CN102544132B - Copper indium gallium selenide cell and preparation method thereof - Google Patents
Copper indium gallium selenide cell and preparation method thereof Download PDFInfo
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- CN102544132B CN102544132B CN201210014456.4A CN201210014456A CN102544132B CN 102544132 B CN102544132 B CN 102544132B CN 201210014456 A CN201210014456 A CN 201210014456A CN 102544132 B CN102544132 B CN 102544132B
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 108
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 104
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 13
- 239000010935 stainless steel Substances 0.000 claims abstract description 13
- 239000002659 electrodeposit Substances 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 46
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 26
- 238000000151 deposition Methods 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052738 indium Inorganic materials 0.000 claims description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 13
- 229940044658 gallium nitrate Drugs 0.000 claims description 13
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 18
- 229910000906 Bronze Inorganic materials 0.000 description 11
- 239000010974 bronze Substances 0.000 description 11
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 11
- 238000009826 distribution Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- -1 this Chemical compound 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a copper indium gallium selenide cell and a preparation method of the copper indium gallium selenide cell. The copper indium gallium selenide cell sequentially comprises a substrate, a P-type sodium-doped CIGS (copper indium gallium selenide) absorbing layer, an n buffer layer, an n-type zinc oxide layer, a transparent conducting layer and a collecting electrode. The P-type sodium-doped CIGS absorbing layer and the n-type zinc oxide layer form a PN junction. The thickness of the P-type sodium-doped CIGS absorbing layer is 1-10mum, and the P-type sodium-doped CIGS absorbing layer sequentially comprises a low-gallium CIGS absorbing layer with a gallium concentration of 1-1.5%, a medium-gallium CIGS absorbing layer with a gallium concentration of 3-5% and a high-gallium CIGS absorbing layer with a gallium concentration of 6-8%. Gallium elements of the P-type sodium-doped CIGS absorbing layer of the copper indium gallium selenide cell of the invention are distributed in a V shape, therefore, the efficiency of the cell is high; in addition, the method can ensure that the gallium elements are distributed in a V shape in the P-type sodium-doped CIGS absorbing layer and overcome the problem that the doping of sodium in the CIGS absorbing layer with a stainless steel substrate is difficult.
Description
Technical field
The present invention relates to battery, relate in particular to the preparation method of copper indium gallium selenide cell and this copper indium gallium selenide cell.
Background technology
Due to reasons such as high cost, complex process, production equipment costlinesses, the universal of traditional crystal silicon solar batteries is restricted, thin-film solar cells be take the features such as it is with low cost, technique is simple and has been opened up new road as new forms of energy replace traditional energy, and how large-scale production thin-film solar cells is the study hotspot of solar energy industry nowadays.
In recent years, copper indium gallium selenide cell (Cu (In, Ga) Se, be called for short CIGS), because it is with low cost, stability is strong, conversion efficiency is high and can prepare in the first-class reason of flexible substrates, has been subject to paying close attention to widely, has obtained swift and violent development.Traditional utilization is steamed the standby CIGS battery of legal system altogether because controlled to the distribution of gallium element, guarantee that gallium element is " V " word shape and distributes in absorbed layer, and make the battery efficiency that makes the highest, but it is low and be subject to device-restrictive to be difficult to realize large-scale production to steam altogether method production efficiency, therefore, how using simple technique to prepare high-quality CIGS absorbed layer is the key making a breakthrough.
In the various techniques of preparation CIGS absorbed layer, electrodeposition process can be by regulating deposition voltage, electrodeposit liquid concentration proportioning etc. effectively to control the effect of deposition preparation with it, and equipment is simple, do not need the advantages such as vacuum condition to become the focus of research, but, how in CIGS absorbed layer, to realize the distribution of gallium element " V " word and how at stainless steel-based end CIGS battery, to mix sodium remaining the technical problem that electrodeposition process faces.
Summary of the invention
The problem that the present invention solves is in CIGS absorbed layer, to realize gallium element " V " type to distribute and take and mix the problem of sodium difficulty in the CIGS absorbed layer that stainless steel is substrate.
