CN109346461A - A kind of photoelectric heat replies the photodetector and preparation method thereof of oneself driving of conjunction by cable - Google Patents
A kind of photoelectric heat replies the photodetector and preparation method thereof of oneself driving of conjunction by cable Download PDFInfo
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- CN109346461A CN109346461A CN201811181611.5A CN201811181611A CN109346461A CN 109346461 A CN109346461 A CN 109346461A CN 201811181611 A CN201811181611 A CN 201811181611A CN 109346461 A CN109346461 A CN 109346461A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/162—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits the devices being mounted on two or more different substrates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/167—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits comprising optoelectronic devices, e.g. LED, photodiodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/50—Multistep manufacturing processes of assemblies consisting of devices, each device being of a type provided for in group H01L27/00 or H01L29/00
Abstract
The invention discloses a kind of photoelectric heats to reply the photodetector and preparation method thereof closed from driving by cable, it is driven using the electrical connection in parallel of perovskite solar battery and thermoelectric generation film as the voltage of perovskite photodetector, perovskite solar battery and thermoelectric generation film can be individually for perovskite photodetector and provide voltage, thermoelectric generation film converts heat into electric energy simultaneously, avoids influence of the thermal energy to the performance and used life of device.The photodetector stability that photoelectric heat prepared by the present invention replies conjunction from driving by cable is good, and long service life realizes round-the-clock optical detection.
Description
Technical field
The invention belongs to technical field of electronic devices, further relate to one of semiconductor light electro-technical field photoelectricity
The compound photodetector and preparation method thereof from driving of thermoelectricity.Photodetector of the invention can be used for detecting ultraviolet-visible
Light-near infrared band optical signal.
Background technique
Photodetector be it is a kind of optical radiation energy is converted into a kind of physical quantity photoelectric device convenient for measurement, in military affairs
It has a wide range of applications with the every field of national economy, such as bio-sensing, optical imagery, optic communication, environmental monitoring, national defence
Military project etc..The principle of photodetector mainly utilizes external photoeffect or inner photoeffect, and the electronics in detector is directly inhaled
The energy for receiving photon, makes motion state change and generates electric signal, is usually used in detecting infra-red radiation and visible light.It is close several
Year, with the development of science and technology, having there is the photodetector of more and more types to occur.
Paper " the High-Performance Flexible Broadband that the authors such as Xin Hu deliver at it
Photodetector Based on Organolead Halide Perovskite”(Advanced Functional
Materials, vol.24, pp.7373-7380,2014) in disclose a kind of organohalogen compounds perovskite photodetector.It should
Although organohalogen compounds perovskite photodetector is on the basis of traditional perovskite photodetector advantage, using spin coating method system
For MAPbI3Film, foring structure is ITO/MAPbI3The coplanar device of/ITO, can be real by carrying out external power supply to device
Existing wide range photodetection, still, the shortcoming which still has is the perovskite photodetector
It needs applied voltage to drive at work, leads to not the application in the case where needing prolonged optical detection occasion.
The patented technology that University Of Suzhou possesses at it is " in conjunction with the driving photodetection certainly of solar battery and photodetector
One kind is disclosed in system and preparation method thereof " (application number: 201510969469.0 Authorization Notice No.: CN105575964 B)
In conjunction with the device architecture and preparation method of solar battery and photodetector.The method that the structure of the patented technology uses spin coating
It prepares perovskite solar battery to drive as voltage, perovskite detector is optoelectronic sensor.The device architecture exist with
Lower two o'clock shortcoming is, first, leading to perovskite too since conversion ratio of the perovskite solar battery for solar energy be not high
During the voltage driving as photodetector, solar energy is dissipated in the form of thermal energy positive energy battery mostly, simultaneously
The thermal energy of dissipation has a great impact to stability and the service life aspect of the performance especially device of entire device.Second,
Photoelectric conversion can not be carried out at night and perovskite solar battery rainy days, the photodetector is caused to can not work normally.
Perovskite solar battery and perovskite photodetector are mainly connected in the preparation method of the patented technology using fine copper wire,
Thus leading to its existing shortcoming is that perovskite solar battery and perovskite photodetector are connected using fine copper wire
It is at high cost, stability is poor.
Summary of the invention
It is an object of the invention in view of the deficiency of the prior art, provide a kind of photoelectric heat to reply conjunction by cable from driving
Photodetector, realize photodetector do not need that optical detection can be carried out for a long time by extra power.
