CN103956431A - Organic-inorganic planar heterojunction solar cell prepared through solutions and preparing method of solutions - Google Patents
Organic-inorganic planar heterojunction solar cell prepared through solutions and preparing method of solutions Download PDFInfo
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- 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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Abstract
The invention belongs to the technical field of photoelectric devices, and discloses an organic-inorganic planar heterojunction solar cell prepared through solutions and a preparing method of the solutions. The solar cell comprises a substrate, an anode, an anode interface layer, a photoactivity layer, a cathode interface layer and a cathode which are all sequentially stacked, wherein the material of the photoactivity layer is an inorganic material which is soluble in a solvent and is of a perovskite structure, and performance of the material can be improved by adding polymer additives. The invention provides a planar heterojunction solar cell device with the photoactivity layer made of the perovskite organic-inorganic hybrid material capable of being prepared through the solutions, and according to the planar heterojunction solar cell device, the anode interface layer and the cathode interface layer are prepared through organic material solutions. According to the method, the problem that energy consumption is high in the cell device machining process is effectively solved, large-scale production is achieved, and high efficiency is achieved; the defects that in the prior art, the inorganic material needs to be machined at high temperature and the cost of the materials in the organic solar cell is high are overcome. The novel material and the new method can be applied to solar cells.
Description
Technical field
The invention belongs to photoelectric device technical field, particularly a kind of organic-inorganic planar heterojunction solar cell and solution preparation for processing thereof of solution processing.
Background technology
Along with the year by year increase of the whole world for energy demand; the exhaustion day by day of the traditional energy such as oil, coal; and the needs to the biological environment of preserving our planet, the increasing scientist in the whole world concentrates on research the inexhaustible renewable and clean energy resources such as hydrogen, solar energy.
The solar cell based on inorganic material such as ripe inorganic silicon, GaAs, indium phosphide has occupied leading position on market, yet due to its for material purity require high, in the course of processing, can produce the problems such as high energy consumption and pollution, and its price is very expensive, therefore in the today of pursuing low-cost and environmental protection, its large-scale application is restricted.
Dye-sensitized solar cells was obtained after 12% high efficiency at the beginning of the nineties in last century, and its application is subject to the obstruction of the problem that encapsulates always.The solid electrolyte of exploitation and the polymer hole material of doping can well solve the encapsulation problem of dye-sensitized cell in recent years, but its efficiency also decreases.In addition, dye-sensitized solar cells needs high-temperature process TiO in the course of processing
2presoma, convert it into TiO
2inorganic semiconductor.These 2 is the major obstacle in dye-sensitized solar cells commercialization process.
The hybrid inorganic-organic semi-conducting material with perovskite structure started by people, to be paid close attention to gradually in last century, and it is high that it possesses mobility, good absorbing, and the advantage that can adopt various ways processing.Early stage researcher focuses on the features such as its mobility height, has prepared the relevant devices such as transistor.And in recent years, along with going deep into gradually of research, have gradually scholar to start to utilize the hybrid inorganic-organic materials of perovskite structure to prepare dye-sensitized cell.2009, Tsutomu Miyasaka seminar prepared dye-sensitized solar cells using the hybrid inorganic-organic materials of perovskite structure as photoactive layer first.Its efficiency has reached 3.81% (J.Am.Chem.Soc.2009,131,6050).
In dye-sensitized solar cells preparation process, need high temperature by TiO
2presoma change into inorganic semiconductor, and efficiently battery device need to adopt the method for evaporation to prepare active layer, preparation technology is comparatively complicated.By contrast, organic photovoltaic cell can adopt low temperature whole soln processing method, and this point not only can, so that energy consumption significantly reduces, can also realize large area and produce.In addition, organic photovoltaic cell also can be prepared flexible device, and quality is light, can meet different needs.Its peak efficiency has surpassed 10% (Nat.Commun.2013,4,1446) at present.But organic photovoltaic cell manufacture of materials cost is high, is difficult to industrialization and criticizes product.
