CN106356453B - A kind of organic semiconductor thin-film orientation preparation method and characterizing method based on unsymmetric structure - Google Patents
A kind of organic semiconductor thin-film orientation preparation method and characterizing method based on unsymmetric structure Download PDFInfo
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- CN106356453B CN106356453B CN201610866170.7A CN201610866170A CN106356453B CN 106356453 B CN106356453 B CN 106356453B CN 201610866170 A CN201610866170 A CN 201610866170A CN 106356453 B CN106356453 B CN 106356453B
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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 a kind of organic semiconductor thin-film orientation preparation method and characterizing method based on unsymmetric structure, it is characterized by: being based on micro-nano inkjet printing technology, using the picoliters grade drop and digitlization direct write patterning techniques of need based jet, in such a way that non-contact material conveys, semiconductor precursor liquid is transported to the designated position of substrate, it is then based on the asymmetric surface tension effects that solvent is subject on substrate and the Surface Energy Gradients being formed on its surface, it realizes to the guiding role of semiconductor growing, obtains the semiconductive thin film of oriented growth.The method of the invention realizes the oriented growths of film in small scale, the film that this orientation of growth and its continuity are effectively controlled, the coherency information for having anisotropic optical characteristics and long-range order concurrently is expected to be applied to high frequency Organic Thin Film Transistors and array light field sensor.
Description
Technical field
The present invention relates to the methods and characterizing method of a kind of organic semiconductor thin-film oriented growth, belong to printed electronics
Field.
Background technique
Printed electronics are based on the solwution methods patterned films such as flexible organic material system and inkjet printing preparation skill
Art realizes the electronic product for producing low cost under cryogenic.Wherein the manufacture of Organic Thin Film Transistors be key technology it
One.The mobility of the organic material of high mobility can achieve 10cm at present2V-1s-1Magnitude, the development of this kind of material is so that be based on
The printed electronic of the device of Organic Thin Film Transistors has quite wide application potential.The application of current organic electronic mainly by
It is formed on its poor high-frequency work ability, the main bottleneck of the relevant technologies is that printed patterns technology itself can be realized first
Precision is limited, therefore device critical dimensions cannot substantially 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 film
Crystallization shape and molecules align direction are closely related, that is, it has anisotropic conductivity, therefore prepares high quality
The uniform device of performance and its array request can be effectively controlled the orientation of molecule in film.
Existing controllable made membrane growth behavior and the film preparing technology of molecules align mode have lifting coating technique, molten
Liquid shears film preparing technology, and there are also some as using inclined substrate instillation precursor liquid or based on the thin of solution evaporation restriction scheme
Film is orientated technology of preparing etc., but the film forming speed of these technologies is slow, is unable to satisfy the needs of oriented growth in zonule.And it is big
Area uses semiconductor material, similar with metal material, can generate bigger parasitic capacitance, bring under device operating rate
Drop.Therefore the Thin Films Tropism Growing technology and its characterizing method for developing minute yardstick region are the weights for developing flexible printing electronic technology
Project is wanted, and expands the necessary process of organic electronic industrial application.
Summary of the invention
The present invention is to avoid above-mentioned existing deficiencies in the technology, it is desirable to provide one kind is suitable for small size device
The thin film alignment preparation method based on unsymmetric structure of part.
