CN106449810B - A kind of CdTe/CIGS Gradient Absorptions layer film solar cell and preparation method thereof - Google Patents

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

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CN106449810B
CN106449810B CN201611048928.2A CN201611048928A CN106449810B CN 106449810 B CN106449810 B CN 106449810B CN 201611048928 A CN201611048928 A CN 201611048928A CN 106449810 B CN106449810 B CN 106449810B
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CN106449810A (en
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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 invention provides a kind of CdTe/CIGS Gradient Absorptions layer film solar cell, includes substrate, conductive layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, gradient energy gap absorbed layer and Top electrode successively from bottom to top；The gradient energy gap absorbed layer includes p-type CdTe absorbed layers and p-type CIGS absorbed layers from bottom to top.The present invention utilizes CIGS absorbed layers and CdTe absorbed layer composition gradient absorbed layers, has widened the solar spectrum utilization scope of absorbed layer, has further increased solar cell conversion efficiency.

Description

A kind of CdTe/CIGS 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 CdTe/CIGS Gradient Absorptions Layer film solar cell and preparation method thereof.
Background technology
Solar cell produces photo-generated carrier to form electricity by absorbing energy more than the photon of absorbed layer energy gap Can, but photon is then lost higher than the portion of energy of energy gap in a manner of Phonon emission.Absorbed using gradient energy gap The solar spectrum utilization scope that layer widens absorbed layer is to lift the important channel of solar cell conversion efficiency.
CIGS (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, and technology maturity is of a relatively high.Mesh Preceding CdTe thin film solar cell laboratory highest conversion efficiency reaches 21.5%, the CdTe battery component conversion of industrialized production Efficiency reaches 16.5%, CIGS solar cells laboratory highest conversion efficiency and reaches 21.7%, the CdTe electricity of industrialized production Pond component conversion 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 scopes, 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, and In and Ga counterdiffusion is tight in preparation process Weight, the composition of design are difficult to.Therefore gradient bandwidth CIGS absorbed layers are prepared by Ga changes of contents to improve absorbed layer pair The absorption region of solar spectrum, and then the battery conversion efficiency for improving solar cell only exists on Theoretical Design, without real Border is worth, and solar film battery conversion efficiency is still difficult to further improve at present.
The content of the invention
In view of this, present invention aims at provide a kind of CdTe/CIGS Gradient Absorption layers of solar energy high conversion efficiency Thin-film solar cells and preparation method thereof.
The invention provides a kind of CdTe/CIGS Gradient Absorptions layer film solar cell, includes lining successively from bottom to top Bottom, conductive layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, gradient energy gap absorbed layer and Top electrode；The gradient Energy gap absorbed layer includes p-type CdTe absorbed layers and p-type CIGS absorbed layers from bottom to top.
Preferably, the thickness of the p-type CdTe absorbed layers is 0.8~1.0 μm.
Preferably, the thickness of the CIGS absorbed layers is 1.0~1.5 μm；Ga doping is 0 in the CIGS absorbed layers ~10%.
Preferably, the conductive layer is in fluorine doped tin oxide conductive layer, conductive indium-tin oxide layer and cadmium stannate conductive layer It is a kind of.
Preferably, the thickness of the conductive layer is 600~800nm.
Preferably, the thickness of the intrinsic zinc oxide insulating barrier is 30~60nm.
Preferably, the thickness of the n-type CdS cushions is 50~100nm.
Preferably, the Top electrode is Mo membrane electrodes；The thickness of the Top electrode is 1.0 μm.
The invention provides a kind of preparation method of thin-film solar cells described in such scheme, comprise the following steps：
Transparency conducting layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, p-type CdTe are sequentially prepared on backing material Absorbed layer, p-type CIGS absorbed layers and Top electrode.
Preferably, comprise the following steps：
(1) conductive layer is sputtered in substrate material surface using magnetron sputtering method；
(2) using magnetron sputtering method in the conductive layer surface sputtering zinc oxide film, formation intrinsic zinc oxide insulating barrier；
(3) in the intrinsic zinc oxide surface of insulating layer chemical deposition n-type CdS, n-type CdS cushions are formed：
(4) inhaled using CdTe powder evaporation in the n-type CdS buffer-layer surfaces depositing p-type CdTe, formation p-type CdTe Receive layer；
(5) layer surface depositing p-type CIGS is absorbed in the p-type CdTe using three stage Co-evaporation method, forms p-type CIGS and absorb Layer；
(6) layer surface sputtering Mo back electrodes are absorbed in the p-type CIGS using magnetron sputtering method.
