CN107248549A - A kind of low temperature flexibility perovskite solar cell and preparation method thereof - Google Patents
A kind of low temperature flexibility perovskite solar cell and preparation method thereof Download PDFInfo
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- CN107248549A CN107248549A CN201710387718.4A CN201710387718A CN107248549A CN 107248549 A CN107248549 A CN 107248549A CN 201710387718 A CN201710387718 A CN 201710387718A CN 107248549 A CN107248549 A CN 107248549A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
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- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
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Abstract
The invention belongs to perovskite area of solar cell, and disclose a kind of low temperature flexibility perovskite solar cell and preparation method thereof.The solar cell includes substrate, light anode layer, light-absorption layer, hole transmission layer and to electrode layer, and light anode is made up of tin ash, and light absorbing layer is made up of perovskite, and hole transmission layer is made up of CuPc, described that electrode layer is made up of conductive carbon paste；Preparation method includes (a) spin coating in substrate and generates tin ash compacted zone；(b) anti-solvent method spin coating generation calcium titanium ore bed is carried out on tin ash compacted zone；(c) by CuPc evaporation to calcium titanium ore bed, conductive carbon paste then is printed in the substrate after evaporation, so as to complete the preparation of solar cell.By the present invention, the preparation temperature of battery is reduced, realizes prepared by the flexibility of battery, and calcium titanium ore bed reduces Carrier recombination, substantially increases battery performance.
Description
Technical field
The invention belongs to perovskite area of solar cell, more particularly, to a kind of low temperature flexibility perovskite solar energy
Battery and preparation method thereof.
Background technology
Solar energy is increasing by people as a kind of cleaning, environmentally friendly, cheap, rich reserves regenerative resources
Concern.In the Solar use mode such as photothermal deformation, opto-electronic conversion and Photochemical convertion, opto-electronic conversion has permanent, clear
The features such as clean property, flexibility, the basic device of solar energy photoelectric conversion is solar cell., Japanese Miyasaka etc. in 2009
People is during research sensitization solar cell, first using the organic metal halide CH with perovskite structure3NH3PbBr3
And CH3NH3PbI3As sensitizer, the prelude of perovskite solar cell research has been pulled open.
Miniaturization, flexibility growth requirement with electronic product, emerge in recent years it is various it is wearable, can
Fold electronic product and intelligent movable device such as Google glass, intelligent watch, health monitoring wrist strap etc., the production of these flexible electronics
Product have requirements at the higher level, such as the flexible electronic paper of Sony companies production and the flexibility of LG company production to the portability of charging
Electronic display, the Scroll rechargeable solar battery treasured of infinityPV companies of Denmark research and development, it is in portable power plants
Further develop on conceptual foundation, add flexible polymer solar battery, can roll and be put in protecting box after punching electricity, chi
Very little is 11.3 × 3.6 × 2.8cm, weight only 105g, and being that IPhone 6 is fully charged is only needed to 2~3 hours, and therefore, exploitation is based on
Efficient micro- energy device of perovskite, makes it to be widely used in flexible electronic product to be significant, but perovskite is too
Prepared by positive energy battery is still related to high-temperature technology, it is impossible to applied to flexible electronic product, the flexibility based on perovskite solar cell
Prepared by micro- energy integration device also need to carry out in-depth study with exploring.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of low temperature flexibility perovskite solar energy
Battery and preparation method thereof, is substrate by using flexible PEN films, while replacing traditional titanium dioxide using tin ash
As light anode, thus solve solar cell and may not apply to flexible electronic product and the high technical problem of preparation temperature.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of low temperature flexibility perovskite solar-electricity
Pond, the solar cell includes substrate, light anode layer, light-absorption layer, hole transmission layer and to electrode layer from the bottom to top, and its feature exists
In,
The substrate is the flexible PEN films for being coated with Fluorin doped tin ash or conductive indium-tin oxide layer, the light anode
It is made up of tin ash, the light absorbing layer is made up of perovskite, the hole transmission layer is made up of CuPc, it is described to electrode
Layer is made up of conductive carbon paste.
