CN107994118B - Perovskite solar battery, double-level-metal electrode and preparation method thereof - Google Patents
Perovskite solar battery, double-level-metal electrode and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- 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
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a kind of perovskite solar battery, for double-level-metal electrode of perovskite solar battery and preparation method thereof, perovskite solar battery includes substrate of glass, transparent conductive electrode, hole transmission layer, perovskite thin film, electron transfer layer and double-level-metal electrode；Double-level-metal electrode includes the first metal film layer and the second metal film layer, and preparation method includes: to deposit one layer of first metal film layer in one side surface of electron transfer layer, and one layer of second metal film layer is deposited on the first metal film layer.One layer of chemically inert first metal film layer is deposited by cryogenic vacuum on the electron transport layer in the present invention, and the second metal film layer of high conductivity is set on the first metal film layer, it can be on the basis of not reducing incident photon-to-electron conversion efficiency, chemical attack of the infiltration and reduction of effective isolation moisture to the second metal film layer, is conducive to the stability for improving perovskite solar battery.
Description
Technical field
The present invention relates to technology solar battery technologies of preparing, more particularly, to a kind of perovskite solar battery, are used for
Double-level-metal electrode of perovskite solar battery and preparation method thereof.
Background technique
With increasingly in short supply, research growing interest of the people to new energy especially solar battery of the energy.Traditional
Silion cell comparatively higher cost, energy consumption is high during the manufacturing, pollution is big, and the dye-sensitized cell of a new generation, has
The efficiency such as machine solar battery are too low and stability is very poor, so they are in industrialization, there is also many problems.
Perovskite solar battery from 2009 for the first time report since, with its ultra-low materials cost, can solution prepare work
Skill and favor by researcher, energy conversion efficiency are promoted by initial 3.8% to 22.1%.It is continuous with research
Deeply, the efficiency of battery is very likely more than the monocrystaline silicon solar cell of current mature.In photovoltaic technology of new generation,
Perovskite solar battery is possible to take the lead in realizing industrialization.
In terms of incident photon-to-electron conversion efficiency, perovskite solar battery has striden into the threshold of industrialization, but the stabilization of device
Property problem constitutes the bottleneck of its industrial application.The stability and halide perovskite material of battery device are under moisture effect
Chemical breakdown occurs, chemical attack, which occurs, with common metal electrode very big relationship, such as metal Au or Ag and perovskite
It can react and generate AuI3Or AgI etc., while Au and Ag can penetrate into calcium titanium ore bed, destroy its electrical properties, thus to device
It can cause the damage of unrepairable.
Summary of the invention
It is an object of the invention to overcome above-mentioned technical deficiency, a kind of bilayer gold for perovskite solar battery is proposed
Belong to electrode and preparation method thereof, the low technology of metal electrode stability for solving perovskite solar battery in the prior art is asked
Topic.
To reach above-mentioned technical purpose, technical solution of the present invention provides a kind of bilayer for perovskite solar battery
Metal electrode including the first metal film layer and is layed in the second metallic film of one side surface of the first metal film layer
Layer；Wherein, first metal film layer has chemical inertness, and second metal film layer has high conductivity.
Meanwhile the present invention also provides a kind of preparation method of double-level-metal electrode for perovskite solar battery, packets
Include following steps:
(1) one layer of chemically inert first metal is deposited in one side surface of electron transfer layer using vacuum deposition method
Film layer；
(2) one layer is deposited on the first metal film layer using the method for vacuum evaporation or magnetron sputtering has high conductivity
The second metal film layer.
Moreover, the present invention also provides a kind of perovskite solar batteries comprising the glass being cascading from the bottom to top
Glass substrate, transparent conductive electrode, hole transmission layer, perovskite thin film, electron transfer layer and above-mentioned double-level-metal electrode, it is described double
First metal film layer of layer metal electrode is arranged close to the electron transfer layer.
