CN107501269B - Organic amidine molecule n-type dopant and its application in semiconductor photoelectric device - Google Patents

Organic amidine molecule n-type dopant and its application in semiconductor photoelectric device Download PDF

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CN107501269B
CN107501269B CN201710678994.6A CN201710678994A CN107501269B CN 107501269 B CN107501269 B CN 107501269B CN 201710678994 A CN201710678994 A CN 201710678994A CN 107501269 B CN107501269 B CN 107501269B
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type dopant
organic
acceptor material
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photoelectric device
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CN107501269A (en
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周印华
胡林
蒋友宇
刘铁峰
覃飞
熊思醒
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Huazhong University of Science and Technology
Shenzhen Huazhong University of Science and Technology Research Institute
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Shenzhen Huazhong University of Science and Technology Research Institute
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/18—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/12—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines
    • C07C259/14—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines having carbon atoms of hydroxamidine groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a kind of organic amidine molecule n-type dopant and its applications in semiconductor photoelectric device, wherein, n-type dopant is organic amidine molecule, n-type dopant mixes with acceptor material or directly acceptor material is exposed in the steam atmosphere of n-type dopant, realizes and adulterates to the n of acceptor material.N-type dopant is added in organic n-type semi-conductor by the present invention, and the properties such as organic semiconductor conductivity, work function and electron mobility are adjusted；After n-type dopant carries out n doping to acceptor material, it is applied to perovskite solar battery, organic solar batteries, Organic Light Emitting Diode and organic field effect tube.

Description

Organic amidine molecule n-type dopant and its application in semiconductor photoelectric device
Technical field
The invention belongs to field of semiconductor devices, more particularly, to a kind of organic amidine molecule n-type dopant and its half Application in conductor photoelectric device.
Background technique
Organic semiconductor is a kind of emerging material, has been widely used in Organic Light Emitting Diode, organic at present In the semiconductor photovoltaic devices such as field effect transistor, organic solar batteries and perovskite solar battery.In these devices In, the injection and extraction of charge are often related to especially between organic semiconductor and electrode.Therefore, the efficiency meeting of electric charge transfer Greatly influence the performance of device.And the electric conductivity of organic semiconducting materials itself and the fermi level of material and adjacent electricity The matching degree of pole work function is to influence the vital factor of electric charge transfer.
Carrying out effective doping to organic semiconducting materials not only can be improved the electric conductivity and carrier concentration of material, also Its fermi level and the intrinsic some charge defects of material for repairing can be regulated and controled, be that a kind of very effective improve above-mentioned is partly led The means of body device performance.And the dopant of usually N-shaped often has very low ionization potential, just they is had in this way Adulterate other abilities by main semiconductor.Currently, only seldom several n-type dopants for capableing of solution preparation have in the literature Report.So developing low-cost and can solution preparation again very effective n dopant to realize high-performance semiconductor photovoltaic device The solution of part prepares of great advantage.
However, the prior art there are development costs technical problem that is high, being difficult to solution preparation and effect difference.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of organic amidine molecule n-type dopants And its application in semiconductor photoelectric device, thus solve the prior art there are development costs it is high, be difficult to solution preparation and effect The technical problem of fruit difference.
To achieve the above object, according to one aspect of the present invention, a kind of organic amidine molecule n-type dopant, institute are provided Stating n-type dopant is organic amidine molecule, and organic amidine molecule has the structure as shown in formula (one):
Wherein, R1, R2, R3, R4It is independently selected from H, OH, C1-C10Alkyl, C1-C10Alkoxy, C1-C10Ester Base, C1-C10Carboxyl, C1-C10Alcoholic extract hydroxyl group and the aryl or heteroaryl that are replaced by any of the above-described group；R1And R4Pass through C2-C10Alkyl or alkoxy connection cyclization；R2And R3Pass through C2-C10Alkyl or alkoxy connection cyclization.
Further, n-type dopant preferably has the structure as shown in formula (two):
Further, n-type dopant DBU.
It is another aspect of this invention to provide that providing a kind of organic amidine molecule n-type dopant in semiconductor photoelectric device Application, the n-type dopant mixes with acceptor material or is directly exposed to acceptor material the steam atmosphere of n-type dopant In, after realizing the n doping to acceptor material, it is applied to perovskite solar battery, organic solar batteries, organic light-emitting diodes Pipe and organic field effect tube.
