CN105244393B - Polymide solar cell and preparation method thereof - Google Patents
Polymide solar cell and preparation method thereof Download PDFInfo
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- CN105244393B CN105244393B CN201410247125.4A CN201410247125A CN105244393B CN 105244393 B CN105244393 B CN 105244393B CN 201410247125 A CN201410247125 A CN 201410247125A CN 105244393 B CN105244393 B CN 105244393B
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Abstract
The invention relates to the field of solar cells, and particularly relates to a polymide solar cell. The polymide solar cell comprises a polymide substrate, a diffusion barrier layer, a first electrode layer, an absorption layer, a buffer layer, a second electrode layer, an anti-reflection layer and a surface electrode layer, wherein the diffusion barrier layer, the first electrode layer, the absorption layer, the buffer layer, the second electrode layer, the anti-reflection layer and the surface electrode layer are formed on the polymide substrate in sequence, the diffusion barrier layer is in a structure with three or more layers, each layer of the diffusion barrier layer is prepared by materials randomly selecting from the following groups: aluminum, molybdenum, titanium, nickel, copper, zirconium, niobium, chromium, ruthenium, rhodium, palladium, tantalum, tungsten, iridium, osmium, platinum, gold or silver, or alloys thereof; nitrides, oxides or carbides of silicon; and titanium nitride, tantalum nitride, tungsten nitride or zirconium nitride. According to the polymide solar cell disclosed by the invention, the diffusion barrier layer can effectively prevent impurity elements of the substrate from getting into the absorption layer, and a binding force of the diffusion barrier layer with the substrate and the first electrode layer can be significantly improved. Meanwhile, the invention provides a preparation method of the polymide solar cell and a diffusion barrier layer of the polymide solar cell.
Description
Technical field
The invention belongs to technical field of solar batteries, more particularly to a kind of polyimides solaode and its preparation side
Method.
Background technology
With being continuously increased for mankind's energy resource consumption, non-renewable exhausting for the energy such as Fossil fuel be urgently to be resolved hurrily
Problem.Will there is flex point in about the year two thousand thirty in fossil energy consumption total amount, and the proportion of regenerative resource will constantly rise, wherein,
Proportion of the solar energy in future source of energy structure will be increasing, and conservative estimation this proportion can be more than 60% in 2100.Too
Sun can be the energy the abundantest in numerous regenerative resources, and the global sunlight energy of a hour is equivalent to the earth 1 year
Energy consumption, significantly larger than wind energy, underground heat, water power, ocean energy, bioenergy equal energy source.
The important development direction of solar cell is multiduty flexible substrates solar cell.With conventional solar cell with rigidity
Material (glass etc.) is that the base material of flexible solar cell is soft, flexible tinsel as the difference of substrate
Or high-molecular organic material, such as stainless steel foil, aluminium foil, Kapton etc..Flexible solar cell is a kind of high-end
Photovoltaic products, it has following clear superiority：(1) battery component can bend, it is adaptable to nonplanar mounting condition；(2) electricity
Pond component lightweight, quality specific power is high；(3) backing material consumption is little, with low cost.
Flexible solar cell is departing from traditional backing material glass so as to possess the bent characteristic of light flexible, but while
Also new problem is brought：Some elements existed in a large number in flexible metal basement, such as Fe, the high temperature for easily preparing in battery
Spread to absorbed layer by metal electrode in technique, cause absorbed layer deep energy level to adulterate, greatly affect the photoelectric properties of battery.
And this impact is almost negligible for soda-lime glass substrate.Therefore, polyimides solar cell needs a layer height
Chemically stable barrier layer, to prevent the diffusion of the harmful element similar to Fe.
Patent CN101268608A discloses a kind of photovoltaic device with conductive barrier layers and with aluminum foil substrate
Part.Barrier layer disclosed in the patent is applied to aluminum foil substrate, and is not suitable for other flexible substrates, such as polyimide substrate.
