CN103173724B - Method for processing microstructure - Google Patents
Method for processing microstructure Download PDFInfo
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- CN103173724B CN103173724B CN201110439939.4A CN201110439939A CN103173724B CN 103173724 B CN103173724 B CN 103173724B CN 201110439939 A CN201110439939 A CN 201110439939A CN 103173724 B CN103173724 B CN 103173724B
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Abstract
The invention provides a kind of method for processing microstructure of Meta Materials, the method takes the mode of planting crystal seed laser induction chemical plating in advance, first by PVP and AgNO
3be dissolved in ethanol, homogeneous heating obtains brown colloidal metal solution, is then cooled to room temperature, is coated on the surface of substrate and dries; Then on substrate, micro structured pattern is write out with laser beam; Then clean substrate with scavenging solution again, remove undosed PVP film; Finally cleaned substrate is placed in pre-configured chemical plating fluid, obtains microstructure.Method according to the present invention carrys out processing micro structure, simply fast efficiently and accurately can prepare metal micro structure on especially flexible base material.
Description
[technical field]
The present invention relates to Meta Materials field, particularly relate to a kind of method for processing microstructure of Meta Materials.
[background technology]
Meta Materials refers to some artificial composite structures with the extraordinary physical properties not available for natural materials or matrix material.By the structurally ordered design on the key physical yardstick of material, the restriction of some apparent natural law can be broken through, thus maybe must exceed the meta-materials function of the intrinsic common character of nature.The character of Meta Materials and function mainly come from the structure of its inside but not form their material.
The special property of Meta Materials depends on the key physical yardstick of material to a great extent.One the most intuitively example be crystal.Crystal is that arrangement is orderly on an atomic scale, just because of this, crystalline material has the physical features not available for some unformed shapes.Analogy thus, the ordered arrangement on other level then may obtain the physical properties not available for material of occurring in nature to a certain degree.Usual man-made structures is of a size of 1/10th of required response wave length, otherwise the arrangement that these man-made structures form can not be regarded as in space continuously.
Meta Materials comprises the material accompanying by man-made structures and man-made structures, this attachment material is played a supporting role to man-made structures, therefore can be any material different from man-made structures, a generation effective dielectric constant and magnetic permeability are in space understood in the superposition of this bi-material, and these two physical parameters distinguish electric field response and the magnetic responsiveness of correspondence material.
The layers of copper that the preparation of Meta Materials plates specific repeat patterns mainly through technology such as photoetch, chemical milling, electrochemical depositions at present on base material realizes.The step of photoetch is many, operates general more complicated, and limits due to the requirement of the technology such as photoetch to material itself, and the base material that present stage uses is generally the FR4 plate of hard, and can not be applied on flexible base material and packaged material.The technology such as chemical milling, electrochemical deposition then may cause the pollution to environment.
Need to provide a kind of new method for processing microstructure, quickly and easily can prepare metal micro structure on especially flexible base material.
[summary of the invention]
The invention provides a kind of method for processing microstructure, take the mode of planting crystal seed laser induction chemical plating in advance to carry out processing micro structure, simply fast efficiently and accurately can prepare metal micro structure on especially flexible base material.
Laser flexible routing is the ultraprecise microstructure processing technology of a kind of new life, belongs to the one in laser writing technology.It and traditional flexibility prepare Line technology as compared with hot padding, static printing, focused particle beam technology, laser processing technology etc., have that minimum feature is low, wire resolving power is high, cloth linear rate fast, without the need to outstanding advantages such as mask plates.Further, laser beam energy density is high, and spot diameter, direction and position easily accurately control.
Laser writing technology and electroless plating technology combine by the present invention, prepare metal micro structure on polyimide base film surface.By using the Kapton of surface doping silver, or Polyvinylpyrolidone (PVP) (PVP) film of silver nanoparticle-containing is coated with at substrate surface, the treated surface of these films can both under the effect of laser focusing bundle on substrate the metal seeds crystal grain of depositing dosed quantities, then can copper be generated after electroless plating process.
According to a main aspect of the present invention, provide a kind of method for processing microstructure, the method comprises the following steps:
A, by PVP and AgNO
3be dissolved in ethanol, this dissolution homogeneity is heated, obtain brown colloidal metal solution;
B, this colloidal metal solution is cooled to room temperature, is coated on the surface of substrate and dries;
C, configuration chemical plating fluid;
D, on substrate, write out micro structured pattern with laser beam;
E, clean substrate with scavenging solution, remove undosed PVP film;
F, cleaned substrate is placed in chemical plating fluid, obtains microstructure.
