CN105762286B - The preparation method of counter opal structure perovskite thin film and corresponding solar battery - Google Patents
The preparation method of counter opal structure perovskite thin film and corresponding solar battery Download PDFInfo
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- H—ELECTRICITY
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- 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
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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Abstract
The present invention provides the preparation methods of counter opal structure perovskite thin film and solar battery.The counter opal structure perovskite thin film, which is characterized in that including：Step 1：Colloid monolayer crystal template is formed on the substrate；Step 2：The certain density perovskite solution of spin coating forms perovskite film on colloidal crystal template, removes colloidal crystal template later, obtains counter opal structure perovskite thin film.The present invention prepares the perovskite thin film with unique two-dimentional counter opal structure, provides a kind of preparation method of new structure perovskite thin film.The present invention is not necessarily to complex device, and easy to operate, cost, low energy consumption.
Description
Technical field
The present invention relates to the perovskite thin films of counter opal structure, and in particular to the perovskite thin film of counter opal structure
The preparation method of preparation method and the solar battery based on such counter opal structure perovskite thin film.
Background technique
In recent years, organic metal halide (organic inorganic hybridization perovskite) light absorbent of a kind of perovskite structure[1]With
Its good light absorption, photoelectric conversion characteristic and excellent photo-generated carrier transport property[2,3,4,5]It attracts extensive attention.This
Kind of perovskite material has compared with high extinction coefficient and ideal bandgap width, and structure is simple, and preparation cost is low, mild condition, is
The novel solar battery material of high comprehensive performance.The method for preparing perovskite thin film at present mainly has liquid phase spin-coating method[6]With
Vapor deposition process[7], it is incomplete wherein to frequently can lead to surface covering in liquid phase spin-coating method technical process, there is pin hole, and steam is heavy
The more demanding vacuum degree of area method, equipment cost is high, operation energy consumption is high.
Bibliography：
1.Kojima,A.,et al.,Organometal Halide Perovskites as Visible-Light
Sensitizers for Photovoltaic Cells.Journal of the American Chemical Society,
2009.131(17):p.6050-6051.
2.Im, J.H., et al., 6.5%efficient perovskite quantum-dot-sensitized
solar cell.Nanoscale,2011.3(10):p.4088-4093.
3.Kim,H.S.,et al.,Lead Iodide Perovskite Sensitized All-Solid-State
Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%
.Scientific Reports,2012.2.
4.Lee,M.M.,et al.,Efficient Hybrid Solar Cells Based on Meso-
Superstructured Organometal Halide Perovskites.Science,2012.338(6107):p.643-
647.
5.Etgar,L.,et al.,Mesoscopic CH3NH3PbI3/TiO2Heterojunction Solar
Cells.Journal of the American Chemical Society,2012.134(42):p.17396-17399.
6.Burschka,J.,et al.,Sequential deposition as a route to high-
performance perovskite-sensitized solar cells.Nature,2013.499(7458):p.316-
319.
7.Mingzhen,L.,M.B.Johnston,and H.J.Snaith,Efficient planar
heterojunction perovskite solar cells by vapour deposition.Nature,2013.501
(7467):p.395-398.
Summary of the invention
The present invention has filled up current techniques blank, and the method preparation for being specifically designed colloidal crystal auxiliary has the anti-egg of two dimension
The large area perovskite thin film of white stone structure provides a kind of preparation method of new structure perovskite thin film.The membrane structure
Novelty, in bright gay color, preparation method is simple, there is better extinction compared with the perovskite thin film of the ordinary construction of same quality
Ability can be used as new and effective light-absorption layer applied in perovskite battery.
In order to achieve the above object, the present invention provides a kind of preparation method of counter opal structure perovskite thin film,
It is characterized in that, including：
Step 1：Colloid monolayer crystal template is formed on the substrate；
Step 2：The certain density perovskite solution of spin coating forms perovskite thin film on colloidal crystal template, removes later
Colloidal crystal template obtains counter opal structure perovskite thin film.
