CN107994118A - Perovskite solar cell, double-level-metal electrode and preparation method thereof - Google Patents
Perovskite solar cell, double-level-metal electrode and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 197
- 239000002184 metal Substances 0.000 title claims abstract description 197
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010408 film Substances 0.000 claims abstract description 104
- 239000010409 thin film Substances 0.000 claims abstract description 23
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 13
- 230000005611 electricity Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
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- 229910052737 gold Inorganic materials 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 15
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- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 238000007738 vacuum evaporation Methods 0.000 claims description 5
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- 239000010410 layer Substances 0.000 description 171
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Abstract
Double-level-metal electrode the invention discloses a kind of perovskite solar cell, for perovskite solar cell and preparation method thereof, perovskite solar cell include substrate of glass, transparent conductive electrode, hole transmission layer, perovskite thin film, electron transfer layer and double-level-metal electrode；Double-level-metal electrode, which includes the first metal film layer and the second metal film layer, its preparation method, to be included：One layer of first metal film layer is deposited in one side surface of electron transfer layer, 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 electricity conversion not be reduced, the infiltration of effective isolation moisture simultaneously reduces the chemical attack to the second metal film layer, it is conducive to the stability for improving perovskite solar cell.
Description
Technical field
The present invention relates to technology solar cell technology of preparing, more particularly, to a kind of perovskite solar cell, is used for
Double-level-metal electrode of perovskite solar cell and preparation method thereof.
Background technology
With increasingly in short supply, research growing interest of the people to new energy especially solar cell of the energy.Traditional
Comparatively cost is higher for silion cell, and energy consumption is big during the manufacturing, pollution is big, and the dye-sensitized cell of a new generation, has
The efficiency such as machine solar cell are too low and stability is very poor, thus they also there are many problems in industrialization.
Perovskite solar cell from 2009 for the first time report since, with its ultra-low materials cost, can solution prepare work
Skill and favored be subject to researcher, energy conversion efficiency is by initial 3.8% lifting to 22.1%.It is continuous with research
Deeply, the efficiency of battery very likely exceedes the monocrystaline silicon solar cell of current mature.In photovoltaic technology of new generation,
Perovskite solar cell is possible to take the lead in realizing industrialization.
In terms of electricity conversion, perovskite solar cell has striden into the threshold of industrialization, but the stabilization of device
Sex chromosome mosaicism constitutes the bottleneck of its commercial application.The stability of battery device is with halide perovskite material under moisture effect
Generation chemical breakdown, chemical attack, which occurs, with common metal electrode very big relation, such as metal Au or Ag and perovskite
Generation AuI can be reacted3Or AgI etc., while Au and Ag can penetrate into calcium titanium ore bed, destroy its electrical properties, so as to device
It can cause the damage of unrepairable.
The content of the invention
It is an object of the invention to overcome above-mentioned technical deficiency, a kind of bilayer gold for perovskite solar cell is proposed
Belong to electrode and preparation method thereof, the low technology of metal electrode stability for solving perovskite solar cell in the prior art is asked
Topic.
To reach above-mentioned technical purpose, technical scheme provides a kind of bilayer for perovskite solar cell
Metal electrode, including the first metal film layer and the second metallic film for being layed in 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 the double-level-metal electrode for perovskite solar cell, bag
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 cell, it includes 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 set close to the electron transfer layer.
Compared with prior art, the present invention is chemically inert by one layer of the evaporation of cryogenic vacuum on the electron transport layer
First metal film layer, and on the first metal film layer set high conductivity the second metal film layer, it can not reduced
On the basis of electricity conversion, the effective infiltration for isolating moisture simultaneously reduces the chemical attack to the second metal film layer, its
Be conducive to improve the stability of perovskite solar cell.
Brief description of the drawings
Fig. 1 is the structure diagram of the perovskite solar cell of the present invention；
Fig. 2 is the interface SEM photograph and EDS energy spectrum analysis figures of the perovskite solar cell of the embodiment of the present invention 1；
Fig. 3 is density of photocurrent-voltage output characteristics curve pair of the perovskite solar cell 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 thermogravimetric/differential thermal contrast schematic diagram that the perovskite powders of the embodiment of the present invention 4 and different metal mix；
Fig. 6 is the storage efficiency change contrast schematic diagram of the perovskite solar cell of the embodiment of the present invention 5；
Fig. 7 is the light durability contrast schematic diagram of the perovskite solar cell of the embodiment of the present invention 6；
Fig. 8 is density of photocurrent-voltage output characteristics curve pair of the perovskite solar cell of the embodiment of the present invention 7
Compare schematic diagram.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is 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 cell, it is included 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 arranged on the first metal film layer 1 of 7 upper surface of electron transfer layer and is 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 preferably uses described in the present embodiment
Bi metal film layers or Bi alloy firm layers.And second metal film layer 2 can then use Ag, Au, Al, Cu, Ti, Ni or Mo
Metal film layer.
