CN106684248B - It is a kind of adjust solar battery absorbing wavelength method and preparation solar battery - Google Patents
It is a kind of adjust solar battery absorbing wavelength method and preparation solar battery Download PDFInfo
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- CN106684248B CN106684248B CN201710182201.1A CN201710182201A CN106684248B CN 106684248 B CN106684248 B CN 106684248B CN 201710182201 A CN201710182201 A CN 201710182201A CN 106684248 B CN106684248 B CN 106684248B
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- 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
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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Abstract
The present invention provides a kind of method for adjusting solar battery absorbing wavelength and the solar batteries of preparation.The method of the adjusting solar battery absorbing wavelength makes marmem that preset automatic deformation occur the following steps are included: marmem is attached in base batteries (flexible perovskite solar battery) (2) by (1) by changing temperature, to drive the light-absorption layer of base batteries to generate deformation, to realize the adjusting to solar battery absorbing wavelength.Scheme provided by the invention creatively utilizes the shape memory effect and super-elasticity of marmem, automatically adjusts to the forbidden bandwidth of solar battery, to change the functional characteristics such as solar battery optics, electricity, stability.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a method of adjust solar battery absorbing wavelength
And the solar battery of preparation.
Background technique
With the sustainable growth of our times industrial expansion and population, global energy requirements also increase sharply therewith, renewable
The related development of clean energy resource is utilized and is had been to be concerned by more and more people.In recent years, solar battery is as a kind of renewable clear
The energy conversion devices of the clean energy, are gradually approved.
Perovskite is as a kind of novel light-sensitive material, due to at low cost, preparation is simple, photo absorption performance is excellent and electronics
The series of advantages such as mobility height received more and more extensive concern since 2009.With new material and new knot
Structure introduces application, and the photoelectric current transfer efficiency of perovskite solar battery is constantly promoted, and has risen to 22.1% from 3.8%,
Efficiency is tentatively suitable with commercialized silicon solar cell.
But the wave-length coverage of sunlight be 300nm-1400nm, perovskite light-sensitive material due to its forbidden bandwidth limit,
Its usual wavelength absorption range is 400nm-800nm, is concentrated mainly on visible-range, it is seen then that perovskite solar battery pair
The utilization efficiency of luminous energy is unsatisfactory.In order to improve such case, researcher is actively seeking various solutions.
The physics such as electricity, optics, magnetics, the catalysis of material and chemical characteristic, technology are adjusted to change atomic distance
Personnel generally use the elastic strain engineering that material is realized in the methods of lattice misfit or doping.For example, logical in semiconductor field
Crossing lattice misfit can make carrier mobility in silicon improve 50%, Pt-Cu binary alloy nanoparticle since is produced from lattice misfit
Its catalytic activity, TiO can be improved in raw strain2Material provides internal stress etc. by other element dopings and improves catalytic activity.
But these methods prepare difficulty mostly, with high costs, deflection is smaller and is difficult to control, therefore limits in practical application
Factor is more, it is also difficult to obtain commercialized popularization and application in terms of improving perovskite solar cell properties.
Summary of the invention
To solve the above problems, the purpose of the present invention is to provide a kind of methods for adjusting solar battery absorbing wavelength.
It is a further object of the present invention to provide a kind of solar batteries of adjustable absorbing wavelength.
It is yet another object of the invention to provide the preparation methods of the solar battery of above-mentioned adjustable absorbing wavelength.
In order to achieve the above objectives, the present invention provides a kind of method for adjusting solar battery absorbing wavelength, this method packets
Include following steps:
Marmem is attached in base batteries, the base batteries are flexible perovskite solar battery；
Make marmem that preset automatic deformation occur by changing temperature, to drive the light-absorption layer of base batteries to produce
Raw deformation, to realize the adjusting to solar battery absorbing wavelength.
Scheme provided by the invention creatively utilizes the shape memory effect and super-elasticity of marmem, to the sun
The forbidden bandwidth of energy battery automatically adjusts.This is the creative spy that elastic strain engineering is applied in area of solar cell
Rope also provides a kind of new approaches and new method for the functionalization improvement of shape memory alloy film material.
In the method for above-mentioned adjusting solar battery absorbing wavelength, it is preferable that the marmem is before attachment
Deformation is passed through and memory processing completes deformation setting；Alternatively, the marmem is to be attached to base batteries
Afterwards, then by deformation and memory it handles, completes deformation setting.
