CN106356453A - Asymmetric-structure-based organic semiconductor thin film oriented-preparation method and characterization method - Google Patents
Asymmetric-structure-based organic semiconductor thin film oriented-preparation method and characterization method Download PDFInfo
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- CN106356453A CN106356453A CN201610866170.7A CN201610866170A CN106356453A CN 106356453 A CN106356453 A CN 106356453A CN 201610866170 A CN201610866170 A CN 201610866170A CN 106356453 A CN106356453 A CN 106356453A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/8422—Investigating thin films, e.g. matrix isolation method
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N2021/8477—Investigating crystals, e.g. liquid crystals
Abstract
The invention discloses an asymmetric-structure-based organic semiconductor thin film oriented-preparation method and a characterization method. The oriented-preparation method is characterized in that a semiconductor precursor solution is delivered to a specified position of a substrate in a non-contact material delivery manner by adopting picoliter-level droplets jetted according to requirements and a digital direct writing patterning technology on the basis of a micro-nano inkjet printing technology, and then a guiding function in semiconductor growth is realized to obtain an oriented-growing semiconductor thin film on the basis of the asymmetric surface tension action on the solvent on the substrate and a surface energy gradient formed on the surface thereof. According to the methods, oriented growth of a small-sized inner thin film is realized, and the thin film of which growth orientation and continuity thereof are effectively controlled has an anisotropic optical characteristic and long-range order coherence information, and is expected to be applied to high-frequency organic thin film transistor and array light field sensors.
Description
Technical field
The present invention relates to a kind of method of organic semiconductor thin-film oriented growth and characterizing method, belong to printed electronics
Field.
Background technology
Printed electronics are to prepare skill based on the solwution method patterned film such as flexible organic material system and inkjet printing
Art is realized producing the electronic product of low cost under cryogenic.The manufacture of wherein OTFT be key technology it
One.The mobility of the organic material of high mobility can reach 10cm at present2v-1s-1Magnitude, the development of this kind of material makes to be based on
The printed electronic of the device of OTFT has quite wide application potential.The application of current organic electronic is mainly subject to
It is formed on its poor high-frequency work ability, the Main Bottleneck of correlation technique is that printed patterns technology is capable of in itself first
Limited precision, therefore device critical dimensions can not significantly reduce as needed, and small-sized and patterns of high precision technique are real
The inevitable requirement of existing high-frequency domain ability to work.Another technical bottleneck is, the conductive capability of organic semiconductor thin-film and thin film
Crystallization shape is closely related with molecules align direction, that is, it has anisotropic electrical conductivity, therefore prepares high-quality
The orientation of molecule in the uniform device of performance and its array request energy effective control thin film.
The film preparing technology of existing controlled made membrane growth behavior and molecules align mode has lifting coating technique, molten
Liquid shears film preparing technology, also has some as using inclined substrate instillation precursor liquid or thin based on solution evaporation restriction scheme
Film orientation technology of preparing etc., but the film forming speed of these technology is slow, cannot meet the needs of oriented growth in zonule.And it is big
Area uses semi-conducting material, similar with metal material, can produce bigger parasitic capacitance, brings under device operating rate
Fall.Therefore the Thin Films Tropism Growing technology in development minute yardstick region and its characterizing method are the weights developing flexible printing electronic technology
Want problem, be also the necessary process expanding organic electronic commercial application.
Content of the invention
The present invention is for avoiding the weak point existing for above-mentioned prior art, it is desirable to provide one kind is applied to small size device
The thin film alignment preparation method based on unsymmetric structure of part.
The present invention is based on micro-nano inkjet technology, and picoliters level drop and digitized direct write using need based jet pattern
Technology, by way of non-contact material conveys, is transported to quasiconductor precursor liquid the specified location of substrate, is then based on molten
The asymmetric surface tension effects that agent is subject on substrate, realize the guide effect to semiconductor growing.Based on asymmetric
Guide effect produced by surface tension effects, its direction is exactly the direction that thin film needs oriented growth, generally also conductive
The best direction of ability, the method is directed at the thin film direction of growth naturally with device architecture, solves polycyclic aromatic hydrocarbon well
Performance difference between the device that the anisotropy of class organic semiconductor thin-film material is brought.