The invention provides a kind of CdTe/CIGS Gradient Absorptions layer film solar cell, includes lining successively from bottom to top Bottom, conductive layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, gradient energy gap absorbed layer and Top electrode；The gradient Energy gap absorbed layer includes p-type CdTe absorbed layers and p-type CIGS absorbed layers from bottom to top.Gradient Absorption layer provided by the invention The absorbed layer of thin-film solar cells includes the CIGS absorbed layers of narrow band gap and the CdTe absorbed layers of broad-band gap, and wherein CIGS absorbs The a width of 1.05ev of band (when Ga dopings are 0) of layer, a width of 1.46ev of band of CdTe absorbed layers, it is wide that the two forms gradient forbidden band Absorbed layer is spent, the solar spectrum utilization scope of absorbed layer is widened using CdTe/CIGS gradient energy gap absorbed layers, is further carried High solar cell conversion efficiency.Result of the test shows that the conversion efficiency of thin-film solar cells provided by the invention can reach To 16.8%.
Brief description of the drawings
Fig. 1 is that CdTe/CIGS gradients energy gap absorbed layer thin-film solar cell structure provided in an embodiment of the present invention shows It is intended to；
1- substrates in Fig. 1；2- conductive layers；3- intrinsic zinc oxide insulating barriers；4-n type CdS cushions；5-p types CdTe absorbs Layer；6-p type CIGS absorbed layers；7- Top electrodes.
Embodiment
The invention provides a kind of CdTe/CIGS Gradient Absorptions layer film solar cell, includes lining successively from bottom to top Bottom, conductive layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, gradient energy gap absorbed layer and Top electrode；The gradient Energy gap absorbed layer includes p-type CdTe absorbed layers and p-type CIGS absorbed layers from bottom to top.
CdTe/CIGS Gradient Absorptions layer film solar cell provided by the invention includes substrate.The present invention is to substrate material Expect no particular/special requirement, using the typical substrate material in this area, preferably glass substrate, the present invention uses lower substrate Mode prepare thin-film solar cells.
CdTe/CIGS Gradient Absorptions layer film solar cell provided by the invention includes being arranged on the substrate surface Conductive layer.In the present invention, the thickness of the conductive layer is preferably 600~800nm, more preferably 700~750nm；It is described to lead The preferably described conductive layer of electric layer is preferably transparency conducting layer, more preferably fluorine doped tin oxide conductive layer, conductive indium-tin oxide layer and One kind in cadmium stannate conductive layer.
CdTe/CIGS Gradient Absorptions layer film solar cell provided by the invention includes being arranged on the conductive layer surface Intrinsic zinc oxide insulating barrier.In the present invention, the thickness of the intrinsic zinc oxide insulating barrier is preferably 30~60nm, more preferably For 40~50nm.
CdTe/CIGS Gradient Absorptions layer film solar cell provided by the invention includes being arranged on the intrinsic zinc oxide The n-type CdS cushions of surface of insulating layer.In the present invention, the thickness of the n-type CdS cushions is preferably 50~100nm, more Preferably 60~80nm.
CdTe/CIGS Gradient Absorptions layer film solar cell provided by the invention includes being arranged on the n-type CdS bufferings The gradient energy gap absorbed layer of layer surface；The gradient energy gap absorbed layer includes p-type CdTe absorbed layers and p from bottom to top Type CIGS absorbed layers.In the present invention, the thickness of the p-type CdTe absorbed layers is preferably 0.8~1.0 μm, more preferably 0.9 μ m。
In the present invention, p-type CIGS absorbed layers are arranged on p-type CdTe absorbed layers upper surface；The thickness of the CIGS absorbed layers Degree is preferably 1.0~1.5 μm, more preferably 1.2~1.3 μm, in the CIGS absorbed layers Ga doping be preferably 0~ 10%, more preferably 2~5%.The present invention is absorbed using CIGS absorbed layers of the low Ga dopings even without Ga admixtures with CdTe Layer collectively constitutes the absorbed layer of gradient energy gap, reduces the counterdiffusion on the combination interface of the two.
CdTe/CIGS Gradient Absorptions layer film solar cell provided by the invention includes being arranged on the CIGS absorbed layers On Top electrode.In the present invention, the Top electrode is preferably Mo membrane electrodes；The thickness of the Top electrode is preferably 1.0 μm.
The present invention prepares thin-film solar cells by the way of lower substrate, and wherein the CdTe absorbed layers of broad stopband are positioned at narrow The CIGS absorbed layers lower floor of forbidden band, sunshine irradiates from the CdTe ends of broad-band gap in application process.