Reason is that the thermal coefficient of expansion of polyimide substrate is different from aluminium foil, therefore the diffusion impervious layer suitable for aluminium foil can not be fitted
Polyimide substrate is answered, it is inadequate with the adhesion of polyimide substrate that this frequently can lead to diffusion impervious layer.
Therefore, metal electrode is passed through in high-temperature technology to suction in the impurity element for effectively preventing polyimide base substrate
While receiving layer diffusion, further add high containment and polyimide substrate and the adhesion problem of first electrode layer, still needing will
Further explore.
The content of the invention
The main object of the present invention is the diffusion resistance for polyimides solaode present in above-mentioned prior art
A kind of undesirable problem of the blocking effect and adhesion of barrier, there is provided polyimides solaode and preparation method thereof, with
This is simultaneously of the invention to provide a kind of polyimides solaode diffusion impervious layer.
In order to realize foregoing invention purpose, the technical solution used in the present invention is as follows：
Polyimides solaode, including polyimide substrate and sequentially form on polyimide substrate diffusion resistance
Barrier, first electrode layer, absorbed layer, cushion, the second electrode lay, anti-reflection layer and surface electrode layer, the diffusion impervious layer is
Three layers or more than three layers structures, each layer of the diffusion impervious layer with the following group optionally by being made：
A groups：Aluminum, molybdenum, titanium, nickel, copper, zirconium, niobium, chromium, ruthenium, rhodium, palladium, tantalum, tungsten, iridium, osmium, platinum, gold or silver, or their conjunction
Gold；Or
B groups：The nitride of silicon, oxide or carbide；Or
C groups：Titanium nitride, tantalum nitride, tungsten nitride or zirconium nitride；
The thickness of the diffusion impervious layer is 10nm～3000nm.
The polyimides solaode of the present invention, selects the diffusion impervious layer of multiple structure, and selects diffusion impervious layer
Composition, the polyimides solaode that the present invention is obtained, its diffusion impervious layer can effectively prevent the miscellaneous of polyimide substrate
Prime element enters absorbed layer, so as to reduce destruction of these impurity elements to absorbed layer, improves the performance of battery.
Preferably, aforesaid polyimides solaode, the first electrode layer is molybdenum film layer.
Preferably, aforesaid polyimides solaode, the diffusion impervious layer is three-decker, including near base
Bottom, intermediate layer and close first electrode layer.The polyimides solaode of the present invention, diffusion impervious layer passes through optimum selecting three-layer
Structure, the impurity element that can not only effectively prevent polyimide substrate enters absorbed layer, and at the same time, can effectively improve expansion
Scattered barrier layer and polyimide substrate and the adhesion of first electrode layer.
Preferably, aforesaid polyimides solaode, the intermediate layer of the diffusion impervious layer is by titanium nitride, nitridation
Any one of tantalum, tungsten nitride or zirconium nitride is made.By the aforementioned component of preferred interlayer, can effectively prevent polyimide-based
The impurity element at bottom diffuses to absorbed layer in the high temperature preparation process of copper indium gallium selenide cell, affects the performance of battery.
Preferably, aforesaid polyimides solaode, the close basal layer of the diffusion impervious layer is by titanium, nitridation
Titanium or tantalum nitride are made.Inventor is by numerous studies discovery, the thermal coefficient of expansion and polyimides of titanium, titanium nitride and titanizing tantalum
Difference is less, thus combines more preferably, and these materials are anti-with selenium generation chemistry in the high temperature preparation process of solaode
Should, do not interfere with the performance of battery and the adhesion of film layer.
Preferably, aforesaid polyimides solaode, the close first electrode layer of the diffusion impervious layer by titanium,
Chromium or titanium nitride are made.The present invention by preferably adjacent to first electrode layer, because titanium and chromium, titanium nitride all grow in preparation process
For columnar crystal structure, and molybdenum is similarly columnar crystal structure, belongs to isoepitaxial growth type, can effectively improve diffusion impervious layer with
Adhesion between first electrode layer.
