CN106356417B - A kind of CIGS/CdTe Gradient Absorptions layer film solar cell and preparation method thereof - Google Patents

A kind of CIGS/CdTe Gradient Absorptions layer film solar cell and preparation method thereof Download PDF

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CN106356417B
CN106356417B CN201611048929.7A CN201611048929A CN106356417B CN 106356417 B CN106356417 B CN 106356417B CN 201611048929 A CN201611048929 A CN 201611048929A CN 106356417 B CN106356417 B CN 106356417B
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屈飞
李辉
古宏伟
丁发柱
张贺
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Institute of Electrical Engineering of CAS
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Abstract

The present invention provides a kind of CIGS/CdTe Gradient Absorptions layer film solar cells, include substrate, Mo back electrodes, gradient energy gap absorbed layer, N-shaped CdS buffer layers, intrinsic zinc oxide insulating layer, conductive layer and top electrode successively from bottom to top；The gradient energy gap absorbed layer includes p-type CIGS absorbed layers and p-type CdTe absorbed layers from bottom to top.The present invention utilizes CIGS bases absorbed layer and CdTe absorbed layer composition gradient absorbed layers, has widened the solar spectrum utilization scope of absorbed layer, has further improved solar cell transfer efficiency.

Description

A kind of CIGS/CdTe Gradient Absorptions layer film solar cell and preparation method thereof
Technical field
The present invention relates to a kind of technical field of thin-film solar cells, more particularly to a kind of CIGS/CdTe Gradient Absorptions Layer film solar cell and preparation method thereof.
Background technology
Solar cell forms electricity by absorbing energy and generating photo-generated carrier more than the photon of absorbed layer energy gap Can, but photon is then lost in a manner of Phonon emission higher than the portion of energy of energy gap.It is absorbed using gradient energy gap The solar spectrum utilization scope that layer widens absorbed layer is to promote the important channel of solar cell transfer efficiency.
Copper indium gallium selenide (CIGS) and cadmium telluride (CdTe) thin-film solar cells have high conversion efficiency, long-time stability Well, the advantages that capability of resistance to radiation is strong, is two the main direction of development in solar cell field, technical maturity is relatively high.Mesh Preceding CdTe thin film solar cell laboratory highest transfer efficiency reaches 21.5%, the CdTe battery component conversion of industrialized production Efficiency reaches 16.5%, CIGS solar cells laboratory highest transfer efficiency and reaches 21.7%, the CdTe electricity of industrialized production Pond component transfer efficiency reaches 15%.CdTe energy gaps are 1.46eV, and CIGS energy gaps change with Ga changes of contents, 1.02eV is adjustable to 1.62eV ranges, the CuIn being most widely used at present0.3Ga0.7Se2Absorbed layer energy gap is 1.15eV Left and right.There is research team to adjust its energy gap by changing Ga contents, the absorbed layer of energy gap consecutive variations is prepared, with this Absorption region of the absorbed layer to solar spectrum is improved, but CIGS preparations need high temperature, In and Ga counterdiffusion is tight in preparation process Weight, the ingredient of design are difficult to realize.Therefore gradient bandwidth CIGS absorbed layers are prepared only on Theoretical Design by Ga changes of contents In the presence of without real value, therefore, how improving absorption region of the absorbed layer to solar spectrum, improve thin-film solar cells Cells convert rate the problem of being still this field urgent need to resolve.
Invention content
In view of this, thin present invention aims at a kind of CIGS/CdTe Gradient Absorption layers that battery conversion efficiency is high are provided Film solar cell and preparation method thereof.
The present invention provides a kind of CIGS/CdTe Gradient Absorptions layer film solar cells, include lining successively from bottom to top Bottom, Mo back electrodes, gradient energy gap absorbed layer, N-shaped CdS buffer layers, intrinsic zinc oxide insulating layer, conductive layer and top electrode； The gradient energy gap absorbed layer includes p-type CIGS absorbed layers and p-type CdTe absorbed layers from bottom to top.
Preferably, the thickness of the Mo back electrodes is 0.8~1.0 μm.
Preferably, the thickness of the p-type CIGS absorbed layers is 1.0~1.5 μm；The doping of Ga in the CIGS absorbed layers It is 0~30%.
Preferably, the thickness of the p-type CdTe absorbed layers is 0.8~1.0 μm.
Preferably, the thickness of the N-shaped CdS buffer layers is 30~60nm.
Preferably, the conductive layer is fluorine doped tin oxide conductive layer, conductive indium-tin oxide layer, cadmium stannate conductive layer zinc oxide One kind in base transparency conducting layer；The thickness of the conductive layer is 500~800nm.
Preferably, the thickness of the intrinsic zinc oxide insulating layer is 50~80nm.
Preferably, the material of the top electrode is one kind in gold, silver and nickel；1.0~3.0 μ of thickness of the top electrode m。
The present invention provides a kind of preparation methods of thin-film solar cells described in said program, include the following steps：
Mo back electrodes, p-type CIGS absorbed layers, p-type CdTe absorbed layers, N-shaped CdS bufferings are sequentially prepared on substrate material Layer, intrinsic zinc oxide insulating layer, conductive layer and top electrode.
Preferably, include the following steps：
(1) magnetron sputtering method is used to sputter Mo back electrodes in substrate material surface；
(2) it uses three stage Co-evaporation method in Mo back electrodes surface depositing p-type CIGS, forms p-type CIGS absorbed layers；
(3) it uses CdTe powder evaporation to absorb layer surface depositing p-type CdTe in p-type CIGS, forms p-type CdTe and absorb Layer；
(4) it uses chemical bath method to absorb layer surface depositing n-type CdS in p-type CdTe, forms N-shaped CdS buffer layers：
(5) intrinsic zinc oxide insulating layer is formed in N-shaped CdS buffer-layer surface sputtering zinc oxides by magnetron sputtering method；
(6) magnetron sputtering method is used to sputter conductive layer in intrinsic zinc oxide surface of insulating layer；
(7) magnetron sputtering method is used to sputter top electrode in conductive layer surface.