For addressing the above problem, the invention provides a kind of copper indium gallium selenide cell, this copper indium gallium selenide cell comprises and comprises that successively substrate, P type mix the CIGS absorbed layer of sodium, N-shaped resilient coating, N-shaped zinc oxide film, transparency conducting layer and acquisition electrode, CIGS absorbed layer and N-shaped zinc oxide film that described P type is mixed sodium form PN junction, the thickness that described P type is mixed the CIGS absorbed layer of sodium is 1～10 micron, comprises successively the high gallium CIGS absorbed layer that gallium concentration is 1%～1.5% low gallium CIGS absorbed layer, gallium concentration is 3%～5% middle gallium CIGS absorbed layer and gallium concentration are 6%～8%.
Alternatively, described low gallium CIGS absorbed layer gallium concentration is 1%, and middle gallium CIGS absorbed layer gallium concentration is 4%, and the gallium concentration of high gallium CIGS absorbed layer is 6%.
The present invention also provides the preparation method of above-mentioned copper indium gallium selenide cell, the method comprises the steps: to prepare electrodeposit liquid raw material: indium metal is dissolved in to concentrated hydrochloric acid and prepares indiumchloride solution, gallium is dissolved in to concentrated hydrochloric acid and prepares gallium chloride solution, gallium is dissolved in to red fuming nitric acid (RFNA) and prepares gallium nitrate solution, prepare electrodeposit liquid: copper chloride and natrium citricum and above-mentioned electrodeposit liquid raw material are dissolved in to deionized water, stir and obtain first part of electrodeposit liquid that gallium ion concentration raises successively, second part of electrodeposit liquid and the 3rd part of electrodeposit liquid, wherein, the pH value of every part of electrodeposit liquid is between 1～1.8, the concentration of the copper chloride of first part of electrodeposit liquid is 0.01～0.025M/L, the concentration of inidum chloride is 0.025～0.125M/L, gallium chloride and gallium nitrate total concentration are respectively 0.02～0.2M/L, the concentration of the copper chloride of second part of electrodeposit liquid is 0.01～0.025M/L, the concentration of inidum chloride is 0.025～0.125M/L, gallium chloride and gallium nitrate total concentration are respectively 0.025～0.25M/L, the concentration of the copper chloride of the 3rd part of electrodeposit liquid is 0.01～0.025M/L, the concentration of inidum chloride is 0.025～0.125M/L, gallium chloride and gallium nitrate total concentration are respectively 0.03～0.3M/L, acid copper indium gallium layer: using and plate at the bottom of the stainless steel lining of molybdenum as negative electrode, successively will deposit three parts of electrodeposit liquids at the bottom of the stainless steel lining of described plating molybdenum from low paramount order according to gallium ion concentration, take out and dry with nitrogen, sodium is mixed in selenizing: described copper indium gallium is placed in selenizing chamber, and using selenization source, this selenization source to contain concentration is 0.1%～1% sodium selenide, by water-bath legal system for N-shaped resilient coating, with sol-gal process, prepare N-shaped zinc oxide film, with sputtering method, prepare transparency conducting layer, with vapour deposition method, prepare acquisition electrode.
Alternatively, in acid copper indium gallium layer step, deposition voltage is 1.0～1.8V, and sedimentation time is 1～3 minute.
Alternatively, selenizing is mixed sodium step specifically: selenizing chamber vacuum is evacuated to below 3 * 10-3Pa, and temperature remains on 300～700 ℃, and the selenizing time is to carry out under the condition of 10～30 minutes
Alternatively, described PH=1.5.
Compared with prior art, the present invention has the following advantages:
The present invention utilizes electrodeposition technology, with gallium ion concentration order from low to high, successively in described electrodeposit liquid, deposit at the bottom of by the stainless steel lining of plating molybdenum, like this, guarantee that gallium element is the distribution of " V " word in CIGS absorbed layer, moreover the present invention is by the sodium selenide that adulterates, in the CIGS absorbed layer that to have overcome at stainless steel be substrate, mix the problem of sodium difficulty in selenization source, improved the conductivity of CIGS absorbed layer, passivation grain boundary defects.In addition, the present invention adopts electrodeposition process, and processing step is simple, prepares copper indium gallium selenide cell compare with vacuum method, does not need expensive vaccum-pumping equipment and highly purified raw material, has reduced widely the production cost of copper indium gallium selenide cell, is applicable to extensive industrialization.