Used as still more preferably, aforesaid polyimides solaode is described to be made of titanium near basal layer, described
Intermediate layer is made up of titanium nitride, described to be made of titanium near first electrode layer, and the thickness of the diffusion impervious layer is 1200nm, institute
First electrode layer is stated for molybdenum film layer.
Used as second object of the present invention, the present invention provides the preparation method of aforementioned polyimides solaode, bag
Include following steps：
(1) diffusion impervious layer is prepared on polyimide substrate, the preparation method is selected from electroless plating, electrochemical plating
Any one of embrane method, chemical vapour deposition technique, vapour deposition method or magnetron sputtering method；
(2) be sequentially prepared on the diffusion barrier first electrode layer, absorbed layer, cushion, the second electrode lay, anti-reflection layer and
Surface electrode layer.
Used as third object of the present invention, the present invention provides polyimides solaode diffusion impervious layer, is arranged at
Between polyimide substrate and first electrode layer, the diffusion impervious layer be three layers or more than three layers structures, the diffusion barrier
Each layer of layer can optionally by being made with the following group：
A groups：Aluminum, molybdenum, titanium, nickel, copper, zirconium, niobium, chromium, ruthenium, rhodium, palladium, tantalum, tungsten, iridium, osmium, platinum, gold or silver, or their conjunction
Gold；Or
B groups：The nitride of silicon, oxide or carbide；Or
C groups：Titanium nitride, tantalum nitride, tungsten nitride or zirconium nitride；
The thickness of the diffusion impervious layer is 10nm～3000nm, and the first electrode layer is molybdenum film layer.
Preferably, aforesaid polyimides solaode diffusion impervious layer, the diffusion impervious layer is three-decker,
Including near basal layer, intermediate layer and near first electrode layer；The intermediate layer is by titanium nitride, tantalum nitride, tungsten nitride or nitridation
Any one of zirconium is made；It is described to be made up of titanium, titanium nitride or tantalum nitride near basal layer；It is described near first electrode layer by titanium,
Chromium or titanium nitride are made.
Used as further preferred, aforesaid polyimides solaode diffusion impervious layer, the close basal layer is by titanium
Make, the intermediate layer is made up of titanium nitride, described to be made of titanium near first electrode layer, the thickness of the diffusion impervious layer is
1200nm。
Aforementioned polyimides solaode diffusion impervious layer, its preparation method can be selected from electroless plating, electrochemistry
Any one of coating method, chemical vapour deposition technique, vapour deposition method or magnetron sputtering method.
Aforesaid polyimides solaode and polyimides solaode diffusion impervious layer, therein first is electric
Pole layer, preferably molybdenum film layer.Any one of the preparation method of first electrode layer in vapour deposition method, magnetron sputtering method.First
The thickness of electrode layer is 500nm～3000nm.
Aforesaid polyimides solaode and polyimides solaode diffusion impervious layer, absorbed layer therein
Can selected from CIGS thin-film, copper-zinc-tin-sulfur film, copper-indium-sulfur film, Cadimium telluride thin film, dye-sensitized solar battery thin film with
And any one of organic solar batteries thin film.The preparation method of absorbed layer can be selected from electrochemical deposition method, nano-crystalline granule
Any one of cladding process, vapour deposition method or magnetron sputtering method.
Aforesaid polyimides solaode and polyimides solaode diffusion impervious layer, cushion is selected from sulfur
Any one of change zinc or cadmium sulfide.The preparation method of cushion is arbitrary selected from solwution method, chemical bath method or magnetron sputtering method
Kind.
Aforesaid polyimides solaode and polyimides solaode diffusion impervious layer, the second electrode lay material
Material is selected from any one of indium-doped stannum oxide, stannum oxide fluorine doped, doped zinc oxide aluminum, Zinc Oxide boron-doping or doped zinc oxide gallium.Second is electric
Any one of the preparation method of pole layer in magnetron sputtering method, reactive sputtering, electron-beam vapor deposition method.
