CN104393177A - Perovskite phase organic metal halide-based solar cell and manufacturing method thereof - Google Patents

Perovskite phase organic metal halide-based solar cell and manufacturing method thereof Download PDF

Info

Publication number
CN104393177A
CN104393177A CN201410579487.3A CN201410579487A CN104393177A CN 104393177 A CN104393177 A CN 104393177A CN 201410579487 A CN201410579487 A CN 201410579487A CN 104393177 A CN104393177 A CN 104393177A
Authority
CN
China
Prior art keywords
solar cell
layer
organic metal
perovskite phase
phase organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410579487.3A
Other languages
Chinese (zh)
Other versions
CN104393177B (en
Inventor
姚冀众
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HANGZHOU QIANNA OPTOELECTRONICS TECHNOLOGY CO., LTD.
Original Assignee
姚冀众
颜步一
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 姚冀众, 颜步一 filed Critical 姚冀众
Priority to CN201410579487.3A priority Critical patent/CN104393177B/en
Publication of CN104393177A publication Critical patent/CN104393177A/en
Application granted granted Critical
Publication of CN104393177B publication Critical patent/CN104393177B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a perovskite phase organic metal halide-based solar cell and a manufacturing method thereof. The solar cell uses a dense titanium dioxide nano film as an electron transfer layer, the surface recombination speed between the electron transfer layer and a semiconductor layer can be reduced, and a photovoltaic conversion rate of a photovoltaic device is improved; the solar cell with the structure can use a normal temperature and pressure full liquid phase synthesis method to manufacture the semiconductor layer of a perovskite phase organic metal halide, thereby saving energy consumption needed by manufacturing and reducing the cost of the solar cell. A two-step synthesis method is adopted during the process of manufacturing the semiconductor layer of the perovskite phase organic metal halide, a PbX2 layer formed in the first step is soaked in a 2-propanol solution between the two steps, the second-step synthesis is carried out, and thus, a chlorine and iodine mixed preparation method can be adopted, the halogen ion concentration and the annealing temperature are controlled, crystal growth during a liquid phase precipitation process is optimized, and the photovoltaic conversion efficiency of the solar cell is improved.