The present invention is based on micro-nano inkjet printing technologies, using the picoliters grade drop and digitlization direct write patterning of need based jet
Technology is transported to semiconductor precursor liquid the designated position of substrate, is then based on molten in such a way that non-contact material conveys
The asymmetric surface tension effects that agent is subject on substrate realize the guiding role to semiconductor growing.Based on asymmetric
Guiding role caused by surface tension effects, direction are exactly the direction that film needs oriented growth, generally also conductive
The best direction of ability, this method are naturally directed at the film direction of growth with device architecture, have well solved polycyclic aromatic hydrocarbons (PAH)
The performance difference between 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, it is characterized in that: it is described asymmetric
Structure is asymmetric planar structure and/or asymmetric stereochemical structure；
The method for preparing organic semiconductor thin-film using asymmetric planar structure orientation are as follows: draw materials A and material B, the two
Between there are surface energy differential, and the contact angle of materials A and organic semiconductor precursor solution to be printed be greater than material B with wait beat
The contact angle of the organic semiconductor precursor solution of print；The patterned film of materials A and material B is respectively formed in substrate, point
There Wei not be a channel among film A and film B, film A and film B, channel length L is between film A and film B for definition
The shortest distance, the corresponding direction of channel length be orientation；It is by way of inkjet printing that organic semiconductor is thin
The precursor solution of membrane material is printed upon in horizontal substrate along the horizontal direction perpendicular to orientation, forms organic half
Conductor thin film, the organic semiconductor thin-film are completely covered the channel between film A and film B and exist with film A, film B
Overlapping region, and without departing from the region where film A and film B；It is right because of the difference of contact angle using film A and film B
Asymmetric surface tension effects present in precursor solution and the Surface Energy Gradients being formed on its surface, while utilizing forerunner
Orientation self assembly effect in liquid solution between molecule organic semiconductor, makes organic semiconductor from the biggish side of contact angle to connecing
The lesser side oriented growth of feeler, to realize organic semiconductor thin-film from mono- side film A to mono- lateral edge channel length of film B
The oriented growth in direction；
The method for preparing organic semiconductor thin-film using asymmetric stereochemical structure orientation are as follows: the interval setting film in substrate
C and film D, and connected between film C and film D by film E arc-shaped transition, the thickness of film C is greater than the thickness of film E,
The thickness of film D is more than or equal to the thickness of film E, the minimum profile curvature radius of the junction film C and film E less than film D with it is thin
The minimum profile curvature radius of the junction film E；Definition is film E width direction or channel length from film C to the septal direction of film D
Direction, by the precursor solution of organic semiconductor thin-film material along perpendicular to film E width direction by way of inkjet printing
Horizontal direction be printed upon in horizontal substrate, the junction of film C Yu film E, the other side is completely covered in the side of print pattern
Organic semiconductor thin-film is formed after solvent volatilization without departing from the boundary of film D；Utilize the wheel of the different curvature on spatial position
The asymmetric surface tension effects and the Surface Energy Gradients being formed on its surface that exterior feature generates precursor solution, while using having
Orientation self assembly effect between machine semiconductor molecule, keeps organic semiconductor bent from the lesser side of minimum profile curvature radius to minimum
The biggish side oriented growth of rate radius, one where a side to film D where realization organic semiconductor thin-film from film C
Side, along the oriented growth of film E width direction.
The present invention is based on the organic semiconductor thin-films of unsymmetric structure to be orientated preparation method, and feature is lain also in: prepared
Organic semiconductor thin-film be organic semiconductor active layer in high frequency Organic Thin Film Transistors, or in array light field sensor
Organic semiconductor oriented film.
The film A and film B is metallic film or insulating material film, and the film C, film D and film E are
Metallic film or insulating material film.
0≤L≤100μm。
The organic semiconductor thin-film is polycyclic aromatic hydrocarbons organic semiconductor thin-film.