The present invention provides a kind of CIGS/CdTe Gradient Absorptions layer film solar cells, from bottom to top according to It is secondary include substrate, Mo back electrodes, gradient energy gap absorbed layer, N-shaped CdS buffer layers, intrinsic zinc oxide insulating layer, conductive layer and Top electrode；The gradient energy gap absorbed layer includes p-type CIGS absorbed layers and p-type CdTe absorbed layers from bottom to top.The present invention The absorbed layer of the Gradient Absorption layer film solar cell of offer includes that the CIGS absorbed layers of narrow band gap and the CdTe of broad-band gap inhale Layer is received, the wherein bandwidth of CIGS absorbed layers is 1.15ev, and the bandwidth of CdTe absorbed layers is 1.46ev, and it is wide that the two forms gradient forbidden band Absorbed layer is spent, the solar spectrum utilization scope of absorbed layer has been widened using CIGS/CdTe gradient energy gap absorbed layers, further Improve solar cell transfer efficiency.Test result shows that the transfer efficiency of thin-film solar cells provided by the invention can be with Reach 16.5%.
Description of the drawings
Fig. 1 is the CIGS/CdTe gradient energy gap absorbed layer thin-film solar cell structures for being preparation of the embodiment of the present invention Schematic diagram；
1- substrates in Fig. 1；2-Mo electrodes；3-p type CIGS absorbed layers；4-p type CdTe absorbed layers；5-n type CdS buffer layers； 6- intrinsic zinc oxide insulating layers；7- conductive layers；8- top electrodes.
Specific implementation mode
The present invention provides a kind of CIGS/CdTe Gradient Absorptions layer film solar cells, include lining successively from bottom to top Bottom, Mo back electrodes, gradient energy gap absorbed layer, N-shaped CdS buffer layers, intrinsic zinc oxide insulating layer, conductive layer and top electrode； The gradient energy gap absorbed layer includes p-type CIGS absorbed layers and p-type CdTe absorbed layers from bottom to top.
CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention includes substrate.The present invention is to substrate material Expect no particular/special requirement, uses the typical substrate material in this field, preferably glass substrate, metal foil etc., this hair It is bright to prepare thin-film solar cells by the way of lower substrate.
CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention includes being arranged in the substrate surface Mo back electrodes.In the present invention, the thickness of the Mo back electrodes is preferably 0.8~1.0 μm, more preferably 0.85~0.95 μm.
CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention includes being arranged in the Mo back electrodes table The gradient energy gap absorbed layer in face；The gradient energy gap absorbed layer includes p-type CIGS absorbed layers and p-type from bottom to top CdTe absorbed layers.In the present invention, the thickness of the p-type CIGS absorbed layers is preferably 1.0~1.5 μm, more preferably 1.2~ 1.3μm；The doping of Ga is preferably 0~30% in the CIGS absorbed layers, and more preferably 5~15%.
In the present invention, the p-type CdTe absorbed layers are arranged in the p-type CIGS absorbed layers upper surface.In the present invention, The thickness of the p-type CdTe absorbed layers is preferably 0.8~1.0 μm, more preferably 0.85~0.95 μm.
CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention includes that setting is inhaled in the p-type CdTe Receive the N-shaped CdS buffer layers of layer surface.In the present invention, the thickness of the N-shaped CdS buffer layers is preferably 30~60nm, more preferably For 40~50nm.
CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention includes that setting is buffered in the N-shaped CdS The intrinsic zinc oxide insulating layer of layer surface.In the present invention, the thickness of the intrinsic zinc oxide insulating layer is preferably 50~80nm, More preferably 60~70nm.
CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention includes that setting is buffered in the N-shaped CdS The conductive layer of layer surface.In the present invention, the conductive layer is preferably transparency conducting layer, and more preferably fluorine doped tin oxide is conductive One kind in layer, conductive indium-tin oxide layer, cadmium stannate conductive layer zinc-oxide-base transparent conductive layer；The thickness of the conductive layer is preferred For 500~800nm, more preferably 600~700nm.
CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention includes being arranged in the conductive layer surface Top electrode.In the present invention, the material of the top electrode is preferably one kind in gold, silver and nickel；The thickness of the top electrode Preferably 1.0~3.0 μm, more preferably 1.5~2.5 μm.
The present invention provides a kind of preparation methods of thin-film solar cells described in said program, include the following steps：
Mo back electrodes, p-type CIGS absorbed layers, p-type CdTe absorbed layers, N-shaped CdS bufferings are sequentially prepared on substrate material Layer, intrinsic zinc oxide insulating layer, conductive layer and top electrode.
The present invention prepares Mo back electrodes on substrate material.In the present invention, it is preferred to by magnetron sputtering method in the lining Bottom surface sputters Mo back electrodes.In the present invention, 3 inches of forgings that the target that the magnetron sputtering uses is 99.99% or more Make fine grain Mo targets；The Cathod magnetic field of the magnetron sputtering is preferably non-equilibrium field；The back end vacuum degree of the magnetron sputtering is preferred It is 4.0 × 10-3Pa~6.0 × 10-3Pa, more preferably 5.0 × 10-3Pa；The sputtering atmosphere is preferably argon gas, the argon gas Purity be preferably 99.99~99.9999%；The air pressure of the magnetron sputtering is preferably 0.1Pa~0.5Pa, and more preferably 0.2 ~0.4Pa；The magnetron sputtering power is preferably 200W~300W, more preferably 220~270W；The target base of the magnetron sputtering Away from preferably 100mm~120mm, more preferably 110~115mm；The material of the substrate is consistent with said program, herein no longer It repeats；The time of the magnetron sputtering is preferably 20~40min, more preferably 25~35min；The present invention is splashed by controlling magnetic control The time is penetrated to control the thickness of Mo back electrodes, the thickness of Mo back electrodes increases with the extension of sputtering time.
