CN105585676A - Laser printing method of flexible electronic device - Google Patents
Laser printing method of flexible electronic device Download PDFInfo
- Publication number
- CN105585676A CN105585676A CN201410557921.8A CN201410557921A CN105585676A CN 105585676 A CN105585676 A CN 105585676A CN 201410557921 A CN201410557921 A CN 201410557921A CN 105585676 A CN105585676 A CN 105585676A
- Authority
- CN
- China
- Prior art keywords
- polyelectrolyte
- carry out
- laser printing
- carbon dust
- precious metal
- 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.)
- Granted
Links
Abstract
The invention relates to a laser printing method of a flexible electronic device. The method comprises the following steps: laser printer toner particles undergo surface modification by the use of polyelectrolyte; the polyelectrolyte modified toner is printed onto the surface of a flexible substrate by the use of a laser printer; and a metal layer is prepared on the surface of a laser printing pattern by normal-temperature precious metal catalytic electroless deposition. In comparison with a traditional printed circuit board technology, the invention has the following advantages: no copper foil substrate is required; lots of waste etching solutions will not be generated; operation is simple; and the method is easy to popularize and promote and is suitable for industrial production. The prepared flexible electronic device has excellent conductivity, mechanical durability and flexibility.
Description
Technical field
The present invention relates to a kind of method of laser printing flexible electronic.
Background technology
Flexible electronic can dressing display, sensor, solar energy and have very huge potential using value for the field such as bioelectronics device and driver aspect human health monitoring and disease treatment at robot skin, large area. Through the development of two more than ten years, it is more and more lighter also more and more thinner that large area flexible electronic becomes, solar energy in large area and the display that can easily hang on quickly on wall at present can reach, and along with the development of technology, flexible display that even can be curling is also within sight from realizing industrialization. Printed electronic is as an important branch in flexible electrical field, and preparation low cost multilayer microelectronic component that can be easier, is subject to very large attention in recent years. Researcher has developed various technology for the preparation of printed electronic device, as micro-contact printing, nano impression, intaglio printing, serigraphy, inkjet printing etc. Wherein, inkjet technology due to its noncontact, low material consumption, without mask, with computer compatibility, the characteristic such as flexible and general, can be to produce compared with low cost the flexible electronic that characteristic size is less and to be had an optimistic view of by industry on the substrate of large format, become current most study, application more a kind of printed electronic technology of preparing.
But inkjet printing itself also has weak point, as printing device and conductor ink cost high, and efficiency is lower. Prepare printed electronic in order to seek method more efficient and with low cost, the present invention has invested laser printing sight. Although laser printer is extensive use, compared with inkjet printing, adopt laser printing technology to prepare the report of printed electronic aspect very little, based on office conventionally laser printing technology used prepare printed electronic aspect have no at present report. It is that conducting particles or semi-conducting material and laser printing technology are incompatible that conventional laser printer technology fails to be applied to main cause prepared by printed electronic: in laser printing, need to utilize laser to carry out imaging, in printing carbon dust, add conductive material can cause imaging failure, the route of therefore directly preparing printed electronic by laser printing conductor material is obviously impracticable. So laser printing technology prepare printed electronic aspect first need solve key issue be the incompatible problem of conductive material and laser printing operation principle, this is also the key technical problem that the present invention solves.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of method of laser printing flexible electronic.
The present invention carries out polyelectrolyte-modified to laser printing carbon dust, then by printing, the mode of rear precious metal catalyst chemical plating obtains having superior electrical conductivity energy, the flexible electronic of mechanical endurance and good flexility.
A method for laser printing flexible electronic, is characterized in that the step of the method is followed successively by:
1) with polyelectrolyte, laser printing carbon powder particle is carried out to surface modification;
2) with laser printer, carbon dust polyelectrolyte-modified step 1) gained is printed to flexible parent metal surface;
3) in step 2) gained laser printing patterned surfaces adopts precious metal catalyst electroless deposition under normal temperature to prepare metal level.
Described step 1) is any one in following method by the method that polyelectrolyte carries out surface modification to carbon powder particle:
Method 1: polyelectrolyte and carbon dust carry out mechanical-physical mixing;
Method 2: adopt surperficial initiated polymerization at carbon powder particle surface grafting polyelectrolyte; Initator used is dopamine, and reaction condition is room temperature;
Method 3: add polyelectrolyte monomer to carry out combined polymerization in carbon dust bonding agent.
The mass ratio of described polyelectrolyte and carbon dust is 1:1 ~ 10:1.