Realizing the concrete thought of the object of the invention is, in parallel with thermoelectric generation film as light using perovskite solar battery
The voltage of electric explorer drives, and realizes for a long time from the optical detection of driving.Thermoelectric generation film and perovskite solar battery and
Connection, can not only reduce influence of the thermal energy generated in perovskite solar cell photoelectric conversion process to device performance, but also
These thermal energy can be converted into electric energy, enable the optical detection of photodetector longer time, while at night and wet weather
Weather is provided voltage using the thermo-electric generation of thermoelectric generation film and carries out optical detection.
Photoelectric heat of the invention replies the photodetector closed from driving, including perovskite solar battery, glass substrate by cable,
The perovskite solar battery includes substrate and the hole transmission layer being from top to bottom sequentially prepared on substrate, light absorption
Layer, electron transfer layer and metal electrode；Light absorbing layer is prepared in the glass substrate, prepares two in the two sides of light absorbing layer
Metal electrode；The photodetector further includes thermoelectric generation film, and the thermoelectric generation film is arranged under metal electrode；It is described
It connects again with perovskite photodetector after perovskite solar battery is in parallel with thermoelectric generation film.
Photoelectric heat of the invention replies the photodetector preparation method closed from driving by cable, connects calcium using inkjet printing technology
The step of titanium ore solar battery, thermoelectric generation film, perovskite photodetector, this method includes the following:
(1) perovskite solar cell substrate is pre-processed:
Substrate is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, surpassed in deionized water by (1a)
Sound cleaning；
The substrate being cleaned by ultrasonic is carried out UV ozone UV-zone processing by (1b), obtains the substrate pre-processed；
(2) hole transmission layer of perovskite solar battery is prepared:
By hole transmission layer precursor solution drop on the substrate pre-processed, spin coating is carried out using sol evenning machine, after spin coating
Substrate be placed in thermal station and anneal, obtain the hole transmission layer of perovskite solar battery；
(3) solution coating method is used, the light absorbing layer of perovskite solar battery is prepared；
(4) electron transfer layer of perovskite solar battery is prepared:
Electron transfer layer precursor solution is spin-coated on the light absorbing layer that preparation is completed using sol evenning machine, obtains perovskite too
The electron transfer layer of positive energy battery；
(5) vacuum coater is used, the metal electrode of perovskite solar battery is prepared；
(6) heat-conducting silicone grease is used, the cell metallic electrode and thermoelectric generation film to perovskite solar energy carry out physical connection；
(7) glass substrate of perovskite photodetector is pre-processed:
The glass substrate of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound clearly
It washes, is dried up using high-purity nitrogen；
(8) solution coating method is used, the light absorbing layer of perovskite photodetector is prepared；
(9) vacuum coater is used, two metal electrodes of perovskite photodetector are prepared；
(10) perovskite solar battery, thermoelectric generation film, perovskite photodetector are connected:
Using inkjet printing technology, by the substrate of perovskite solar battery respectively with the anode and calcium titanium of thermoelectric generation film
One metal electrode of mine photodetector connects, by the metal electrode of perovskite solar battery respectively with thermoelectric generation film
Cathode is connected with another metal electrode of perovskite photodetector.
Compared with prior art, the present invention has the advantage that
First, it is visited again with perovskite photoelectricity after using perovskite solar battery in parallel with thermoelectric generation film due to the present invention
Device series connection is surveyed, photodetector is overcome and applied voltage is needed to drive at work, leads to not needing prolonged light
The shortcomings that detecting the application under occasion does not need so that photoelectric heat of the invention replies the photodetector closed from driving by cable by outer
Portion's energy can carry out optical detection for a long time.
Second, since the present invention is in parallel with thermoelectric generation film using perovskite solar battery, so that perovskite solar energy
Battery and thermoelectric generation film can be individually for the power supply of perovskite photodetector, also, thermoelectric generation film can be by perovskite solar energy
The thermal energy generated in cell photoelectric conversion process is converted to electric energy, overcomes following two disadvantage, first, due to the perovskite sun
Energy battery is not high for the conversion ratio of solar energy, and perovskite solar battery is caused to drive in the voltage as photodetector
Cheng Zhong, solar energy are dissipated in the form of thermal energy mostly, while the thermal energy to dissipate is to the performance especially device of entire device
Stability and service life in terms of have a great impact；Second, since perovskite solar battery is at night and rainy weather
Photoelectric conversion can not be carried out, the photodetector is caused to can not work normally.So that photoelectric heat of the invention replies conjunction by cable from driving
Photodetector stability and service life get a promotion, and can realize round-the-clock optical detection.