Aforesaid polyimides solaode and polyimides solaode diffusion impervious layer, the choosing of anti-reflection layer material
From Afluon (Asta), titanium dioxide, silicon nitride, silicon dioxide, aluminium sesquioxide, magnesium oxide or ceria any one.Anti-reflection layer
Preparation method is selected from as any one in evaporation, sputtering method or chemical method.
Aforesaid polyimides solaode and polyimides solaode diffusion impervious layer, surface electrode layer material
Material is selected from nickel, aluminum, silver etc..The preparation method of surface electrode layer is usually evaporation.
Compared with prior art, the invention has the beneficial effects as follows：
The polyimides solaode and diffusion impervious layer of the present invention, by the structure and each knot of screening diffusion impervious layer
The constituent of structure, the diffusion impervious layer of acquisition can effectively stop that the impurity element of polyimides enters absorbed layer, improve battery
Performance, meanwhile, it is capable to dramatically increase diffusion impervious layer and polyimides, the adhesion of first electrode layer.
Description of the drawings
Fig. 1 is the structural representation of polyimides solaode of the present invention；
Fig. 2 is the photo after solar battery thin film selenizing obtained in embodiment 1；
Fig. 3 is the EDS test result figures of the diffusion impervious layer of solaode obtained in embodiment 1.
In Fig. 1,1- substrates, 2- diffusion impervious layers, near basal layer, 202- intermediate layers, 203- is near first electrode for 201-
Layer, 3- first electrode layers, 4- absorbed layers, 5- cushions, 6- the second electrode lays, 7- anti-reflection layers, 8- surface electrode layers.
Specific embodiment
The foregoing invention content of the present invention is described in further detail with reference to specific embodiment.
But this scope for being interpreted as above-mentioned theme of the invention should not be only limitted to following embodiments.On without departing from the present invention
In the case of stating technological thought, according to ordinary skill knowledge and customary means, various replacements and change are made, all should be included
Within the scope of the invention.
The present embodiment of embodiment 1 is with regard to polyimides solaode, diffusion impervious layer and preparation method.
Polyimides solaode, structure is：Substrate 1 is polyimides；Diffusion impervious layer 2 be three-decker, thickness
For 1200nm, wherein being titanium near basal layer 201, intermediate layer 202 is titanium nitride, is titanium near first electrode layer 203；First is electric
Pole layer 3 is molybdenum；Absorbed layer 4 is CIGS thin-film；Cushion 5 is cadmium sulfide；The second electrode lay 6 is doped zinc oxide aluminum；Anti-reflection
Layer 7 is Afluon (Asta)；Surface electrode layer 8 is nickel aluminum/nickel.
Preparation method：
(1) process of polyimide substrate 1：Polyimide foil substrate surface is very smooth, and surface roughness is very little, because
This need not carry out surface polishing, process surface degreasing twice is done using front needs.One-time surface deoiling method is 60 DEG C
Detergent solution in be cleaned by ultrasonic, be cleaned by ultrasonic time 20min.The method of secondary oil removing is the sodium hydroxide in 30% concentration
In solution, at 60 DEG C of heating-up temperature 30min is cleaned by ultrasonic.
(2) preparation of diffusion impervious layer 2：
The close basal layer 201 of diffusion impervious layer 2 is titanium：Magnetron sputtering method, adopts in the argon of air pressure 4mtorr
The power sputtering titanium target of 240W is prepared, and thickness is about 300nm.
The intermediate layer 202 of diffusion impervious layer 2 is titanium nitride, using magnetron sputtering method, air pressure for 4mtorr argon with
In the mixed gas of nitrogen, power is to sputter titanium target under the conditions of 210W to obtain, and thickness is about 600nm.
The close first electrode layer 203 of diffusion impervious layer 2 is titanium, using magnetron sputtering method, in the argon that air pressure is 4mtorr
Under gas, power is to sputter titanium target under the conditions of 240W to obtain, and thickness is about 300nm.
