CN104993053B - Method for improving performance of organic thin-film transistor - Google Patents
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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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
- H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/20—Organic diodes
- H10K10/26—Diodes comprising organic-organic junctions
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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
- H10K71/30—Doping active layers, e.g. electron transporting layers
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- Optics & Photonics (AREA)
- Thin Film Transistor (AREA)
Abstract
The invention discloses a method for improving performance of an organic thin-film transistor (OTFT). The method comprises steps of cutting a P-type doped silicon sheet of silicon dioxide into small sheets; cleaning and drying the small sheets by deionized water, acetone and ethyl alcohol; dropping OTS on the small sheets; coating mixed solution of OTFT new type active layer material BFTII and the classic material P3HT in a spinning manner; and then performing thermal annealing. According to the invention, manufacturing cost is low and technology is simple; by doping polymers on and performing thermal annealing on the new type oligomeric OTFT active layer material, even if the OTFT is kept in quite low threshold voltage, carrier mobility can be increased by more than two order of magnitudes and the switch ration can be increased by one order of magnitude; and the method is widely applicable for industrial application.
Description
Technical field
The present invention relates to the preparation method of organic field effect tube, more particularly to one kind improves organic thin-film transistor
The method of pipe performance.
Background technology
After inorganic electronic device comes out, the application prospect based on organic semi-conductor electronic device is As time goes on
And wide all the more, such as organic solar batteries, Organic Light Emitting Diode, organic field effect tube, organic photoelectric memorizer
Deng nano-device.Wherein, organic field thin film transistor (TFT), abbreviation organic thin-film transistor (OTFT), in Jing
After having gone through investigation for many years, its feature for having much captivation gradually mirrors popular eyes.
The unique advantage of OTFT is that it is capable of achieving large area mechanical flexibility and shows, while possessing high-performance, low-power consumption, low
The technical characterstic such as cost and easy processing, it is abundant clear as display color.One of pursuit today for OTFT is into one
Step ground shortens response time and lifts its cost performance, and many effort also cause OTFT in the sensing detection side in the fields such as environmental organism
Have place to show one's prowess in face.Such as, one kind that Narayan and his team's original research go out is based on poly (3-octylthiophene-
2,5-diyl) OTFT optical sensors, just can obtain ratio (the K.S.Narayan and of 100 switching current
N.Kumar,Appl.Phys.Lett.2001,79,1891-1893)..Thus, each company of various countries, institution of higher learning and scientific research institutions
Start anxiety densely to study, to contend the leading enterprise of this industry, strive for researching and developing the one seat of OTFT application products.
Organic material used in OTFT is basically divided into two classes, and one is polymer, such as commercialization medicine poly (3-
Hexylthiophene), abbreviation P3HT；It is another kind of, it is small molecule, exemplary is then Benzo[b.Due in numerous polymer
Effect between powerful π-π keys can greatly promote the transmission of carrier, and increasing research is devoted to various to improve OTFT
Organic new function material of the performance parameters such as carrier mobility, current on/off ratio, threshold voltage and subthreshold swing makes
With.In order to further enhance OTFT performances, work hard and be concentrated mainly on the following aspects：(1) synthetic route is sought in research
To construct the material model of more conducively carrier transport, it is mainly used in active layer, dielectric layer and part decorative layer material.
(2) compared with traditional technology for coating, the organic film that the new approach such as solwution method is obtained is in large area, the OTFT of low cost
More there are potential advantages in device technology of preparing.Even in 2014, S.Tiwari et al. has found what suspension film transfer method was obtained
OTFT electric properties it is more better than device prepared by spin-coating film method (S.Tiwari, W.Takashima, S.Nagamatsu,
S.K.Balasubramanian,and R.Prakash,J.Appl.Phys.2014,116,094306).(3) due to carrier
The active layer for flowing through and the thickness that the distance of dielectric layer is only several molecules, so the interfacial effect of quasiconductor and dielectric layer becomes
Improve one of important way of OTFT performances, processing by appropriate modifying interface or self assembly can be obviously improved its carrier
Mobility (X.Zhao, Q.Tang, H.Tian, Y.Tong, and Y.Liu, Org.Electron.2015,16,171-176).
(4) additionally, increasing group starts each organic molecular species that adulterate in active layer, its electric conductivity is further enhanced with this.
