CN104617186B - A kind of surface treatment method of custerite structural membrane solar cell light absorption layer - Google Patents
A kind of surface treatment method of custerite structural membrane solar cell light absorption layer Download PDFInfo
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- CN104617186B CN104617186B CN201510062290.7A CN201510062290A CN104617186B CN 104617186 B CN104617186 B CN 104617186B CN 201510062290 A CN201510062290 A CN 201510062290A CN 104617186 B CN104617186 B CN 104617186B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000012528 membrane Substances 0.000 title claims abstract description 25
- 230000031700 light absorption Effects 0.000 title claims abstract description 23
- 238000004381 surface treatment Methods 0.000 title claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000007654 immersion Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000011669 selenium Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 238000005457 optimization Methods 0.000 claims description 2
- 230000009466 transformation Effects 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- 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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Abstract
The invention discloses a kind of surface treatment method of custerite structural membrane solar cell light absorption layer, this method is by light absorbing layer (Cu1‑aAga)2(Zn1‑bCdb)(Sn1‑cGec)(S1‑dSed)4(wherein, a, b, c, d be each independently selected from 0~1) be placed in and soaked in the solution of metal ion after, made annealing treatment；Custerite structural membrane solar cell light absorption layer after this method processing can improve the surface defect of light-absorption layer well, the open-circuit voltage, fill factor, curve factor and photoelectric transformation efficiency of solar cell can be effectively improved, and this method raw material availability is high, environment-friendly, with low cost, can be in large-scale application in production.
Description
Technical field
The invention discloses a kind of surface treatment method of custerite structural membrane solar cell light absorption layer, belong to
Technical field of solar batteries.
Background technology
In recent years, it is increasingly serious due to environmental pollution and energy crisis, facilitate weight of the people to the renewable class energy
Depending on and study, be also greatly facilitated the new energy field industry such as solar cell flourish.And compound film solar energy
Battery because its theoretical light photoelectric transformation efficiency with low cost and higher turn into most application prospect solar cell it
One, as photovoltaic art develop key object, wherein CIGS based solar battery by nearly 40 years development by
Gradually industrial circle has been moved towards from academia, and obtain electricity conversion of the highest more than 21%, but such solar cell
In In and Ga be dissipated metal, expensive and reserves are limited, this turns into the obstacle that further develops of such solar cell.
New custerite structural membrane solar cell light absorption layer (Cu1-aAga)2(Zn1-bCdb)(Sn1-cGec)
(S1-dSed)4With adjustable energy gap, the absorption coefficient of light be larger, performance is stable and in the absence of light decay effect, with very high
Theoretical conversion efficiencies and wide development potentiality, and as the focus studied at present.Scholars endeavour to improve the conversion of battery
Efficiency, wherein, Cu2ZnSn(S,Se)4Thin-film solar cells efficiency alreadys exceed 12%, shows good application prospect.
The preparation of custerite structural membrane solar cell light absorption layer material has obtained substantial amounts of research, vacuum method
The thin-film material of better quality has been prepared with antivacuum method.In order to further improve the photoelectricity of the based thin film solar cell
Conversion efficiency, faster realizes the industrialization of battery, it is necessary to further improve the physico-chemical property of custerite structural membrane material, special
It is not surface and interface property.At present, the custerite structural membrane that prepared by various methods has a surface defect, and with buffering
The p-n junction that layer is formed can produce substantial amounts of Carrier recombination center, sternly there is also the problems such as energy level is mismatched, defect concentration is high
Ghost image rings the electricity conversion of solar cell.
The content of the invention
The defect existed for custerite structural membrane solar cell light absorption layer of the prior art, has a strong impact on
The electricity conversion of solar cell, the purpose of the present invention be provide it is a kind of by way of ion doping to light absorbs
Layer surface is handled to improve solar cell open-circuit voltage, fill factor, curve factor and the method for photoelectric transformation efficiency；This method is former
Expect that utilization rate is high, environment-friendly, with low cost, can be in large-scale application in production.
The invention provides a kind of surface treatment method of custerite structural membrane solar cell light absorption layer, the party
Method is placed in light absorbing layer in the solution of metal ion after immersion, is made annealing treatment at a temperature of 100~600 DEG C；Institute
The light absorbing layer stated is (Cu1-aAga)2(Zn1-bCdb)(Sn1-cGec)(S1-dSed)4, wherein, a, b, c, d are each independently selected from 0
~1.
The method on the surface of the processing custerite structural membrane solar cell light absorption layer of the present invention also includes following
Preferred scheme：
It is preferred that scheme in metal ion solution in contain Na+、K+、Ag+、Ca2+、Mg2+、Cu2+、Cd2+、Zn2+、Fe3 +、Cr3+、In3+At least one of.