Description

Based on halid solar cell of Perovskite Phase organic metal and preparation method thereof
Technical field
The present invention relates to field of photovoltaic technology, be specifically related to a kind of based on halid solar cell of Perovskite Phase organic metal and preparation method thereof.
Background technology
Along with the progressively exhausted of fossil energy and social environmental protection consciousness are strengthened gradually, solar energy power generating has an opportunity alternative fossil energy to meet the electricity needs of people's daily life.Photovoltaic cell is a kind of electronic device luminous energy directly being changed into electric energy.
In photovoltaic field, silica-based solar cell successfully achieves commercialization.But, the basis of silica-based solar cell during silicon materials, and the purification of silicon and production process need to carry out under high temperature and high pressure environment usually, consume energy high, cause the cost of silica-based solar cell high.
In recent years, along with the further investigation to photovoltaic semiconductors material, the novel thin film solar cell being representative with the organic metal halide of Perovskite Phase has progressively possessed industrialized possibility.The organic metal halide solar-energy photo-voltaic cell of Perovskite Phase, has good photovoltaic efficiency.YangYang as UCLA university teaches team and successfully develops the highest organic metal halide solar-energy photo-voltaic cell based on Perovskite Phase of current laboratory photovoltaic conversion efficiency, and its photovoltaic conversion efficiency is up to 19.3%.
The organic metal halide solar-energy photo-voltaic cell of existing Perovskite Phase mostly is stepped construction, comprises substrate, electron transfer layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode from bottom to up successively.
Document J.Burschka, N.Pellet, S.J.Moon, R.Humphry-Baker, P.Gao, M.K.Nazeeruddin, M.Gratzel, Nature, 2013,499,316 preparation methods disclosing a kind of Perovskite Phase organic metal halide semiconductor layer, specific as follows: the compact titanium dioxide layer first forming 20 ~ 40nm on substrate, then form by spin-coating method the nano titania porous structure layer that granular size is 20nm on this layer, then on nano titania porous structure layer, lead iodide layer is sprawled, finally by lead iodide (PbI 2) layer and methylpyridinium iodide ammonia (CH 3nH 3i) solution reaction obtains Perovskite Phase organic metal iodide (CH 3nH 3pbI 3) semiconductor layer.
There is following shortcoming in the method: in semiconductor forming process, its halogens used is iodine, due to iodine high-dissolvability in the solution, the growth rate changing semiconductor crystal is caused to be difficult to be controlled, the crystallite dimension of the final semiconductor layer obtained is less than normal, there is the transmission that a large amount of crystal boundaries is unfavorable for electronics and hole, thus reduce the photovoltaic performance of semiconductor.
In addition, be ensure the complete covering device surface of Perovskite Phase organic metal halide, existing electron transfer layer many employings rough surface, there is the titanium dioxide nano-film of loose structure.Form nano titania loose structure by spin coating titania nanoparticles, complex process, is unfavorable for carrying out commercialization large-scale production.
Prior art cannot overcome lead chloride low solubility in organic solvent and the problem of the organic metal chloride semiconductor growth layer difficulty caused due to it, and therefore prior art can only use the lead iodide that solubility is higher.Although use lead iodide can form the semiconductor layer of thickness 500n, the growth course due to lead iodide crystal is difficult to control, and Perovskite Phase organic metal halide semiconductor layer can not overlay electronic transport layer uniformly, causes photovoltaic device efficiency to decline.Therefore, in order to make iodate lead layer, overlay electronic transport layer is surperficial completely, uniformly, additionally must use nano titania porous structure layer.Although introduce nano titania porous structure layer can improve surface coverage, but loose structure also can cause covering, and semiconductor layer crystal growth is thereon irregular, cause the increase of the surface recombination between semiconductor layer and titanium dioxide layer, and then reduce the photovoltaic efficiency of device.
The present invention adopts two-step method, first in step (1), form the halogenation lead layer of the amorphous state of thickness 500nm, again by using 2-propanol solution to carry out surface treatment to halogenation lead layer, the surface characteristic of the halogenation lead layer of unformed shape can be changed on the one hand, on the other hand, 2-propanol solution can be adopted to wash away remain in the DMF solution in halogenation lead layer, make halogenation lead layer can effectively and CH 3nH 3y combines, and then makes CH 3nH 3y molecule more easily enters halogenation lead layer and participates in crystal growth, forms organic metal halide semiconductor layer.Pass through the CH at 100 ~ 150 DEG C again 3nH 3anneal 15 minutes in the saturated atmosphere of Y, reach the object of crystallization control temperature, high crystalline quality.