The present invention preferably cleans substrate surface using ion source before Mo is deposited, and the cleaning process intermediate ion adds Fast voltage is preferably 240~260eV, more preferably 250eV；The particle beam is preferably 70~90mA, more preferably 80mA； The scavenging period is preferably that 3~10min. is more preferably 5~8min.
After obtaining Mo back electrodes, the present invention prepares p-type CIGS absorbed layers on Mo back electrodes surface.In the present invention, p Type CIGS absorbed layers can be prepared by selenizing method after metal and coevaporation method, and present invention preferably uses three stage Co-evaporation legal systems Standby p-type CIGS absorbed layers.
In the present invention, the three stage Co-evaporation method prepares p-type CIGS absorbed layers and preferably includes following steps：
(1) there are the solar cell semi-finished product of Mo back electrodes as the first substrate sputtering obtained in the previous step, in vacuum Under the conditions of heat respectively substrate, indium source, gallium source and selenium source temperature to 400 DEG C~550 DEG C, 800 DEG C~850 DEG C, 900 DEG C~950 DEG C and 270 DEG C~300 DEG C, first in the first substrate carry out indium, gallium and selenium deposition, obtain (In, Ga)2Se3Precursor film；
(2)(In,Ga)2Se3After the completion of precursor film deposition, stop indium, gallium deposition, at (In, Ga)2Se3It is deposited on precursor film Copper and selenium form copper selenium alloy phase；
(3) after forming copper selenium alloy phase, stop the deposition of copper, carry out the co-deposition of indium, gallium and selenium, obtain p-type CIGS Absorbed layer.
In the present invention, the sedimentation time of indium, gallium and selenium is preferably 15~25min in the step (1), and more preferably 18 ~20min；The vacuum degree of the vacuum condition is preferably 4.0 × 10-5Pa~6.0 × 10-5Pa, more preferably 5 × 10-5Pa；It will After each evaporation source is heated to temperature, the present invention preferably keeps the temperature 5~10min and deposits again.
The present invention heats copper source, so as to (In, Ga) preferably in the deposition process of indium, gallium and selenium2Se3Precursor film has deposited Cheng Hou carries out the deposition of copper immediately.In the present invention, the rate of heat addition of copper source is preferably 5~15 DEG C/min, more preferably 8~12 DEG C/min；The heating temperature of copper source is preferably 1230 DEG C~1300 DEG C, more preferably 1250 DEG C~1280 DEG C；Institute It states after copper source is heated to temperature, the present invention carries out copper deposition again after preferably balancing 5~10min.
In the present invention, with the extension of copper source sedimentation time, on growing film surface, copper is excessive, forms copper selenium alloy Phase, copper selenium alloy phase fusing point are 230 DEG C or so, and heat-absorbing liquefaction under the conditions of underlayer temperature, sample surface temperature drastically declines, this Invention is monitored sample surface temperature in deposition process, and sample surface temperature stops copper source deposition when declining 1min.
After forming copper selenium alloy phase, stop the deposition of copper, carry out the co-deposition of indium, gallium and selenium, obtains p-type CIGS and absorb Layer.In the present invention, with the deposition of indium, gallium, selenium, sample surfaces low melting-point coper selenium is mutually persistently consumed, sample surface temperature It is gradually increasing, when waiting for that the climbing speed of surface temperature is less than 0.5 DEG C/min, and keeping 1min, stops the deposition of indium, gallium and selenium.
After the completion of the p-type CIGS absorbed layers deposition, the present invention absorbs layer surface in the p-type CIGS and prepares p-type CdTe Absorbed layer.In the present invention, CdTe absorbed layers can apply the methods of close spaced sublimation, thermal evaporation and magnetron sputtering to prepare, this Invention it is preferable to use CdTe powder evaporations on p-type CIGS absorbed layers depositing p-type CdTe absorbed layers.
In the present invention, CdTe powder evaporation depositing p-type CdTe absorbed layers on p-type CIGS absorbed layers preferably wrap Include following steps：
(1) there are the solar cell semi-finished product of p-type CIGS absorbed layers as the second substrate deposition, add under vacuum For hot second substrate to 200~350 DEG C, heating CdTe source carries out CdTe precursor film depositions to 500~600 DEG C in the second substrate；
(2) after the completion of CdTe precursor films deposition, underlayer temperature is increased to 350 DEG C~400 DEG C, carries out CdCl2At chlorination Reason, obtains p-type CdTe absorbed layers.
In the present invention, in the present invention, the CdTe source is CdTe powder；The grain size of the CdTe powder is preferably 1 ~5mm, more preferably 3~4mm；The vacuum degree of the vacuum condition is preferably 4.0 × 10-5Pa~6.0 × 10-5Pa, more preferably It is 5 × 10-5Pa；The heating temperature of the second substrate is preferably 250~300 DEG C in the step (1), the heating temperature of the CdTe source Preferably 550~580 DEG C of degree；The time of the CdTe precursor films deposition is preferably 15~25min, more preferably 18~22min； In the present invention, after CdTe source is heated to set temperature, the present invention deposits again after preferably balancing 5~10min.
The present invention is preferably in CdTe deposition process, to CdCl2Source is slowly heated, the heating CdCl2The heating in source Rate is preferably 1~10 DEG C/min, more preferably 3~5 DEG C/min, and the heating rate of substrate is preferably 10 in the step (2) ~20 DEG C/min, more preferably 15~18 DEG C/min；The CdCl2The time of deposition is preferably 5~10min, more preferably 6~ 8min。
The present invention is by depositing CdCl2Obtained CdTe precursor films are made annealing treatment, gained CdTe thin film is increased Grain size improves the interface cohesion degree with p-type CIGS absorbed layers of p-type CdTe absorbed layers；And the present invention passes through to p-type The optimization of CdTe absorbed layer preparation conditions, shortens CdCl2The high-temperature process time, CdCl2Processing time be only 5~ 10min impacts CIGS absorbed layers so as to avoid the deposition process of CdTe, keeps diffusion at the combination interface of the two few, Good compatibility.