Summary of the invention
In order to overcome inorganic material in above-mentioned prior art, need the shortcoming of high temperature process and the high deficiency of organic material cost, primary and foremost purpose of the present invention is to provide a kind of organic-inorganic planar heterojunction solar cell of solution processing.This solar cell photoactive layer is prepared by solution processing method, there is high performance perovskite structure, realize the cryogenic fluid processing of solar cell, and the adding of polymeric additive in photoactive layer, open circuit voltage and the device performance of solar cell improved greatly.
Another object of the present invention is to provide a kind of solution preparation for processing of organic-inorganic planar heterojunction solar cell of above-mentioned solution processing.
Object of the present invention realizes by following proposal:
An organic-inorganic planar heterojunction solar cell for solution processing, comprises the substrate, anode, anodic interface layer, photoactive layer, cathode interface layer and the negative electrode that stack gradually.
The material of described photoactive layer is to dissolve in the inorganic material that solvent has perovskite structure.
Described photoactive layer is the blend that compd A and compd B mol ratio are 1:1~10:1.
Described compd A is halogen-containing organic salt or inorganic salts, is preferably at least one in following compound: CH
3nH
3i, CH
3nH
3br, CH
3nH
3cl, CH
3cH
2nH
3i, CH
3cH
2nH
3br, CH
3cH
2nH
3cl, CH
3cH
2cH
2nH
3i, CH
3cH
2cH
2nH
3br, CH
3cH
2cH
2nH
3cl, CsI, CsBr, CsCl, CH (NH
2)
2i, CH (NH
2)
2br, CH (NH
2)
2cl, CH
3cH (NH
2)
2i, CH
3cH (NH
2)
2br, CH
3cH (NH
2)
2cl.
Described compd B is halogen-containing metal inorganic salt, is preferably at least one in following compound: PbI
2, PbBr
2, PbCl
2, SnI
2, SnBr
2, SnCl
2, GeI
2, GeBr
2, GeCl
2.
The present invention also provides a kind of solution processing method of described photoactive layer, specific as follows: compd A and compd B are mixed in proportion, be dissolved in organic solvent, add after thermal response, be coated in anodic interface layer and form photoactive layer.
Described organic solvent is preferably at least one in cyclohexanone, cyclopentanone, gamma-butyrolacton, δ-valerolactone, gamma-valerolactone, 6-caprolactone, DMF, dimethylacetylamide, dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE.
The described thermal response that adds is preferably reacted 12h at 60 ℃.
The method of described coating can be revolve Tu, brushing, spray, soak Tu, roller Tu, silk screen printing, printing or inkjet printing mode.
Photoactive layer in the organic-inorganic planar heterojunction solar cell of solution processing of the present invention is high performance perovskite structure, and can prepare by solwution method, can obtain efficient solar cell.
In order to improve better open circuit voltage and the device performance of the organic-inorganic planar heterojunction solar cell of solution processing of the present invention, in photoactive layer, can add a series of polymeric additives.
Described polymeric additive is the polymer with linear structure or branched structure dissolving in organic solvent.
Preferably, described polymeric additive has at least one in structure shown in formula (I)~(VI):
Wherein, the natural number that n is 1~100000000; R
1for having straight chain, side chain, the oxyalkyl chain of 1~6 carbon atom, one or more carbon atom can be by oxygen atom, hydroxyl, amino, aryl, ester group, carbonyl substituted; R
2, R
3for hydrogen atom or there is the straight chain of 1~20 carbon atom, side chain, cyclic alkyl chain, oxyalkyl chain, wherein one or more carbon atoms can be by oxygen atom, hydroxyl, amino, aryl, ester group, carbonyl substituted.
Described polymeric additive is preferably the P2O with following structure.
The amount of polymeric additive used be compd A and compd B quality and 0.5~10%.
It is synthetic that described polymeric additive can be artificial orientation, also can be commercially produced product.