In the method for above-mentioned adjusting solar battery absorbing wavelength, it is preferable that the marmem is attached to soft
Property perovskite solar battery to electrode layer.
The present invention also provides a kind of solar batteries of adjustable absorbing wavelength, wherein the solar battery includes base
Plinth battery and marmem, at least one side of the base batteries are attached with the suction that can directly or indirectly drive base batteries
The marmem of photosphere generation deformation；The base batteries are flexible perovskite solar battery.
In the solar battery of above-mentioned adjustable absorbing wavelength, " attachment " is not meant to that marmem must be with
Perovskite solar battery carries out directly contact and fixes, and carries out indirectly contact fixation by auxiliary layer or supplementary structure and all may be used
With.In addition, auxiliary layer can be the material layer for increasing the two bonding or fixing intensity.
In the solar battery of above-mentioned adjustable absorbing wavelength, since flexible perovskite solar battery itself has one
Fixed extension/shrinkage, therefore being substantially all can be suitable for the present invention.Preferably scheme is perovskite solar battery
Each layer preferably select the preferable material of extension/shrinkage, can be especially adapted with the deformation range of marmem
Material.Control for temperature can use pure natural way (day and night temperature), can also manually be adjusted when necessary certainly
Control.
In the solar battery of above-mentioned adjustable absorbing wavelength, it is preferable that the marmem is round trip shape
Memorial alloy；Further preferably Ti-Ni based alloy.It is highly preferred that the Ti-Ni based alloy includes TiNi alloy, TiNiFe
Alloy, TiNiNb alloy, TiNiCu alloy or TiNiPd alloy.The phase transition temperature of marmem is preferably moderate, avoids meeting
Stability and service life to solar battery bring adverse effect.
In the solar battery of above-mentioned adjustable absorbing wavelength, it is preferable that the memorial alloy has preset 2%-
10% tensile deformation amount shrinks deformation quantity.The deformation quantity of this range is that most of flexible perovskite solar batteries can
The range of receiving, and forbidden bandwidth can efficiently be adjusted.
In the solar battery of above-mentioned adjustable absorbing wavelength, it is preferable that the marmem is attached to flexibility
Perovskite solar battery to electrode layer；Described is non-metal electrode to electrode layer.It is further preferred that the nonmetallic electricity
Pole includes Graphene electrodes；The Graphene electrodes are metal-doped Graphene electrodes；The doping metals are Au or Pt.More
Preferably, in the metal-doped Graphene electrodes, the doping of metal is 1-3at%.By metal-doped graphene electricity
Pole as perovskite solar battery to electrode in use, compared with metal electrode, have the advantage that and guaranteeing to electrode
In the case where conductive capability, the cost of material can be substantially reduced, while increasing the flexibility of perovskite solar battery again, because
This, perovskite solar battery of being more convenient for combines closely with marmem and generates Compression and Expansion deformation.
In the solar battery of above-mentioned adjustable absorbing wavelength, it is preferable that the flexibility perovskite solar battery packet
Include basal layer, conductive layer, electron transfer layer, perovskite light-absorption layer, hole transmission layer and to electrode layer.Provided by the invention one
In kind preferred embodiment, the basal layer is PET material, and the conductive layer is ITO material, and the electron transfer layer is densification
TiO2Material, the perovskite light-absorption layer are CH3NH3PbCl3Material, the hole transmission layer are Spiro-OMeTAD material, institute
Stating to electrode layer is metal-doped grapheme material.
The present invention separately provides the preparation method of the solar battery of above-mentioned adjustable absorbing wavelength, wherein this method is
Using magnetron sputtering deposition method on the predetermined patterns of base batteries depositing shape memory alloy material；Then shape memory is closed
Gold carries out deformation and memory processing, to obtain the solar battery of adjustable absorbing wavelength.
In the preparation method of the solar battery of above-mentioned adjustable absorbing wavelength, it is preferable that described to be closed to shape memory
Gold deformed and remember processing specifically includes the following steps:
(1) shape memory alloy tensile is handled under heating environment, marmem is made to reach the first deformation quantity, this
State is first state by marmem memory；At this point, base batteries also produce under the drive of marmem
Raw corresponding tensile deformation, and obtain stretching strain；
(2) cooling processing is carried out to the marmem in first state, acts on marmem in phase transformation
Under be contracted to the second deformation quantity, this state by marmem memory be the second state；At this point, base batteries are in shape memory
It is also generated under the drive of alloy and shrinks deformation, and obtain compressive strain.