The present invention solves technical problem, adopts the following technical scheme that
A kind of organic semiconductor thin-film orientation preparation method based on unsymmetric structure, its feature is: described asymmetric
Structure is asymmetric planar structure and/or asymmetric stereochemical structure；
Using the method that asymmetric planar structure orientation prepares organic semiconductor thin-film it is: draw materials a and material b, both
Between there is surface energy differential, and the contact angle of material a and organic semiconductor precursor solution to be printed is more than material b and waits to beat
The contact angle of the organic semiconductor precursor solution of print；The patterned film of material a and material b is formed respectively on substrate, point
Wei not there is a raceway groove in the middle of thin film a and thin film b, thin film a and thin film b, defining channel length l is between thin film a and thin film b
Beeline, the corresponding direction of channel length be orientation；By way of inkjet printing, organic semiconductor is thin
In the substrate that the precursor solution of membrane material is printed upon level along the horizontal direction perpendicular to orientation, form organic half
Conductor thin film, described organic semiconductor thin-film is completely covered the raceway groove between thin film a and thin film b and is existed with thin film a, thin film b
Overlapping region, and the region being located without departing from thin film a and thin film b；Right because of the difference of contact angle using thin film a and thin film b
Asymmetric surface tension effects existing for precursor solution and the Surface Energy Gradients being formed on its surface, utilize forerunner simultaneously
Orientation self assembly effect between molecule organic semiconductor in liquid solution, makes organic semiconductor from larger one laterally the connecing of contact angle
Feeler less side oriented growth, thus realize organic semiconductor thin-film from the lateral thin film b side of thin film a mono- along channel length
The oriented growth in direction；
Using the method that asymmetric stereochemical structure orientation prepares organic semiconductor thin-film it is: interval setting thin film in substrate
Pass through thin film e arc-shaped transition between c and thin film d, and thin film c and thin film d to connect, the thickness of thin film c is more than the thickness of thin film e,
The thickness of thin film d is more than or equal to the thickness of thin film e, the minimum profile curvature radius of thin film c and thin film e junction less than thin film d with thin
The minimum profile curvature radius of film e junction；Definition from thin film c to the septal direction of thin film d be thin film e width or channel length
Direction, by the precursor solution of organic semiconductor thin-film material along perpendicular to thin film e width by way of inkjet printing
Horizontal direction be printed upon in horizontal substrate, the side of print pattern is completely covered the junction of thin film c and thin film e, opposite side
Without departing from the border of thin film d, after solvent volatilization, form organic semiconductor thin-film；The wheel of the different curvature on utilization space position
The wide asymmetric surface tension effects that precursor solution is produced and the Surface Energy Gradients being formed on its surface, simultaneously using having
Orientation self assembly effect between machine semiconductor molecule, makes organic semiconductor from the less lateral minimum song of minimum profile curvature radius
The larger side oriented growth of rate radius, realizes the one of the lateral thin film d place that organic semiconductor thin-film is located from thin film c
Side, the oriented growth along thin film e width.
The organic semiconductor thin-film based on unsymmetric structure for the present invention is orientated preparation method, and its feature lies also in: prepared
Organic semiconductor thin-film be organic semiconductor active layer in high frequency OTFT, or in array light field sensor
Organic semiconductor oriented film.
Described thin film a and described thin film b is metallic film or insulating material film, and described thin film c, thin film d and thin film e are
Metallic film or insulating material film.
0≤l≤100μm.
Described organic semiconductor thin-film is polycyclic aromatic hydrocarbons organic semiconductor thin-film.
Described inkjet printing is using non-contact spatterwork equipment, along the symmetrical centre of raceway groove or two edges of thin film e
The precursor solution of line spray printing single line bar form on demand, the liquid volume of single injection event is less than 100 picoliters, and injection frequency is 500-
5000hz.
Invention further provides the characterizing method of the orientation intensity of oriented growth organic semiconductor thin-film, it is to pass through
Outside face, x-ray diffraction stave levies the orientation intensity of oriented growth organic semiconductor thin-film, and described orientation intensity comprises two quantizations
Evaluation index: the concordance in oriented growth direction and the seriality of oriented growth, embodiments step is:
(1) first pass through metallurgical microscope and judge that organic semiconductor thin-film to be characterized, whether as oriented growth, if so, then continues
Continue and carry out step (2)；
(2) define the x-ray plane of incidence of x-ray diffraction and organic semiconductor thin-film target to be characterized outside face and expect growth side
To between angle be test azimuth angle alpha, with δ α for test azimuthal change step, to organic semiconductor thin-film to be characterized
Carry out x-ray diffraction analysis outside face, obtain x-ray diffraction spectrum the face in multiple orientation from 0 ° to 90 ° or from 0 ° to 180 ° for the α,
And obtain the ratio r of the strongest even number crystallographic plane diffraction peak intensity and the strongest odd number crystallographic plane diffraction peak intensity in each diffraction spectra21(generally
Strong even number crystallographic plane diffraction peak is (002), and the strongest odd number crystallographic plane diffraction peak is (001)), the r corresponding to each diffraction spectra21Minima
It is designated as rmin, corresponding azimuth is designated as αmin, maximum is designated as rmax, corresponding azimuth is designated as αmax；
(3) for the organic semiconductor thin-film of two oriented growths, both r are comparedmin, rminLess, then this organic is partly led
The seriality of body thin film oriented growth is better；
(4) to organic semiconductor thin-film to be characterized, with α as abscissa, with the r corresponding to each α21For vertical coordinate, mapping is simultaneously
Connect r21Minima and the corresponding data point of maximum, corresponding line slope k=(rmax-rmin)/(αmax-αmin)；
For the organic semiconductor thin-film of two oriented growths, compare both k, k is bigger, then this organic semiconductor thin-film
The concordance in oriented growth direction is better.K is typically larger than 0, if k≤0, shows that expected orientation mechanism does not occur substantive work
With though prepared organic semiconductor thin-film is oriented growth, its oriented growth direction is not expected direction.
Generally, δ α≤10 °, to ensure to obtain sufficiently high sign precision.
Compared with the prior art, beneficial effects of the present invention are embodied in:
1st, the orientation mechanism of the present invention and prior art (inductive technology as based on nucleation time difference) are diverse,
The present invention relates to orientation mechanism be fundamentally based on the Herba Kalimeridis dagger-axe Buddhist nun stream that asymmetric contact angle brings, this orientation effect phase
To relatively strong, orientation can be produced in little yardstick；Prior art, such as lifting film preparing technology, gold electrode induction is required for longer
Growing space coordinate mechanism realization, remarkable effect therefore can not occur in little yardstick.In application aspect, contrast two kinds of machines
The feature of system understands, technical scheme is suitable for preparing undersized device, and this small size device generally has less
Parasitic capacitance, therefore switching speed faster, is suitably applied in high frequency printed circuit；The inventive method achieves little yardstick
The thin film that the oriented growth of interior thin film, this orientation of growth and its seriality are effectively controlled, has anisotropic optics concurrently
Characteristic and the coherency information of long-range order, are expected to be applied to the sensing to light field.
2nd, the shape based on oriented growth in the intensity rate between characteristic peak in xrd diffraction spectra outside face and pellicular front for the present invention
Association between looks achieves the sign of oriented film in opposite, takes full advantage of the existing commonly used and side of operation
Just outside face, xrd characterization technique completes the sign of oriented growth in opposite, it is to avoid or decrease expensive to test equipment and can not
The dependence of xrd characterization technique in the face commonly using, is capable of the acquisition of the quantitation two important indicators letters related to oriented growth
Breath, i.e. the seriality of the concordance in oriented growth direction and oriented growth.
Brief description
Fig. 1 is the schematic diagram preparing tips-pen thin film using asymmetric planar structure orientation.
Fig. 2 be channel length l be 80 μm symmetrical and asymmetric planar electrode structure on printing list lines thin film shape
Looks: a, b are symmetrical au-au structure, c, d are asymmetrical au-ag structure, and e, f are symmetrical ag-ag structure；B, d, f are respectively
For a, c, e corresponding polarisation picture.
Fig. 3 is the schematic diagram that asymmetric planar electrode structure induces Thin Films Tropism Growing.
Fig. 4 is the light field induction apparatuss schematic diagram based on asymmetric electrode structure.
Fig. 5 is the structural representation preparing thin film using asymmetric stereochemical structure orientation.
Fig. 6 is to prepare the schematic diagram of tips-pen thin film having to print above the substrat structure of stereo profile.
Fig. 7 be respectively smooth pvp substrate and having print on the substrat structure of stereo profile preparation tips-pen thin
The MIcrosope image of membrane crystallization pattern and its petrographic microscope image.
Fig. 8 is inclined in different angles as the tips-pen thin film of solvent lifting preparation using chloroform and dichloromethane respectively
Outside light microscope photo and face, xrd diffraction peak intensity is than with respect to the azimuthal variation relation figure of measurement.
Fig. 9 is the r being given based on the variation relation of peakedness ratio azimuthalminResult of calculation with k.
Figure 10 is the atomic force microscopy of the tips-pen thin film using chloroform and dichloromethane as solvent lifting preparation respectively
(contact line refers to lift the boundary line of initial time liquid level and substrate the polarizing microscope figure of mirror figure (a) and various location.?
The i.e. upper border line of prepared tips-pen thin film), wherein with chloroform for pull rate during solvent as 7mm/min, with dichloro
Methane is that during solvent, pull rate is 9mm/min.
The orientation of preparation is printed according to different resolution (i.e. different dot spacing ds) on the raceway groove of tri- kinds of different structures of Figure 11
Thin film, in the xrd diffraction spectra of 0 ° and 90 ° azimuth collection, and its corresponding rminAnd k value.
The corresponding r of semiconductive thin film of preparation is printed according to different resolution on the raceway groove of tri- kinds of different structures of Figure 12minWith
K value collects comparison.
Specific embodiment
The method that embodiment 1 prepares organic semiconductor thin-film using asymmetric planar structure orientation
The present embodiment using the method that asymmetric planar structure orientation prepares organic semiconductor thin-film is: draw materials a and material
, there is surface energy differential in material b, and material a is more than material with the contact angle of organic semiconductor precursor solution to be printed between the two
Material b and the contact angle of organic semiconductor precursor solution to be printed；The pattern of material a and material b is formed respectively on substrate
Change thin film, there is a raceway groove in the middle of respectively thin film a and thin film b, thin film a and thin film b, define channel length l be thin film a and
Beeline between thin film b, the corresponding direction of channel length is orientation；Will be organic by way of inkjet printing
In the substrate that the precursor solution of semiconductor film material is printed upon level along the horizontal direction perpendicular to orientation, shape
Become organic semiconductor thin-film, this organic semiconductor thin-film be completely covered raceway groove between thin film a and thin film b and with thin film a, thin film
There is overlapping region, and the region being located without departing from thin film a and thin film b in b；Using thin film a and thin film b because of the difference of contact angle
And to the asymmetric surface tension effects existing for precursor solution and the Surface Energy Gradients in the formation of its surface, utilize simultaneously
In precursor solution, the orientation self assembly effect between molecule organic semiconductor, makes organic semiconductor from the larger side of contact angle
To contact angle less side oriented growth, thus realizing organic semiconductor thin-film from the lateral thin film b side of thin film a mono- along raceway groove
The oriented growth of length direction.
Specifically, the semiconductive thin film that the present embodiment prints is that 6,13- is double (triisopropylsilyl acetenyl) five
Benzene (tips-pen), dielectric layer is poly- (4-Vinyl phenol) (pvp).In surface sio2Thickness of insulating layer is the highly doped of 300nm
On miscellaneous si piece, as substrate, ink is as solute, with tetrahydronaphthalene as solvent using tips-pen to the thick pvp layer of spin coating 120nm
Prepare according to mass fraction 2wt%.
As shown in figure 1, Ag films are prepared by way of mask lithography, electron beam evaporation plating on substrate as thin film a, make
Standby gold thin film, as thin film b, forms au-ag unsymmetric structure thin film, and two film thicknesses are 30nm, minimum spacing therebetween
Namely channel length l is 80 μm；Then adopt non-contact spatterwork equipment, along the symmetrical center line spray printing at two edges of raceway groove
Tips-pen ink, forms the thin film of single line bar form, the liquid volume of single-pulse injection is 10pl, and pulse frequency is
1000hz.Can see that the thin film direction of growth is to contact angle from the larger side of contact angle (ag) by microscope field observation
Less side (au) oriented growth.
For being contrasted, thin film a is equally changed to gold thin film, forms au-au symmetrical structure substrate, obtain in the same fashion
Obtain tips-pen thin film；Thin film b is equally changed to Ag films, forms ag-ag symmetrical structure substrate, obtain in the same fashion
Tips-pen thin film.
Fig. 2 a is the single line bar film morphology printing in au-au symmetrical structure substrate, and Fig. 2 b is that its corresponding polarisation shows
Micro mirror image；Fig. 2 c is the single line bar film morphology printing in au-ag dissymmetrical structure substrate, and Fig. 2 d is its corresponding polarisation
MIcrosope image；Fig. 2 e is the single line bar film morphology printing in ag-ag symmetrical structure substrate, and Fig. 2 f is its corresponding polarisation
MIcrosope image.Contrast understands, has more existing edge in asymmetric au-ag suprabasil single line bar pattern thin perpendicular to trench edges
The crystalline orientation of film width, this is because tips-pen ink has contact angle difference (ag mono- side contacts in width
Angle is bigger than au side contact angle), form Herba Kalimeridis dagger-axe Buddhist nun stream (morangoni flow) of width, so that solute molecule
From the lateral au side self assembly of ag mono-, lead to the unidirectional growth of molecule organic semiconductor, and au-au, ag-ag symmetrical structure substrate
On single line bar pattern be then the crystalline orientation pointing to center along the crystalline orientation of film length direction or surrounding, and in channel region
Domain forms a large amount of crystal boundaries, and that is, solute molecule does not have the Herba Kalimeridis dagger-axe Buddhist nun stream along orientation in symmetrical substrate
(morangoni flow), leads to the unfavorable orientation of molecule organic semiconductor or mixed and disorderly orientation, is formed and be unfavorable for carrier transport
Crystallization shape.
Fig. 3 induces the schematic diagram of organic semiconductor thin-film crystalline orientation for asymmetric electrode structure, using au thin film and ag
Thin film is because of the difference of surface energy to the asymmetric surface tension effects existing for precursor solution with the formation of its surface
Surface Energy Gradients, thus realize organic semiconductor thin-film to be orientated life from the lateral thin film au side of thin film ag mono- along orientation
Long.
The preparation method of the oriented film of the suitable single line bar spray printing that the present embodiment is proposed based on asymmetric electrode structure, disappears
Except single line bar thin film is in the competition mechanism of length direction oriented growth, it is suitable for preparing smaller size of oriented film.Based on this
The device of class oriented film is expected to be applied to the identification of the polarization state to light field and transmission direction.As shown in figure 4, a is light field sense
Answer the minimum composition unit of device；B is the light field induction apparatuss of planar structure；C is the light field induction apparatuss of 3-D solid structure.
Because orientation mechanism comes from contact angle difference, therefore equally can the dissymmetrical structure orientation based on single-sided electrode prepare
Organic semiconductor thin-film, directly utilizes the difference in metal surface and surface of insulating layer contact angle for the organic semiconductor precursor solution
Different, obtain the oriented film growth perpendicular to electrode side.After completing to prepare the semiconductive thin film of oriented growth, up
The electrode of preparation pairing, is expected to obtain less channel dimensions by the method printing.Thus improving the switching speed of device.
The method that embodiment 2 prepares thin film using asymmetric stereochemical structure orientation
The present embodiment using the method that asymmetric stereochemical structure orientation prepares thin film is: as shown in figure 5, being spaced in substrate
Connected by thin film e arc-shaped transition between setting thin film c and thin film d, and thin film c and thin film d, the thickness of thin film c is more than thin film e
Thickness, the thickness of thin film d is more than or equal to the thickness of thin film e, and the minimum profile curvature radius of thin film c and thin film e junction are less than thin
Film d and the minimum profile curvature radius of thin film e junction；Definition from thin film c to the septal direction of thin film d be thin film e width or
Orientation, by the precursor solution of organic semiconductor thin-film material along perpendicular to thin film e by way of inkjet printing
The horizontal direction of width is printed upon in horizontal substrate, and the side of print pattern is completely covered the connection of thin film c and thin film e
Place, the border without departing from thin film d for the opposite side, after solvent volatilization, form organic semiconductor thin-film；Difference on utilization space position
Asymmetric surface tension effects and the Surface Energy Gradients being formed on its surface that the profile of curvature produces to precursor solution, with
Orientation self assembly effect between Shi Liyong molecule organic semiconductor, makes organic semiconductor from the less side of minimum profile curvature radius
To the side oriented growth that minimum profile curvature radius are larger, realize the lateral thin film d institute that organic semiconductor thin-film is located from thin film c
Side, along thin film e width oriented growth.
Specifically, semiconductive thin film, the ink prepared and the substrate used that the present embodiment is printed and embodiment 1 phase
With.As shown in fig. 6, in sio2Upper spin coating a layer thickness is the pvp material of 300nm, then carves using photoresist, by dry method
Erosion, the pvp layer of institute's spin coating is carved into figure (retention position is the position of thin film c), then spin coating second layer 500nm thereon again
Pvp, that is, formed and there is the stereo profile of Curvature varying, the thin film d that this method makes is highly identical with thin film e, operation letter
Singly, it is easily achieved.Then adopt non-contact spatterwork equipment, thin in the tips-pen of stereo profile region spray printing single line bar form
Film, the liquid volume of individual pulse injection is 10pl, and pulse frequency is 1000hz.
Contrasted using smooth pvp substrate, the MIcrosope image of gained thin film crystallization pattern and its partially under two kinds of substrates
Light image is as shown in fig. 7, wherein Fig. 7 a and Fig. 7 c corresponding flat substrate, Fig. 7 b stereo profile substrate corresponding with Fig. 7 d.From Fig. 7 a
With Fig. 7 c more in disorder, crystalline orientation that can be seen that the smooth pvp substrate i.e. suprabasil film morphology of no microcosmic stereochemical structure
Center is pointed to by edge, the growth of thin film starts from end points rather than the pattern boundaries of pattern；Can be seen that thin from Fig. 7 b and Fig. 7 d
The edge that covered by ink from stereo profile of membrane crystallization orientation starts to grow, and boundary definition is clear, and semiconductive thin film is along vertical
The direction oriented crystalline at stereo profile edge, thus realize the film morphology with certain crystalline orientation.
The characterizing method of the orientation intensity of embodiment 3 oriented growth thin film
The characterizing method of the orientation intensity of the present embodiment oriented growth thin film, is to be collected by x-ray diffraction stave outside face
Be orientated intensity into the face of growing film, orientation intensity comprises two quantitatively evaluating indexs: the concordance in oriented growth direction and
The seriality of oriented growth, embodiments step is:
(1) first pass through polarizing microscope and judge that organic semiconductor thin-film to be characterized, whether as oriented growth, if so, then continues
Continue and carry out step (2)；
(2) define the x-ray plane of incidence of x-ray diffraction and organic semiconductor thin-film target to be characterized outside face and expect growth side
To between angle be test azimuth angle alpha, with δ α for test azimuthal change step, to organic semiconductor thin-film to be characterized
Carry out x-ray diffraction analysis outside face, compose by x-ray diffraction from 0 ° to 90 ° or 0 ° to 180 ° of the face in multiple orientation for acquisition α, and
Obtain the ratio r of the strongest even number crystallographic plane diffraction peak intensity and the strongest odd number crystallographic plane diffraction peak intensity in each diffraction spectra21, each diffraction spectra
Corresponding r21Minima be designated as rmin, corresponding azimuth is designated as αmin, maximum is designated as rmax, corresponding azimuth is designated as
αmax；
(3) for the organic semiconductor thin-film of two oriented growths, both r are comparedmin, rminLess, then this organic is partly led
The seriality of body thin film oriented growth is better；
(4) to organic semiconductor thin-film to be characterized, with α as abscissa, with the r corresponding to each α21For vertical coordinate, mapping is simultaneously
Connect r21Minima and the corresponding data point of maximum, corresponding line slope k=(rmax-rmin)/(αmax-αmin)；
For the organic semiconductor thin-film of two oriented growths, compare both k, k is bigger, then this organic semiconductor thin-film
The concordance in oriented growth direction is better.
Concrete example is as follows: to lift plated film preparation tips-pen thin film, in surface sio2Thickness of insulating layer is 300nm's
On highly doped si piece, as substrate, ink is as solute, with chloroform or dichloro using tips-pen to the thick pvp layer of spin coating 120nm
Methane is that solvent is prepared according to 10mg/ml.
As shown in figure 8, a, g be respectively chloroform, dichloromethane lifting preparation film morphology figure, b, c, d, e, f and h, i,
J, k, l correspond to the chloroform and dichloromethane petrographic microscope image in the case of 0 ° of deflection, 30 °, 45 °, 60 °, 90 ° respectively.M is
Measurement azimuth schematic diagram；N is to lift the thin film of preparation using chloroform and dichloromethane in the case of different orientations as solvent
Its 002/001 peakedness ratio variation tendency.
Fig. 9 gives result of calculation: the thin film of chloroformic solution lifting preparation based on the variation relation of peakedness ratio azimuthal
Corresponding rminFor 0.248, the thin film r of dichloromethane solution lifting preparationminFor 0.214, the latter is less, shows that dichloromethane is molten
The seriality of the Thin Films Tropism Growing of liquid preparation is more preferable.According to the definition of k value, the corresponding k of thin film of chloroformic solution lifting preparation
It is worth for 2.07 × 10-3, the corresponding k value of thin film of dichloromethane solution lifting preparation is 3.23 × 10-3, the latter is bigger, shows two
The concordance in the Thin Films Tropism Growing direction of chloromethanes solution preparation more preferably it is seen that in thin film diffraction each diffraction maximum strength ratio
Value, can be used as the conforming quantization signifying means of the seriality judging Thin Films Tropism Growing and oriented growth direction.
