CN104761956B - Nano copper selenide conductive ink, its preparation method and application - Google Patents
Nano copper selenide conductive ink, its preparation method and application Download PDFInfo
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- CN104761956B CN104761956B CN201410003080.6A CN201410003080A CN104761956B CN 104761956 B CN104761956 B CN 104761956B CN 201410003080 A CN201410003080 A CN 201410003080A CN 104761956 B CN104761956 B CN 104761956B
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- copper
- conductive ink
- nano copper
- copper selenide
- selenide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
Abstract
The invention discloses a kind of nano copper selenide conductive ink, its preparation method and application.The conductive ink is the main mobility liquid-phase system being made up of dispersant and the nano copper selenide being dispersed in dispersant；Its preparation method includes：It is 1 by mol ratio:2~4:After 1 copper source and selenium source are uniformly mixed with reducing agent, it is placed in microwave reactor and is reacted, reaction temperature is 140 ~ 200 DEG C, microwave power is 100 ~ 300W, reaction obtains nano copper selenide after terminating, thereafter the nano copper selenide is dispersed in dispersant, forms the nano copper selenide conductive ink.The conductive ink of the present invention has good stability, and the advantages of electric conductivity is excellent can be widely used in preparing the layer materials such as conductive film, and its simple production process, low cost, preparation time is short, is adapted to batch production.
Description
Technical field
The present invention relates to a kind of conductive ink, more particularly, to a kind of nano copper selenide conductive ink, its preparation method and
Using belonging to field of nanometer material technology.
Background technology
With flexible electronic device of new generation such as intelligent wireless identification (RFID) electronic tag, printed circuit board (PCB)
(PCB), flexible printed circuit board (FPCB), electromagnetic shielding material, solar-energy photo-voltaic cell and flexible display electrodes is quick
Development, conductive ink will likely turn into highly integrated, high-accuracy flexible PCB plate production primary raw material of future generation.Relative to tradition
Thin film electronic processing technology, the green printing technology such as emerging ink-jet, aerosol spray printing also make it that conductive ink has more
Wide potential market space.Printed using conductive ink, the waste of raw material can be reduced, while simplifying technique journey
Sequence；While production efficiency is improved, the environmental pollution in manufacturing process can also be reduced as far as.
The conductive ink in research is generally divided into two classes at present：One class is agranular type conductive ink；One class is particle
Type conductive ink.Granular pattern conductive ink is main by conductive particle, solvent, dispersion stabilizer, surfactant and other auxiliary agents
Composition, its essence is the dispersion of conductive particle.Document it has been reported that including nanogold, Nano Silver and Nanometer Copper
A variety of nano conductive printing inks.In addition, emerging graphene and CNT are also already used to prepare conductive ink.But often
The metallic conduction particulate gold and silver seen, their extensive uses in industrial field are have impact on because its is expensive；And metal
Although copper particle takes advantage in electric conductivity and cost, nano level copper particle faces oxidation in actual applications
Problem, its commercial Application similarly has certain limitation.Emerging CNT and graphene conductive ink also due to
The limitation of electric conductivity hinders their applications in wide range of areas.Therefore, inexpensive high conductivity and stability are developed
Novel conductive ink will have broad application prospects, and new conductive ink will also promote the quick of related industry field
Development.
The content of the invention
In view of deficiency of the prior art, it is a primary object of the present invention to provide a kind of nano copper selenide conductive ink and
Its preparation method, it has low cost, and process conditions are gentle, efficiency high, the advantages of being adapted to batch production.
Another object of the present invention is to provide foregoing nano copper selenide conductive ink in electrically conductive layer material is prepared
Using.
To realize aforementioned invention purpose, present invention employs following technical scheme：
A kind of nano copper selenide conductive ink, it is main by dispersant and the nanometer selenizing being dispersed in dispersant
The mobility liquid-phase system of copper composition, and include 20-30wt% nano copper selenides in the ink.
Further, the mobility liquid-phase system can also include stabilizer, and the stabilizer may be selected from but be not limited to pyrrole
Pyridine, ethylenediamine, dithioglycol or TGA etc..
Further, the nano copper selenide includes the nano copper selenide with two-dimensional slice and/or linear structure.
Further, the dispersant may be selected from but be not limited to chloroform, n-hexane or toluene.
