CN105731365B - PDMS elastomer micro-nano processing method based on crosslinking control control transfer printing - Google Patents

PDMS elastomer micro-nano processing method based on crosslinking control control transfer printing Download PDF

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Publication number
CN105731365B
CN105731365B CN201610112350.6A CN201610112350A CN105731365B CN 105731365 B CN105731365 B CN 105731365B CN 201610112350 A CN201610112350 A CN 201610112350A CN 105731365 B CN105731365 B CN 105731365B
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China
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pdms
substrate
stamp
seal
micro
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CN201610112350.6A
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CN105731365A (en
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鲁从华
汪娟娟
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Tianjin University
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Tianjin University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/00444Surface micromachining, i.e. structuring layers on the substrate
    • B81C1/0046Surface micromachining, i.e. structuring layers on the substrate using stamping, e.g. imprinting

Abstract

The invention discloses a PDMS elastomer micro-nano processing method based on crosslinking control control transfer printing. The PDMS elastomer micro-nano processing method comprises the following steps: preparing a PDMS film to serve as a transfer printing substrate by using a pouring method; preparing a PDMS film with a surface microstrucutre to serve as a transfer printing stamp by using a replica casting method; importing a cohesive energy (soft/hard) difference between the PDMS stamp and the planar PDMS substrate by different crosslinking agent contents in the process of preparing the substrate and the stamp; and simultaneously carrying out an OP treatment on the prepared substrate and the stamp for 0.5 min, immediately adhering the substrate and the stamp, and carrying out a heating treatment to improve the contact adhesion of the substrate and the stamp, taking off the stamp, generating cohesive energy breakage on the soft party during the separation to transfer PDMS ink to the hard party, so as to obtain a PDMS film with concave or convex patterns on the surface. The PDMS elastomer micro-nano processing method disclosed by the method is simple and convenient to operate, low in cost, and is used for avoiding the defects of limited applicable range of other related technology and simple processing patterns.