The invention provides a kind of preparation method of thin-film solar cells described in such scheme, comprise the following steps： Conductive layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, p-type CdTe absorbed layers, p-type CIGS are sequentially prepared on backing material Absorbed layer and Top electrode.
The present invention prepares conductive layer on backing material, is preferably sputtered and led on the backing material by magnetron sputtering method Electric layer.In the present invention, the atmosphere of the magnetron sputtering is preferably the mixed gas of argon gas and oxygen；Argon in the mixed gas Oxygen flow ratio preferably 80~90：10~20, more preferably 85~88:12~15；The air pressure of the sputtering be preferably 1.0Pa~ 3.0Pa, more preferably 1.5~2.5Pa；The power of the sputtering is preferably 60W~100W, more preferably 80~90W, the magnetic The target-substrate distance of control sputtering is preferably 80mm~100mm, more preferably 90~95mm；The time of the magnetron sputtering is preferably 20~ 40min, more preferably 25~35min；The present invention controls the thickness of conductive layer by controlling sputtering time, conductive layer thickness with The extension of sputtering time and increase.In the present invention, the material one of the target that the magnetron sputtering uses and above-mentioned conductive layer Cause, will not be repeated here；The material of the substrate is consistent with such scheme, will not be repeated here.
After forming conductive layer, the present invention prepares intrinsic zinc oxide insulating barrier in the conductive layer upper surface, and the present invention is preferably By magnetron sputtering method on the transparency conducting layer sputtering zinc oxide, formed intrinsic zinc oxide insulating barrier.In the present invention, institute State magnetron sputtering zinc oxide and preferably use rf magnetron sputtering, the target of the magnetron sputtering is the ZnO potteries of purity 99.99% Porcelain target, the ZnO ceramic targets are preferably dimensioned to be 2~5 inches, more preferably 3 inches；The sputter cathode magnetic field is preferably flat Heng Chang；The back end vacuum is preferably 4.0 × 10-3~6.0 × 10-3Pa, more preferably 5.0 × 10-3Pa.In the present invention, The sputtering atmosphere is preferably the mixed gas of argon gas and oxygen；The volume ratio of argon gas and oxygen is preferably in the mixed gas 40~60：1, more preferably 45~55:1.In the present invention, the sputtering pressure is preferably 3Pa~5Pa, more preferably 4Pa； The sputtering power is preferably 40W~80W, more preferably 50~60W；The target-substrate distance of the magnetron sputtering be preferably 130mm~ 160mm, more preferably 140~150mm；The time of the magnetron sputtering is preferably 20~40min, more preferably 25~35min； The present invention controls the thickness of intrinsic zinc oxide insulating barrier by controlling the magnetron sputtering time, intrinsic zinc oxide thickness of insulating layer with The extension of sputtering time and increase.
In the present invention, the deposition process of intrinsic zinc oxide insulating barrier requires high-energy argon ion caused by magnetic control sputtering cathode Weaker to electrically conducting transparent film bombardment, in order to avoid destroying conductive layer, the present invention will be largely high using radio-frequency power supply and balancing fields Energy ar-ion beam is tied to target surface, reduces the bombardment to substrate surface, so as to obtain the intrinsic zinc oxide insulating barrier of high quality, and Obtained intrinsic zinc oxide insulating barrier and the interface cohesion of conductive layer is good.
After obtaining intrinsic zinc oxide insulating barrier, the present invention in the intrinsic zinc oxide insulating barrier upper surface depositing n-type CdS, Form n-type CdS cushions.In the present invention, depositing n-type CdS cushions can use magnetron sputtering method or chemical bath method to enter Prepared by row, present invention preferably uses chemical bath method to prepare n-type CdS cushions.
In the present invention, the chemical bath method prepares n-type CdS cushions and preferably includes following steps：
Mixed solution, thiourea solution and the ammoniacal liquor of cadmium acetate and ammonium acetate are prepared respectively；
The mixed solution of cadmium acetate and ammonium acetate, thiourea solution, ammoniacal liquor and water are mixed, obtain deposition solution；
First substrate is put into the deposition to be deposited with solution, formed in the intrinsic zinc oxide surface of insulating layer N-type CdS cushions；First substrate has the solar cell semi-finished product of intrinsic zinc oxide insulating barrier for deposition.
The present invention prepares mixed solution, thiourea solution and the ammoniacal liquor of cadmium acetate and ammonium acetate respectively.In the present invention, it is 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 ammoniacal liquor it is dense Degree is preferably 3~5mol/L, more preferably 4mol/L.
