CN106025087A - Tandem solar cell and manufacturing method thereof - Google Patents
Tandem solar cell and manufacturing method thereof Download PDFInfo
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- CN106025087A CN106025087A CN201610550655.5A CN201610550655A CN106025087A CN 106025087 A CN106025087 A CN 106025087A CN 201610550655 A CN201610550655 A CN 201610550655A CN 106025087 A CN106025087 A CN 106025087A
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- 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
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- 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
- H10K30/10—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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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Abstract
The invention relates to the field of solar cells, and particularly discloses a tandem solar cell, which comprises a top cell unit of a perovskite cell, a bottom cell unit of a silicon cell and a middle layer located between the top cell unit and the bottom cell unit. The chemical formula for the perovskite material in the perovskite cell is: [(NH2CHNH2)1-a(CH3NH3)a]Pb[I1-xBrx]3 or [(NH2CHNH2)1-bCsb]Pb[I1-xBrx]3, and 0.3</=x</=0.5, 0.3</=a</=0.5 and 0.1</=b</=0.5. According to the above tandem solar cell, band gaps of the top perovskite cell and the bottom silicon cell are matched, the problem of current matching between top and bottom cells can be well solved, and the cell efficiency can be improved. The invention also discloses a method of manufacturing the tandem solar cell.
Description
Technical field
The present invention relates to area of solar cell, particularly relate to a kind of lamination solar cell and preparation method thereof.
Background technology
The Energy distribution of solar spectrum is wider, and a kind of semi-conducting material can only absorb the photon that energy is higher than its edge energy.
The photon that in sunlight, energy is less will transmit through battery and can not be utilized；High-energy photon exceeds the excess energy of energy gap width,
Then calorimetric can release effect and pass to the lattice atoms of battery material itself and make material itself generate heat by photo-generated carrier.These energy
Amount all can not pass to load by photo-generated carrier, becomes effective electric energy.Therefore the theoretical transformation effect of unijunction solar cell
Rate the most relatively low.
Then occurring in that lamination solar cell, it is typically by top battery unit, intermediate layer and the arrowband of broad stopband band gap
End battery three part of band gap stacks gradually and forms.Lamination solar cell can allow the light of short wavelength be pushed up battery unit profit
With, longer wavelengths of light transmission top battery unit is utilized by end battery unit, is become by luminous energy the most to greatest extent
Become electric energy, improve the theoretical conversion efficiencies of solaode.
Laminated cell is prepared in silion cell combination the most ripe to lower-cost perovskite battery and technology it is considered to be one
Plant very promising high-efficiency battery new technique.But the perovskite material used in current perovskite battery all unsuitable for
Form lamination solar cell with silion cell collocation, and then affect the raising of the conversion efficiency of lamination solar cell.
Summary of the invention
Based on this, it is necessary to for the unmatched problem of material in existing lamination solar cell, it is provided that a kind of material
The lamination solar cell of coupling.
A kind of lamination solar cell, including:
Top battery unit, end battery unit and the centre between described top battery unit and battery unit of the described end
Layer；
Described top battery unit is perovskite battery, and battery unit of the described end is silion cell；
The chemical formula of the perovskite material in described perovskite battery is [(NH2CHNH2)1-a(CH3NH3)a]Pb[I1- xBrx]3Or [(NH2CHNH2)1-bCsb]Pb[I1-xBrx]3；
Wherein, 0.3≤x≤0.5,0.3≤a≤0.5,0.1≤b≤0.5.
Above-mentioned lamination solar cell, owing to top battery unit uses mixed-cation and the calcium titanium of mixed halogen ion
Pit wood material, itself and silion cell mate so that laminated cell obtains higher efficiency.
Wherein in an embodiment, the energy gap of described perovskite material is 1.7～1.8eV.
Wherein in an embodiment, described top battery unit includes: photosensitive layer containing described perovskite material, be positioned at
The electron transfer layer of described photosensitive layer side and be positioned at the hole transmission layer of described photosensitive layer opposite side.
Wherein in an embodiment, described electron transfer layer is titanium dioxide dense layer.
Wherein in an embodiment, the material structure formula of described hole transmission layer is as follows:
Wherein in an embodiment, described intermediate layer is transparent conductive film layer.