Preferably, the substrate in the step 1 is glass slide, is first pre-processed using preceding, specific steps include：
Glass slide is respectively cleaned by ultrasonic 5~20 minutes using deionized water and dehydrated alcohol first, is finally immersed in glass slide anhydrous
Spare in ethyl alcohol, when use, needs to be dried up with nitrogen air gun.
Preferably, the perovskite thin film in the step 2 with a thickness of 50nm-1000nm.
Preferably, in the step 1, the specific steps that colloid monolayer crystal template is formed on the substrate include：
Step a：Polystyrene (PS) microballoon that partial size is 100~2000nm is diluted to the water that concentration is 2~3vol%
Solution, later by it with spreading agent ethyl alcohol according to volume ratio 1：1 mixing obtains the polystyrene that concentration is 1~1.5vol%
Microballoon lotion；
Step b：Using gas-liquid interface construction from part, mass fraction is added dropwise in the round culture dish equipped with deionized water first
For 1~5wt% lauryl sodium sulfate (SDS) solution as surfactant, later dropwise by polystyrene microsphere lotion
It is added drop-wise in the round culture dish, polystyrene microsphere is sprawled under the action of spreading agent ethyl alcohol and surfactant SDS
Onto gas-liquid interface, microballoon has part immersed in liquid level hereinafter, due to the diffusion of ethyl alcohol and the surface tension of water, makes microballoon
Single layer structure is formed, the adelphotaxy between microballoon makes it spontaneously form ordered arrangement, colloid monolayer crystal template is formed, then
It is transferred on substrate.
It is highly preferred that the SDS solution and the mass ratio of polystyrene microsphere lotion are 1:5~1:40.
Preferably, the perovskite in the step 2 is MAPbI3、MAPbBr3And FAPbI3At least one of, it is described
The solvent of perovskite solution is dimethyl sulfoxide (DMSO).
Preferably, when the partial size of the polystyrene microsphere be 100nm, 250nm, 500nm, 750nm, 1000nm,
When 1700nm and 2000nm, the concentration of the perovskite solution be respectively 0.1M, 0.3M, 0.6M, 0.7M, 0.8M, 0.9M and
1.0M。
Preferably, the partial size of the polystyrene microsphere is 500nm.
Preferably, the specific steps of the certain density perovskite solution of the spin coating on colloidal crystal template include：
The certain density perovskite solution of 40 μ L is dripped on the colloidal crystal template of 15mm × 15mm size, with 4000rpm's
Glass slide is heated 60s at 100 DEG C later by revolving speed spin coating 15s.
Preferably, in the step 2, the specific steps for removing colloidal crystal template include：Glue by substrate and thereon
Body crystal template and perovskite film are impregnated in toluene solvant to remove colloidal crystal template, and soaking time is 3~10min, it
Substrate taking-up is dried afterwards.
Preferably, the counter opal structure perovskite thin film with a thickness of 50nm~1000nm.
The present invention also provides a kind of preparation methods of solar battery, which is characterized in that specific steps include：With light sun
It is thin to prepare counter opal structure perovskite using the preparation method of above-mentioned counter opal structure perovskite thin film for extremely substrate
Film, spin coating hole transmission layer (HTM), evaporation metal electrode obtain solar battery.
Preferably, the preparation method of the light anode includes：Electro-conductive glass conductive layer is etched, electronic barrier layer is sprayed,
Spin coating electron transfer layer, obtains light anode.