After obtaining p-type CdTe absorbed layers, present invention depositing n-type CdS buffer layers on the p-type CdTe absorbed layers.At this In invention, the depositing n-type CdS buffer layers can use magnetron sputtering method or chemical bath method to be prepared, and the present invention is preferred N-shaped CdS buffer layers are prepared using chemical bath method.
In the present invention, the chemical bath method prepares N-shaped CdS buffer layers and preferably includes following steps：
Mixed solution, thiourea solution and the ammonium hydroxide of cadmium acetate and ammonium acetate are prepared respectively；
The mixed solution of cadmium acetate and ammonium acetate, thiourea solution, ammonium hydroxide and water are mixed, deposition solution is obtained；
Third substrate is put into deposition to be deposited in solution, obtains N-shaped CdS buffer layers；The third substrate is heavy Product has the solar cell semi-finished product of p-type CdTe absorbed layers.
The present invention prepares the mixed solution, thiourea solution and ammonium hydroxide of cadmium acetate and ammonium acetate respectively.In the present invention, described It is 0.004~0.006mol/L that the concentration of cadmium acetate is excellent in the mixed solution of cadmium acetate and ammonium acetate, more preferably 0.005mol/ L；The concentration of ammonium acetate is preferably 0.04~0.06mol/L in the mixed solution of the cadmium acetate and ammonium acetate, more preferably 0.05mol/L；The concentration of the thiourea solution is preferably 0.2~0.4mol/L, more preferably 0.3mol/L；The ammonium hydroxide it is dense Degree is preferably 3~5mol/L, more preferably 4mol/L.
After obtaining the mixed solution, thiourea solution and ammonium hydroxide of cadmium acetate and ammonium acetate, the present invention is by cadmium acetate and ammonium acetate Mixed solution, thiourea solution, ammonium hydroxide and water mixing, obtain deposition solution.In the present invention, the cadmium acetate and ammonium acetate Mixed solution, thiourea solution, ammonium hydroxide and water volume ratio be preferably 3~5:2~4:4~6:85~90, more preferably 4:3: 5:88.In the present invention, the mixed solution of the cadmium acetate and ammonium acetate, thiourea solution, ammonium hydroxide and water preferably pass through following step Rapid mixing：
Will the mixed solution of cadmium acetate and ammonium acetate, thiocarbamide and first part water mix after heat, be heated to 70~ It is middle thereto that ammonium hydroxide is added dropwise after 85 DEG C, after ammonium hydroxide is added dropwise, remaining water is added.In the present invention, the dropwise addition of the ammonium hydroxide Speed is preferably 1~5 drop/sec, more preferably 3~4 drops/sec；The ratio between total volume of first part's water and water is preferably 1: 1.1~1.3.
It, can be by 4ml cadmium acetates/ammonium acetate mixed solution, 3ml thiourea solutions in some embodiments of the present invention Mixing, adds pure water to 80ml, is put into the water bath of preheating, waits for that solution temperature reaches 70 DEG C~85 DEG C, it is molten that 5ml ammonium hydroxide is added dropwise Liquid, after ammonium hydroxide is added dropwise, it is 100ml to add pure water to reaction solution volume, obtains deposition solution.
It obtains depositing with after solution, third substrate is put into deposition and is deposited in solution by the present invention, obtains N-shaped CdS Buffer layer.In the present invention, the time of the deposition is preferably 10~15min, more preferably 12~13min；The deposition Temperature is preferably 70 DEG C~85 DEG C, more preferably 75~80 DEG C.It in a specific embodiment of the present invention, can be straight by third substrate It connects and is put into deposition and is deposited in solution.
After the completion of the N-shaped CdS buffer layer depositions, the present invention prepares intrinsic zinc oxide in the N-shaped CdS buffer-layer surfaces Insulating layer.The present invention preferably sputters intrinsic zinc oxide insulating layer by magnetron sputtering method on N-shaped CdS buffer layers.In the present invention In, the magnetron sputtering is preferably rf magnetron sputtering, and the target of the magnetron sputtering is the ZnO ceramics of purity 99.99% Target, the ZnO ceramic targets are preferably dimensioned to be 2~5 inches, more preferably 3 inches；The sputter cathode magnetic field preferably balances ?；The back end vacuum degree of the sputtering is preferably 4.0 × 10-3~6.0 × 10-3Pa, more preferably 5.0 × 10-3Pa；It is described to splash Atmosphere of emanating is preferably the mixed gas of argon gas and oxygen；In the mixed gas volume ratio of argon gas and oxygen be preferably 40~ 60：1, more preferably 45~55:1；The sputtering pressure is preferably 3Pa~5Pa, more preferably 4Pa；The sputtering power is preferred For 40W~80W, more preferably 50~60W；The target-substrate distance of the magnetron sputtering is preferably 130mm~160mm, and more preferably 140 ~150mm；The time of the magnetron sputtering is preferably 20~40min, more preferably 25~35min；The present invention is by controlling magnetic Control sputtering time controls the thickness of intrinsic zinc oxide insulating layer, intrinsic zinc oxide thickness of insulating layer with sputtering time extension And increase.
