CN107768478A - A kind of organic/perovskite bulk-heterojunction nanowire photodiode detector and preparation method thereof - Google Patents
A kind of organic/perovskite bulk-heterojunction nanowire photodiode detector and preparation method thereof Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims abstract description 184
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000007639 printing Methods 0.000 claims abstract description 11
- 238000004528 spin coating Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
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- 238000012545 processing Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000009975 flexible effect Effects 0.000 claims description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
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- 229920001721 polyimide Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- ADMUKNAKSUNXOQ-UHFFFAOYSA-N 2,7-dioctyl-1-benzothiophene Chemical class C1=CC(CCCCCCCC)=C2SC(CCCCCCCC)=CC2=C1 ADMUKNAKSUNXOQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 7
- ORUNRWHFUKDCTM-UHFFFAOYSA-N 2,3-dioctyl-1-benzothiophene Chemical compound C1=CC=C2C(CCCCCCCC)=C(CCCCCCCC)SC2=C1 ORUNRWHFUKDCTM-UHFFFAOYSA-N 0.000 abstract 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
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- NXCSDJOTXUWERI-UHFFFAOYSA-N [1]benzothiolo[3,2-b][1]benzothiole Chemical compound C12=CC=CC=C2SC2=C1SC1=CC=CC=C21 NXCSDJOTXUWERI-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229920000547 conjugated polymer Polymers 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- OFPPMFSHIKARPG-UHFFFAOYSA-N thieno[3,2-b][1]benzothiole Chemical compound S1C2=CC=CC=C2C2=C1C=CS2 OFPPMFSHIKARPG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a kind of organic/perovskite bulk-heterojunction nanowire photodiode detector, including substrate, perovskite/2,7 dioctyl [1] benzothiophene simultaneously [3,2 b] benzothiophene bulk-heterojunction nano wire light absorbing layer and electrode three parts.The preparation method of the present invention, comprises the following steps：Substrate prepares and cleaning, processing；Prepare perovskite material solution；Prepare dioctyl [1] benzothiophene of perovskite/2,7 simultaneously [3,2 b] benzothiophene mixing material precursor solution；Perovskite/2,7 dioctyl [1] benzothiophene simultaneously [3,2 b] benzothiophene bulk-heterojunction nano wire is prepared using spin coating, blade coating and mode of printing, obtains high-quality light absorbed layer；Electrode is prepared using evaporation or printing.The product of the present invention has the advantages that the response time is fast, optical responsivity is high, stable in air, has important application prospect.
Description
Technical field
The invention belongs to field of photoelectric devices, and in particular to a kind of organic/perovskite bulk-heterojunction nanowire photodiode is visited
Survey device and preparation method thereof.
Background technology
Photodetector is to refer to incident optical signal (infrared, visible, near infrared region) being converted into electric signal (electric current
Or voltage) signal photoelectric device, be widely used in being imaged, communicate, the field such as spectroscopy and biomedicine.At present, it is traditional
Photodetector mainly prepared using following several typical materials, such as conventional semiconductor material (silicon, germanium), two-dimensional material
(graphene, molybdenum sulfide) and conjugated polymer.
Recent years, the halide perovskite material of hybrid inorganic-organic gradually grow up, and it is primarily referred to as
CH3NH3PbX3(X=Cl, Br, I) material.It is such as suitable straight because such perovskite material has outstanding semiconductor property
Connect band gap width (~1.6eV), it is small excite with reference to can (~20meV), wide Absorber Bandwidth (300~900nm), long swash
Carrier diffusion length (100~1000nm), long carrier lifetime etc., it has obtained widely studied in photovoltaic art.At present, calcium titanium
Ore deposit photoelectric detector has been obtained for very big lifting, 3.49AW of the optical responsivity from beginning in performance-1Till now
Up to 180AW-1, and be increasingly becoming study hotspot (Adv.Funct.Mater.2014,24,7373；Adv.Mater.2015,
27,41).In addition, for perovskite thin film, perovskite nano wire has the added advantage that, such as lower dark current, more
High external quantum efficiency, the mechanical performance of enhancing and the device suitable for high flexible.That is commonly used in experiment prepares perovskite
The method of nano wire has spin-coating method, drop-coating, knife coating, evaporation-induced self-assembly method and volume to volume printing.Generally we use
The perovskite nano wire that simple solwution method is prepared all is unordered, and device performance can be caused relatively low.Moreover, perovskite material
Material is very sensitive to moisture in air, and when exposing in atmosphere, perovskite material can react with the water in air, cause
Perovskite material is decomposed and failed.Therefore, performance that perovskite nanowire photodiode detects and steady is improved by suitable means
Surely there is very meaning.