The present invention deposits single layer polystyrene colloid on the glass slide that hydrophilic treated is crossed, using gas-liquid interface self-assembly method
Perovskite liquid deposition is filled in template gap therein, removes mould later by crystal template, the method for recycling spin coating
Plate obtains the perovskite thin film of respective two-dimensional ordered big hole structure.The present invention is prepared for simultaneously based on two-dimentional counter opal structure
The solar battery of perovskite thin film, and test the photovoltaic performance of battery.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention is a kind of new structure by the two-dimentional counter opal structure perovskite thin film that colloidal crystal template is grown
Perovskite thin film has structure novel, the characteristics such as in bright gay color.There is voidage height, pore structure periodic arrangement, hole ruler simultaneously
The very little uniformly characteristics such as adjustable and long-range order, there is better extinction compared with the perovskite thin film of the ordinary construction of phase homogenous quantities
Ability.Two-dimentional counter opal structure perovskite thin film can be used as new and effective light-absorption layer and be applied in perovskite battery,
At the same time as catalyst, function carrier, adsorbent material, there is very wide answer in catalysis, chemical industry and electronics industry
Use prospect.The present invention prepares the perovskite thin film with unique two-dimentional counter opal structure, provides a kind of new structure calcium
The preparation method of titanium ore film.The present invention is not necessarily to complex device, and easy to operate, cost, low energy consumption.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of polystyrene two-dimensional colloidal crystal template；
Fig. 2 is the scanning electron microscope (SEM) photograph of two-dimentional counter opal structure perovskite thin film；
Fig. 3 is the VA characteristic curve of counter opal structure perovskite battery.
A)-g in Fig. 1) respectively correspond embodiment 2,3,1,4,5,6,7.A)-f in Fig. 2) respectively correspond embodiment 3,1,4,
5、6、7。
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of preparation method of counter opal structure perovskite thin film, the specific steps are：
One, glass slide is pre-processed：
Glass slide is used into deionized water and dehydrated alcohol (AR, Sinopharm Chemical Reagent Co., Ltd.) each ultrasound first
Glass slide, is finally immersed in spare in dehydrated alcohol by cleaning 10 minutes, and when use needs to be dried up with nitrogen air gun.
Two, colloid monolayer crystal template is formed on glass slide：
Polystyrene (PS) microballoon (DS050, hundred peptide Biotechnology Co., Ltd of Shanghai) that partial size is 500nm is diluted to
Concentration is the aqueous solution of 3vol%, later by itself and dehydrated alcohol according to volume ratio 1：1 mixing, obtaining concentration is 1.5vol%
PS microballoon lotion.
Using gas-liquid interface construction from part, taking a diameter first is the round culture dish of 8.5cm, is packed into 35mL deionized water,
The mass fraction that 50 μ L are added dropwise into culture dish is lauryl sodium sulfate (SDS, AR, the Aladdin biochemical technology share of 2wt%
Co., Ltd) 400 μ L PS microballoon lotions as surfactant, are added drop-wise to described round cultivate later by aqueous solution dropwise
In ware, polystyrene microsphere is spread on gas-liquid interface under the action of spreading agent ethyl alcohol and surfactant SDS, and microballoon has portion
Point immersed in liquid level makes microballoon form single layer structure hereinafter, due to the diffusion of ethyl alcohol and the surface tension of water, between microballoon
Adelphotaxy makes it spontaneously form ordered arrangement, forms colloid monolayer crystal film, then is transferred on glass slide and obtains
To colloid monolayer crystal template, attached drawing 1c is seen).
Three, the certain density perovskite solution of spin coating forms perovskite film on colloidal crystal template, removes colloid later
Crystal template obtains counter opal structure perovskite thin film：
Prepare the MAPbI of 0.6M concentration3(>99%, Ningbo Bo Run new material Science and Technology Ltd.) solution, it is used molten
Agent is dimethyl sulfoxide (DMSO, anhydrous solvent grade, Aladdin biochemical technology limited liability company).
By 40 μ LMAPbI3Solution drips on the colloidal crystal template of 1.5cm × 1.5cm size, with 4000rpm's
Glass slide is heated 60s at 100 DEG C later by revolving speed spin coating 15s.To glass slide it is cooling after, glue by glass slide and thereon
Body crystal template and perovskite film (with a thickness of 500nm) impregnate removal polystyrene moulding, soaking time 3 in toluene solvant
~10min takes out dry later, obtains the corresponding counter opal structure perovskite thin film with a thickness of 250nm, see attached drawing 2b)
Embodiment 2-7
Similar to embodiment 1, difference be the partial size of polystyrene microsphere used in embodiment 2-7 be followed successively by 100nm,
250nm, 750nm, 1000nm, 1700nm and 2000nm, corresponding MAPbI3The concentration of solution be respectively 0.1M, 0.3M, 0.7M,
0.8M,0.9M,1.0M.For colloid monolayer crystal template see attached drawing 1a), b), d), e), f), g), embodiment 3-7 is obtained
Counter opal structure perovskite thin film is successively shown in attached drawing 2a), c), d), e), f).