Wherein in an embodiment, the thickness of described transparent conductive film layer is 100～200nm.
Wherein in an embodiment, described silion cell is hetero-junction silicon battery or two-sided crystal silicon cell.
Present invention also offers the preparation method of a kind of above-mentioned lamination solar cell.
The preparation method of a kind of lamination solar cell, comprises the steps:
Thering is provided end battery unit, battery unit of the described end is silion cell；
Battery unit of the described end is formed intermediate layer；
Forming top battery unit on described intermediate layer, described top battery unit is perovskite battery.
Above-mentioned preparation method, technique is simple, it is easy to preparation large area perovskite-crystalline silicon laminated cell.
Present invention also offers the preparation method of another kind of above-mentioned lamination solar cell.
Thering is provided substrate, described substrate has sacrifice layer；
The sacrifice layer of described substrate is formed intermediate layer and perovskite battery module；
By hydrolysis, described intermediate layer and perovskite battery module are peeled off from described substrate, and transfer to silion cell mould
On block；
Described perovskite battery module forms the first external electrode.
Above-mentioned preparation method, it is adaptable to any kind of silion cell module, and compatible in the silion cell having suede structure
Module.
Accompanying drawing explanation
Fig. 1 is the structural representation of the lamination solar cell of one embodiment of the invention.
Fig. 2 is the structural representation of the lamination solar cell of another embodiment of the present invention.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with detailed description of the invention, right
The present invention is further elaborated.Should be appreciated that detailed description of the invention described herein only in order to explain the present invention,
It is not intended to limit the present invention.
It should be noted that when element is referred to as " being arranged at " another element, and it can be directly on another element
Or element placed in the middle can also be there is.When an element is considered as " connection " another element, and it can be to be directly connected to
To another element or may be simultaneously present centering elements.Term as used herein " vertical ", " level ", " left ",
For illustrative purposes only, being not offered as is unique embodiment for " right " and similar statement.
Unless otherwise defined, all of technology used herein and scientific terminology and the technical field belonging to the present invention
The implication that technical staff is generally understood that is identical.The term used the most in the description of the invention is intended merely to describe tool
The purpose of the embodiment of body, it is not intended that in limiting the present invention.Term as used herein " and/or " include one or more
Arbitrary and all of combination of relevant Listed Items.
Seeing Fig. 1, the lamination solar cell 1000 of one embodiment of the invention, including top battery unit 100, end battery list
Unit 120 and the intermediate layer 300 between top battery unit 100 and end battery unit 200.Specifically, top battery unit 100
For perovskite battery；It is to say, top battery unit 100 is to utilize perovskite material absorb photon and produce electron hole pair.
End battery unit 200 is silion cell；It is to say, end battery unit 200 is to utilize silica-base material absorb photon and produce electronics
Hole pair.
Wherein, top battery unit 100 includes photosensitive layer 110, is sequentially located at photosensitive layer 110 side (upside in Fig. 1)
Hole transmission layer (Hole Transport Layer, HTL) 120, protective layer the 130, first transparent conductive film layer 140, first
External electrode 150 and be positioned at photosensitive layer 110 opposite side (downside in Fig. 1) electron transfer layer (Electron Transport
Layer, ETL) 160.
In the battery unit 100 of top, photosensitive layer 110 is the core layer of top battery unit 100.Containing calcium in photosensitive layer 110
Titanium ore material, perovskite material can produce electron hole pair after absorbing photon.In the present embodiment, photosensitive layer 110 is
The semiconductive thin film that perovskite material is formed.It is highly preferred that photosensitive layer 110 is formed by chemical spray method.It will of course be understood that
, photosensitive layer 110 can also is that the meso-hole structure that perovskite material is filled.
The formula of the perovskite material of the present invention is A Pb [I1-xBrx]3；Wherein, A is selected from [(NH2CHNH2)1-a
(CH3NH3)a] or [(NH2CHNH2)1-bCsb]；Specifically, perovskite material is selected from [(NH2CHNH2)1-a(CH3NH3)a]Pb[I1- xBrx]3, or [(CH3NH3)1-bCsb]Pb[I1-xBrx]3；Wherein, 0.3≤x≤0.5,0.3≤a≤0.5,0.1≤b≤0.5.