Description

PDMS elastomer micro-nano processing methods based on crosslinking control trans-printing
Technical field
The present invention relates to the micro-nano process technology of soft material, and in particular to one kind is entered using crosslinking control trans-printing method The process of row PDMS patterned surfaces.
Background technology
Dimethyl silicone polymer (PDMS) is a kind of most widely used silicon substrate organic polymer material.PDMS is used as one kind Organic silicon rubber, out of doors insulating materials, gap filler, lubricant, human body shaping implantation etc. aspect have many purposes, more attach most importance to What is wanted is that it has unique application prospect in minute manufacturing.On micro/nano-scale, PDMS thickness/film is widely used in soft quarter It is erosion technology, micro-/to receive the numerous areas such as fluid control, micro-/naiio-electro-meclianical systems, bio-sensing.These applications are all relied on The surface micro-structure of PDMS.But the micro-nano process technology of PDMS elastomers is extremely limited at present, and it is limited to processing Form, it is difficult to prepare complicated fine surface patterning.At the same time, print process is extensive as a kind of simple, convenient, applicability Patterning techniques increasingly paid attention to by academia.
The content of the invention
For above-mentioned prior art, the present invention provides a kind of micrometastasis print process based on crosslinking control, prepares PDMS micro- Nanostructured pattern.The present invention is substrate from plane PDMS pieces, and simple micro-structural is carried with the surface for replicating die casting preparation The PDMS of pattern is trans-printing seal, introduces interior by the different of content of crosslinking agent in PDMS seals and substrate preparation process Cumulative (" soft/hard ") difference, shifts " ink " from the side in seal or substrate compared with " soft ", so as to realize plane PDMS substrates Surface it is controllable patterned.Use and the operating procedure of very complicated this process avoids expensive instrument, are a kind of logical PDMS micro-nano processing methods.
In order to solve the above-mentioned technical problem, a kind of PDMS elastomers based on crosslinking control trans-printing proposed by the present invention Micro-nano processing method, comprises the following steps:
Step one, by the use of replicate die casting prepare with surface micro-structure PDMS films as trans-printing seal:Will PDMS performed polymers and crosslinking agent are m in mass ratio:1 mixing, wherein, m=10 or 20;It is sufficiently stirred for forming uniform with glass bar Prepolymer;After above-mentioned prepolymer is deaerated 1 hour in multiplex vavuum pump of circulating water type, it is poured on caster;70 4h is heated at DEG C to be solidified;The film taken off is gained;
Step 2, PDMS films as the substrate of trans-printing are prepared by the use of casting method:PDMS performed polymers and crosslinking agent are pressed Mass ratio is n:1 mixing, wherein n=5~30, and m=n+10 or m=n-10;It is sufficiently stirred for forming uniform pre- with glass bar Polymer;After above-mentioned prepolymer is deaerated 1 hour in multiplex vavuum pump of circulating water type, it is poured into surface plate;At 70 DEG C Lower heating 4h is solidified;Obtain the adjustable PDMS films of thickness;
Step 3, the seal prepared to step one or the substrate that is prepared to step 2 are while carry out oxygen plasma Body surface activation process 0.5min, immediately after fits and 100 in air dry oven the seal after above-mentioned treatment and substrate Heating and thermal insulation 1h at DEG C, cools to room temperature with the furnace, removes seal, and obtaining surface has the PDMS films of depression or raised design.
Further, the mass ratio of PDMS performed polymers and crosslinking agent and PDMS performed polymers and crosslinking in step one in step 2 Agent mass ratio is different, so as to obtain one group of combination or one group of combination of soft seal/hard substrate of embossing seal chapter/flexible subserate.
If the mass ratio of PDMS performed polymers and crosslinking agent during prepared by step one into seal and step 2 preparation substrate It is designated as:Crosslinking parameter is PDMS(m:1)/PDMS(n:1), preferred crosslinking parameter is as follows in the present invention:PDMS(10:1)/PDMS(20:1)、 PDMS(10:1)/PDMS(30:1)、PDMS(20:1)/PDMS(5:1)、PDMS(20:1)/PDMS(10:1)
Compared with prior art, the beneficial effects of the invention are as follows:
In preparation method of the present invention, by being pre-adjusted PDMS seals and substrate preparation process in content of crosslinking agent regulate and control PDMS " ink " shift direction, so as to reach to the controllable patterned of PDMS planar substrates.The method of the present invention has simply, just Victory, the characteristics of applied widely.The fine of PDMS picture on surface especially can be realized simply by changing content of crosslinking agent Regulation and control, this is that current other technologies are unapproachable.
Brief description of the drawings
Fig. 1 is the atomic force microscope images of the PDMS seals that the embodiment of the present invention 1 is obtained;
Fig. 2 is the atomic force microscope images of the patterned surface PDMS substrates that the embodiment of the present invention 1 is obtained;
Fig. 3 is the atomic force microscope images of the patterned surface PDMS substrates that the embodiment of the present invention 2 is obtained.
Specific embodiment
Technical solution of the present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, described is specific Embodiment is only explained to the present invention, is not intended to limit the invention.
Embodiment 1:The PDMS films of patterned surface are prepared, step is as follows:
Step one, by the use of replicate die casting prepare with surface micro-structure PDMS as trans-printing seal:First, In mass ratio it is 10 by PDMS performed polymers and crosslinking aid S ylgard184 (being purchased from Dow corning company):1 mixing, uses glass bar It is sufficiently stirred for forming uniform prepolymer;After above-mentioned prepolymer is deaerated 1 hour in multiplex vavuum pump of circulating water type, pour Build in the silicon template (i.e. caster) with cylindrical-array, pour thickness about 1mm;4h is heated at 70 DEG C to be solidified; Carefully take the PDMS films as PDMS seals in the silicon template off, the duplication die casting prepare with surface micro-structure PDMS(10:1)The surface texture of seal is as shown in Figure 1.
Step 2, the PDMS thick films of thickness about 1mm as the substrate of trans-printing are prepared by the use of casting method;Particular content It is:First, in mass ratio it is 20 by PDMS performed polymers and crosslinking aid S ylgard184 (being purchased from Dow corning company):1 mixing, It is sufficiently stirred for forming uniform prepolymer with glass bar;Above-mentioned prepolymer is deaerated 1 in multiplex vavuum pump of circulating water type After hour, it is poured into surface plate, pours thickness about 1mm;4h is heated at 70 DEG C to be solidified;Obtain plane PDMS substrates.
Step 3, by the above-mentioned PDMS seals for preparing and substrate while carrying out oxygen plasma surface active (OP) place Reason 0.5min;The two is fitted immediately after and heats 1h at 100 DEG C in the air dry oven;Cool to room temperature with the furnace, remove PDMS seals, obtain the PDMS films of patterned surface.
Crosslinking parameter in the preparation method of the present embodiment 1 is denoted as PDMS(10:1)/PDMS(20:1).Surveyed by AFM Amount, the regular depression round dot pattern of the PDMS films surface band.The atom of the gained patterning PDMS films of the present embodiment 1 such as Fig. 2 is tried hard to It is shown.
Embodiment 2:The PDMS films of patterned surface are prepared, preparation process is substantially the same manner as Example 1, is different only in that, The mass ratio of PDMS performed polymers and crosslinking agent in step one is changed to 20:1, by the matter of PDMS performed polymers and crosslinking agent in step 2 Amount ratio is changed to 10:1, that is, parameter is crosslinked by PDMS(10:1)/PDMS(20:1)It is changed to PDMS(20:1)/PDMS(10:1), the final table for obtaining Shown in the atom of PDMS films such as Fig. 3 of the regular round dot raised design of face band is tried hard to.
Ibid, by changing preparation process in content of crosslinking agent be crosslinked parameter, such as:Can be PDMS(10:1)/ PDMS(20:1)、PDMS(10:1)/PDMS(30:1)、PDMS(20:1)/PDMS(5:1)、PDMS(20:1)/PDMS(10:1)In any group of.
To sum up, the inventive method mainly use content of crosslinking agent in PDMS preparation process it is different introduce PDMS seals with Cohesive energy (i.e. soft/hard) difference between PDMS substrates, and by surface active and heat raising seal contact between substrate Adhesive attraction, when separating the two, is utilized " soft side " that cohesive energy fracture occurs and provides PDMS " ink " and be transferred to by contact " hard side ", so as to realize the controllable fine patterning of plane PDMS substrates.By " soft/hard " combination of the difference of seal and substrate with And repeatedly printing can obtain complicated fine PDMS surface micro-structures.This method not only avoids other correlation techniques and is applicable model Limit, the simple shortcoming of processing graphic pattern are with, and avoid the use of complex and expensive instrument, therefore, its is applied widely, operation Simplicity, low cost can be used as a kind of micro-nano process technologies of general PDMS.
Although above in conjunction with figure, invention has been described, the invention is not limited in above-mentioned specific embodiment party Formula, above-mentioned specific embodiment is only schematical, and rather than restricted, one of ordinary skill in the art is in this hair Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to guarantor of the invention Within shield.

