CN100541824C - A kind of mechanical laminated AlSb/CIS thin film solar cell - Google Patents
A kind of mechanical laminated AlSb/CIS thin film solar cell Download PDFInfo
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Abstract
A kind of mechanical laminated AlSb/CIS thin film solar cell belongs to a kind of structural design of semiconductor film solar cell, and it is by the superimposed binode that forms on battery at the bottom of the CIS four end thin film solar cells of AlSb top battery machine.AlSb top battery wherein, refer to 7459 n of deposition earlier type Al-Doped ZnO conductive layers on glass at Corning, depositing zinc oxide resistive formation then, deposit the cadmium sulfide resilient coating again, deposit aluminium antimonide absorbed layer and carbon nanotube coating subsequently as transparency conducting layer, at last, nickel deposited/alum gate line and the solar cell made; And battery at the bottom of the CIS, refer at Soda lime deposition on glass molybdenum, deposit absorbed layer selenium indium copper then, deposit the resilient coating cadmium sulfide again, deposit high resistant zinc oxide and Al-Doped ZnO subsequently, at last the solar cell made with the identical shaped and big or small nickel/alum gate line of top battery of deposition.Adopt the laminated cell of said structure, can optionally absorb the energy with the zones of different of conversion solar spectrum, the scope of spread spectrum response improves the conversion efficiency of thin film solar cell effectively.
Description
Technical field
The invention belongs to a kind of structural design of semiconductor film solar cell, particularly a kind of mechanical laminated thin film solar cell.
Background technology
The thin film solar cell of unijunction structure can only absorb and change the sunlight of special spectrum scope, and photoelectric conversion efficiency is not high.If the material with different energy gap width (Eg) is overlapped into binode or multijunction solar cell from top to down by its size, can selectivity absorb and the energy of the zones of different of conversion solar spectrum, just can improve the conversion efficiency of thin film solar cell greatly.
The people such as Coutts of U.S. regenerative resource laboratory (NREL) (see Proceedings of the 12
ThPhotovoltaicScience and Engineering Conference, Cheju Island, Korea 2001:277) has calculated at AM1.5 100mW/cm
2, under 25 ℃ of conditions, the efficient of binode lamination polycrystal film solar cell can reach 28%, and wherein the energy gap of top battery and end battery obsorbing layer will satisfy 1.7eV and 1.1eV respectively.Because suitable end battery obsorbing layer energy gap is 1.1eV, just in time with CuInSe
2(CIS) energy gap is approaching, and CIS is as the preparation technology of the battery of absorbed layer (being called for short the CIS battery) also comparative maturity, therefore, end battery is often selected the CIS battery for use in the binode pellicular cascade battery, the structure of battery of this end is generally: glass/Mo/CIS/ZnO or glass/Mo/CIS/CdS/TCO, but the end battery efficiency of said structure is not high usually.For the top battery, the energy gap that requires absorbed layer is than broad, and therefore the scope of selecting mainly concentrates in I-III-VI and the II-VI group iii v compound semiconductor material, as Ag (InGa) Se
2(1.7eV), CuGaSe
2(1.6eV), CdSe (1.7eV) etc., the energy gap of these materials is near 1.7eV, though having obtained 9.3% (seeing Proceedings of the 2005 Spring MRS, 2005) and 10.2% at the NREL of the green hill of the Japan university of institute (Aoyama Gakuin University) and the U.S. respectively, the above two (see Proceedings of the 31
StIEEE PVSEC, Lake Buena Vista, Florida, single junction cell efficient 2005:299), but have following shortcoming:
1. this class ternary or multi-element compounds preparation difficulty is difficult to the control stoicheiometry.
2. especially this class ternary or multi-element compounds material need to such an extent that opaque back of the body contact is changed into transparent back of the body contact material as the absorbed layer of top battery, and as transparent conductive oxide film (TCO), but the pyroprocess of preparation causes Ga
2O
3Formation and TCO in the disappearance of component, have a strong impact on the performance of device, thereby efficient reduced greatly.