So energy gap of perovskite material is easily controlled in 1.7～1.8eV scopes, and stable to illumination, is difficult to
There is crystal transition, and Heat stability is good.
The energy gap of the perovskite material of the present invention is preferably 1.7～1.8eV.So can make as top battery unit
The energy gap of silicon of the energy gap of photosensitive layer 110 and the silion cell as end battery unit 200 in the perovskite battery of 100
Match, and then make the currents match of top battery unit 100 and end battery unit 200, thus improve laminate solar further
The current efficiency of battery 1000.
In the battery unit 100 of top, the Main Function of hole transmission layer 120 is, photosensitive layer 110 produces hole separation and leads
Go out.In the present embodiment, the structural formula of hole transmission layer 120 material is as follows:
Above-mentioned hole mobile material its there is special molecular structure so that it is and the interface of photosensitive layer 110 more mates, and then
The open-circuit voltage making top battery unit 100 increases.The more important thing is, this only spiro-OMeTAD of the synthesis of above-mentioned material
1/5, it is also possible to effectively reduce the cost of lamination solar cell.
Preferably, the thickness of hole transmission layer 120 is 150～190nm.So can ensure that efficiently separating of hole, with
Time reduce the hole transmission layer 120 absorption to light.
Preferably, hole transmission layer 120 is formed by chemical spray method.
It is, of course, understood that the material of hole transmission layer 120 can also is that Spiro-OMeTAD (2,2', 7,7'-
Four [N, N-bis-(4-methoxyphenyl) amino]-9,9'-spiral shell two fluorenes), can also be PEDOT:PSS or non-stoichiometric
Nickel oxide etc..
Wherein, protective layer 130 Main Function is that protection hole transmission layer 120 is not damaged in subsequent fabrication process.
In the present embodiment, protective layer 130 is the molybdenum oxide of non-stoichiometric.It is, of course, understood that protective layer
130 tungsten oxides etc. that can also is that non-stoichiometric.
Preferably, the thickness of protective layer 130 is 8～12nm.So it is easy to control its dead resistance.
Preferably, protective layer 130 is formed by thermal evaporation.
In the battery unit 100 of top, the Main Function of the first transparency conducting layer 140 is to collect transmission carrier, in this reality
Executing in example, the first transparent conductive film layer 140 is ITO, it is, of course, understood that the first transparent conductive film layer 140 also may be used
To be FTO, ZTO, AZO, IWO etc..In the present embodiment, the first transparent conductive film layer 140 is by physical vaporous deposition shape
Become.
In the battery unit 100 of top, the first external electrode 150 is as the external electricity of whole lamination solar cell 1000
Pole.In the present embodiment, the first external electrode 150 is silver grating line electrode.It is, of course, understood that the first external electrode 150
Can also is that copper gate line electrode.First external electrode 150 can use thermal evaporation process or silk-screen printing technique to be formed.
In the battery unit 100 of top, the Main Function of electron transfer layer 160 is by being electrically separated that photosensitive layer 110 produces
Derive.In the present embodiment, electron transfer layer 160 is titanium dioxide dense layer.It is, of course, understood that electron transfer layer
160 can also is that ZnO, SnO etc..
Preferably, the thickness of electron transfer layer 160 is 300～400nm.So can ensure that efficiently separating of electronics, with
Time reduce dead resistance.
In top battery unit 100 in the present embodiment, top battery unit 100 is injected in sunlight upside from Fig. 1, photosensitive
Layer 110 absorbs the short wavelength light in sunlight, produces electronics and hole simultaneously, and electronics is derived by electron transfer layer 160, and hole leads to
Cross hole transmission layer 120 and derive and be finally transmitted to the first transparent conductive film layer 140 and the first electrode 150, thus produce light
Raw voltage, produces photoelectric current after connecting external circuit.
End battery unit 200 in the present invention can be one side solaode, can also be double-sided solar battery.Excellent
Choosing uses double-sided solar battery, so can improve end battery unit 200 further and absorb the utilization of light.