It is of the invention by cadmium acetate and ammonium acetate after obtaining the mixed solution, thiourea solution and ammoniacal liquor of cadmium acetate and ammonium acetate Mixed solution, thiourea solution, ammoniacal liquor and water mixing, obtain deposition solution.In the present invention, the cadmium acetate and ammonium acetate Mixed solution, thiourea solution, the volume ratio of ammoniacal liquor and water be preferably 3~5:2~4:4~6:85~90, more preferably 4:3: 5:88.In the present invention, mixed solution, thiourea solution, ammoniacal liquor and the water of the cadmium acetate and ammonium acetate preferably pass through following step Rapid mixing：
Will the mixed solution of cadmium acetate and ammonium acetate, thiocarbamide and Part I water mix after heated, be heated to 70~ After 85 DEG C, middle dropwise addition ammoniacal liquor, after ammoniacal liquor is added dropwise, adds remaining water thereto.In the present invention, the drop of the ammoniacal liquor Acceleration is preferably 1~5 drop/sec, more preferably 3~4 drops/sec；The ratio between cumulative volume of the Part I water and water is preferably 1:1.1~1.3.
, can be by 4ml cadmium acetates/ammonium acetate mixed solution, 3ml thiourea solutions in some embodiments of the present invention Mixing, pure water is added to be put into the water bath of preheating to 80ml, treat that solution temperature reaches 70 DEG C~85 DEG C, it is molten that 5ml ammoniacal liquor is added dropwise Liquid, after ammoniacal liquor is added dropwise, it is 100ml to add pure water to reaction solution volume.
Obtain depositing with after solution, the first substrate is put into the deposition and deposited with solution by the present invention, obtains n-type GdS cushions.In the present invention, the time of the deposition is preferably 10~15min, more preferably 12~13min；The deposition Temperature be preferably 70 DEG C~85 DEG C, more preferably 75~80 DEG C.In a particular embodiment of the present invention, can be by the first substrate Deposition is directly placed into be deposited with solution.
After the completion of the deposition, the present invention takes out the first substrate, is rinsed, dried with pure water.In this hair In bright, the drying is preferably nitrogen drying.
After the completion of prepared by n-type GdS cushions, the present invention prepares CdTe absorbed layers in n-type GdS cushions upper surface.At this In invention, CdTe absorbed layers can be applied and prepared the methods of close spaced sublimation, thermal evaporation and magnetron sputtering, present invention preferably uses CdTe powder evaporation depositing p-type CdTe absorbed layers on n-type CdS cushions.
In the present invention, CdTe powder evaporation depositing p-type CdTe absorbed layers on n-type CdS cushions preferably wrap Include following steps：
(1) obtained in the previous step deposit there are into the solar cell semi-finished product of n-type CdS cushions as the second substrate, For heated under vacuum solar cell semi-finished product to 200~350 DEG C, heating CdTe source is enterprising in substrate to 500~600 DEG C Row CdTe precursor films deposit；
(2) after the completion of CdTe precursor films deposition, the temperature of the second substrate is increased to 350 DEG C~400 DEG C, carries out CdCl2 Chlorination is handled, and obtains CdTe absorbed layers.
In the present invention, the CdTe source is CdTe powder；The particle diameter of the CdTe powder is preferably 1~5mm, more preferably For 3~4mm；The vacuum of the vacuum condition is preferably 4.0 × 10-5Pa~6.0 × 10-5Pa, more preferably 5 × 10-5Pa； The heating-up temperature of the second substrate is preferably 250~300 DEG C in the step (1), and the heating-up temperature of the CdTe source is preferably 550 ~580 DEG C；The time of the CdTe precursor films deposition is preferably 15~30min, more preferably 20~25min；In the present invention, After CdTe source is heated to design temperature, deposited again after 5~10min of the preferred balance of the present invention.
In the present invention, the CdCl2The heating-up temperature in source is 450~500 DEG C, and the present invention is preferably in CdTe deposition process In, to CdCl2Source is slowly heated, and the speed of the heating is preferably 1~10 DEG C/min, more preferably 3~5 DEG C/min, The heating rate of the second substrate is preferably 10~20 DEG C/min in the step (2), more preferably 15~18 DEG C/min；It is described 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, increase gained CdTe thin film Grain size, improve the interface cohesion degree with n-type GdS cushions of CdTe absorbed layers.