In the preparation method of the solar battery of above-mentioned adjustable absorbing wavelength, it is preferable that by above-mentioned steps (1) to step
Suddenly the operation of (2) repeats 2-10 times.
In the preparation method of the solar battery of above-mentioned adjustable absorbing wavelength, it is preferable that at the cooling in step (2)
The temperature of reason is to be down to room temperature.
In a kind of preferred embodiment provided by the invention, passes through following steps and prepare flexible perovskite solar battery
(basal layer PET, conductive layer ITO, electron transfer layer are densification TiO2, perovskite light-absorption layer is CH3NH3PbCl3, hole passes
Defeated layer is Spiro-OMeTAD):
(1) PET/ITO substrate acetone, isopropanol, deionized water are cleaned, is passed through in inert gas dry；
(2) depositing Ti O2Ti target is put into magnetic control sputtering deposition device growth room when film, keeps target and PET/ITO
The distance of substrate is 4.5cm, and growth room's vacuum degree is evacuated to 10-3Pa is hereinafter, be passed through Ar, O in growth room2Gas, Ar/O2Gas stream
For amount than being maintained at 100:15, it is 0.001-100Pa that control, which grows indoor pressure,；Unlatching sputter, sputtering power 200W,
By depositing Ti O on pretreated step (1) resulting conductive layer2Electron transfer layer is made in film；
(3) by CH3NH3Cl and PbCl2Uniformly mixing, is placed in above-mentioned steps (2) resulting electron transfer layer using spin coating
On, 150 DEG C of heat preservation 20min are heated to, perovskite light-absorption layer is made；
(4) Spiro-OMeTAD is spun on the resulting perovskite light-absorption layer of step (3), revolving speed 4500rpm, duration
1min；
(5) one layer of HAuCl is uniformly smeared on copper foil4(or H2PtCl6), then copper foil is put into tube furnace, is used
CVD method prepares Au (or Pt) monatomic doped graphene；
(6) Au (or Pt) monatomic doped graphene in (5) is transferred to step (4) institute using PMMA liquid phase transfer method
On the perovskite light-absorption layer obtained, it is made to electrode layer.
In a kind of preferred embodiment provided by the invention, marmem is attached to flexibility by following steps
Perovskite solar battery to electrode layer:
(1) according to Ni:Ti:X=a:a:(100%-2a) atomic ratio, X be doped chemical (Cu, Fe, Nb, Pd etc.), choosing
Take cast alloy (Ф 100mm × 4mm) as target；For the ingredient for controlling film, suitable pure Ti is added to supplement on target surface
Ti in film；
(2) sputtered film is carried out after surface particle cleans；The major parameter of sputtering process: Ar operating air pressure is 5 × 10- 1Pa；Sputtering voltage is 3000V；Sputtering power is 300W；The flexible perovskite electricity for being deposited with shape memory alloy film is made
Pond.
In a kind of preferred embodiment provided by the invention, by following steps to marmem carry out deformation and
Memory processing:
(1) marmem deposited in flexible perovskite solar battery substrate is heated to 60 DEG C, by shape
Memory alloy tensile 2%-10%, at this point, the dynamic flexible perovskite solar battery of Shape memory alloy strip generates stretching strain；
(2) it is subsequently decreased to room temperature, 2%-10% has been shunk since marmem is undergone phase transition, has realized shape memory
Alloy drives flexible perovskite solar battery compressive strain；
(3) after repeatedly carrying out above-mentioned steps (1) to the operation of step (2), flexible perovskite solar battery can be
Under Shape memory alloy strip is dynamic, autonomous stretching strain is generated at 60 DEG C, temperature generates autonomous compressive strain after being reduced to room temperature, is made
The solar battery A of adjustable absorbing wavelength.
By taking the solar battery A of above-mentioned adjustable absorbing wavelength as an example, when under daylight, sunlight irradiation temperature is high, so that
Marmem independently stretches the flexible perovskite solar battery of drive and stretches, and spacing of lattice increases, and forbidden bandwidth reduces, and increases
Add the wavelength and absorption efficiency of absorbable light；Exactly the opposite when being in night, the dynamic flexible perovskite of Shape memory alloy strip is too
Positive energy battery is shunk, and spacing of lattice reduces, while squeezing out internal water and air, keeps the stability of battery.