Specifically, end battery unit 200 includes crystal silicon chip 210, is positioned at side (upper in Fig. 1 of crystal silicon chip 210
Side) the first diffusing, doping layer 220, the first insulating passivation layer 230 being positioned on the first diffusing, doping layer 220 and run through
The point electrode 240 that one insulating passivation layer 230 connects with the first diffusing, doping layer 220；It is positioned at opposite side (Fig. 1 of crystal silicon chip 210
In downside) the second diffusing, doping layer 260, the second insulating passivation layer 270 of being positioned on the second diffusing, doping layer 260；And
Second electrode 280.
Wherein, in the present embodiment, crystal silicon chip 210 is N-type, and the first diffusing, doping layer 220 is p-type, and the second diffusion is mixed
Diamicton 260 is N+Type.It is, of course, understood that be not limited to above-mentioned form, in end battery unit 200, it is also possible to be
Crystal silicon chip 210 is p-type, and accordingly, the first diffusing, doping layer 220 is N-type, and the second diffusing, doping layer 260 is P+Type；It is simultaneously
Ensureing the most consistent with top battery unit 100, the first diffusing, doping layer 220 is positioned at crystal silicon chip 210 away from pushing up battery unit
The side of 100, the second diffusing, doping layer 260 is positioned at the crystal silicon chip 210 side near top battery unit 100.
In the present embodiment, crystal silicon chip 210 uses N-type crystalline silicon sheet (n-c-Si), can make the property of end battery unit 200
Can be more superior, it is possible to overcome the photic decay of battery using p-type, it addition, the density at its high efficiency composition center is far below P
Type so that carrier has higher life-span and diffusion length.Specifically, crystalline silicon can be monocrystal silicon or polysilicon.More
Body ground, the crystal silicon chip 210 of present embodiment is n type single crystal silicon sheet.
Specifically, the thickness of crystal silicon chip 210 is generally less than 200 μm.Preferably, the thickness of crystal silicon chip 210 be 100～
200μm.The most both can save the use of silicon materials, and then reduce cost；Technology stability can be improved again.
Preferably, the surface of crystal silicon chip 210 is matte；It is to say, crystalline silicon is carried out making herbs into wool.So can reduce
The reflection of battery surface so that more photon can be absorbed by crystal silicon chip 210.In the present embodiment, matte is pyramid
Shape matte, is so more beneficial for light and slants the inside of crystal silicon chip 210, reduce the reflectance of the light of battery surface, make
Obtaining light path and become big, the number of photons quantitative change of absorption is many.
Wherein, the first insulating passivation layer 230 primarily serve effective antireflective and passivation.
The Main Function of the second insulating passivation layer 270 is, suppression carrier being combined at battery surface, can also increase simultaneously
Reflection to long wave, plays the effect of back reflector, increases the absorption to long wave.
First insulating passivation layer 230 and the second insulating passivation layer 270 are laminated construction, generally SiO2/SiNxOr
Al2O3/SiNxLaminated construction.
Owing to the first insulating passivation layer 230 and the second insulating passivation layer 270 insulate, therefore at the first insulating passivation layer
230 and second offer through hole on insulating passivation layer 270, fill conductive materials in through hole, thus by the electricity of PN junction
Conductance goes out.In the present embodiment, point electrode 240 connects with the first diffusing, doping layer 220；The upper end of the second electrode 280 is directly filled out
Fill in the through hole on the second insulating passivation layer 270, make the second electrode 280 connect with the second diffusing, doping layer 260.
Specifically, the material of point electrode 240 is silver, it is, of course, understood that point electrode 240 can also be copper, nickel
Deng.
It will of course be understood that be, it is also possible to be not provided with second diffusing, doping layer the 260, second insulating passivation layer
270。
In the present invention, the Main Function in intermediate layer 300 is to be electrically connected top battery unit 100 and end battery unit
200。
In the present embodiment, intermediate layer 300 is the second transparent conductive film layer (TCO).TCO is as intermediate layer in employing, its
Have and tie higher electric conductivity than tunnel, can effectively reduce the series resistance between top battery unit and end battery unit, and
The loss of extra electric leakage and cell active area will not be increased, lamination solar cell in hgher efficiency.
