CN108198892A - A kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell - Google Patents

A kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell Download PDF

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CN108198892A
CN108198892A CN201711405851.4A CN201711405851A CN108198892A CN 108198892 A CN108198892 A CN 108198892A CN 201711405851 A CN201711405851 A CN 201711405851A CN 108198892 A CN108198892 A CN 108198892A
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preparation
cigs
film solar
solar cell
layers
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王金晓
左华平
王虎
高恒蛟
李坤
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Lanzhou Institute of Physics of Chinese Academy of Space Technology
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Lanzhou Institute of Physics of Chinese Academy of Space Technology
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Abstract

The present invention relates to a kind of preparation methods for mixing potassium flexible copper indium gallium selenide thin-film solar cell, belong to field of surface engineering technique.The present invention mainly generates smooth, fine and close, uniform high quality CIGS absorbed layers at a lower temperature using the realization of ion beam selenizing magnetron sputtering one-step method, reduces CIGS absorbed layer preparation temperatures, and simplify CIGS absorbed layer preparation processes；And before CIGS absorbed layers are grown, potassium fluoride initialization layer is first prepared, it realizes and potassium doping is carried out to CIGS absorbed layers, be conducive to improve the electric property of CIGS absorbed layers, the method for the invention realizes the preparation of the flexible CIGS solar battery of high conversion efficiency.

