CN102201495A - CuInGaSe (CIGS) thin-film solar cell prepared by all-solution method - Google Patents

CuInGaSe (CIGS) thin-film solar cell prepared by all-solution method Download PDF

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CN102201495A
CN102201495A CN2011101130901A CN201110113090A CN102201495A CN 102201495 A CN102201495 A CN 102201495A CN 2011101130901 A CN2011101130901 A CN 2011101130901A CN 201110113090 A CN201110113090 A CN 201110113090A CN 102201495 A CN102201495 A CN 102201495A
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cigs
layer
described
produced
active layer
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CN2011101130901A
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钱磊
谢承智
张智恒
刘德昂
顾龙棣
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苏州瑞晟太阳能科技有限公司
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/52Manufacturing of products or systems for producing renewable energy
    • Y02P70/521Photovoltaic generators

Abstract

The invention discloses a GIGS thin-film solar cell prepared by an all-solution method. A CIGS active layer of a CIGS solar cell is fabricated on a conductive substrate by a solution method and the thickness of the CIGS active layer is 0.1 to 10 mu m; and then the CIGS active layer is finally subjected to high-temperature annealing at 200-1,000 DEG C to obtain a CIGS continuous film. The CIGS solar cell is prepared by the all-solution method, and the active layer of the entire device can be prepared in a non-vacuum roll-to-roll manner, such as spraying and printing and the like. The invention can greatly lower the production cost of the CIGS solar cell and provides a powerful means for the industrial development of the CIGS solar cell.

Description

The whole soln legal system is equipped with Copper Indium Gallium Selenide (CIGS) thin-film solar cells

Technical field

The invention belongs to field of optoelectronic devices, relate to a kind of new copper (Cu) indium (In) gallium (Ga) selenium (Se) and (be called for short: the CIGS) preparation method of thin-film solar cells and this hull cell.

Background technology

Along with being on the rise of energy crisis, regenerative resource more and more is subject to people's attention.And wherein, solar energy is inexhaustible with it, and cleanliness without any pollution becomes the technology of tool potentiality.The silica-based solar technology is the most ripe at present, also is that occupation rate of market is the highest, but is limited by the preparation process of highly energy-consuming, high pollution, makes it can not become optimal heliotechnics.In recent years, the thin film solar technology begins to rise, and has in light weight, advantages such as cost is low, easy installation.CIGS then is most effective in the thin film solar technology (20.1%), and its preparation process mainly is a vacuum deposition method.Be multi-element compounds but, as utilize evaporating deposition technique owing to CIGS, no matter be sputter/selenizing, or coevaporation, the process complexity is all arranged, the problem of difficult scale.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, lowers cost of manufacture greatly, and scale easily.But in this class technology, the preparation of Window layer is still needs to rely on vacuum-deposited method.Here, we have reported a kind of new method of utilizing solwution method to prepare the zinc oxide Window layer, and in conjunction with the solution preparation of CIGS and n type semiconductor layer, thereby realized that the whole soln method prepares the CIGS solar photocell, be large-scale preparation high conversion efficiency, the CIGS solar photocell provides possibility cheaply.

Summary of the invention

At above-mentioned the deficiencies in the prior art, the technical problem to be solved in the present invention provides a kind of preparation method of cheap quick, CIGS thin-film solar cells whole soln that production cost is low.

For solving the problems of the technologies described above, the present invention adopts following technical scheme:

A kind of whole soln legal system is equipped with Copper Indium Gallium Selenide (CIGS) thin-film solar cells, and described CIGS solar photocell comprises conductive substrates; The CIGS active layer, this CIGS active layer preparation is on described conductive substrates, mainly as light-absorption layer; The n type semiconductor layer, this n semiconductor layer is produced on the described CIGS active layer, and forms the pn knot with it, can effectively increase dissociating and exporting of photoproduction exciton; Window layer, this Window layer are produced on described n type semiconductor layer and are used for protecting described n type semiconductor layer; Transparent electrode layer, this transparent electrode layer are produced on the described Window layer; Acquisition electrode, this acquisition electrode is produced on the described transparent electrode layer, has the effect of gathering the photoproduction light stream; Described CIGS active layer is produced on the conductive substrates by solwution method, and thickness is the 0.1-10 micron, at last the continuous film of high annealing formation CIGS under the environment of 200-1000 degree.

Preferably, described solwution method comprises spin-coating method, spraying process, poor modulus method.

Preferably, the n type semiconductor layer adopts CBD or vacuum-deposited method to be produced on and forms the pn knot on the CIGS active layer, the photoproduction exciton is dissociated and exports.

Preferably; the material of described Window layer adopts spraying/spin coating/impact system that Zinc oxide nanoparticle or sol-gel solution are produced on the n N-type semiconductor N substrate; thickness is the 10-1000 nanometer, and high annealing under the environment of 20-1000 degree forms fine and close ZnO film at last.