In the present embodiment, intermediate layer 300 is ITO, and its photoelectric properties are excellent, mature preparation process.It will of course be understood that
, intermediate layer can also is that other transparent conductive oxide, such as FTO, ZTO, AZO, IWO etc..
Preferably, the thickness in intermediate layer is 100～200nm.So can ensure that intermediate layer has relatively low square resistance
And reduce the intermediate layer absorption to light.
It is, of course, understood that the intermediate layer 300 of the present invention can also is that tunnel is tied.Tunnel knot can use ability
Structure well known to field technique personnel and material, do not repeat them here！
Above-mentioned lamination solar cell, owing to top battery unit uses mixed-cation and the calcium titanium of mixed halogen ion
Pit wood material, itself and silion cell mate so that lamination solar cell obtains higher efficiency.
See the structural representation of the lamination solar cell that Fig. 2, Fig. 2 are another embodiment of the present invention.In the present embodiment
Lamination solar cell 2000 and the lamination solar cell 1000 in a upper embodiment, its top battery unit 100 is with middle
Layer 300 is identical, does not repeats them here！With a upper embodiment except that, end battery unit 400 be heterojunction solar electricity
Pond.
Specifically, end battery unit 400 includes: crystal silicon chip 410, is sequentially located at the side of crystal silicon chip 410 (in Fig. 1
Upside) on first intrinsic layer the 420, first doped amorphous silicon layer 430；And it is sequentially located at the opposite side of crystal silicon chip 410
Second intrinsic layer the 460, second doped amorphous silicon layer the 470, the 3rd transparent conductive film layer 480 and second of (downside in Fig. 1)
Electrode 490.
In the present embodiment, end battery unit 400 the most symmetrically structure, so can reduce thermal stress in production process
And the thinning development of mechanical stress, the most beneficially crystal silicon chip 410.Generated energy is made to increase it addition, two sides all can absorb light
Add.
In the present embodiment, crystal silicon chip 410 and the first doped amorphous silicon layer 430 constitute PN junction.Crystal silicon chip 410 and
Two doped amorphous silicon layers 470 compositions add highfield (being also back of the body electric field).End battery list can be improved further by adding highfield
The open-circuit voltage of unit 400.Highfield is added, say, that do not set the second doping amorphous it is, of course, understood that can not also set
Silicon layer 470.
In the present embodiment, crystal silicon chip 410 is N-type crystalline silicon sheet (n-c-Si), accordingly, the first doped amorphous silicon layer
430 is P-type non-crystalline silicon layer (p-a-Si), and the second doped amorphous silicon layer 470 is N-type non-crystalline silicon layer (n-a-Si).Of course, it is possible to reason
Solve is, it is not limited to above-mentioned form, in end battery unit 400, it is also possible to be crystal silicon chip 410 be p-type, accordingly,
First doped amorphous silicon layer 430 is N-type, and the second doped amorphous silicon layer 470 is p-type；Simultaneously the most consistent in order to ensure, first mixes
Miscellaneous amorphous silicon layer 430 is positioned at the crystal silicon chip 410 side away from top battery unit 100, and the second doped amorphous silicon layer 470 is positioned at crystalline substance
Body silicon chip 410 is near the side of top battery unit 100.
In the present embodiment, crystal silicon chip 410 uses N-type crystalline silicon sheet (n-c-Si), can make the property of end battery unit 400
Can be more superior, it is possible to overcome the photic decay of battery using p-type, it addition, the density at its high efficiency composition center is far below P
Type so that carrier has higher life-span and diffusion length.Specifically, crystalline silicon can be monocrystal silicon or polysilicon.More
Body ground, the crystal silicon chip 410 of present embodiment is n type single crystal silicon sheet.
Specifically, the thickness of crystal silicon chip 410 is generally less than 200 μm.Preferably, the thickness of crystal silicon chip 410 be 100～
200μm.The most both can save the use of silicon materials, and then reduce cost；Technology stability can be improved again.
Preferably, the surface of crystal silicon chip 410 is matte；It is to say, crystalline silicon is carried out making herbs into wool.So can reduce
The reflection of battery surface so that more photon can be absorbed by crystal silicon chip 410.In the present embodiment, matte is pyramid
Shape matte, is so more beneficial for light and slants the inside of crystal silicon chip 410, reduce the reflectance of the light of battery surface, make
Obtaining light path and become big, the number of photons quantitative change of absorption is many.