As preferably, work as CH 3nH 3y is CH 3nH 3cl and CH 3nH 3during the mixture of I, CH 3nH 3cl and CH 3nH 3the mol ratio of I is 1:(1 ~ 9).Further preferably, CH 3nH 3cl and CH 3nH 3the mol ratio of I is 1:9.
Use the PbX of high concentration 2dMF solution be that scraping blade method is disposable to be sprawled solution and form the PbX of about 500nm in order to use 2, PbX in described step (1) 2dMF solution in PbX 2concentration be 0.5 ~ 1mol/L.Further preferably, PbX in described step (1) 2dMF solution in PbX 2concentration be 1mol/L.Now, PbX is worked as 2for PbI 2time, PbI 2concentration be 1mol/L; Work as PbX 2for PbCl 2and PbI 2mixture time, PbCl 2concentration be 0.1mol/L, PbI 2concentration be 0.9mol/L.
Further preferably, described CH 3nH 3cH in the 2-propanol solution of Y 3nH 3the concentration of Y is 5 ~ 15mg/ml, is preferably 10mg/ml.CH 3nH 3the speed that the concentration of Y effectively can control Crystallization has reached the object optimizing crystal structure.Regulate the concentration of chloride ion in preparation process can play the important function optimizing crystal structure.
Compared with prior art, the invention has the advantages that:
A () is using fine and close titanium dioxide nano-film group as electron transfer layer, be conducive to the contact area reducing electron transfer layer and Perovskite Phase organic metal halide crystal, the recombination-rate surface between electron transfer layer and semiconductor layer can be reduced, open circuit voltage and the fill factor, curve factor of photovoltaic device can be improved, and then improve the effect of photoelectric conversion rate;
B () Perovskite Phase organic metal halide semiconductor layer adopts the full liquid phase synthesizing method of normal temperature and pressure, reduce the required energy consumption of preparation, reduce the cost of solar cell;
(c) in the organic metal halide semiconductor layer process preparing Perovskite Phase, adopt two-step synthesis method, by between two steps to the first step formed PbX 2layer carries out second step synthesis again after soaking layer in 2-propanol solution, thus two kinds of halogens (chlorine and iodine) can be adopted to be mixed with method, by the control to halogen ion concentration, and then in liquid-phase precipitation process, optimize the growth of crystal, and then the quality of Perovskite Phase organic metal halide semiconductor layer can be improved, the photovoltaic conversion efficiency of solar cell can be improved further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of based on halid solar cell of Perovskite Phase organic metal and preparation method thereof.
A kind of based on the halid solar cell of Perovskite Phase organic metal, comprise substrate, electron transfer layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode layer from bottom to up successively, described electron transfer layer is compact titanium dioxide nano thin-film, and the surface roughness of described compact titanium dioxide nano thin-film is less than 20nm.
The test condition of surface roughness is as follows:
Tester is Alpha-step D-500 step instrument, probe radius 1 micron, probe pressure 2mg, error range 5nm.
The effect of electron transfer layer forms ohmic contact with electro-conductive glass, plays the effect of electric transmission.The imbibition characteristic of conductive glass surface can also be changed simultaneously, arrive the effect controlling the semiconductor light-absorption layer pattern covered thereon.Energy isolation of semiconductor layer and electrode, play the effect in passivated surface complex centre simultaneously.
Compared with the electron transfer layer of existing nano titania loose structure, compact titanium dioxide nano thin-film is more suitable for the growth of Perovskite Phase organic metal halide crystal, adds crystalline size, reduces the quantity of crystal boundaries.In addition, compact titanium dioxide nano thin-film also reduces the contact area of itself and Perovskite Phase organic metal halide crystal, be conducive to reducing the recombination-rate surface between electron transfer layer and semiconductor layer, and then improve open circuit voltage and the fill factor, curve factor of photovoltaic device, reach the effect improving photoelectric conversion rate.
In solar cell of the present invention, the material of substrate, electron transfer layer, hole transmission layer and thickness can adopt existing material and thickness.Wherein substrate mostly is transparent conducting glass, as the electro-conductive glass of indium tin oxide (ITO, Indium Tin Oxides) or fluorine tin-oxide (FTO, Fluorine Doped Tin Oxide).The material of hole transmission layer is Spiro-OMeTAD (2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes), and thickness is 300 ~ 500nm.
Electrode layer 5 can use Ag (silver), Au (gold) or conductive carbon, and thickness is 60nm.
The thickness of described electron transfer layer is 150 ~ 350nm.
In solar cell of the present invention, electron transfer layer plays conduction electron and completely cuts off hole, needs the structure according to electron transfer layer and electron transport property reasonable set thickness.The raw-material use amount of too thick increase and add unnecessary internal resistance, too thinly can not cover substrate surface completely uniformly, there is the risk of shorted devices.