It is further preferred that the thickness of the light anode layer is 50nm~80nm；The thickness of the light absorbing layer is 400nm
~600nm；The thickness of the hole transmission layer is 30nm~40nm；The thickness to electrode layer is 10um~100um.
According to another aspect of the present invention, a kind of preparation method of solar cell as described above, it is characterised in that
This method comprises the following steps：
(a) by two hydrated stannous chlorides or Tin tetrachloride pentahydrate spin coating substrate after cleaning, then to spin coating after
Substrate heating so that adhere to one layer of tin ash compacted zone on the substrate, the tin ash compacted zone is used as light anode
Layer, wherein, the temperature of the heating is 180 DEG C~190 DEG C, and the heat time is 1h~3h；
(b) anti-solvent method spin coating is carried out on the tin ash compacted zone that step (a) is obtained, then the substrate is added
Heat so that in one layer of calcium titanium ore bed of Surface Creation of the tin ash compacted zone, the calcium titanium ore bed is used as light absorbing layer；
(c) CuPc is deposited on the calcium titanium ore bed obtained to step (b) and forms phthalocyanine layers of copper, the phthalocyanine layers of copper is used as sky
Cave transport layer, then prints conductive carbon paste in the phthalocyanine layers of copper and is formed to electrode layer, so far complete the place to the substrate
Reason, so as to obtain required solar cell.
It is further preferred that in step (a), after the heating, the substrate after preferred pair heating carries out ultraviolet smelly
Oxygen processing or plasma treatment.
It is further preferred that in step (b), spin coating agent used in the spin coating is ABX3Compound, wherein, X be F,
Cl, Br or I, B is Pb or Sn, A are CH3、NH3 +Or FA+, spin speed is preferably 4000rpm~5000rpm, and spin-coating time is excellent
Elect 30s~40s as.
It is further preferred that in step (b), the anti-solvent method spin coating refers to 6s~8s after spin coating starts,
Polar organic solvent is added dropwise on the tin ash compacted zone, spin coating is then proceeded to.
It is further preferred that in step (b), the temperature range of the heating is 90 DEG C~100 DEG C, and the heat time is
5min~10min.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1st, the present invention by using flexible PEN films as substrate, compared to other flexible substrates, with higher stabilization
Property and heat-resisting quantity, highest bearing temperature is up to 200 DEG C, in addition, replacing traditional titanium dioxide TiO by using tin ash2
As light anode, the highest technological temperature of preparation method is reduced to 180 DEG C, the low temperature preparation of solar cell is realized；
2nd, it is of the invention because flexible substrates highest heatproof can only achieve 200 DEG C hence in so that being coated with FTO (Fluorin doped titanium dioxides
Tin) or the flexible PEN films of ITO (tin indium oxide) conductive layer be possibly realized as conductive substrates so that battery can be prepared
In in flexible substrates, it is achieved thereby that the flexibility of device；It is steady with higher illumination in addition, the band gap of tin ash is wider
It is qualitative, and the translucency of tin dioxide thin film is very good, substantially reduces illumination loss；
3rd, the present invention prepares organic-inorganic calcium titanium ore bed by using anti-solvent, with traditional calcium titanium ore bed preparation method phase
Than the calcium titanium ore bed of preparation has minute surface flatness, and coverage rate nearly 100%, leakage current is substantially reduced, so as to improve
Battery performance；
4th, the present invention by using CuPc CuPc as hole transmission layer, it is big compared to traditional spiro-OMeTAD costs
Big reduction, possibility is provided for the commercialization of battery, in addition, CuPc does not adulterate compared to conventional hole transport layer, therefore tool
There is higher stability；
5th, the present invention collects electric charge by using carbon as to electrode, and compared with traditional metal electrodes, cost is substantially reduced,
" the roll to roll " large-scale production of battery can be achieved.
Brief description of the drawings
Fig. 1 is the cross section structure schematic diagram according to the solar cell constructed by the preferred embodiments of the present invention；
Fig. 2 is the flow chart according to the preparation method of solar battery constructed by the preferred embodiments of the present invention；
Fig. 3 is the actual cross-section figure according to the solar cell constructed by the preferred embodiments of the present invention.