After obtaining CdTe absorbed layers, the present invention prepares p-type CIGS absorbed layers on CdTe absorbed layers.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 the preparation of three stage Co-evaporation method 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 is CdTe to absorb layer solar cell semi-finished product as the 3rd substrate deposition, add respectively under vacuum Hot 3rd substrate, indium source, gallium source and selenium source temperature are 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, selenium deposition are carried out first in the 3rd substrate, obtains In2Se3Precursor film, the insulation of gallium source；
(2)In2Se3After the completion of precursor film deposition, stop indium deposition, in In2Se3Copper and selenium are deposited on precursor film, forms copper Selenium alloy phase；
(3) after forming copper selenium alloy phase, stop copper deposition, carry out the co-deposition of indium, gallium and selenium, obtain p-type CIGS suctions Receive layer.
In the present invention, indium, the sedimentation time of selenium are preferably 15~25min in the step (1), more preferably 10~ 20min；The vacuum of the vacuum condition is preferably 4.0 × 10-5Pa~6.0 × 10-5Pa, more preferably 5 × 10-5Pa；Will be each After evaporation source is heated to temperature, 5~10min of the preferred insulation of the present invention is deposited again.
The present invention preferably indium, selenium deposition process in, Heated Copper source, copper source is heated, so as to In2Se3Precursor film deposits After the completion of, immediately carry out copper deposition.In the present invention, 5~15 DEG C/min, more preferably 8~12 DEG C/min；The copper The heating-up temperature in source is preferably 1230 DEG C~1300 DEG C, more preferably 1250 DEG C~1280 DEG C；After copper source is heated to temperature, this Copper deposition is carried out again after 5~10min of the preferred balance of invention.
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 the heat-absorbing liquefaction under the conditions of underlayer temperature, sample surface temperature drastically declines, this Invention is monitored in deposition process to sample surface temperature, and sample surface temperature stops copper source deposition when declining 1min.
After forming copper selenium alloy phase, stop copper deposition, carry out the co-deposition of indium, gallium and selenium, obtain p-type CIGS absorptions Layer.In the present invention, with indium, gallium, selenium deposition, sample surfaces low melting-point coper selenium mutually persistently consumed, sample surface temperature It is gradually increasing, when treating 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 obtaining p-type CIGS absorbed layers, the present invention prepares Top electrode on p-type CIGS absorbed layers.Present invention preferably uses Magnetron sputtering method prepares Top electrode.
In the present invention, the target material that the magnetron sputtering uses is consistent with such scheme, will not be repeated here；It is described It is more than 99.99% that the purity of target, which is preferably,；The Cathod magnetic field of the magnetron sputtering is preferably balanced field；The magnetron sputtering Back end vacuum be preferably 4.0 × 10-3Pa~6.0 × 10-3Pa, more preferably 5.0 × 10-3Pa；The sputtering atmosphere is preferred For argon gas, the purity of the argon gas is preferably 99.99~99.9999%；The air pressure of the magnetron sputtering be preferably 0.1Pa~ 0.5Pa, more preferably 0.2~0.4Pa；The magnetron sputtering power is preferably 200W~300W, more preferably 220~270W； The target-substrate distance of the magnetron sputtering is preferably 100mm~120mm, more preferably 110~115mm；The time of the magnetron sputtering Preferably 20~40min, more preferably 25~35min；The present invention controls the thickness of Top electrode by controlling the magnetron sputtering time Degree, the thickness of Top electrode increase with the extension of sputtering time.
The present invention prepares Top electrode using one-step method magnetron sputtering, simplifies preparation technology, reduces process costs.
In the present invention, the conductive layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, p-type CdTe absorbed layers, p-type CIGS absorbed layers and the thickness of Top electrode are consistent with such scheme, will not be repeated here.
With reference to embodiment to CdTe/CIGS Gradient Absorptions layer film solar cell provided by the invention and its preparation Method is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Step 1：Magnetron sputtering prepares transparency conducting layer：It is glass substrate from substrate, target is that 3 inches of cadmium stannates are made pottery Porcelain target, back end vacuum are evacuated to 1.5 × 10-3Pa, sputtering atmosphere are the mixed gas of argon gas and oxygen, and argon oxygen flow ratio is 90：10, Sputtering pressure is 1.0Pa, sputtering power 60W, target-substrate distance 80mm；Sputtering time is 20min, controls the cadmium stannate thickness degree to be 600nm；Deposited cadmium stannate is under nitrogen or argon gas atmosphere, 450 DEG C~550 DEG C annealing 10min~15min.
Step 2：It is prepared by intrinsic zinc oxide insulating barrier
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, it is 30nm to obtain ZnO thickness of insulating layer；
Step 3：Chemical bath method depositing n-type CdS cushions.