Described Perovskite Phase organic metal halide is CH 3nH 3pbI 3-ncl n, n is 0.005 ~ 0.1.
Containing a small amount of chlorine (Cl) in Perovskite Phase organic metal halide, at the initial stage that crystal generates, Cl ion due to solubility lower, easier separate out to be combined with lead ion from solution form nucleus, and then can crystal growth be promoted, obtain the semiconductor crystal optimized, improve the conversion efficiency of solar cell.
Present invention also offers the preparation method of above-mentioned solar cell, substrate prepared electron transfer layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode layer successively, prepares electron transfer layer as follows:
Surface treatment is carried out to substrate, then makes the ethanolic solution of titanium dioxide film forming calcining on the substrate after surface treatment, namely obtain compact titanium dioxide nano thin-film.
As preferably, surfactant and ozone-plasma is used to carry out surface treatment to substrate.First use surfactant washing substrate, and then utilize ozone-plasma method to etch transparent substrates surface.
Surface-treated may be attached to surperficial organic pollution mainly for thoroughly removing and can play the surface work function increasing substrate, the object improving the surface wetting characteristic of substrate, thus arrive the quality improving the electron transfer layer be grown on substrate, play reduction intrinsic impedance, improve the effect of the photovoltaic conversion efficiency of solar cell.
Adopt knife coating to make the ethanolic solution of titanium dioxide film forming on the substrate after surface treatment in the present invention, the rete now formed is process amorphous state.Remove the residual organic solvent in amorphous state film by calcination processing and make the amorphous state layer crystallization of titanium dioxide, obtaining the titanium dioxide nano-film of crystalline state.
As preferably, described calcining heat is 450 ~ 600 DEG C.Can form too much titanium dioxide nucleus number when calcining heat is too high, cause the monocrystalline size of titanium dioxide to reduce, crystal boundaries increases, and then reduces conductivity; When calcining heat is too low, then effectively can not makes the mono-crystalline structures of formation titanium dioxide, cause low conductivity.
Described Perovskite Phase organic metal halide semiconductor layer prepares as follows:
(1) on described electron transfer layer, PbX is sprawled 2dMF (N, N-dimethylformamideN, dinethylformamide) solution, form PbX after drying 2layer, described X is Cl or I;
(2) by PbX 2be placed on CH 3nH 320 ~ 60s is soaked, at CH after taking-up in the 2-propanol solution of Y (methylammonium halide, methyl halogenation ammonia) 3nH 3carry out annealing in process in the saturated atmosphere of Y and namely obtain Perovskite Phase organic metal halide semiconductor layer, annealing in process temperature is 100 ~ 150 DEG C, the time be under 10 ~ 25min;
Work as PbX 2for PbI 2time, CH 3nH 3y is CH 3nH 3cl; Work as PbX 2for PbCl 2and PbI 2mixture time, CH 3nH 3y is CH 3nH 3i.
The halogens (iodine and chlorine) that step (1) is different with (2) middle two kinds of adopting mixes, advantage and the chloride crystals of having taken into account iodide high-dissolvability grow controlled advantage, finally can form the organic metal halide semiconductor layer that thickness and crystal structure are all optimized.
First by PbX that step (1) is formed in described step (2) 2layer is placed in CH soak 1 ~ 2s in 2-propanol solution after again 3nH 3the 2-propanol solution of Y.
Accompanying drawing explanation
Fig. 1 is the structure chart of the solar cell of the present embodiment;
Fig. 2 is the i-v curve of solar cell.
Embodiment
Describe the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1
Fig. 1 is the structure chart of the solar cell of the present embodiment, comprises substrate 1, electron transfer layer 2, Perovskite Phase organic metal halide semiconductor layer 3, hole transmission layer 4 and to electrode layer 5 from bottom to up successively.
In the present embodiment, substrate 1 is indium tin oxide glass.Electron transfer layer 2 is compact titanium dioxide nano thin-film, and its surface roughness is less than 10nm, and thickness is 350nm.The thickness of Perovskite Phase organic metal halide semiconductor layer 3 is 350nm, and this Perovskite Phase organic metal halide is CH 3nH 3pbI 3-ncl n, in the present embodiment, n is 0.05.The material of hole transmission layer 4 is Spiro-OMeTAD (2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes), and thickness is 350nm.The material of electrode layer 5 is Au, and thickness is 60nm.
The solar cell of the present embodiment is prepared as follows:
(S1) on substrate, electron transfer layer is prepared
First surfactant washing substrate is used, and then utilize ozone-plasma process substrate surface, after completing, film after adopting knife coating to make the ethanolic solution of titanium dioxide form 350nm on surface treated substrate is also calcined 20 minutes at 450 DEG C, namely obtains compact titanium dioxide nano thin-film as electron transfer layer;