The inkjet printing is using non-contact spatterwork equipment, along the symmetrical centre at two edges of channel or film E
The precursor solution of the on-demand spray printing single line form of line, the liquid volume of single injection event is less than 100 picoliters, injection frequency 500-
5000Hz。
Invention further provides the characterizing methods of the orientation intensity of oriented growth organic semiconductor thin-film, are to pass through
The orientation intensity of X-ray diffraction spectrum characterization oriented growth organic semiconductor thin-film outside face, the orientation intensity include two quantizations
Evaluation index: the consistency in oriented growth direction and the continuity of oriented growth, embodiments step are as follows:
(1) determine whether organic semiconductor thin-film to be characterized is oriented growth by metallographic microscope first, if so, after
It is continuous to carry out step (2)；
(2) the X-ray plane of incidence and organic semiconductor thin-film target to be characterized for defining X-ray diffraction outside face it is expected growth side
Angle between is test azimuth angle alpha, is to test azimuthal change step with Δ α, to organic semiconductor thin-film to be characterized
The outer X-ray diffraction analysis in carry out face obtains X-ray diffraction spectrum outside the face in multiple orientation of the α from 0 ° to 90 ° or from 0 ° to 180 °,
And obtain the ratio R of most strong even number crystallographic plane diffraction peak intensity and most strong odd number crystallographic plane diffraction peak intensity in each diffraction spectra21(usually most
Strong even number crystallographic plane diffraction peak is (002), and most strong odd number crystallographic plane diffraction peak is (001)), R corresponding to each diffraction spectra21Minimum value
It is denoted as Rmin, corresponding azimuth is denoted as αmin, maximum value is denoted as Rmax, corresponding azimuth is denoted as αmax；
(3) for the organic semiconductor thin-film of two oriented growths, compare the R of the twomin, RminSmaller, then this organic is partly led
The continuity of body thin film oriented growth is better；
(4) to organic semiconductor thin-film to be characterized, using α as abscissa, the R to correspond to each α21For ordinate, mapping is simultaneously
Connect R21Minimum value and the corresponding data point of maximum value, corresponding line slope k=(Rmax-Rmin)/(αmax-αmin)；
For the organic semiconductor thin-film of two oriented growths, the k both compared, k is bigger, then the organic semiconductor thin-film
The consistency in oriented growth direction is better.K is typically larger than 0, if k≤0, shows that there is no substantive works for expected orientation mechanism
With though organic semiconductor thin-film obtained is oriented growth, its oriented growth direction is not expected direction.
Under normal circumstances, Δ α≤10 °, to guarantee to obtain sufficiently high characterization precision.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, orientation mechanism of the invention and the prior art (inductive technology such as based on nucleation time difference) are entirely different,
The present invention relates to orientation mechanism be fundamentally based on asymmetric contact angle bring kalimeris dagger-axe Buddhist nun stream, the orientation effect phase
To relatively by force, orientation can be generated in small scale；The prior art, such as lifts film preparing technology, and gold electrode induction requires longer
Growing space cooperation mechanism realization, therefore remarkable effect cannot occur in small scale.In application aspect, two kinds of machines are compared
The characteristics of processed, this small size device usually had smaller it is found that technical solution of the present invention is suitble to prepare the device of small size
Parasitic capacitance, therefore switching speed is faster, is suitably applied in high frequency printed circuit；The method of the invention realizes small scales
The film that the oriented growth of interior film, this orientation of growth and its continuity are effectively controlled, has anisotropic optics concurrently
The coherency information of characteristic and long-range order is expected to be applied to the sensing to light field.
2, the present invention is based on the shapes of oriented growth in the intensity rate and pellicular front outside face in XRD diffraction spectra between characteristic peak
Association between looks realizes the characterization of oriented film in opposite, takes full advantage of the existing commonly used and side of operation
Just XRD characterization technology completes the characterization of oriented growth in opposite outside face, avoid or reduce it is expensive to test equipment and cannot
The dependence of XRD characterization technology in the face generally used, the acquisition that can be quantified two important indicators letter relevant to oriented growth
Breath, the i.e. continuity of the consistency in oriented growth direction and oriented growth.
Detailed description of the invention
Fig. 1 is the schematic diagram that TIPS-PEN film is prepared using asymmetric planar structure orientation.
Fig. 2 is the film shape of the printing list lines on the symmetrical and asymmetric planar electrode structure that channel length L is 80 μm
Looks: a, b are symmetrical Au-Au structure, and c, d are asymmetrical Au-Ag structure, and e, f are symmetrical Ag-Ag structure；B, d, f distinguish
For the corresponding polarisation picture of a, c, e.
Fig. 3 is the schematic diagram that asymmetric planar electrode structure induces Thin Films Tropism Growing.
Fig. 4 is the light field inductor schematic diagram based on asymmetric electrode structure.
Fig. 5 is the structural schematic diagram that film is prepared using asymmetric stereochemical structure orientation.
Fig. 6 is the schematic diagram that printing prepares TIPS-PEN film above the substrat structure with stereo profile.
Fig. 7 be printed in smooth PVP substrate and substrat structure with stereo profile respectively preparation TIPS-PEN it is thin
The MIcrosope image and its petrographic microscope image of membrane crystallization pattern.