Description

A kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell
Technical field
The present invention relates to a kind of preparation methods for mixing potassium flexible copper indium gallium selenide thin-film solar cell, belong to Surface Engineering skill Art field.
Background technology
With the development that space, Near Space Flying Vehicles, unmanned plane and ground military intellectualities are equipped, energy resource supply system System proposes solar cell many new requirements, such as：Lightweight, efficient and strong capability of resistance to radiation etc..Flexible copper and indium gallium The photoelectric conversion efficiency of selenium thin-film solar cells Yin Qigao, strong capability of resistance to radiation, the battery performance of stabilization, good dim light are special Property and low manufacture cost become current photovoltaic art research hot spot, it is considered to be most promising solar cell One of.
Copper-indium-galliun-selenium film solar cell is generally inhaled by flexible polyimide substrate, back electrode, copper indium gallium selenide (CIGS) Receive layer, buffer layer, transparent window layer and the several part compositions of top electrode.Wherein, for copper-indium-galliun-selenium film solar cell Core film layer copper indium gallium selenide (CIGS) absorbed layer preparation there are many technology and method, it is most common to have three stage Co-evaporation Selenizing method after method and CuInGa alloy firm pre-sputterings.Wherein, polynary three stage Co-evaporation method requirement must in film deposition process Selenium amount need to be kept sufficient, while base reservoir temperature must be maintained at 400 DEG C~600 DEG C；And selenium after CuInGa alloy firm pre-sputterings Change method must pass through selenization process, and selenizing temperature is at 550 DEG C or so.When preparing CIGS absorbed layers using above two method, base Bottom will bear 400 DEG C~600 DEG C of high temperature, to ensure complete selenizing in CIGS absorbed layers, have CIGS absorbed layers Ingredient and institutional framework, but this temperature be higher than polyimide substrate tolerable temperature, it is therefore necessary to develop new low temperature skill Art carries out the low temperature depositing of high quality CIGS absorbed layers to realize on polyimide substrate.
Invention content
It is inhaled to reduce the preparation temperature of CIGS thin film solar cell core film layer CIGS absorbed layers and promote CIGS The electric property of layer is received, the present invention provides a kind of preparation methods for mixing potassium flexible CIGS thin-film solar cells, utilize ion Beam selenizing magnetron sputtering one-step method realizes the preparation of high quality CIGS absorbed layers on polyimide substrate, reduces CIGS absorbed layers Preparation temperature, and simplify CIGS absorbed layer preparation processes；And before CIGS absorbed layers are grown, it is preset first to prepare potassium fluoride Layer is realized and carries out potassium doping to CIGS absorbed layers, promotes the electric property of CIGS absorbed layers.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of preparation method for mixing potassium flexible CIGS thin-film solar cells, the method step are as follows：
(1) back electrode is first prepared in substrate, then the substrate after deposition back electrode is placed in pressure no more than 2 × 10-3Pa Vacuum chamber in, when the temperature of substrate being made to reach the temperature of 200 DEG C~300 DEG C and KaF evaporation sources reach 820 DEG C~850 DEG C, 1min~2min is evaporated, KaF initialization layers are formed on back electrode；
(2) after the substrate after deposition KaF initialization layers being heated to 250 DEG C~350 DEG C, magnetron sputtering is carried out, is utilized simultaneously The Se ion beams that ion source generates carry out selenylation reaction, magnetron sputtering and selenylation reaction 30min~3h, on KaF initialization layers Form CIGS middle layers；
Wherein, the distance between ion source and magnetic controlled sputtering target are 5cm~10cm, generate the work of the Se evaporators of Se steams Make 175 DEG C~190 DEG C of temperature, into the Se steams and argon gas mixed gas in the plasma chamber of ion source, Se steams Flow is 4sccm~9sccm, and the volume fraction of Se steams is 30%~50%, ion beam voltage 100V~400V, ion beam electricity Flow 0.25A~1.2A；
When magnetic controlled sputtering target is CuGa alloys targets and In targets, sputtering power 50W~150W, operating air pressure 0.4Pa~ 1.5Pa；
When magnetic controlled sputtering target is CuGa alloys targets and CuIn alloys targets, sputtering power 70W~100W, operating air pressure 0.8Pa ~1.5Pa；
When magnetic controlled sputtering target is CuInGa alloys targets, sputtering power 80W~150W, operating air pressure 0.1Pa~2.0Pa；
(3) in the substrate after depositing CIGS middle layers, buffer layer, transparent window layer and top electrode are sequentially depositing, i.e., It obtains mixing potassium flexible CIGS thin-film solar cells.
Technical solutions according to the invention are suitable for conventional flexible polymer substrate, are not limited to polyimides.It has reported Copper-indium-galliun-selenium film solar cell in back electrode, buffer layer, transparent window layer and top electrode component and its phase The preparation method answered be suitable for it is of the present invention mix potassium flexible CIGS thin-film solar cells, so in skill of the present invention Component of back electrode, buffer layer, transparent window layer and top electrode and preparation method thereof is no longer done specifically in art scheme It is bright.
Advantageous effect：
Utilize ion beam selenizing magnetron sputtering one-step method that can generate at a lower temperature in the present invention smooth, fine and close, equal Even high quality CIGS absorbed layers are lived this is because ion beam selenizing can utilize the energy entrained by Se ions to increase its chemistry Property, enhance response intensity, while the kinetic energy of Se ions can enhance the absorption, dissociation and diffusion on surface, so as to have Conducive to CIGS thin film fast deposition at a lower temperature；In addition, before CIGS absorbed layers are grown, it is preset first to prepare potassium fluoride Layer realizes that potassium doping is carried out to CIGS absorbed layers increases the particle in CIGS absorbed layers, and then promote the electricity of CIGS absorbed layers Learn performance.The method of the invention reduces the preparation temperature of CIGS absorbed layers in the prior art, and simplifies CIGS absorptions The preparation process of layer further improves the electrology characteristic of CIGS absorbed layers, it is achieved thereby that the flexible CIGS of high conversion efficiency The preparation of solar cell.
Specific embodiment
The present invention is further elaborated With reference to embodiment, wherein, the method is equal unless otherwise instructed For conventional method, the raw material can obtain unless otherwise instructed from open commercial sources.
Embodiment 1
One kind mix potassium flexible CIGS thin-film solar cells by Kapton substrate, Mo back electrodes, KaF initialization layers, CIGS middle layers, CdS buffer layers, transparent window layer and Al upper electrode layers composition, specific preparation process are as follows：
(1) Kapton that thickness is 50 μm is placed in vacuum chamber, to vacuum chamber to vacuum intraventricular pressure Strong is 2.0 × 10-4Pa then carries out argon ion bombardment processing with ion source to Kapton, is carried on the back with improving the Mo of deposition Adhesive force of the electrode on Kapton；Wherein, argon flow amount 15sccm, ion beam discharge voltage be 280V, ion Beam current is 1A；
(2) by argon ion bombardment treated Kapton is placed in vacuum degree less than 2 × 10-3In the vacuum chamber of Pa, It is 10cm to adjust the distance between magnetic controlled sputtering target and Kapton, is first sputtered later in 1.6Pa sputtering pressures and 50W Power dip accumulates the Mo films of 0.2 μm of a layer thickness, then deposits a thickness under 0.3Pa sputtering pressures and 70W sputtering powers 0.8 μm of Mo films of degree, wherein, Kapton temperature is room temperature during magnetron sputtering, and working gas is 4N high-purity argon gas, The double-deck Mo films formed on Kapton are Mo back electrodes, resistivity 10-5Ω·cm；
(3) temperature that the Kapton after deposition Mo back electrodes is heated to 280 DEG C and KaF evaporation sources reaches At 850 DEG C, 1min is evaporated, KaF initialization layers are formed on Mo back electrodes；
(4) by deposit KaF initialization layers after Kapton be heated to 350 DEG C after, 90W sputtering power and Sputter CuGa alloys targets and CuIn alloys targets under the operating air pressure of 0.75Pa, the argon gas that purity is 4N is passed through magnetic control and splashed by when sputtering It shoots at the target surface, while the plasma selenium Shu Jinhang selenylation reactions generated with ion source, magnetron sputtering and ion beam selenylation reaction Time is 60min, and CIGS middle layers are formed on KaF initialization layers；
Wherein, the distance between ion source and magnetic controlled sputtering target are 10cm, generate the work temperature of the Se evaporators of Se steams It is 180 DEG C to spend, and into the Se steams and argon gas mixed gas in the plasma chamber of ion source, the flow of Se steams is The volume fraction of 6sccm, Se steam is 40%, ion beam voltage 300V, ion beam current 0.85A；
(5) first by 1mL mass fractions be 25% NH4OH is diluted with 100mL water, then the ammonium hydroxide measured after 35mL dilutions is molten Liquid, and with 0.0806g CdCl2、0.304g NH2CSNH2With 0.32g NH4Tri- kinds of powder of Cl uniformly mix, and water is added to be configured to 200mL mixed solutions；Kapton after deposition CIGS middle layers is put into prepared mixed solution, then be placed in 75 DEG C constant temperature water bath in react 13min, take out Kapton, CdS buffer layers formed in CIGS middle layers；
(6) transparent window is deposited on the Kapton of magnetic control deposition CdS buffer layers using radio-frequency magnetron sputter method Layer；Wherein, intrinsic ZnO uses ZnO ceramic targets, sputtering power 30W, sputtering pressure 1.0Pa, sedimentation time 7min；ZAO Target is used as Al2O3The ZAO targets that the purity of doping 2.5at% is 4N, sputtering power 100W, sputtering pressure 0.8Pa, Sedimentation time is 60min；
(7) using radio-frequency magnetron sputter method deposition transparent window layer Kapton on depositing Al top electrode, i.e., The preparation of potassium flexible CIGS thin-film solar cells is mixed described in completion；Wherein, in the deposition process of Al top electrodes, sputtering power is 300W, operating air pressure 0.5Pa, sedimentation time 30min.
In conclusion the foregoing is merely a prefered embodiment of the invention, it is not intended to limit the scope of the present invention. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's Within protection domain.