Described polyelectrolyte is polymethyl acyl-oxygen ethyl-trimethyl salmiac.
Described flexible parent metal is paper, fabric, Kapton, polypropylene film or polyester film.
Described step 3) electroless deposition is to carry out under precious metal catalyst, and noble metal catalyst adopts precious metal salt and modification carbon dust to carry out ion-exchange; Described ion-exchange be before printing, soak by modification carbon dust or print pattern after soak and carry out; Described precious metal salt is ammonium chloropalladite, gold chloride or chloroplatinic acid.
The mol ratio of described precious metal salt and polyelectrolyte is 10:1 ~ 1:2.
Metal level prepared by described electroless deposition is copper, nickel or silver metal layer.
Compared with prior art, the present invention has following beneficial effect: first, raw materials used in order to carry out modification on existing laser printing carbon dust, raw material is easy to get, and method of modifying is simple, and cost is lower, is suitable for industrial production; Secondly, polyelectrolyte carried noble metal catalytic chemistry plates rapidly and efficiently, and gained metallic conductor and substrate have good adhesion, makes electronic device prepared by this method more tough, reliable and durable in the time that bending, distortion, fold etc. is out of shape; Again, compared with traditional printing circuit engineering, after printing, do not need copper clad laminate through chemically plating on the one hand for metallic conductor, do not produce on the other hand a large amount of metal etch waste liquids, little to ambient influnence, and cost is lower; Finally, the equipment that the present invention adopts is common laser printer, and equipment is universal and cost is very low, is easy to promote.
Detailed description of the invention
Embodiment 1:
In the round-bottomed flask of 250mL, add 10g carbon powder particle, then add the 1.5mg/mL(distilled water of 100mL new system: absolute ethyl alcohol=4:1) dopamine initiator solution, under nitrogen protection, lucifuge stir 24 hours. Carry out with absolute ethyl alcohol centrifugal, centrifugal three times to wash away the initator that is adsorbed on carbon powder particle surface, be put in vacuum drying chamber 40 degree dried overnight, obtain black powder.
In propping up test tube, the tool of 100 milliliters adds the mixed solution of 40mL MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (METAC) and 40mL methanol/water (volume ratio is 1:2), under nitrogen protection, stir after 20 minutes, add successively 2 of the cuprous bromide of 400mg and 800mg, 2-bipyridyl, stir the carbon powder particle 10g that adds dopamine initator to modify after 20 minutes, under nitrogen atmosphere, stirring at normal temperature is used absolute ethyl alcohol centrifuge washing 3 times after 4 hours, sample is put in to 40 degree dried overnight in vacuum drying chamber, obtain polymer P METAC modified carbon powder particles (PMETAC-carbon powder particle).
In 250mL round-bottomed flask, add the aqueous solution of the ammonium chloropalladite of PMETAC-carbon powder particle 10g and 100mL0.1mol/L, under nitrogen protection, stir and carry out anion exchange. After reaction 2h, carry out centrifuge washing 3 times with distilled water and absolute ethyl alcohol, 40 С dried overnight in vacuum drying chamber, the powder that obtains black is the carbon powder particle of the sub-palladium acid group of load chlorine.
Pack carbon powder particle compound Metal Palladium into toner cartridge and print to paper surface by HPLaserJetM1522MFP laser printer, then electroless deposition copper, concrete steps: substrate is immersed to new system for 50mLCu(II) mixed solution (12g/L NaOH, 13g/L cupric sulfate pentahydrate, 29g/L Rochelle salt), then add 50mL9.5ml/L formalin reducing metal copper, the static placement of normal temperature 1-4 hour, reaction finishes rear water and cleans substrate surface 3 times, and nitrogen dries up the papery flexible conductor material that can obtain conducting metal copper deposition.
Embodiment 2:
The round-bottomed flask of 25mL adds the 10g80% MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution, adds 0.1g potassium peroxydisulfate under concussion, after mixing, is warmed up to 80 DEG C of reaction 2-4 hour under room temperature, obtains polymethyl acyl-oxygen ethyl-trimethyl salmiac.
In 250mL round-bottomed flask, add the aqueous solution of the chloroplatinic acid of 10g polymethyl acyl-oxygen ethyl-trimethyl salmiac and 100mL0.1mol/L, under nitrogen protection, stir and carry out anion exchange. React and carry out centrifuge washing 3 times with distilled water and absolute ethyl alcohol afterwards in 2 hours, 40 degree dried overnight in vacuum drying chamber, the powder that obtains brown is chloroplatinic acid root load P METAC composite.