Embodiment 8
A kind of preparation method of solar battery, the specific steps are：
One, the preparation of light anode：
The SnO adulterated using F2Transparent conductive oxide (FTO, NSG 10) glass as substrate, size be 15mm ×
15mm, taking 0.2g zinc powder (AR, Sinopharm Chemical Reagent Co., Ltd.) and 1mL hydrochloric acid first, (AR, safe smooth scientific and technological share are limited
Company) solution (concentrated hydrochloric acid of mass fraction 37wt% by volume 1：1 dilutes with water) it is etched to remove conductive oxygen
Compound layer, etching area are 15mm × 4mm.FTO substrate after etching is rinsed well, then successively uses deionized water and anhydrous second
Alcohol is cleaned by ultrasonic respectively, spare after dry.
By the aqueous isopropanol (Sigma- for bis- (levulinic ketone group) diisopropyl titanate esters that mass fraction is 75wt%
Aldrich), acetylacetone,2,4-pentanedione (AR, Sinopharm Chemical Reagent Co., Ltd.) and dehydrated alcohol (AR, Chinese medicines group chemical reagent
Co., Ltd) by volume 3:2:45 are uniformly mixed as electronic barrier layer solution.Densification TiO is prepared using spray pyrolysis2
Layer.The FTO substrate that etching process is crossed is heated slowly to 450 DEG C, it, later will lining to its spraying above-mentioned electronic barrier layer solution
Bottom keeps the temperature 10min, obtains fine and close TiO2Film is as electronic barrier layer (bl-TiO2)。
By porous TiO2Slurry (18NR-T, Dyesol) and dehydrated alcohol are according to weight ratio 1:3.5 are configured to mesoporous TiO2
(meso-TiO2) slurry, 60 μ L meso-TiO are added dropwise2To above-mentioned bl-TiO2On film, with the revolving speed spin coating 30s of 5000rpm,
Then anneal 30min at 500 DEG C, obtains the mesoporous TiO of thickness about 300nm2Layer is used as electron transfer layer, obtains light anode.
Two, colloid monolayer crystal template is formed in light anode：Polystyrene (PS) microballoon that partial size is 500nm is diluted
At concentration be 2~3vol% aqueous solution, later by it with spreading agent ethyl alcohol according to volume ratio 1：1 mixing, obtaining concentration is
Polystyrene (PS) microballoon lotion of 1.5vol%；
Using gas-liquid interface construction from part, taking a diameter first is the round culture dish of 8.5cm, is packed into 35mL deionized water,
The mass fraction that 50 μ L are added dropwise into culture dish is lauryl sodium sulfate (SDS, AR, the Aladdin biochemical technology share of 2wt%
Co., Ltd) 400 μ L polystyrene (PS) microballoon lotions as surfactant, are added drop-wise to described by aqueous solution dropwise later
In round culture dish, polystyrene microsphere is spread on gas-liquid interface under the action of spreading agent ethyl alcohol and surfactant SDS,
Microballoon has part immersed in liquid level hereinafter, due to the diffusion of ethyl alcohol and the surface tension of water, and microballoon is made to form single layer structure,
Adelphotaxy between microballoon makes it spontaneously form ordered arrangement, forms colloid monolayer crystal film, then be transferred into light
Colloid monolayer crystal template is obtained on anode.
Three, the certain density perovskite solution of spin coating forms perovskite film on colloidal crystal template, removes colloid later
Crystal template obtains counter opal structure perovskite thin film：
Prepare the MAPbI of 0.6M concentration3Solution, used solvent are dimethyl sulfoxide (DMSO).