For II-VI group iii v compound semiconductor material CdSe, though the energy gap size is suitable for making the top battery very much, but the absorption coefficient of material own is not high, therefore, with the battery (be called for short CdSe battery) of CdSe as absorbed layer, its conversion efficiency is not high, has only obtained 1.9% efficient as the Nan Folida university (University of South Florida) of the U.S. and (has seen Proceedings of the 19
ThEuropean Photovoltaic Solar Energy Conference and Exhibition, Paris, France, 2004:1651).What deserves to be mentioned is, the NREL of the U.S. adopts the absorbed layer of II-VI compound semiconductor CdTe as top battery in the mechanical laminated battery of binode, and employing CIS is as the absorbed layer of end battery, obtain 15.31% laminated cell conversion efficiency and (seen Prog Photovolt:Res Appl, 2006,14:471), but also there is tangible deficiency in this structure.At first, CdTe is as the absorbed layer of top battery, and its energy gap is less than normal; Secondly, the work function of CdTe is very high, is difficult to directly form ohmic contact with the metal of back, need add complicated composite bed usually and form transparent back of the body contact, as ZnTe:Cu/ITO, Cu
xTe/ITO.
Summary of the invention
The objective of the invention is in order to eliminate above-mentioned deficiency or defective, further improve the structural design of binode laminated film solar battery, propose a kind ofly to make top battery (be called for short AlSb top battery) with AlSb, and make the AlSb/CIS binode stacked solar cell, cascade solar cell structure of end battery with CIS, optionally absorb and the energy of the different-waveband of conversion solar spectrum, thus the higher photoelectric conversion efficiency of acquisition.
For realizing the object of the invention, technical scheme of the present invention is: directly superimposed on the end battery of CIS AlSb as absorbed layer as the top battery of absorbed layer, and the mechanical laminated thin film solar cell of formation binode four ends.So-called AlSb is as the top battery (being called for short AlSb top battery) of absorbed layer, refer to and between glass substrate and absorbed layer AlSb, add ZnO:Al conductive layer, ZnO resistive formation and CdS resilient coating in proper order, and behind absorbed layer AlSb, increase carbon nano-tube (CNT) coating and make transparent back contact, make the solar cell of this spline structure of Ni/Al grid line at last; So-called CIS is as the end battery (battery at the bottom of the abbreviation CIS) of absorbed layer, refer between glass substrate and absorbed layer CIS deposition Mo and make back electrode, then, order prepares the solar cell that CdS resilient coating, ZnO resistive formation, ZnO:Al conductive layer and making and AlSb top cell shapes are made with big or small identical Ni/Al grid line on absorbed layer CIS.
Because the energy gap～1.65eV of AlSb film, the energy gap～1.1eV of CIS film, the condition of the high-efficiency double-junction laminated cell that proposes with people such as Coutts is very identical.In addition, the work function of AlSb is not high, about 3.65eV, and as a kind of photovoltaic material of excellence, its theoretical transformation efficient higher (～28%).And making end battery, CIS can good spectral response be arranged at 900nm～1300nm.Therefore, AlSb/CIS binode laminated cell, effectively spread spectrum response, the photoelectric conversion efficiency of raising thin film solar cell.
Description of drawings
Fig. 1 is the structural representation of mechanical laminated AlSb/CIS thin film solar cell.
Fig. 2 is the scheme of installation of mechanical laminated AlSb/CIS thin film solar cell.