A kind of nano copper selenide conductive ink, comprises the following steps：It is 1 by mol ratio:2~4:1 copper source and selenium source are with going back
Former agent uniformly after mixing, is placed in microwave reactor and reacted, and reaction temperature is 140 ~ 200 DEG C, microwave power for 100 ~
300W, reaction obtains nano copper selenide after terminating, and the nano copper selenide is dispersed in dispersant thereafter, forms described
Nano copper selenide conductive ink, the nano copper selenide conductive ink is mobility liquid-phase system.
Further, the reaction time is 10min ~ 2h.
Further, copper source may be selected from but be not limited to stannous chloride, copper chloride, copper acetate or copper nitrate.
The selenium source may be selected from but be not limited to selenium dioxide.
The reducing agent may be selected from but be not limited to oleyl amine.
A kind of preparation method of electrically conductive layer material, including：Foregoing nano copper selenide conductive ink is applied to base material table
Face forms laminate structure, and in 40-120 DEG C of annealing sintering, obtains electrically conductive layer material, and the square of the electrically conductive layer material
Resistance is between 5 ~ 30 Ω/.
As one of concrete application scheme, the preparation method can be comprised the following specific steps that：
1）In microwave reaction container, according to 1:2~4:1 molar ratio adds copper source and selenium source, and with reducing agent and matching somebody with somebody
Solution is made；
2）By step（1）Obtained hybrid reaction system is stirred at room temperature overnight, and is then transferred in microwave reactor, if
Determine microwave reaction parameter as follows：Temperature is 140~200 DEG C, and the time is 10min~2h, and microwave power is 100~300W；
3）After reaction terminates, successively with cleaning products such as ethanol and chloroforms, enrichment is handled by stabilizer and dispersant
Copper selenide, obtains the selenizing copper conductive ink that mass percent is 20-30%.
Compared with prior art, the present invention at least has the following advantages that：
（1）Use Microwave Assisted Process and copper selenide for raw material, the cost of raw material of conductive ink is further reduced；
（2）Optimize obtained selenizing copper conductive ink environmental stability high, in lower temperature（40-120℃）It is i.e. sinterable
As conductive film；
（3）The conductive film of acquisition has excellent electric conductivity, and its film rectangular resistance is far below other conductive inks
Water, is between 5 ~ 30 Ω/.
Brief description of the drawings
Fig. 1 is obtained the SEM photograph of copper selenide nanometer sheet by the embodiment of the present invention 1；
Fig. 2 is obtained the XRD of copper selenide nanometer sheet by the embodiment of the present invention 1；
Fig. 3 be the embodiment of the present invention 1 in conductive film made annealing treatment at 120 DEG C after I-V characteristic curve.
Embodiment
Technical scheme is further described below in conjunction with some embodiments.
Embodiment 1
In 10ml microwave reaction pipe, 10 mg copper acetate monohydrate, 5.5 mg selenium dioxide and 5 is separately added into
ML oleyl amines（Mol ratio is 1：1）, 5ml oleyl amine solution is configured to, system is stirred overnight at ambient temperature；By microwave reaction pipe
Moving in microwave reactor, set microwave parameters --- reaction temperature is 180 DEG C, and the reaction time is 1 hour, and microwave power is
100W.After reaction terminates, successively with ethanol and chloroform, centrifugal enrichment obtains homogeneous copper selenide nanometer sheet.By enrichment
Copper selenide nanometer sheet is handled with pyridine, is then dispersed in chloroform solvent.
In Fig. 1, SEM photograph shows that copper selenide nanometer sheet is hexagonal, and its size exists（200-500nm）×（400-
800nm）.Basic peak position is all attributed to hexagonal crystal system in Fig. 2 XRD spectra（klockmannite phase）Copper selenide spreads out
Penetrate peak.Fig. 3 I-V characteristic curve shows that copper selenide conductive film has good conductive characteristic --- in 0.5 V bias conditions
Under, its current value reaches 0.06 A.