According to an aspect of the present invention, substrate is flexible substrate.
According to an aspect of the present invention, flexible substrate is polyimide (PI) substrate.
According to an aspect of the present invention, PVP and AgNO
3weight ratio be 2: 1.
According to an aspect of the present invention, alcohol concn is at about 0.03g/ml.
According to an aspect of the present invention, type of heating heats 1 minute every 1 minute for using microwave oven under 300w power, heats 6 times altogether.
According to an aspect of the present invention, with whirler, colloidal metal solution is coated on substrate.
According to an aspect of the present invention, chemical plating fluid comprise by 1: 1 the first solution of volume ratio mixing match and the second solution, wherein, the first solution consist of CuSO
416g/l, Seignette salt 48g/l, NaOH28g/l, and the concentrated formaldehyde solution consisting of 12ml/l of the second solution.
According to an aspect of the present invention, scavenging solution is the NaOH solution of 0.5%.
According to an aspect of the present invention, the chemical plating fluid that cleaned substrate is placed in 30 DEG C reaches about 15 minutes.
According to an aspect of the present invention, microstructure comprises the microstructure unit of multiple array arrangement, and described microstructure unit is I shape or I-shaped derivative type metal wire structure.
According to an aspect of the present invention, microstructure comprises the microstructure unit of multiple array arrangement, and described microstructure unit is the ring-like or split ring derivative type metal wire structure of opening.
According to another main aspect of the present invention, provide a kind of method for processing microstructure, the method comprises the following steps:
A, substrate is immersed in the KOH aqueous solution, with the KOH that water cleaning removing is unnecessary after taking out after soaking;
B, again substrate is immersed AgNO
3in the aqueous solution, with the potassium ion on Ag ion exchange surface, clean with water after taking-up and dry;
C, configuration chemical plating fluid;
D, on substrate, write out micro structured pattern with laser beam;
E, clean substrate with scavenging solution, remove undosed PVP film, then heat-treat;
F, cleaned substrate is placed in chemical plating fluid, obtains microstructure.
According to an aspect of the present invention, substrate is flexible substrate.
According to an aspect of the present invention, flexible substrate is polyimide (PI) substrate.
According to an aspect of the present invention, the KOH aqueous solution is the KOH aqueous solution of 0.5M.
According to an aspect of the present invention, substrate soaks about 20 minutes in the KOH aqueous solution under 50 DEG C of conditions.
According to an aspect of the present invention, AgNO
3the aqueous solution is the AgNO of 0.1M
3the aqueous solution.
According to an aspect of the present invention, substrate is at AgNO
3about 30 minutes are soaked in the aqueous solution.
According to an aspect of the present invention, chemical plating fluid comprise by 1: 1 the first solution of volume ratio mixing match and the second solution, wherein, the first solution consist of CuSO
416g/l, Seignette salt 48g/l, NaOH28g/l, and the concentrated formaldehyde solution consisting of 12ml/l of the second solution.
According to an aspect of the present invention, scavenging solution is the H of 5%
2sO
4solution.
According to an aspect of the present invention, thermal treatment carries out 30 minutes under 250 DEG C of conditions.
According to an aspect of the present invention, the chemical plating fluid that cleaned substrate is placed in 30 DEG C reaches about 15 minutes.
According to an aspect of the present invention, microstructure comprises the microstructure unit of multiple array arrangement, and described microstructure unit is I shape or I-shaped derivative type metal wire structure.
According to an aspect of the present invention, microstructure comprises the microstructure unit of multiple array arrangement, and described microstructure unit is the ring-like or split ring derivative type metal wire structure of opening.
Will be appreciated that, the feature in the above each side of the present invention can independent assortment within the scope of the invention, as long as and not by the restriction of its order---the technical scheme after combination drops in connotation of the present invention.
Utilize method of the present invention, laser technology and electroless plating are combined, can realize at flexible base board as metal micro structure prepared by polyimide (PI).And laser beam accurately can control its location and size, can obtain structure metal micro structure pattern accurately thus, preparation precision can be low to moderate micron level.Further, pattern writes direct, without the need to mask plate.Simple to operate, program is few, and speed is fast, and efficiency is high, and cost is lower.Compared with other laser technologies, method of the present invention turn avoid the use of organic metal salt and organic solvent, environmental sound.Further, except PI substrate, method of the present invention also can be widely used in all kinds of substrate, as pottery, glass and organic resin substrate; Institute's metallizing also can unrestricted choice.