The present invention utilizes marmem by adhering to marmem on flexible perovskite solar battery
Shape memory effect and super-elasticity realize shape memory alloy film by the methods of pre-processing to shape memory alloy film
Large deformation, realize film is generated in different temperatures drawing or compressive strain, and then adjusting perovskite solar battery forbidden band
Width, to change various functional characteristics such as optics, electricity, stability.And this strain regime can be different
Stable presence under the conditions of temperature, effect is obvious, and method is simple.
Detailed description of the invention
Fig. 1 is the stress-strain curve diagram of NiTi film in embodiment 1；
Fig. 2 is that embodiment 1 is unprocessed bent with the light absorption for the perovskite solar battery crossed by NiTi alloy treatment
Line comparison diagram.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
A kind of solar battery of adjustable absorbing wavelength is present embodiments provided, which can rely on NiTi alloy firm
To realize the adjusting of perovskite solar battery absorbing wavelength, specific preparation process are as follows:
1, flexible perovskite solar battery is prepared
(1) PET/ITO substrate acetone, isopropanol, deionized water are cleaned, is passed through in inert gas dry；
(2) depositing Ti O2Ti target is put into magnetic control sputtering deposition device growth room when film, keeps target and PET/ITO
The distance of substrate is 4.5cm, and growth room's vacuum degree is evacuated to 10-3Pa is hereinafter, be passed through Ar, O in growth room2Gas, Ar/O2Gas stream
For amount than being maintained at 100:15, it is 0.001Pa that control, which grows indoor pressure,；Sputter is opened, sputtering power 200W is passing through
Depositing Ti O on the resulting ITO conductive layer of pretreated step (1)2Electron transfer layer is made in film；
(3) by CH3NH3Cl and PbCl2Uniformly mixing, is placed in above-mentioned steps (2) resulting electron transfer layer using spin coating
On, 150 DEG C of heat preservation 20min are heated to, perovskite light-absorption layer is made；
(4) Spiro-OMeTAD is spun on the resulting perovskite light-absorption layer of step (3), revolving speed 4500rpm, duration
1min；
(5) one layer of H is uniformly smeared on copper foil2PtCl6, then copper foil is put into tube furnace, is prepared using CVD method
The monatomic 1at% doped graphene of Pt；
(6) the monatomic doped graphene of Pt in (5) is transferred to step (4) resulting calcium using PMMA liquid phase transfer method
On titanium ore light-absorption layer, it is made to electrode layer；Complete the preparation of flexible perovskite solar battery.
2, by marmem be attached to flexible perovskite solar battery to electrode layer
(1) it according to the atomic ratio of Ni:Ti=50:50, chooses cast alloy (Ф 100mm × 4mm) and is used as target；For control
The ingredient of film adds suitable pure Ti on target surface to supplement the Ti in film；
(2) sputtered film is carried out after surface particle cleans；The major parameter of sputtering process: Ar operating air pressure is 5 × 10- 1Pa；Sputtering voltage is 3000V；Sputtering power is 300W；The flexible perovskite battery for being deposited with TiNi alloy film is made.
3, deformation is carried out to marmem and memory is handled
(1) TiNi alloy deposited in flexible perovskite solar battery substrate is heated to 60 DEG C, by TiNi alloy
8% or so are stretched, at this point, TiNi alloy drives flexible perovskite solar battery to generate stretching strain；
(2) it is subsequently decreased to room temperature, has shunk 8% or so since TiNi alloy is undergone phase transition, realizes TiNi alloy drive
Flexible perovskite solar battery compressive strain；
(3) after repeatedly carrying out above-mentioned steps (1) to the operation of step (2), flexible perovskite solar battery can be
Under TiNi alloy drives, autonomous stretching strain is generated at 60 DEG C, temperature generates autonomous compressive strain after being reduced to room temperature, is made adjustable
Save the solar battery of absorbing wavelength.
Performance test:
The solar battery that absorbing wavelength is adjusted made from the present embodiment is tested, stress-strain diagram is as schemed
Shown in 1.
By the solar battery that absorbing wavelength is adjusted made from the present embodiment with prepare under identical growth conditions
NiTi film and perovskite solar battery are put into methylene blue solution, find: not having after being irradiated 3 hours with fluorescent light source
The perovskite solar battery conversion ratio of NiTi film is 9.4%, and the perovskite battery thin film after the covering training of NiTi film
Conversion ratio is 15%；Finding that the optical energy gap of film is changed by 1.88eV by uv-visible absorption spectra is 1.62eV.