Configuration cadmium acetate and ammonium acetate molar concentration are respectively 0.005mol/L and 0.05mol/L mixed solution, are configured Molar concentration is 0.3mol/L thiourea solution, and the ammonia spirit that molar concentration is 4mol/L, is stored up after above-mentioned solution allocation Deposit standby；
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, treat that solution temperature reaches 70 DEG C, add 5ml ammonia spirits, solution persistently stirs in solution process for preparation, Reaction solution volume is adjusted to 100ml with pure water, is subsequently placed into CIGS samples, is deposited 10min, take out CIGS samples, use is pure Water purification rinses repeatedly, is subsequently dried nitrogen drying；The thickness for controlling n-type CdS cushions is 50nm；
Step 4：Cadmium Telluride powder powder stock thermal evaporation prepares p-type CdTe absorbed layers.
Back end vacuum is evacuated to 5.0 × 10-5Pa, underlayer temperature and CdTe source temperature are heated respectively to 200 DEG C and 500 DEG C, is treated CdTe source temperature is to temperature and balances 5min, opens source baffle plate and sample baffle plate, deposits 15min；
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 quickly is increased into 350 DEG C, opens CdCl2Source baffle plate, simultaneously Close CdTe source baffle plate and power supply, after 5min~10min, close CdCl2Source baffle plate and sample baffle plate, and close power supply；Control p The thickness of type CdTe absorbed layers is 1.0 μm；
Step 5：Using coevaporation 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 4550 DEG C, , each evaporation source is treated to temperature and balances 10min, open indium source baffle plate, selenium source baffle plate and sample baffle plate by 850 DEG C, 950 DEG C and 300 DEG C, Start to deposit In2Se3Precursor film 15min；
In first step In2Se3During precursor film depositional remanent 10min, copper source is heated to 1230 DEG C, In2Se3Precursor film deposits After the completion of, copper source temperature balance 10min, copper source baffle plate is opened, indium source and gallium source baffle plate are simultaneously closed off, in copper source deposition process In, indium source and the insulation of gallium source, sample surface temperature close copper source baffle plate when declining 1min；
Indium source is opened while copper source baffle plate is closed and gallium source baffle plate, sample surface temperature are gradually increasing, and is become to obvious When changing and keeping 1min, the baffle plate of copper source, indium source, gallium source, selenium source and sample stage is simultaneously closed off, and close power supply；Control p-type The thickness of CIGS absorbed layers is 1.0 microns；
Step 6：Magnetron sputtering prepares Top electrode
Selection Mo membrane electrodes are Top electrode, and target is 3 inches of purity 99.99% and forges fine grain Mo targets, sputter cathode Magnetic field is balanced field, and back end vacuum is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.1Pa, sputter work( Rate 200W, target-substrate distance 100mm, obtained Mo back electrodes thickness are 1.0 μm.
The cell conversion rate of Gradient Absorption layer film battery to obtaining detects, and can obtain cell conversion rate and be 15.5%.
Embodiment 2
Step 1：Magnetron sputtering prepares transparency conducting layer：It is glass substrate from substrate, target is that 3 inches of fluorine dopeds aoxidize Tin ceramic target, back end vacuum are evacuated to 2.0 × 10-3Pa, sputtering atmosphere are the mixed gas of argon gas and oxygen, and argon oxygen flow ratio is 80：20, sputtering pressure 3.0Pa, sputtering power 100W, target-substrate distance 100mm；Sputtering time is 40min, controls fluorine doped tin oxide Thickness degree is 800nm；Deposited fluorine doped tin oxide is under nitrogen or argon gas atmosphere, 550 DEG C of annealing 15min.
Step 2：It is prepared by intrinsic zinc oxide insulating barrier
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 4W, target base Away from 130mm, it is 60nm to control ZnO thickness of insulating layer；
Step 3：Chemical bath method depositing n-type CdS cushions.
Configuration cadmium acetate and ammonium acetate molar concentration are respectively 0.004mol/L and 0.06mol/L mixed solution, are configured Molar concentration is 0.2mol/L thiourea solution, and the ammonia spirit that molar concentration is 5mol/L, is stored up after above-mentioned solution allocation Deposit standby；
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, treat that solution temperature reaches 75 DEG C, add 5ml ammonia spirits, solution persistently stirs in solution process for preparation, Reaction solution volume is adjusted to 100ml with pure water, is subsequently placed into CIGS samples, is deposited 15min, take out CIGS samples, use is pure Water purification rinses repeatedly, is subsequently dried nitrogen drying；The thickness for controlling n-type CdS cushions is 100nm；
Step 4：Cadmium Telluride powder powder stock thermal evaporation prepares p-type CdTe absorbed layers.
