CN104752535B - Solar cell - Google Patents
Solar cell Download PDFInfo
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- CN104752535B CN104752535B CN201410712963.4A CN201410712963A CN104752535B CN 104752535 B CN104752535 B CN 104752535B CN 201410712963 A CN201410712963 A CN 201410712963A CN 104752535 B CN104752535 B CN 104752535B
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- solaode
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- 239000004065 semiconductor Substances 0.000 claims abstract description 86
- 239000000126 substance Substances 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 238000000137 annealing Methods 0.000 claims description 27
- 238000000498 ball milling Methods 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 229910052738 indium Inorganic materials 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 18
- 230000007704 transition Effects 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 3
- 229910052773 Promethium Inorganic materials 0.000 abstract 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 abstract 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 abstract 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 abstract 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 abstract 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 abstract 1
- 229910052706 scandium Inorganic materials 0.000 abstract 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 abstract 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 abstract 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 abstract 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000002994 raw material Substances 0.000 description 22
- 239000010949 copper Substances 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 17
- 229910052761 rare earth metal Inorganic materials 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052711 selenium Inorganic materials 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 2
- 229940056582 human hair preparation Drugs 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a semiconductor material as well as a preparation method and an application thereof. The semiconductor material comprises chemical compositions: CuIn[x]Ga[y]R[1-x-y]Se[2], wherein x is more than 0 and is less than 1, y is more than 0 and is less than 0.5, and x+y is less than 1; R is at least one selected from La (Lanthanum), Ce (Cerium), Pr (praseodymium), Nd (Neodymium), Pm (Promethium), Sm (Samarium), Eu (Europium), Gd (Gadolinium), Tb (Terbium), Dy (Dysprosium), Ho (Holmium), Er (Erbium), Tm (Thulium), Yb (Ytterbium), Ru (Ruthenium), Sc (Scandium) and Y (Yttrium). The semiconductor can be used for an absorbing layer of a solar panel.
Description
Technical field
The present invention relates to area of solar cell, in particular it relates to solaode.
Background technology
As a kind of inexhaustible regenerative resource, it possesses spatter property, unlimitedness and universal to solar energy
Property the features such as, become and solve lack of energy, environmental pollution and effective way the problems such as global warming, so photovoltaic is sent out
The development of electricity has very profound significance.
Solaode can be divided into silica-based solar cell, compound solar cell, Organic substance too according to material at present
Sun energy battery etc..In the solaode of numerous classes, CuInSe2(CIS) energy gap of solaode is 1.04eV, too
Positive electricity pond opto-electronic conversion theoretical efficiency is 25%～30% about, and the thin film only needing to 1～2 μ m-thick just can absorb 99%
Above sunlight, such that it is able to substantially reduce the cost of solar cell, therefore, it is that a kind of have good development prospect too
Positive electricity pond.In is replaced by appropriate Ga, becomes CuIn1-xGaxSe2Polycrystalline solid solution, its energy gap can 1.04～
Continuously adjust in the range of 1.67eV, can absorb the sunlight of wider wavelength.
People are many to the research of CIGS (CIGS) solaode to appear in the newspapers.In recent years, in order to improve its conversion
Efficiency, scientists are constantly improved to it in technology and preparation technology：The CIGS thin film table prepared by three stage Co-evaporation method
Face is smooth, crystallite dimension is big and compact, is to prepare the maximally effective technique of high efficiency CIGS solaode at present；Micro sodium unit
Element can be effectively improved structural behaviour and the electric property of material in CIGS compound.2008, National Renewable energy
Source laboratory prepares the copper indium gallium selenium solar cell that highest light conversion efficiency in the world is 20.8%.
However, in the flow of research to CIGS solaode, also exposing its own shortcoming：Because Ga does not have
Photosensitiveness, the optical condition that when as lamination solar cell, lower floor's battery cannot be provided；Additionally, CIGS solaode
In, CdS is also another essential condition restricting its industrialization to the pollution of environment.The shortcomings of CIGS solaode limit
Its extensive industrialized development.