As shown in Figure 1, when preparing perovskite solar cell, electrically conducting transparent electricity can be set in 3 upper surface of substrate of glass
Pole 4, hole transmission layer 5 is set in the upper surface of transparent conductive electrode 4, and sets perovskite in the upper surface of hole transmission layer 5
Film 6, then sets electron transfer layer 7 on 6 surface of perovskite thin film, and above-mentioned preparation method can use existing usual manner system
Make, such as spin coating can be used, the plated film such as scraper for coating or slot coated mode plated film successively；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 layers, during evaporation generally at less than 1000 DEG C, and its vacuum
The vacuum of evaporation is less than 10-3Pa, evaporation rate areAfter the first metal film layer 1 is deposited, then it can use true
The method of sky evaporation 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.
The present embodiment uses the thickness of Bi or its alloy coating as 5~80nm, its form a film fine and close, difficult and water, oxygen and halogenation
Thing 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 cell；Moreover, metal Bi and its alloy low temperature easily evaporate, process is deposited
The thermal decomposition of perovskite solar cell will not be caused, ensures that it plates membrane stability.
Wherein, when the second metal film layer 2 is Ag, Au or Al metal film layer, it uses vacuum deposition method, and very
The vacuum of sky evaporation<10-3Pa, 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 evaporation can cause the thermal decomposition of perovskite thin film, cause the poor performance of corresponding solar cell device.
Therefore these metallic film generally use low-power magnetically controlled sputter methods carry out plated film.In order to avoid damaging perovskite too in sputtering
It is positive can battery performance, operation air pressure during the present embodiment magnetron sputtering plating is 0.1-100Pa, Sputtering power density 1-
100W/cm2, sputtering thickness be 100-2000nm.The Bi metal film layers or Bi alloy firms layer of the present embodiment are as key
Cushion, prevents sputtering Ti, Ni, Mo damage of the high energy plasma to bottom perovskite film when metallic film, in not shadow
The material cost of device is greatly reduced on the premise of ringing device efficiency, is conducive to the industrialization of perovskite solar cell.
The present embodiment has more preferably performance using the perovskite solar cell of double-level-metal electrode for convenience of description,
Now different perovskite thin film and the perovskite solar cells under identical preparation condition are compared and analyzed.
Embodiment 1
As shown in Fig. 2, it is the interface SEM of the perovskite solar cell based on Bi/Ag and Bi/Mo double-level-metal electrodes
Photo and EDS energy spectrum analysis figures, wherein, Fig. 2 a are Bi/Ag double-level-metal electrodes, i.e. the first metal film layer is the Bi of 20nm thickness
Metal layer, the second metal film layer are the Ag metal layers of 150nm thickness；Fig. 2 b are Bi/Mo double-level-metal electrodes, i.e. the first metal foil
Film layer is the Bi metal layers of 20nm thickness, and the second metal film layer is the Mo metal layers of 500nm thickness.
Embodiment 2
Prepare five groups of perovskite solar cells in the same terms, five groups of perovskite solar cells cannot be in
In：First group of individual layer Ag metal electrodes；Second group is double-level-metal electrode, and first layer is Bi metal layers, second layer Ag
Metal layer, Bi metal layer thickness are 10nm；3rd group is double-level-metal electrode, and first layer is Bi metal layers, 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 metals layer, second
Layer is Ag metal layers, and Bi-Sn alloying metals layer thickness is 10nm；5th group is double-level-metal electrode, and first layer closes for Bi-Cu
Gold metal layer, the second layer are Ag metal layers, and Bi-Cu alloying metals layer thickness is 10nm.
Selection area is 1cm2Above-mentioned five groups of perovskite solar cells, and be 100mW/cm in intensity of illumination2Lower acquisition
Its photoelectric conversion efficiency, from the figure 3, it may be seen that first group to the 5th group of electricity conversion is respectively：Standard Ag electrodes, efficiency are
17.53%；10nm Bi and Ag double-level-metal electrodes, efficiency 16.94%；80nm Bi and Ag double-level-metal electrodes, efficiency are
13.21%；10nm Bi-Sn alloys and Ag double-level-metal electrodes, efficiency 18.06%；10nm Bi-Cu alloys and the double-deck gold of Ag
Belong to electrode, efficiency 18.25%.From above-mentioned data, when the thickness of Bi metal layers in double-level-metal electrode is suitable, its energy
It is enough to obtain the electricity conversion similar with standard Ag metal electrodes.