Wherein, the Main Function of the first intrinsic layer 420 is, is used for being passivated crystal silicon chip 410, makes crystal silicon chip 410 and
The interface of one doped amorphous silicon layer 430 obtains purification, and then makes the open-circuit voltage of end battery unit 400 increase.
Usually, the thickness of the first intrinsic layer 420 is not more than 10nm, preferably 5～10nm.So can be so that end battery
Unit 400 has higher open-circuit voltage, reduces the absorption to light of first intrinsic layer 420 simultaneously, reduces cell resistance simultaneously, carry
High fill factor.In the present embodiment, the first intrinsic layer 420 is intrinsic hydrogenated non-crystalline silicon.
Second intrinsic layer 460 is similar with the first intrinsic layer 420.The Main Function of the second intrinsic layer 460 is to be used for being passivated crystalline substance
Body silicon chip 410, makes the interface of crystal silicon chip 410 and the second doped amorphous silicon layer 470 obtain purification, and then makes end battery unit
The open-circuit voltage of 400 increases.
In the case of usually, the thickness of the second intrinsic layer 460 is also not more than 10nm, preferably 5～10nm.The most permissible
Make end battery unit 400 have higher open-circuit voltage, reduce the absorption to light of second intrinsic layer 460 simultaneously, reduce electricity simultaneously
Pond resistance, improves fill factor, curve factor.In the present embodiment, the second intrinsic layer 460 is intrinsic hydrogenated non-crystalline silicon.
In the present embodiment, the second electrode 490 is silver grating line electrode.It is, of course, understood that the second electrode also may be used
To be copper grid line.
Wherein, the effect of the 3rd transparent conductive film layer 480 is, improves the second doped amorphous silicon layer 470 and the second electrode
490 electric conductivities, increase the collection of carrier effectively.
3rd transparent conductive film layer 480 is tungsten-doped indium oxide (IWO) layer.Tungsten-doped indium oxide (IWO) layer has potential
High carrier mobility characteristic, in the case of ensureing identical electrical conductivity, compared with ITO layer, IWO layer has relatively low carrier
Concentration, therefore has less Carriers Absorption and bigger plasma wavelength, and then IWO layer has high saturating in near-infrared region
Light rate and low absorptivity.Certainly, transparent conductive film layer 480 can also is that tin indium oxide (ITO) layer, also or fluorine oxide stannum
(FTO) layer.
Preferably, the thickness of the 3rd transparent conductive film layer 480 is 60～100nm.So its electric property and optical
Can be more excellent.
Present invention also offers the preparation method of a kind of above-mentioned lamination solar cell.
The preparation method of a kind of lamination solar cell, comprises the steps:
Thering is provided end battery unit, battery unit of the described end is silion cell；
Battery unit of the described end is formed intermediate layer；
Forming top battery unit on described intermediate layer, described top battery unit is perovskite battery.
The preparation of the silion cell of end battery unit, can use method known in those skilled in the art, at this no longer
Repeat.In order to ensure the quality of forming film of photosensitive layer in perovskite battery, without suede structure in the preferred silion cell of this preparation method.
Wherein, intermediate layer uses the mode of deposition to be formed, and specifically, uses PVD physical vapour deposition (PVD) or RPD activity etc.
Plasma deposition.
Wherein, the formation of perovskite battery forms each layer of perovskite battery using intermediate layer as substrate.Art technology
Personnel select suitable each layer preparation method according to practical situation, do not repeat them here.
Present invention also offers the preparation method of another above-mentioned lamination solar cell.
The preparation method of a kind of lamination solar cell, it comprises the steps:
S1, offer substrate, substrate has sacrifice layer.
Specifically, substrate includes substrate and is formed at suprabasil sacrifice layer；Preferably, substrate also includes being positioned at sacrificial
Transition zone between domestic animal layer and substrate.
