CN102263145A - CIGS (CuInGaSe) solar photocell and manufacturing method thereof - Google Patents
CIGS (CuInGaSe) solar photocell and manufacturing method thereof Download PDFInfo
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- CN102263145A CN102263145A CN2011102468012A CN201110246801A CN102263145A CN 102263145 A CN102263145 A CN 102263145A CN 2011102468012 A CN2011102468012 A CN 2011102468012A CN 201110246801 A CN201110246801 A CN 201110246801A CN 102263145 A CN102263145 A CN 102263145A
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Abstract
The invention discloses a CIGS (CuInGaSe) solar photocell and a manufacturing method thereof. The solar photocell comprises a CIGS active layer, an N-type semiconductor layer, a window layer, a transparent electrode layer and a collection electrode, which are formed on a conducting substrate in sequence, wherein the N-type semiconductor layer and the CIGS active layer form a PN junction; and the CIGS active layer is provided with a photonic crystal structure and the thickness of the CIGS active layer is between 0.5mu m and 10mu m. The manufacturing method comprises the following steps: forming the above structure layers on the conducting substrate in sequence, wherein the concrete operations of forming the CIGS active layer on the conducting substrate comprise the following steps: firstly, adopting a solution method to cover the CIGS layer on the conducting substrate; then adopting an impressing technology to machine and shape the CIGS layer in accordance with the set photonic crystal structure; and finally, annealing to form the continuous CIGS active layer at the temperature of 200-1000 DEG C. The solar photocell is improved in the absorption efficiency and conversion efficiency of light greatly due to having the CIGS active layer with the photonic crystal structure; and the solar photocell is simple in manufacturing technology and low in cost, and has good controllability. The large-scale and low-cost production of the CIGS solar photocells can be possible.
Description
Technical field
Present invention is specifically related to a kind of thin-film solar cells and preparation method thereof, belong to field of optoelectronic devices with New-type photon crystal structure C IGS absorbed layer,
Background technology
Along with being on the rise of the energy and environmental crisis, seeking new forms of energy is becoming needing to be resolved hurrily of a task.Solar energy is inexhaustible with it, and cleanliness without any pollution becomes the technology of tool potentiality.Wherein the thin film solar technology begins to rise in recent years, because it has in light weight, advantages such as cost is low, easy installation.CIGS (copper (Cu) indium (In) gallium (Ga) selenium (Se), be called for short CIGS) then be most effective in the thin film solar technology (20.6%), its preparation process adopts three stage deposition processs, form the V-type level structure, higher external quantum efficiency can be arranged in the long-wavelength region, thereby can improve the short circuit current of device, and also have higher open circuit voltage.The seminar of NANOSOLAR and IBM has developed the technology of utilizing solwution method to prepare the CIGS active membrane respectively recently; this class technology does not need vacuum evaporation equipment; lower cost of manufacture greatly; and scale easily; but; because the crystallinity of the CIGS film of solwution method preparation is not high; need high temperature after annealing processing procedure; this has increased production cost of products virtually; in addition; the degree of crystallinity of CIGS film is not high, causes its efficiency of light absorption to reduce, and has reduced the photoelectric current and the energy conversion efficiency of device.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of CIGS thin film solar photocell and preparation method thereof is provided, it adopts stamping technique that the CIGS active layer of solwution method preparation is formed the photon crystal structure with special shape, can effectively improve the absorption efficiency of photocell to light, thereby increase the conversion efficiency of solar energy, for on a large scale, produce the CIGS solar photocell cheaply possibility is provided.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of CIGS solar photocell, comprise the CIGS active layer, n type semiconductor layer, Window layer, transparent electrode layer and the acquisition electrode that are formed at successively on the conductive substrates, this n semiconductor layer and CIGS active layer form PN junction, it is characterized in that: described CIGS active layer has photon crystal structure, and its thickness is between 0.5 μ m～10 μ m.
Further say, described CIGS active layer is to adopt following prepared: at first adopt solwution method to cover cigs layer on conductive substrates, adopt stamping technique with cigs layer machine-shaping according to setting photon crystal structure again, form continuous CIGS active layer 200-1000 ℃ of annealing at last.
Described photon crystal structure is selected from any one in sphere, cylinder and the anchor ring at least, and its bore 10nm-1000 μ m, its arrangement mode are selected from cube and six sides at least, and its fill factor, curve factor is 100nm-2000nm.