Third, due to using inkjet printing technology to connect perovskite solar battery, the temperature difference in preparation process of the invention
Power generation sheet, perovskite photodetector overcome the prior art and the problem that metal connecting line is at high cost, stability is poor are used to adopt
At low cost with preparation process of the invention, stock utilization is high, and preparation efficiency is high, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of photodetector of the present invention；
Fig. 2 is the process flow chart of photodetector preparation method of the present invention.
Specific embodiment
The present invention is described further with reference to the accompanying drawings and examples.
Referring to Fig.1, the structure closed from the photodetector of driving is replied by cable to photoelectric heat of the invention to be further described.
It includes perovskite solar battery, glass substrate 7 that photoelectric heat of the invention, which is replied by cable and closed from the photodetector of driving,
The perovskite solar battery includes that substrate 1 and the hole transmission layer being from top to bottom sequentially prepared on substrate 12, light are inhaled
Receive layer 3, electron transfer layer 4 and metal electrode 5.Light absorbing layer 8 is prepared in the glass substrate 7, in the two sides of light absorbing layer 8
Prepare two metal electrodes.The photodetector further includes thermoelectric generation film 6, and the setting of thermoelectric generation film 6 is in metal electricity
Under pole 5.It connects again with perovskite photodetector after the perovskite solar battery is in parallel with thermoelectric generation film.
The solar cell substrate 1 uses tin indium oxide ITO substrate or fluorine-doped tin oxide FTO substrate.
Referring to Fig. 2, replies the photodetector preparation method closed from driving by cable to photoelectric heat of the invention, utilize inkjet printing
The step of technology connection perovskite solar battery, thermoelectric generation film, perovskite photodetector, this method includes as follows.
Step 1, perovskite solar cell substrate is pre-processed.
Substrate 1 is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, that ultrasound is carried out in deionized water is clear
It washes.
The substrate 1 being cleaned by ultrasonic is subjected to UV ozone UV-zone processing, obtains the substrate 1 pre-processed.
Step 2, the hole transmission layer of perovskite solar battery is prepared.
By hole transmission layer precursor solution drop on the substrate 1 pre-processed, spin coating is carried out using sol evenning machine, after spin coating
Substrate 1 be placed in thermal station and anneal, obtain the hole transmission layer 2 of perovskite solar battery.
The hole transmission layer precursor solution refers to, triphenylamine derivative solution, poly- 3,4-ethylene dioxythiophene: polyphenyl
Vinyl sulfonate PEDOT:PSS solution, poly- (3- hexyl thiophene) P3HT solution, cuprous sulfocyanide CuSCN solution, nickel oxide NiO
Any one in solution.
Step 3, using solution coating method, the light absorbing layer 3 of perovskite solar battery is prepared.
The solution coating method refers to, using any one in three kinds of one-step method spin coating, two-step method spin coating, blade coating methods
Kind method.
The structure of the light absorbing layer is ABX3Any one in the perovskite material of type, wherein A is MA+、FA+、
(CsxMA1-x)+、(CsxFA1-x)+、(FAxMA1-x)+、(CsxFAyMA1-x-y)+One of, B Pb2+, X I-And
(IxBr1-x)-、(ClxI1-x)-、(ClxBr1-x)-、(I1-x-yBrxCly)-One of.
Step 4, the electron transfer layer of perovskite solar battery is prepared.
Electron transfer layer precursor solution is spin-coated on the light absorbing layer 3 that preparation is completed using sol evenning machine, obtains perovskite
The electron transfer layer 4 of solar battery.
The electron transfer layer precursor solution refers to, zinc oxide ZnO solution, stannic oxide SnO2Solution, C60Solution,
[6,6] any one in-phenyl C61 methyl butyrate PCBM solution.
Step 5, using vacuum coater, the metal electrode 5 of perovskite solar battery is prepared.
The metal electrode is using any one in gold Au, silver Ag, with a thickness of 100~300nm；
Step 6, using heat-conducting silicone grease, cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out physics
Connection.
Step 7, the glass substrate of perovskite photodetector is pre-processed.
The glass substrate 7 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, is dried up using high-purity nitrogen.
Step 8, using solution coating method, the light absorbing layer 8 of perovskite photodetector is prepared.
The solution coating method refers to, using any one in three kinds of one-step method spin coating, two-step method spin coating, blade coating methods
Kind method.
The structure of the light absorbing layer is ABX3Any one in the perovskite material of type, wherein A is MA+、FA+、
(CsxMA1-x)+、(CsxFA1-x)+、(FAxMA1-x)+、(CsxFAyMA1-x-y)+One of, B Pb2+, X I-And
(IxBr1-x)-、(ClxI1-x)-、(ClxBr1-x)-、(I1-x-yBrxCly)-One of.
