CN100431190C - Organic field effect transistor orientation layer and its preparing method and use - Google Patents
Organic field effect transistor orientation layer and its preparing method and use Download PDFInfo
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- CN100431190C CN100431190C CNB2004100541988A CN200410054198A CN100431190C CN 100431190 C CN100431190 C CN 100431190C CN B2004100541988 A CNB2004100541988 A CN B2004100541988A CN 200410054198 A CN200410054198 A CN 200410054198A CN 100431190 C CN100431190 C CN 100431190C
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Abstract
The present invention provides an orientation layer used for an organic field effect tube, a method used for forming the orientation layer and a new-type device method which uses the orientation layer as an insulating layer to increase the carrier mobility of the organic field effect tube (OFET). The orientation layer is prepared from polyimide (PI) polymers and is treated by light orientation, according to the present invention, good orientation effects are obtained on the PI orientation layer, the order degree of the molecular arrangement of organic semiconductor transmission layers can be increased, and the carrier mobility of the organic semiconductor transmission layers is increased. Therefore, the characteristic of the channel carrier mobility of the organic field effect tube (OFET) which uses the orientation layer as the insulating layer is greatly increased.
Description
Technical field
The invention belongs to organic field effect tube (OFET) technical field, be specifically related to a kind of oriented layer and its production and application with good orientation characteristic.
Technical background
Field-effect transistor (FET) is to utilize grid voltage to control the break-make of channel current, thereby forms required switching characteristic.Organic field effect tube (OFET) or OTFT (OTFT) be with semiconducting organic polymer as insulating barrier and organic semiconductor transport layer, principle is consistent with common field effect transistor.Compare with the inorganic electronic device, the organic electronic device preparation method is simple, and is with low cost, is fit to make broad area device, but also can prepares on polymer matrix film, obtains flexible device, therefore, has very wide application prospect.From people such as A.Tsumura
[1]Be that the performance of OTFT had obtained continuous raising, people such as Y.-Y.Lin after semi-conducting material prepared OTFT with polythiophene first
[2]Having obtained carrier mobility with the pentacene material is 1.5cm
2The organic transistor of/Vs, switch current ratio reaches 10
8Also obtained gratifying achievement in some application facet, its performance can compare favourably with the non-setting silicon transistor of present use fully, and it then is far superior to non-setting silicon transistor in manufacturing cost on creating conditions simultaneously.
Even so, in the higher application facet of ask for something, still there is very big deficiency in organic field effect tube, especially aspect carrier mobility and the switch current ratio aspect.
Because a lot of semiconducting organic polymers are except having general semi-conductive character, also have and many character like the liquid crystalline phase, again because the structure of organic semiconductor transistor also has some similitude with LCD, so can use for reference some technological means in LCD field.Traditional friction orientation method is the organic polymer thin film by formation one deck such as polyimides (PI) and polyamide on substrate, solidifies this film, uses then such as cotton, and artificial silk, nylon wait the method for this product that rubs to form oriented layer.
This method that is used for forming oriented layer is simply easy, and very effective, obtains the extensive employing of industrial quarters.But a large amount of dust that produces in the friction process and charged particle may pollute attached on this oriented layer, increase the defect concentration of oriented layer; And surface irregularities such as artificial silk, nylon may cause the inhomogeneities that is orientated; And the electrostatic charge that is produced in friction process also can exert an influence to the switching characteristic of OFET, and serious words may puncture the raceway groove of OFET, destroys the OFET device.
For addressing the above problem, we attempt using contactless orientation technology.Because the arrangement of liquid crystal molecule is not because the existence of oriented layer surface rill, but since the interaction between liquid crystal surfactant and the liquid crystal molecule cause
[3]So the researcher has carried out the research of noncontact orientation technology, mainly contains oblique side's vapour deposition method, LB (Langmuir-Blodgett) embrane method, photolithography, optical alignment method etc.Particularly with filming on the polarizing light irradiation substrate, the optical alignment method that makes it to produce the liquid tropism is simple and easy to do because of it, studies more.As far back as the eighties middle period in last century, people such as M.Schardt have just developed a kind of novel liquid crystal aligning technology, be polarized ultraviolet polymer (Liner Photopolymerization by Polarized UVLight, LPP), its basic principle is to utilize the photochemical reaction of UV photosensitive polymer monomer material, the network that the substrate surface that scribbles this light-sensitive material or photosensitive polymer monomer are formed produces anisotropic character, thereby liquid crystal molecule is aligned under the effect of this anisotropy power, this technology has overcome the shortcoming of friction techniques, make simultaneously friction techniques can't realize that the multidomain technology that substantially improves visual angle of liquid crystal display is achieved.We will use for reference this technology, be used for the preparation field of OFET, develop a kind of non-contact optical method for alignment that can not produce dust or static.According to a kind of so harmless method for alignment, the linear polarization ultraviolet lighting is mapped on the light oriented layer, makes the light oriented layer have the orientation characteristic, and uniform thus induced orientation organic semiconductor transport layer, improves the carrier mobility characteristic of organic semiconductor transport layer.The polymeric material that is used for the light orientation mainly comprises cinnamate derivative, Coumarins, photic isomery class and polyimides (PI) etc.Photo orientated mechanism can be divided into from different perspectives that body is induced and spatial induction, photopolymerization, photolysis and light isomery etc.
[3,4]Wherein, the oriented layer material of photopolymerization is cinnamate derivative normally, contains the polyimide and the asymmetrical Coumarins of optical active group; The normally photic isomery class of the oriented layer material material of photic isomerization; The oriented layer material of photodecomposition, according to existing report,
[5]Mainly be that the monomer that is used for rubbing contains cyclobutane, cyclohexane, the polyimides base polymer of construction units such as pentamethylene.
List of references:
[1]A.Tsumura，H.Koezuka，and?T.Ando，Appl.Phys.Lett.，49，1210(1986).
[2]Y.-Y.Lin，D.J.Gundlach，S.F.Nelson，and?T.N.Jackson，IEEE?Electron?Device?Letters，18，606(1997).
[3]S.Gong，J.Kanicki，M.Lan，et?al.，Jpn.J.Appl.Phys.38，5996(1999).
[4]E.Kim，O.Park，H.Li，et?al.，IDW’97，105-108(1997).
[5]M.Nishikawa，J.L.West，Mol.Cryst.&Liq?Cryst.，333，165(1999).
Summary of the invention
Purpose of the present invention is as follows:
(a) provide a kind of oriented layer that is used for the good orientation characteristic of having of organic field-effect tube;
(b) provide a kind of method that is used for forming this kind oriented layer;
(c) provide a kind of organic field effect tube (OFET) that adopts this oriented layer as insulating barrier.
To solve the lower problem of channel carrier mobility in the organic field effect tube (OFET).
The present invention includes three contents: a kind of oriented layer with good orientation characteristic; A kind of method for preparing this kind oriented layer and a kind of with the organic field effect tube (OFET) of this kind oriented layer as insulating barrier.
Oriented layer with good orientation characteristic provided by the invention is that a kind of polyimides (PI) base polymer is formed (shown in 3 among Fig. 1 or shown in 3 among Fig. 2).Contain cyclobutane in this polyimides (PI) monomer, cyclohexane, construction units such as pentamethylene, or contain the acetal structure on the main chain.These polymer are not subjected to thermal degradation when from polymer molecule, can be easy to form motion state and consider that vitrification point is preferably lower than 200 ℃.
The method that is used for forming this polyimides (PI) oriented layer provided by the invention, it may further comprise the steps:
(a) filming performance of formation is good on a substrate, the polyimides of stable performance (PI) layer (oriented layer, insulating barrier);
(b) the linear polarization ultraviolet lighting is mapped on made polyimides (PI) insulating barrier (oriented layer), it is carried out orientation process.
In conjunction with the accompanying drawings 2～5, we can be more directly perceived, understands the particular content of the method in more detail.As shown in Figure 2,3 expressions are deposited on polyimides (PI) oriented layer on this substrate, 2 expression ITO (tin indium oxide) figures, and 1 certain substrat structure of expression under the irradiation of online polarized ultraviolet, carries out orientation process.Fig. 3 represents the molecular long axis distribution situation of PI layer before the illumination for the first time, clearly, is uniformly in the distribution of all directions, on figure, show, exactly with vertical with the parallel direction in polarization direction in have equal extent distribution.Fig. 4 is through the PI layer molecularly oriented situation after the linear polarization UV-irradiation.Because the ultraviolet photon parallel with the PI molecular chain orientation is absorbed, and interrupted thereby cause at the molecule side chain with this linear polarization ultraviolet light parallel direction, as shown in Figure 4.Fig. 5 represents through after the linear polarization UV-irradiation (step of Fig. 4), shown PI layer, at this moment, through after the linear polarization UV-irradiation of certain intensity, owing to interrupted with the molecule side chain of this linear polarization ultraviolet light parallel direction, just cause the side chain of the direction vertical to occupy certain advantage, thereby caused the orientations of PI molecule, thereby reached our processing intent with this linear polarization.