Accompanying drawing explanation
Fig. 1 is the structural representation of copper indium gallium selenide cell of the present invention
Fig. 2 is that the present invention is for the preparation of the structural representation of the device of CIGS absorbed layer.
Embodiment
By describing technology contents of the present invention, structural feature in detail, being reached object and effect, below in conjunction with embodiment and coordinate accompanying drawing to be described in detail.
Refer to Fig. 1, copper indium gallium selenide cell of the present invention comprises that substrate 1, P type mix the CIGS absorbed layer 2 of sodium, N-shaped resilient coating 3, N-shaped zinc oxide film 4, transparency conducting layer 5 and acquisition electrode 6 successively.Described substrate 1 be plating molybdenum stainless steel lining at the bottom of.The CIGS absorbed layer 2 that described P type is mixed sodium is positioned on described substrate 1, form PN junctions with N-shaped zinc oxide film 4, comprise that gallium concentration is the high gallium CIGS absorbed layer 23 that 1%～1.5% low gallium CIGS absorbed layer 21, the gallium concentration middle gallium CIGS absorbed layer 22 that is 3%～5% and gallium concentration are 6%～8%.Described middle gallium CIGS absorbed layer 22 is between low gallium CIGS absorbed layer 21 and high gallium CIGS absorbed layer 23.Described low gallium CIGS absorbed layer 21, middle gallium CIGS absorbed layer 22 and high gallium CIGS absorbed layer 23 have been guaranteed the V-shaped distribution of gallium element of the CIGS absorbed layer 2 of copper indium gallium selenide cell in above-mentioned concentration range, in a preferred embodiment, described low gallium CIGS absorbed layer gallium concentration is 2%, middle gallium CIGS absorbed layer gallium concentration is 4%, the gallium concentration of high gallium CIGS absorbed layer is 6%, reduced like this impact that the gallium ion that produces causes to the elegant diffusion of stainless steel electrode in selenizing process, guaranteed the distribution of gallium, also the concentration that has guaranteed gallium ion in Copper Indium Gallium Selenide layer 2 in zone of reasonableness simultaneously, make Copper Indium Gallium Selenide layer 2 possess optimum energy gap.Described N-shaped resilient coating 3 is cadmium sulfide resilient coatings, preparation is mixed between the CIGS absorbed layer 2 and N-shaped zinc oxide film 4 of sodium in described P type, like this, can reduce CIGS absorbed layer 2 and the Lattice Matching defect between N-shaped zinc oxide film 4 and excessive the caused impact of band gap difference that P type is mixed sodium.Described N-shaped zinc oxide film 4 is positioned on described N-shaped resilient coating 3.Described transparency conducting layer 5 is AZO transparency conducting layers, is positioned on N-shaped zinc oxide film 4, for preventing the diffusion of acquisition electrode metal.Described acquisition electrode 6 is aluminium electrodes, is positioned on transparency conducting layer 5, for gathering electronics.
In above-mentioned copper indium gallium selenide cell, the V-shaped distribution of gallium element of mixing the CIGS absorbed layer 2 of sodium due to P type, reduced the impact that the gallium ion that produces causes to the elegant diffusion of stainless steel electrode in selenizing process, guaranteed the distribution of gallium, also the concentration that has guaranteed gallium ion in Copper Indium Gallium Selenide layer, in zone of reasonableness, makes Copper Indium Gallium Selenide layer possess optimum energy gap simultaneously.