Technique scheme has following beneficial effect: the CIGS active layer of this CIGS solar photocell, solwution method is all adopted in the preparation of n type semiconductor layer and Window layer, has cheaply advantage efficiently, greatly reduces the production cost of solar cell.

Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.

Description of drawings

Fig. 1 is the structural representation of embodiment of the invention CIGS solar photocell.

Embodiment

Below in conjunction with accompanying drawing the preferred embodiments of the present invention are described in detail.

As shown in Figure 1, be the structural representation of CIGS solar photocell.This device comprises: conductive substrates 1; CIGS active layer 2, this CIGS active layer 2 are to be produced on the conductive substrates 1 with three solwution methods; N type semiconductor layer 3, this n type semiconductor layer 3 utilize the CBD sedimentation to be produced on the CIGS active layer 2; Window layer 4, this semiconductor layer utilize solwution method that nano particle or sol-gel are produced on the n type semiconductor layer 3; Transparent electrode layer 5; With metal acquisition electrode 6.

Conductive substrates 1 is a conductive metal film, is generally molybdenum electrode thickness 200-2000 nanometer but is not limited to molybdenum, also comprises other suitable metal materials, as aluminium, titanium, copper and stainless steel etc.It above the conductive substrates 1 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.As use spin-coating method, just by controlling the thickness that spin speed, solution concentration and different spin coating number of times can change this CIGS active layer 2, generally the thickness of this resilient coating is between the 0.1-10 micron.N type semiconductor layer 3 above the CIGS active layer 2 is to adopt CBD or nano particle/sol-gel solution method preparation, 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, are to adopt nano particle/sol-gel solution method preparation.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.

Be that example is equipped with Copper Indium Gallium Selenide (CIGS) thin-film solar cells to above-mentioned whole soln legal system and describes in detail below with the spin-coating method.

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.Then reaction temperature is elevated to 225 degree, and injects 3 milliliters of OLEYLAMINE that contain 1 molar sulphur rapidly.React after 30 minutes, be cooled to 60 degree and add 10 milliliters toluene.Add a milliliter ethanol at last, centrifugation is come out, and 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. getting method with vacuum moulding machine prepares about molybdenum electrode 800 nanometers.

4. the solution with certain chemical constituent ratio after will filtering is spin-coated on the metal substrate with 800 rev/mins rotating speed, after the process annealing (150-350 degree), repeats same spin coating process again, reaches required thickness, and its chemical constituent ratio is respectively: Cu 0.92In 1-xGa xS 1-ySe yAfter finishing whole spin coatings, high temperature (250-550 degree) was annealed 30 minutes more at last, made the presoma reactive crystallization, formed continuous CIGS film.

5. adopt CBD or nano particle/sol-gel process to make n type cadmium sulfide layer

6. adopt nano particle/sol-gel process to make Window layer

The technology of preparation burnett's solution is as follows:

(1) nanoparticles solution: the ethanolic solution (0.55M) of slowly that stoichiometric proportion is identical Tetramine is added drop-wise in the dimethyl sulphoxide solution of zinc acetate dihydrate, continuous stirring reaction one hour, and centrifugation is come out then.

(2) sol-gel solution: the methanol solution of zinc acetate dihydrate of preparation 0.02M, fully the dissolving back the sol-gel solution of zinc oxide.

7. and then with sputter pellet Films Prepared with Vacuum Evaporation Deposition indium tin oxide transparent electrode.

8. use prepared by heat evaporation nickel/aluminium acquisition electrode at last.

This CIGS solar photocell adopts the preparation method of whole soln to have cheaply advantage efficiently, provides strong means to the development of its industrialization.

More than a kind of whole soln legal system that the embodiment of the invention provided be equipped with the photronic method of CIGS thin-film solar be described in detail; for one of ordinary skill in the art; thought according to the embodiment of the invention; part in specific embodiments and applications all can change; in sum; this description should not be construed as limitation of the present invention, and all any changes of making according to design philosophy of the present invention are all within protection scope of the present invention.

Claims (4)

1. a whole soln legal system is equipped with Copper Indium Gallium Selenide (CIGS) thin-film solar cells, and described CIGS solar photocell comprises conductive substrates;
The CIGS active layer, this CIGS active layer preparation is on described conductive substrates, mainly as light-absorption layer;
The n type semiconductor layer, this n semiconductor layer is produced on the described CIGS active layer, and forms the pn knot with it, can effectively increase dissociating and exporting of photoproduction exciton;
Window layer, this Window layer are produced on described n type semiconductor layer and are used for protecting described n type semiconductor layer;
Transparent electrode layer, this transparent electrode layer are produced on the described Window layer;
Acquisition electrode, this acquisition electrode is produced on the described transparent electrode layer, has the effect of gathering the photoproduction light stream;
It is characterized in that described CIGS active layer is produced on the conductive substrates by solwution method, thickness is the 0.1-10 micron, at last the continuous film of high annealing formation CIGS under the environment of 200-1000 degree.
2. whole soln legal system according to claim 1 is equipped with Copper Indium Gallium Selenide (CIGS) thin-film solar cells, and it is characterized in that: described solwution method comprises spin-coating method, spraying process, poor modulus method.
3. whole soln legal system according to claim 1 is equipped with Copper Indium Gallium Selenide (CIGS) thin-film solar cells, it is characterized in that: the n type semiconductor layer adopts CBD or vacuum-deposited method to be produced on and forms the pn knot on the CIGS active layer, the photoproduction exciton is dissociated and exports.
4. whole soln legal system according to claim 1 is equipped with Copper Indium Gallium Selenide (CIGS) thin-film solar cells; it is characterized in that: the material of described Window layer adopts spraying/spin coating/impact system that Zinc oxide nanoparticle or sol-gel solution are produced on the n N-type semiconductor N substrate; thickness is the 10-1000 nanometer; high annealing under the environment of 20-1000 degree forms fine and close ZnO film at last.
CN2011101130901A 2011-05-04 2011-05-04 CuInGaSe (CIGS) thin-film solar cell prepared by all-solution method CN102201495A (en)