Step 9, using vacuum coater, two metal electrodes 9 and 10 of perovskite photodetector are prepared.
The metal electrode is using any one in gold Au, silver Ag, with a thickness of 100~300nm.
Step 10, perovskite solar battery, thermoelectric generation film, perovskite photodetector are connected.
Using inkjet printing technology, by the substrate 1 of perovskite solar battery respectively with the anode and calcium of thermoelectric generation film 6
One metal electrode 9 of titanium ore photodetector connects, by the metal electrode 5 of perovskite solar battery respectively with thermo-electric generation
Another metal electrode 10 connection of the cathode and perovskite photodetector of piece 6.The sintering temperature of the inkjet printing technology
Degree is 80~120 DEG C, and the time is 10~15min.
The thermal energy generated in perovskite solar cell photoelectric conversion process is transmitted to thermoelectric generation film hot-face layer, temperature difference hair
Semiconductor layer among electric piece utilizes the thermo-electric generation of hot-face layer and huyashi-chuuka (cold chinese-style noodles) layer, converts heat energy into electric energy, reduces thermal energy to calcium
The influence of titanium ore photodetector improves the performance and service life of device.
Using inkjet printing technology by perovskite solar battery it is in parallel with thermoelectric generation film after again with perovskite photoelectricity visit
Device series connection is surveyed, perovskite solar battery is individually powered with thermoelectric generation film for perovskite photodetector, daytime
Mainly perovskite solar battery is the power supply of perovskite detector, and only leaning on thermoelectric generation film at night and rainy weather is calcium titanium
The power supply of mine photodetector.
Preparation process of the invention is described further below with reference to three embodiments.
Embodiment 1:
Step 1 pre-processes perovskite solar cell substrate.
Tin indium oxide ITO substrate 1 is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, deionized water
In be cleaned by ultrasonic, the cleaning temperature of ultrasonic cleaning is 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min.
The tin indium oxide ITO substrate 1 being cleaned by ultrasonic is subjected to UV-zone and handles 30min, obtains the oxidation pre-processed
Indium tin ITO substrate 1.
Step 2 prepares the hole transmission layer of perovskite solar battery.
The 35mg CuSCN salt of 99% concentration is dissolved in the 1mL diethyl thioether of 98% concentration, at room temperature constant temperature
CuSCN solution is prepared in 30 minutes in stirring, and the CuSCN solution of 35 μ L is spin-coated on to the tin indium oxide ITO substrate 1 pre-processed
On, revolving speed 5000rpm, spin coating 30s obtain the hole transmission layer 2 of perovskite solar battery.
Step 3 prepares the light absorbing layer of perovskite solar battery.
Perovskite precursor solution is prepared, according to dimethyl sulfoxide: the volume of gamma-hydroxybutyric acid lactone DMSO:GBL=3:7
Than preparing mixed solvent, jog is allowed to be sufficiently mixed after mixing, and the methylpyridinium iodide ammonium MAI of 215mg is taken to be dissolved in above-mentioned 1mL mixing
In solvent, methylpyridinium iodide ammonium MAI solution is obtained, the lead iodide PbI of 640mg is taken2, methylpyridinium iodide ammonium with the 1mL of above-mentioned preparation
The mixing of MAI solution, 75 DEG C of heating stirrings obtain MAPbI up to being completely dissolved3Solution.
Configured solution is placed on 60 DEG C of heating in thermal station, it is rear to accelerate with the revolving speed spin coating 20s of 1000rpm
4000rpm spin coating 30s again is added dropwise toluene in total time 45s, is placed in thermal station later, and annealing temperature is 100 DEG C, when annealing
Between be 20min, obtain the light absorbing layer 3 of perovskite solar cell.
Step 4 prepares the electron transfer layer of perovskite solar battery.
By [6,6]-phenyl C of 20mg in glove box61Methyl butyrate PCBM is dissolved in the chlorobenzene of 1mL, is stirred with magnetic force
Mixing platform and stirring 8 hours dissolves it sufficiently, and being with revolving speed using sol evenning machine is that 45s carries out spin coating the 2000rpm time, obtains electronics
Transport layer 4.
Step 5 prepares the metal electrode of perovskite solar battery.
It is 10 in Chamber vacuum degree condition-5Pa hereinafter, withRate vapor deposition 100nm Ag, obtain metal electrode
5, perovskite solar battery is completed in preparation.
Step 6, using heat-conducting silicone grease, cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out physics
Connection.