Fig. 8 is respectively using chloroform and methylene chloride as the TIPS-PEN film of solvent lifting preparation in the inclined of different angle
XRD diffraction peak intensity ratio is relative to the azimuthal variation relation figure of measurement outside light microscope photo and face.
Fig. 9 is to compare the R that azimuthal variation relation provides based on peak valueminWith the calculated result of k.
Figure 10 is respectively using chloroform and methylene chloride as the atomic force microscopy of the TIPS-PEN film of solvent lifting preparation
(contact line refers to the boundary line of lifting initial time liquid level and substrate to petrographic microscope figure at mirror figure (a) and different location.?
That is the upper border line of prepared TIPS-PEN film), wherein pull rate is 7mm/min when using chloroform as solvent, with dichloro
Pull rate is 9mm/min when methane is solvent.
According to the orientation of different resolution (i.e. difference space D S) printing preparation on the channel of tri- kinds of different structures of Figure 11
Film, the XRD diffraction spectra of the azimuth acquisition at 0 ° and 90 ° and its corresponding RminWith k value.
According to the corresponding R of semiconductive thin film of different resolution printing preparation on the channel of tri- kinds of different structures of Figure 12minWith
K value summarizes comparison.
Specific embodiment
The method that embodiment 1 prepares organic semiconductor thin-film using asymmetric planar structure orientation
The present embodiment is using the method that asymmetric planar structure orientation prepares organic semiconductor thin-film: draw materials A and material
Expect B, there is surface energy differential between the two, and the contact angle of materials A and organic semiconductor precursor solution to be printed is greater than material
Expect the contact angle of B and organic semiconductor precursor solution to be printed；The pattern of materials A and material B is respectively formed in substrate
Change film, there is a channel among respectively film A and film B, film A and film B, define channel length L be film A with
The shortest distance between film B, the corresponding direction of channel length are orientation；It will be organic by way of inkjet printing
The precursor solution of semiconductor film material is printed upon in horizontal substrate along the horizontal direction perpendicular to orientation, shape
At organic semiconductor thin-film, the organic semiconductor thin-film be completely covered the channel between film A and film B and with film A, film
There are overlapping regions by B, and without departing from the region where film A and film B；Using film A and film B because of the difference of contact angle
And to asymmetric surface tension effects present in precursor solution and the Surface Energy Gradients being formed on its surface, it utilizes simultaneously
Orientation self assembly effect in precursor solution between molecule organic semiconductor, makes organic semiconductor from the biggish side of contact angle
To the lesser side oriented growth of contact angle, to realize organic semiconductor thin-film from mono- side film A to mono- lateral edge channel of film B
The oriented growth of length direction.
Specifically, the semiconductive thin film of the present embodiment printing is 6,13- bis- (triisopropylsilyl acetenyls) and five
Benzene (TIPS-PEN), dielectric layer are poly- (4-Vinyl phenol) (PVP).In surface SiO2Thickness of insulating layer is the highly doped of 300nm
The PVP layer of miscellaneous Si on piece spin coating 120nm thickness is used as substrate, and ink is using TIPS-PEN as solute, using tetrahydronaphthalene as solvent
It is prepared according to mass fraction 2wt%.
As shown in Figure 1, Ag films are prepared in substrate by way of mask lithography, electron beam evaporation plating as film A, system
Standby gold thin film forms Au-Ag unsymmetric structure film as film B, and two film thicknesses are 30nm, minimum spacing between the two
Namely channel length L is 80 μm；Then non-contact spatterwork equipment is used, along the symmetrical center line spray printing at two edges of channel
TIPS-PEN ink forms the film of single line form, and the liquid volume of single-pulse injection is 10pL, and pulse frequency is
1000Hz.Can see the film direction of growth by microscope field observation is from the biggish side of contact angle (Ag) to contact angle
Lesser side (Au) oriented growth.
To compare, film A is equally changed to gold thin film, Au-Au symmetrical structure substrate is formed, obtains in the same fashion
Obtain TIPS-PEN film；Film B is equally changed to Ag films, Ag-Ag symmetrical structure substrate is formed, obtains in the same fashion
TIPS-PEN film.
