CN100495640C

CN100495640C - Making method of self-limited boundary film graphics

Info

Publication number: CN100495640C
Application number: CNB2007100365937A
Authority: CN
Inventors: 许军; 富春
Original assignee: Fudan University
Current assignee: Sino flexible opto electronic (Chuzhou) Co., Ltd.
Priority date: 2007-01-18
Filing date: 2007-01-18
Publication date: 2009-06-03
Anticipated expiration: 2027-01-18
Also published as: CN101055830A

Abstract

The invention belongs a thin film producing technic field, in particular, a boundary slef-restriction thin film producing method. The method comprises steps of firstly forming an obstructing layer on a glass or plastic substrate, forming a thin film above the obstructing layer by using a solution or a suspension of a film forming material of the obstructing layer having solubility or dispersibility and by a printing method, etc., forming a boundary at edges of a film-forming region by a self-bank effect, then performing anneal process on the substrate based on request, and removing the obstructing layer. The formed boundary slef-restriction thin film has a continuous boundary and a good film thickness uniformity. The produced thin film can be used in a printed circuit board (PCB), an organic light emitting diode (OLED), an organic field effect tube (OFET), a color filer (CF), a micro-lens, etc.

Description

The film pattern preparation method of self-limited boundary

Technical field

The invention belongs to the film preparing technology field, be specifically related to a kind of can be graphically, surface method for manufacturing thin film, particularly a kind of film pattern preparation method of self-limited boundary uniformly.

Background technology

At present, traditional film preparing technology, that is used widely in the industry generally has methods such as vacuum coating, photoetching, ion beam etching, silk screen printing, chemical vapor deposition (CVD).But except not high silk screen printing of precision etc., existing in order to prepare superfine film as photoetching, ion beam etching technical method, all there are shortcomings such as cost height, step complexity, very flexible.Therefore, many enterprises and research institution are all in the new technology of attempting seeking to be used to prepare high-performance and superfine thin-film device, to be adapted to the application in Organic Light Emitting Diode (OLED), organic field-effect tube (OTFT), colored filter (Color Filter), microsensor fields such as (Microsensor).

Traditional photolithographicallpatterned step complexity, cost are big, template (mask) cost of manufacture is higher, lack flexibility, and need to use a large amount of chemical agents in the process of preparation, cause environmental pollution.The photoetching process preparation process of the conductive pattern film of knowing as shown in Figure 1, its process must be through many steps such as deposition film forming, coating photoresist, exposure, development, etching, cleaning and oven dry.

Recently there is the new technology of a class to be called as directly print (Direct Printing), is hopeful to replace prior art to become new low cost and superfine film preparing technology.Directly print (Direct Printing) be meant that complex processes such as obstructed over etching, mask directly deposit to the surface with used thin-film material, its representative is inkjet technology (Ink-jet Printing).The characteristics of utilizing inkjet technology to prepare film have that cost is low, step simple, not high to environment and equipment requirements, be fit to large-scale production, high accuracy and graphical flexible etc.

NSK one Seiko Epson Corporation and the cooperation of Dutch PHILIPS Co. utilize inkjet technology to prepare polymer LED (PLED), and its luminous efficiency and performance have reached commercial application requirements.The nano particle metal material (Nanopaste) of the Harima company exploitation of Japan forms printable ink with gold or silver-colored nano-particle material, utilizes inkjet technology to prepare the precision that the plain conductor live width reaches high (live width 10 μ m).

But, one of major defect that inkjet technology exists at present is that formed film runs into coffee ring (coffee ring) effect easily in preparation process, promptly, cause the inhomogeneous and defective of thickness because the volatilization of liquid forms the surface topography of the thick intermediate thin in edge.This shortcoming has influenced film forming uniformity of inkjet printing and planarization to a great extent, causes that further there is the possibility of decreased performance or generation defective in the prepared film device.At present, solution to this problem is being devoted in many researchs.

Summary of the invention

The objective of the invention is to propose a kind ofly can overcome the coffee toroidal effect that in the graphical thin-film process of preparation, is produced, thereby can improve the preparation method of film planarization and inhomogeneity film pattern.

The film pattern preparation method that the present invention proposes, be in order to inkjet printing mode or other directly print (Direct Printing) be the film pattern preparation method of the self-limited boundary on basis, concrete steps are as follows:

(1) provides a substrate;

(2) above this substrate, form a barrier layer;

(3) filmogen is dissolved or dispersed in the solvent, preparation forms solution or suspension;

(4) according to the prior figure of design, the solution or the suspension of filmogen is deposited on the barrier layer top, form the film of one deck patterning, and become diaphragm area at the edge spontaneous formation border;

(5) anneal as required, remove barrier layer.