After obtaining intrinsic zinc oxide insulating layer, the present invention prepares conductive layer in the intrinsic zinc oxide surface of insulating layer.This Conductive layer is preferably sputtered in intrinsic zinc oxide surface of insulating layer by magnetron sputtering method in invention.In the present invention, the magnetic control Sputtering is preferably rf magnetron sputtering；The sputtering atmosphere is preferably the mixed gas of argon gas and oxygen；In the mixed gas Argon oxygen flow ratio is 150~200：10, more preferably 160~180:10；The sputtering pressure is preferably 20Pa~3.0Pa, more Preferably 2.5~2.8Pa；The sputtering power is preferably 60W~100W, more preferably 80~90W, the target of the magnetron sputtering Cardinal distance is preferably 80mm~100mm, more preferably 90~95mm；The time of the magnetron sputtering is preferably 20~40min, more excellent It is selected as 25~35min；The present invention controls the thickness of conductive layer by controlling the magnetron sputtering time, and conductive layer thickness is with sputtering The extension of time and increase.In the present invention, the target that the magnetron sputtering uses is consistent with the material of above-mentioned conductive layer, herein It repeats no more.
In the present invention, the deposition process of conductive layer requires the high-energy argon ion that magnetic control sputtering cathode generates to native oxide The bombardment of zinc surface of insulating layer is weaker, in order to avoid destroying intrinsic zinc oxide insulating layer, the present invention will using radio-frequency power supply and balancing fields A large amount of high-energy argon ions are strapped in target surface, to obtain the conductive layer of high quality, and obtained intrinsic zinc oxide insulating layer and The interface cohesion of conductive layer is good.
After obtaining conductive layer, the present invention prepares top electrode in the conductive layer surface.In the present invention, it is preferred to use magnetic control Sputtering method sputters top electrode in conductive layer surface.In the present invention, the sputter cathode magnetic field is preferably balanced field；The magnetic control The back end vacuum degree of sputtering is preferably 4.0 × 10-3~6.0 × 10-3Pa, more preferably 5.0 × 10-3Pa；The magnetron sputtering Sputtering atmosphere is preferably argon gas, and the purity of the argon gas is preferably 99.99~99.999%；The air pressure of the magnetron sputtering is preferred For 0.1Pa~0.5Pa, it is more selected as 0.2~0.4Pa；The power of the magnetron sputtering is preferably 60W~80W, and more preferably 65 ~75W；The target-substrate distance of the magnetron sputtering is preferably 100mm~120mm, more preferably 105~115mm；The magnetron sputtering Target material is consistent with said program, is not repeating again；The time of the magnetron sputtering is preferably 20~40min, more Preferably 25~35min；The present invention controls the thickness of top electrode by controlling the magnetron sputtering time, the thickness of top electrode with The extension of sputtering time and increase.
In the present invention, Mo back electrodes, p-type CIGS absorbed layers, p-type CdTe absorbed layers, N-shaped CdS buffer layers, intrinsic The thickness of zinc oxide insulating layer, conductive layer and top electrode is consistent with said program, is not repeating herein.
With reference to embodiment to CIGS/CdTe Gradient Absorptions layer film solar cell provided by the invention and its preparation Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Step 1：Magnetron sputtering prepares Mo back electrodes
Target is 3 inches of forging fine grain Mo targets of purity 99.99%, and sputter cathode magnetic field is non-equilibrium field, back end vacuum It is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.1Pa, sputtering power 250W, target-substrate distance 100mm, control Mo thickness of electrode processed is 800nm；Substrate surface is cleaned using ion source before Mo is deposited, ion accelerating voltage is 250eV, particle beam 80mA, scavenging period 5min.
Step 2：Three stage Co-evaporation method depositing p-type CIGS absorbed layers
Back end vacuum is evacuated to 5.0 × 10-5Pa, respectively heating sink to the bottom temperature, indium source, gallium source and selenium source temperature to 400 DEG C DEG C, 800 DEG C, 900 DEG C and 270 DEG C, each evaporation source is waited for temperature and balances 10min, source baffle and sample baffle is opened, starts to deposit (In, Ga)2Se3Precursor film 15min；
At the first step (In, Ga)2Se3When precursor film depositional remanent 10min, copper source is heated to 1230 DEG C, (In, Ga)2Se3 After the completion of precursor film deposition, copper source equalized temperature 10min opens copper source baffle, indium source and gallium source baffle is simultaneously closed off, in copper source In deposition process, indium source and the heat preservation of gallium source, sample surface temperature close copper source baffle when declining 1min；
Indium source and gallium source baffle are opened while closing copper source baffle, sample surface temperature gradually rises up to become without apparent Change, and keep simultaneously closing off after 1min copper source, indium source, gallium source, selenium source and sample stage baffle, and close power supply, sample cooling When to 200 DEG C or so, it is transferred to Sample Room；P-type CIGS absorbed layers are obtained, the thickness of control p-type CIGS absorbed layers is 1.0 μm；
Step 3：Cadmium Telluride powder powder stock thermal evaporation prepares N-shaped CdTe absorbed layers
Back end vacuum is evacuated to 5.0 × 10-5Pa heats underlayer temperature and CdTe source temperature respectively to 200 DEG C and 500 DEG C, waits for CdTe source temperature is to temperature and balances 5min, opens source baffle and sample baffle, deposits 15min.