(S2) Perovskite Phase organic metal halide semiconductor layer is prepared on the electron transport layer
(1) PbX is sprawled on the electron transport layer 2dMF solution, form the PbX after 300nm after dry 2layer, X is Cl or I;
(2) by PbX 2be placed on CH 3nH 3soak 20s in the 2-propanol solution of Y, take out the CH being placed in 150 DEG C 3nH 3anneal in the saturated atmosphere of Y after 15min and be cooled to the CH that namely room temperature obtains Perovskite Phase 3nH 3pbI 2.95cl 0.05film is as Perovskite Phase organic metal halide semiconductor layer; Work as PbX 2for PbI 2time, CH 3nH 3y is CH 3nH 3cl; Work as PbX 2for PbCl 2and PbI 2mixture time, CH 3nH 3y is CH 3nH 3i.
In the present embodiment, X is I, Y is Cl.PbX 2dMF solution in PbX 2concentration be 460mg/ml (i.e. 1mol/L), CH 3nH 3cH in the 2-propanol solution of Y 3nH 3the concentration of Y is 10mg/ml.
(S3) use knife coating Perovskite Phase organic metal halide semiconductor layer is formed the Spiro-OMeTAD film that thickness is 350nm as hole transmission layer, wherein the structural formula of Spiro-OMeTAD is as follows:
(S4) adopt the Au of the thick 60nm of thermal evaporation evaporation on hole transmission layer as to electrode layer, each layer (substrate, electron transfer layer, Perovskite Phase organic metal halide semiconductor layer and hole pass transport layer) is assembled to form solar cell.
The solar cell of the present embodiment is at 100mW/cm 2aM1.5 sunlight under i-v curve as shown in the curve of embodiment in Fig. 21 correspondence.Its volt-ampere of performance curve is shown in Table 1.
Table 1
Embodiment 2
The structure of the solar cell of the present embodiment is identical with embodiment 1, preparation method is identical with embodiment 1, difference is step (S2) when preparing Perovskite Phase organic metal halide semiconductor layer on the electron transport layer, by PbX in step (2) 2be placed on CH 3nH 3soak in the 2-propanol solution of Y before 20s first by PbX 2be placed in 2-propanol solution and soak 1 ~ 2s with to PbX 2layer carries out surface treatment, directly the substrate of step (1) is placed in 2-propanol solution and soaks 1 ~ 2s during practical operation.
The solar cell of the present embodiment is at 100mW/cm 2aM1.5 sunlight under i-v curve as shown in the curve of embodiment in Fig. 22 correspondence.Its volt-ampere of performance curve is shown in Table 1.
Embodiment 3
The structure of the solar cell of the present embodiment is identical with embodiment 1, and preparation method is identical in embodiment 2, and difference is the PbX in step (1) 2for PbCl 2and PbI 2mixture, and PbCl 2and PbI 2the mol ratio of mixture be 1:9.CH in step (2) 3nH 3y is CH 3nH 3i.
The solar cell of the present embodiment is at 100mW/cm 2aM1.5 sunlight under i-v curve as shown in the curve of embodiment in Fig. 23 correspondence.Its volt-ampere of performance curve is shown in Table 1.
Comparative example
The structure of the solar cell of this comparative example is identical with embodiment 1, and difference is that electron transfer layer 2 comprises compact titanium dioxide nano thin-film and poriferous titanium dioxide nano thin-film from the bottom to top successively.
Preparation method is identical with embodiment 1, difference is that step (S1) is when forming the electron transfer layer of titanium dioxide, need to form nano titania porous structure layer again in the titanic oxide electronic transport layer of densification, its concrete steps are that (model is Dyesol 18NRT by the titania nanoparticles of 20nm size, Dyesol) be dissolved in (concentration is 2:7 mass ratio) in ethanolic solution, spin-coating method is used to form 200nm liquid-phase precipitation layer, room temperature is cooled to after annealing 15 minutes under 500 DEG C of environment again, final formation nano titania porous structure layer (i.e. poriferous titanium dioxide nano thin-film).When step (S2) prepares Perovskite Phase organic metal halide semiconductor layer on the electron transport layer, X and Y is I (i.e. PbX 2for PbI 2, CH 3nH 3y is CH 3nH 3i), the final Perovskite Phase organic metal halide semiconductor layer formed is CH 3nH 3pbI 3film.
The solar cell of this comparative example i-v curve under the AM1.5 sunlight of 100mW/cm2 as Fig. 2 in embodiment 3 correspondence curve shown in.Its volt-ampere of performance curve is shown in Table 1.
From Fig. 2 and table 1, use the combination of different halogenss to increase open circuit voltage, improve the photovoltaic conversion efficiency of solar cell.When preparing by electron transfer layer Perovskite Phase organic metal halide semiconductor layer in solar cell preparation process, by simple surface treatment (first PbX2 is placed in 2-propanol solution and soaks 1 ~ 2s), increase open circuit voltage and fill factor, curve factor while effectively can reducing manufacturing cycle, improve battery efficiency.
Above-described embodiment has been described in detail technical scheme of the present invention and beneficial effect; be understood that and the foregoing is only most preferred embodiment of the present invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement and equivalent to replace, all should be included within protection scope of the present invention.