9g carbon powder particle and 1g chloroplatinic acid root load P METAC composite powerful are uniformly mixed, ball milling mixing 2-8 hour, ball milling obtains the homogeneous mixture of platinum load P METAC-carbon dust after evenly.
Pack metal platinum load P METAC-carbon powder particle mixture into toner cartridge, print to Kapton surface by the laser printer M7205 of association, then electroless deposition nickel, concrete steps: by polyimides substrate immerse new system for 80mLNi(II) the aqueous solution (40g/L nickel sulfate hexahydrate, 20g/L natrium citricum, 10g/L lactic acid), then add the aqueous solution of the dimethylamino borine of 20mL, with the PH to 8 of ammoniacal liquor regulator solution, static placement 1-4 hour, reaction finishes rear water and cleans substrate 3 times, nitrogen dries up the Kapton flexible conductor material that obtains conducting metal nickel deposition.
Claims (10)
1. a method for laser printing flexible electronic, is characterized in that the step of the method is followed successively by:
1) with polyelectrolyte, laser printing carbon powder particle is carried out to surface modification;
2) with laser printer, carbon dust polyelectrolyte-modified step 1) gained is printed to flexible parent metal surface;
3) in step 2) gained laser printing patterned surfaces adopts precious metal catalyst electroless deposition under normal temperature to prepare metal level.
2. the method for claim 1, is characterized in that method that described step 1) polyelectrolyte carries out surface modification to carbon powder particle is any one in following method:
Method 1: polyelectrolyte and carbon dust carry out mechanical-physical mixing;
Method 2: adopt surperficial initiated polymerization at carbon powder particle surface grafting polyelectrolyte;
Method 3: add polyelectrolyte monomer to carry out combined polymerization in carbon dust bonding agent.
3. method as claimed in claim 2, is characterized in that the initator that described method 2 adopts is dopamine, and reaction condition is room temperature.
4. the method for claim 1, the mass ratio that it is characterized in that described polyelectrolyte and carbon dust is 1:1 ~ 10:1.
5. the method for claim 1, is characterized in that described polyelectrolyte is polymethyl acyl-oxygen ethyl-trimethyl salmiac.
6. the method for claim 1, is characterized in that described flexible parent metal is paper, fabric, Kapton, polypropylene film or polyester film.
7. the method for claim 1, is characterized in that described step 3) electroless deposition is to carry out under precious metal catalyst, and noble metal catalyst adopts precious metal salt and modification carbon dust to carry out ion-exchange; Described ion-exchange be before printing, soak by modification carbon dust or print pattern after soak and carry out.
8. method as claimed in claim 7, is characterized in that described precious metal salt is ammonium chloropalladite, gold chloride or chloroplatinic acid.
9. method as claimed in claim 7 or 8, the mol ratio that it is characterized in that described precious metal salt and polyelectrolyte is 10:1 ~ 1:2.
10. the method for claim 1, is characterized in that metal level prepared by described electroless deposition is copper, nickel or silver metal layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410557921.8A CN105585676B (en) | 2014-10-21 | 2014-10-21 | A kind of method of laser printing flexible electronic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410557921.8A CN105585676B (en) | 2014-10-21 | 2014-10-21 | A kind of method of laser printing flexible electronic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105585676A true CN105585676A (en) | 2016-05-18 |
| CN105585676B CN105585676B (en) | 2018-06-22 |
Family
ID=55925606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410557921.8A Active CN105585676B (en) | 2014-10-21 | 2014-10-21 | A kind of method of laser printing flexible electronic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105585676B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106550548A (en) * | 2016-10-31 | 2017-03-29 | 中国科学院理化技术研究所 | A kind of laser printing forming method of flexible circuit |
| CN107462343A (en) * | 2017-08-10 | 2017-12-12 | 上海幂方电子科技有限公司 | A kind of full printing flexible sensor and its preparation technology |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004325596A (en) * | 2003-04-22 | 2004-11-18 | Fuji Photo Film Co Ltd | Dry film photoresist |
| JP2012207007A (en) * | 2011-03-30 | 2012-10-25 | Osaka Gas Chem Kk | Polyether resin having fluorene skeleton |
| CN103249255A (en) * | 2013-04-17 | 2013-08-14 | 复旦大学 | Method for directly preparing conducting circuit on resin baseplate |