The characterizing method of the existing orientation characteristic of organic semiconductor thin-film characterizing oriented growth mainly has: polarized light microscopy
Xrd diffraction in photo, atomic force microscope or face, wherein in face, xrd diffraction can not commonly use because test equipment is expensive.Figure
10 is the atomic force microscopy diagram (a) and not of the above-mentioned tips-pen thin film using chloroform and dichloromethane as solvent lifting preparation
With polarizing microscope figure (b) at position.It can be seen that being obtained in that preferably by the thin film of dichloromethane solvent lifting preparation
Oriented growth seriality (atomic force micrograph find out thickness evenly, edge is more straight, polarizing microscope show along
More consistent, the less generation bifurcated of width ratio of direction of growth ribbon crystal) and oriented growth direction concordance (polarized light microscopy
Mirror shows less generation bifurcated, and the orientation ratio of ribbon crystal is more consistent).
It can be seen that the characterizing method of the present invention can draw identical conclusion, and can quantify, more accurate.
In conjunction with the embodiments in 1 three kinds of structure preparations thin film, as shown in figure 11, corresponding xrd diffraction spectra is (right at 0 ° respectively
The x direction in (a) should be schemed, result is shown in figure (b)) and 90 ° of (the y direction in corresponding diagram (a), result is shown in figure (c)) azimuth collections,
According to the xrd diffraction spectra of collection, also with above-mentioned analysis method, obtain corresponding rminAs shown in figure 12 with k value.Contrast phase
Answer data, easily find that the thin film of preparation on asymmetry electrode has concordance and the orientation life in preferable oriented growth direction
Long seriality.As an example, the xrd data of collection is limited for the present embodiment, if appropriateness expand collection azimuth coverage and
Azimuth value density, it is possible to obtain more accurately data.The present embodiment is a kind of sign case of simplification, despite this,
Still can correctly reflect the difference between the oriented growth feature of thin film and different sample, fully demonstrate having of the method
Effect property.
The present invention passes through the selection of material and/or the structure of asymmetric microcosmic stereochemical structure, using the surface energy differential of material
The solvent causing or the precursor solution of quasiconductor form asymmetric contact angle on its surface, form surface tension in the solution
Gradient, can promote in solution solute molecule in this gradient direction oriented growth.This is a kind of stronger orientation effect mechanism, can
To obtain obvious orientation effect in range of small, can apply to the printed circuit of high-frequency work, or array optical
Field sensor.Xrd diffraction spectra from different orientations gather the face of oriented film, extracts the characteristic peaks under the conditions of each azimuth
Its minima r of ratiomin, can be used for characterizing the seriality of Thin Films Tropism Growing, connect the line segment that minima is worth to maximum
Slope k, can be used for characterizing the concordance in Thin Films Tropism Growing direction.
Claims (8)
1. a kind of based on unsymmetric structure organic semiconductor thin-film orientation preparation method it is characterised in that: described unsymmetrical knot
Structure is asymmetric planar structure and/or asymmetric stereochemical structure；
Using the method that asymmetric planar structure orientation prepares organic semiconductor thin-film it is: draw materials a and material b, between the two
There is surface energy differential, and the contact angle of material a and organic semiconductor precursor solution to be printed be more than material b with to be printed
The contact angle of organic semiconductor precursor solution；The patterned film of material a and material b is formed on substrate, respectively respectively
There is a raceway groove in the middle of thin film a and thin film b, thin film a and thin film b, define channel length l be between thin film a and thin film b
Short distance, the corresponding direction of channel length is orientation；By organic semiconductor presoma by way of inkjet printing
In the substrate that solution is printed upon level along the horizontal direction perpendicular to orientation, form organic semiconductor thin-film, described
Organic semiconductor thin-film is completely covered the raceway groove between thin film a and thin film b and there is overlapping region with thin film a, thin film b, and
The region being located without departing from thin film a and thin film b；Precursor solution is deposited because of the difference of contact angle using thin film a and thin film b
Asymmetric surface tension effects and the Surface Energy Gradients being formed on its surface, utilize organic half in precursor solution simultaneously
Orientation self assembly effect between conductor molecule, makes organic semiconductor from the larger less side of a lateral contact angle of contact angle
Oriented growth, thus realize organic semiconductor thin-film give birth to from the lateral thin film b side of thin film a mono- along the orientation of orientation
Long；
Using the method that asymmetric stereochemical structure orientation prepares organic semiconductor thin-film be: in substrate interval setting thin film c and
Pass through thin film e arc-shaped transition between thin film d, and thin film c and thin film d to connect, the thickness of thin film c is more than the thickness of thin film e, thin film
The thickness of d is more than or equal to the thickness of thin film e, and thin film c is less than thin film d and thin film e even with the minimum profile curvature radius of thin film e junction
Connect the minimum profile curvature radius at place；Definition from thin film c to the septal direction of thin film d be thin film e width or orientation,
By way of inkjet printing, organic semiconductor precursor solution is printed upon along the horizontal direction perpendicular to thin film e width
In horizontal substrate, the side of print pattern is completely covered the junction of thin film c and thin film e, the side without departing from thin film d for the opposite side
Boundary, after solvent volatilization, forms organic semiconductor thin-film；The profile of the different curvature on utilization space position produces to precursor solution
Raw asymmetric surface tension effects and the Surface Energy Gradients being formed on its surface, utilize between molecule organic semiconductor simultaneously
Orientation self assembly effect, make organic semiconductor from the larger side of the less lateral minimum profile curvature radius of minimum profile curvature radius
Oriented growth, realizes the side at the lateral thin film d place that organic semiconductor thin-film is located from thin film c, along thin film e width
Oriented growth.