Symbolic representation among Fig. 1 and Fig. 2 is: G1 is Corning 7059 glass, G2 is a Soda lime glass, and Z1 is Al-Doped ZnO (ZnO:Al), and Z is zinc oxide (ZnO), B is cadmium sulfide (CdS), A is aluminium antimonide (AlSb), and A2 is a selenium indium copper (CIS), and T is a carbon nanotube coating, M is nickel/aluminium (Ni/Al), M2 is molybdenum (Mo), and S is a pillar, and AIR is an air.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Energy gap～the 1.65eV of AlSb film, the energy gap～1.1eV of CIS film satisfies the primary condition of high-efficiency double-junction laminated cell, so we select these two kinds of materials to make the top battery and the end battery of binode laminated cell, and the two is superimposed together up and down.
In Fig. 1, the structure of AlSb (A) top battery is Corning 7059 glass (G1)/Al-Doped ZnO (Z1)/zinc oxide (Z)/cadmium sulfide (B)/aluminium antimonide (A)/carbon nanotube coating (T)/Ni/Al (M), promptly at first go up n type Al-Doped ZnO (Z1) conductive layer of deposition 0.3～0.5 μ m at Corning 7059 glass (G1), deposition～50nm zinc oxide (Z) resistive formation then, deposition～50nm cadmium sulfide (B) resilient coating again, the carbon nanotube coating (T) that deposits 2～8 μ m aluminium antimonide (A) absorbed layers and 100～500nm subsequently is as transparency conducting layer, at last, the aluminium of the nickel of sequential aggradation～50nm and～3 μ m is formed nickel/aluminium (M) grid line.And the structure of CIS (A2) end battery is Soda lime glass (G2)/molybdenum (M2)/selenium indium copper (A2)/cadmium sulfide (B)/zinc oxide (Z)/Al-Doped ZnO (Z1)/nickel/aluminium (M), promptly at first go up about 1～2 μ m of deposition molybdenum (M2) at Soda lime glass (G2), deposit the absorbed layer selenium indium copper (A2) of 2～4 μ m then, the resilient coating cadmium sulfide (B) of deposition～50nm again, deposition～50nm high resistant zinc oxide (Z) and 0.3～0.5 μ m Al-Doped ZnO (Z1) deposit with the top battery identical shaped at last subsequently, size and thickness are respectively～nickel of 50nm and nickel/aluminium (M) grid line of～3 μ m aluminium.Fig. 2 shows the superimposed situation of AlSb/CIS laminated cell machinery, at first, go up weldering indium (In) at Al-Doped ZnO (Z1) transparency conducting layer and the metal electrode molybdenum (M2) of AlSb (A) top battery and CIS (A2) end battery respectively, and pick out lead-in wire as the negative pole (-) of top battery and the positive pole (+) of end battery, nickel/aluminium (M) grid line from AlSb (A) top battery and CIS (A2) end battery picks out lead-in wire as the positive pole (+) of top battery and the negative pole (-) of end battery respectively, place AlSb (A) top battery three highly identical insulation columns of CIS (A2) end battery (on 1～8mm) then, aiming at AlSb (A) top battery and CIS (A2) end battery nickel/aluminium (M) grid line makes it to overlap, at last, fixedly AlSb (A) top battery and CIS (A2) end battery, like this, just made the mechanical laminated battery of AlSb/CIS of binode four ends.
In the battery of AlSb (A) top, adopt p type carbon nanotube coating (T) to do the transparent back of the body contact of top battery in the above-mentioned laminated cell, main cause is that common nesa coating is the n type, if directly be deposited on and do back of the body contact on the p type absorbed layer, can produce and the opposite knot of main knot, hinder transporting of charge carrier; If choose p type nesa coating commonly used, its carrier concentration is then than low one to two order of magnitude of common n type nesa coating.Because carbon nanotube coating (T) has high conductance and transparency, in the wave band of 800～1500nm, carbon nanotube coating (T) has 40%～50% transmitance and (sees Appl Phys Lett, 2007,90:243503), therefore be suitable for very much making the transparent back contact of top battery, the particularly important is, the conduction type of carbon nanotube coating (T) is the p type, n type layer effect with main knot, the depletion region of p type absorbed layer AlSb (A) is broadened, help improving the open circuit voltage and the fill factor, curve factor of battery, increase the efficient of device.In AlSb (A) top battery and CIS (A2) end battery, all adopted cadmium sulfide (B) as resilient coating, cadmium sulfide (B) can be that nanostructure can not be a nanostructure also, its effect comprises two aspects: on the one hand, can improve the lattice match of zinc oxide (Z) and absorbed layer AlSb (A) or CIS (A2), reduce interface state density, on the other hand, band structure to AlSb (A) top battery and CIS (A2) end battery also has modification, makes the abrupt change knot become progressive junction.Like this, greatly improve the structure of pellicular cascade battery, thereby improved the performance of laminated cell, greatly improved the efficient of pellicular cascade battery.