Preferably, above-mentioned solution processing method is prepared photoactive layer, after polymeric additive can being mixed with compd A, compd B, dissolves, applies.
Polymeric additive is incorporated in photoactive layer, can effectively improves the film forming of photoactive layer film.The present invention's polymeric additive used has and structure like solvent based, by the interaction with solvent and the interaction when the film forming with the material of photoactive layer, polymeric additive can significantly improve the film forming of photoactive layer film, and the use of its polymeric additive of the present invention can significantly improve open circuit voltage and the energy conversion efficiency of battery device.
In solar cell of the present invention, described cathode interface layer is preferably carbon 60 and derivative thereof (as [6,6]-phenyl-C61-methyl butyrate), at least one in carbon 70 and derivative thereof (as [6,6]-phenyl-C71-methyl butyrate), conjugated polymer, inorganic semiconductor nanometer, Graphene and derivative thereof.
Cathode material is preferably aluminium, silver, gold, calcium/aluminium alloy or calcium/silver alloy.
Anodic interface layer of the present invention is preferably conjugatd polymers (as poly-3,4-ethylene dioxythiophene/poly styrene sulfonate) or inorganic semiconductor.Anodic interface layer can improve the compound interface layer after light absorption for adding nano particle.
Anode of the present invention is preferably metal, metal oxide (as indium tin oxide conductive film (ITO), doping stannic oxide (FTO), zinc oxide (ZnO), indium gallium zinc oxide (IGZO)) at least one and in Graphene and derivative thereof.
Substrate of the present invention is preferably at least one in glass, flexible material (as polyimides, PETG, ethylene terephthalate, PEN or other polyester materials), metal, alloy and stainless steel film.
The present invention also provides a kind of solution processing method of organic-inorganic planar heterojunction solar cell of above-mentioned solution processing, comprises the following steps:
(1) at the anode surface spin coating last layer anodic interface layer being coated on substrate;
(2) on anodic interface layer, use solution processing method to apply one deck photoactive layer;
(3) on photoactive layer, adopt solution processing method to apply one deck cathode interface layer;
(4) evaporation layer of metal layer on cathode interface layer, as negative electrode.
The present invention is innovatively in conjunction with take perovskite hybrid inorganic-organic materials as basic planar heterojunction solar cell and the advantage of organic photovoltaic cell, the perovskite hybrid inorganic-organic materials that provides a kind of photoactive layer to adopt solution processable, anodic interface layer and cathode interface layer adopt the planar heterojunction solar cell device of organic material solution processing.This kind of combination can effectively improve energy consumption and the large area production problem in battery device processing, and can obtain higher efficiency.Than inorganic solar cell and dye-sensitized solar cells, overcome the shortcoming that needs high temperature process inorganic material, than organic photovoltaic cell, overcome the high shortcoming of its material cost.Can be used as a kind of novel materials and methods applies in solar cell.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) the present invention adopts cryogenic fluid process technology to prepare solar cell, and preparation technology is simple, less energy consumption, and preparation cost is low.
(2) the present invention adopts hybrid inorganic-organic materials as photoactive layer, and it has wider absorption at visible ray and near infrared region, and its absorption coefficient is high, is better than most of organic materials.
(3) the present invention adopts inorganic material can obtain as photoactive layer the solar cell performance that efficiency is higher, adds after polymeric additive, can significantly improve open circuit voltage and the energy conversion efficiency of device.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic-inorganic planar heterojunction solar cell of the present invention, and wherein, 1 is that substrate, 2 is that anode, 3 is that anodic interface layer, 4 is that photoactive layer, 5 is that cathode interface layer, 6 is negative electrode.
Fig. 2 is photoactive layer (CH of the present invention
3nH
3pbI
3) study of ultraviolet-visible-near infrared.
Fig. 3 is photoactive layer (CH of the present invention
3nH
3pbI
3) luminescence generated by light spectrogram.