[accompanying drawing explanation]
In order to be illustrated more clearly in the technical scheme in the present invention, will be briefly described accompanying drawing of the present invention below, wherein:
Fig. 1 show schematically show the flow process according to a kind of method for processing microstructure of the present invention.
Fig. 2 then show schematically show the flow process according to another kind of method for processing microstructure of the present invention.
Fig. 3-6 show schematically show the shape of the elementary cell of the microstructure that method according to the present invention obtains.
[embodiment]
Hereafter will be described in detail to technical scheme of the present invention in conjunction with the preferred embodiments of the present invention.
Need to understand, following description (comprising accompanying drawing) is only exemplary, but not limitation of the present invention describes.Can relate to the concrete quantity of parts in the following description, but also it is to be understood that these quantity are also only exemplary, those skilled in the art can choose arbitrarily the parts of proper amt with reference to the present invention.Further, wordings such as mentioned in the present invention " first ", " second ", not represents the sequence to parts importance, is only used as difference name of parts and is referred to as.
Unless otherwise defined explicitly, the term used in the application's context has implication usually used in this field.
According to embodiments of the invention, adopt Nd:YAG laser apparatus 266nm Ultra-Violet Laser as radiating light source, laser beam after lens again substrate surface focus on, substrate is placed on one by computer-controlled mobile platform, work as platform mobile, laser beam writes out the graphic structure designed at substrate surface, and namely metallic copper microstructure is realize by controlling laser beam selectivity focusing illumination.
Fig. 1 and Fig. 2 show schematically show the flow process according to method for processing microstructure of the present invention.Its concrete preparation method can see following specific embodiment.
Embodiment one:
PVP and the AgNO3 of weight ratio 2: 1 is dissolved in concentration be about in 0.03g/ml ethanol.With microwave oven, this dissolution homogeneity is heated, heated 1 minute under 300w power every 1 minute, heat 6 times altogether, obtain brown colloidal metal solution thus.
Reaction solution is cooled to room temperature, is coated on the surface of PI substrate with whirler and dries.
Get CuSO
416g/l, Seignette salt 48g/l, NaOH28g/l are made into the first solution, get the concentrated formaldehyde solution of 12ml/l as the second solution, then mix the first solution and the second solution to form chemical plating fluid by the volume ratio of 1: 1.
PI substrate is placed on by computer-controlled platform, moves this platform by computer program, utilize laser beam to write out default micro structured pattern on this PI substrate.
By the PI substrate finished writing from after platform takes off, with the NaOH solution cleaning PI substrate of 0.5%, the PVP film that removing surface free irradiates.
Cleaned substrate is placed in the chemical plating fluid 15 minutes of 30 DEG C, obtains the metallic copper microstructure of electroless plating.
Embodiment two:
Immersed by PI substrate in the KOH aqueous solution of 0.5M, the Heating K OH aqueous solution to 50 DEG C, soaks 20 minutes, with the KOH that water cleaning removing is unnecessary after taking-up.
Again substrate is immersed in the AgNO3 aqueous solution of 0.1M, soak 30 minutes, with the potassium ion making Ag ion exchange go out surface, clean with water after taking-up and dry.
Get CuSO
416g/l, Seignette salt 48g/l, NaOH28g/l are made into the first solution, get the concentrated formaldehyde solution of 12ml/l as the second solution, then mix the first solution and the second solution to form chemical plating fluid by the volume ratio of 1: 1.
PI substrate is placed on by computer-controlled platform, moves this platform by computer program, utilize laser beam to write out default micro structured pattern on this PI substrate.
By the PI substrate finished writing from after platform takes off, the H2SO4 with 5% cleans substrate, then thermal treatment 30 minutes at 250 DEG C.
PI substrate after thermal treatment is placed in the chemical plating fluid 15 minutes of 30 DEG C, obtains the metallic copper microstructure of electroless plating.
Fig. 3-6 show schematically show the unit cell shapes of the microstructure that method according to the present invention obtains, and these shapes are pre-designed.Fig. 3 and the microstructure unit that Figure 4 shows that I shape and I-shaped derivative type metal wire structure.And Fig. 5 and Figure 6 shows that the microstructure unit of the ring-like or split ring derivative type metal wire structure of opening.Metal micro structure comprises the microstructure unit of multiple array arrangement.