Embodiment one:
1 preparation CIS (A2) end battery
1.1 on Soda lime glass (G2), with the molybdenum target of purity 99.999%, in base vacuum～10
-4Pa, working gas are under the condition of argon, sputtering pressure～1Pa, sputtering power 20～300W, direct current sputtering molybdenum (M2) at first, thickness 0.1～0.5 μ m, change then sputtering pressure for～0.1Pa, the molybdenum (M2) of about 0.9～1.5 μ m of sputter thickness again;
1.2 the sample Soda lime glass (G2) after the taking-up sputter/molybdenum (M2) is in vacuum degree～10
-4Pa, adopt copper, indium, selenium three sources (purity all is 99.99%) coevaporation method to prepare CIS (A2), when 300 ℃ of sample temperatures, adjust the speed ratio (0.3～0.7) of copper, indium, selenium: (0.8～1.2): (2.2～2.6), deposit the rich copper CIS of thickness 0.5～1.5 μ m, adjusting sample temperature subsequently is 450 ℃, and regulate the speed than being (0.1～0.5): (0.8～1.2): (1.8～2.2) deposit poor copper CIS 1.5～2.5 μ m again;
Take out 1.3 treat sample Soda lime glass (G2)/molybdenum (M2)/CIS (A2) cooling back, adopt the chemical bath legal system to be equipped with cushioning layer material cadmium sulfide (B), used medicine is analytical reagent, adopts the secondary deionized water preparation, and the concentration of each composition is [CdCl
2]=0.0012M, [NH
3H
2O]=0.1M, [(NH
2)
2CS]=0.004M, [NH
4Cl]=0.02M, during the deposition cadmium sulphide membrane, samples vertical is put into closed container, add cadmium salt, ammonium salt and ammoniacal liquor, when reaction temperature is maintained at about 82 ℃, add thiocarbamide again, pH value about 8.5～8.8 in the deposition process, rotor rotates with suitable speed, sedimentation time 10～30 minutes, thickness pact～50nm takes out post-depositional sample, washed with de-ionized water dries up with nitrogen again;
1.4 then, more above-mentioned Soda lime glass (G2)/molybdenum (M2)/CIS (A2)/cadmium sulfide (B) sample is put into sputtering chamber, base vacuum～10
-4Pa, under the room temperature, earlier under the argon oxygen atmosphere (oxygen concentration 1%～3%), operating air pressure～1Pa, sputtering power 20～300W, radio frequency sputtering zinc oxide target (99.999%), deposition high resistant zinc oxide (Z)～50nm, the change working gas is an argon, adjusts operating air pressure～0.1Pa, radio frequency sputtering Al-Doped ZnO target (Al wherein
2O
3Percentage by weight 1%～4%), deposition Al-Doped ZnO (Z1) 0.35～0.55 μ m;
1.5 last, taking out structure is the sample of Soda lime glass (G2)/molybdenum (M2)/selenium indium copper (A2)/cadmium sulfide (B)/zinc oxide (Z)/Al-Doped ZnO (Z1), in vacuum～10
-4Pa, by the grid line mask, nickel/aluminium (M) grid line that electron-beam vapor deposition method sequential aggradation nickel～50nm and aluminium～3 μ m form, wherein nickel, aluminium source purity 99.99%, pick out lead-in wire by grid line, finishing structure is the end cell preparation of Soda lime glass (G2)/molybdenum (M2)/selenium indium copper (A2)/cadmium sulfide (B)/zinc oxide (Z)/Al-Doped ZnO (Z1)/nickel/aluminium (M) grid line.In addition, go up making 3 at molybdenum (M2), highly identical (1～8mm) insulation column (S) is used for supporting al Sb (A) top battery.