In CdTe deposition process, CdCl2Source is slowly heated, in CdTe precursor film depositional remanent 5min, CdCl2Source adds Heat is to 450 DEG C, and after the completion of CdTe precursor films deposit, underlayer temperature is quickly increased to 350 DEG C, opens the sources CdCl2 baffle, simultaneously It closes CdTe source baffle and power supply, after 5min, closes CdCl2Source baffle and sample baffle, and power supply is closed, obtain N-shaped CdTe The thickness of absorbed layer, control N-shaped CdTe absorbed layers is 0.8 μm；
Step 4：Chemical bath method depositing n-type CdS buffer layers
Configuration cadmium acetate and ammonium acetate molar concentration are respectively the mixed solution of 0.005mol/L and 0.05mol/L, configuration The thiourea solution that molar concentration is 0.3mol/L and the ammonia spirit that molar concentration is 4mol/L store up after above-mentioned solution allocation It deposits spare；
4ml cadmium acetates/ammonium acetate mixed solution is taken, 3ml thiourea solutions, it is 80ml to add pure water to solution, is put into preheating Water bath in, wait for that solution temperature reaches 70 DEG C, 5ml ammonia spirits be added.Solution persistently stirs in solution process for preparation, ammonia Aqueous solution adition process is slow, is adjusting reaction solution volume to 100ml with pure water, is being subsequently placed into CIGS samples deposition 10min takes out CIGS samples, is rinsed repeatedly with pure water, is subsequently dried nitrogen drying, obtains N-shaped CdS buffer layers, controls N-shaped The thickness of CdS buffer layers is 30nm；
Step 5：Rf magnetron sputtering prepares intrinsic zinc oxide insulating layer
Target is 3 inches of ZnO ceramic targets of purity 99.99%, and sputter cathode magnetic field is balanced field, and back end vacuum is evacuated to 5.0×10-3Pa, sputtering atmosphere are argon gas：Oxygen=200：4 mixed atmosphere, sputtering pressure 3Pa, sputtering power 40W, target Cardinal distance 130mm, ZnO thickness is 50nm；
Step 6：Magnetron sputtering method prepares transparency conducting layer
For zinc-oxide-base transparent conductive film as conductive layer, target is 3 inches of zinc oxide for mixing aluminium 2% of purity 99.99% Ceramic target, sputter cathode magnetic field are balanced field, and back end vacuum is evacuated to 1.5 × 10-3Pa, sputtering atmosphere are the mixing of argon gas and oxygen Gas, argon oxygen flow ratio are 150：10, sputtering pressure 2.0Pa, sputtering power 60W, target-substrate distance 80mm control transparent conductive film Thickness is 500nm.
Step 7：Magnetron sputtering method prepares top electrode
Selection nickel is upper electrode material, and target is 3 inches of Ni targets of purity 99.99%, and sputter cathode magnetic field is balanced field, Back end vacuum is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.1Pa, sputtering power 60W, target-substrate distance 100mm, control nickel electrode thickness are 1.0 μm.
The battery conversion efficiency of gained thin-film solar cells is measured, it is 16.1% that can obtain battery conversion efficiency.
Embodiment 2
Step 1：Magnetron sputtering prepares Mo back electrodes
Target is 3 inches of forging fine grain Mo targets of purity 99.99%, and sputter cathode magnetic field is non-equilibrium field, back end vacuum It is evacuated to 4.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.5Pa, sputtering power 260W, target-substrate distance 120mm, control Mo thickness of electrode processed is 1000nm；Substrate surface is cleaned using ion source before Mo is deposited, ion accelerating voltage is 250eV, particle beam 80mA, scavenging period 5min.
Step 2：Three stage Co-evaporation method depositing p-type CIGS absorbed layers
Back end vacuum is evacuated to 6.0 × 10-5Pa, respectively heating sink to the bottom temperature, indium source, gallium source and selenium source temperature to 550 DEG C DEG C, 850 DEG C, 950 DEG C and 300 DEG C, each evaporation source is waited for temperature and balances 10min, source baffle and sample baffle is opened, starts to deposit (In, Ga)2Se3Precursor film 25min；
In the first step (In, Ga) 2Se3 precursor film depositional remanent 10min, copper source is heated to 1300 DEG C, (In, Ga)2Se3 After the completion of precursor film deposition, copper source equalized temperature 10min opens copper source baffle, indium source and gallium source baffle is simultaneously closed off, in copper source In deposition process, indium source and the heat preservation of gallium source, sample surface temperature close copper source baffle when declining 1min；
Indium source and gallium source baffle are opened while closing copper source baffle, sample surface temperature gradually rises up to become without apparent Change, and keep simultaneously closing off after 1min copper source, indium source, gallium source, selenium source and sample stage baffle, and close power supply, sample cooling When to 200 DEG C or so, it is transferred to Sample Room；P-type CIGS absorbed layers are obtained, the thickness of control p-type CIGS absorbed layers is 1.5 μm；
Step 3：Cadmium Telluride powder powder stock thermal evaporation prepares N-shaped CdTe absorbed layers
Back end vacuum is evacuated to 5.0 × 10-5Pa heats underlayer temperature and CdTe source temperature respectively to 350 DEG C and 600 DEG C, waits for CdTe source temperature is to temperature and balances 5min, opens source baffle and sample baffle, deposits 25min.
In CdTe deposition process, CdCl2Source is slowly heated, in CdTe precursor film depositional remanent 5min, CdCl2Source adds Heat is to 500 DEG C, and after the completion of CdTe precursor films deposit, underlayer temperature is quickly increased to 400 DEG C, opens CdCl2Source baffle, simultaneously It closes CdTe source baffle and power supply, after 10min, closes CdCl2Source baffle and sample baffle, and power supply is closed, obtain N-shaped CdTe The thickness of absorbed layer, control N-shaped CdTe absorbed layers is 1.0 μm；
Step 4：Chemical bath method depositing n-type CdS buffer layers
Configuration cadmium acetate and ammonium acetate molar concentration are respectively the mixed solution of 0.004mol/L and 0.06mol/L, configuration The thiourea solution that molar concentration is 0.4mol/L and the ammonia spirit that molar concentration is 3mol/L store up after above-mentioned solution allocation It deposits spare；
4ml cadmium acetates/ammonium acetate mixed solution is taken, 3ml thiourea solutions, it is 80ml to add pure water to solution, is put into preheating Water bath in, wait for that solution temperature reaches 85 DEG C, 5ml ammonia spirits be added.Solution persistently stirs in solution process for preparation, ammonia Aqueous solution adition process is slow, is adjusting reaction solution volume to 100ml with pure water, is being subsequently placed into CIGS samples deposition 15min takes out CIGS samples, is rinsed repeatedly with pure water, is subsequently dried nitrogen drying, obtains N-shaped CdS buffer layers, N-shaped CdS The thickness of buffer layer is 60nm；
Step 5：Rf magnetron sputtering prepares intrinsic zinc oxide insulating layer
Target is 3 inches of ZnO ceramic targets of purity 99.99%, and sputter cathode magnetic field is balanced field, and back end vacuum is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are argon gas：Oxygen=200：4 mixed atmosphere, sputtering pressure 5Pa, sputtering power 80W, target Cardinal distance 160mm, ZnO thickness is 80nm；
Step 6：Magnetron sputtering method prepares transparency conducting layer
For indium tin oxide conductive film as conductive layer, target is 3 inch oxidized indium tin ceramic targets of purity 99.99%, sputtering Cathod magnetic field is balanced field, and back end vacuum is evacuated to 1.5 × 10-3Pa, sputtering atmosphere are the mixed gas of argon gas and oxygen, argon oxygen stream Amount is than being 200：10, sputtering pressure 3.0Pa, sputtering power 100W, target-substrate distance 100mm, control electrically conducting transparent layer thickness are 800nm。
Step 7：Magnetron sputtering method prepares top electrode
Selection nickel is upper electrode material, and target is 3 inches of Ni targets of purity 99.99%, and sputter cathode magnetic field is balanced field, Back end vacuum is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.5Pa, sputtering power 80W, target-substrate distance 120mm, nickel electrode thickness are 3.0 μm.