Na in the solution of metal ion in further preferred scheme+、K+And Ag+Respective concentration range exists
Between 0.00001~1mol/L, Ca2+、Mg2+、Cu2+、Cd2+And Zn2+Respective concentration range is in 0.00001~0.8mol/L
Between, Fe3+、Cr3+And In3+Respective concentration range is between 0.00001~0.6mol/L, and the total concentration of metal ion
Scope is between 0.00001~3.0mol/L.
It is preferred that scheme in metal ion solution temperature be 5~95 DEG C.
It is preferred that scheme in time for being soaked in the solution of metal ion of light absorbing layer be 0.001~4h.
It is preferred that scheme in annealing the time be 5~100 minutes.
Annealing can be carried out in nitrogen atmosphere or inert atmosphere or atmosphere reactive in further preferred scheme.
Inert atmosphere is argon gas in further preferred scheme.
Atmosphere reactive is sulphur steam, selenium steam, hydrogen sulfide or selenizing nitrogen atmosphere in further preferred scheme.
It is preferred that scheme in light absorbing layer can repeat repeatedly immersion and annealing process, that realizes surface enters one
Step optimization.
The custerite structural membrane solar cell light absorption layer of the present invention is by vacuum or non-real in substrate
Empty method is prepared.
Compared with the prior art, beneficial effects of the present invention：The method that the present invention uses metal ion mixing first, to zinc yellow
Tin ore structural membrane solar cell light absorption layer is surface-treated, and can be effectively improved the open-circuit voltage of solar cell and be filled out
The factor is filled, photoelectric transformation efficiency is improved.Metal ion is immersed custerite structural membrane by the method that the present invention first passes through dipping
In solar cell light absorption layer lattice surface, and uniform load, in conjunction with annealing, doped chemical is improved into lattice
The defect chemistry property of material, forms on film top layer and buries knot, and reduction Interface composites or useful effect are passivated boundary in crystal boundary
Planar defect, reduces Carrier recombination center；Both effects can be conducive to improving open-circuit voltage and the filling of solar cell
The factor, improves photoelectric transformation efficiency, the surface defect that custerite structural membrane in the prior art can be overcome to exist, and with
There is also the problems such as energy level is mismatched, defect concentration is high for the p-n junction of cushion formation.This method is simple, raw material availability is high, ring
Border is friendly, with low cost, can large-scale promotion in production.
Brief description of the drawings
【Fig. 1】The light absorbing layer film surface SEM made from embodiment 1 schemes；
【Fig. 2】The XPS of the light absorbing layer film surface made from embodiment 3 detects the matched curve figure of In elements.
Specific embodiment
With reference to embodiment, present invention is described in further detail, but must not be using these embodiments as right
The limitation of the claims in the present invention protection domain.
Embodiment 1
Prepare custerite structural membrane solar cell light absorption layer Cu2CdGeSe4Afterwards, first by sample containing
0.1mol/L Na+、0.7mol/L Ca2+With 0.5mol/L Fe3+Aqueous metal salt in immersion (10 DEG C of solution temperature, immersion
Time 3.5h), 90 minutes then are incubated under 150 DEG C of nitrogen atmosphere, device is finally prepared to.
The Cu of preparation2CdGeSe4The open-circuit voltage of thin-film solar cells is 403mV, and short-circuit current density is 26.98mA/
cm2, fill factor, curve factor 48%, the photoelectric transformation efficiency of battery is 5.22%.As shown in figure 1, being surface after ion immersion treatment
SEM schemes, and as seen from Figure 1, surface topography is fine and close, smooth, and crystallite dimension is larger, without obvious hole or defect.
Embodiment 2
Prepare custerite structural membrane solar cell light absorption layer Cu2ZnSnS4Afterwards, first by sample containing
0.3mol/LK+、0.5mol/LAg+、0.6mol/LMg2+、0.5mol/LCu2+、0.4mol/LZn2+、0.4mol/LCr3+Metal
(30 DEG C of solution temperature, soak time 2.5h) is soaked in saline solution, then 70 minutes are incubated under 250 DEG C of argon gas atmosphere,
It is finally prepared to device.
Contrast as shown in table 1 without the device performance of immersion annealing process processing, from table, device after treatment
Open-circuit voltage, fill factor, curve factor and the photoelectric transformation efficiency of part have a certain degree of lifting.
The device performance of table 1 is contrasted
Embodiment 3
Prepare custerite structural membrane solar cell light absorption layer Ag4CdGeS4Afterwards, first by sample containing
0.3mol/L In3+Aqueous metal salt in soak (50 DEG C of solution temperature, soak time 2h), then in 350 DEG C of sulphur steam
50 minutes are incubated under atmosphere, device is finally prepared to.