2 preparation AlSb (A) top batteries
2.1 on Corning 7059 glass (G1), radio frequency sputtering Al-Doped ZnO (Z1) 0.35～0.55 μ m of elder generation, radio frequency sputtering high resistant zinc oxide (Z)～50nm subsequently, identical in this two processes and step 1.4 reversed in order, condition of work and parameter and step 1.4;
2.2 taking out structure is the sample of Corning 7059 glass (G1)/Al-Doped ZnO (Z1)/zinc oxide (Z), according to step 1.3 chemical bath method preparation～50nm resilient coating cadmium sulfide (B);
2.3 then, the sample of step 2.2 is put into vacuum chamber (～10
-5Pa), sample is heated to 550 ℃, utilizes Sb and Al double source (purity all is 99.999%) coevaporation Sb and Al, speed ratio 2～4, depositing Al Sb (A) thickness 2～8 μ m charge into air, again when vacuum degree 5 * 10 when being cooled to 70 ℃ subsequently
4Pa stops inflation, and after 10～20 minutes, progressively elevated temperature to 180 ℃ is evacuated to 10
-4Pa stops heating, and natural cooling took out sample after 10～20 hours;
2.4 subsequently, even carbon nanotube is distributed to 1% CH
3(CH
2)
11OSO
3(carbon nano-tube concentration is 1～2mg/ml) formation suspensoid in the Na aqueous solution, with the piston air brush suspensoid is painted on the sample in the step 2.3 then and forms carbon nanotube coating (T), keeping sample temperature in the spraying process is 100 ℃, use washed with de-ionized water at last, and, be the sample of Corning 7059 glass (G1)/Al-Doped ZnO (Z1)/zinc oxide (Z)/aluminium antimonide (A)/carbon nanotube coating (T) so obtain structure at air drying;
2.5 it is last, the sample in the step 2.4, put into vacuum chamber, adopt electron-beam evaporation and end cell shapes nickel/aluminium (M) grid line (nickel～50nm identical with size, aluminium～3 μ m), pick out lead-in wire by grid line, its technological parameter and flow process and step 1.5 are together complete, so produce the top battery that structure is Corning 7059 glass (G1)/Al-Doped ZnO (Z1)/zinc oxide (Z)/cadmium sulfide (B)/aluminium antimonide (A)/carbon nanotube coating (T)/nickel/aluminium (M);
The mechanical laminated battery of 3 preparation AlSb/CIS
Go up weldering indium (In) (purity 99.999%) at the transparency conducting layer Al-Doped ZnO (Z1) and the metal electrode molybdenum (M2) of AlSb (a) top battery and CIS (A2) end battery respectively, pick out lead-in wire as the negative pole (-) of top battery and the positive pole (+) of end battery, nickel/aluminium (M) grid line from AlSb (A) top battery and CIS (A2) end battery picks out lead-in wire as the positive pole (+) of top battery and the negative pole (-) of end battery respectively, place AlSb (A) top battery three highly identical insulation columns of CIS (A2) end battery (on 1～8mm) then, aim at AlSb (A) top battery and CIS (A2) end battery nickel/aluminium (M) grid line, at last, fixedly AlSb (A) top battery and CIS (A2) end battery, like this, just made the mechanical laminated battery of binode four end AlSb/CIS.