Fig. 4 is that organic-inorganic planar heterojunction solar cell of the present invention is (with CH
3nH
3pbI
3for photoactive layer) external quantum efficiency.
Fig. 5 is photoactive layer (CH of the present invention
3nH
3pbI
3) X ray film diffraction pattern.
Fig. 6 is that organic-inorganic planar heterojunction solar cell of the present invention is (with CH
3nH
3pbI
3for photoactive layer) add the scanning electron microscope (SEM) photograph of the photoactive layer polymeric additive of different proportion.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: the preparation of photoactive layer material
The CH of described compd A
3nH
3i, CH
3nH
3br, CH
3nH
3cl, CH
3cH
2nH
3i, CH
3cH
2nH
3br, CH
3cH
2nH
3cl, CH
3cH
2cH
2nH
3i, CH
3cH
2cH
2nH
3br, CH
3cH
2cH
2nH
3cl, CH (NH
2)
2i, CH (NH
2)
2br, CH (NH
2)
2cl, CH
3cH (NH
2)
2i, CH
3cH (NH
2)
2br, CH
3cH (NH
2)
2cl.Synthetic according to document (J.Am.Chem.Soc.2012,134, the method in 17396-17399) prepares.
CH
3nH
3pbI
3synthetic by by CH
3nH
3i and PbI
2be dissolved in altogether reaction in gamma-butyrolacton or other organic solvent and generate, specific as follows:
Get CH
3nH
3i (32mg) and PbI
2(93mg) blend is dissolved in 1mL gamma-butyrolacton, is heated to 60 ℃, stirs and within 12 hours, obtains photoactive layer material.
Containing being prepared as follows of the photoactive layer material of polymeric additive:
In above-mentioned solution, add CH
3nH
3i and PbI
2the polymeric additive of 0.5~10wt% of gross mass, heating at 60 ℃, slowly dissolving obtains the photoactive layer material containing polymeric additive.
CH
3nH
3pbI
xcl
3-xand CH
3nH
3pbI
xbr
3-xthe preparation of (x is less than 3, is greater than 0), passes through CH respectively
3nH
3i and PbCl
2, PbBr
2in blend dissolution solvent, add thermal agitation and obtain, according to required x ratio, suitable adjustment raw material amount ratio obtains.
It is the same that other compd As and compd B combination in any obtain the preparation method of photoactive layer material.
Embodiment 2: the preparation of organic-inorganic heterogeneous solar cell:
By ITO electro-conductive glass, square resistance~20 Europe/square centimeter, is cut into 15 millimeters * 15 millimeters square pieces in advance.Use successively acetone, micron order semiconductor special purpose detergent, deionized water, isopropyl alcohol ultrasonic cleaning, it is standby that nitrogen blowing is placed on constant temperature oven.Before use, ito glass sheet in oxygen plasma etch instrument with plasma bombardment 10 minutes.PEDOT:PSS aqueous dispersions (approximately 1%) is purchased from Bayer company, resilient coating adopts the spin coating of sol evenning machine (KW-4A) high speed, thickness is determined by solution concentration and rotating speed, with surface profiler (Alpha-Tencor-500 of Tritek company type) actual measurement monitoring.After film forming, in constant-temperature vacuum baking oven, drive away solvent residues, perpendicular film.On ITO substrate, get rid of the thickness 40 nanometer left and right of PEDOT:PSS for good.Cathode interface layer passes through at photoactive layer surface spin coating one deck PC
61bM layer obtains, PC
61bM solution is configured by chlorobenzene, dichloro-benzenes, toluene, chloroform, dimethylbenzene equal solvent, and concentration range is 1~20mg/mL.