In all of the figs, identical reference is used for representing identical element or structure, wherein：
1- substrate 2- light anode 3- calcium titanium ore bed 4- hole transmission layer 5- carbon is to electrode
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
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 each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
Fig. 1 is the cross section structure schematic diagram according to the solar cell constructed by the preferred embodiments of the present invention；Such as Fig. 1 institutes
Show, the present invention proposes a kind of low temperature flexibility perovskite solar cell based on tin ash light anode, device is tradition n-
I-p types, battery structure be conductive substrates, light anode, calcium titanium ore bed, hole transmission layer, carbon to electrode, wherein light anode is dioxy
Change tin, due to its can low temperature preparation characteristic, the conductive substrates of solar cell can use flexible conducting substrate, realize device
Flexibility, calcium titanium ore bed be organic-inorganic mixing perovskite, hole transmission layer be CuPc CuPc.
The conductive substrates of solar cell refer to FTO (Fluorin doped tin ash) using flexible PEN films as substrate/
PEN or ITO (tin indium oxide)/PEN；Light anode refers to tin ash, and thickness control plays transmission in 50nm~80nm or so
The effect of electronics, and light absorbing layer is opened with electrode isolation, reduce Carrier recombination；Calcium titanium ore bed is referred to by organic perovskite
The light absorbing layer of material deposition, the CH prepared by anti-solvent method3NH3PbI3Film, thickness control is in 400nm~600nm；
Hole transmission layer refers to the CuPc prepared by thermal evaporation, and thickness control plays a part of transporting holes in 30nm~40nm, and
By light absorbing layer with opening electrode isolation, reduce Carrier recombination；It is to refer to carbon pastes through being screen printed onto overhead to electrode
Conductive C film in the transport layer of cave.The film is used to collect electric charge, and thickness control is in 10um~100um.
Fig. 2 is the flow chart according to the preparation method of solar battery constructed by the preferred embodiments of the present invention；Such as Fig. 2 institutes
Show, the present invention provides the low temperature flexibility perovskite solar cell preparation technology based on tin ash light anode, including following step
Suddenly：
(a) the flexible PEN films that will be coated with FTO (Fluorin doped tin ash) or ITO (tin indium oxide) conductive layer are carried out in advance
Processing；By the method for spin coating, tin ash light anode is prepared in the conductive substrates that step one is pre-processed；
The preprocessing process of the transparent flexible conductive substrates is specially：Respectively 15min is cleaned with acetone and EtOH Sonicate
~20min, removes the organic matter of substrate surface, is then washed with deionized water only, is finally putting into UV ozone cleaning machine and handles
20min~30min carries out surface modification, increases the hydrophily on its surface；
Tin ash light anode preparation process is as follows：By 0.1M~0.15M SnCl2·2H2O ethanol solutions, which are spin-coated on, leads
In electric substrate, spin speed is 2000rpm~3000rpm, and spin-coating time is 30s~40s, is placed on hot plate and heats afterwards, plus
Hot temperature is 180 DEG C~190 DEG C, and the heat time is 1h~2h, and last UV ozone handles 10min~15min；
(b) in the light anode prepared by step 2, anti-solvent spin coating CH is passed through3NH3I-PbI2Solution；
Light-absorption layer preparation process is：Take 461mgPbI2, 159mgCH3NH3I, 75mg~90mgDMSO and 600mg~
800mgDMF is configured to CH3NH3I-PbI2Solution, by CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, rotation
Painting speed be 4000rpm~5000rpm, spin-coating time be 30s~40s, the 6s~8s started in spin coating, by 0.3ml~
0.5ml ether fast drop afterwards, is placed on hot plate and heated, heating-up temperature is 90 DEG C~100 DEG C, heating on spin coated substrate
Time is 5min~10min；
(c) thermal evaporation prepares CuPc on the calcium titanium ore bed prepared by step 3；By being screen printed onto prepared by step 4
Hole transmission layer on print conductive carbon paste, so far, device prepare finish.