According to method of the present invention, can fast, simply, efficiently and accurately at flexible base board as metal micro structure prepared by PI substrate.Further, present method avoids the use of organic metal salt and organic solvent, environmental sound.
Need to understand, except the PI substrate of flexibility, method of the present invention also can be widely used in all kinds of substrate, as pottery, glass and organic resin substrate; And institute's metallizing in addition to copper also can unrestricted choice.
Also need to understand, above according to preferred embodiment having done detailed description to the present invention, it is to be appreciated, however, that scope of the present invention is not limited to these concrete embodiments, but comprise those skilled in the art according to any modifications and changes openly can made of the present invention.
Claims (6)
1. a method for processing microstructure, the method comprises the following steps:
A, by PVP and AgNO
3being dissolved in concentration is in 0.03g/ml ethanol, is heated by this dissolution homogeneity, obtains brown colloidal metal solution; The compound method of described colloidal metal solution: heated by this dissolution homogeneity with microwave oven, heated 1 minute under 300w power every 1 minute, heated 6 times altogether;
B, described colloidal metal solution is cooled to room temperature, is coated on the surface of substrate and dries;
C, configuration chemical plating fluid; Described chemical plating fluid comprises the first solution by the volume ratio mixing match of 1:1 and the second solution, wherein, the first solution consist of CuSO
416g/l, Seignette salt 48g/l, NaOH28g/l, and the concentrated formaldehyde solution consisting of 12ml/l of the second solution;
D, write out micro structured pattern on the substrate with laser beam; Described laser beam is provided as radiating light source by Nd:YAG laser apparatus 266nm Ultra-Violet Laser;
E, clean described substrate with scavenging solution, remove undosed PVP film;
F, cleaned substrate is placed in described chemical plating fluid, obtains microstructure.
2. method according to claim 1, is characterized in that, PVP and AgNO
3weight ratio be 2:1.
3. method according to claim 2, is characterized in that, described substrate is flexible substrate.
4. method according to claim 3, is characterized in that, described flexible substrate is polyimide base film.
5. method according to claim 1, is characterized in that, described microstructure comprises the microstructure unit of multiple array arrangement, and described microstructure unit is I shape or I-shaped derivative type metal wire structure.
6. method according to claim 1, is characterized in that, described microstructure comprises the microstructure unit of multiple array arrangement, and described microstructure unit is the ring-like or split ring derivative type metal wire structure of opening.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110439939.4A CN103173724B (en) | 2011-12-26 | 2011-12-26 | Method for processing microstructure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110439939.4A CN103173724B (en) | 2011-12-26 | 2011-12-26 | Method for processing microstructure |
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| CN103173724A CN103173724A (en) | 2013-06-26 |
| CN103173724B true CN103173724B (en) | 2016-01-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI615448B (en) * | 2017-05-25 | 2018-02-21 | Donbon Paints Industrial Co Ltd | Method for preparing metal colloid for laser sintering molding |
| CN111012290A (en) * | 2019-12-20 | 2020-04-17 | 浙江清华柔性电子技术研究院 | Conformal capsule antenna structure, preparation method and wireless capsule endoscope system |
| CN111487702B (en) * | 2020-05-12 | 2021-02-12 | 深圳大学 | Grating manufacturing process for adhering heavy metal colloid to light metal film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772949A (en) * | 2005-11-17 | 2006-05-17 | 上海交通大学 | Laser induced selective chemical plating process |
| CN1772948A (en) * | 2005-11-17 | 2006-05-17 | 上海交通大学 | Laser induced selective chemical plating process for polyimide film |
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- 2011-12-26 CN CN201110439939.4A patent/CN103173724B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772949A (en) * | 2005-11-17 | 2006-05-17 | 上海交通大学 | Laser induced selective chemical plating process |
| CN1772948A (en) * | 2005-11-17 | 2006-05-17 | 上海交通大学 | Laser induced selective chemical plating process for polyimide film |
Non-Patent Citations (2)
| Title |
|---|
| 聚乙烯吡咯烷酮/AgNO3胶体用于激光诱导图形化化学镀铜;陈东升 等;《材料保护》;20101031;第43卷(第10期);第17页右栏第2段-第18页左栏第2段，图3 * |
| 聚酰亚胺膜分子自组装与激光诱导图形化学镀铜;陈东升 等;《材料保护》;20091130;第42卷(第11期);第1-4页 * |
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