Wherein:

Employed substrate is glass, plastics or organic material.

Employed barrier material is the material with solubility, for example polymethyl methacrylate (PMMA) and polyimides (PI).

Employed filmogen is the material with solubility or dispersibility, for example gold nano grain and silver nano-grain material.

Employed solvent has dissolubility or dispersiveness simultaneously to described barrier material and described filmogen.

Before film forming step, be formed at the substrate top with barrier layer earlier, the method that forms barrier layer is spin-coating method or non-spin-coating method.

The method that forms graphical film is inkjet printing methods, transfer printing or silk screen print method, or other wet method film build methods.When film forming, filmogen forms from the border that limits under the effect of barrier layer.

Can be by being controlled to the volume and the membrane formation times of film temperature (spending to 100 degree), filmogen droplet, pattern, size and the film forming thickness of control thin film boundary from 0.

When film forming, it is graphical to adopt mode of printing to realize.

The temperature of described annealing process is that annealing time is between 10 minutes to 90 minutes between 200 degree are spent to 1000.

Can overcome coffee cup effect in the existing method by the film pattern of the inventive method preparation, thereby the planarization of film and uniformity are all very good, can be used for preparing high-performance and superfine thin-film device, as be applied in printed substrate (PCB), Organic Light Emitting Diode (OLED), organic field-effect tube (OTFT), colored filter (CF), the lenticule etc.

Description of drawings

Fig. 1 (a)-(g) is that the photoetching process of the conductive pattern film known is made the flow process profile.

Fig. 2 (a)-(e) is that the conductive pattern film in the embodiment of the invention is made the flow process profile.

Number in the figure: substrate-10; Need the material-20 of film forming; Photoresist-30; Mask plate-40; Graphic films-21, substrate-100; PMMA barrier layer-110; Metal nanoparticle suspension-130; Conductive pattern film-120; From the border-121 that limits.

Embodiment

For above-mentioned purpose of the present invention, feature and advantage can be become apparent, a preferred embodiment cited below particularly, and cooperate appended diagram, be described in detail below.But scope of the present invention is not limited by it, should be as the criterion with claim institute restricted portion.

Embodiment 1: please refer to the flow chart of Fig. 2 (a) to Fig. 2 (e).

At first, please refer to shown in Fig. 2 (a), a glass substrate 100 is provided, and clean, and preferably above glass substrate 100, form a polymethyl methacrylate (PMMA) barrier layer 110 with deionized water.The method that forms PMMA barrier layer 110 can be rotary coating (Spin Coating) or non-rotating coating (Spinless Coating).Then silver nano-grain is scattered in and forms suspension 130 in the acetone solvent.

Then, please refer to shown in Fig. 2 (b), the suspension 130 of silver nano-grain is deposited on the top of PMMA barrier layer 110, carry out graphically according to prior design when deposition, be the conductive pattern film 120 of circle herein.The method that forms conductive membrane layer 120 can be an inkjet printing, perhaps other wet method film build methods.Then, please refer to shown in Fig. 2 (c), when silver-colored nano suspending liquid 130 is deposited to the top of PMMA barrier layer of glass substrate, the solvent of suspension will be deposited the PMMA material dissolves in zone, form the groove with certain depth and the border 121 of periphery.Treat only to stay silver conductive film 120 and border 121 thereof after the solvent evaporates.The about 0.1 μ m-0.3 μ m of the thickness range of silver conductive film 120, the height on formed border 121 is 1.0 μ m-1.5 μ m.Then, please refer to shown in Fig. 2 (d), carry out annealing process.The temperature of annealing is 300 degree, and annealing time is 20 minutes, makes PMMA barrier layer 110 be heated removal.Simultaneously, at high temperature the anti-condensation product matter of silver nano-grain coated outside is removed in the conductive membrane layer 120, and forms more smooth film pattern.At last, please refer to Fig. 2 (e), formed conductive silver graphic films is the homogeneous film that has self-limited boundary.

Embodiment 2, please refer to the flow chart of Fig. 2 (a) to Fig. 2 (e) equally.