Hole transmission layer preparation process is：Using resistance-type thermal evaporation apparatus, by CuPc evaporations to light absorbing layer, it is deposited
Thickness be 30nm~40nm；
It is to electrode production process：Carbon pastes are printed on to the hole prepared by step 4 by the method for silk-screen printing to pass
On defeated layer, thickness is 10 μm~100 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 70 DEG C~80 DEG C, and the heat time is
15min~20min；
Carbon pastes preparation process is as follows：First, weigh 1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks,
0.5g50nmZrO2Poured into after mixing in ball grinder；It is subsequently poured into and is dissolved with ethyl cellulose and polyvinylacetate DBE (nylon
Dimethyl phthalate) 15mL as carbon pastes organic carrier；Zirconium pearl is finally putting into, ball milling is after 6 hours, and prepared by carbon pastes completes.
According to Fig. 1 flow chart, the present invention is further illustrated below in conjunction with specific embodiment：
Embodiment 1
(a) the PEN films for being coated with FTO for cutting and having etched are cleaned 15 minutes with acetone and EtOH Sonicate respectively, gone
Except the organic matter of substrate surface, then it is washed with deionized water only, is finally putting into UV ozone cleaning machine and handles progress in 20 minutes
Surface is modified；By 0.1M SnCl2·2H2O ethanol solutions are spin-coated in conductive substrates, and spin speed is 2000rpm, during spin coating
Between be 30s, be placed on hot plate and heat afterwards, heating-up temperature is 180 DEG C, and the heat time is 1h, last ultraviolet processing 10min；
(b) 461mgPbI is taken2, 159mgCH3NH3I, 70mgDMSO and 600mgDMF are configured to CH3NH3I-PbI2Solution, will
CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, and spin speed is 4000rpm, and spin-coating time is 30s,
The 6s that spin coating starts, by 0.3ml ether fast drop to spin coated substrate, afterwards, is placed on hot plate and heats, heating-up temperature is
90 DEG C, the heat time is 5min；
(c) resistance-type thermal evaporation apparatus is utilized, by CuPc evaporations to light absorbing layer, the thickness of evaporation is 30nm；Weigh
1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks, 0.5g50nmZrO2, poured into after mixing in ball grinder；Then fall
Enter to be dissolved with ethyl cellulose and polyvinylacetate DBE (nylon acid dimethyl ester) 15mL as the organic carrier of carbon pastes, most
After be put into zirconium pearl, ball milling is after 6 hours, and prepared by carbon pastes completes；Carbon pastes are printed on step 4 institute by the method for silk-screen printing
On the hole transmission layer of preparation, thickness is 10 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 70 DEG C, and the heat time is
15min。
Embodiment 2
(a) the PEN films for being coated with FTO for cutting and having etched are cleaned 17 minutes with acetone and EtOH Sonicate respectively, gone
Except the organic matter of substrate surface, then it is washed with deionized water only, is finally putting into UV ozone cleaning machine and handles progress in 20 minutes
Surface is modified；By 0.1M SnCl2·2H2O ethanol solutions are spin-coated in conductive substrates, and spin speed is 2000rpm, during spin coating
Between be 30s, be placed on hot plate and heat afterwards, heating-up temperature is 182 DEG C, and the heat time is 1h, last ultraviolet processing 10min；
(b) 461mgPbI is taken2, 159mgCH3NH3I, 70mgDMSO and 600mgDMF are configured to CH3NH3I-PbI2Solution, will
CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, and spin speed is 4200rpm, and spin-coating time is 32s,
The 6s that spin coating starts, by 0.3ml ether fast drop to spin coated substrate, afterwards, is placed on hot plate and heats, heating-up temperature is
90 DEG C, the heat time is 5min；
(c) resistance-type thermal evaporation apparatus is utilized, by CuPc evaporations to light absorbing layer, the thickness of evaporation is 34nm；Weigh
1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks, 0.5g50nmZrO2, poured into after mixing in ball grinder；Then fall
Enter to be dissolved with ethyl cellulose and polyvinylacetate DBE (nylon acid dimethyl ester) 15mL as the organic carrier of carbon pastes；Most