Claims (10)

1. one kind based on the halid solar cell of Perovskite Phase organic metal, comprise substrate, electron transfer layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode layer from bottom to up successively, it is characterized in that, described electron transfer layer is compact titanium dioxide nano thin-film, and the surface roughness of described compact titanium dioxide nano thin-film is less than 20nm.
2. as claimed in claim 1 based on the halid solar cell of Perovskite Phase organic metal, it is characterized in that, the thickness of described electron transfer layer is 150 ~ 350nm.
3. as claimed in claim 2 based on the halid solar cell of Perovskite Phase organic metal, it is characterized in that, described Perovskite Phase organic metal halide is CH 3nH 3pbI 3-ncl n, n is 0.005 ~ 0.1.
4. the preparation method as the solar cell in claims 1 to 3 as described in any one claim, be included in and substrate prepared successively electron transfer layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode layer, it is characterized in that, prepare described electron transfer layer as follows:
Surface treatment is carried out to substrate, then makes the ethanolic solution of titanium dioxide film forming calcining on surface treated substrate, namely obtain compact titanium dioxide nano thin-film.
5. the preparation method of solar cell as claimed in claim 4, it is characterized in that, described calcining heat is 450 ~ 600 DEG C.
6. the preparation method of solar cell as claimed in claim 4, it is characterized in that, described Perovskite Phase organic metal halide semiconductor layer prepares as follows:
(1) on described electron transfer layer, PbX is sprawled 2dMF solution, form PbX after drying 2layer, described PbX 2for PbI 2, or be PbCl 2and PbI 2mixture;
(2) by PbX 2be placed on CH 3nH 320 ~ 60s is soaked, at CH after taking-up in the 2-propanol solution of Y 3nH 3carry out annealing in process in the saturated atmosphere of Y and namely obtain Perovskite Phase organic metal halide semiconductor layer, annealing in process temperature is 100 ~ 150 DEG C, the time be under 10 ~ 25min;
Work as PbX 2for PbI 2time, CH 3nH 3y is CH 3nH 3cl; Work as PbX 2for PbCl 2and PbI 2mixture time, CH 3nH 3y is CH 3nH 3i.
7. the preparation method of solar cell as claimed in claim 6, is characterized in that, first by PbX that step (1) is formed in described step (2) 2layer is placed in CH soak 1 ~ 2s in 2-propanol solution after again 3nH 3the 2-propanol solution of Y.
8., as right wants the preparation method of the solar cell as described in 7, it is characterized in that, when X is Cl, PbX in described step (1) 2dMF solution in PbX 2concentration be 0.5 ~ 1.5mol/L.
9. the preparation method of solar cell as claimed in claim 8, is characterized in that, work as CH 3nH 3y is CH 3nH 3cl and CH 3nH 3during the mixture of I, CH 3nH 3cl's and CH 3nH 3the mol ratio of I is 1:(1 ~ 9).
10. as right wants the preparation method of the solar cell as described in 7, it is characterized in that, described CH 3nH 3cH in the 2-propanol solution of Y 3nH 3the concentration of Y is 5 ~ 15mg/ml.
CN201410579487.3A 2014-10-24 2014-10-24 Solar cell based on Perovskite Phase organic metal halide and preparation method thereof Active CN104393177B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410579487.3A CN104393177B (en) 2014-10-24 2014-10-24 Solar cell based on Perovskite Phase organic metal halide and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410579487.3A CN104393177B (en) 2014-10-24 2014-10-24 Solar cell based on Perovskite Phase organic metal halide and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104393177A true CN104393177A (en) 2015-03-04
CN104393177B CN104393177B (en) 2017-07-14