Back end vacuum is evacuated to 5.0 × 10-5Pa, underlayer temperature and CdTe source temperature are heated respectively to 350 DEG C and 600 DEG C, is treated CdTe source temperature is to temperature and balances 5min, opens source baffle plate and sample baffle plate, deposits 20min；
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 quickly is increased into 400 DEG C, opens CdCl2Source baffle plate, simultaneously Close CdTe source baffle plate and power supply, after 10min, close CdCl2 source baffle plates and sample baffle plate, and close power supply；Control p-type CdTe The thickness of absorbed layer is 0.8 μm；
Step 5：Using coevaporation 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, , each evaporation source is treated to temperature and balances 10min, open indium source baffle plate, selenium source baffle plate and sample baffle plate by 800 DEG C, 900 DEG C and 270 DEG C, Start to deposit In2Se3Precursor film 25min；
In first step In2Se3During precursor film depositional remanent 10min, copper source is heated to 1300 DEG C, In2Se3Precursor film deposits After the completion of, copper source temperature balance 10min, copper source baffle plate is opened, indium source and gallium source baffle plate are simultaneously closed off, in copper source deposition process In, indium source and the insulation of gallium source, sample surface temperature close copper source baffle plate when declining 1min；
Indium source is opened while copper source baffle plate is closed and gallium source baffle plate, sample surface temperature are gradually increasing, and is become to obvious When changing and keeping 1min, the baffle plate of copper source, indium source, gallium source, selenium source and sample stage is simultaneously closed off, and close power supply；Control p-type The thickness of CIGS absorbed layers is 1.5 microns；
Step 6：Magnetron sputtering prepares Top electrode
Selection Mo membrane electrodes are Top electrode, and target is 3 inches of purity 99.99% and forges fine grain Mo targets, sputter cathode Magnetic field is balanced field, and back end vacuum is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.5Pa, sputter work( Rate 220W, target-substrate distance 120mm, it is 1.0 μm to control Mo back electrodes thickness.
The cell conversion rate of Gradient Absorption layer film battery to obtaining detects, and can obtain cell conversion rate and be 16.2%.
Embodiment 3
Step 1：Magnetron sputtering prepares transparency conducting layer：It is glass substrate from substrate, target is 3 inches of indium tin Ceramic target, back end vacuum are evacuated to 2.0 × 10-3Pa, sputtering atmosphere are the mixed gas of argon gas and oxygen, and argon oxygen flow ratio is 85： 15, sputtering pressure 2.0Pa, sputtering power 80W, target-substrate distance 90mm；Sputtering time is 25min, controls indium tin thickness For 700nm；Deposited indium tin is under nitrogen or argon gas atmosphere, 550 DEG C of annealing 15min.
Step 2：It is prepared by intrinsic zinc oxide insulating barrier
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=220：4 mixed atmosphere, sputtering pressure 4Pa, sputtering power 60W, target Cardinal distance 150mm, it is 50nm to control ZnO thickness of insulating layer；
Step 3：Chemical bath method depositing n-type CdS cushions.
Configuration cadmium acetate and ammonium acetate molar concentration are respectively 0.004mol/L and 0.06mol/L mixed solution, are configured Molar concentration is 0.4mol/L thiourea solution, and the ammonia spirit that molar concentration is 4mol/L, is stored up after above-mentioned solution allocation Deposit standby；
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, treat that solution temperature reaches 85 DEG C, add 5ml ammonia spirits, solution persistently stirs in solution process for preparation, Reaction solution volume is adjusted to 100ml with pure water, is subsequently placed into CIGS samples, is deposited 12min, take out CIGS samples, use is pure Water purification rinses repeatedly, is subsequently dried nitrogen drying；The thickness for controlling n-type CdS cushions is 70nm；
Step 4：Cadmium Telluride powder powder stock thermal evaporation prepares p-type CdTe absorbed layers.