Compared with prior art, the present invention is chemically inert by one layer of the vapor deposition of cryogenic vacuum on the electron transport layer
First metal film layer, and on the first metal film layer be arranged high conductivity the second metal film layer, can not reduce
On the basis of incident photon-to-electron conversion efficiency, the chemical attack of the effective infiltration that moisture is isolated and reduction to the second metal film layer,
Be conducive to improve the stability of perovskite solar battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of perovskite solar battery of the invention；
Fig. 2 is the interface SEM photograph and EDS energy spectrum analysis figure of the perovskite solar battery of the embodiment of the present invention 1；
Fig. 3 is density of photocurrent-voltage output characteristics curve pair of the perovskite solar battery of the embodiment of the present invention 2
Compare schematic diagram；
Fig. 4 is the XRD spectrum contrast schematic diagram of the perovskite thin film of the embodiment of the present invention 3；
Fig. 5 is the perovskite powders of the embodiment of the present invention 4 and thermogravimetric/differential thermal contrast schematic diagram that different metal mixes；
Fig. 6 is the storage efficiency variation contrast schematic diagram of the perovskite solar battery of the embodiment of the present invention 5；
Fig. 7 is the light durability contrast schematic diagram of the perovskite solar battery of the embodiment of the present invention 6；
Fig. 8 is density of photocurrent-voltage output characteristics curve pair of the perovskite solar battery of the embodiment of the present invention 7
Compare schematic diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Referring to Fig. 1, the embodiment provides a kind of perovskite solar batteries comprising from the bottom to top successively
Substrate of glass 3, transparent conductive electrode 4, hole transmission layer 5, perovskite thin film 6, electron transfer layer 7 and the double-deck gold being stacked
Belong to electrode, the double-level-metal electrode includes being set to the first metal film layer 1 of 7 upper surface of electron transfer layer and being layed in
Second metal film layer 2 of 1 one side surface of the first metal film layer；Wherein, first metal film layer 1 has chemistry
Inertia, second metal film layer 2 have high conductivity.Wherein, the first metal film layer 1 described in the present embodiment preferably uses
Bi metal film layer or Bi alloy firm layer.And Ag, Au, Al, Cu, Ti, Ni or Mo then can be used in second metal film layer 2
Metal film layer.
As shown in Figure 1, electrically conducting transparent electricity can be arranged in 3 upper surface of substrate of glass when preparing perovskite solar battery
Pole 4 is arranged hole transmission layer 5 in the upper surface of transparent conductive electrode 4, and perovskite is arranged in the upper surface of hole transmission layer 5
Then electron transfer layer 7 is arranged on 6 surface of perovskite thin film in film 6, and existing usual manner system can be used in above-mentioned preparation method
Make, such as spin coating can be used, the plated films such as blade coating or slot coated mode successively plated film；Then, vacuum evaporation side can be used
Method deposits one layer of chemically inert first metal film layer 1 in 7 one side surface of electron transfer layer, specifically in electron transfer layer
7 upper surfaces are deposited one layer of Bi metal film layer or Bi alloy firm layer, when vapor deposition generally at lower than 1000 DEG C, and its vacuum
The vacuum degree of vapor deposition is less than 10-3Pa, evaporation rate areAfter the first metal film layer 1 vapor deposition, then it can be used true
The method of sky vapor deposition or magnetron sputtering deposits one layer of second metal film layer with high conductivity on the first metal film layer 1
2, one layer of Ag, Au, Al, Cu, Ti, Ni or Mo metal film layer specifically is set in 1 upper surface of the first metal film layer.
For the present embodiment using Bi or its alloy coating with a thickness of 5~80nm, film forming is fine and close, difficult with water, oxygen and halogenation
Object perovskite thin film reacts, therefore it can prevent water to perovskite thin film 6 and perovskite thin film 6 to metal electrode well
Corrosion, and then improve the stability of perovskite solar battery；Moreover, metal Bi and its alloy low temperature easily evaporate, process is deposited
The thermal decomposition that not will cause perovskite solar battery guarantees that it plates membrane stability.
Wherein, when the second metal film layer 2 is Ag, Au or Al metal film layer, vacuum deposition method is used, and true
Vacuum degree < 10 of sky vapor deposition-3Pa, evaporation rate areEvaporation thickness is 50-200nm.But in practical application,
The metal prices such as Ag, Au are expensive, improve the material cost of device.
And when the second metal film layer 2 is Cu, Ti, Ni or Mo metal film layer, since its evaporating temperature is generally higher than
1200 DEG C, the fuel factor of vapor deposition will cause the thermal decomposition of perovskite thin film, cause the poor performance of corresponding solar cell device.
Therefore these metallic films generally use low-power magnetically controlled sputter method and carry out plated film.In order to avoid damaging perovskite too in sputtering
It is positive can battery performance, operation air pressure when the present embodiment magnetron sputtering plating is 0.1-100Pa, Sputtering power density 1-
100W/cm2, sputtering with a thickness of 100-2000nm.The Bi metal film layer or Bi alloy firm layer of the present embodiment are as key
Buffer layer, damage of the high energy plasma to bottom perovskite film when preventing from sputtering the metallic films such as Ti, Ni, Mo, in not shadow
The material cost that device is greatly reduced under the premise of ringing device efficiency, is conducive to the industrialization of perovskite solar battery.