Family

ID=52611046

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410579487.3A Active CN104393177B (en) 2014-10-24 2014-10-24 Solar cell based on Perovskite Phase organic metal halide and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104393177B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993060A (en) * 2015-07-20 2015-10-21 苏州大学 No-annealing perovskite type solar cell and preparing method thereof
CN105206749A (en) * 2015-08-31 2015-12-30 中国电子科技集团公司第四十八研究所 Perovskite solar cell and preparation process thereof
CN105280819A (en) * 2015-06-16 2016-01-27 郑州大学 Planar heterojunction perovskite solar cell and preparation method thereof
CN107452879A (en) * 2017-09-13 2017-12-08 武汉理工大学 A kind of perovskite solar cell with silver/titanium dioxide nano composite material dense film
CN109148687A (en) * 2017-06-16 2019-01-04 韩国化学研究院 Perovskite series solar battery and its manufacturing method comprising broad-band gap
RU2692110C1 (en) * 2018-09-20 2019-06-21 АО "Красноярская ГЭС" Method of forming perovskite-like material film
RU2694086C1 (en) * 2018-12-25 2019-07-09 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Hybrid photoconverter modified with maxenes
CN111471961A (en) * 2015-09-11 2020-07-31 学校法人冲绳科学技术大学院大学学园 Method for forming lead-free perovskite film and solar cell device comprising same
RU2815603C1 (en) * 2023-09-14 2024-03-19 федеральное государственное автономное образовательное учреждение высшего образования "Казанский (Приволжский) федеральный университет" (ФГАОУ ВО КФУ) Method of controlling phase composition of inorganic halide perovskites and thermally controlled light source obtained using said method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012182439A (en) * 2011-01-14 2012-09-20 Sumitomo Chemical Co Ltd Organic photoelectric conversion element
CN102891259A (en) * 2012-09-28 2013-01-23 北京大学 Organic solar cell with vertical separation between donor and receptor and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012182439A (en) * 2011-01-14 2012-09-20 Sumitomo Chemical Co Ltd Organic photoelectric conversion element
CN102891259A (en) * 2012-09-28 2013-01-23 北京大学 Organic solar cell with vertical separation between donor and receptor and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GILES E. EPERON, ET AL.: "Morphological Control for High Performance, Solution-Processed Planar Heterojunction Perovskite Solar Cells", 《ADVANCED FUNCTIONAL MATERIALS》 *
SILVIA COLELLA, ET AL.: "MAPbI3‑xClx Mixed Halide Perovskite for Hybrid Solar Cells: The Role of Chloride as Dopant on the Transport and Structural Properties.", 《CHEMISTRY OF MATERIALS》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105280819A (en) * 2015-06-16 2016-01-27 郑州大学 Planar heterojunction perovskite solar cell and preparation method thereof
CN104993060A (en) * 2015-07-20 2015-10-21 苏州大学 No-annealing perovskite type solar cell and preparing method thereof
CN104993060B (en) * 2015-07-20 2017-08-25 苏州大学 A kind of Ca-Ti ore type solar cell without annealing and preparation method thereof
CN105206749A (en) * 2015-08-31 2015-12-30 中国电子科技集团公司第四十八研究所 Perovskite solar cell and preparation process thereof
CN111471961A (en) * 2015-09-11 2020-07-31 学校法人冲绳科学技术大学院大学学园 Method for forming lead-free perovskite film and solar cell device comprising same
CN109148687A (en) * 2017-06-16 2019-01-04 韩国化学研究院 Perovskite series solar battery and its manufacturing method comprising broad-band gap
CN107452879A (en) * 2017-09-13 2017-12-08 武汉理工大学 A kind of perovskite solar cell with silver/titanium dioxide nano composite material dense film
RU2692110C1 (en) * 2018-09-20 2019-06-21 АО "Красноярская ГЭС" Method of forming perovskite-like material film
RU2694086C1 (en) * 2018-12-25 2019-07-09 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Hybrid photoconverter modified with maxenes
RU2815603C1 (en) * 2023-09-14 2024-03-19 федеральное государственное автономное образовательное учреждение высшего образования "Казанский (Приволжский) федеральный университет" (ФГАОУ ВО КФУ) Method of controlling phase composition of inorganic halide perovskites and thermally controlled light source obtained using said method