Carrying out with polarized ultraviolet in the process of orientation process, used ultraviolet source can be Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon sympathetic response lamp, xenon lamp, excimer laser etc., spectrum peak are preferably the ultraviolet ray of 320～450nm wavelength, and power density is 5～30mW/cm
2
The ultraviolet ray in above-mentioned optimal wavelength zone can be by also using filter with above-mentioned light source, and methods such as diffraction grid obtain, and for for simplicity, also can use polarization plate with above-mentioned light source.
Use the organic field effect tube (OFET) of oriented layer of the present invention, as shown in Figure 1, comprising: be used as the glass substrate (1) of substrate down; Be formed at down the ITO layer (2) on the substrate, the grid of this OFET of double as, be formed at polyimides (PI) insulating barrier (3) on this ITO layer, this oriented layer (insulating barrier) is through aforesaid smooth orientation process; Form with the PI layer on organic semiconductor transport layer (shown in 4), require this semiconducting organic polymer that the liquid crystalline phase temperature of broad, promptly higher T are arranged
N-1Temperature, and the source electrode on this, drain electrode, wherein source, drain electrode are metal and make.
The oriented layer that insulating barrier is made by as above desired polyimides (PI) base polymer is made, and film forming and light orientation process through as noted above have obtained good orientation effect.By the induction of orientation insulating barrier, organic semiconductor transport layer molecularly oriented is arranged, thereby improved the carrier mobility characteristic of organic semiconductor transport layer.
Description of drawings
Fig. 1 is a side cutaway view of organic field effect tube of the present invention (OFET);
Fig. 2 is the section of structure of the light method for orientation treatment of oriented layer of the present invention;
Fig. 3 is the molecular long axis distribution diagram of PI layer before the illumination for the first time.
Fig. 4 is for illustrating through the postradiation PI layer of primary line polarized ultraviolet molecular distribution.
Fig. 5 is the postradiation PI layer of a warp polarized ultraviolet molecularly oriented diagram.
Fig. 3-Fig. 5 has represented the molecularly oriented process under the online polarized ultraviolet irradiation of polyimide layer.
Number in the figure: 1 is substrate, and 2 is the ITO layer, and 3 is oriented layer, and 4 is the organic semiconductor transport layer, and 5 is source electrode, and 6 are drain electrode, and 7 is the linear polarization ultraviolet light.
Embodiment
Describe content of the present invention in detail with embodiment below, but the present invention has more than and is limited to this scope.
Embodiment
The RN-1333 type PI that the polyimides that we use (PI) provides as Hitachi chemical industry (Nissan Chemical Industry), concentration is 5wt%.We are diluted to 2wt% with it during use.On a clean glass substrate, form the ITO electrode earlier, use the method for photoetching then, form gate patterns on substrate, used polyimides (PI) solution is after ultrasonic wave disperses 20-30 minute, be spun on the ito glass substrate, control certain spin speed and time.The substrate of will filming then placed on 100 ℃ the hot platform dry 5 minutes, carried out prebake and handled, and placed 250 ℃ cleaning oven 1 hour again, carried out the post bake cured.Afterwards, naturally cool to room temperature.
Then, be 10mW/cm with power density
2Ultrahigh pressure mercury lamp with spectrum peak be the direct vertical irradiation of linear polarization ultraviolet light about 365nm to above-mentioned orientation insulating barrier, shown in accompanying drawing 2～5, irradiation time was controlled at 8 minutes, so that the PI layer is carried out orientation process.This polarization plate does not see through the ultraviolet light that wavelength ratio 320nm lacks for send the polarization plate etc. of lachs (registered trade mark) glass.
After PI orientation insulating barrier disposes, use the method for vacuum evaporation again, the organic semiconducting materials pentacene evaporation that will have liquid crystalline phase forms the organic semiconductor transport layer on oriented layer.Be lower than 10 again
-3Under the Pa air pressure, evaporation metal gold (Au) serves as source electrode and drain electrode lentamente.At last, device is carried out encapsulation process, make organic field effect tube (OFET) thus, as shown in Figure 1.