By organic semiconductor 2,7- dioctyls [1] benzothiophene, simultaneously [3,2-b] benzothiophene is mixed into perovskite to the present invention
In solution, and successfully pass simple solution method and perovskite/2,7- dioctyl [1] benzothiophene simultaneously [3,2- is prepared in substrate
B] benzothiophene bulk-heterojunction nano wire, and utilize the height of 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene
Mobility and air stability, it have developed a kind of perovskite/2,7- dioctyl [1] benzothiophene simultaneously [3,2-b] benzothiophene
Bulk-heterojunction nanowire photodiode detector.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one
The perovskite nanowire photodiode detector of stable performance in kind photodetection excellent performance, air, and a kind of technical process is provided
Simply, the low foregoing perovskite of good product performance, cost/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase
The preparation method of heterojunction nano-wire photodetector.
Received in order to solve the above technical problems, technical scheme proposed by the present invention is a kind of organic/perovskite bulk-heterojunction
Rice noodles photodetector, described substrate are hard substrate or flexible substrates, described hard substrate be glass, silica or
Quartz, described flexible substrates are polyethylene terephthalate (PET), PEN (PEN) or polyamides
Imines (PI)；
Above-mentioned organic/perovskite bulk-heterojunction nanowire photodiode detector, described perovskite material are
CH3NH3PbI3、 CH3NH3PbCl3、CH3NH3PbBr3、CH3NH3PbA3-xBx、CH(NH2)2PbI3、CH(NH2)2PbCl3、 CH
(NH2)2PbBr3、CH(NH2)2PbA3-xBxOr Csy[CH(NH2)2]z[CH3NH3](1-y-z)A3-xBx, wherein A and B are in I, Cl, Br
One kind, x is between 0 and 3, and between zero and one, z is between zero and one by y；
Above-mentioned organic/perovskite bulk-heterojunction nanowire photodiode detector, described bulk-heterojunction nano wire are
Refer to the mutual of perovskite material and organic semiconducting materials 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene formation
It is uniformly distributed, the nano-wire array of interpenetrating networks shape structure, the lateral dimension of nano wire is between 50nm to 800nm；
Above-mentioned organic/perovskite bulk-heterojunction nanowire photodiode detector, described electrode layer are in gold, silver, aluminium
One or more, photoresponse raceway groove length-width ratio is formed between symmetry electrode 1:5 to 1:Between 20.
For perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene bulk-heterojunction nanowire photodiode
The use condition of detector, the technical scheme of foregoing invention propose a kind of perovskite/2,7- dioctyl [1] benzothiophene simultaneously
[3,2-b] benzothiophene nano wire as light-absorption layer body to heterojunction structure, be characterized in passing through based on following thinking and research
Test：Perovskite material is outstanding light absorbing material, and it is special to absorb preferable light absorbs in ultraviolet, visible ray, near infrared region
Property, but the photodetector of perovskite nano wire is usually because the randomness of nano wire causes performance not high.And simple
The photoelectric detector of perovskite nano wire can not meet the requirement of atmospheric environment, and perovskite material can be with the water in air
Molecule reacts and decomposed, so as to cause photoelectric properties to fail.And 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene
With excellent air stability and higher hole mobility, the energy level of two class materials can be realized by rational experimental design
Matching, reach the purpose of light absorbs enhancing.By our research repeatedly, 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzene
Bithiophene is added directly into perovskite solution, forms perovskite/2,7- dioctyl [1] in substrate by simple solwution method
Simultaneously [3,2-b] benzothiophene bulk-heterojunction nano wire, such a bulk-heterojunction structure can realize photoproduction to benzothiophene
The separation of electron hole pair, the compound of electron hole pair is greatly reduced, so as to improve the performance of photodetector.It is finally this hair
The implementation and realization of bright technical thought provide premise and basis.
The technical concept total as one, the present invention also provide a kind of above-mentioned flexible perovskite/2,7- dioctyl [1]
The preparation method of benzothiophene simultaneously [3,2-b] benzothiophene bulk-heterojunction nanowire photodiode detector, comprises the following steps：
(1) substrate prepares and cleaning, processing；
(2) perovskite solution is prepared；
(3) simultaneously [3,2-b] benzothiophene mixing material presoma is molten for preparation perovskite/2,7- dioctyls [1] benzothiophene
Liquid；
(4) perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzene is prepared using spin coating, blade coating and mode of printing
Bithiophene mixing material film, high-quality thin film light absorbing layer is obtained after thermal anneal process；
(5) electrode is prepared using evaporation or printing, photoresponse raceway groove length-width ratio is formed between symmetry electrode 1:5 to 1:20 it
Between.