Fig. 2 a is the single line film morphology printed in Au-Au symmetrical structure substrate, and Fig. 2 b is aobvious for its corresponding polarisation
Micro mirror image；Fig. 2 c is the single line film morphology printed in Au-Ag dissymmetrical structure substrate, and Fig. 2 d is its corresponding polarisation
MIcrosope image；Fig. 2 e is the single line film morphology printed in Ag-Ag symmetrical structure substrate, and Fig. 2 f is its corresponding polarisation
MIcrosope image.Comparison is it is found that the single line pattern in asymmetric Au-Ag substrate often has along perpendicular to the thin of trench edges
The crystalline orientation of film width direction, this is because TIPS-PEN ink is in width direction, there are contact angle difference (mono- side contacts of Ag
The angle side ratio Au contact angle is bigger), the kalimeris dagger-axe Buddhist nun in formation width direction flows (Morangoni flow), to make solute molecule
From mono- side Ag to the self assembly of the side Au, lead to the unidirectional growth of molecule organic semiconductor, and Au-Au, Ag-Ag symmetrical structure substrate
On single line pattern be then the crystalline orientation that center is directed toward along the crystalline orientation or surrounding of film length direction, and in channel region
Domain forms a large amount of crystal boundaries, i.e., there is no the kalimeris dagger-axe Buddhist nuns along orientation to flow in symmetrical substrate for solute molecule
(Morangoni flow) causes the unfavorable orientation of molecule organic semiconductor or mixed and disorderly orientation, formation to be unfavorable for carrier transport
Crystallization shape.
Fig. 3 is the schematic diagram that asymmetric electrode structure induces organic semiconductor thin-film crystalline orientation, utilizes Au film and Ag
Film because surface can difference due to asymmetric surface tension effects present in precursor solution and be formed on its surface
Surface Energy Gradients, to realize that organic semiconductor thin-film is orientated life from mono- side film Ag to mono- lateral edge orientation of film Au
It is long.
The preparation method of the oriented film for the suitable single line spray printing that the present embodiment is proposed based on asymmetric electrode structure, disappears
In addition to single line film is in the competition mechanism of length direction oriented growth, it is suitble to prepare smaller size of oriented film.Based on this
The device of class oriented film is expected to be applied to the identification to the polarization state and transmission direction of light field.As shown in figure 4, a is light field sense
Answer the minimum constituent unit of device；B is the light field inductor of planar structure；C is the light field inductor of three-dimensional structure.
Since orientation mechanism is derived from contact angle difference, it can be equally orientated and be prepared based on the dissymmetrical structure of single-sided electrode
Organic semiconductor thin-film, the directly difference using organic semiconductor precursor solution in metal surface and surface of insulating layer contact angle
Different, the oriented film obtained perpendicular to electrode side is grown.After completion prepares the semiconductive thin film of oriented growth, above
The electrode for preparing pairing, is expected to obtain smaller channel dimensions by the method for printing.To improve the switching speed of device.
The method that embodiment 2 prepares film using asymmetric stereochemical structure orientation
The method that the present embodiment prepares film using asymmetric stereochemical structure orientation are as follows: as shown in figure 5, being spaced in substrate
Film C and film D is set, and is connected between film C and film D by film E arc-shaped transition, the thickness of film C is greater than film E
Thickness, the thickness of film D is more than or equal to the thickness of film E, and the minimum profile curvature radius of the junction film C and film E is less than thin
The minimum profile curvature radius of film D and the junction film E；Definition from film C to the septal direction of film D be film E width direction or
Orientation, by the precursor solution of organic semiconductor thin-film material along perpendicular to film E by way of inkjet printing
The horizontal direction of width direction is printed upon in horizontal substrate, and the connection of film C Yu film E is completely covered in the side of print pattern
Place, boundary of the other side without departing from film D form organic semiconductor thin-film after solvent volatilization；Utilize the difference on spatial position
The asymmetric surface tension effects and the Surface Energy Gradients being formed on its surface that the profile of curvature generates precursor solution, together
Orientation self assembly effect between Shi Liyong molecule organic semiconductor, makes organic semiconductor from the lesser side of minimum profile curvature radius
To the biggish side oriented growth of minimum profile curvature radius, realize a side where organic semiconductor thin-film from film C to film D institute
Side, along the oriented growth of film E width direction.