Step 7 pre-processes the glass substrate of perovskite photodetector.
The glass substrate 7 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, cleaning temperature are 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min, is then dried up using high-purity nitrogen.
Step 8 prepares the light absorbing layer of perovskite photodetector.
By the 99% concentration C H of iodine methylamine of 99% concentration3NH3I and lead iodide PbI2, 1:1 is dissolved in 1mLN-N bis- in molar ratio
In methylformamide DMF, perovskite precursor solution is formed, and heating stirring 8h dissolves it sufficiently at 60 DEG C, with 2000rpm
Revolving speed spin coating 20s, it is rear to accelerate 5000rpm spin coating 30s again, toluene is added dropwise in total time 45s, being placed in temperature later is 100
Anneal 15min in DEG C thermal station, obtains the light absorbing layer 8 of perovskite photodetector.
Step 9 prepares two metal electrodes of perovskite photodetector.
The glass substrate that the light absorbing layer of perovskite photodetector is completed in above-mentioned preparation is put into vacuum chamber, by covering
Film version is deposited to obtain the electrode 10 of the Au electrode 9 of 300nm.
Step 10 connects perovskite solar battery, thermoelectric generation film, perovskite photodetector.
Using inkjet printing technology, sintering temperature is 100 DEG C, time 10min, by the substrate of perovskite solar battery
1 connect with a metal electrode 9 of the anode of thermoelectric generation film 6 and perovskite photodetector respectively, by perovskite solar energy
The metal electrode 5 of battery connects with another metal electrode 10 of the cathode of thermoelectric generation film 6 and perovskite photodetector respectively
It connects.
Embodiment 2:
The first step pre-processes perovskite solar cell substrate.
By fluorine-doped tin oxide FTO substrate 1 be sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, go from
It is cleaned by ultrasonic in sub- water, the cleaning temperature of ultrasonic cleaning is 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min.
The fluorine-doped tin oxide FTO substrate 1 being cleaned by ultrasonic is subjected to UV-zone and handles 30min, obtains having pre-processed
Fluorine-doped tin oxide FTO substrate 1.
Second step prepares the hole transmission layer of perovskite solar battery.
Under magnetic stirring by the NiCl of 12.885g2·6H2O is dissolved in the deionized water of 100mL, and 10M is added dropwise
For NaOH solution until pH value reaches 10, precipitating is washed with deionized twice, later in the muddy green solution centrifugation that will be obtained
Powder is dry at 80 DEG C, 2 hours are then annealed at different temperatures by 150mg NiOxNano particle is added to 5mL isopropyl
In alcohol, then the mixing liquid is ultrasonically treated in ultrasonic cleaner with the power of 100W, the total time of ultrasonication
About 8 hours.Acquired solution is filtered by the polytetrafluoroethylene (PTFE) TPFE filter of 0.45um.
Using spin-coating method, by obtained solution with the revolving speed of 2000rpm in the fluorine-doped tin oxide FTO substrate pre-processed
Spin coating 30s on 1, then anneal at 120 DEG C 20min, obtains the hole transmission layer 2 of perovskite solar battery.
Third step prepares the light absorbing layer of perovskite solar battery.
Perovskite precursor solution is prepared, according to dimethyl sulfoxide: the volume of gamma-hydroxybutyric acid lactone DMSO:GBL=3:7
Than preparing mixed solvent, jog is allowed to be sufficiently mixed after mixing, and the methylpyridinium iodide ammonium MAI of 215mg is taken to be dissolved in above-mentioned 1mL mixing
In solvent, methylpyridinium iodide ammonium MAI solution is obtained, the lead iodide PbI of 640mg is taken2, methylpyridinium iodide ammonium with the 1mL of above-mentioned preparation
The mixing of MAI solution, 75 DEG C of heating stirrings obtain MAPbI up to being completely dissolved3Solution.
In humidity 5%, the atmospheric environment that 25 DEG C of temperature, adjustment blade coating platform to assigned temperature adjusts scraper height extremely
1230 microns, fluorine-doped tin oxide FTO substrate 1 is placed on blade coating platform preheats 1 minute later, take perovskite precursor solution
20 microlitres are added dropwise in substrate, drive scraper at the uniform velocity to advance blade coating according to the speed of setting later, will be coated with perovskite has active layer
Substrate is placed in thermal station, and annealing temperature is 100 DEG C, and anneal 30min, obtains perovskite light absorbing layer 3.
4th step prepares the electron transfer layer of perovskite solar battery.