The doping content of different organic materials can cause the change of OTFT active layer surface topographies, and part can also be due to the difference of degree of crystallinity
Affect its performance (H.Kleemann, C.Schuenemann, A.A.Zakhidov, M.Riede, B.L ü ssem, and K.Leo,
Org.Electron.2012,13,58-65)。
Although the scientific research level of China is almost synchronous with developed country, OTFT classics the single of active layer material uses
So that cost performance cannot be lifted further, cause the industrialization production application based on OTFT devices substantially not enough.
But the problem that prior art is present has：(1) the frequent use of traditional classical material causes preparation cost too high；
(2) OTFT process meanses are prepared complex；(3) traditional devices energy consumption is too big etc..
The content of the invention
To solve above-mentioned technical problem, the invention provides one kind doped polymer in new oligomeric materials improves organic
The method of thin-film transistor performance, its technical scheme is as follows：
A kind of method for improving OTFT performance, its step is as follows：
Step one：P-type doped silicon wafer by one side with thickness for 300nm silicon dioxide is pressed on dust-free paper, along scale
Scale diamond sharp knife draws cutting-up to be cut into small pieces；
Step 2：By the silicon chip processed through step one successively Jing deionized waters clean 10 minutes, acetone clean 20 minutes,
Ethanol purge 15 minutes, takes out after drying 30 minutes at 80 DEG C；
Step 3：The silicon chip processed through step 2 is placed in culture dish and is put into vacuum drying oven, the silicon in culture dish
One is instilled by piece with capillary pipette and drip OTS, take out after drying 3 hours at 120 DEG C.
Step 4：The silicon chip processed through step 3 is transferred to into inert atmosphere glove box, OTFT novel actives in spin coating
The mixed solution of layer material BFTII and classical material P3HT, thermal annealing, the molecular structure of BFTII is as follows：
Step 5：Vacuum chamber is transferred to after thermal anneal process, metal mask plate, one layer of gold electrode of vacuum moulding machine is installed.
Step 6：After electrode evaporation is finished, electric property is carried out to obtained OTFT with testboard and Keithley sources table
Test.
Step 7：Apply uv-curable glue, cover sheet glass, ultra-violet curing, encapsulation is finished.
Single silicon chip cut lengths are 1.6cm × 1.4cm in the step one.
Mix BFTII chloroforms to do the concentration of solvent solution-forming by P3HT in the step 4 is 4mg/mL, and P3HT is accounted for
The mass percent of solute starts once to be compared per 10% increase from 0%.
Spin coating rotating speed is 3000r/min in the step 4, and 30 seconds persistent period, thickness is 60nm.
Thermal annealing is 130 DEG C of vacuum annealings 10 minutes in the step 4.
The raceway groove of metal mask plate is a length of 80 μm in the step 5, and raceway groove is a width of 8800 μm.
The deposition velocity of electrode is in the step 5
Low cost of manufacture of the present invention, process is simple, by the doped polymer in new oligomeric OTFT active layer materials and
Thermal annealing process, you can so that OTFT is under conditions of lower threshold voltage is kept, carrier mobility lifts two or more number
Magnitude, on-off ratio can also rise an order of magnitude, be suitable to extensive commercial application.
Description of the drawings
OTFT structural representations obtained in Fig. 1.
X ray diffracting spectrum of Fig. 2 BFTII active layers under different P3HT doping contents.
The atomic force microscopy image of the pure BFTII active layers of Fig. 3.
Atomic force microscopy image of Fig. 4 BFTII active layers under 10%P3HT doping contents.
Atomic force microscopy image of Fig. 5 BFTII active layers under 20%P3HT doping contents.
Atomic force microscopy image of Fig. 6 BFTII active layers under 30%P3HT doping contents.
Atomic force microscopy image of Fig. 7 BFTII active layers under 40%P3HT doping contents.
The optimal OTFT devices of performance obtained in Fig. 8 are that transfer characteristics of the P3HT in active layer during doping content 20% is bent
Line.
The optimal OTFT devices of performance obtained in Fig. 9 are that output characteristics of the P3HT in active layer during doping content 20% is bent
Line.
Comparison of Figure 10 OTFT carrier mobilities under different P3HT doping contents.