In order to obtain above-mentioned copper indium gallium selenide cell, the present invention also provides the method for preparing copper indium gallium selenide cell, below by three embodiment, describes preparation method of the present invention in detail
The first embodiment
Prepare electrodeposit liquid raw material: get 0.5mol indium and be dissolved in 250ml concentrated hydrochloric acid, add distilled water heating evaporation excessive hydrochloric acid to obtain the indiumchloride solution that concentration is 2mol/L, measure this solution 250ml; The gallium of getting 0.15mol is dissolved in the concentrated hydrochloric acid of 100ml, and adding distilled water heating evaporation excessive hydrochloric acid to obtain concentration is 0.5mol/L gallium chloride solution, measures this solution 300ml; The gallium of getting 0.15mol is dissolved in the red fuming nitric acid (RFNA) of 60ml, adds the excessive nitric acid of distilled water heating evaporation to obtain the gallium nitrate solution that concentration is 0.5mol/L, measures this solution 300ml.
Prepare electrodeposit liquid: above-mentioned electrodeposit liquid raw material, copper chloride and natrium citricum are prepared to first part of electrodeposit liquid of 1L, the 3rd part of electrodeposit liquid of second part of electrodeposit liquid of 1L and 1L, the PH of every part of electrodeposit liquid is 1.5, in the time of PH=1.5, deposition effect is best, can meet each element deposits according to atom ratio, wherein, the concentration of each composition of three parts of electrodeposit liquids is as follows:
| Copper chloride | Inidum chloride | Natrium citricum | Gallium chloride | Gallium nitrate | |
| First part | 0.015mol/L | 0.025mol/L | 1mol/L | 0.02mol/L | 0.02mol/L |
| Second part | 0.015mol/L | 0.025mol/L | 1mol/L | 0.025mol/L | 0.025mol/L |
| The 3rd part | 0.015mol/L | 0.025mol/L | 1mol/L | 0.03mol/L | 0.03mol/L |
Acid copper indium gallium layer: prepare the device of three cover preparation CIGS absorbed layers as shown in Figure 2, every suit equipment all comprises container 7 for holding electrodeposit liquid, as platinum guaze 8 and the HF switch electroplating power supply 10 of anode.First, the container 7 of first set device holds first part of electrodeposit liquid, and the container 7 of the second covering device holds second part of electrodeposit liquid, holds the 3rd part of electrodeposit liquid in the container of the 3rd covering device; Then, making the output voltage of HF switch electroplating power supply 10 is 2.0V, usings at the bottom of the stainless steel lining of plating molybdenum of 5cm * 5cm and at first part of electrodeposit liquid, deposits 10 minutes as negative electrode 9, forms the first bronze medal indium gallium absorbed layer, takes out and dries up with nitrogen; Then, the described negative electrode 9 depositing at first part of electrodeposit liquid is positioned in 7 second parts of electrodeposit liquids of container of the second complete equipment, the output voltage that makes HF switch electroplating power supply 10 is 2.0V, sedimentation time is 10 minutes, taking-up dries up with nitrogen, forms the second bronze medal indium gallium layer on the first bronze medal indium gallium layer; Finally, the negative electrode 9 depositing in second part of electrodeposit liquid is positioned in the electrodeposit liquid of container 7 of the 3rd complete equipment and carries out electro-deposition, the output voltage of HF switch electroplating power supply 10 is 2.0V, sedimentation time is 10 minutes, like this, on the second bronze medal indium gallium layer, form the 3rd bronze medal indium gallium layer, take out and dry up with nitrogen.
Sodium is mixed in selenizing: the negative electrode 9 with the first bronze medal indium gallium floor, the second bronze medal indium gallium floor and the 3rd bronze medal indium gallium floor is placed in to selenizing chamber, uses selenization source, this selenization source doping has the sodium selenide of X concentration, and selenizing chamber vacuum is evacuated to 3 * 10
-3below Pa, temperature remains on 550 ℃, the selenizing time is 20 minutes, thereby, the P type CIGS absorbed layer 2 of sodium is mixed in acquisition, and wherein, described the first bronze medal indium gallium floor forms described low gallium CIGS absorbed layer 21 in selenizing chamber, described the second bronze medal indium gallium floor forms middle gallium CIGS absorbed layer 22 in selenizing chamber, described the 3rd bronze medal indium gallium floor forms high gallium CIGS absorbed layer 23 in selenizing chamber.