Described conductive substrates is a conductive metal film, and its thickness is 200-2000nm.
Described n type semiconductor layer is made up of II-VI group ternary compound, and its thickness is between 20-200nm, and described II-VI organizes ternary compound and is selected from least more than in cadmium sulfide, zinc sulphide, cadmium selenide, zinc selenide, cadmium telluride and the zinc telluridse any one.
The material of described Window layer is selected from any one in zinc-oxide film and the doping zinc-oxide film at least, and wherein doped chemical is selected from more than in aluminium, gallium and the cadmium any one at least, and this Window layer thickness is the 20-200 nanometer.
The material of described transparent electrode layer is selected from indium tin oxide films at least and mixes the zinc-oxide film of aluminium, gallium or cadmium; The material of described acquisition electrode is selected from more than in nickel, aluminium, gold, silver, copper, titanium and the chromium any one at least.
The preparation method of CIGS solar photocell comprises the operation that forms CIGS active layer, n type semiconductor layer, Window layer, transparent electrode layer and acquisition electrode successively on conductive substrates as mentioned above, it is characterized in that,
Be specially in the operation that forms the CIGS active layer on the conductive substrates in this method: at first adopt solwution method on conductive substrates, to cover cigs layer, adopt stamping technique with cigs layer machine-shaping according to setting photon crystal structure again, form continuous CIGS active layer 200-1000 ℃ of annealing at last.
Described photon crystal structure is selected from sphere, cylinder and anchor ring at least, and its bore 10nm-1000 μ m, its arrangement mode are selected from cube and six sides at least, and its fill factor, curve factor is 100nm-2000nm.
Described solwution method is selected from more than in spin-coating method, spraying process and the poor modulus method any one at least.
Compared with prior art, the present invention has following beneficial effect at least: the CIGS active layer of this CIGS solar photocell is owing to have specific photon crystal structure, can utilize its slow light effect that has and structure complicated in the space, make be detained time and the average photon path of photon in solar cell increase, this photon crystal structure can increase the roughness of active layer simultaneously, increase to overflow and launch, thereby play sunken light action, to reach the effect of the absorptivity that promotes solar cell; Simultaneously, its preparation technology is simple, and is with low cost, and has good controllability.
Description of drawings
Fig. 1 is the photronic structural representation of CIGS thin film solar of the present invention, wherein: conductive substrates 1, CIGS active layer 2, n type semiconductor layer 3, Window layer 4, transparent electrode layer 5, metal acquisition electrode 6.
Embodiment
Below in conjunction with an accompanying drawing and a preferred embodiment technical scheme of the present invention is further described.
Consult Fig. 1, this CIGS thin film solar photocell comprises:
Conductive substrates 1;
CIGS active layer 2, this CIGS active layer 2 utilize solution/stamped method to be produced on the conductive substrates 1, mainly as light-absorption layer;
N type semiconductor layer 3, this n type semiconductor layer 3 is to utilize CBD or vacuum deposition method (to comprise thermal evaporation, physical vapour deposition (PVD) that sputter etc. are different and chemical gaseous phase depositing process) be produced on the CIGS active layer 2, and form the pn knot with it, can effectively increase dissociating and exporting of photoproduction exciton;
Metal acquisition electrode 6, this acquisition electrode is produced on the transparent electrode layer, has the effect of gathering the photoproduction light stream.
Aforementioned conductive substrates 1 adopts conductive metal film, it typically is molybdenum electrode, thickness 200-2000 nanometer, but be not limited to molybdenum, also comprise other suitable metal materials, as aluminium, titanium, copper and stainless steel etc.
This is the CIGS active layer 2 that adopts solwution method (make a general reference all coating methods, as spin-coating method, spraying process, poor modulus method etc.) preparation above conductive substrates 1.As use spin-coating method, just can change the thickness of this CIGS active layer 2 by control spin speed, solution concentration and different spin coating number of times, generally the thickness of this active layer is between the 0.5-10 micron, utilize then stamping technique with the CIGS active layer according to specific photon crystal structure moulding, it comprises sphere, cylinder, anchor ring etc., bore 10 nanometers-1000 micron, arrangement mode comprise cube, six sides etc.; Fill factor, curve factor 100 nanometers are to 2000 nanometers, and last 200-1000 degree high annealing forms continuous CIGS active layer.