The absorption curves comparison of the two is as shown in Figure 2.It is can be found that by comparison: untreated perovskite solar battery, 7
Efficient output can not be just provided in the future；And the perovskite solar battery of NiTi alloy is covered, it can still be protected after 14 days
15% conversion ratio is held, stability is fine.
Embodiment 2
A kind of solar battery of adjustable absorbing wavelength is present embodiments provided, which can be thin by NiTiNb alloy
Film realizes the adjusting of perovskite solar battery absorbing wavelength, specific preparation process are as follows:
1, flexible perovskite solar battery is prepared
(1) PET/ITO substrate acetone, isopropanol, deionized water are cleaned, is passed through in inert gas dry；
(2) depositing Ti O2Ti target is put into magnetic control sputtering deposition device growth room when film, keeps target and PET/ITO
The distance of substrate is 4.5cm, and growth room's vacuum degree is evacuated to 10-3Pa is hereinafter, be passed through Ar, O in growth room2Gas, Ar/O2Gas stream
For amount than being maintained at 100:15, it is 0.01Pa that control, which grows indoor pressure,；Sputter is opened, sputtering power 200W is passing through
Depositing Ti O on the resulting ITO conductive layer of pretreated step (1)2Electron transfer layer is made in film；
(3) by CH3NH3Cl and PbCl2Uniformly mixing, is placed in above-mentioned steps (2) resulting electron transfer layer using spin coating
On, 150 DEG C of heat preservation 20min are heated to, perovskite light-absorption layer is made；
(4) Spiro-OMeTAD is spun on the resulting perovskite light-absorption layer of step (3), revolving speed 4500rpm, duration
1min；
(5) one layer of H is uniformly smeared on copper foil2PtCl6, then copper foil is put into tube furnace, is prepared using CVD method
The monatomic 3at% doped graphene of Pt；
(6) the monatomic doped graphene of Pt in (5) is transferred to step (4) resulting calcium using PMMA liquid phase transfer method
On titanium ore light-absorption layer, it is made to electrode layer；Complete the preparation of flexible perovskite solar battery.
2, by marmem be attached to flexible perovskite solar battery to electrode layer
(1) it according to the atomic ratio of Ni:Ti:Nb=45:45:10, chooses cast alloy (Ф 100mm × 4mm) and is used as target；
For the ingredient for controlling film, suitable pure Ti is added to supplement the Ti in film on target surface；
(2) sputtered film is carried out after surface particle cleans；The major parameter of sputtering process: Ar operating air pressure is 5 × 10- 1Pa；Sputtering voltage is 3000V；Sputtering power is 300W；The flexible perovskite battery for being deposited with NiTiNb alloy firm is made.
3, deformation is carried out to marmem and memory is handled
(1) the NiTiNb alloy deposited in flexible perovskite solar battery substrate is heated to 60 DEG C, by NiTiNb
Alloy tensile 2% or so, at this point, NiTiNb alloy drives flexible perovskite solar battery to generate stretching strain；
(2) it is subsequently decreased to room temperature, 2% or so has been shunk since NiTiNb alloy is undergone phase transition, has realized NiTiNb alloy
Drive flexible perovskite solar battery compressive strain；
(3) after repeatedly carrying out above-mentioned steps (1) to the operation of step (2), flexible perovskite solar battery can be
Under NiTiNb alloy drives, autonomous stretching strain is generated at 60 DEG C, temperature generates autonomous compressive strain after being reduced to room temperature, and being made can
Adjust the solar battery of absorbing wavelength.
Embodiment 3
A kind of solar battery of adjustable absorbing wavelength is present embodiments provided, which can be thin by NiTiFe alloy
Film realizes the adjusting of perovskite solar battery absorbing wavelength, specific preparation process are as follows:
1, flexible perovskite solar battery is prepared
(1) PET/ITO substrate acetone, isopropanol, deionized water are cleaned, is passed through in inert gas dry；
(2) depositing Ti O2Ti target is put into magnetic control sputtering deposition device growth room when film, keeps target and PET/ITO
The distance of substrate is 4.5cm, and growth room's vacuum degree is evacuated to 10-3Pa is hereinafter, be passed through Ar, O in growth room2Gas, Ar/O2Gas stream
For amount than being maintained at 100:15, it is 0.1Pa that control, which grows indoor pressure,；Open sputter, sputtering power 200W, by pre-
Depositing Ti O on the step of processing (1) resulting ITO conductive layer2Electron transfer layer is made in film；
(3) by CH3NH3Cl and PbCl2Uniformly mixing, is placed in above-mentioned steps (2) resulting electron transfer layer using spin coating
On, 150 DEG C of heat preservation 20min are heated to, perovskite light-absorption layer is made；
(4) Spiro-OMeTAD is spun on the resulting perovskite light-absorption layer of step (3), revolving speed 4500rpm, duration
1min；
(5) one layer of H is uniformly smeared on copper foil2PtCl6, then copper foil is put into tube furnace, is prepared using CVD method
The monatomic 2at% doped graphene of Pt；
(6) the monatomic doped graphene of Pt in (5) is transferred to step (4) resulting calcium using PMMA liquid phase transfer method
On titanium ore light-absorption layer, it is made to electrode layer；Complete the preparation of flexible perovskite solar battery.