By 40 μ LMAPbI3Solution drips on the colloidal crystal template of 1.5cm × 1.5cm size, with 4000rpm's
Film is heated 60s at 100 DEG C later by revolving speed spin coating 15s.After to be cooled, colloidal crystal mould by light anode and thereon
Plate and perovskite thin film (with a thickness of 250nm) impregnated in toluene solvant removal polystyrene moulding, soaking time be 3~
10min takes out dry later, corresponding counter opal structure perovskite thin film obtained, with a thickness of 250nm.
Four, spin coating hole transport layer material and evaporation metal electricity on the perovskite thin film of two-dimentional counter opal structure
Pole：
By 9.1mg bis-trifluoromethylsulfoandimide lithium (Li-TFSI, 99.95%, Sigma-Aldrich) be dissolved in 17.5 μ L without
Water-acetonitrile (99.8%, Sigma-Aldrich).By the 1- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9 of 72.3mg,-spiral shell
Two fluorenes (Spiro-OMeTAD, >=99.7%, Ningbo Bo Run new material Science and Technology Ltd.) be dissolved in 1mL chlorobenzene (99.8%,
Sigma-Aldrich), it is uniformly mixed later with above-mentioned Li-TFSI solution, and 28.8 μ L tetra-tert pyridines is added thereto
(tBP, 96%, Sigma-Aldrich) it is used as hole transmission layer (HTM) solution.It is revolved on counter opal structure perovskite thin film
It applies HTM solution and the HTM that thickness is about 200nm is obtained with the revolving speed spin coating 15s of 2000rpm.
Finally the Ag metallic film of hot evaporation thickness 80nm obtains solar-electricity as back electrode on the hole transport layer
Pond.
Embodiment 9
Similar to embodiment 8, difference is that the partial size of polystyrene microsphere used in embodiment 9 is 1000nm, calcium titanium
The concentration of mineral solution be 1.0M, obtained corresponding counter opal structure perovskite thin film with a thickness of 500nm.
Battery C-V characteristic (I-V) curve can reflect the open-circuit voltage (V of solar batteryoc), short circuit current (Jsc)、
The characteristic parameters such as fill factor (FF) and photoelectric conversion efficiency (PCE).500nm, 1000nm polystyrene moulding are based on to above-mentioned
Counter opal structure perovskite battery carry out I-V curve test, using xenon source (CEL-S500, Beijing source Zhong Jiaojin section
Skill Co., Ltd) with electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.), light intensity used in test is
AM 1.5(100mW/cm2).Since electric current I is related with cell active area, electric current I is generally converted into electric current in actual use
Density J, obtained J-V curve are shown in Fig. 3.Curve IOP500 indicates the perovskite thin film based on 500nm polystyrene moulding too
Positive energy battery, open-circuit voltage 0.84V, short circuit current 11.1mA/cm2, fill factor 61%, photoelectric conversion efficiency is
5.7%.Curve IOP1000 indicates the perovskite thin film solar battery based on 1000nm polystyrene moulding, open-circuit voltage
For 0.91V, short circuit current 15.7mA/cm2, fill factor 66.6%, photoelectric conversion efficiency 9.5%.This is current generation
The peak efficiency that the counter opal structure perovskite battery reported in boundary obtains.
Claims (8)
1. a kind of preparation method of counter opal structure perovskite thin film, which is characterized in that including step 1：It is formed on the substrate
Colloid monolayer crystal template；The specific steps that colloid monolayer crystal template is formed on the substrate include：Step a：By grain
The polystyrene microsphere that diameter is 100 ~ 2000nm is diluted to the aqueous solution that concentration is 2 ~ 3 vol%, later by itself and spreading agent ethyl alcohol
According to volume ratio 1：1 mixing obtains the polystyrene microsphere lotion that concentration is 1 ~ 1.5vol%；Step b：Using gas-liquid interface
Construction from part, is added dropwise sodium dodecyl sulfate solution as surfactant in the round culture dish equipped with deionized water first,
Polystyrene microsphere lotion is added drop-wise to dropwise in the round culture dish later, polystyrene microsphere in spreading agent ethyl alcohol and
It is spread on gas-liquid interface under the action of surfactant SDS, microballoon has part immersed in liquid level hereinafter, the diffusion due to ethyl alcohol is made
With and water surface tension, so that microballoon is formed single layer structure, the adelphotaxy between microballoon makes it spontaneously form orderly row
Column form colloid monolayer crystal template, then are transferred on substrate；Step 2：Spin coating a certain concentration on colloidal crystal template
Perovskite solution formed perovskite thin film, the perovskite be MAPbI3、MAPbBr3And FAPbI3At least one of, it is described
Perovskite solution solvent be dimethyl sulfoxide, remove colloidal crystal template later, it is thin to obtain counter opal structure perovskite
Film.