2.95g acetic acid zinc powder is added in 125mL methanol solution, is warming up to 70 DEG C immediately, is stirred continuously to obtain
Prescribed liquid A；In the methanol solution that 1.48g potassium hydroxide powder is dissolved in 65mL at 70 DEG C, it is stirred continuously to obtain mixed solution
B；Solution B is added dropwise to solution A dropwise in stirring, then stirs 2h, after standing allows to cool to room temperature, removal upper layer is clear
70mL n-butanol, 5mL methanol and 5mL chloroform are added in precipitating, at the uniform velocity stir after cleaning precipitating with methanol by liquid, filter
Obtain zinc oxide nano-particle solution.
By burnett's solution with the revolving speed spin coating 30s on the perovskite light absorbing layer 3 that preparation is completed, repetition for 3000rmp
Spin coating three times, obtains electron transfer layer 4.
5th step prepares the metal electrode of perovskite solar battery.
It is 10 in Chamber vacuum degree condition-5Pa hereinafter, withRate vapor deposition 100nm Ag, obtain metal electrode
5, perovskite solar battery is completed in preparation.
6th step, using heat-conducting silicone grease, cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out object
Reason connection.
7th step pre-processes the glass substrate of perovskite photodetector.
The glass substrate 7 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, cleaning temperature are 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min, is then dried up using high-purity nitrogen.
8th step prepares the light absorbing layer of perovskite photodetector.
By the iodine methylamine CH of 99% concentration3NH3The lead iodide PbI of I and 99% concentration21:1 is dissolved in 1mLN-N bis- in molar ratio
In methylformamide DMF, perovskite precursor solution is formed, and heating stirring 8h dissolves it sufficiently at 60 DEG C, is in humidity
Under the conditions of 120 DEG C of 40%, perovskite precursor solution is dropped in above-mentioned substrate of glass, control scraper is at a distance from substrate
100um, and it is at the uniform velocity passed through into substrate, it is uniformly coated on perovskite solution on glass basic surface, perovskite will be coated with
There is the substrate of active layer to be placed in thermal station, annealing temperature is 100 DEG C, and anneal 15min, and the light for obtaining perovskite photodetector is inhaled
Receive layer 8.
9th step prepares two metal electrodes of perovskite photodetector.
The glass substrate that the light absorbing layer of perovskite photodetector is completed in above-mentioned preparation is put into vacuum chamber, by covering
Film version is deposited to obtain the electrode 10 of the Au electrode 9 of 300nm.
Tenth step connects perovskite solar battery, thermoelectric generation film, perovskite photodetector.
Using inkjet printing technology, sintering temperature is 100 DEG C, time 10min, by the substrate of perovskite solar battery
1 connect with a metal electrode 9 of the anode of thermoelectric generation film 6 and perovskite photodetector respectively, by perovskite solar energy
The metal electrode 5 of battery connects with another metal electrode 10 of the cathode of thermoelectric generation film 6 and perovskite photodetector respectively
It connects.
Embodiment 3:
Step A pre-processes perovskite solar cell substrate.
Tin indium oxide ITO substrate 1 is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, deionized water
In be cleaned by ultrasonic, the cleaning temperature of ultrasonic cleaning is 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min.
The tin indium oxide ITO substrate 1 being cleaned by ultrasonic is subjected to UV-zone and handles 30min, obtains the oxidation pre-processed
Indium tin ITO substrate 1.
Step B prepares the hole transmission layer of perovskite solar battery.
Take filtered 3,4-ethylene dioxythiophene: poly styrene sulfonate PEDOT:PSS (P VP Al 4083) drop exists
On the tin indium oxide ITO substrate 1 pre-processed, using sol evenning machine carry out spin coating, spin coating revolving speed be 6000rmp, time 48s,
Then 150 DEG C of annealing 15min in thermal station, obtain the hole transmission layer 2 of perovskite solar battery.
Step C prepares the light absorbing layer of perovskite solar battery.
By 1.36M PbI2 and 0.24M PbCl2It is dissolved in DMF, 75 DEG C is heated and stirs 2 hours.The MAI's and 30mg of 70mg
FAI is dissolved in the IPA of 1mL, additionally incorporates the DMF of 10 μ L.Later, PbX2Precursor solution spin coating on substrate, revolving speed 3000rpm
Spin-coating time 45s, the mixed solution of MAI and FAI is spin-coated on PbX later2On substrate, revolving speed 3000rpm spin-coating time 45s.It
Sample obtains the light absorbing layer 3 of perovskite solar cell in 100 DEG C of thermal station annealing 10min afterwards.
Step D prepares the electron transfer layer of perovskite solar battery.
