 15-30min dry at a temperature of 180 DEG C under certain temperature in step (3).
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| CN112038452B (en) * | 2020-09-10 | 2023-03-03 | 哈尔滨工业大学 | Rapid patterning etching method of PEDOT (polyethylene glycol terephthalate): PSS (patterned sapphire substrate) electrode based on ultraviolet lithography process |
| CN113054058B (en) * | 2021-03-16 | 2023-07-25 | 哈尔滨工业大学 | Ultraviolet lithography method for patterning and etching PEDOT (polymer radical) PSS (power grid system) transparent electrode on flexible hydrophobic substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103077888A (en) * | 2013-01-11 | 2013-05-01 | 西安交通大学 | Method for preparing electrode on single nano wire |
| CN104934301A (en) * | 2015-06-13 | 2015-09-23 | 复旦大学 | Manufacturing method of non-invasive graphene nano-scale device |
| CN105259715A (en) * | 2015-11-20 | 2016-01-20 | 深圳市华星光电技术有限公司 | Patterned electrode manufacturing method, liquid crystal display panel and liquid crystal display panel manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103077888A (en) * | 2013-01-11 | 2013-05-01 | 西安交通大学 | Method for preparing electrode on single nano wire |
| CN104934301A (en) * | 2015-06-13 | 2015-09-23 | 复旦大学 | Manufacturing method of non-invasive graphene nano-scale device |
| CN105259715A (en) * | 2015-11-20 | 2016-01-20 | 深圳市华星光电技术有限公司 | Patterned electrode manufacturing method, liquid crystal display panel and liquid crystal display panel manufacturing method |
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