2, by marmem be attached to flexible perovskite solar battery to electrode layer
(1) it according to the atomic ratio of Ni:Ti:Fe=47:47:6, chooses cast alloy (Ф 100mm × 4mm) and is used as target；
For the ingredient for controlling film, suitable pure Ti is added to supplement the Ti in film on target surface；
(2) sputtered film is carried out after surface particle cleans；The major parameter of sputtering process: Ar operating air pressure is 5 × 10- 1Pa；Sputtering voltage is 3000V；Sputtering power is 300W；The flexible perovskite battery for being deposited with NiTiFe alloy firm is made.
3, deformation is carried out to marmem and memory is handled
(1) the NiTiFe alloy deposited in flexible perovskite solar battery substrate is heated to 60 DEG C, by NiTiFe
Alloy tensile 5% or so, at this point, NiTiFe alloy drives flexible perovskite solar battery to generate stretching strain；
(2) it is subsequently decreased to room temperature, 5% or so has been shunk since NiTiFe alloy is undergone phase transition, has realized NiTiFe alloy
Drive flexible perovskite solar battery compressive strain；
(3) after repeatedly carrying out above-mentioned steps (1) to the operation of step (2), flexible perovskite solar battery can be
Under NiTiFe alloy drives, autonomous stretching strain is generated at 60 DEG C, temperature generates autonomous compressive strain after being reduced to room temperature, and being made can
Adjust the solar battery of absorbing wavelength.
Embodiment 4
A kind of solar battery of adjustable absorbing wavelength is present embodiments provided, which can be thin by NiTiCu alloy
Film realizes the adjusting of perovskite solar battery absorbing wavelength, specific preparation process are as follows:
1, flexible perovskite solar battery is prepared
(1) PET/ITO substrate acetone, isopropanol, deionized water are cleaned, is passed through in inert gas dry；
(2) depositing Ti O2Ti target is put into magnetic control sputtering deposition device growth room when film, keeps target and PET/ITO
The distance of substrate is 4.5cm, and growth room's vacuum degree is evacuated to 10-3Pa is hereinafter, be passed through Ar, O in growth room2Gas, Ar/O2Gas stream
For amount than being maintained at 100:15, it is 10Pa that control, which grows indoor pressure,；Open sputter, sputtering power 200W, by pre-
Depositing Ti O on the step of processing (1) resulting ITO conductive layer2Electron transfer layer is made in film；
(3) by CH3NH3Cl and PbCl2Uniformly mixing, is placed in above-mentioned steps (2) resulting electron transfer layer using spin coating
On, 150 DEG C of heat preservation 20min are heated to, perovskite light-absorption layer is made；
(4) Spiro-OMeTAD is spun on the resulting perovskite light-absorption layer of step (3), revolving speed 4500rpm, duration
1min；
(5) one layer of HAuCl is uniformly smeared on copper foil4, then copper foil is put into tube furnace, is prepared using CVD method
The monatomic 1at% doped graphene of Au；
(6) the monatomic doped graphene of Au in (5) is transferred to step (4) resulting calcium using PMMA liquid phase transfer method
On titanium ore light-absorption layer, it is made to electrode layer；Complete the preparation of flexible perovskite solar battery.
2, by marmem be attached to flexible perovskite solar battery to electrode layer
(1) it according to the atomic ratio of Ni:Ti:Cu=45:45:10, chooses cast alloy (Ф 100mm × 4mm) and is used as target；
For the ingredient for controlling film, suitable pure Ti is added to supplement the Ti in film on target surface；
(2) sputtered film is carried out after surface particle cleans；The major parameter of sputtering process: Ar operating air pressure is 5 × 10- 1Pa；Sputtering voltage is 3000V；Sputtering power is 300W；The flexible perovskite battery for being deposited with NiTiCu alloy firm is made.
3, deformation is carried out to marmem and memory is handled
(1) the NiTiCu alloy deposited in flexible perovskite solar battery substrate is heated to 60 DEG C, by NiTiCu
Alloy tensile 2% or so, at this point, NiTiCu alloy drives flexible perovskite solar battery to generate stretching strain；
(2) it is subsequently decreased to room temperature, 2% or so has been shunk since NiTiCu alloy is undergone phase transition, has realized NiTiCu alloy
Drive flexible perovskite solar battery compressive strain；
(3) after repeatedly carrying out above-mentioned steps (1) to the operation of step (2), flexible perovskite solar battery can be
Under NiTiCu alloy drives, autonomous stretching strain is generated at 60 DEG C, temperature generates autonomous compressive strain after being reduced to room temperature, and being made can
Adjust the solar battery of absorbing wavelength.
Embodiment 5
A kind of solar battery of adjustable absorbing wavelength is present embodiments provided, which can be thin by NiTiPd alloy
Film realizes the adjusting of perovskite solar battery absorbing wavelength, specific preparation process are as follows:
1, flexible perovskite solar battery is prepared
(1) PET/ITO substrate acetone, isopropanol, deionized water are cleaned, is passed through in inert gas dry；
(2) depositing Ti O2Ti target is put into magnetic control sputtering deposition device growth room when film, keeps target and PET/ITO
The distance of substrate is 4.5cm, and growth room's vacuum degree is evacuated to 10-3Pa is hereinafter, be passed through Ar, O in growth room2Gas, Ar/O2Gas stream
For amount than being maintained at 100:15, it is 100Pa that control, which grows indoor pressure,；Open sputter, sputtering power 200W, by pre-
Depositing Ti O on the step of processing (1) resulting ITO conductive layer2Electron transfer layer is made in film；
(3) by CH3NH3Cl and PbCl2Uniformly mixing, is placed in above-mentioned steps (2) resulting electron transfer layer using spin coating
On, 150 DEG C of heat preservation 20min are heated to, perovskite light-absorption layer is made；
(4) Spiro-OMeTAD is spun on the resulting perovskite light-absorption layer of step (3), revolving speed 4500rpm, duration
1min；
(5) one layer of HAuCl is uniformly smeared on copper foil4, then copper foil is put into tube furnace, is prepared using CVD method
The monatomic 3at% doped graphene of Au；
(6) the monatomic doped graphene of Au in (5) is transferred to step (4) resulting calcium using PMMA liquid phase transfer method
On titanium ore light-absorption layer, it is made to electrode layer；Complete the preparation of flexible perovskite solar battery.
2, by marmem be attached to flexible perovskite solar battery to electrode layer
(1) it according to the atomic ratio of Ni:Ti:Cu=45:45:10, chooses cast alloy (Ф 100mm × 4mm) and is used as target；
For the ingredient for controlling film, suitable pure Ti is added to supplement the Ti in film on target surface；
(2) sputtered film is carried out after surface particle cleans；The major parameter of sputtering process: Ar operating air pressure is 5 × 10- 1Pa；Sputtering voltage is 3000V；Sputtering power is 300W；The flexible perovskite battery for being deposited with NiTiCu alloy firm is made.
3, deformation is carried out to marmem and memory is handled
(1) the NiTiPd alloy deposited in flexible perovskite solar battery substrate is heated to 60 DEG C, by NiTiPd
Alloy tensile 10% or so, at this point, NiTiPd alloy drives flexible perovskite solar battery to generate stretching strain；
(2) it is subsequently decreased to room temperature, 10% or so has been shunk since NiTiPd alloy is undergone phase transition, has realized NiTiPd alloy
Drive flexible perovskite solar battery compressive strain；
(3) after repeatedly carrying out above-mentioned steps (1) to the operation of step (2), flexible perovskite solar battery can be
Under NiTiPd alloy drives, autonomous stretching strain is generated at 60 DEG C, temperature generates autonomous compressive strain after being reduced to room temperature, and being made can
Adjust the solar battery of absorbing wavelength.