Device battery structure of the present invention as shown in Figure 1, on ITO, revolve the PEDOT:PSS film that Tu one deck 40nm is thick, then configuration quality concentration is 10% photoactive layer material (solvent is gamma-butyrolacton), under the rotating speed of 3000rpm, revolved Tu to PEDOT:PSS layer, then 100 ℃ of heating anneal 15min, then revolve the thick PC of Tu one deck 25nm thereon
61bM layer.Finally adopt method evaporation one deck aluminium electrode of evaporation.Photoactive layer material is the CH that embodiment 1 prepares
3nH
3pbI
3.
Or in photoactive layer material, add the polymeric additive P2O of 0.5~10wt%, then carry out spin coating.
The photoactive layer preparing is carried out to ultraviolet-visible light-near infrared spectrum and photoluminescence spectrum scanning, the results are shown in Figure 2 and Fig. 3.The device battery preparing is carried out to external quantum efficiency test, the results are shown in Figure 4.To photoactive layer (CH
3nH
3pbI
3) carry out X ray film diffraction pattern, the results are shown in Figure 5.To DMF dicyandiamide solution, the battery device of different P2O additions carries out photoelectric device performance measurement, the results are shown in Table 1.Different solvents system is obtained, and the photoactive layer of different polymeric additive consumptions carries out scanning electron microscopic observation, the results are shown in Figure 6.
The battery device performance index of the different P2O additions of table 1
? | Voc(V) | Jsc(mA/cm 2) | FF(%) | PCE(%) |
0wt%P2O | 0.71 | 7.47 | 44.6 | 2.37 |
1wt%P2O | 0.93 | 7.84 | 67.3 | 4.91 |
1.5wt%P2O | 1.07 | 8.46 | 64.5 | 5.83 |
3wt%P2O | 1.1 | 6.8 | 62.3 | 4.66 |
5wt%P2O | 1.1 | 7.04 | 54.5 | 4.22 |
7wt%P2O | 1.01 | 2.55 | 42.4 | 1.09 |
From table 1 and Fig. 6, the organic-inorganic heterogeneous solar cell that the present invention prepares can improve by changing the consumption of additive filming performance and the device performance of perovskite material, and the increase with the consumption of polymeric additive, filming performance and the device performance of the photoactive layer material of gained improve and improve, and wherein the highest can the raising respectively of open circuit voltage and device efficiency reaches 54% and 146.
Embodiment 3: the photovoltaic performance of the organic-inorganic heterogeneous solar cell of different photoactive layer materials
To respectively with CH
3nH
3pbI
3, CH
3nH
3pbI
xcl
3-xand CH
3nH
3pbI
xbr
3-x(x is less than 3, is greater than 0) measured for the photovoltaic performance of the organic-inorganic heterogeneous solar cell that photoactive layer material prepares, and the results are shown in Table 2.
The battery device performance index of the different photoactive layer materials of table 2
? | Voc(V) | Jsc(mA/cm2) | FF(%) | PCE(%) |
CH 3NH 3PbI 3 | 0.71 | 7.47 | 44.6 | 2.37 |
CH 3NH 3PbI xCl 3-x | 0.94 | 10.19 | 64.9 | 6.21 |
CH 3NH 3PbI xBr 3-x | 1.01 | 2.55 | 42.4 | 1.09 |
From table 2, by changing the component of active layer material, improve wherein bromo element or content of Cl element, can effectively improve device performance.
From embodiment 1~3, organic-inorganic heterogeneous solar cell of the present invention can prepare by solution processing method, and by adding photoactive layer polymeric additive, can improve significantly the filming performance of perovskite material, improve the open circuit voltage of device, and finally improve the opto-electronic conversion performance of device.
Above-described embodiment is preferably execution mode of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. an organic-inorganic planar heterojunction solar cell for solution processing, is characterized in that comprising the substrate, anode, anodic interface layer, photoactive layer, cathode interface layer and the negative electrode that stack gradually;
The material of described photoactive layer is to dissolve in the inorganic material that solvent has perovskite structure.
2. the organic-inorganic planar heterojunction solar cell of solution processing according to claim 1, is characterized in that: described photoactive layer is the blend that compd A and compd B mol ratio are 1:1~10:1; Described compd A is halogen-containing organic salt or inorganic salts; Described compd B is halogen-containing metal inorganic salt.