2. the preparation method of counter opal structure perovskite thin film as described in claim 1, which is characterized in that the step
Substrate in 1 is glass slide, is first pre-processed using preceding, specific steps include：Glass slide is used into deionized water first
Respectively it is cleaned by ultrasonic with dehydrated alcohol 5 ~ 20 minutes, is finally immersed in glass slide spare in dehydrated alcohol, when use needs to use nitrogen
The drying of gas air gun.
3. the preparation method of counter opal structure perovskite thin film as described in claim 1, which is characterized in that when described gathers
When the partial size of phenylethylene micro ball is 100nm, 250nm, 500nm, 750nm, 1000nm, 1700nm and 2000nm, the calcium titanium
The concentration of mineral solution is respectively 0.1M, 0.3M, 0.6M, 0.7M, 0.8M, 0.9M and 1.0M.
4. the preparation method of counter opal structure perovskite thin film as described in claim 1, which is characterized in that described in glue
The specific steps of the certain density perovskite solution of spin coating include on body crystal template：By the certain density perovskite solution of 40 μ L
It drips on the colloidal crystal template of 15mm × 15mm size, with the revolving speed spin coating 15s of 4000rpm, glass slide exists later
60s is heated at 100 DEG C.
5. the preparation method of counter opal structure perovskite thin film as described in claim 1, which is characterized in that the step
In 2, the specific steps for removing colloidal crystal template include：Colloidal crystal template by substrate and thereon and perovskite film are in toluene
It is impregnated in solvent to remove colloidal crystal template, soaking time is 3 ~ 10min, later dries substrate taking-up.
6. the preparation method of counter opal structure perovskite thin film as described in claim 1, which is characterized in that the anti-egg
White stone structure perovskite thin film with a thickness of 50nm ~ 1000nm.
7. a kind of preparation method of solar battery, which is characterized in that specific steps include：Using light anode as substrate, using power
Benefit requires the preparation method of counter opal structure perovskite thin film described in any one of 1-6 to prepare counter opal structure perovskite
Film, spin coating hole transmission layer, evaporation metal electrode obtain solar battery.
8. the preparation method of solar battery as claimed in claim 7, which is characterized in that the preparation method of the light anode
Including：Electro-conductive glass conductive layer is etched, electronic barrier layer is sprayed, the mesoporous electron transfer layer of spin coating obtains light anode.
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| CN107746072B (en) * | 2017-09-25 | 2019-08-20 | 东南大学 | A kind of preparation method of perovskite micron ring array |
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| CN113980249B (en) * | 2021-09-30 | 2022-11-25 | 北京理工大学 | Inverse opal phase perovskite Cs 3 Bi x Sb (2-x) Br 9 Application in EDOT photocatalytic polymerization |
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| CN101992089A (en) * | 2010-10-29 | 2011-03-30 | 中国石油大学(北京) | Three-dimensional ordered porous-mesoporous iron-based perovskite oxide catalyst and preparation method thereof |
| CN102760579A (en) * | 2011-04-29 | 2012-10-31 | 中国科学院过程工程研究所 | Titanium dioxide thin-film electrode material for dye-sensitized solar cell and method for preparing titanium oxide thin-film electrode material |
| JP2015060948A (en) * | 2013-09-19 | 2015-03-30 | 株式会社日立製作所 | Organic thin-film solar cell and organic thin-film solar cell system using the same |
| CN105070837A (en) * | 2015-08-26 | 2015-11-18 | 电子科技大学 | Iridium-complex-doped three-element solar cell |
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