Embodiment 3
Take four groups of halide perovskite (CH3NH3PbI3) film under 35 DEG C, 70% humidity, selects different covering sides
Formula, measures the catabolite (PbI that its chemical breakdown under moisture effect is formed2) quantity, as shown in figure 3, from the bottom to top
For the XRD spectrum of first to Article 8.Wherein, first is：First group of halide perovskite thin film is in standard metal Ag electricity
(its equivalent to do not cover Bi) two days under extremely；Article 2 is：Second group of halide perovskite thin film covers two in Bi metallic films
My god, it equivalent to the first metal film layer is Bi metallic films, the second metal film layer is Ag metal film layers；Article 3 is：
3rd group of halide perovskite thin film covers two days in Bi-Sn metallic films, it is closed equivalent to the first metal film layer for Bi-Sn
Gold thin film, the second metal film layer are Ag metal film layers；Article 4 is：4th group of halide perovskite thin film is in Bi-Cu gold
Belong to film to cover two days, it equivalent to the first metal film layer is Bi-Cu alloy firms, the second metal film layer is Ag metal foils
Film layer；Article 5 is：First group of halide perovskite thin film (its equivalent to do not cover Bi) 30 under standard metal Ag electrodes
My god；Article 6 is：Second group of halide perovskite thin film covers 30 days in Bi metallic films, it is equivalent to the first metallic film
Layer is Bi metallic films, the second metal film layer is Ag metal film layers；7th group is：3rd group of halide perovskite thin film exists
Bi-Sn metallic films cover 30 days, it is Bi-Sn alloy firms, the second metal film layer equivalent to the first metal film layer
For Ag metal film layers；Article 8 is：4th group of halide perovskite thin film covers 30 days in Bi-Cu metallic films, its phase
When be Bi-Cu alloy firms in the first metal film layer, the second metal film layer be Ag metal film layers.
As shown in Figure 4, the protective effect of first group of standard Ag electrode pair perovskites is weaker, 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 alloys
Double-level-metal electrode, can effectively shield moisture, delays the decomposition of perovskite thin film, after aging 30 days, PbI2Diffraction
Peak is still weaker, illustrates perovskite degree of decomposition very little, i.e. protective effect of the Bi and Bi alloys to perovskite thin film is more obvious.
Embodiment 4
By perovskite (CH3NH3PbI3) powder is respectively with Bi, Ag, Al, Cu metal powder with mass ratio 1:1 mixes respectively, and
In room temperature in the range 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 stronger that it illustrates that Bi metals have without chemically reacting between Bi metals and perovskite thin film
Resistance to corrosion, and the metal such as Ag, Al, Cu within 100 DEG C i.e. there are exothermic heat of reaction and mass loss, it illustrates very low
Within the temperature range of, halide perovskite generates chemical attack to above-mentioned metal.
Embodiment 5
Eight groups of perovskite solar cells are prepared in the same terms, the difference of eight groups of perovskite solar cells exists
In：First group is individual layer Al metal electrodes；Second group is individual layer Cu metal electrodes；3rd group is individual layer Ag metal electrodes；4th
Group is double-level-metal electrode, and first layer is Bi metal layers, the second layer is Al metal layers；5th group is double-level-metal electrode, and
First layer is Bi metal layers, the second layer is Cu metal layers；6th group is double-level-metal electrode, and first layer is Bi metal layers, the
Two layers are Ag metal layers；7th group is double-level-metal electrode, and first layer is Bi-Sn alloy-layers, the second layer is Ag metal layers；The
Eight groups are double-level-metal electrode, and first layer is Bi-Cu alloy-layers, the second layer is Ag metal layers.
Above-mentioned eight groups of perovskite solar cells are subjected to long-term efficiency of storage test, test condition is：Unpackaged devices
Dark-state preserves, 50-70% humidity, 25 DEG C of environment temperatures.Test result is as shown in fig. 6, the bilayer based on metal Bi or Bi alloy
The stability of the corresponding perovskite solar cell of metal electrode is substantially more preferable, its stability is electric apparently higher than conventional single layer metal
Pole.
Embodiment 6
Eight groups of perovskite solar cells are prepared in the same terms, the difference of eight groups of perovskite solar cells exists
In：First group is individual layer Al metal electrodes；Second group is individual layer Cu metal electrodes；3rd group is individual layer Ag metal electrodes；4th
Group is double-level-metal electrode, and first layer is Bi metal layers, the second layer is Al metal layers；5th group is double-level-metal electrode, and
First layer is Bi metal layers, the second layer is Cu metal layers；6th group is double-level-metal electrode, and first layer is Bi metal layers, the
Two layers are Ag metal layers；7th group is double-level-metal electrode, and first layer is Bi-Sn alloy-layers, the second layer is Ag metal layers；The
Eight groups are double-level-metal electrode, and first layer is Bi-Cu alloy-layers, the second layer is Ag metal layers.
Above-mentioned eight groups of perovskite solar cells are subjected to light durability test, test condition is：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 in battery most
High-power point continuously detects, and experimental result is as shown in fig. 7, the illumination of the perovskite solar cell based on double-level-metal electrode is steady
Qualitative to be significantly improved, practicality greatly improves.