Comparison of Figure 11 OTFT current on/off ratios under different P3HT doping contents.
Comparison of Figure 12 OTFT threshold voltages under different P3HT doping contents.
Specific embodiment
Below in conjunction with the accompanying drawings, the present invention is further elaborated.
The invention provides a kind of method for improving OTFT performance, it is comprised the following steps that：
Step one：The main selection including base material of enforcement of scheme, the moditied processing of dielectric layer, the system of active layer
Standby, thermal anneal process, electrode deposition and product encapsulation etc., the device architecture schematic diagram for preparing as shown in Figure 1, from bottom to top
It is followed successively by gate electrode substrate (Si), dielectric layer (SiO2), decorative layer (OTS), doping active layer (P3HT+BFTII) and gold
Source-drain electrode (Au).Base material can both select glass, silicon chip, and other flexible base materials, such as PC, PET can be selected again
Plastics etc..Base material is mainly according to the purposes of target product to determine, if necessary to be used for illuminating transmission, selects glass base
Bottom is the most suitable；If to be used as the deformable display panel of laminating or sensing detection, then select flexible substrates more preferable.The invention
Have selected monochromatic light and throw the p-type doped silicon wafer in face simultaneously as substrate and grid, the silicon dioxide layer of one side is used as gate dielectric,
It is " a piece of three use ".P-type doped silicon wafer by one side with thickness for 300nm silicon dioxide is pressed on dust-free paper, along scale
Scale diamond sharp knife draws cutting-up to be cut into small pieces.
Single silicon chip cut lengths are 1.6cm × 1.4cm in the step one.
Step 2：By the silicon chip processed through step one successively Jing deionized waters clean 10 minutes, acetone clean 20 minutes,
Ethanol purge 15 minutes, takes out after drying 30 minutes at 80 DEG C；
Step 3：There are the thick silicon dioxide dielectric layers of one layer of 300nm on the surface of silicon chip, next needs to enter it with OTS
Row modification.The silicon chip processed through step 2 is placed in culture dish and is put into vacuum drying oven, hair is used by silicon chip in culture dish
Thin suction pipe instills one and drips Octadecyltrimethoxysilane, abbreviation OTS, takes out after drying 3 hours at 120 DEG C.
Step 4：Inert atmosphere glove box will be transferred to through the silicon chip of back moditied processing, OTFT is new in spin coating
The mixed solution of active layer material BFTII and classical material P3HT, thermal annealing 10 minutes at 130 DEG C.
X ray diffracting spectrum of the BFTII active layers under different P3HT doping contents from accompanying drawing 2, with activity
The P3HT concentration that layer is mixed changes to 20% from 0, and the active layer molecule after thermal annealing process is presented good crystallinity, continues to increase
Concentration, then corresponding degree of crystallinity also declined, and from corresponding atomic force microscopy figure surface topography it is also seen that corresponding
Relation.The atomic force microscopy image of BFTII active layers shows that pure BFTII molecules are presented the state of bar-shaped stacking, phase in accompanying drawing 3
There are many spaces between mutually, during gradually increasing from 0 with the P3HT concentration that active layer is mixed, P3HT molecules are gradually filled
Between space before having entered so that surface is further smooth, accompanying drawing 4, accompanying drawing 5, accompanying drawing 6 and accompanying drawing 7 are respectively BFTII active layers
Atomic force microscopy figure under 10%, 20%, 30% and 40% P3HT doping contents.
The molecular structure of new material BFTII is as follows in the step 4：
Active layer material BFTII is a kind of new oligomeric organic semiconductor, its highest occupied molecular orbital energy level
(HOMO) and lowest unoccupied molecular orbital energy level (LUMO) is respectively -5.09eV and -3.60eV, as the active layer energy of OTFT
Show good field effect characteristic.
Mix BFTII chloroforms to do the concentration of solvent solution-forming by P3HT in the step 4 is 4mg/mL, and P3HT is accounted for
The mass percent of solute starts once to be compared per 10% increase from 0%.
Spin coating rotating speed is 3000r/min in the step 4, and 30 seconds persistent period, thickness is 60nm.
Thermal annealing is 130 DEG C of vacuum annealings 10 minutes in the step 4.