Further, acceptor material PC61BM, N2200 or ITIC.
Further, the device architecture of perovskite solar battery are as follows: ITO electro-conductive glass is as battery cathode, NiOxMake For battery hole transmission layer, MAPbI3For perovskite light-absorption layer, n-type dopant is used as battery after carrying out n doping to acceptor material Electron transfer layer, metal Ag is as anode.
Further, the device architecture of organic field effect tube are as follows: SiO2For insulating layer, n-type dopant is to receptor material Material is used as n-type semiconductor layer after carrying out n doping, and top electrodes Au is as source-drain electrode.
Further, when n-type dopant is to n-type semiconductor layer is used as after acceptor material progress n doping, doping concentration is 1%.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show Beneficial effect:
(1) n-type dopant solution processable of the invention, above-mentioned n-type dopant is added in organic n-type semi-conductor, The properties such as adjustable organic semiconductor conductivity, work function and electron mobility；Further by the organic n-type semi-conductor of doping It is applied in perovskite battery and organic field-effect transistor and is remarkably improved device performance, in other semiconductor photoelectric devices also It is with a wide range of applications.
(2) a kind of amidine organic micromolecule of the invention can be used as effective n-type dopant and mix semiconductor progress n It is miscellaneous.Doping process is very easy, only dopant need to be blended with acceptor material and be dissolved in organic solvent or expose acceptor material It can be realized in the steam of dopant.The present invention is using organic amidine molecule n-type dopant respectively to PC61BM, N2200 and ITIC Equal acceptor materials are doped.And it verifies, the PC after doping61BM has higher electric conductivity；Fermi level can move up, more Close to PC61Lowest unoccupied molecular orbital (LUMO) energy level of BM.
(3) PC after present invention doping61The electric conductivity of BM significantly improves, so that being used for perovskite as electron transfer layer It can be improved the incident photon-to-electron conversion efficiency of device in battery device.And the PC after adulterating61BM fermi level moves, energy level with The work content of metallic silver (Ag) electrode used in perovskite battery device more matches, and poly- second can not be used in battery device The modification layer material of this reduction electrode work content of alkene imines (PEI), technique are more simplified.
(4) in scene effect transistor of the present invention, the PC after doping61BM mobility significantly improves, and threshold voltage obviously subtracts It is small, and preferably when doping concentration reaches 1%, the on-off ratio of device almost disappears.
(5) currently preferred DBU material is cheap and easy to get, and doping process is simple, easily controllable, thus more other half It is applied and promotes in conductor device.
Detailed description of the invention
Fig. 1 (a) is PC in the embodiment of the present invention61Ultraviolet-visible absorption spectroscopy figure of the BM before and after DBU doping；
Fig. 1 (b) is ultraviolet-visible absorption spectroscopy figure of the N2200 before and after DBU doping in the embodiment of the present invention；
Fig. 1 (c) is ultraviolet-visible absorption spectroscopy figure of the ITIC before and after DBU doping in the embodiment of the present invention；
Fig. 2 (a) is the photo in kind in the embodiment of the present invention before and after DBU reduction treatment PEDOT:PSS；
Fig. 2 (b) is the ultraviolet-visible absorption spectroscopy figure in the embodiment of the present invention before and after DBU reduction treatment PEDOT:PSS；
Fig. 3 (a) is PC in the embodiment of the present invention61BM conductivity tests device structural schematic diagram；
Fig. 3 (b) is that DBU adulterates PC in the embodiment of the present invention61Current-voltage figure before and after BM；
Fig. 4 is that perovskite solar battery uses DBU to adulterate PC in the embodiment of the present invention61BM is as before and after electron transfer layer Current-voltage figure；
Fig. 5 (a) is in the embodiment of the present invention based on doping front and back PC61Bottom gate top contact organic field of the BM as semiconductor layer The schematic diagram of effect transistor；
Fig. 5 (b) is in the embodiment of the present invention based on doping front and back PC61Bottom gate top contact organic field of the BM as semiconductor layer The I of effect transistorDS-VGSTransfer curve.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of organic amidine molecule n-type dopant, the n-type dopant is organic amidine molecule, described to have Machine amidine molecule has the structure as shown in formula (one):
Wherein, R1, R2, R3, R4It is independently selected from H, OH, C1-C10Alkyl, C1-C10Alkoxy, C1-C10Ester Base, C1-C10Carboxyl, C1-C10Alcoholic extract hydroxyl group and the aryl or heteroaryl that are replaced by any of the above-described group；R1And R4Pass through C2-C10Alkyl or alkoxy connection cyclization；R2And R3Pass through C2-C10Alkyl or alkoxy connection cyclization.