The present embodiment has more preferably performance using the perovskite solar battery of double-level-metal electrode for ease of description,
Now by under identical preparation condition different perovskite thin films and perovskite solar battery compare and analyze.
Embodiment 1
As shown in Fig. 2, it is the interface SEM of the perovskite solar battery based on Bi/Ag and Bi/Mo double-level-metal electrode
Photo and EDS energy spectrum analysis figure, wherein Fig. 2 a is Bi/Ag double-level-metal electrode, i.e. the first metal film layer is the Bi of 20nm thickness
Metal layer, the second metal film layer are the Ag metal layer of 150nm thickness；Fig. 2 b is Bi/Mo double-level-metal electrode, i.e. the first metal foil
Film layer is the Bi metal layer of 20nm thickness, and the second metal film layer is the Mo metal layer of 500nm thickness.
Embodiment 2
Prepare five groups of perovskite solar batteries in the same terms, five groups of perovskite solar batteries cannot be in
In: first group of single layer Ag metal electrode；Second group is double-level-metal electrode, and first layer is Bi metal layer, second layer Ag
Metal layer, Bi metal layer thickness are 10nm；Third group is double-level-metal electrode, and first layer is Bi metal layer, second layer Ag
Metal layer, Bi metal layer thickness are 80nm；4th group is double-level-metal electrode, and first layer is Bi-Sn alloying metal layer, second
Layer is Ag metal layer, and Bi-Sn alloying metal layer is with a thickness of 10nm；5th group is double-level-metal electrode, and first layer is Bi-Cu conjunction
Gold metal layer, the second layer are Ag metal layer, and Bi-Cu alloying metal layer is with a thickness of 10nm.
Selection area is 1cm2Above-mentioned five groups of perovskite solar batteries, and intensity of illumination be 100mW/cm2Lower acquisition
Its photoelectric conversion efficiency, from the figure 3, it may be seen that first group to the 5th group of incident photon-to-electron conversion efficiency is respectively as follows: standard Ag electrode, efficiency is
17.53%；10nm Bi and Ag double-level-metal electrode, efficiency 16.94%；80nm Bi and Ag double-level-metal electrode, efficiency are
13.21%；10nm Bi-Sn alloy and Ag double-level-metal electrode, efficiency 18.06%；10nm Bi-Cu alloy and the double-deck gold of Ag
Belong to electrode, efficiency 18.25%.By above-mentioned data it is found that when the thickness of Bi metal layer in double-level-metal electrode is suitable, energy
It is enough to obtain the incident photon-to-electron conversion efficiency similar with standard Ag metal electrode.
Embodiment 3
Take four groups of halide perovskite (CH3NH3PbI3) film under 35 DEG C, 70% humidity, selects different covering sides
Formula measures the decomposition product (PbI that its chemical breakdown under moisture effect is formed2) quantity, as shown in figure 3, from the bottom to top
For first to Article 8 XRD spectrum.Wherein, first are as follows: first group of halide perovskite thin film is in standard metal Ag electricity
(it, which is equivalent to, does not cover Bi) two days under extremely；Article 2 are as follows: second group of halide perovskite thin film covers two in Bi metallic film
It, is equivalent to that the first metal film layer is Bi metallic film, the second metal film layer is Ag metal film layer；Article 3 are as follows:
Third group halide perovskite thin film covers two days in Bi-Sn metallic film, is equivalent to the first metal film layer as Bi-Sn conjunction
Gold thin film, the second metal film layer are Ag metal film layer；Article 4 are as follows: the 4th group of halide perovskite thin film is in Bi-Cu gold
Belong to film to cover two days, is equivalent to that the first metal film layer is Bi-Cu alloy firm, the second metal film layer is Ag metal foil
Film layer；Article 5 are as follows: first group of halide perovskite thin film (it, which is equivalent to, does not cover Bi) 30 under standard metal Ag electrode
It；Article 6 are as follows: second group of halide perovskite thin film covers 30 days in Bi metallic film, is equivalent to the first metallic film
Layer is Bi metallic film, the second metal film layer is Ag metal film layer；7th group are as follows: third group halide perovskite thin film exists
Bi-Sn metallic film covers 30 days, and being equivalent to the first metal film layer is Bi-Sn alloy firm, the second metal film layer
For Ag metal film layer；Article 8 are as follows: the 4th group of halide perovskite thin film covers 30 days in Bi-Cu metallic film, phase
When be Bi-Cu alloy firm in the first metal film layer, the second metal film layer is Ag metal film layer.