2.95g acetic acid zinc powder is added in 125mL methanol solution, is warming up to 70 DEG C immediately, is stirred continuously to obtain
Prescribed liquid A；In the methanol solution that 1.48g potassium hydroxide powder is dissolved in 65mL at 70 DEG C, it is stirred continuously to obtain mixed solution
B；Solution B is added dropwise to solution A dropwise in stirring, then stirs 2h, after standing allows to cool to room temperature, removal upper layer is clear
70mL n-butanol, 5mL methanol and 5mL chloroform are added in precipitating, at the uniform velocity stir after cleaning precipitating with methanol by liquid, filter
Obtain zinc oxide nano-particle solution.
By burnett's solution with the revolving speed spin coating 30s on the perovskite light absorbing layer 3 that preparation is completed, repetition for 3000rmp
Spin coating three times, obtains electron transfer layer 4.
Step E prepares the metal electrode of perovskite solar battery.
It is 10 in Chamber vacuum degree condition-5Pa hereinafter, withRate vapor deposition 100nm Ag, obtain metal electrode
5, perovskite solar battery is completed in preparation.
Step F, using heat-conducting silicone grease, cell metallic electrode 5 and thermoelectric generation film 6 to perovskite solar energy carry out physics
Connection.
Step G pre-processes the glass substrate of perovskite photodetector.
The glass substrate 7 of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound
Cleaning, cleaning temperature are 50 DEG C, and the time of every kind of ultrasonic cleaning is 20min, is then dried up using high-purity nitrogen.
Step H prepares the light absorbing layer of perovskite photodetector.
0.46M PbI2 is dissolved in DMF, is that 2000rpm is spun on hole transport layer surface, time 40s with revolving speed；Rotation
It is painted with to be placed in glove box and stands 10 minutes or anneal at a temperature of 70 DEG C 2 minutes to remove remaining DMF solvent.Immediately
, the MAI that concentration is 50mg/mL is spun on PbI2On layer, revolving speed 4000rpm, time 35s；Sample is placed in heat later
Platform is annealed, and annealing temperature is 100 DEG C, annealing time 20min, obtains the light absorbing layer 8 of perovskite photodetector.
Step I prepares two metal electrodes of perovskite photodetector.
The glass substrate that the light absorbing layer of perovskite photodetector is completed in above-mentioned preparation is put into vacuum chamber, by covering
Film version is deposited to obtain the electrode 10 of the Au electrode 9 of 300nm.
Step J connects perovskite solar battery, thermoelectric generation film, perovskite photodetector.
Using inkjet printing technology, sintering temperature is 100 DEG C, time 10min, by the substrate of perovskite solar battery
1 connect with a metal electrode 9 of the anode of thermoelectric generation film 6 and perovskite photodetector respectively, by perovskite solar energy
The metal electrode 5 of battery connects with another metal electrode 10 of the cathode of thermoelectric generation film 6 and perovskite photodetector respectively
It connects.
Claims (9)
1. a kind of photoelectric heat replies the photodetector closed from driving, including perovskite solar battery, glass substrate (7), institute by cable
State perovskite solar battery include substrate (1) and the hole transmission layer (2) being from top to bottom sequentially prepared on substrate (1),
Light absorbing layer (3), electron transfer layer (4) and metal electrode (5)；Prepared on the glass substrate (7) light absorbing layer (8),
The two sides of light absorbing layer (8) prepare two metal electrodes (9) and (10)；It is characterized in that, the photodetector further includes temperature
Poor power generation sheet (6), the thermoelectric generation film (6) are arranged under metal electrode (5)；The perovskite solar battery and the temperature difference
It connects again with perovskite photodetector after power generation sheet is in parallel.
2. a kind of photoelectric heat according to claim 1 replies the photodetector closed from driving by cable, which is characterized in that described
Solar cell substrate (1) uses tin indium oxide ITO substrate or fluorine-doped tin oxide FTO substrate.