Specifically, semiconductive thin film, prepared ink and substrate used and 1 phase of embodiment that the present embodiment is printed
Together.As shown in fig. 6, in SiO2Upper spin coating a layer thickness is the PVP material of 300nm, is then carved using photoresist, by dry method
Erosion, is carved into figure (the retention position i.e. position of film C) for the PVP layer of institute's spin coating, then spin coating second layer 500nm on it again
PVP, that is, form the stereo profile with Curvature varying, the film D and film E height of this method production are identical, operation letter
List is easily achieved.Then non-contact spatterwork equipment is used, the TIPS-PEN of spray printing single line form is thin in stereo profile region
Film, the liquid volume of single pulse injection are 10pL, pulse frequency 1000Hz.
Compared using smooth PVP substrate, under two kinds of substrates gained film crystallization shape MIcrosope image and its partially
Light image is as shown in fig. 7, wherein Fig. 7 a and Fig. 7 c corresponding flat substrate, Fig. 7 b and Fig. 7 d correspond to stereo profile substrate.From Fig. 7 a
More in disorder, the crystalline orientation that can be seen that the film morphology in substrate of the smooth PVP substrate i.e. without microcosmic stereochemical structure with Fig. 7 c
Center is directed toward by edge, the growth of film starts from the endpoint of pattern rather than pattern boundaries；It can be seen that from Fig. 7 b and Fig. 7 d thin
Membrane crystallization orientation is grown since stereo profile is by edge that ink covers, and boundary definition is clear, and semiconductive thin film is along vertical
The direction oriented crystalline at stereo profile edge, so that realizing has the film morphology of certain crystalline orientation.
The characterizing method of the orientation intensity of 3 oriented growth film of embodiment
The characterizing method of the orientation intensity of the present embodiment oriented growth film is taken by X-ray diffraction spectrum characterization outside face
Be orientated intensity into the face of growing film, orientation intensity includes two quantitatively evaluating indexs: the consistency in oriented growth direction and
The continuity of oriented growth, embodiments step are as follows:
(1) determine whether organic semiconductor thin-film to be characterized is oriented growth by petrographic microscope first, if so, after
It is continuous to carry out step (2)；
(2) the X-ray plane of incidence and organic semiconductor thin-film target to be characterized for defining X-ray diffraction outside face it is expected growth side
Angle between is test azimuth angle alpha, is to test azimuthal change step with Δ α, to organic semiconductor thin-film to be characterized
The outer X-ray diffraction analysis in carry out face obtains α X-ray diffraction spectrum from 0 ° to 90 ° or outside the face in 0 ° to 180 ° of multiple orientation, and
Obtain the ratio R of most strong even number crystallographic plane diffraction peak intensity and most strong odd number crystallographic plane diffraction peak intensity in each diffraction spectra21, each diffraction spectra
Corresponding R21Minimum value be denoted as Rmin, corresponding azimuth is denoted as αmin, maximum value is denoted as Rmax, corresponding azimuth is denoted as
αmax；
(3) for the organic semiconductor thin-film of two oriented growths, compare the R of the twomin, RminSmaller, then this organic is partly led
The continuity of body thin film oriented growth is better；
(4) to organic semiconductor thin-film to be characterized, using α as abscissa, the R to correspond to each α21For ordinate, mapping is simultaneously
Connect R21Minimum value and the corresponding data point of maximum value, corresponding line slope k=(Rmax-Rmin)/(αmax-αmin)；
For the organic semiconductor thin-film of two oriented growths, the k both compared, k is bigger, then the organic semiconductor thin-film
The consistency in oriented growth direction is better.
Concrete example is as follows: film preparation TIPS-PEN film is plated with lifting, in surface SiO2Thickness of insulating layer is 300nm's
The PVP layer of highly doped Si on piece spin coating 120nm thickness is used as substrate, and ink is using TIPS-PEN as solute, with chloroform or dichloro
Methane is that solvent is prepared according to 10mg/mL.