The battery conversion efficiency of gained thin-film solar cells is measured, it is 16.5% that can obtain battery conversion efficiency.
Embodiment 3
Step 1：Magnetron sputtering prepares Mo back electrodes
Target is 3 inches of forging fine grain Mo targets of purity 99.99%, and sputter cathode magnetic field is non-equilibrium field, back end vacuum It is evacuated to 4.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.4Pa, sputtering power 250W, target-substrate distance 110mm, control Mo thickness of electrode processed is 900nm；Substrate surface is cleaned using ion source before Mo is deposited, ion accelerating voltage is 250eV, particle beam 80mA, scavenging period 5min.
Step 2：Three stage Co-evaporation method depositing p-type CIGS absorbed layers
Back end vacuum is evacuated to 6.0 × 10-5Pa, respectively heating sink to the bottom temperature, indium source, gallium source and selenium source temperature to 450 DEG C DEG C, 830 DEG C, 920 DEG C and 280 DEG C, each evaporation source is waited for temperature and balances 10min, source baffle and sample baffle is opened, starts to deposit (In, Ga) 2Se3 precursor films 20min；
At the first step (In, Ga)2Se3When precursor film depositional remanent 10min, copper source is heated to 1250 DEG C, (In, Ga)2Se3 After the completion of precursor film deposition, copper source equalized temperature 10min opens copper source baffle, indium source and gallium source baffle is simultaneously closed off, in copper source In deposition process, indium source and the heat preservation of gallium source, sample surface temperature close copper source baffle when declining 1min；
Indium source and gallium source baffle are opened while closing copper source baffle, sample surface temperature gradually rises up to become without apparent Change, and keep simultaneously closing off after 1min copper source, indium source, gallium source, selenium source and sample stage baffle, and close power supply, sample cooling When to 200 DEG C or so, it is transferred to Sample Room；P-type CIGS absorbed layers are obtained, the thickness of p-type CIGS absorbed layers is 1.2 μm；
Step 3：Cadmium Telluride powder powder stock thermal evaporation prepares N-shaped CdTe absorbed layers
Back end vacuum is evacuated to 5.0 × 10-5Pa heats underlayer temperature and CdTe source temperature respectively to 250 DEG C and 550 DEG C, waits for CdTe source temperature is to temperature and balances 5min, opens source baffle and sample baffle, deposits 20min.
In CdTe deposition process, CdCl2Source is slowly heated, in CdTe precursor film depositional remanent 5min, CdCl2Source adds Heat is to 480 DEG C, and after the completion of CdTe precursor films deposit, underlayer temperature is quickly increased to 380 DEG C, opens CdCl2Source baffle, simultaneously It closes CdTe source baffle and power supply, after 7min, closes CdCl2Source baffle and sample baffle, and power supply is closed, obtain N-shaped CdTe The thickness of absorbed layer, control N-shaped CdTe absorbed layers is 0.9 μm；
Step 4：Chemical bath method depositing n-type CdS buffer layers
Configuration cadmium acetate and ammonium acetate molar concentration are respectively the mixed solution of 0.004mol/L and 0.05mol/L, configuration The thiourea solution that molar concentration is 0.3mol/L and the ammonia spirit that molar concentration is 3mol/L store up after above-mentioned solution allocation It deposits spare；
4ml cadmium acetates/ammonium acetate mixed solution is taken, 3ml thiourea solutions, it is 80ml to add pure water to solution, is put into preheating Water bath in, wait for that solution temperature reaches 80 DEG C, 5ml ammonia spirits be added.Solution persistently stirs in solution process for preparation, ammonia Aqueous solution adition process is slow, is adjusting reaction solution volume to 100ml with pure water, is being subsequently placed into CIGS samples deposition 13min takes out CIGS samples, is rinsed repeatedly with pure water, is subsequently dried nitrogen drying, obtains N-shaped CdS buffer layers, N-shaped CdS The thickness of buffer layer is 50nm；
Step 5：Rf magnetron sputtering prepares intrinsic zinc oxide insulating layer
Target is 3 inches of ZnO ceramic targets of purity 99.99%, and sputter cathode magnetic field is balanced field, and back end vacuum is evacuated to 5.0×10-3Pa, sputtering atmosphere are argon gas：Oxygen=200：4 mixed atmosphere, sputtering pressure 4Pa, sputtering power 60W, target Cardinal distance 150mm, ZnO thickness is 60nm；
Step 6：Magnetron sputtering method prepares transparency conducting layer
For cadmium stannate transparent conductive film as conductive layer, target is 3 inches of cadmium stannate ceramic targets of purity 99.99%, sputtering Cathod magnetic field is balanced field, and back end vacuum is evacuated to 1.5 × 10-3Pa, sputtering atmosphere are the mixed gas of argon gas and oxygen, argon oxygen stream Amount is than being 180：10, sputtering pressure 2.5Pa, sputtering power 80W, target-substrate distance 90mm, control electrically conducting transparent film thickness are 600nm。
Step 7：Magnetron sputtering method prepares top electrode
Selection nickel is upper electrode material, and target is 3 inches of Ni targets of purity 99.99%, and sputter cathode magnetic field is balanced field, Back end vacuum is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.3Pa, sputtering power 70W, target-substrate distance 110mm, nickel electrode thickness are 2.0 μm.