After be put into zirconium pearl, ball milling is after 6 hours, and prepared by carbon pastes completes；Carbon pastes are printed on step 4 institute by the method for silk-screen printing
On the hole transmission layer of preparation, thickness is 20 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 72 DEG C, and the heat time is
15min。
Embodiment 3
(a) the PEN films for being coated with FTO for cutting and having etched are cleaned 16 minutes with acetone and EtOH Sonicate respectively, gone
Except the organic matter of substrate surface, then it is washed with deionized water only, is finally putting into UV ozone cleaning machine and handles progress in 20 minutes
Surface is modified；By 0.11M SnCl2·2H2O ethanol solutions are spin-coated in conductive substrates, and spin speed is 2200rpm, during spin coating
Between be 32s, be placed on hot plate and heat afterwards, heating-up temperature is 184 DEG C, and the heat time is 1.5h, last ultraviolet processing 10min；
(b) 461mgPbI is taken2, 159mgCH3NH3I, 75mgDMSO and 630mgDMF are configured to CH3NH3I-PbI2Solution, will
CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, and spin speed is 4400rpm, and spin-coating time is 34s,
The 6s that spin coating starts, by 0.3ml ether fast drop to spin coated substrate, afterwards, is placed on hot plate and heats, heating-up temperature is
95 DEG C, the heat time is 6min；
(c) resistance-type thermal evaporation apparatus is utilized, by CuPc evaporations to light absorbing layer, the thickness of evaporation is 35nm；Weigh
1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks, 0.5g50nmZrO2, poured into after mixing in ball grinder；Then fall
Enter to be dissolved with ethyl cellulose and polyvinylacetate DBE (nylon acid dimethyl ester) 15mL as the organic carrier of carbon pastes；Most
After be put into zirconium pearl, ball milling is after 6 hours, and prepared by carbon pastes completes；Carbon pastes are printed on step 4 institute by the method for silk-screen printing
On the hole transmission layer of preparation, thickness is 40 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 75 DEG C, and the heat time is
17min；
Embodiment 4
(a) the PEN films for being coated with FTO for cutting and having etched are cleaned 18 minutes with acetone and EtOH Sonicate respectively, gone
Except the organic matter of substrate surface, then it is washed with deionized water only, is finally putting into UV ozone cleaning machine and handles progress in 25 minutes
Surface is modified；By 0.12M SnCl2·2H2O ethanol solutions are spin-coated in conductive substrates, and spin speed is 2400rpm, during spin coating
Between be 34s, be placed on hot plate and heat afterwards, heating-up temperature is 186 DEG C, and the heat time is 1.5h, last ultraviolet processing 10min；
(b) 461mgPbI is taken2, 159mgCH3NH3I, 78mgDMSO and 650mgDMF are configured to CH3NH3I-PbI2Solution, will
CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, and spin speed is 4600rpm, and spin-coating time is 36s,
The 7s started in spin coating, by 0.4ml ether fast drop to spin coated substrate, afterwards, is placed on hot plate and heats, heating-up temperature
For 95 DEG C, the heat time is 7min；
(c) resistance-type thermal evaporation apparatus is utilized, by CuPc evaporations to light absorbing layer, the thickness of evaporation is 36nm；Weigh
1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks, 0.5g50nmZrO2, poured into after mixing in ball grinder；Then fall
Enter to be dissolved with ethyl cellulose and polyvinylacetate DBE (nylon acid dimethyl ester) 15mL as the organic carrier of carbon pastes；Most
After be put into zirconium pearl, ball milling is after 6 hours, and prepared by carbon pastes completes；Carbon pastes are printed on step 4 institute by the method for silk-screen printing
On the hole transmission layer of preparation, thickness is 60 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 78 DEG C, and the heat time is
18min；
Embodiment 5
(a) the PEN films for being coated with FTO for cutting and having etched are cleaned 19 minutes with acetone and EtOH Sonicate respectively, gone
Except the organic matter of substrate surface, then it is washed with deionized water only, is finally putting into UV ozone cleaning machine and handles progress in 25 minutes