As shown in figure 8, a, g be respectively chloroform, methylene chloride lifting preparation film morphology figure, b, c, d, e, f and h, i,
J, k, l respectively correspond the petrographic microscope image of chloroform and methylene chloride when deflecting 0 °, 30 °, 45 °, 60 °, 90 °.M is
Measure azimuth schematic diagram；N is to lift the film of preparation in different orientations using chloroform and methylene chloride as solvent
Its 002/001 peak value compares variation tendency.
Fig. 9 is based on the azimuthal variation relation of peak value comparison and gives calculated result: the film of chloroformic solution lifting preparation
Corresponding RminIt is 0.248, the film R of dichloromethane solution lifting preparationminIt is 0.214, the latter is smaller, shows that methylene chloride is molten
The continuity of the Thin Films Tropism Growing of liquid preparation is more preferable.According to the definition of k value, the corresponding k of film of chloroformic solution lifting preparation
Value is 2.07 × 10-3, the corresponding k value of film of dichloromethane solution lifting preparation is 3.23 × 10-3, the latter is bigger, shows two
The consistency in the Thin Films Tropism Growing direction of chloromethanes solution preparation is more preferable, it is seen that the intensity ratio of each diffraction maximum in thin film diffraction
Value, can be used as the quantization signifying means of the consistency in the continuity for judging Thin Films Tropism Growing and oriented growth direction.
The characterizing method of the orientation characteristic of the organic semiconductor thin-film of existing characterization oriented growth mainly has: polarized light microscopy
XRD diffraction in photo, atomic force microscope or face, wherein XRD diffraction cannot be used generally because of test equipment valuableness in face.Figure
10 for the above-mentioned TIPS-PEN film using chloroform and methylene chloride as solvent lifting preparation atomic force microscopy diagram (a) with not
With the petrographic microscope figure (b) at position.It can be seen that can be obtained preferably by the film of dichloromethane solvent lifting preparation
Oriented growth continuity (atomic force micrograph find out thickness more evenly, edge is more straight, petrographic microscope show along
The width of direction of growth ribbon crystal is than more consistent, less generation bifurcated) and oriented growth direction consistency (polarized light microscopy
Mirror shows that less generation bifurcated, the orientation ratio of ribbon crystal are more consistent).
It can be seen that characterizing method of the invention is it can be concluded that identical conclusion, and it can quantify, is more accurate.
In conjunction with the embodiments in 1 the preparation of three kinds of structures film, as shown in figure 11, corresponding XRD diffraction spectra is (right at 0 ° respectively
Should scheme the X-direction in (a), as a result see figure (b)) and 90 ° of (Y-direction in corresponding diagram (a), as a result see figure (c)) azimuth acquisitions,
Corresponding R is obtained also with above-mentioned analysis method according to the XRD diffraction spectra of acquisitionminIt is as shown in figure 12 with k value.Compare phase
Data are answered, consistency and orientation life that the film that discovery is prepared on asymmetry electrode has preferable oriented growth direction are easy
Long continuity.As an example, the XRD data of acquisition are limited for the present embodiment, if appropriateness expand acquisition azimuth coverage and
Azimuth value density, can obtain more accurate data.The present embodiment is a kind of most simplified characterization case, despite this,
Still it can correctly reflect the difference between the oriented growth feature of film and different samples, sufficiently demonstrate having for this method
Effect property.
The present invention utilizes the surface energy differential of material by the selection of material and/or the building of asymmetric microcosmic stereochemical structure
The precursor solution of caused solvent or semiconductor is formed on its surface asymmetric contact angle, forms surface tension in the solution
Gradient can promote in solution solute molecule in the gradient direction oriented growth.This is a kind of stronger orientation effect mechanism, can
To obtain apparent orientation effect in range of small, the printed circuit or array optical of high-frequency work can be applied to
Field sensor.XRD diffraction spectra outside the face of angle acquisition oriented film from different directions, extracts the characteristic peaks under the conditions of each azimuth
Than minimum value Rmin, can be used for characterizing the continuity of Thin Films Tropism Growing, the line segment that connection minimum value and maximum value obtain
Slope k can be used for characterizing the consistency in Thin Films Tropism Growing direction.