Also Published As

Publication number Publication date
CN104393177B (en) 2017-07-14

Similar Documents

Publication Publication Date Title
CN104393177B (en) Solar cell based on Perovskite Phase organic metal halide and preparation method thereof
CN104157788B (en) It is a kind of to be based on SnO2Perovskite thin film photovoltaic cell and preparation method thereof
CN106025085B (en) Based on Spiro OMeTAD/CuXPerovskite solar cell of S composite hole transporting layers and preparation method thereof
CN108598268B (en) Method for preparing planar heterojunction perovskite solar cell by printing under environmental condition
CN102176472B (en) Bulk effect solar cell material and preparation method thereof
CN110120455A (en) A kind of perovskite photovoltaic film preparation method based on economic benefits and social benefits seed mediated growth method
CN108878661A (en) A kind of preparation method of the perovskite solar battery of carbon quantum dot modification
CN106384785A (en) Tin-doped CH3NH3SnxPb1-xI3 perovskite solar cell
CN105226187A (en) Film crystal silicon perovskite heterojunction solar cell and preparation method thereof
CN104576929A (en) Perovskite-lead sulfide quantum dot stacked solar cell and preparation method thereof
CN106169537A (en) A kind of preparation method of solaode
CN108281550B (en) Based on the titania-doped perovskite solar battery and preparation method thereof of magnesium
CN108539026B (en) Preparation method of perovskite thin film with micron tube array structure
CN109768167A (en) The perovskite solar cell and preparation method thereof of no current sluggishness
CN105990524A (en) Solar cell of high-efficiency planar heterojunction perovskite structure having interface modification layer formed by [6,6]-phenyl group-C61-butyric acid (PCBA)
CN108649124A (en) A kind of inorganic perovskite solar cell of high efficiency and preparation method thereof
Zheng et al. Enhancing the performance and stability of carbon-based CsPbI2Br perovskite solar cells via tetrabutylammonium iodide surface passivation
CN107170894A (en) A kind of perovskite solar cell and preparation method thereof
CN108023018A (en) The preparation method of inversion perovskite solar cell based on the continuously adjustable control of band gap
CN107799655A (en) Perovskite thin film, solar cell device and preparation method
CN105244171B (en) A kind of fabricated in situ ZnO nano piece photo-anode film and preparation method thereof
CN109888100B (en) Preparation of rubidium-doped nickel oxide thin film and application of rubidium-doped nickel oxide thin film as hole transport layer in perovskite solar cell
CN114400263B (en) Preparation method and application of substrate-supported bismuth halide/bismuth sulfide nanosheet heterojunction device
CN113363394B (en) Perovskite battery preparation method
CN114824095A (en) Preparation method of solar cell with passivated organic/inorganic hybrid perovskite thin film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20170926

Address after: Hangzhou City, Zhejiang province 311121 Yuhang District No. 998 West Street Wuchang Haichuang Park Building No. 18 room 111

Patentee after: HANGZHOU QIANNA OPTOELECTRONICS TECHNOLOGY CO., LTD.

Address before: 310013 Qiushi village, Zhejiang University, Zhejiang, 35, 304, Hangzhou

Co-patentee before: Yan Buyi

Patentee before: Yao Jizhong