2. the organic semiconductor thin-film orientation preparation method based on unsymmetric structure according to claim 1, its feature exists
In: prepared organic semiconductor thin-film is the organic semiconductor active layer in high frequency OTFT, or is array light
Organic semiconductor oriented film in field sensor.
3. the organic semiconductor thin-film orientation preparation method based on unsymmetric structure according to claim 1, its feature exists
In: described thin film a and described thin film b is metallic film or insulating material film, and described thin film c, thin film d and thin film e are metal
Thin film or insulating material film.
4. the organic semiconductor thin-film orientation preparation method based on unsymmetric structure according to claim 1, its feature exists
In: 0≤l≤100 μm.
5. the organic semiconductor thin-film orientation preparation method based on unsymmetric structure according to claim 1, its feature exists
In: described organic semiconductor thin-film is polycyclic aromatic hydrocarbons organic semiconductor thin-film.
6. the organic semiconductor thin-film orientation preparation method based on unsymmetric structure according to claim 1, its feature exists
Using non-contact spatterwork equipment in: described inkjet printing, along raceway groove or two edges of thin film e symmetrical center line on demand
The precursor solution of spray printing single line bar form, the liquid volume of single injection event is less than 100 picoliters, and injection frequency is 500-
5000hz.
7. a kind of characterizing method of the orientation intensity of oriented growth organic semiconductor thin-film it is characterised in that: by x-ray outside face
Diffraction spectra characterizes the orientation intensity of oriented growth organic semiconductor thin-film, and described orientation intensity comprises two quantitatively evaluating indexs:
The concordance in oriented growth direction and the seriality of oriented growth, embodiments step is:
(1) first pass through metallurgical microscope and judge organic semiconductor thin-film to be characterized whether as oriented growth, if so, then continue into
Row step (2)；
(2) define the x-ray plane of incidence of the outer x-ray diffraction in face and organic semiconductor thin-film target to be characterized expect the direction of growth it
Between angle be test azimuth angle alpha, with δ α for test azimuthal change step, organic semiconductor thin-film to be characterized is carried out
X-ray diffraction analysis outside face, obtains x-ray diffraction spectrum the face in multiple orientation from 0 ° to 90 ° or from 0 ° to 180 ° for the α, and obtains
Obtain the ratio r of the strongest even number crystallographic plane diffraction peak intensity and the strongest odd number crystallographic plane diffraction peak intensity in each diffraction spectra21, each diffraction spectra institute
Corresponding r21Minima be designated as rmin, corresponding azimuth is designated as αmin, maximum is designated as rmax, corresponding azimuth is designated as
αmax；
(3) for the organic semiconductor thin-film of two oriented growths, both r are comparedmin, rminLess, then this organic semiconductor is thin
The seriality of film oriented growth is better；
(4) to organic semiconductor thin-film to be characterized, with α as abscissa, with the r corresponding to each α21For vertical coordinate, map and connect
r21Minima and the corresponding data point of maximum, corresponding line slope k=(rmax-rmin)/(αmax-αmin)；
For the organic semiconductor thin-film of two oriented growths, compare both k, k is bigger, then the orientation of this organic semiconductor thin-film
The concordance of the direction of growth is better.
8. the orientation intensity of oriented growth thin film according to claim 7 characterizing method it is characterised in that: δ α≤
10°.
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