Claims (6)
1. a kind of organic semiconductor thin-film based on unsymmetric structure is orientated preparation method, it is characterised in that: the unsymmetrical knot
Structure is asymmetric planar structure and/or asymmetric stereochemical structure；
The method for preparing organic semiconductor thin-film using asymmetric planar structure orientation are as follows: draw materials A and material B, between the two
There are surface energy differential, and the contact angle of materials A and organic semiconductor precursor solution to be printed is greater than material B and to be printed
The contact angle of organic semiconductor precursor solution；The patterned film of materials A and material B is respectively formed in substrate, respectively
There is a channel among film A and film B, film A and film B, definition channel length L between film A and film B most
Short distance, the corresponding direction of channel length are orientation；By organic semiconductor presoma by way of inkjet printing
Solution is printed upon in horizontal substrate along the horizontal direction perpendicular to orientation, forms organic semiconductor thin-film, described
Organic semiconductor thin-film be completely covered the channel between film A and film B and with film A, there are overlapping regions by film B, and
Without departing from the region where film A and film B；Precursor solution is deposited because of the difference of contact angle using film A and film B
Asymmetric surface tension effects and the Surface Energy Gradients that are formed on its surface, while utilizing in precursor solution organic half
Orientation self assembly effect between conductor molecule, makes organic semiconductor from the biggish side of contact angle to the lesser side of contact angle
Oriented growth, to realize that organic semiconductor thin-film is raw from mono- side film A to the orientation of mono- lateral edge orientation of film B
It is long；
The method for preparing organic semiconductor thin-film using asymmetric stereochemical structure orientation are as follows: in substrate interval setting film C and
Film D, and connected between film C and film D by film E arc-shaped transition, the thickness of film C is greater than the thickness of film E, film
The thickness of D is more than or equal to the thickness of film E, and film C and the minimum profile curvature radius of the junction film E connect less than film D and film E
Connect the minimum profile curvature radius at place；Definition from film C to the septal direction of film D be film E width direction or orientation,
Organic semiconductor precursor solution is printed upon along the horizontal direction perpendicular to film E width direction by way of inkjet printing
In horizontal substrate, the junction of film C Yu film E, side of the other side without departing from film D is completely covered in the side of print pattern
Boundary forms organic semiconductor thin-film after solvent volatilization；Precursor solution is produced using the profile of the different curvature on spatial position
Raw asymmetric surface tension effects and the Surface Energy Gradients being formed on its surface, while using between molecule organic semiconductor
Orientation self assembly effect, make organic semiconductor from the lesser side of minimum profile curvature radius to the biggish side of minimum profile curvature radius
Oriented growth, realize organic semiconductor thin-film from film C where a side to film D where side, along film E width direction
Oriented growth.
2. the organic semiconductor thin-film according to claim 1 based on unsymmetric structure is orientated preparation method, feature exists
In: prepared organic semiconductor thin-film is the organic semiconductor active layer in high frequency Organic Thin Film Transistors, or is array light
Organic semiconductor oriented film in field sensor.
3. the organic semiconductor thin-film according to claim 1 based on unsymmetric structure is orientated preparation method, feature exists
In: the film A and film B is metallic film or insulating material film, and the film C, film D and film E are metal
Film or insulating material film.
4. the organic semiconductor thin-film according to claim 1 based on unsymmetric structure is orientated preparation method, feature exists
In: 0≤L≤100 μm.
5. the organic semiconductor thin-film according to claim 1 based on unsymmetric structure is orientated preparation method, feature exists
In: the organic semiconductor thin-film is polycyclic aromatic hydrocarbons organic semiconductor thin-film.
6. the organic semiconductor thin-film according to claim 1 based on unsymmetric structure is orientated preparation method, feature exists
In: the inkjet printing is using non-contact spatterwork equipment, and the symmetrical center line along two edges of channel or film E is on-demand
The precursor solution of spray printing single line form, the liquid volume of single injection event is less than 100 picoliters, injection frequency 500-
5000Hz。
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| CN109786552B (en) * | 2019-01-22 | 2020-10-16 | 合肥京东方光电科技有限公司 | Organic thin film, manufacturing method thereof, display device and optical device |
| CN110487788B (en) * | 2019-07-12 | 2021-08-20 | 中国科学院金属研究所 | Method for evaluating small-angle grain boundary forming tendency of single crystal superalloy |
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