Surface is modified；By 0.13M SnCl2·2H2O ethanol solutions are spin-coated in conductive substrates, and spin speed is 2600rpm, during spin coating
Between be 36s, be placed on hot plate and heat afterwards, heating-up temperature is 188 DEG C, and the heat time is 1.5h, last ultraviolet processing 12min；
(b) 461mgPbI is taken2, 159mgCH3NH3I, 80mgDMSO and 700mgDMF are configured to CH3NH3I-PbI2Solution, will
CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, and spin speed is 4800rpm, and spin-coating time is 38s,
The 7s started in spin coating, by 0.4ml ether fast drop to spin coated substrate, afterwards, is placed on hot plate and heats, heating-up temperature
For 96 DEG C, the heat time is 8min；
(c) resistance-type thermal evaporation apparatus is utilized, by CuPc evaporations to light absorbing layer, the thickness of evaporation is 38nm；Weigh
1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks, 0.5g50nmZrO2, poured into after mixing in ball grinder；Then fall
Enter to be dissolved with ethyl cellulose and polyvinylacetate DBE (nylon acid dimethyl ester) 15mL as the organic carrier of carbon pastes；Most
After be put into zirconium pearl, ball milling is after 6 hours, and prepared by carbon pastes completes；Carbon pastes are printed on step 4 institute by the method for silk-screen printing
On the hole transmission layer of preparation, thickness is 80 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 80 DEG C, and the heat time is
20min；
Embodiment 6
(a) the PEN films for being coated with FTO for cutting and having etched are cleaned 20 minutes with acetone and EtOH Sonicate respectively, gone
Except the organic matter of substrate surface, then it is washed with deionized water only, is finally putting into UV ozone cleaning machine and handles progress in 30 minutes
Surface is modified；By 0.14M SnCl2·2H2O ethanol solutions are spin-coated in conductive substrates, and spin speed is 2800rpm, during spin coating
Between be 38s, be placed on hot plate and heat afterwards, heating-up temperature is 190 DEG C, and the heat time is 1.5h, last ultraviolet processing 15min；
(b) 461mgPbI is taken2, 159mgCH3NH3I, 85mgDMSO and 750mgDMF are configured to CH3NH3I-PbI2Solution, will
CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, and spin speed is 4700rpm, and spin-coating time is 39s,
The 8s that spin coating starts, by 0.5ml ether fast drop to spin coated substrate, afterwards, is placed on hot plate and heats, heating-up temperature is
96 DEG C, the heat time is 8min；
(c) resistance-type thermal evaporation apparatus is utilized, by CuPc evaporations to light absorbing layer, the thickness of evaporation is 40nm；Weigh
1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks, 0.5g50nmZrO2, poured into after mixing in ball grinder；Then fall
Enter to be dissolved with ethyl cellulose and polyvinylacetate DBE (nylon acid dimethyl ester) 15mL as the organic carrier of carbon pastes；Most
After be put into zirconium pearl, ball milling is after 6 hours, and prepared by carbon pastes completes；Carbon pastes are printed on step 4 institute by the method for silk-screen printing
On the hole transmission layer of preparation, thickness is 100 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 80 DEG C, and the heat time is
20min；
Embodiment 7
(a) the PEN films for being coated with FTO for cutting and having etched are cleaned 20 minutes with acetone and EtOH Sonicate respectively, gone
Except the organic matter of substrate surface, then it is washed with deionized water only, is finally putting into UV ozone cleaning machine and handles progress in 30 minutes
Surface is modified；By 0.15M SnCl2·2H2O ethanol solutions are spin-coated in conductive substrates, and spin speed is 3000rpm, during spin coating
Between be 40s, be placed on hot plate and heat afterwards, heating-up temperature is 190 DEG C, and the heat time is 2h, last ultraviolet processing 15min；
(b) 461mgPbI is taken2, 159mgCH3NH3I, 90mgDMSO and 800mgDMF are configured to CH3NH3I-PbI2Solution, will
CH3NH3I-PbI2Solution is spun in the light anode prepared by step 2, and spin speed is 5000rpm, and spin-coating time is 40s,
The 8s that spin coating starts, by 0.5ml ether fast drop to spin coated substrate, afterwards, is placed on hot plate and heats, heating-up temperature is
100 DEG C, the heat time is 10min；