As shown in Figure 4, first group of standard Ag electrode is weaker to the protective effect of perovskite, through in 30 days aged samples
PbI2Diffraction maximum is remarkably reinforced, and it is serious to illustrate that perovskite decomposes.And second group to the 4th group based on Bi or Bi based alloy
Double-level-metal electrode can effectively shield moisture, delay the decomposition of perovskite thin film, after aging 30 days, PbI2Diffraction
Peak is still weaker, illustrates perovskite degree of decomposition very little, i.e. Bi and Bi alloy is more obvious to the protective effect of perovskite thin film.
Embodiment 4
By perovskite (CH3NH3PbI3) powder mixes with Bi, Ag, Al, Cu metal powder with mass ratio 1:1 respectively respectively, and
In room temperature within the scope of 400 DEG C, slowly heat up by 5 DEG C/min of speed, N2Its weightless and heat release, test knot are tested under atmospheric condition
Fruit is as shown in figure 5, it illustrates that it is relatively strong to illustrate that Bi metal has there is no chemical reaction between Bi metal and perovskite thin film
Resistance to corrosion, and the metals such as Ag, Al, Cu within 100 DEG C i.e. there are exothermic heat of reaction and mass loss, illustrate very low
Within the temperature range of, halide perovskite produces chemical attack to above-mentioned metal.
Embodiment 5
Eight groups of perovskite solar batteries are prepared in the same terms, the difference of eight groups of perovskite solar batteries exists
In: first group is single layer Al metal electrode；Second group is single layer Cu metal electrode；Third group is single layer Ag metal electrode；4th
Group is double-level-metal electrode, and first layer is Bi metal layer, the second layer is Al metal layer；5th group is double-level-metal electrode, and
First layer is Bi metal layer, the second layer is Cu metal layer；6th group is double-level-metal electrode, and first layer is Bi metal layer, the
Two layers are Ag metal layer；7th group is double-level-metal electrode, and first layer is Bi-Sn alloy-layer, the second layer is Ag metal layer；The
Eight groups are double-level-metal electrode, and first layer is Bi-Cu alloy-layer, the second layer is Ag metal layer.
Above-mentioned eight groups of perovskite solar batteries are subjected to long term storage efficiency test, test condition are as follows: unpackaged devices
Dark-state saves, 50-70% humidity, 25 DEG C of environment temperatures.Test results are shown in figure 6, the bilayer based on metal Bi or Bi alloy
The stability of the corresponding perovskite solar battery of metal electrode is obviously more preferable, and stability is apparently higher than conventional single layer metal electricity
Pole.
Embodiment 6
Eight groups of perovskite solar batteries are prepared in the same terms, the difference of eight groups of perovskite solar batteries exists
In: first group is single layer Al metal electrode；Second group is single layer Cu metal electrode；Third group is single layer Ag metal electrode；4th
Group is double-level-metal electrode, and first layer is Bi metal layer, the second layer is Al metal layer；5th group is double-level-metal electrode, and
First layer is Bi metal layer, the second layer is Cu metal layer；6th group is double-level-metal electrode, and first layer is Bi metal layer, the
Two layers are Ag metal layer；7th group is double-level-metal electrode, and first layer is Bi-Sn alloy-layer, the second layer is Ag metal layer；The
Eight groups are double-level-metal electrode, and first layer is Bi-Cu alloy-layer, the second layer is Ag metal layer.
Above-mentioned eight groups of perovskite solar batteries are subjected to light durability test, test condition are as follows: unpackaged devices, nothing
Water anaerobic N2Compression ring border, 25 DEG C of environment temperatures, white light LEDs provide 100mW/cm2The continuous light of intensity；And then battery most
High-power point continuously detects, and experimental result is as shown in fig. 7, the illumination of the perovskite solar battery based on double-level-metal electrode is steady
Qualitative to be significantly improved, practicability greatly improves.
Embodiment 7
Eight groups of perovskite solar batteries are prepared in the same terms, the difference of eight groups of perovskite solar batteries exists
In: first group is directly surface magnetic control sputtering forms Ti metal electrode on the electron transport layer；Second group is directly in electronics biography
Defeated layer upper surface magnetron sputtering forms Ni metal electrode；Third group is that directly surface magnetic control sputtering forms Mo on the electron transport layer
Metal electrode；4th group is deposited one layer of Bi metal layer as buffer layer for first surface on the electron transport layer, and then magnetic control splashes again
It penetrates to form Ti metal electrode；5th group is first one layer of Bi metal layer is deposited as buffer layer, then in surface on the electron transport layer
Magnetron sputtering forms Ni metal electrode again；6th group is first one layer of Bi metal layer is deposited as buffering in surface on the electron transport layer
Layer, then magnetron sputtering forms Mo metal electrode again；7th group is first one layer of Bi-Sn alloy is deposited in surface on the electron transport layer
Layer is used as buffer layer, and then magnetron sputtering forms Mo metal electrode again；8th group first surface is deposited one layer on the electron transport layer
Bi-Cu alloy-layer is as buffer layer, and then magnetron sputtering forms Mo metal electrode again.