| CN103619128A (en) * | 2013-11-25 | 2014-03-05 | 深圳大学 | Preparing method of flexible circuit board based on ink-jet printing technique |
| CN103709339A (en) * | 2013-12-25 | 2014-04-09 | 武汉大学 | Ionic ball polyelectrolyte brush employing micro-nano carbon sphere as kernel and preparation method thereof |
-
2014
- 2014-10-21 CN CN201410557921.8A patent/CN105585676B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004325596A (en) * | 2003-04-22 | 2004-11-18 | Fuji Photo Film Co Ltd | Dry film photoresist |
| JP2012207007A (en) * | 2011-03-30 | 2012-10-25 | Osaka Gas Chem Kk | Polyether resin having fluorene skeleton |
| CN103249255A (en) * | 2013-04-17 | 2013-08-14 | 复旦大学 | Method for directly preparing conducting circuit on resin baseplate |
| CN103619128A (en) * | 2013-11-25 | 2014-03-05 | 深圳大学 | Preparing method of flexible circuit board based on ink-jet printing technique |
| CN103709339A (en) * | 2013-12-25 | 2014-04-09 | 武汉大学 | Ionic ball polyelectrolyte brush employing micro-nano carbon sphere as kernel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 马全喜，等: "《电子元器件与电子实习》", 30 September 2006, 机械工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106550548A (en) * | 2016-10-31 | 2017-03-29 | 中国科学院理化技术研究所 | A kind of laser printing forming method of flexible circuit |
| CN106550548B (en) * | 2016-10-31 | 2019-03-15 | 中国科学院理化技术研究所 | A kind of laser printing forming method of flexible circuit |
| CN107462343A (en) * | 2017-08-10 | 2017-12-12 | 上海幂方电子科技有限公司 | A kind of full printing flexible sensor and its preparation technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105585676B (en) | 2018-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cai et al. | Laser direct writing and selective metallization of metallic circuits for integrated wireless devices | |
| CN106782757B (en) | A kind of printable compliant conductive slurry and its conducting wire and preparation method | |
| CN103249255B (en) | A kind of method directly preparing conducting wire on resin substrate | |
| CN102400115B (en) | Preparation method of flexible copper electrode pattern in micron level wire width | |
| Jin et al. | Site-selective growth of patterned silver grid networks as flexible transparent conductive film by using poly (dopamine) at room temperature | |
| CN101384425A (en) | Porous film and multilayer assembly using the same | |
| JP4485508B2 (en) | Method for producing conductive particles and anisotropic conductive film using the same | |
| JP4853774B2 (en) | Method for producing plated film on which patterned metal film is formed using reducing polymer fine particles | |
| Liang et al. | Microfluidic patterning of metal structures for flexible conductors by in situ polymer‐assisted electroless deposition | |
| Hu et al. | SU-8-induced strong bonding of polymer ligands to flexible substrates via in situ cross-linked reaction for improved surface metallization and fast fabrication of high-quality flexible circuits | |
| CN102056738A (en) | Layered product having porous layer and functional layered product made with the same | |
| JP4853775B2 (en) | Method for producing plated film with patterned metal film using reducing polymer fine particles | |
| CN101768386B (en) | Ink and method adopting ink to prepare conductive line | |
| CN108288513A (en) | A kind of flexibility based on fractal structure silver particles and stretchable conductor and preparation method thereof | |
| CN109427449A (en) | A kind of preparation method of flexibility base transparent conducting film | |
| CN107504893A (en) | High sensitivity graphene net/elastomer strain transducer and preparation method thereof | |
| CN104464973A (en) | High-strength aramid fiber transparent conducting thin film and manufacturing method and application thereof | |
| CN110265190A (en) | A kind of preparation method of three-dimension flexible conductor | |
| CN107072039A (en) | The method for preparing conducting wire | |
| CN105585676A (en) | Laser printing method of flexible electronic device | |
| Chen et al. | PET Surface Modification with Inkjet-Printing Pd2+/Epoxy Resin Solution for Selective Electroless Copper Plating | |
| CN103379747B (en) | The method of high adhesion high conductivity circuit is prepared in a kind of addition | |
| Cheng et al. | Multifunctional Ti3C2Tx MXene/Poly (Styrene‐Methacrylic Acid)@ Polypyrrole Nanospheres/Thermoplastic Polyurethane Electrospinning Membrane for High Sensitivity Pressure Sensing and Pressure‐Electrothermal | |
| CN109246870A (en) | A kind of preparation method of full printing low pressure high-performance pattern heating device flexible | |
| CN104349585B (en) | Circuit board and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |