CN109841742A - A kind of high stability perovskite solar battery for using graphene as conductive electrode - Google Patents
A kind of high stability perovskite solar battery for using graphene as conductive electrode Download PDFInfo
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- CN109841742A CN109841742A CN201910244457.XA CN201910244457A CN109841742A CN 109841742 A CN109841742 A CN 109841742A CN 201910244457 A CN201910244457 A CN 201910244457A CN 109841742 A CN109841742 A CN 109841742A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000010409 thin film Substances 0.000 claims abstract description 24
- 239000010408 film Substances 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 229910003460 diamond Inorganic materials 0.000 claims description 10
- 239000010432 diamond Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002114 nanocomposite Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- -1 oxygen Graphite alkene Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses use graphene as the high stability perovskite solar battery of conductive electrode, the solar battery structure is from the bottom up successively are as follows: transparent conductive substrate, local heavily doped region, composite conductive thin film layer and metal electrode, the part heavily doped region is directly contacted with the composite conductive thin film layer and metal electrode, and the composite conductive thin film layer is by local heavily doped region and the high stability perovskite solar battery composite unit structure of linking into an integrated entity of metal electrode；The composite conductive thin film layer includes: N-type perovskite thin film, p-type graphene film and p-type silver nanoparticle laminated film.The present invention improves the stability of perovskite solar battery, extends perovskite solar battery service life, increases photoelectric conversion efficiency, meets actual operation requirements.
Description
Technical field
The present invention relates to the high stability perovskite solar batteries that conductive electrode is used as with graphene, belong to new energy
Technical field.
Background technique
Ca-Ti ore type solar battery (perovskite solar cells) is the organic metal halogen using Ca-Ti ore type
Solar battery of the compound semiconductor as light absorbent belongs to third generation solar cell, also referred to as new concept solar-electricity
Pond.Perovskite crystal is ABX3 structure, generally cube or octahedral structure.In perovskite crystal, A ion be located at cube
The center of structure cell is surrounded by 12 X ions into coordination cuboctahedron, ligancy 12；B ion is located at the angle of cubic cell
Top is surrounded, ligancy 6 octahedra at coordination by 6 X ions, as shown in the figure, wherein A ion and X ionic radius are close, altogether
Isomorphism is at cubic closest packing.
Graphene is to be currently known most thin (monoatomic layer thickness about 0.34nm), most hard nano material (Young's modulus
1TPa, inherent strength 130GPa) be almost it is fully transparent, only absorb 2.3% light, thermal coefficient is up to 5300W/m K, room
Warm electron mobility is greater than 15000cm2/Vs, and resistivity is only 10-6 Ω cm, is the smallest material of current resistivity.Together
When, graphene possesses high air-tightness, and any gas cannot be completely through.And since its resistivity is extremely low, electronics is moved
It moves speed to be exceedingly fast, be very suitable to for making solar battery.According to the atomic structure of graphene, carbon atom is formed by six sides
Shape gap only allows radius to be that the atom of 0.032nm size passes through, and size atom more the smallest than radius (hydrogen: 0.079nm) is also
It is small, therefore graphene film has unique impermeability.Since noble metal nano compound particle is in optics, electricity and biology etc.
All there is potential application prospects in field, so becoming to the research of metal nano compound particle, mesh is previous to induce one to infuse very much
Purpose research field.The high-termal conductivity and electric conductivity and higher surface-active and catalytic performance of nano silver composite material, make
Nano silver composite material is widely paid close attention in recent years.With deepening continuously for domestic and international correlative study in recent years, calcium titanium
The incident photon-to-electron conversion efficiency of mine solar battery is continuously improved.Although perovskite solar battery current situation is good, if having
Dry key factor constrains the development of perovskite solar battery, and wherein the factor of most critical is exactly the stability problem of battery,
Perovskite solar battery easily causes calcium titanium ore bed to decompose because of the entrance of water oxygen in an atmosphere, its photoelectric conversion is caused to imitate
Rate deep fades, seeking the stable perovskite solar battery of performance is always that researcher pursues a goal.For this reason, it may be necessary to set
It counts corresponding technical solution and gives and solve.
Summary of the invention
The present invention be directed to the shortcomings of the prior art, provide a kind of high stable that conductive electrode is used as with graphene
Property perovskite solar battery, improve perovskite solar battery stability, extend perovskite solar battery service life,
Increase photoelectric conversion efficiency, meets actual operation requirements.
To solve the above problems, the technical solution used in the present invention is as follows:
A kind of high stability perovskite solar battery for using graphene as conductive electrode, the solar battery structure
From the bottom up successively are as follows: transparent conductive substrate, local heavily doped region, composite conductive thin film layer and metal electrode, the part weight
Doped region is directly contacted with the composite conductive thin film layer and metal electrode, and the composite conductive thin film layer is by local heavily doped region
And the high stability perovskite solar battery composite unit structure of linking into an integrated entity of metal electrode；
The composite conductive thin film layer includes: N-type perovskite thin film, p-type graphene film and p-type silver nanoparticle THIN COMPOSITE
Film.
As an improvement of the above technical solution, the transparent conductive substrate is FTO electro-conductive glass or ITO electro-conductive glass or has
Machine flexible and transparent conductive plastics or graphene oxide.
As an improvement of the above technical solution, the metal electrode is positive-negative-positive structure, i.e., the described metal electrode is to contain graphite
The metal electrode of alkene and argentum nano composite material.
As an improvement of the above technical solution, the local heavily doped region is to be arranged using array pattern, pattern one
Dimension, two-dimentional geometric figure or one-dimensional and combination or diamond lattic structure of two-dimentional geometric figure；One-dimensional geometric figure is selected from: line segment,
Phantom line segments, camber line or grid line shape；Two-dimentional geometric figure is selected from: circle, ellipse, spindle, annular, polygon, polygonal or
It is fan-shaped.
As an improvement of the above technical solution, the line width of the one-dimensional geometric figure be 30~100um, length be 0.05~
1.5mm；Be 0.5~2mm with linear spacing two neighboring in a line, in same row two neighboring linear spacing be 0.5~
2mm。
As an improvement of the above technical solution, the size of the two-dimentional geometric figure is 30~200um, two neighboring figure
Shape center is away from for 0.8~2mm.
As an improvement of the above technical solution, the diamond lattic structure includes integrally formed table top, bizet, waistline, pavilion portion
And bottom surface, the diamond lattic structure are tetrahedral structure, there are four angles, four faces for each tetrahedron, and each face is triangle
Shape.
Compared with prior art, implementation result of the invention is as follows by the present invention:
This programme is using the unique impervious and unique guiding performance of argentum nano composite material of graphene film, by itself and calcium
Titanium ore film constitutes the positive-negative-positive structure of solar battery, both can effectively stop under high temperature metal electrode to the nocuousness of calcium titanium ore bed
Diffusion, and can effectively prevent the water oxygen in air and enter calcium titanium ore bed making its decomposition, to substantially increase perovskite solar energy
The water oxygen stability and thermal stability of battery, extend its service life；In addition, and graphene and argentum nano composite material have
At low cost, high conductivity, the advantages such as high transparency and good illumination thermal stability greatly improve perovskite solar battery
Output power and photoelectric conversion efficiency.
Detailed description of the invention
Fig. 1 is that the high stability perovskite solar battery structure of the present invention for using graphene as conductive electrode shows
It is intended to；
Fig. 2 is for dotted local heavy doping distribution schematic diagram；
Fig. 3 is for line segment shape part heavy doping distribution schematic diagram；
Fig. 4 is for diamond lattic structure schematic diagram.
Specific embodiment
Illustrate the contents of the present invention below in conjunction with specific embodiments.
It is as shown in Figures 1 to 4: for the high stability perovskite sun of the present invention for using graphene as conductive electrode
It can battery structure schematic diagram.
The high stability perovskite solar battery of the present invention that graphene is used as conductive electrode, the solar energy
Battery structure is from the bottom up successively are as follows: transparent conductive substrate 1, local heavily doped region 2, composite conductive thin film layer and metal electrode 4,
Local heavily doped region 2 is directly contacted with composite conductive thin film layer and metal electrode 4, and composite conductive thin film layer is by local heavily doped region
2 and 4 linking into an integrated entity of metal electrode high stability perovskite solar battery composite unit structure；The composite conductive thin film
Layer includes: N-type perovskite thin film 31, p-type graphene film 32 and p-type silver nanoparticle laminated film 33.Preparation method is as follows: first
First, one piece of clean FTO Conducting Glass is taken, FTO Conducting Glass is cleaned using sonochemistry, utilizes liquid phase one
P-type graphene film 32 is deposited on the heavily doped region of footwork part；Then, using chemical vapour deposition technique in p-type graphene film
Deposited n-type perovskite thin film 31 on 32, then p-type silver nanoparticle laminated film 33 is deposited on N-type perovskite thin film 31；Finally, adopting
With silk screen print method on composite conductive thin film and layer FTO Conducting Glass deposit metal electrodes, obtain required calcium
Titanium ore thin-film solar cells.This programme utilizes the unique impervious and unique guiding of argentum nano composite material of graphene film
Property, itself and perovskite thin film are constituted to the positive-negative-positive structure of solar battery, both can effectively stop under high temperature metal electrode to calcium titanium
Harmful diffusion of ore bed, and can effectively prevent the water oxygen in air and enter calcium titanium ore bed making its decomposition, to substantially increase calcium
The water oxygen stability and thermal stability of titanium ore solar battery, extend its service life；In addition, and graphene and silver nanoparticle it is multiple
Condensation material has at low cost, high conductivity, and the advantages such as high transparency and good illumination thermal stability greatly improve perovskite
The output power and photoelectric conversion efficiency of solar battery.
It is further improved ground, the transparent conductive substrate 1 is that FTO electro-conductive glass or ITO electro-conductive glass or organic flexible are saturating
Bright conductive plastics or graphene oxide；The metal electrode 4 is positive-negative-positive structure, i.e., metal electrode 4 is to contain graphene and silver nanoparticle
The metal electrode of composite material.
Specifically, as shown in Figures 2 and 3: local heavily doped region 2 is to be arranged using array pattern, and pattern is one-dimensional, two-dimentional
Geometric figure or one-dimensional and combination or diamond lattic structure 5 of two-dimentional geometric figure；One-dimensional geometric figure is selected from: line segment, phantom line segments,
Camber line or grid line shape；Two-dimentional geometric figure is selected from: circle, ellipse, spindle, annular, polygon, polygonal or sector；One
The line width for tieing up geometric figure is 30~100um, and length is 0.05~1.5mm；It is 0.5 with linear spacing two neighboring in a line
~2mm, two neighboring linear spacing is 0.5~2mm in same row；The size of the two-dimentional geometric figure is 30~
200um, two neighboring centre of figure is away from for 0.8~2mm.
Wherein, the operation of local heavily doped region is as follows:
(1) method for using ion implanting is distinguished in the n type single crystal silicon piece front by surface-texturing processing with the back side
Form the uniform diffusion layer of 90 Ω/ and 50 Ω/；
(2) front and the back side of chemical cleaning silicon wafer；
(3) aluminium oxide of 25nm or so and the silicon nitride of 80nm or so are successively deposited in front side of silicon wafer；
(4) silica of 25nm or so and the silicon nitride of 80nm or so are successively deposited in silicon chip back side；
(5) boron doped agent is sprayed respectively with containing phosphorus dopant in front and the back side, spraying figure is spotted array, individually
The diameter of point is 100um, and spacing between points is 1.5mm；
(6) PULSE HEATING is carried out to dopant by figure described in step (5) using laser, make positive boron atom with
The phosphorus atoms at the back side penetrate antireflective coating and passivating film and spread to silicon substrate, form spotted array at front and the back side of silicon wafer
Local heavily doped region；
(7) ITO nesa coating of 150nm is prepared at front and the back side using sputtering method respectively, the transparent conductive film with
The silicon substrate in heavily doped area directly contacts, and the local heavily doped region that spotted array is distributed is connected to become perovskite solar-electricity
The conductive composition body in pond front and rear electrode.
More specifically, as shown in Figure 4: diamond lattic structure 5 includes integrally formed table top 51, bizet 52, waistline 53, pavilion portion
54 and bottom surface 55, diamond lattic structure 5 is tetrahedral structure, and there are four angles, four faces for each tetrahedron, and each face is triangle
Shape, structural strength is big, and the structure makes the stability of conductive layer very good.
Actual production and application has been put into the product that this programme is protected at present, especially in field of new energy technologies
Application achieve certain success, it is clear that confirmed the product technical solution be it is beneficial, meet society need,
It also is suitable for batch production and popularization and use.
The foregoing is a detailed description of the present invention in conjunction with specific embodiments, and it cannot be said that the present invention is specifically real
It applies and is only limitted to these explanations.For those skilled in the art to which the present invention belongs, before not departing from present inventive concept
It puts, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the scope of protection of the invention.
Claims (7)
1. a kind of high stability perovskite solar battery for using graphene as conductive electrode, it is characterised in that: the sun
Can battery structure from the bottom up successively are as follows: transparent conductive substrate (1), local heavily doped region (2), composite conductive thin film layer and metal
Electrode (4), the part heavily doped region (2) directly contacts with the composite conductive thin film layer and metal electrode (4), described compound
Conductive membrane layer is by local heavily doped region (2) and the high stability perovskite solar-electricity of metal electrode (4) linking into an integrated entity
Pond composite unit structure；
The composite conductive thin film layer includes: that N-type perovskite thin film (31), p-type graphene film (32) and p-type silver nanoparticle are compound
Film (33).
2. using graphene as the high stability perovskite solar battery of conductive electrode, feature according to claim 1
Be: the transparent conductive substrate (1) is FTO electro-conductive glass or ITO electro-conductive glass or organic flexible electrically conducting transparent plastics or oxygen
Graphite alkene.
3. using graphene as the high stability perovskite solar battery of conductive electrode, feature according to claim 1
Be: the metal electrode (4) is positive-negative-positive structure, i.e., the described metal electrode (4) is containing graphene and argentum nano composite material
Metal electrode.
4. using graphene as the high stability perovskite solar battery of conductive electrode, feature according to claim 1
Be: it is described part heavily doped region (2) be arranged using array pattern, pattern be one-dimensional, two-dimentional geometric figure or it is one-dimensional with
The combination of two-dimentional geometric figure or diamond lattic structure (5)；One-dimensional geometric figure is selected from: line segment, phantom line segments, camber line or grid line shape；
Two-dimentional geometric figure is selected from: circle, ellipse, spindle, annular, polygon, polygonal or sector.
5. using graphene as the high stability perovskite solar battery of conductive electrode, feature according to claim 4
Be: the line width of the one-dimensional geometric figure is 30~100um, and length is 0.05~1.5mm；With two neighboring linear in a line
Spacing be 0.5~2mm, two neighboring linear spacing is 0.5~2mm in same row.
6. using graphene as the high stability perovskite solar battery of conductive electrode, feature according to claim 4
Be: the size of the two-dimentional geometric figure is 30~200um, and two neighboring centre of figure is away from for 0.8~2mm.
7. using graphene as the high stability perovskite solar battery of conductive electrode, feature according to claim 4
Be: the diamond lattic structure (5) includes integrally formed table top (51), bizet (52), waistline (53), pavilion portion (54) and bottom surface
(55), the diamond lattic structure (5) is tetrahedral structure, and there are four angles, four faces for each tetrahedron, and each face is triangle
Shape.
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