Embodiment two:
In step 1.3 and the step 2.2 among the embodiment one～preparation method of 50nm resilient coating cadmium sulfide (B) changes radio frequency sputtering method into, to obtain the resilient coating cadmium sulfide (B) of nanostructure.CdS target purity 99.99% wherein, base vacuum～10
-4Pa, working gas are argon oxygen (oxygen 1%～2%), operating air pressure 1～2Pa, and sputtering power 30～100W under these conditions, deposits～1 hour, can obtain the resilient coating cadmium sulfide (B) of nanostructure.Other technology does not change, and is identical with embodiment one.Equally, can make the AlSb/CIS mechanical laminated battery of resilient coating cadmium sulfide (B) for binode four ends of nanostructure.
Claims (5)
1. thin film solar cell, its structure is AlSb/CIS, it is characterized in that: AlSb is directly superimposed on the end battery of CIS as absorbed layer as the top battery of absorbed layer, forms the mechanical laminated thin film solar cell of binode four ends.
2. thin film solar cell according to claim 1, it is characterized in that: described AlSb is following structure as the top battery of absorbed layer, between glass substrate and absorbed layer AlSb, be followed successively by ZnO:Al conductive layer, ZnO resistive formation and CdS resilient coating, being carbon nanotube coating behind absorbed layer AlSb, is the Ni/Al grid line at last.
3. thin film solar cell according to claim 1, it is characterized in that: described CIS is following structure as the end battery of absorbed layer, between glass substrate and absorbed layer CIS, be the Mo back electrode, behind absorbed layer CIS, be followed successively by CdS resilient coating, ZnO resistive formation, ZnO:Al conductive layer and the Ni/Al grid line identical shaped and big or small with AlSb top battery.
4. thin film solar cell according to claim 1 is characterized in that: AlSb is fashionable as the end cell stack of absorbed layer as the top battery and the CIS of absorbed layer, and the Ni/Al grid line of the two will align.
5. according to claim 2 and 3 described thin film solar cells, it is characterized in that: the CdS resilient coating can be nanostructure, also can be the non-nano structure.
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| CN101944541B (en) * | 2009-07-08 | 2013-01-02 | 深圳先进技术研究院 | Thin-film photovoltaic cell and manufacturing method thereof |
| CN101840960A (en) * | 2010-02-11 | 2010-09-22 | 昆山正富机械工业有限公司 | Multi-stage cadmium sulfide thin film deposition method |
| CN101820027A (en) * | 2010-02-11 | 2010-09-01 | 昆山正富机械工业有限公司 | Deposition method of multi-section camium sulfide thin film |
| CN101847583B (en) * | 2010-05-25 | 2012-05-23 | 陕西科技大学 | Method for preparing spherical cadmium sulfide (CdS) semiconductor film |
| CN103098226A (en) * | 2010-12-17 | 2013-05-08 | 三洋电机株式会社 | Photoelectric conversion device and method for manufacturing same |
| TWI492399B (en) * | 2012-12-13 | 2015-07-11 | Univ Nat Taiwan | Method for manufacturing a thin film solar cell |
| CN103278662B (en) * | 2013-05-10 | 2016-08-10 | 福州大学 | Nano-nickel rod array atomic force microscope tip characterization sample and manufacture method thereof |
| CN104716261A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Absorption spectrum complementary silicon thin film/organic laminated thin film solar cell |
| CN110120436B (en) * | 2019-04-26 | 2021-02-05 | 圣晖莱南京能源科技有限公司 | Double-section CIGS solar cell and preparation method thereof |
| CN111403558B (en) * | 2020-04-02 | 2023-01-03 | 深圳先进技术研究院 | High-efficiency flexible laminated thin-film solar cell and preparation method thereof |
| CN114361283B (en) * | 2021-03-08 | 2022-09-23 | 常熟理工学院 | Deep ultraviolet detector and preparation method thereof |
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