Preferably, a kind of organic amidine molecule n-type dopant has the structure as shown in formula (two):
N-type dopant can carry out n doping to acceptor material, adjust organic semiconductor conductivity, work function and electronics The properties such as mobility.The acceptor material is respectively as follows: [6,6]-phenyl C61Methyl butyrate (PC61BM), poly- (2,7- bis- (2- octyls Dodecyl) benzo [LMN] [3,8] phenanthrolene -1,3,6,8 (2H, 7H)-tetrone -4,9- diyls) ([2,2 '] Dithiophene 5,5 '-diyl of base -) (N2200) and 3, bis- (2- methylene-(3- (1,1- the methylene dicyanoethyl)-indones)) -5,5,11,11- tetra- of 9- (4- hexyl phenyl) -1,4-Dithiapentalene base [2,
3-d:2 ', 3 '-d '] and the indacene-s- [1,2-b:5,6-b '] Dithiophene) (ITIC), the exemplary construction of acceptor material As shown in following formula (three):
The embodiment of the present invention is by by DBU and common acceptor material such as PC61BM, N2200 and ITIC etc. are blended in organic It is exposed in the steam atmosphere of DBU in solvent or directly by acceptor material, to realize to the n doping by main semiconductor.It is excellent Selection of land, when DBU adulterates PC61When the mass percent of BM is 1%, the PC after the doping61BM conductivity is from 7.8 × 10-8S/cm It is increased to 3.6 × 10-4S/cm, fermi level move on to 4.4eV from 4.9eV.And by the PC after doping61BM is passed as electronics Defeated layer is in perovskite battery device, the device efficiency of battery to be compared to original PC61The device of BM electron transfer layer from 10.45% is increased to 16.59%.In addition, the current density voltage curve of the battery after doping does not have S-shaped.
Embodiment 1
DBU is to PC61BM, N2200 and ITIC carry out n doping
According to different technique, respectively using DBU to PC61BM, N2200 and ITIC carry out n doping.It is being full of nitrogen first Glove box, by PC61BM is dissolved in spectroscopic pure chlorobenzene solvent, and the concentration of acquired solution is 20mg/ml.Then in PC61BM solution The middle DBU that different quality is added, 50 DEG C of heating stirrings are stayed overnight, be can be realized to PC61The doping of BM.By above-mentioned different levels of doping Solution with 1000 revs/min of revolving speed spin-coating films, the following Fig. 1 (a) of the ultraviolet-visible absorption spectroscopy figure of gained film.It is preferred that Ground, the doping concentration for perovskite battery device electron transfer layer are 0.1wt%.Taking 50 microlitres of doping concentrations is 0.1wt% Mixed solution be spun on the perovskite surface prepared, can be used as battery electron transport layer.Similarly, by N2200 It is dissolved in spectroscopic pure chlorobenzene solvent respectively with ITIC receptor, 50 DEG C of heating stirrings are stayed overnight.Wherein, the concentration of N2200 chlorobenzene solution For 5mg/ml；The concentration of ITIC chlorobenzene solution is 10mg/ml.50 microlitres of above-mentioned solution are taken to revolve with 1000 revs/min of revolving speeds respectively Film forming is applied in substrate of glass, gained N2200 and ITIC film is placed in surface plate, and 30 microlitres are added dropwise in surface plate DBU.Then surface plate is placed in 100 DEG C of thermal station and heats different time, can realized respectively different degrees of to N2200 and ITIC Doping.Wherein, the following Fig. 1 (b) of ultraviolet-visible absorption spectroscopy figure of the N2200 and ITIC film of different levels of doping and (c).