The battery conversion efficiency of gained thin-film solar cells is measured, it is 15.6% that can obtain battery conversion efficiency.
As seen from the above embodiment, CIGS/CdTe Gradient Absorptions layer film solar cell battery provided by the invention turns It changes efficient, has effectively widened the solar spectrum utilization scope of absorbed layer.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (9)

1. a kind of CIGS/CdTe Gradient Absorptions layer film solar cell includes substrate, Mo back electrodes, ladder successively from bottom to top Spend energy gap absorbed layer, N-shaped CdS buffer layers, intrinsic zinc oxide insulating layer, conductive layer and top electrode；The gradient forbidden band is wide It includes p-type CIGS absorbed layers and p-type CdTe absorbed layers to spend absorbed layer from bottom to top；The thickness of the p-type CIGS absorbed layers is 1.0 ~1.5 μm；The doping of Ga is 0~30% in the p-type CIGS absorbed layers；The conductive layer is cadmium stannate conductive layer；
Using three stage Co-evaporation method in Mo back electrodes surface depositing p-type CIGS, p-type CIGS absorbed layers are formed,
The three stage Co-evaporation method prepares p-type CIGS absorbed layers and includes the following steps：
(a) there are the solar cell semi-finished product of Mo back electrodes as the first substrate sputtering obtained in the previous step, in vacuum condition It is lower heat respectively substrate, indium source, gallium source and selenium source temperature to 400 DEG C~550 DEG C, 800 DEG C~850 DEG C, 900 DEG C~950 DEG C and 270 DEG C~300 DEG C, indium, gallium and selenium deposition are carried out first in the first substrate, is obtained (In, Ga)2Se3Precursor film；
(b)(In,Ga)2Se3After the completion of precursor film deposition, stop indium, gallium deposition, at (In, Ga)2Se3On precursor film deposit copper and Selenium forms copper selenium alloy phase；
(c) after forming copper selenium alloy phase, stop the deposition of copper, carry out the co-deposition of indium, gallium and selenium, obtain p-type CIGS and absorb Layer.
2. thin-film solar cells according to claim 1, which is characterized in that the thickness of the Mo back electrodes be 0.8~ 1.0μm。
3. thin-film solar cells according to claim 1, which is characterized in that the thickness of the p-type CdTe absorbed layers is 0.8~1.0 μm.
4. thin-film solar cells according to claim 1, which is characterized in that the thickness of the N-shaped CdS buffer layers is 30 ~60nm.
5. thin-film solar cells according to claim 1, which is characterized in that the thickness of the conductive layer be 500~ 800nm。
6. thin-film solar cells according to claim 1, which is characterized in that the thickness of the intrinsic zinc oxide insulating layer For 50~80nm.
7. thin-film solar cells according to claim 1, which is characterized in that the material of the top electrode be gold, silver and One kind in nickel；1.0~3.0 μm of the thickness of the top electrode.
8. the preparation method of claim 1~7 thin-film solar cells, which is characterized in that include the following steps：
Mo back electrodes, p-type CIGS absorbed layers, p-type CdTe absorbed layers, N-shaped CdS buffer layers, sheet are sequentially prepared on substrate material Levy zinc oxide insulating layer, conductive layer and top electrode.
9. preparation method according to claim 8, which is characterized in that include the following steps：
(1) magnetron sputtering method is used to sputter Mo back electrodes in substrate material surface；
(2) it uses three stage Co-evaporation method in Mo back electrodes surface depositing p-type CIGS, forms p-type CIGS absorbed layers；
The three stage Co-evaporation method prepares p-type CIGS absorbed layers and includes the following steps：
(a) there are the solar cell semi-finished product of Mo back electrodes as the first substrate sputtering obtained in the previous step, in vacuum condition It is lower heat respectively substrate, indium source, gallium source and selenium source temperature to 400 DEG C~550 DEG C, 800 DEG C~850 DEG C, 900 DEG C~950 DEG C and 270 DEG C~300 DEG C, indium, gallium and selenium deposition are carried out first in the first substrate, is obtained (In, Ga)2Se3Precursor film；
(b)(In,Ga)2Se3After the completion of precursor film deposition, stop indium, gallium deposition, at (In, Ga)2Se3On precursor film deposit copper and Selenium forms copper selenium alloy phase；
(c) after forming copper selenium alloy phase, stop the deposition of copper, carry out the co-deposition of indium, gallium and selenium, obtain p-type CIGS and absorb Layer；
(3) it uses CdTe powder evaporation to absorb layer surface depositing p-type CdTe in p-type CIGS, forms p-type CdTe absorbed layers；
(4) in p-type CdTe absorbed layer surface chemistry depositing n-type CdS, N-shaped CdS buffer layers are formed；
(5) it uses magnetron sputtering method in N-shaped CdS buffer-layer surface sputtering zinc oxides, forms intrinsic zinc oxide insulating layer；
(6) magnetron sputtering method is used to sputter conductive layer in intrinsic zinc oxide surface of insulating layer；
Top electrode is sputtered in conductive layer surface using magnetron sputtering method.
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