3. the organic-inorganic planar heterojunction solar cell of solution processing according to claim 2, is characterized in that: described compd A is at least one in following compound: CH
3nH
3i, CH
3nH
3br, CH
3nH
3cl, CH
3cH
2nH
3i, CH
3cH
2nH
3br, CH
3cH
2nH
3cl, CH
3cH
2cH
2nH
3i, CH
3cH
2cH
2nH
3br, CH
3cH
2cH
2nH
3cl, CsI, CsBr, CsCl, CH (NH
2)
2i, CH (NH
2)
2br, CH (NH
2)
2cl, CH
3cH (NH
2)
2i, CH
3cH (NH
2)
2br, CH
3cH (NH
2)
2cl; Described compd B is at least one in following compound: PbI
2, PbBr
2, PbCl
2, SnI
2, SnBr
2, SnCl
2, GeI
2, GeBr
2, GeCl
2.
4. the organic-inorganic planar heterojunction solar cell that solution according to claim 1 is processed, it is characterized in that: described photoactive layer is obtained by solution processing method, specific as follows: compd A and compd B are mixed in proportion, be dissolved in organic solvent, add after thermal response, be coated in anodic interface layer and form photoactive layer.
5. the organic-inorganic planar heterojunction solar cell that solution according to claim 4 is processed, it is characterized in that: described organic solvent is at least one in cyclohexanone, cyclopentanone, gamma-butyrolacton, δ-valerolactone, gamma-valerolactone, 6-caprolactone, DMF, dimethylacetylamide, dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE; The described thermal response that adds is reacted 12h at 60 ℃.
6. the organic-inorganic planar heterojunction solar cell of solution processing according to claim 1, is characterized in that: in described photoactive layer, contain a series of polymeric additives; Described polymeric additive is the polymer with linear structure or branched structure dissolving in organic solvent.
7. the organic-inorganic planar heterojunction solar cell of solution according to claim 6 processing, is characterized in that: the amount of polymeric additive used be compd A and compd B quality and 0.5~10%.
8. the organic-inorganic planar heterojunction solar cell that solution according to claim 6 is processed, is characterized in that: described polymeric additive has at least one in structure shown in formula (I)~(VI):
Wherein, the natural number that n is 1~100000000; R
1for having straight chain, side chain, the oxyalkyl chain of 1~6 carbon atom, one or more carbon atom can be by oxygen atom, hydroxyl, amino, aryl, ester group, carbonyl substituted; R
2, R
3for hydrogen atom or there is the straight chain of 1~20 carbon atom, side chain, cyclic alkyl chain, oxyalkyl chain, wherein one or more carbon atoms can be by oxygen atom, hydroxyl, amino, aryl, ester group, carbonyl substituted.
9. the organic-inorganic planar heterojunction solar cell of solution processing according to claim 1, is characterized in that: described cathode interface layer is at least one in carbon 60 and derivative, carbon 70 and derivative thereof, conjugated polymer, inorganic semiconductor nanometer, Graphene and derivative thereof; Described cathode material is aluminium, silver, gold, calcium/aluminium alloy or calcium/silver alloy; Described anodic interface layer is conjugatd polymers or inorganic semiconductor; Described anode is at least one in metal, metal oxide and Graphene and derivative thereof; Described substrate is at least one in glass, flexible material, metal, alloy and stainless steel film.
10. the preparation method of the organic-inorganic planar heterojunction solar cell that solution according to claim 1 is processed, is characterized in that comprising the following steps:
(1) at the anode surface spin coating last layer anodic interface layer being coated on substrate;
(2) on anodic interface layer, use solution processing method to apply one deck photoactive layer;
(3) on photoactive layer, adopt solution processing method to apply one deck cathode interface layer;
(4) evaporation layer of metal layer on cathode interface layer, as negative electrode.
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