Preferably, substrate is formed in the following way: at grown above silicon silicon dioxide, then deposited by electron beam evaporation or heat
Hydatogenesis metal；Metal and SiO in deposition process2Reaction generates metal silicide or metal-oxide, thus is formed sacrificial
Domestic animal layer.It is to say, the material of substrate is silicon, the material of transition zone is silicon dioxide, and the material of sacrifice layer is metal and SiO2
Reaction generates metal silicide or metal-oxide.Wherein it is preferred to, metal is selected from Ni, Cu or Ti.In the present embodiment, gold
Belong to for Ni.
The thickness of growth silicon dioxide is not particularly limited by the present invention.In the present embodiment, the growth of silicon dioxide is thick
Degree is 300nm.
Preferably, the deposit thickness of metal is 3～10nm.The most both can save sedimentation time, can have been formed again good
Sacrifice layer.In the present embodiment, the deposit thickness of metal is 3nm.
The substrate of the present invention is reusable.When reusing, only need to deposit metal re-forms sacrifice layer.
S2, on the sacrifice layer of substrate, form intermediate layer and perovskite battery module.
Wherein, intermediate layer is preferably transparent conductive film layer.Preferably, intermediate layer use PVD physical vapour deposition (PVD) or
RPD plasma active deposits.In the present embodiment, being made as of intermediate layer: RPD deposits ITO on sacrifice layer.
Wherein, perovskite battery module herein refers to push up the part not including the first external electrode in battery unit.In
The concrete steps forming perovskite battery module on interbed include:
Sequentially form electron transfer layer, photosensitive layer, hole transmission layer, protective layer and the first electrically conducting transparent on the intermediate layer
Thin layer.
Preferably, concretely comprising the following steps of perovskite battery module is formed on the intermediate layer: spraying metatitanic acid is different on the intermediate layer
Propyl ester solution, then sinters 30min at 500 DEG C, forms TiO2Dense film (i.e. electron transfer layer).At TiO2Dense film
Upper chemical spray or thermal evaporation form perovskite thin film (i.e. photosensitive layer).On perovskite thin film, chemical spray forms hole transport
Layer, then thermal evaporation forms the molybdenum oxide MoO of non-stoichiometricx(i.e. protective layer), finally deposits the first transparent conductive film
Layer.
It is, of course, understood that the forming step of perovskite battery module of the present invention is not limited to above-mentioned form, this
Skilled person can make the appropriate adjustments according to practical situation.
S3, by hydrolysis, intermediate layer and perovskite battery module are peeled off from substrate, and transfer in silion cell module.
In order to protect perovskite battery module not by Hydrolysis, it is preferable that before hydrolysis, at perovskite battery module
Upper formation transparent watertight protective layer.
It is highly preferred that transparent watertight protective layer uses ProTeK, transparent watertight protective layer is formed by the way of spraying.
Shift for convenience, preferably employ heat release adhesive tape when transfer as transfer vector.Specifically, transparent in formation
Heat release adhesive tape is pasted on the perovskite battery module of fish tail and waterproof layer.It is, of course, understood that have at heat release adhesive tape
In the case of water-proof function, it is also possible to do not include the step forming transparent waterproof layer.
Preferably, before hydrolysis, heat is discharged adhesive tape sticking on transparent watertight protective layer.So easily facilitate hydrolysis
Operation.
Wherein, hydrolysis operation is substrate and perovskite battery module entirety to be immersed in the water, and water penetrates into sacrificial from both sides
Domestic animal layer, in sacrifice layer, silicide or the oxide of metal hydrolyze with water, thus sacrifice layer dissolves, and intermediate layer is divided with substrate
From, i.e. realize perovskite battery module and peel off from substrate.
Wherein, the silion cell module of the present embodiment specifically includes: crystal silicon chip, is sequentially located on the side of crystal silicon chip
First intrinsic layer, the first doped amorphous silicon layer, the 3rd transparent conductive film layer；And be sequentially located at the opposite side of crystal silicon chip
Second intrinsic layer, the second doped amorphous silicon layer, the 4th transparent conductive film layer and the second electrode.
It is, of course, understood that silion cell module and preparation method thereof is all not particularly limited by the present invention, this area
Technical staff can according to practical situation select suitable silion cell module with and preparation method thereof.