N type semiconductor layer 3 above the CIGS active layer 2 is to adopt CBD or pellet Films Prepared with Vacuum Evaporation Deposition, this functional layer is in order to form effective pn knot with cigs layer, thereby improve the separation and the output of photoproduction exciton, the thickness of this n type semiconductor layer 3 is generally between the 20-200 nanometer, this n type semiconductor layer 3 is generally cadmium sulfide (CdS) material, but be not limited to this, also comprise other n N-type semiconductor Ns, for example zinc sulphide, cadmium selenide, zinc selenide, cadmium telluride, zinc telluridse, and other II-VI group ternary compounds.
Above the n type semiconductor layer 3 Window layer 4 and transparent electrode layer 5.The material selection zinc oxide of Window layer 4 or doping zinc-oxide film, doped chemical are aluminium, gallium or cadmium, and thickness is the 20-200 nanometer.Transparent electrode layer is indium tin oxide films or the zinc-oxide film of mixing aluminium, gallium, cadmium.Be metal acquisition electrode 6 at last, generally be nickel/aluminium, but be not limited to this, also comprise other metals, comprise gold, silver, copper, titanium, chromium etc.
Being example below with the spin-coating method describes in detail to the preparation method of above-mentioned CIGS solar photocell.
1. the technology of preparation CIGS precursor is as follows:
(1) nanometer precursor: with 12 milliliters OLEYLAMIN, the inidum chloride that copper chloride that 1.5 millis rub and 1.0 millis rub, the gallium chloride that 0.5 milli rubs is put into three neck reaction bulbs of 100 milliliters of volumes.Under argon shield, be warmed up to 130 degree, kept 30 minutes.Reaction temperature is elevated to 225 ℃ then, and injects 3 milliliters of OLEYLAMINE that contain 1 molar sulphur rapidly.React after 30 minutes, be cooled to 60 ℃ and add 10 milliliters toluene.Add ethanol at last, the centrifugation nanometer precursor of coming out is distributed in the toluene precursor as CIGS by desired concn.
(2) solution precursor: prepare four kinds of different precursor earlier, be mixed into final solution precursor according to required different element ratio of components then.Precursor A:0.955 restrains copper sulfide, 0.3848 gram sulphur and 12 milliliters of anhydrous hydrazines; Precursor B:1.8661 restrains indium selenide, 0.3158 gram selenium and 12 milliliters of anhydrous hydrazines; Precursor C:0.4183 restrains gallium, 0.9475 gram selenium and 12 milliliters of anhydrous hydrazines; Precursor D:0.9475 gram selenium and 6 milliliters of anhydrous hydrazines.
2. soda-lime glass is cleaned in cleaning agent repeatedly, and then through deionized water, acetone and aqueous isopropanol soak and ultrasonic each 15 minutes, dry up with nitrogen at last and handle 15 minutes through UV ozone.
3. get method with vacuum moulding machine on soda-lime glass and prepare molybdenum electrode, its thickness is about 800 nanometers.
4. the solution after will filtering with certain chemical constituent ratio (ratio of Copper Indium Gallium Selenide was respectively 1: 0.7: 0.3 in the solution precursor: 2) or the nanometer precursor be spin-coated on the metal substrate with 800 rev/mins rotating speed, after the process annealing (room temperature-330 ℃), adopt nanometer embossing, according to parameters such as lattice constant, bore, arrangement mode, fill factor, curve factors, preparation photonic crystal array film, high temperature (250-1000 ℃) was annealed 30 minutes more at last, make the presoma reactive crystallization, form continuous CIGS film.
5. adopt the CBD method to make n type cadmium sulfide layer
6. and then with sputter pellet Films Prepared with Vacuum Evaporation Deposition zinc-oxide film and indium tin oxide transparent electrode.
7. use prepared by heat evaporation nickel/aluminium acquisition electrode at last.
The CIGS active layer of this CIGS solar photocell adopts solution/stamped method preparation, has specific photon crystal structure, can utilize its slow light effect that has and structure complicated in the space, make be detained time and the average photon path of photon in solar cell increase, this photon crystal structure can increase the roughness of active layer simultaneously, increase to overflow and launch, thereby play sunken light action, to reach the effect of the absorptivity that promotes solar cell.