(3) first electrode layer 3 is molybdenum：Magnetron sputtering method, air pressure is the argon of 4mtorr, and sputtering power is 210W, sputtering
Target is molybdenum target, and thickness is about 1000nm.
(4) absorbed layer 4 is CIGS thin-film, and using magnetron sputtering method, air pressure is the argon of 4mtorr, and sputtering power is
120W, target is CIGS target material, obtains the prefabricated membrane that thickness is about 800nm.After film preparation, in quick selenizing stove,
Using the heating mode being rapidly heated to absorbing layer film at a temperature of 600 DEG C, selenization 30nm obtains CIGS thin
Film.
(5) cushion 5 is cadmium sulfide：Prepared by chemical bath method, bath temperature is 80 DEG C, and film thickness is about 60nm.
(6) the second electrode lay 6 is doped zinc oxide aluminum：Using magnetron sputtering, target is doped zinc oxide aluminum, and sputtering power is
180W, sample stage temperature is 200 DEG C, and air pressure is 4mtorr argon, and thickness is about 500nm.
(7) anti-reflection layer 7 is Afluon (Asta)：Evaporated using resistance-type, temperature is 1300 DEG C or so, and thickness is about 80nm.
(8) surface electrode layer 8 is nickel aluminum/nickel：Nickel thin film adopts electron-beam vapor deposition method, and the thickness of ground floor nickel thin film is about
For 200nm, the thickness for preventing the diffusion of aluminum, second layer nickel thin film is about 200nm, prevents the oxidation of aluminum, aluminum interlayer thin film from adopting
The method evaporated with resistance-type, thickness is about 3000nm.
Obtained polyimide foil solaode, Jing after high temperature selenizing as shown in Fig. 2 thin film flawless and existing without coming off
As.Obtained solar cell device, Jing tests, even across bending, thin film also will not fall off.
Obtained not polyimides solaode, EDS test results are as shown in figure 3, EDS test datas are as shown in table 1：
Table 1.EDS test datas
From Fig. 3 and the data of table 1, the blocking effect of the diffusion impervious layer 2 of obtained polyimides solaode is very
It is good, diffuse to absorbed layer without the impurity element in any polyimide substrate.
The present embodiment of embodiment 2 is with regard to polyimides solaode and diffusion impervious layer
Polyimides solaode, structure is：Substrate 1 is polyimides；Diffusion impervious layer 2 be three-decker, thickness
For 1200nm, wherein being titanium near basal layer 201, intermediate layer 202 is carborundum, is chromium near first electrode layer 203；First is electric
Pole layer 3 is molybdenum；Absorbed layer 4 is CIGS thin-film；Cushion 5 is cadmium sulfide；The second electrode lay 6 is doped zinc oxide aluminum；Anti-reflection
Layer 7 is Afluon (Asta)；Surface electrode layer 8 is nickel aluminum/nickel.
The present embodiment of embodiment 3 is polyimides solaode and diffusion impervious layer
Polyimides solar battery structure：Substrate 1 is polyimides；Diffusion impervious layer 2 be three-decker, diffusion barrier
The close basal layer 201 of layer 2 is titanium nitride, and intermediate layer 202 is tantalum nitride, is titanium nitride near first electrode layer 203, and diffusion hinders
The thickness of barrier 2 is 3000nm；First electrode layer 3 is molybdenum；Absorbed layer 4 is CIGS thin-film；Cushion 5 is cadmium sulfide；Second
Electrode layer 6 is doped zinc oxide aluminum；Anti-reflection layer 7 is Afluon (Asta)；Surface electrode layer 8 is nickel aluminum/nickel.