Embodiment 7
Eight groups of perovskite solar cells are prepared in the same terms, the difference of eight groups of perovskite solar cells exists
In：First group is directly surface magnetic control sputtering forms Ti metal electrodes on the electron transport layer；Second group is directly in electronics biography
Defeated layer upper surface magnetron sputtering forms Ni metal electrodes；3rd group is 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 cushion for first surface on the electron transport layer, and then magnetic control splashes again
Penetrate to form Ti metal electrodes；5th group for first one layer of Bi metal layer is deposited as cushion in surface on the electron transport layer, then
Magnetron sputtering forms Ni metal electrodes 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 electrodes again；7th group is first one layer of Bi-Sn alloy is deposited in surface on the electron transport layer
Layer is used as cushion, and then magnetron sputtering forms Mo metal electrodes again；8th group first surface is deposited one layer on the electron transport layer
Bi-Cu alloy-layers are as cushion, and then magnetron sputtering forms Mo metal electrodes again.
The area of above-mentioned eight groups of perovskite solar cells is arranged to 1cm2, it is produced by optical mask, and at 3A grades
The 100mW/cm of solar simulator2Irradiated under output intensity, measure its photoelectric conversion efficiency.
As shown in figure 8, its " density of photocurrent-voltage " output characteristic curve for eight groups of perovskite solar cells, by
Above-mentioned correlation curve understands that direct magnetron sputtering metal electrode can significantly damage battery, the efficiency of battery it is very low (<4%)；
And Bi the or Bi based alloys of low temperature evaporation are used as cushion, it is possible to prevente effectively from sputter procedure is to perovskite and boundary material
Damage.Base metal Ti, Ni, Mo based on Bi or Bi based alloys and magnetron sputtering etc. form double-level-metal electrode, substitute expensive
Ag or Au, so that the cost of electrode material is greatly reduced while battery efficiency is not lost.Wherein, it is 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 electrodes is 14.05%, based on Bi/
The battery efficiency of Mo double-level-metal electrodes is 15.45%, and the battery efficiency based on Bi-Sn/Mo double-level-metal electrodes is
16.04%, the battery efficiency based on Bi-Sn/Mo double-level-metal electrodes is 16.61%.Realizing the same of high-photoelectric transformation efficiency
When reduce the cost of electrode material, be conducive to industrialization.
The embodiment of present invention described above, is not intended to limit the scope of the present invention..Any basis
The various other corresponding changes and deformation that the technical concept of the present invention is made, should be included in the guarantor of the claims in the present invention
In the range of shield.
Claims (10)
- A kind of 1. double-level-metal electrode for perovskite solar cell, it is characterised 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.
- 2. double-level-metal electrode according to claim 1, it is characterised in that first metal film layer is Bi metal foils Film layer or Bi alloy firm layers.
- 3. double-level-metal electrode according to claim 2, it is characterised in that second metal film layer for Ag, Au, Al, Cu, Ti, Ni or Mo metal film layer.
- 4. the preparation method of a kind of double-level-metal electrode for perovskite solar cell, it is characterised in that including following step Suddenly：(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) one layer of the with high conductivity deposit on the first metal film layer using the method for vacuum evaporation or magnetron sputtering Two metal film layers.
- 5. preparation method according to claim 4, it is characterised in that first metal film layer is Bi metal film layers Or Bi alloy firm layers；Second metal film layer is Ag, Au, Al, Cu, Ti, Ni or Mo metal film layer.
- 6. preparation method according to claim 5, it is characterised in that the vacuum of vacuum evaporation is small in the step (1) In 10-3Pa, evaporation rate areEvaporating temperature is less than 1000 DEG C.
- 7. preparation method according to claim 6, it is characterised in that the thickness of the first metal film layer evaporation for 5~ 80nm。
- 8. preparation method according to claim 5, it is characterised in that when the second metal film layer is Ag, Au or Al metal During film layer, it uses vacuum deposition method, and the vacuum of vacuum evaporation<10-3Pa, evaporation rate areEvaporation Thickness is 50-200nm.
- 9. preparation method according to claim 5, it is characterised in that when the second metal film layer is Cu, Ti, Ni or Mo gold When belonging to film layer, it uses magnetically controlled sputter method, and operation air pressure is 0.1-100Pa, Sputtering power density 1-100W/cm2、 Sputtering thickness is 100-2000nm.
- A kind of 10. perovskite solar cell, it is characterised in that including be cascading from the bottom to top substrate of glass, thoroughly Bright conductive electrode, hole transmission layer, perovskite thin film, electron transfer layer and any double-level-metal electricity of claims 1 to 3 Pole, the first metal film layer of the double-level-metal electrode are set close to the electron transfer layer.
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