Below only technical scheme of the present invention is introduced, but,, should be able to be changed in specific embodiments and applications according to the thought of the embodiment of the invention for one of ordinary skill in the art with a preferred embodiment.So in sum, this description should not be construed as limitation of the present invention, all any changes of making according to design philosophy of the present invention are all within protection scope of the present invention.
Claims (10)
1. CIGS solar photocell, comprise the CIGS active layer, n type semiconductor layer, Window layer, transparent electrode layer and the acquisition electrode that are formed at successively on the conductive substrates, this n semiconductor layer and CIGS active layer form PN junction, it is characterized in that: described CIGS active layer has photon crystal structure, and its thickness is between 0.5 μ m～10 μ m.
2. CIGS solar photocell according to claim 1, it is characterized in that: described CIGS active layer is to adopt following prepared: at first adopt solwution method to cover cigs layer on conductive substrates, adopt stamping technique with cigs layer machine-shaping according to setting photon crystal structure again, form continuous CIGS active layer 200-1000 ℃ of annealing at last.
3. CIGS solar photocell according to claim 1 and 2, it is characterized in that: described photon crystal structure is selected from any one in sphere, cylinder and the anchor ring at least, its bore 10nm-1000 μ m, its arrangement mode is selected from cube and six sides at least, and its fill factor, curve factor is 100nm-2000nm.
4. CIGS solar photocell according to claim 1 and 2 is characterized in that: described conductive substrates is a conductive metal film, and its thickness is 200-2000nm.
5. CIGS solar photocell according to claim 1, it is characterized in that: described n type semiconductor layer is made up of II-VI group ternary compound, its thickness is between 20-200nm, and described II-VI group ternary compound is selected from more than in cadmium sulfide, zinc sulphide, cadmium selenide, zinc selenide, cadmium telluride and the zinc telluridse any one at least.
6. CIGS solar photocell according to claim 1, it is characterized in that: the material of described Window layer is selected from any one in zinc-oxide film and the doping zinc-oxide film at least, wherein doped chemical is selected from more than in aluminium, gallium and the cadmium any one at least, and this Window layer thickness is the 20-200 nanometer.
7. CIGS solar photocell according to claim 1 is characterized in that: the material of described transparent electrode layer is selected from indium tin oxide films at least and mixes the zinc-oxide film of aluminium, gallium or cadmium; The material of described acquisition electrode is selected from more than in nickel, aluminium, gold, silver, copper, titanium and the chromium any one at least.
8. the preparation method of CIGS solar photocell according to claim 1 comprises the operation that forms CIGS active layer, n type semiconductor layer, Window layer, transparent electrode layer and acquisition electrode successively on conductive substrates, it is characterized in that,
Be specially in the operation that forms the CIGS active layer on the conductive substrates in this method: at first adopt solwution method on conductive substrates, to cover cigs layer, adopt stamping technique with cigs layer machine-shaping according to setting photon crystal structure again, form continuous CIGS active layer 200-1000 ℃ of annealing at last.
9. the preparation method of CIGS solar photocell according to claim 8, it is characterized in that: described photon crystal structure is selected from sphere, cylinder and anchor ring at least, its bore 10nm-1000 μ m, its arrangement mode are selected from cube and six sides at least, and its fill factor, curve factor is 100nm-2000nm.
10. the preparation method of CIGS solar photocell according to claim 8 is characterized in that: described solwution method is selected from more than in spin-coating method, spraying process and the poor modulus method any one at least.
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| CN104157709A (en) * | 2014-08-04 | 2014-11-19 | 苏州瑞晟纳米科技有限公司 | CIGS solar cell with novel photonic crystal structure and preparation method thereof |
| CN104362186A (en) * | 2014-10-21 | 2015-02-18 | 苏州瑞晟纳米科技有限公司 | Bilayer structure window layer applied to efficient thin-film photocell |
| CN104465864A (en) * | 2013-09-20 | 2015-03-25 | 株式会社东芝 | Method for manufacturing photoelectric conversion device |
| CN106435534A (en) * | 2010-07-26 | 2017-02-22 | L·皮尔·德罗什蒙 | Liquid-phase chemical deposition apparatus, method and products thereof |
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| CN106435534A (en) * | 2010-07-26 | 2017-02-22 | L·皮尔·德罗什蒙 | Liquid-phase chemical deposition apparatus, method and products thereof |
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Application publication date: 20111130 |