Embodiment 2
DBU restores conducting polymer PEDOT:PSS
Then PEDOT:PSS (PH1000) is placed it in 1000 revs/min of revolving speed spin-coating films in substrate of glass It anneals 10 minutes in 140 DEG C of thermal station and obtains light blue PEDOT:PSS film, shown in following Fig. 2 (a).By sheet glass to hemisection It opens, and half therein is placed in drop to have in the surface plate of DBU, then surface plate is placed in 100 DEG C of thermal station and is heated 5 minutes, The color of observation discovery PEDOT:PSS film is gradually deepened to navy blue, shows that PEDOT:PSS is restored by DBU.In Fig. 2 (b) Ultraviolet-visible absorption spectroscopy figure for PEDOT:PSS by DBU before and after the processing, it is evident that PEDOT:PSS be reduced after in visible light The absorption for composing area becomes strong.
Embodiment 3
PC61The variation of BM doping front and back electric conductivity
PC61The device architecture of BM doping front and back electric conductivity test is indium oxide tin glass/[6,6]-phenyl C61Butyric acid first Ester/silver (ITO/PC61BM layer/Ag).Wherein, hearth electrode is ITO electro-conductive glass (indium tin oxide-coated glass), and centre is to mix The PC of miscellaneous front and back61BM layers, top electrode Ag, structure such as Fig. 3 (a).Embodiment 3 specific the preparation method is as follows:
(1) ito glass is successively cleaned through suds, deionized water, acetone, isopropanol ultrasonic cleaning, then through Plasma.
(2) in the glove box full of nitrogen atmosphere, configured PC in above-described embodiment 1 is taken61BM solution with 2000 turns/ Minute revolving speed is spun on above-mentioned cleaned ito glass, so that the pure PC of 40nm thickness be made61The BM or PC being doped61BM Film.The Ag of one layer of 70nm is then deposited by vacuum coater again.
(3) current-voltage relation that above-mentioned device is tested by 2400 ammeter of Keithley, such as Fig. 3 (b).Wherein survey Examination voltage sweeps to 1V from -1V, and sweep speed is 20mV s-1.Intermediate PC61BM layers of conductivity is calculated by formula σ=L/ (RA) Out, R is represented resistance (V/I) in formula, and A is effective area (10.58mm2), L is the thickness of film.
Embodiment 4
The preparation of perovskite solar battery
The device architecture of perovskite solar battery are as follows: glass/tin indium oxide/nickel oxide/methylamine lead iodine perovskite/[6, 6]-phenyl C61Methyl butyrate or doping [6,6]-phenyl C61Methyl butyrate/silver (glass/ITO/NiOx/MAPbI3/PC61BM or doped PC61BM/Ag).Wherein, ITO electro-conductive glass is as battery cathode, NiOxAs battery hole transmission layer, MAPbI3For Perovskite light-absorption layer, PC61The BM or PC of doping61BM is as battery electron transport layer, and metal Ag is as anode.Embodiment 4 It is specific the preparation method is as follows:
(1) ito glass is successively through suds, deionized water, acetone, isopropanol ultrasonic cleaning, then through plasma (Plasma) it cleans 2 minutes.
(2) with 4000 revs/min of revolving speed spin coatings prepared NiO on cleaned ito glassxPresoma is molten Liquid.Wherein, NiOxPrecursor solution is by being hydrated the ethylene glycol list first that nickel acetate and 0.1g ethanol amine are dissolved in 10g for 0.3g tetra- Ether, then vigorous stirring overnight is made.By the good NiO of spin coatingxThe ITO substrate of presoma first heats 10 minutes in 200 DEG C of thermal station, It is then transferred in 400 DEG C of thermal station and heats 20 minutes.
(3) by the above-mentioned ITO/NiO preparedxFilm is handled 5 minutes with Plasma, by perovskite precursor solution [iodine methylamine (the CH of 0.3M3NH3) and 1.3M lead iodide (PbI I2) it is dissolved in N,N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) volume ratio of in the mixed solvent, DMF and DMSO are 9: 1] it 15s is turned with 6000rpm is spin-coated on NiOxSurface, with will It is reduced to 3700rpm in revolving speed 2s, CH is added dropwise immediately3NH3I solution (0.2M is dissolved in isopropanol), and 3700rpm is kept to turn 45s.100 DEG C are heated 30 minutes up to MAPbI3Perovskite light-absorption layer.
(4) then again on perovskite surface with the PC in 2000 revs/min revolving speed spin coating above-described embodiment 161BM mixes Miscellaneous PC61BM solution is as battery electron transport layer.Preferably, when doping concentration is 0.1wt%, the device performance of battery is most It is good.