Claims (2)

1. it is a kind of based on the PDMS elastomer micro-nano processing methods for being crosslinked control trans-printing, it is characterised in that including following step Suddenly:
Step one, by the use of replicate die casting prepare with surface micro-structure PDMS films as trans-printing seal:
In mass ratio it is m by PDMS performed polymers and crosslinking agent:1 mixing, wherein, m=10 or 20;It is sufficiently stirred for being formed with glass bar Uniform prepolymer;After above-mentioned prepolymer is deaerated 1 hour in multiplex vavuum pump of circulating water type, caster is poured into On;4h is heated at 70 DEG C to be solidified;The film taken off is gained seal;
Step 2, PDMS films as the substrate of trans-printing are prepared by the use of casting method:
In mass ratio it is n by PDMS performed polymers and crosslinking agent:1 mixing, wherein, during m=10, when n=20 or n=30, m=20, n =5 or n=10;It is sufficiently stirred for forming uniform prepolymer with glass bar;Above-mentioned prepolymer is multiplex true in circulating water type After being deaerated 1 hour in empty pump, it is poured into surface plate;4h is heated at 70 DEG C to be solidified;Obtain the adjustable PDMS films of thickness;
The substrate that step 3, the seal and step 2 that are prepared to step one are prepared is while carry out oxygen plasma surface Activation process 0.5min, immediately after by the seal after above-mentioned treatment and substrate fit and in the air dry oven at 100 DEG C plus Heat insulation 1h, cools to room temperature with the furnace, removes seal, and obtaining surface has the PDMS films of depression or raised design.
2. a kind of based on the PDMS elastomer micro-nano processing methods for being crosslinked control trans-printing according to claim 1, it is special Levy and be, PDMS performed polymers and crosslinking agent quality ratio be not in the mass ratio of PDMS performed polymers and crosslinking agent and step one in step 2 Together, so as to obtain one group of combination or one group of combination of soft seal/hard substrate of embossing seal chapter/flexible subserate.
CN201610112350.6A 2016-02-29 2016-02-29 PDMS elastomer micro-nano processing method based on crosslinking control control transfer printing Expired - Fee Related CN105731365B (en)

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CN107522163B (en) * 2016-09-26 2019-07-05 西北工业大学 A kind of high guarantor's type transfer method of PDMS structure
CN109021270A (en) * 2017-06-11 2018-12-18 吴浪 PDMS elastomer micro-nano processing method based on crosslinking control trans-printing
CN109808319B (en) * 2017-11-20 2020-09-22 Tcl科技集团股份有限公司 Stamp and preparation method thereof and quantum dot transfer printing method
CN111268640A (en) * 2020-03-04 2020-06-12 电子科技大学 Adaptive super-hydrophobic surface and preparation method thereof
CN114953797A (en) * 2022-06-22 2022-08-30 合肥工业大学 Anti-distortion transfer printing method and transfer printing device for micro-nano structure

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US6805809B2 (en) * 2002-08-28 2004-10-19 Board Of Trustees Of University Of Illinois Decal transfer microfabrication
CN1686781A (en) * 2005-04-28 2005-10-26 上海交通大学 Method for making epoxy resin microstructure device
KR100879790B1 (en) * 2007-07-23 2009-01-22 한국과학기술원 Method for fabricating various fine patterns using a polymer mold
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