1cm is set by the area of above-mentioned eight groups of perovskite solar batteries2, generated by optical mask, and at 3A grades
The 100mW/cm of solar simulator2It is irradiated under output intensity, measures its photoelectric conversion efficiency.
As shown in figure 8, it is " density of photocurrent-voltage " output characteristic curve of eight groups of perovskite solar batteries, by
For above-mentioned correlation curve it is found that directly magnetron sputtering metal electrode, meeting significantly damages battery, the efficiency of battery is very low (< 4%)；
And Bi the or Bi based alloy of low temperature vapor deposition is used as buffer layer, it is possible to prevente effectively from sputtering process is to perovskite and boundary material
Damage.Base metal Ti, Ni, Mo based on Bi or Bi based alloy and magnetron sputtering etc. constitute double-level-metal electrode, and substitution is expensive
Ag or Au, the cost of electrode material is greatly reduced.Wherein, double-deck based on Bi/Ti
The battery efficiency of metal electrode is 11.48%, and the battery efficiency based on Bi/Ni double-level-metal electrode is 14.05%, is based on Bi/
The battery efficiency of Mo double-level-metal electrode is 15.45%, and the battery efficiency based on Bi-Sn/Mo double-level-metal electrode is
16.04%, the battery efficiency based on Bi-Sn/Mo double-level-metal electrode is 16.61%.Realizing the same of high-photoelectric transformation efficiency
When reduce the cost of electrode material, be conducive to industrialization.
The above described specific embodiments of the present invention are not intended to limit the scope of the present invention..Any basis
Any other various changes and modifications that technical concept of the invention is made should be included in the guarantor of the claims in the present invention
It protects in range.
Claims (7)
1. a kind of double-level-metal electrode for perovskite solar battery, which is characterized in that including the first metal film layer and
It is layed in the second metal film layer of one side surface of the first metal film layer；Wherein, first metal film layer has
Chemical inertness, second metal film layer have high conductivity；First metal film layer is Bi metal film layer or Bi
Alloy firm layer；Second metal film layer is Ag, Au, Al, Cu, Ti, Ni or Mo metal film layer.
2. a kind of preparation method of the double-level-metal electrode for perovskite solar battery, which is characterized in that including walking as follows
It is rapid:
(1) one layer of chemically inert first metallic film is deposited in one side surface of electron transfer layer using vacuum deposition method
Layer；
(2) deposit one layer on the first metal film layer using the method for vacuum evaporation or magnetron sputtering has the of high conductivity
Two metal film layers；
First metal film layer is Bi metal film layer or Bi alloy firm layer；Second metal film layer be Ag, Au,
Al, Cu, Ti, Ni or Mo metal film layer.
3. preparation method according to claim 2, which is characterized in that the vacuum degree of vacuum evaporation is small in the step (1)
In 10-3Pa, evaporation rate areEvaporating temperature is less than 1000 DEG C.
4. preparation method according to claim 3, which is characterized in that the first metal film layer vapor deposition with a thickness of 5~
80nm。
5. preparation method according to claim 2, which is characterized in that when the second metal film layer is Ag, Au or Al metal
When film layer, vacuum deposition method, and vacuum degree < 10 of vacuum evaporation are used-3Pa, evaporation rate areIt steams
Plating is with a thickness of 50-200nm.
6. preparation method according to claim 2, which is characterized in that when the second metal film layer is Cu, Ti, Ni or Mo gold
When belonging to film layer, magnetically controlled sputter method is used, and operation air pressure is 0.1-100Pa, Sputtering power density 1-100W/cm2、
Sputtering is with a thickness of 100-2000nm.
7. a kind of perovskite solar battery, which is characterized in that including the substrate of glass, transparent being cascading from the bottom to top
Conductive electrode, hole transmission layer, perovskite thin film, electron transfer layer and double-level-metal electrode described in claim 1, it is described double
First metal film layer of layer metal electrode is arranged close to the electron transfer layer.
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