Refer to Fig. 1, then, with immersion method, on described CIGS absorbed layer 2, prepare N-shaped resilient coating 3; With sol-gal process, on described N-shaped resilient coating 3, prepare N-shaped zinc oxide film 4; With sputtering method, on described N-shaped zinc oxide film 4, prepare transparency conducting layer 5; With vapour deposition method, on transparency conducting layer 5, prepare acquisition electrode 6, these methods are all prior aries, do not repeat them here.
The second embodiment
The difference of this second embodiment and the first embodiment is: sedimentation time and deposition voltage need not, in this second embodiment, the deposition voltage at described negative electrode 9 in three covering devices is 1.5V, sedimentation time is equal 15 minutes, after taking-up, with nitrogen, dries up.
The 3rd embodiment
The 3rd embodiment is from the difference of the first embodiment: it is different that sodium step is mixed in selenizing, and in the 3rd embodiment, the negative electrode 9 with copper indium gallium floor is placed in selenizing chamber, and selenizing chamber vacuum is evacuated to 3 * 10
-3below Pa, temperature remains on 500 ℃, and the selenizing time is 30 minutes.
Based on technical thought of the present invention, the parameter of technique of the present invention can also be selected in following scope:
In preparing the step of electrodeposit liquid: the PH of every part of electrodeposit liquid is 1～1.8, for example 1.2V, 1.5V, 1.7V, higher than 1.8 precipitations that can form gallium salt, lower than 1 a large amount of defect of generation, cannot form required membrane material.The concentration of the copper chloride of first part of electrodeposit liquid is 0.01～0.025M/L, and for example 0.01M/L, 0.015M/L, 0.02M/L, if concentration lower than 0.01M/L, causes deposition not enough, affect membrane structure; If concentration is higher than 0.025M/L, it is excessive to deposit, and causes the atom ratio of film component unbalance; The concentration of inidum chloride is 0.025～0.125M/L, 0.025M/L for example, and 0.05M/L, 0.1M/L, if concentration lower than 0.025M/L, causes deposition not enough, affects membrane structure; If concentration is higher than 0.125M/L, it is excessive to deposit, and causes the atom ratio of film component unbalance; Gallium chloride and gallium nitrate total concentration are respectively 0.02～0.2M/L, 0.02M/L for example, and 0.1M/L, 0.15M/L, take this concentration that guarantees gallium in copper indium gallium film of deposition is 1%～1.5%; The concentration of the copper chloride of second part of electrodeposit liquid is 0.01～0.025M/L, 0.01M/L for example, 0.015M/L, 0.02M/L, the concentration of inidum chloride is 0.025～0.125M/L, 0.025M/L for example, 0.05M/L, 0.1M/L, gallium chloride and gallium nitrate total concentration are respectively 0.025～0.25M/L, 0.05M/L for example, 0.15M/L, 0.2M/L, take that this guarantees that in copper indium gallium film of deposition, the concentration of gallium is 3%～5%; The concentration of the copper chloride of the 3rd part of electrodeposit liquid is 0.01～0.025M/L, 1.2V for example, 1.5V, 1.7V, the concentration of inidum chloride is 0.025～0.125M/L, 0.025M/L for example, 0.05M/L, 0.1M/L, gallium chloride and gallium nitrate total concentration are respectively 0.03～0.3M/L, 0.03M/L for example, 0.0.15M/L, 0.25M/L, take that this guarantees that in copper indium gallium film of deposition, the concentration of gallium is 6%～8%.
In acid copper indium gallium layer step: deposition voltage is 1.0～1.8V, 1.0V for example, 1.5V, lower than 1.0V, causes deposition not enough, affects membrane structure; Higher than 1.8V, early once deposition velocity was too fast, and evolving hydrogen reaction strengthens, and in conjunction with not firm, crackle increases; Sedimentation time is 1～3 minute, for example 1.5 minutes, and 2 minutes, lower than within 1 minute, causing deposition not enough, higher than within 3 minutes, causing deposition excessive and occur dephasign.