Claims (3)
1, a kind of oriented layer of organic field effect tube is characterized in that being made up of the polyimides base polymer, contains in the monomer whose on cyclobutane, cyclohexane, cyclopentane structure unit or the main chain and contains the acetal structure; Wherein:
The vitrification point of described polymer is lower than 200 ℃;
This oriented layer is coated on the ITO electrode, and this ITO electro-deposition is on substrate, and oriented layer has been passed through the light orientation process.
2, one forms the method for oriented layer according to claim 1, it is characterized in that may further comprise the steps:
(a) on an ITO electrode, form the polyimide insulating barrier;
(b) the linear polarization ultraviolet lighting is mapped on the made insulating barrier, utilizes the photolysis effect that it is carried out orientation process;
Wherein: contain cyclobutane in the monomer of described insulating barrier, cyclohexane contains the acetal structure on cyclopentane structure unit or the main chain;
Described polyimide is polymer-coated to form insulating barrier on the ITO electrode, and this ITO electro-deposition is on substrate; Described light source with the linear polarization UV-irradiation is Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon sympathetic response lamp, xenon lamp, excimer laser, and its spectrum peak is 320-450nm, and power density is 5-30mW/cm
2
3, a kind of use organic field effect tube of oriented layer according to claim 1, it is characterized in that comprising: substrate (1), the ITO layer (2) and the insulating barrier that are formed on the substrate also are oriented layer (3) simultaneously, be formed at the organic semiconductor transport layer (4) on this insulating barrier, and source electrode on this (5) and drain electrode (6) formation; Wherein, said insulating barrier is through orientation process as claimed in claim 2.
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| CN100555702C (en) * | 2006-04-29 | 2009-10-28 | 中国科学院长春应用化学研究所 | Organic semiconductor crystal thin film and method for preparation of weak oriented epitaxial growth and application |
| CN101924182B (en) * | 2009-06-12 | 2012-07-11 | 中国科学院化学研究所 | Method for measuring glass transition temperature of polymer |
| CN101894913B (en) * | 2010-06-11 | 2011-09-07 | 吉林大学 | Method for preparing macromolecular field effect transistor with ultrahigh charge mobility |
| JP6110801B2 (en) * | 2014-03-07 | 2017-04-05 | 富士フイルム株式会社 | Organic thin film transistor |
| CN109360906B (en) * | 2018-09-13 | 2020-10-09 | 云谷（固安）科技有限公司 | Method of manufacturing organic light emitting display device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1366685A (en) * | 2000-02-28 | 2002-08-28 | 东丽株式会社 | Polyester film for heat-resistant capacitor, metallized film thereof, and heat-resistant film capacitor containing the same |
| CN1099138C (en) * | 1991-01-07 | 2003-01-15 | 国际商业机器公司 | Superconducting field-effect transistors with inverted misfet structure and method for making the same |
| WO2003107450A1 (en) * | 2002-06-13 | 2003-12-24 | Siemens Aktiengesellschaft | Substrate for an organic field effect transistor, use of said substrate, method for increasing the charge carrier mobility, and organic field effect transistor (ofet) |
| US6676857B2 (en) * | 2001-07-25 | 2004-01-13 | Merck Patent Gesellschaft Mit | Mono-, oligo- and poly-4-fluorothiophenes and their use as charge transport materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1099138C (en) * | 1991-01-07 | 2003-01-15 | 国际商业机器公司 | Superconducting field-effect transistors with inverted misfet structure and method for making the same |
| CN1366685A (en) * | 2000-02-28 | 2002-08-28 | 东丽株式会社 | Polyester film for heat-resistant capacitor, metallized film thereof, and heat-resistant film capacitor containing the same |
| US6676857B2 (en) * | 2001-07-25 | 2004-01-13 | Merck Patent Gesellschaft Mit | Mono-, oligo- and poly-4-fluorothiophenes and their use as charge transport materials |
| WO2003107450A1 (en) * | 2002-06-13 | 2003-12-24 | Siemens Aktiengesellschaft | Substrate for an organic field effect transistor, use of said substrate, method for increasing the charge carrier mobility, and organic field effect transistor (ofet) |
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