At first please refer to shown in Fig. 2 (a), a glass substrate 100 is provided, and clean with deionized water.Form a polyimides (PI) barrier layer 110 above glass substrate 100, the method that forms barrier layer 110 can be rotary coating (SpinCoating) or non-rotating coating (Spinless Coating).Then silver nano-grain is scattered in and forms suspension 130 in the chloroform solvent.Then, please refer to shown in Fig. 2 (b), the suspension 130 of silver nano-grain is deposited on the top of polyimides barrier layer 110, carry out graphically according to prior design when deposition, be rectangle herein.The method that forms rectangular conductive thin layer 120 can be an inkjet printing, perhaps other wet method film build methods.

Then please refer to Fig. 2 (c), when silver-colored nano suspending liquid 130 is deposited to the top of polyimides barrier layer of glass substrate, the solvent of suspension will dissolve the polyimides of deposition region, form the groove with certain depth and the border 121 of periphery.Treat only to stay silver conductive film 120 and border 121 thereof after the solvent evaporates.Then, please refer to shown in Fig. 2 (d), anneal, the temperature of annealing is 400 degree, and the time is 30 minutes, makes polyimides (PI) barrier layer 110 be heated removal, simultaneously, conductive membrane layer 120 at high temperature, the anti-condensation product matter of silver nano-grain coated outside is removed, and forms more smooth film pattern.At last, please refer to Fig. 2 (e), formed conduction rectangular film is the homogeneous film that has self-limited boundary.

According to the foregoing description, before depositing metal films conductive layer 120, form a barrier layer 110 films earlier, for example be to form the PMMA layer that thickness is 100nm in the spin coating mode.Owing to form groove from boundary effect, the higher border 121 of spontaneous formation thickness in the marginal portion makes the interior metal particle suspension of groove form the conductive layer 120 of preferable distribution, has the function of planarization in the time of above metal material deposits to barrier layer.Except the planarization effect; barrier layer can also stop the metal material of deposition to contact with the surface of barrier layer below; if in manufacturing process, between glass substrate and barrier layer, add other conducting function materials; this barrier layer can stop in preparation process metal electrode with below the contacting of conducting function material layer; thereby reach the effect of insulation protection; after barrier layer is removed in annealing, make the electrode material of exposed below conducting function material layer and top form selective exposure.

Technology contents of the present invention and technical characterstic disclose as above, yet those of ordinary skills still may be based on instruction of the present invention and enlightenments and done all replacement and modifications that does not deviate from spirit of the present invention.Therefore, protection scope of the present invention should be not limited to those disclosed embodiments, and should comprise various do not deviate from replacement of the present invention and modifications, and is contained by claim of the present invention.

List of references

1.R.Satoh，S.Naka，M.Shibata，H.Okada，H.Onnagawa，Self-Aligned?Bank?Formation?ofOrganic?Electroluminescent?Devices?Using?Ink-Jet?Printing?Method，Jpn.J.Appl.Phys.43，2004，7725-7728.

2.B.-J.de?Gans，P.C.Duineveld，U.S.Schubert，Inkjet?Printing?of?Polymers?State?of?the?Art?andFuture?Developments，Adv.Mater.16，2004，203-213.

3.Robert?D.Deegan?et?al.，Capillary?flow?as?the?cause?of?ringstains?from?dried?liquid?dropsNATURE，389，1997，827-829.

Claims

1, a kind of preparation method of film pattern of self-limited boundary is characterized in that, concrete steps are as follows:

(1) provides a substrate;

(2) above this substrate, form a barrier layer;

(5) whether basis is removed barrier layer and is determined whether anneal, and removes barrier layer as needs, then anneals;

Wherein: employed substrate is glass, plastics;

Described barrier material is the material with solubility;

Employed filmogen is the material with solubility or dispersibility;

2, the film pattern preparation method of self-limited boundary according to claim 1 is characterized in that the method for formation barrier layer in the step (2) is spin-coating method or non-spin-coating method.

3, the film pattern preparation method of self-limited boundary according to claim 1 is characterized in that the method for formation patterned film in the step (4) is inkjet printing methods, transfer printing or silk screen print method.

4, the film pattern preparation method of self-limited boundary according to claim 1, when it is characterized in that in the step (4) film forming, filmogen forms from the border that limits under the effect of barrier layer.

5, the film pattern preparation method of self-limited boundary according to claim 1 is characterized in that pattern, size and film forming thickness that volume by being controlled to film temperature, filmogen droplet and membrane formation times are controlled thin film boundary.

6, the film pattern preparation method of self-limited boundary according to claim 1, the temperature that it is characterized in that described annealing be 200 the degree to 1000 the degree, annealing time is 10 minutes to 90 minutes.