Wherein, concretely comprising the following steps of transfer: with heat release adhesive tape for supporting, perovskite battery module is passed through electrically conducting transparent
Binding agent is pasted onto in silion cell module.
Preferably, in advance at end face spraying Polyglycolic acid fibre (PEDOT, the Poly (3,4-of silion cell module
Ethylenedioxythiophene)), then perovskite battery module is bonded in silion cell module.It is understood that
Electrically conducting transparent binding agent can also is that other electrically conducting transparent macromolecular materials.
After transfer is complete, heating heat release adhesive tape, heat is discharged adhesive tape and peels off from the end face of perovskite battery module.
S5, form the first external electrode at the end face of perovskite battery module 100.
Preferably, the first external electrode can be formed by silk-screen or thermal evaporation.
It is, of course, understood that step S5 can also be before step S3, the most before hydrolysis, perovskite is being formed
It is next formed into the first external electrode after battery module, the most directly forms top battery unit.
The preparation method of above-mentioned lamination solar cell, uses and prepares perovskite battery on present substrate, then by calcium titanium
Ore deposit battery is stripped out, and transfers in silion cell module, forms the lamination solar cell of integration.The preparation of top end battery
Separately, the most unaffected, thus add the material selectivity of each functional layer in battery and the selectivity of processing technology, and
And can also the suede structure of compatible silion cell.
Each technical characteristic of above-described embodiment can combine arbitrarily, for making description succinct, not to above-described embodiment
In all possible combination of each technical characteristic be all described, but, as long as there is not lance in the combination of these technical characteristics
Shield, is all considered to be the scope that this specification is recorded.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that, come for those of ordinary skill in the art
Saying, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a lamination solar cell, it is characterised in that including: push up battery unit, end battery unit and be positioned at described top
Intermediate layer between battery unit and battery unit of the described end；
Described top battery unit is perovskite battery, and battery unit of the described end is silion cell；
The chemical formula of the perovskite material in described perovskite battery is [(NH2CHNH2)1-a(CH3NH3)a]Pb[I1-xBrx]3Or
[(NH2CHNH2)1-bCsb]Pb[I1-xBrx]3；
Wherein, 0.3≤x≤0.5,0.3≤a≤0.5,0.1≤b≤0.5.
Lamination solar cell the most according to claim 1, it is characterised in that the energy gap of described perovskite material is
1.7～1.8eV.
Lamination solar cell the most according to claim 1, it is characterised in that described top battery unit includes: containing
Photosensitive layer, the electron transfer layer being positioned at described photosensitive layer side of stating perovskite material and be positioned at described photosensitive layer opposite side
Hole transmission layer.
Lamination solar cell the most according to claim 3, it is characterised in that described electron transfer layer is that titanium dioxide causes
Close layer.
Lamination solar cell the most according to claim 3, it is characterised in that the material structure formula of described hole transmission layer
As follows:
Lamination solar cell the most according to claim 1, it is characterised in that described intermediate layer is transparent conductive film
Layer.
Lamination solar cell the most according to claim 6, it is characterised in that the thickness of described transparent conductive film layer is
100～200nm.
Lamination solar cell the most according to claim 1, it is characterised in that described silion cell be hetero-junction silicon battery or
Two-sided crystal silicon cell.
9. the preparation method of the lamination solar cell described in a claim 1, it is characterised in that comprise the steps:
Thering is provided end battery unit, battery unit of the described end is silion cell；
Battery unit of the described end is formed intermediate layer；
Forming top battery unit on described intermediate layer, described top battery unit is perovskite battery.
10. the preparation method of the lamination solar cell described in a claim 1, it is characterised in that comprise the steps:
Thering is provided substrate, described substrate has sacrifice layer；
The sacrifice layer of described substrate is formed intermediate layer and perovskite battery module；
By hydrolysis, described intermediate layer and perovskite battery module are peeled off from described substrate, and transfer to silion cell module
On；
Described perovskite battery module forms the first external electrode.
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| CN111244210A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Flexible perovskite/microcrystalline silicon laminated solar cell and manufacturing method thereof |
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| CN113193002A (en) * | 2021-04-08 | 2021-07-30 | 电子科技大学 | Perovskite/silicon laminated solar cell and preparation method thereof |
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