The Ag of preparation4CdGeS4The open-circuit voltage of thin-film solar cells is 615mV, and short-circuit current density is 17.74mA/
cm2, fill factor, curve factor 47%, the photoelectric transformation efficiency of battery is 5.13%.As shown in Fig. 2 detecting the fitting of lower In elements for XPS
Curve, it can be seen from the test results that, it can realize that the Effective Doping of metallic element is incorporated to by the method for immersion.
Embodiment 4
Prepare custerite structural membrane solar cell light absorption layer Cu2ZnSn(S0.3Se0.7)4Afterwards, first by sample containing
There is 0.7mol/LK+、0.3mol/LCd2+Aqueous metal salt in immersion (solution temperature be 70 DEG C, soak time 1.5h), so
30 minutes are incubated under 450 DEG C of selenium steam atmosphere again afterwards, then sample is being contained into 0.2mol/LCu2+、0.2mol/LCr3+Gold
Belong in saline solution and soak (80 DEG C of solution temperature, soak time 1h), 20 points are then incubated in 500 DEG C of hydrogen sulfide atmosphere
Clock, is finally prepared to device.
Contrast as shown in table 2 without the device performance of immersion annealing process processing, from table, device after treatment
Open-circuit voltage, fill factor, curve factor and the photoelectric transformation efficiency of part have a certain degree of lifting.
The device performance of table 2 is contrasted
Embodiment 5
Prepare custerite structural membrane solar cell light absorption layer Cu2(Zn0.4Cd0.6)(Ge0.7Sn0.3)Se4Afterwards, first
By sample in 0.9mol/LNa+、0.1mol/LZn2+、0.05mol/LCa2+、0.1mol/LFe3+Metal salt solution in soak
(90 DEG C of solution temperature, soak time 30 minutes), is then incubated 10 minutes in 550 DEG C of selenizing nitrogen atmosphere, is finally prepared to
Device.
The Cu of preparation2(Zn0.4Cd0.6)(Ge0.7Sn0.3)Se4The open-circuit voltage of thin-film solar cells is 409mV, short circuit electricity
Current density is 29.08mA/cm2, fill factor, curve factor 41%, the photoelectric transformation efficiency of battery is 4.88%.
Claims (4)
1. a kind of surface treatment method of custerite structural membrane solar cell light absorption layer, it is characterised in that inhale light
Receipts are placed in the solution of metal ion after immersion, annealing are carried out at a temperature of 100~600 DEG C 5~100 minutes；Institute
The light absorbing layer stated is (Cu1-aAga)2(Zn1-bCdb)(Sn1-cGec)(S1-dSed)4, wherein, a, b, c, d are each independently selected from 0
~1；
Contain Ag in the solution of described metal ion+、Ca2+、Mg2+、Cu2+、Cd2+、Zn2+、Fe3+、Cr3+、In3+In at least
It is a kind of；Or contain Ag+、Ca2+、Mg2+、Cu2+、Cd2+、Zn2+、Fe3+、Cr3+、In3+At least one of and Na+And/or K+；
Described annealing is carried out in atmosphere reactive；
Described atmosphere reactive is sulphur steam, selenium steam, hydrogen sulfide or selenizing nitrogen atmosphere；
Na in the solution of described metal ion+、K+And Ag+Respective concentration range between 0.00001~1mol/L,
Ca2+、Mg2+、Cu2+、Cd2+And Zn2+Respective concentration range is between 0.00001~0.8mol/L, Fe3+、Cr3+And In3+Respectively
From concentration range between 0.00001~0.6mol/L, and metal ion total concentration scope 0.00001~
3.0mol/L between；
The described annealing time is 5~100 minutes.
2. the surface treatment method of custerite structural membrane solar cell light absorption layer according to claim 1, its
It is characterised by, the temperature of the solution of described metal ion is 5~95 DEG C.
3. the surface treatment method of custerite structural membrane solar cell light absorption layer according to claim 1 or 2,
Characterized in that, the time that described light absorbing layer soaks in the solution of metal ion is 0.001~4h.
4. the surface treatment method of custerite structural membrane solar cell light absorption layer according to claim 1, its
It is characterised by, light absorbing layer repeats repeatedly immersion and annealing process, realizes the further optimization on surface.
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| CN103474505A (en) * | 2012-06-06 | 2013-12-25 | 尚越光电科技有限公司 | Alkali metal doping method in large-scale production of CIGS (copper, indium, gallium, selenium) thin-film solar cell |
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| CN103094422A (en) * | 2013-01-29 | 2013-05-08 | 电子科技大学 | Doping craft in copper-zinc oxide tin sulphur selenium film preparation |
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Effective date of registration: 20211025 Address after: 410083 floor 2, building 7, No. 966, Lushan South Road, Yuelu street, Yuelu District, Changsha City, Hunan Province Patentee after: Hunan iridium Technology Co.,Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University |