The present embodiment of embodiment 4 is polyimides solaode and diffusion impervious layer
Polyimides solar battery structure：Substrate 1 is polyimides；Diffusion impervious layer 2 be three-decker, diffusion barrier
The close basal layer 201 of layer 2 is titanium, and intermediate layer 202 is titanium nitride, is chromium near first electrode layer 203, and diffusion impervious layer 2 is thick
Spend for 2000nm；First electrode layer 3 is molybdenum；Absorbed layer 4 is CIGS thin-film；Cushion 5 is cadmium sulfide；The second electrode lay 6
For doped zinc oxide aluminum；Anti-reflection layer 7 is Afluon (Asta)；Surface electrode layer 8 is nickel aluminum/nickel.
The present embodiment of embodiment 5 is polyimides solaode and diffusion impervious layer
Polyimides solar battery structure：Substrate 1 is polyimides；Diffusion impervious layer 2 be four-layer structure, diffusion barrier
The close basal layer 201 of layer 2 is two-layer, respectively titanium layer and titanium nitride, and intermediate layer 202 is tantalum nitride, near first electrode layer
203 is titanium, and the thickness of diffusion impervious layer 2 is 3000nm；First electrode layer 3 is molybdenum；Absorbed layer 4 is CIGS thin-film；Cushion 5
For cadmium sulfide；The second electrode lay 6 is doped zinc oxide aluminum；Anti-reflection layer 7 is Afluon (Asta)；Surface electrode layer 8 is nickel aluminum/nickel.
Claims (2)
1. polyimides solaode, including polyimide substrate and the diffusion barrier sequentially formed on polyimide substrate
Layer, first electrode layer, absorbed layer, cushion, the second electrode lay, anti-reflection layer and surface electrode layer, it is characterised in that the diffusion
Barrier layer is three-decker, including near basal layer, intermediate layer and near first electrode layer；The close basal layer is by titanium system
Into the intermediate layer is made up of titanium nitride, and described to be made of titanium near first electrode layer, the thickness of the diffusion impervious layer is
1200nm, the first electrode layer is molybdenum film layer.
2. the preparation method of polyimides solaode described in claim 1, it is characterised in that comprise the steps：
（1）Diffusion impervious layer is prepared on polyimide substrate, the preparation method is selected from electroless plating, electrochemical filming
Any one of method, chemical vapour deposition technique, vapour deposition method or magnetron sputtering method；
（2）First electrode layer, absorbed layer, cushion, the second electrode lay, anti-reflection layer and surface are sequentially prepared on the diffusion barrier
Electrode layer；
Described to be made of titanium near basal layer, the intermediate layer is made up of titanium nitride, described to be made of titanium near first electrode layer,
The thickness of the diffusion impervious layer is 1200nm.
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| WO2018234878A1 (en) * | 2017-06-23 | 2018-12-27 | King Abdullah University Of Science And Technology | Hole-blocking layers for electronic devices and method of producing an electronic device having a hole-blocking layer |
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| CN109192791A (en) * | 2018-08-31 | 2019-01-11 | 北京铂阳顶荣光伏科技有限公司 | Solar battery and its barrier layer |
| CN114041212A (en) * | 2019-07-05 | 2022-02-11 | 东友精细化工有限公司 | Transparent electrode structure and electric device comprising same |
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| CN101093863A (en) * | 2007-06-12 | 2007-12-26 | 南开大学 | Thin film solar cell of using ZnO as electrical isolation layer and impurity barrier layer, and preparation method |
| CN103456802A (en) * | 2013-09-04 | 2013-12-18 | 南开大学 | Back electrode used for Cu-In-Ga-Se film solar cell with polyimide substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101093863A (en) * | 2007-06-12 | 2007-12-26 | 南开大学 | Thin film solar cell of using ZnO as electrical isolation layer and impurity barrier layer, and preparation method |
| CN103456802A (en) * | 2013-09-04 | 2013-12-18 | 南开大学 | Back electrode used for Cu-In-Ga-Se film solar cell with polyimide substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018234878A1 (en) * | 2017-06-23 | 2018-12-27 | King Abdullah University Of Science And Technology | Hole-blocking layers for electronic devices and method of producing an electronic device having a hole-blocking layer |
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