Above-mentioned preparation method, in the step (1), substrate prepares to refer to substrate using deionization with cleaning, processing
Water, acetone, absolute ethyl alcohol are cleaned by ultrasonic 20 minutes respectively, are then dried up using high-purity gas, finally UV-ozone processing 20 again
Minute.It is cleaned by ultrasonic organic matter, impurity that can effectively remove substrate surface etc. by above-mentioned steps, so as to uniform beneficial to being formed
Perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene nano wire film；Dried up, gone using high-purity gas
Except the solid particle of substrate surface attachment, it is equally beneficial for being formed uniform perovskite/2,7- dioctyl [1] benzo of high quality
Thieno [3,2-b] benzothiophene nano wire film；In addition, handling substrate by UV-ozone, perovskite pioneer can be improved
Liquid solution is advantageous to uniform perovskite/2,7- dioctyl [1] benzothiophene simultaneously [3,2-b] benzene in the wellability of substrate surface
The formation of bithiophene nano wire film.
Above-mentioned preparation method, in the step (2), perovskite solution concentration described in the perovskite solution is 300mg/
Ml to 800mg/ml perovskite solution.
Above-mentioned preparation method, in the step (3), perovskite/2,7- dioctyl [1] benzothiophene simultaneously [3,2-b] benzene
Bithiophene mixing material precursor solution, by 2,7- dioctyls [1] benzothiophene, simultaneously [3,2-b] benzothiophene is dissolved in chlorobenzene first
In, form the solution that concentration is 5mg/ml to 30mg/ml, then by this 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzo thiophene
Fen solution is with above-mentioned perovskite solution with 1:2 to 1:5 volume ratio mixing, heating stirring 1 hour under 60 degree.
Above-mentioned preparation method, in the step (4), the spin coating, blade coating and mode of printing prepare perovskite/2,7- bis-
The thermal anneal process of octyl group [1] benzothiophene simultaneously [3,2-b] benzothiophene mixing material film is in 60 degree to 80 degree temperature models
Enclose interior annealing 30 to 60 minutes.
Compared with prior art, the advantage of the invention is that：
1. the present invention organic/perovskite bulk-heterojunction nanowire photodiode detector, light absorbing layer using perovskite with
The intermingling material of 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene, perovskite material have outstanding photo electric
Can, as direct band gap width is suitable, excite with reference to can it is smaller, Absorber Bandwidth is wider, exciton diffusion length is longer, carrier lifetime
It is longer.Simultaneously [3,2-b] benzothiophene has higher hole mobility and good stabilization to 2,7- dioctyls [1] benzothiophene
Property, and perovskite and 2, simultaneously [3,2-b] benzothiophene level-density parameter is good for 7- dioctyls [1] benzothiophene, is formed perfect
Body is to heterojunction structure.
2. organic/perovskite bulk-heterojunction nanowire photodiode detector of the present invention, more simple perovskite nano wire
Performance is greatly improved, and optical responsivity is higher than perovskite nano wire prepared by same process more than 10 times.In addition, by
In perovskite/2,7- dioctyl [1] benzothiophene, simultaneously [3,2-b] benzothiophene bulk-heterojunction structure, device are aerial
Service life has also obtained significant raising.
3. organic/perovskite bulk-heterojunction nanowire photodiode detector of the present invention, utilizes the excellent machinery of nano wire
Performance simultaneously applies to flexible device, and good bending performance is shown under differently curved radius, shows excellent flexible
Property, greatly expand its application field, particularly portable set.
On the whole, a kind of organic/perovskite bulk-heterojunction nanowire photodiode detector of product design of the invention,
The photodetector finally obtained has the distinguishing feature that excellent performance, air stability are high and pliability is good, changes significantly
It has been apt to the optical detection performance and used life of perovskite nanowire photodiode detector, has widened it in this field of flexible device
With practical significant to improving perovskite-based photodetector.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is perovskite/2,7- dioctyls [1] benzothiophene of the invention simultaneously [3,2-b] benzothiophene bulk-heterojunction
Nanowire photodiode panel detector structure schematic diagram.
Fig. 2 is perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase in the embodiment of the present invention
Heterojunction nano-wire stereoscan photograph.