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Cited By (7)

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CN103198884A (en) * 2013-03-04 2013-07-10 中国科学院长春光学精密机械与物理研究所 Full-solution-processed multilayered-structure transparent conductive thin film and preparation method thereof
CN103840027A (en) * 2012-11-20 2014-06-04 株式会社东芝 Photoelectric conversion element and solar cell
CN104157738A (en) * 2014-08-19 2014-11-19 苏州瑞晟纳米科技有限公司 CIGS solar photocell prepared by all-solution method
CN104285279A (en) * 2012-05-15 2015-01-14 日本麦可罗尼克斯股份有限公司 N-type light-absorbing layer alloy, method for producing same, and solar cell
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
CN104600144A (en) * 2015-01-26 2015-05-06 苏州瑞晟纳米科技有限公司 High-efficiency copper indium gallium selenium thin-film photocell based on bulk heterojunction structure light absorption layer
CN105470338A (en) * 2015-12-29 2016-04-06 中国电子科技集团公司第十八研究所 Flexible stacked solar cell and preparation method

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CN101924144A (en) * 2009-06-09 2010-12-22 黄麟 Crystalline silicon solar battery and preparation method thereof
CN101944552A (en) * 2010-07-30 2011-01-12 合肥工业大学 Method for preparing CIGS film serving as solar battery light absorption material
CN102163637A (en) * 2011-01-20 2011-08-24 苏州瑞晟太阳能科技有限公司 CIGS (copper-indium-gallium-selenium) solar photocell and preparation method thereof
CN202025785U (en) * 2011-01-20 2011-11-02 苏州瑞晟太阳能科技有限公司 CIGS solar photoelectric cell

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CN101527332A (en) * 2009-04-08 2009-09-09 华东师范大学 Method for preparing efficient thin-film solar cell light absorption layer
CN101924144A (en) * 2009-06-09 2010-12-22 黄麟 Crystalline silicon solar battery and preparation method thereof
CN101944552A (en) * 2010-07-30 2011-01-12 合肥工业大学 Method for preparing CIGS film serving as solar battery light absorption material
CN102163637A (en) * 2011-01-20 2011-08-24 苏州瑞晟太阳能科技有限公司 CIGS (copper-indium-gallium-selenium) solar photocell and preparation method thereof
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104285279A (en) * 2012-05-15 2015-01-14 日本麦可罗尼克斯股份有限公司 N-type light-absorbing layer alloy, method for producing same, and solar cell
CN104285279B (en) * 2012-05-15 2017-05-31 日本麦可罗尼克斯股份有限公司 N-shaped light absorbing zone alloy and its manufacture method and solar cell
CN103840027A (en) * 2012-11-20 2014-06-04 株式会社东芝 Photoelectric conversion element and solar cell
JP2014103264A (en) * 2012-11-20 2014-06-05 Toshiba Corp Photoelectric conversion element and solar cell
CN103198884A (en) * 2013-03-04 2013-07-10 中国科学院长春光学精密机械与物理研究所 Full-solution-processed multilayered-structure transparent conductive thin film and preparation method thereof
CN103198884B (en) * 2013-03-04 2016-03-02 中国科学院长春光学精密机械与物理研究所 Full-solution-procesmultilayered-structutransparent multilayered-structutransparent transparent conductive thin film and preparation method thereof
CN104157738A (en) * 2014-08-19 2014-11-19 苏州瑞晟纳米科技有限公司 CIGS solar photocell prepared by all-solution method
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
CN104600144A (en) * 2015-01-26 2015-05-06 苏州瑞晟纳米科技有限公司 High-efficiency copper indium gallium selenium thin-film photocell based on bulk heterojunction structure light absorption layer
CN105470338A (en) * 2015-12-29 2016-04-06 中国电子科技集团公司第十八研究所 Flexible stacked solar cell and preparation method
CN105470338B (en) * 2015-12-29 2017-03-08 中国电子科技集团公司第十八研究所 A kind of flexible overlapping solar cell and preparation method

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Application publication date: 20110928