Step 5：Vacuum chamber is transferred to after thermal anneal process, metal mask plate, vacuum deposited metal are installed on substrate
Electrode, deposition source electrode and drain electrode, metal material is gold, is deposited with gold electrode.
The raceway groove of metal mask plate is a length of 80 μm in the step 5, and raceway groove is a width of 8800 μm.
The deposition velocity of electrode is in the step 5
Step 6：After electrode evaporation is finished, connect three electrodes of OTFT respectively with testboard probe and pass through
Keithley sources table can carry out electrical performance testing to obtained OTFT, and the optimal OTFT devices of performance are P3HT in active layer
Situation during doping content 20%, its transfer characteristic curve and output characteristic curve as shown in accompanying drawing 8 and accompanying drawing 9, are migrated respectively
Rate reaches 1.83 × 10-2cm2V-1s-1, while current on/off ratio also reaches high 104.4.Each OTFT carrier mobilities and electricity
Stream on-off ratio is shown in more respectively accompanying drawing 10 and accompanying drawing 11 under different P3HT doping contents, as P3HT doping contents are increased to
20%, carrier mobility improves two orders of magnitude when comparing undoped p, and on-off ratio also rises an order of magnitude, continues to mix
Miscellaneous to 40% is gradually reduced again.Can be seen by comparison of the OTFT threshold voltages in accompanying drawing 12 under different P3HT doping contents
Go out, during the change of doping content, OTFT threshold voltages remain at lower value.
Step 7：After being completed, uv-curable glue is coated in surrounding, cover cover glass, ultra-violet curing completes envelope
Dress, prepared by whole device, test and encapsulation process are finished.
Claims (7)
1. a kind of method for improving OTFT performance, its step is as follows：
Step one：P-type doped silicon wafer by one side with thickness for 300nm silicon dioxide is pressed on dust-free paper, along graduated scale
Cutting-up is drawn to be cut into small pieces with diamond sharp knife；
Step 2：The silicon chip processed through step one successively Jing deionized waters is cleaned into 10 minutes, acetone cleaning 20 minutes, ethanol
Cleaning 15 minutes, takes out after drying 30 minutes at 80 DEG C；
Step 3：The silicon chip processed through step 2 is placed in culture dish and is put into vacuum drying oven, in culture dish by silicon chip
One is instilled with capillary pipette and drip OTS, take out after drying 3 hours at 120 DEG C；
Step 4：The silicon chip processed through step 3 is transferred to into inert atmosphere glove box, OTFT active layer materials in spin coating
The mixed solution of BFTII and P3HT, thermal annealing, the molecular structure of BFTII is as follows：
Step 5：Vacuum chamber is transferred to after thermal anneal process, metal mask plate, one layer of gold electrode of vacuum moulding machine is installed；
Step 6：After electrode evaporation is finished, electrical performance testing is carried out to obtained OTFT with testboard and Keithley sources table；
Step 7：Apply uv-curable glue, cover sheet glass, ultra-violet curing, encapsulation is finished.
2. a kind of method for improving OTFT performance according to claim 1, single silicon in the step one
Piece cut lengths are 1.6cm × 1.4cm.
3. a kind of method for improving OTFT performance according to claim 1, by P3HT in the step 4
It is 4mg/mL that incorporation BFTII chloroforms do the concentration of solvent solution-forming, and P3HT accounts for the mass percent of solute and starts often from 0%
10% increase is once compared.
4. a kind of method for improving OTFT performance according to claim 1, spin coating in the step 4 turns
Speed is 3000r/min, and 30 seconds persistent period, thickness is 60nm.
5. a kind of method for improving OTFT performance according to claim 1, thermal annealing in the step 4
For 130 DEG C of vacuum annealings 10 minutes.
6. a kind of method for improving OTFT performance according to claim 1, metal is covered in the step 5
The raceway groove of lamina membranacea is a length of 80 μm, and raceway groove is a width of 8800 μm.
7. a kind of method for improving OTFT performance according to claim 1, electrode in the step 5
Deposition velocity is
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| CN105679939A (en) * | 2016-03-15 | 2016-06-15 | 南京邮电大学 | Doped thiophene isoindigo-based organic thin-film field effect transistor and preparation method thereof |
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| CN104993053A (en) | 2015-10-21 |
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