Fig. 3 is that perovskite/2,7- dioctyls [1] benzothiophene [3,2-b] benzothiophene body phase is different in the embodiment of the present invention
The X-ray diffraction spectrum of matter junction nanowire.
Fig. 4 is perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase in the embodiment of the present invention 1
Photoelectric current-voltage curve of heterojunction nano-wire photodetector.
Fig. 5 is perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase in the embodiment of the present invention 1
Optical responsivity-wavelength curve of heterojunction nano-wire photodetector.
Fig. 6 is perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase in the embodiment of the present invention 1
The response time of heterojunction nano-wire photodetector-photocurrent curve.
Fig. 7 is perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase in the embodiment of the present invention 1
The stability curve of heterojunction nano-wire photodetector.
Fig. 8 is perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase in the embodiment of the present invention 1
The bending performance curve of heterojunction nano-wire photodetector.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and embodiment more comprehensively, it is careful
Ground describes, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene bulk-heterojunction as shown in Figure 1
Nanowire photodiode detector, including polyethylene terephthalate (PET) substrate, CH3NH3PbI3/ 2,7- dioctyls [1] benzene
Bithiophene simultaneously [3,2-b] benzothiophene bulk-heterojunction nano wire light absorbing layer and gold electrode three parts.
Preparation method in the present embodiment on the glass substrate comprises the following steps：
(1) PET base is cleaned by ultrasonic respectively 20 minutes using deionized water, acetone, absolute ethyl alcohol, then using high-purity
Gas is dried up, and then UV-ozone is handled 20 minutes again.
(2) by CH3NH3I:PbI2In molar ratio 1:After 1 weighs, first by CH3NH3I is dissolved in N-N dimethylformamides, so
Afterwards by CH3NH3I solution and PbI2Mixing, wherein finally heated stirring, heating-up temperature are 80 degree, and mixing time is 10 hours, is obtained
To 550mg/ml CH3NH3PbI3Precursor solution.
(3) by 2,7- dioctyls [1] benzothiophene, simultaneously [3,2-b] benzothiophene is dissolved in chlorobenzene, and it is 20mg/ to form solubility
Ml solution, then simultaneously the chlorobenzene solution of [3,2-b] benzothiophene and above-mentioned perovskite are molten by this 2,7- dioctyls [1] benzothiophene
Liquid is with 1:3 volume ratio mixing, heating stirring 1 hour under 60 degree, obtains perovskite/2,7- dioctyl [1] benzothiophene simultaneously
[3,2-b] benzothiophene mixing material precursor solution.
(3) light absorbing layer is prepared using spin-coating method.Sample is placed, instills perovskite/2,7- dioctyl [1] benzo thiophene
Fen simultaneously [3,2-b] benzothiophene mixing material precursor solution.Rotating technics are to accelerate within 10 seconds 4000rpm to be kept for 30 seconds.Rotation
After painting terminates, by wet film under 60 degree, anneal 60 minutes, obtain CH3NH3PbI3/ 2,7- dioctyls [1] benzothiophene simultaneously [3,2-
B] benzothiophene bulk-heterojunction nano wire light absorbing layer.
(6) gold electrode is prepared using evaporation, forming photoresponse raceway groove between symmetry electrode grows at 80 microns, wide 1000 microns.
Pass through above-mentioned steps, you can a kind of flexible CH is prepared3NH3PbI3/ 2,7- dioctyls [1] benzothiophene is simultaneously
[3,2-b] benzothiophene bulk-heterojunction nanowire photodiode detector, structure intention, the surface scan Electronic Speculum of the photodetector
Photo, X-ray diffraction spectrum, photoelectric current-voltage curve, optical responsivity-wavelength curve, response time-photocurrent curve, stability
Test curve, bending performance curve are distinguished as shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7 and Fig. 8.
Pass through flexible perovskite/2,7- dioctyls [1] benzothiophene of the present embodiment made from the above method simultaneously [3,2-
B] benzothiophene bulk-heterojunction nanowire photodiode detector, ultraviolet light, visible ray and near infrared light are respectively provided with good
Photoresponse, after placing 50 days in atmosphere, performance reaches target without obvious decay.And 10000 times bending after according to
So keep higher performance.Above-mentioned flexible perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene body phase
Heterojunction nano-wire photodetector specific performance is as shown in the table：
Embodiment 2：
Simultaneously [3,2-b] benzothiophene body phase is heterogeneous for a kind of perovskite as shown in Figure 1/2,7- dioctyls [1] benzothiophene
Junction nanowire photodetector, including PEN (PEN) substrate, CH3NH3PbBr3/ 2,7- dioctyls [1] benzene
Bithiophene simultaneously [3,2-b] benzothiophene bulk-heterojunction nano wire light absorbing layer and silver electrode three parts.