Claims (18)
1. a kind of method for adjusting solar battery absorbing wavelength, which is characterized in that method includes the following steps:
Marmem is attached in base batteries, the base batteries are flexible perovskite solar battery；
Make marmem that preset automatic deformation occur by changing temperature, to drive the light-absorption layer of base batteries to generate shape
Become, to realize the adjusting to solar battery absorbing wavelength.
2. the method according to claim 1 for adjusting solar battery absorbing wavelength, which is characterized in that the shape memory
Alloy has passed through deformation before attachment and memory processing completes deformation setting；Alternatively,
The marmem is handled after being attached to base batteries, then through deformation and memory, and deformation setting is completed.
3. the method according to claim 1 or 2 for adjusting solar battery absorbing wavelength, which is characterized in that the shape
Memorial alloy be attached to flexible perovskite solar battery to electrode layer.
4. a kind of solar battery of adjustable absorbing wavelength, which is characterized in that the solar battery includes base batteries and shape
Shape memory alloys,
At least one side of the base batteries is attached with the shape that can directly or indirectly drive the light-absorption layer of base batteries to generate deformation
Shape memory alloys；
The base batteries are flexible perovskite solar battery.
5. the solar battery of adjustable absorbing wavelength according to claim 4, which is characterized in that the shape memory closes
Gold is two-way shape memory alloy.
6. the solar battery of adjustable absorbing wavelength according to claim 5, which is characterized in that the round trip shape note
Recalling alloy includes Ti-Ni based alloy.
7. the solar battery of adjustable absorbing wavelength according to claim 6, which is characterized in that the Ti-Ni base closes
Gold includes TiNi alloy, TiNiFe alloy, TiNiNb alloy, TiNiCu alloy or TiNiPd alloy.
8. the solar battery of adjustable absorbing wavelength according to claim 4, which is characterized in that the memorial alloy tool
There is the tensile deformation amount of preset 2%-10% or shrinks deformation quantity.
9. the solar battery of adjustable absorbing wavelength according to claim 4, which is characterized in that the shape memory closes
Gold be attached to flexible perovskite solar battery to electrode layer；Described is to have malleable non-metal electrode to electrode layer.
10. the solar battery of adjustable absorbing wavelength according to claim 9, which is characterized in that the nonmetallic electricity
Pole includes Graphene electrodes.
11. the solar battery of adjustable absorbing wavelength according to claim 10, which is characterized in that the graphene electricity
Extremely metal-doped Graphene electrodes；The doping metals are Au or Pt.
12. the solar battery of adjustable absorbing wavelength according to claim 11, which is characterized in that described metal-doped
Graphene electrodes in, the doping of metal is 1-3at%.
13. according to the solar battery of the described in any item adjustable absorbing wavelengths of claim 4-12, which is characterized in that described
Flexible perovskite solar battery includes basal layer, conductive layer, electron transfer layer, perovskite light-absorption layer, hole transmission layer and right
Electrode layer.
14. the solar battery of adjustable absorbing wavelength according to claim 13, which is characterized in that the basal layer is
PET material, the conductive layer are ITO material, and the electron transfer layer is densification TiO2Material, the perovskite light-absorption layer are
CH3NH3PbCl3Material, the hole transmission layer are Spiro-OMeTAD material, and described is metal-doped graphite to electrode layer
Alkene material.
15. the preparation method of the solar battery of the described in any item adjustable absorbing wavelengths of claim 4-14, feature exist
In this method is using magnetron sputtering deposition method depositing shape memory alloy material on the predetermined patterns of base batteries；Then
Deformation and memory processing are carried out to marmem, to obtain the solar battery of adjustable absorbing wavelength.
16. the preparation method of solar battery according to claim 15, which is characterized in that described to marmem
Deformed and remember processing specifically includes the following steps:
(1) shape memory alloy tensile is handled under heating environment, marmem is made to reach the first deformation quantity, this state
It is first state by marmem memory；At this point, base batteries also generate phase under the drive of marmem
The tensile deformation answered, and obtain stretching strain；
(2) cooling processing is carried out to the marmem in first state, receives marmem under phase transformation effect
It is reduced to the second deformation quantity, this state is the second state by marmem memory；At this point, base batteries are in marmem
Drive under also generate and shrink deformation, and obtain compressive strain.
17. the preparation method of solar battery according to claim 16, which is characterized in that by above-mentioned steps (1) to step
Suddenly the operation of (2) repeats 2-10 times.
18. the preparation method of solar battery according to claim 16, which is characterized in that at the cooling in step (2)
The temperature of reason is to be down to room temperature.
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