(5) above-mentioned device is transferred in vacuum coating system, by vacuum coater in PC61One layer of 90nm is deposited on BM Ag electrode, i.e., successfully prepare perovskite solar battery.The effective area of battery is 10.58mm2.By battery in simulated solar Light 100mW cm-2Under the light intensity of AM 1.5G, the variation of test current-voltage is carried out with Keithley 2400, in test process Sweep speed is 20mV s-1, Fig. 4 is to use pure PC61BM and it is doped PC61Device current-of the BM as electron transfer layer battery Voltage curve.
Embodiment 5
The preparation of organic field effect tube
The embodiment of the present invention is prepared for based on PC61Organic field effect tube (OFET) of the BM as semiconductor layer, crystal The device architecture of pipe uses bottom gate top contact form, specially silicon/silicon dioxide/[6,6]-phenyl C61Methyl butyrate/gold (Si/ SiO2/PC61BM/Au), shown in following Fig. 5 (a).Wherein, SiO2For insulating layer, PC61The BM or PC of doping61BM is as N-shaped half Conductor layer, top electrodes Au is as source-drain electrode.The specific implementation method of embodiment 5 is as follows:
(1) by the silicon wafer cut 10ml hydrogen peroxide (H2O2) and the 25ml concentrated sulfuric acid (H2SO4) mixed liquor at 100 DEG C plus Heat 20 minutes, starts the cleaning processing silicon chip surface；
(2) after being cleaned by ultrasonic above-mentioned cleaned silicon wafer with isopropanol, it is placed in vacuum oven, in surface plate, And a few drop octadecyl trichlorosilane alkane (OTS) liquid are added dropwise around it.By vacuum oven heat temperature raising, OTS is promoted to volatilize And it reacts with the hydroxyl of silicon chip surface, and then to SiO2The charge defects on surface play passivation；
(3) silicon wafer after OTS is passivated successively is cleaned with chloroform, heptane, acetone, EtOH Sonicate spare；
(4) in the above-mentioned Si/SiO handled well2The PC prepared in advance in spin coating embodiment 1 in substrate61BM or doping PC61BM solution, as n-type semiconductor layer；
Above-mentioned device is transferred in vacuum coating system, by vacuum coater in PC61It is deposited one layer of 70nm's on BM Au electrode is successfully prepared based on PC61Transistor of the BM as n-type semiconductor layer.Wherein the road ditch length-width ratio of transistor is 30 Micron/270 microns.It is being full of N2The glove box of atmosphere carries out the I of test transistor with Keithley 4200DS-VGSTransfer curve And IDS-VDSCurve of output.Wherein IDS-VGSThe following Fig. 5 (b) of transfer curve.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include Within protection scope of the present invention.

Claims (4)

1. a kind of application of organic amidine molecule n-type dopant in semiconductor photoelectric device, which is characterized in that the n-type doping Agent mixes with acceptor material or directly acceptor material is exposed in the steam atmosphere of n-type dopant, realizes to acceptor material N doping after, be applied to semiconductor photoelectric device, the semiconductor photoelectric device be perovskite solar battery, organic sun Energy battery, Organic Light Emitting Diode and organic field effect tube, the n-type dopant are DBU.
2. application of organic amidine molecule n-type dopant in semiconductor photoelectric device as described in claim 1, feature exist In the acceptor material is PC61BM, N2200 or ITIC.
3. a kind of application of the organic amidine molecule n-type dopant as claimed in claim 1 or 2 in semiconductor photoelectric device, It is characterized in that, the device architecture of the perovskite solar battery are as follows: ITO electro-conductive glass is as battery cathode, NiOxAs electricity Pond hole transmission layer, MAPbI3For perovskite light-absorption layer, n-type dopant is used as battery electron after carrying out n doping to acceptor material Transport layer, metal Ag is as anode.
4. a kind of application of the organic amidine molecule n-type dopant as claimed in claim 1 or 2 in semiconductor photoelectric device, It is characterized in that, the device architecture of the organic field effect tube are as follows: SiO2For insulating layer, n-type dopant to acceptor material into It is used as n-type semiconductor layer after row n doping, top electrodes Au is as source-drain electrode.
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