Preparation method in the present embodiment in PEN (PEN) substrate comprises the following steps：
(1) PET base is cleaned by ultrasonic respectively 20 minutes using deionized water, acetone, absolute ethyl alcohol, then using high-purity
Gas is dried up, and then UV-ozone is handled 20 minutes again.
(2) by CH3NH3Br:PbBr2In molar ratio 1:After 1 weighs, first by CH3NH3Br is dissolved in N-N dimethylformamides,
Then by CH3NH3Br solution and PbBr2Mixing, wherein finally heated stirring, heating-up temperature are 60 degree, and mixing time is 8 hours,
Obtain 300mg/ml CH3NH3PbBr3Precursor solution.
(3) by 2,7- dioctyls [1] benzothiophene, simultaneously [3,2-b] benzothiophene is dissolved in chlorobenzene, and it is 5mg/ to form solubility
Ml solution, then simultaneously the chlorobenzene solution of [3,2-b] benzothiophene and above-mentioned perovskite are molten by this 2,7- dioctyls [1] benzothiophene
Liquid is with 1:3 volume ratio mixing, heating stirring 1 hour under 60 degree, obtains perovskite/2,7- dioctyl [1] benzothiophene simultaneously
[3,2-b] benzothiophene mixing material precursor solution.
(3) light absorbing layer is prepared using spin-coating method.Sample is placed, instills perovskite/2,7- dioctyl [1] benzo thiophene
Fen simultaneously [3,2-b] benzothiophene mixing material precursor solution.Rotating technics are to accelerate within 10 seconds 4000rpm to be kept for 30 seconds.Rotation
After painting terminates, wet film is made annealing treatment 30 minutes for 60 degree in the steam atmosphere of N-N dimethylformamides, obtained
CH3NH3PbBr3/ 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene bulk-heterojunction nano wire light absorbing layer.
(6) silver electrode is prepared using evaporation, forming photoresponse raceway groove between symmetry electrode grows at 100 microns, wide 1000 microns.
Pass through flexible perovskite/2,7- dioctyls [1] benzothiophene of the present embodiment made from the above method simultaneously [3,2-
B] benzothiophene bulk-heterojunction nanowire photodiode detector, ultraviolet light, visible ray and near infrared light are respectively provided with good
Photoresponse, after placing 30 days in atmosphere, performance reaches target without obvious decay.Above-mentioned flexible perovskite/2,7- bis-
Simultaneously [3,2-b] benzothiophene bulk-heterojunction nanowire photodiode detector specific performance is as shown in the table for octyl group [1] benzothiophene：
Embodiment 3：
Simultaneously [3,2-b] benzothiophene body phase is heterogeneous for a kind of perovskite as shown in Figure 1/2,7- dioctyls [1] benzothiophene
Junction nanowire photodetector, including polyimides (PI) substrate, CH3NH3PbCl3-xIx/ 2,7- dioctyls [1] benzothiophene is simultaneously
[3,2-b] benzothiophene bulk-heterojunction nano wire and aluminium electrode three parts.
Preparation method in the present embodiment in polyimides (PI) substrate comprises the following steps：
(1) glass chip bottom is cleaned by ultrasonic 20 minutes respectively using deionized water, acetone, absolute ethyl alcohol, then used
High-purity gas is dried up, and last then UV-ozone is handled 20 minutes again.
(2) by CH3NH3I:PbCl2In molar ratio 1:After 1 weighs, first by CH3NH3I is dissolved in N-N dimethylformamides, so
Afterwards by CH3NH3I solution and PbCl2Mixing, wherein finally heated stirring, heating-up temperature are 70 DEG C, mixing time 8h, are obtained
600mg/ml CH3NH3PbCl3-xIxSolution.
(3) by 2,7- dioctyls [1] benzothiophene, simultaneously [3,2-b] benzothiophene is dissolved in chlorobenzene, and it is 10mg/ to form solubility
Ml solution, then simultaneously the chlorobenzene solution of [3,2-b] benzothiophene and above-mentioned perovskite are molten by this 2,7- dioctyls [1] benzothiophene
Liquid is with 1:3 volume ratio mixing, heating stirring 1 hour, obtains CH under 60 degree3NH3PbCl3-xIx/ 2,7- dioctyls [1] benzo
Thieno [3,2-b] benzothiophene mixing material precursor solution.