In selenizing, mix in the step of sodium: it is 0.1%～1% that concentration is contained in described selenization source, for example 0.5%, 0.8% sodium selenide, undesirable lower than 0.1% doping effect, excessive higher than 1% doping, affects structure and the atom ratio of film.Selenizing chamber vacuum is evacuated to 3 * 10
-3below Pa, temperature remains on 300～700 ℃, and for example 550 ℃, 600 ℃, lower than 300 ℃, cannot form needed yellow copper structure, higher than 700 ℃, form other dephasigns.The selenizing time is 10～30 minutes, for example 15 minutes, under the condition of 25 minutes, carry out, and not enough lower than 10 minutes selenizing degree, cannot form required film; Higher than 30 minutes, gallium element migration was too much, affected membrane structure.
Claims (4)
1. a preparation method for copper indium gallium selenide cell, is characterized in that: the method comprises the steps:
Prepare electrodeposit liquid raw material: indium metal is dissolved in to concentrated hydrochloric acid and prepares indiumchloride solution, gallium is dissolved in to concentrated hydrochloric acid and prepares gallium chloride solution, gallium is dissolved in to red fuming nitric acid (RFNA) and prepares gallium nitrate solution;
Prepare electrodeposit liquid: copper chloride and natrium citricum and above-mentioned electrodeposit liquid raw material are dissolved in to deionized water, stir and obtain first part of electrodeposit liquid that gallium ion concentration raises successively, second part of electrodeposit liquid and the 3rd part of electrodeposit liquid, wherein, the pH value of every part of electrodeposit liquid is between 1-1.8, the concentration of the copper chloride of first part of electrodeposit liquid is 0.01～0.025M/L, the concentration of inidum chloride is 0.025～0.125M/L, gallium chloride and gallium nitrate total concentration are respectively 0.02～0.2M/L, the concentration of the copper chloride of second part of electrodeposit liquid is 0.01～0.025M/L, the concentration of inidum chloride is 0.025～0.125M/L, gallium chloride and gallium nitrate total concentration are respectively 0.025～0.25M/L, the concentration of the copper chloride of the 3rd part of electrodeposit liquid is 0.01～0.025M/L, the concentration of inidum chloride is 0.025～0.125M/L, gallium chloride and gallium nitrate total concentration are respectively 0.03～0.3M/L,
Acid copper indium gallium layer: using and plate at the bottom of the stainless steel lining of molybdenum as negative electrode, successively will deposit three parts of electrodeposit liquids at the bottom of the stainless steel lining of described plating molybdenum from low paramount order according to gallium ion concentration, take out and dry with nitrogen;
Sodium is mixed in selenizing: described copper indium gallium is placed in selenizing chamber, and using selenization source, this selenization source to contain concentration is 0.1%～1% sodium selenide;
By water-bath legal system for N-shaped resilient coating;
With sol-gal process, prepare N-shaped zinc oxide film;
With sputtering method, prepare transparency conducting layer;
With vapour deposition method, prepare acquisition electrode.
2. the preparation method of copper indium gallium selenide cell according to claim 1, is characterized in that: in acid copper indium gallium layer step, deposition voltage is 1.0～1.8V, and sedimentation time is 1～3 minute.
3. the preparation method of copper indium gallium selenide cell according to claim 1, is characterized in that: selenizing is mixed sodium step specifically: selenizing chamber vacuum is evacuated to 3 * 10
-3below Pa, temperature remains on 300～700 ℃, and the selenizing time is to carry out under the condition of 10～30 minutes.
4. the preparation method of copper indium gallium selenide cell according to claim 1, is characterized in that: described PH=1.5.
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| CN103668361B (en) * | 2013-10-18 | 2016-06-15 | 国家电网公司 | A kind of preparation method of the copper and indium zinc selenium thin film of the photovoltaic cell for photovoltaic generating system |
| CN106229362B (en) * | 2016-09-22 | 2018-03-16 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of copper indium gallium selenide thin film and copper indium gallium selenide thin film |
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| CN1585140A (en) * | 2004-06-14 | 2005-02-23 | 王东生 | Multi-absorbing-layer solar battery and manufacturing method thereof |
| CN201549520U (en) * | 2009-12-11 | 2010-08-11 | 郑州金土地能源科技有限公司 | Copper, indium, gallium, tin, sulfur thin film solar cell |
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