3. a kind of photoelectric heat replies the photodetector preparation method closed from driving by cable, which is characterized in that utilize inkjet printing technology
Connect perovskite solar battery, thermoelectric generation film, perovskite photodetector；The step of this method includes the following:
(1) perovskite solar cell substrate is pre-processed:
Substrate (1) is sequentially placed into Decon-90 cleaning agent, deionized water, acetone, alcohol, carries out ultrasound in deionized water by (1a)
Cleaning；
The substrate being cleaned by ultrasonic (1) is carried out UV ozone UV-zone processing by (1b), obtains the substrate (1) pre-processed；
(2) hole transmission layer of perovskite solar battery is prepared:
By hole transmission layer precursor solution drop on the substrate (1) pre-processed, spin coating is carried out using sol evenning machine, after spin coating
Substrate (1), which is placed in thermal station, anneals, and obtains the hole transmission layer (2) of perovskite solar battery；
(3) solution coating method is used, the light absorbing layer (3) of perovskite solar battery is prepared；
(4) electron transfer layer of perovskite solar battery is prepared:
Electron transfer layer precursor solution is spin-coated on the light absorbing layer (3) that preparation is completed using sol evenning machine, obtains perovskite too
The electron transfer layer (4) of positive energy battery；
(5) vacuum coater is used, the metal electrode (5) of perovskite solar battery is prepared；
(6) heat-conducting silicone grease is used, the cell metallic electrode (5) and thermoelectric generation film (6) to perovskite solar energy carry out physics company
It connects；
(7) glass substrate of perovskite photodetector is pre-processed:
The glass substrate (7) of perovskite photodetector is sequentially placed into ionized water, acetone and dehydrated alcohol and carries out ultrasound clearly
It washes, is dried up using high-purity nitrogen；
(8) solution coating method is used, the light absorbing layer (8) of perovskite photodetector is prepared；
(9) vacuum coater is used, two metal electrodes (9) and (10) of perovskite photodetector are prepared；
(10) perovskite solar battery, thermoelectric generation film, perovskite photodetector are connected:
Using inkjet printing technology, by the substrate (1) of the perovskite solar battery anode and calcium with thermoelectric generation film (6) respectively
One metal electrode (9) of titanium ore photodetector connects, by the metal electrode (5) of perovskite solar battery respectively with the temperature difference
Another metal electrode (10) connection of the cathode and perovskite photodetector of power generation sheet (6).
4. a kind of photoelectric heat according to claim 3 replies the photodetector preparation method closed from driving by cable, feature exists
In hole transmission layer precursor solution described in step (2) refers to, triphenylamine derivative solution, poly- 3,4-ethylene dioxythiophene:
Poly styrene sulfonate PEDOT:PSS solution, poly- (3- hexyl thiophene) P3HT solution, cuprous sulfocyanide CuSCN solution, nickel oxide
Any one in NiO solution.
5. a kind of photoelectric heat according to claim 3 replies the photodetector preparation method closed from driving by cable, feature exists
In solution coating method described in step (3), step (8) refers to, using three kinds of one-step method spin coating, two-step method spin coating, blade coating sides
Any one method in method.
6. a kind of photoelectric heat according to claim 3 replies the photodetector preparation method closed from driving by cable, feature exists
In the structure of light absorbing layer described in step (3), step (8) is ABX3Any one in the perovskite material of type, wherein
A is MA+、FA+、(CsxMA1-x)+、(CsxFA1-x)+、(FAxMA1-x)+、(CsxFAyMA1-x-y)+One of, B Pb2+, X I-
And (IxBr1-x)-、(ClxI1-x)-、(ClxBr1-x)-、(I1-x-yBrxCly)-One of.
7. a kind of photoelectric heat according to claim 3 replies the photodetector preparation method closed from driving by cable, feature exists
In electron transfer layer precursor solution described in step (4) refers to, zinc oxide ZnO solution, stannic oxide SnO2Solution, C60It is molten
Any one in liquid, [6,6]-phenyl C61 methyl butyrate PCBM solution.
8. a kind of photoelectric heat according to claim 3 replies the photodetector preparation method closed from driving by cable, feature exists
In metal electrode described in step (5), step (9) is using any one in gold Au, silver Ag, with a thickness of 100~300nm.
9. a kind of photoelectric heat according to claim 3 replies the photodetector preparation method closed from driving by cable, feature exists
In the sintering temperature of inkjet printing technology described in step (10) is 80~120 DEG C, and the time is 10~15min.
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| CN106024775A (en) * | 2016-07-15 | 2016-10-12 | 华中科技大学 | Integrated device with thermoelectric power generation sheet and manufacturing method thereof |
| CN106533326A (en) * | 2016-11-03 | 2017-03-22 | 中国地质大学（武汉） | Micro-nano multi-light trap type solar composite generating integrated device |
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| CN106024775A (en) * | 2016-07-15 | 2016-10-12 | 华中科技大学 | Integrated device with thermoelectric power generation sheet and manufacturing method thereof |
| CN106533326A (en) * | 2016-11-03 | 2017-03-22 | 中国地质大学（武汉） | Micro-nano multi-light trap type solar composite generating integrated device |
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