Embodiment 2
In 10ml microwave reaction pipe, 20 mg copper acetate monohydrate, 5.5 mg selenium dioxide and 5 is separately added into
ML oleyl amines（Mol ratio is 2：1）, 5ml oleyl amine solution is configured to, system is stirred overnight at ambient temperature；By microwave reaction pipe
Moving in microwave reactor, set microwave parameters --- reaction temperature is 160 DEG C, and the reaction time is 30 min, and microwave power is
150W.After reaction terminates, successively with ethanol and chloroform, centrifugal enrichment obtains homogeneous selenizing copper nano-wire（Or nanometer
Rod）；By the selenizing copper nano-wire of enrichment（Or nanometer rods）Handled, be then dispersed in chloroform solvent with ethylenediamine.Using drop coating
Film-forming process, its square resistance of the conductive film prepared only has 10 Ω/ or so.
It is pointed out that described above, drawing and embodiment can not resolve to the design philosophy to limiting the present invention.
Identical skill is held in the ken of the present invention can be such to technological thought of the invention with the improvement of various form
Improvement and change should also belong to protection scope of the present invention.
Claims (6)
1. a kind of nano copper selenide conductive ink, it is characterised in that it be it is main by chloroform or n-hexane or toluene, it is dispersed
The mobility liquid-phase system of nano copper selenide and stabilizer composition in chloroform or n-hexane or toluene, and in the ink
Include 20wt%~30wt% nano copper selenides；The nano copper selenide is selected from the nanometer selenizing with two-dimensional slice structure
Copper, the stabilizer is selected from pyridine, ethylenediamine, dithioglycol or TGA；And the preparation method of the nano copper selenide
Including：It is 1 by mol ratio:2~4:After 1 copper source and selenium source are uniformly mixed with reducing agent, it is placed in microwave reactor and carries out instead
Should, reaction temperature is 140~200 DEG C, and microwave power is 100~300W, obtains nano copper selenide after reacting 10min~2h, institute
State copper source and be selected from stannous chloride, copper chloride, copper acetate or copper nitrate, the selenium source uses selenium dioxide, and the reducing agent is used
Oleyl amine.
2. a kind of preparation method of nano copper selenide conductive ink, it is characterised in that comprise the following steps：It is 1 by mol ratio:2~
4:After 1 copper source and selenium source are uniformly mixed with reducing agent, it is placed in microwave reactor and is reacted, reaction temperature is 140~200
DEG C, microwave power is 100~300W, and nano copper selenide is obtained after reacting 10min~2h, thereafter that the nano copper selenide is uniform
It is scattered in chloroform or n-hexane or toluene, forms the nano copper selenide conductive ink, the nano copper selenide conductive ink
For mobility liquid-phase system.
3. the preparation method of nano copper selenide conductive ink as claimed in claim 2, it is characterised in that including：
1) in microwave reaction container, according to 1:2~4:1 molar ratio adds copper source and selenium source, and with reducing agent and preparing
Into hybrid reaction system；
2) step (1) is obtained into hybrid reaction system to be stirred at room temperature overnight, be then transferred in microwave reactor, set micro-
Ripple response parameter is as follows：Temperature is 140~200 DEG C, and the time is 10min~2h, and microwave power is 100~300W；
3) step 2) reaction terminate after, cleaning product, pass through stabilizer and chloroform or n-hexane or toluene processing enrichment nanometer
Copper selenide, obtains the selenizing copper conductive ink that concentration is 20wt%~30wt%.
4. the preparation method of nano copper selenide conductive ink as described in Claims 2 or 3, it is characterised in that copper source is selected from
Stannous chloride, copper chloride, copper acetate or copper nitrate.
5. the preparation method of nano copper selenide conductive ink as described in Claims 2 or 3, it is characterised in that the selenium source is used
Selenium dioxide, the reducing agent uses oleyl amine.
6. a kind of preparation method of electrically conductive layer material, it is characterised in that including：Nano copper selenide described in claim 1 is conductive
Ink applies to substrate surface formation laminate structure, and in 40-120 DEG C of annealing sintering, obtains electrically conductive layer material, and described lead
The square resistance of electric layer material is between 5~30 Ω/.
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| CN106800279A (en) * | 2015-11-26 | 2017-06-06 | 新纶科技（常州）有限公司 | A kind of sheet copper selenide and preparation method thereof |
| CN109134853A (en) * | 2018-07-07 | 2019-01-04 | 盐城师范学院 | A kind of preparation method of two dimension organic material |
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| WO2013154374A1 (en) * | 2012-04-13 | 2013-10-17 | Korea Reserach Institute Of Chemical Technology | Fabrication method of photo active layer for solar cell |
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