Claims (5)

1. a kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell, it is characterised in that：The method step is such as Under：
(1) back electrode is first prepared in substrate, then the substrate after deposition back electrode is placed in pressure no more than 2 × 10-3Pa's is true It in empty room, is evaporated by evaporation source of KaF, KaF initialization layers is formed on back electrode；
(2) using CuGa alloys targets and In targets as magnetic controlled sputtering target, using CuGa alloys targets and CuIn alloys targets as magnetic controlled sputtering target or Person carries out magnetron sputtering using CuInGa alloys targets as magnetic controlled sputtering target in the substrate after depositing KaF initialization layers, at the same using from The Se ion beams that component generates carry out selenylation reaction, and CIGS middle layers are formed on KaF initialization layers；
(3) in the substrate after depositing CIGS middle layers, be sequentially depositing buffer layer, transparent window layer and top electrode to get to Mix potassium flexible CIGS thin-film solar cells.
2. a kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell according to claim 1, feature It is：In KaF initialization layer preparation process, the temperature of substrate is 200 DEG C~300 DEG C, and the temperature of KaF evaporation sources is 820 DEG C~850 DEG C, evaporation time is 1min~2min.
3. a kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell according to claim 1, feature It is：When preparing CIGS middle layers, base reservoir temperature is 250 DEG C~350 DEG C, and magnetron sputtering and selenylation reaction time are 30min ~3h；
The magnetic controlled sputtering target be CuGa alloys targets and In targets when, sputtering power be 50W~150W, operating air pressure for 0.4Pa~ 1.5Pa；
When the magnetic controlled sputtering target is CuGa alloys targets and CuIn alloys targets, sputtering power is 70W~100W, and operating air pressure is 0.8Pa~1.5Pa；
The magnetic controlled sputtering target be CuInGa alloys targets when, sputtering power be 80W~150W, operating air pressure for 0.1Pa~ 2.0Pa；
The distance between ion source and magnetic controlled sputtering target are 5cm~10cm, into the Se steams in the plasma chamber of ion source Flow for 4sccm~9sccm, ion beam voltage is 100V~400V, and ion beam current is 0.25A~1.2A.
4. a kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell according to claim 3, feature It is：Mixed gas into the gas in the plasma chamber of ion source for Se steams and argon gas, wherein, the volume of Se steams Score is 30%~50%.
5. a kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell according to claim 3, feature It is：The Se steams are generated by the Se evaporators that operating temperature is 175 DEG C~190 DEG C.
CN201711405851.4A 2017-12-22 2017-12-22 A kind of preparation method for mixing potassium flexible copper indium gallium selenide thin-film solar cell Pending CN108198892A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108123001A (en) * 2017-12-25 2018-06-05 北京铂阳顶荣光伏科技有限公司 The preparation method of copper indium gallium selenium solar cell absorbed layer
CN111129206A (en) * 2018-10-31 2020-05-08 北京铂阳顶荣光伏科技有限公司 Preparation method of CIGS thin film solar cell

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