Back end vacuum is evacuated to 5.0 × 10-5Pa, underlayer temperature and CdTe source temperature are heated respectively to 300 DEG C and 550 DEG C, is treated CdTe source temperature is to temperature and balances 5min, opens source baffle plate and sample baffle plate, deposits 30min；
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 quickly is increased into 360 DEG C, opens CdCl2Source baffle plate, simultaneously Close CdTe source baffle plate and power supply, after 8min, close CdCl2Source baffle plate and sample baffle plate, and close power supply；Control p-type CdTe The thickness of absorbed layer is 0.9 μm；
Step 5：Using coevaporation 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 450 DEG C, , each evaporation source is treated to temperature and balances 10min, open indium source baffle plate, selenium source baffle plate and sample baffle plate by 820 DEG C, 930 DEG C and 280 DEG C, Start to deposit In2Se3Precursor film 20min；
In first step In2Se3During precursor film depositional remanent 10min, copper source is heated to 1250 DEG C, In2Se3Precursor film deposits After the completion of, copper source temperature balance 10min, copper source baffle plate is opened, indium source and gallium source baffle plate are simultaneously closed off, in copper source deposition process In, indium source and the insulation of gallium source, sample surface temperature close copper source baffle plate when declining 1min；
Indium source is opened while copper source baffle plate is closed and gallium source baffle plate, sample surface temperature are gradually increasing, and is become to obvious When changing and keeping 1min, the baffle plate of copper source, indium source, gallium source, selenium source and sample stage is simultaneously closed off, and close power supply；Control p-type The thickness of CIGS absorbed layers is 1.3 μm；
Step 6：Magnetron sputtering prepares Top electrode
Selection Mo membrane electrodes are Top electrode, and target is 3 inches of purity 99.99% and forges fine grain Mo targets, sputter cathode Magnetic field is balanced field, and back end vacuum is evacuated to 5.0 × 10-3Pa, sputtering atmosphere are high-purity argon gas, sputtering pressure 0.3Pa, sputter work( Rate 220W, target-substrate distance 110mm, it is 1.0 μm to control Mo back electrodes thickness.
The cell conversion rate of Gradient Absorption layer film battery to obtaining detects, and can obtain cell conversion rate and be 16.8%.
As seen from the above embodiment, CdTe/CIGS Gradient Absorptions layer film solar cell battery provided by the invention turns Efficiency high is changed, has effectively widened the solar spectrum utilization scope of absorbed layer.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (7)

1. a kind of CdTe/CIGS Gradient Absorptions layer film solar cell, include substrate, conductive layer, intrinsic successively from bottom to top Zinc oxide insulating barrier, n-type CdS cushions, gradient energy gap absorbed layer and Top electrode；The gradient energy gap absorbed layer is certainly It is upper down to include p-type CdTe absorbed layers and p-type CIGS absorbed layers；The thickness of the p-type CdTe absorbed layers is 0.8~1.0 μm；Institute The thickness for stating CIGS absorbed layers is 1.0~1.3 μm；Ga doping is 0~10% in the CIGS absorbed layers；The conductive layer For cadmium stannate conductive layer.
2. thin-film solar cells according to claim 1, it is characterised in that the thickness of the conductive layer be 600~ 800nm。
3. thin-film solar cells according to claim 1, it is characterised in that the thickness of the intrinsic zinc oxide insulating barrier For 30~60nm.
4. thin-film solar cells according to claim 1, it is characterised in that the thickness of the n-type CdS cushions is 50 ~100nm.
5. thin-film solar cells according to claim 1, it is characterised in that the Top electrode is Mo membrane electrodes；Institute The thickness for stating Top electrode is 1.0 μm.
6. the preparation method of thin-film solar cells, comprises the following steps described in Claims 1 to 5 any one：
Transparency conducting layer, intrinsic zinc oxide insulating barrier, n-type CdS cushions, p-type CdTe is sequentially prepared on backing material to absorb Layer, p-type CIGS absorbed layers and Top electrode.
7. preparation method according to claim 6, it is characterised in that comprise the following steps：
(1) conductive layer is sputtered in substrate material surface using magnetron sputtering method；
(2) using magnetron sputtering method in the conductive layer surface sputtering zinc oxide film, formation intrinsic zinc oxide insulating barrier；
(3) in the intrinsic zinc oxide surface of insulating layer chemical deposition n-type CdS, n-type CdS cushions are formed：
(4) using CdTe powder evaporation in the n-type CdS buffer-layer surfaces depositing p-type CdTe, formation p-type CdTe absorbed layers；
(5) layer surface depositing p-type CIGS is absorbed in the p-type CdTe using three stage Co-evaporation method, forms p-type CIGS absorbed layers；
(6) layer surface sputtering Top electrode is absorbed in the p-type CIGS using magnetron sputtering method.
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TWI430466B (en) * 2010-12-23 2014-03-11 Univ Nat Sun Yat Sen Device structure for high efficiency cdte thin-film solar cell
CN104241439A (en) * 2013-06-09 2014-12-24 北京恒基伟业投资发展有限公司 Method for preparing cadmium telluride thin-film solar cell
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