(c) resistance-type thermal evaporation apparatus is utilized, by CuPc evaporations to light absorbing layer, the thickness of evaporation is 40nm；Weigh
1g10um crystalline flake graphites, 2g400nm graphite, 1g40nm carbon blacks, 0.5g50nmZrO2, poured into after mixing in ball grinder；Then fall
Enter to be dissolved with ethyl cellulose and polyvinylacetate DBE (nylon acid dimethyl ester) 15mL as the organic carrier of carbon pastes；Most
After be put into zirconium pearl, ball milling is after 6 hours, and prepared by carbon pastes completes；Carbon pastes are printed on step 4 institute by the method for silk-screen printing
On the hole transmission layer of preparation, thickness is 100 μm, and hot plate heating is placed in afterwards, and heating-up temperature is 80 DEG C, and the heat time is
20min；
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, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (7)
1. a kind of low temperature flexibility perovskite solar cell, the solar cell includes substrate, light anode layer, extinction from the bottom to top
Layer, hole transmission layer and to electrode layer, it is characterised in that
The substrate is the flexible PEN films for being coated with Fluorin doped tin ash or conductive indium-tin oxide layer, and the light anode is by two
Tin oxide is constituted, and the light absorbing layer is made up of perovskite, and the hole transmission layer is made up of CuPc, it is described to electrode layer by
Conductive carbon paste is constituted.
2. low temperature flexibility perovskite solar cell as claimed in claim 1, it is characterised in that the thickness of the light anode layer
For 50nm~80nm；The thickness of the light absorbing layer is 400nm~600nm；The thickness of the hole transmission layer be 30nm~
40nm；The thickness to electrode layer is 10um~100um.
3. the preparation method of the low temperature flexibility perovskite solar cell as described in claim 1-5, it is characterised in that this method
Comprise the following steps：
(a) by two hydrated stannous chlorides or Tin tetrachloride pentahydrate spin coating substrate after cleaning, then to the base after spin coating
Bottom heat so that on the substrate adhere to one layer of tin ash compacted zone, the tin ash compacted zone as light anode layer, its
In, the temperature of the heating is 180 DEG C~190 DEG C, and the heat time is 1h~3h；
(b) anti-solvent method spin coating is carried out on the tin ash compacted zone that step (a) is obtained, then the substrate is heated, made
One layer of calcium titanium ore bed of Surface Creation in the tin ash compacted zone is obtained, the calcium titanium ore bed is used as light absorbing layer；
(c) CuPc is deposited on the calcium titanium ore bed obtained to step (b) and forms phthalocyanine layers of copper, the phthalocyanine layers of copper is passed as hole
Defeated layer, then prints conductive carbon paste in the phthalocyanine layers of copper and is formed to electrode layer, so far complete the processing to the substrate, from
And obtain required solar cell.
4. preparation method as claimed in claim 3, it is characterised in that in step (a), after the heating, preferred pair
Substrate after heating carries out UV ozone processing or plasma treatment.
5. the preparation method as described in claim 3 or 4, it is characterised in that in step (b), spin coating agent used in the spin coating
For ABX3Compound, wherein, X is F, Cl, Br or I, and B is that Pb or Sn, A are CH3、NH3 +Or FA+, spin speed is preferably
4000rpm~5000rpm, spin-coating time is preferably 30s~40s.
6. the preparation method as described in claim any one of 3-5, it is characterised in that in step (b), the anti-solvent method rotation
Painting refers to 6s~8s after spin coating starts, and polar organic solvent is added dropwise on the tin ash compacted zone, then proceedes to
Spin coating.
7. the preparation method as described in claim any one of 3-6, it is characterised in that in step (b), the temperature of the heating
Scope is 90 DEG C~100 DEG C, and the heat time is 5min~10min.
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| CN111864071A (en) * | 2019-04-25 | 2020-10-30 | 湖北大学 | Flexible carbon-based perovskite solar cell and preparation method thereof |
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