(4) light absorbing layer is prepared using volume to volume mode of printing (specific volume to volume mode of printing refers to Chinese granted patent：
ZL201610005162.3).Volume to volume printing is carried out with 0.5m/min speed to prepare, after solvent volatilization, obtained film exists
60 degree of thermal annealings, form the CH of high quality3NH3PbCl3-xIx/ 2,7- dioctyls [1] benzothiophene simultaneously receive by [3,2-b] benzothiophene
Rice noodles.
(5) gold electrode is prepared using evaporation, forming photoresponse raceway groove between symmetry electrode grows at 80 microns, wide 1000 microns.
Pass through above-mentioned steps, you can be prepared a kind of flexible perovskite/2,7- dioctyl [1] benzothiophene simultaneously [3,
2-b] benzothiophene bulk-heterojunction nanowire photodiode detector.
Pass through flexible perovskite/2,7- dioctyls [1] benzothiophene of the present embodiment made from the above method simultaneously [3,2-
B] benzothiophene bulk-heterojunction nanowire photodiode detector, ultraviolet light, visible ray and near infrared light are respectively provided with good
Photoresponse, after placing 30 days in atmosphere, performance reaches target without obvious decay.
Claims (4)
1. a kind of organic/perovskite bulk-heterojunction nanowire photodiode detector, it is characterised in that the photodetector includes
Substrate, perovskite material and organic semiconducting materials 2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene (C8BTBT)
The bulk-heterojunction nano wire light absorbing layer and electrode layer three parts of formation；
Described substrate is hard substrate or flexible substrates, and described hard substrate is glass, silica or quartz, described
Flexible substrates are polyethylene terephthalate (PET), PEN (PEN) or polyimides (PI)；
Described perovskite material is CH3NH3PbI3、CH3NH3PbCl3、CH3NH3PbBr3、CH3NH3PbA3-xBx、CH(NH2)2PbI3、CH(NH2)2PbCl3、CH(NH2)2PbBr3、CH(NH2)2PbA3-xBxOr Csy[CH(NH2)2]z[CH3NH3](1-y-z)A3- xBx, wherein A and B are one kind in I, Cl, Br, and x is between 0 and 3, and between zero and one, z is between zero and one by y；
Described bulk-heterojunction nano wire refers to perovskite material and organic semiconducting materials 2,7- dioctyls [1] benzothiophene
And [3,2-b] benzothiophene formed be mutually uniformly distributed, the nano-wire array of interpenetrating networks shape structure, the horizontal chi of nano wire
It is very little between 50nm to 800nm；
Described electrode layer is the one or more in gold, silver, aluminium, and photoresponse raceway groove length-width ratio is formed between symmetry electrode 1:5
To 1:Between 20.
2. the preparation method of organic/perovskite bulk-heterojunction nanowire photodiode detector as described in claim 1, including
Following steps：
(1) substrate prepares and cleaning, processing；
(2) perovskite solution is prepared, the perovskite solution concentration is 300mg/ml to 800mg/ml perovskite solution；
(3) perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzothiophene mixing material precursor solution is prepared；
(4) perovskite/2,7- dioctyls [1] benzothiophene simultaneously [3,2-b] benzo thiophene is prepared using spin coating, blade coating and mode of printing
Fen mixing material film, obtain after thermal anneal process high quality it is organic/perovskite bulk-heterojunction nano wire light absorbing layer；
(5) electrode is prepared using evaporation or printing.
3. preparation method according to claim 2, it is characterised in that perovskite/2,7- dioctyl in the step (3)
[1] benzothiophene simultaneously [3,2-b] benzothiophene mixing material precursor solution, first by 2,7- dioctyls [1] benzothiophene simultaneously
[3,2-b] benzothiophene is dissolved in chlorobenzene, forms the solution that concentration is 5mg/ml to 30mg/ml, then by this 2,7- dioctyl [1]
Benzothiophene simultaneously [3,2-b] benzothiophene solution and above-mentioned perovskite solution with 1:2 to 1:5 volume ratio mixing, under 60 degree
Heating stirring 1 hour.
4. preparation method according to claim 2, it is characterised in that in the step (4), the spin coating, blade coating and print
Brush mode prepares perovskite/2,7- dioctyls [1] benzothiophene simultaneously at the thermal annealing of [3,2-b] benzothiophene mixing material film
Reason is made annealing treatment 30 to 60 minutes in 60 degree to 80 degree temperature ranges.
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