Thus, the research with regard to CIGS solaode at present still needs to be goed deep into.
Content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.For this reason, the present invention
One purpose is to propose the semi-conducting material of a kind of light transmission that can improve solaode and conversion efficiency.
In one aspect of the invention, the invention provides a kind of semi-conducting material.According to embodiments of the invention, described
The chemical composition of semi-conducting material is：CuInxGayR1-x-ySe2, wherein, 0 ＜ x<1,0 ＜ y ＜ 0.5, and x+y ＜ 1, R is choosing
At least one from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ru, Sc and Y.Inventor finds,
This semi-conducting material of the present invention can be by rare earth doped element R, permissible effective for preparing the absorbed layer of solaode
In the case of not affecting conversion efficiency of solar cell, effectively improve its light transmission, carry for lower floor's battery in multijunction cell
For good optical condition, the solaode for photovoltaic curtain wall can provide good indoor light.In addition, rare earth element has
The feature of " up-conversion luminescence ", makes rear-earth-doped semi-conducting material discharge and can be inhaled after absorbing larger range of sunlight
Receive the visible ray of layer double absorption, improve conversion efficiency.
Semi-conducting material according to embodiments of the present invention can also have following additional technical feature：
According to embodiments of the invention, R is at least one in Nd, Pm, Sm, Eu and Gd, Tb and Dy.Thus, will
When this semi-conducting material is used for the absorbed layer of solaode, there is preferable light transmission and conversion efficiency.
According to embodiments of the invention, 0.5 ＜ x<1.Thus, this semi-conducting material is used as the absorbed layer of solaode,
Preferably, conversion efficiency is higher for light transmission.
According to embodiments of the invention, x is more than y.Thus, this semi-conducting material is used as the absorbed layer of solaode, has
Beneficial to its light transmission of raising and conversion efficiency.
According to embodiments of the invention, its chemical composition is one of following：CuIn0.6Ga0.3Sm0.1Se2；
CuIn0.6Ga0.3Gd0.1Se2；CuIn0.7Ga0.2Nd0.1Se2；CuIn0.6Ga0.35Pm0.05Se2；CuIn0.6Ga0.35Eu0.05Se2；
CuIn0.7Ga0.25Tb0.05Se2；And CuIn0.56Ga0.42Dy0.02Se2.Thus, this semi-conducting material is used as solaode
Absorbed layer, light transmission and conversion efficiency are preferable.
In a second aspect of the present invention, the invention provides a kind of method preparing semi-conducting material noted earlier.According to
Embodiments of the invention, the method includes：(1) provide metal simple-substance mixture, described metal simple-substance mixture contains pre- definite proportion
Metal simple-substance Cu, In, Ga, R and Se of example；And (2) are based on described metal simple-substance mixture, formed containing Cu, In, Ga, R and
Five yuan of composites of Se, to obtain described semi-conducting material.Using the method, can fast and effeciently prepare before
Described semi-conducting material, and simple to operate, convenient and swift, suitable industrialized production.
The according to embodiments of the present invention method preparing semi-conducting material noted earlier can also include following distinguishing technology
Feature：
According to embodiments of the invention, in step (2), by containing described in mechanical attrition method or coevaporation method preparation
Five yuan of composites of Cu, In, Ga, R and Se.Thus, simple to operate, production efficiency is higher, does not have particular/special requirement to equipment, easily
In realizing industrialized production.
According to embodiments of the invention, the purity of described metal simple-substance Cu, In, Ga, R and Se is all not less than 99.99%.By
This, the semi-conducting material preparing has preferably photoelectric properties.
According to embodiments of the invention, the method preparing semi-conducting material noted earlier includes：(a) by Cu, In, Ga, R and
The mixture of Se simple substance carries out ball milling, to obtain described metal simple-substance mixture；B described metal simple-substance mixture is suppressed by ()
Molding, to obtain moulding material；And described moulding material is made annealing treatment by (c), obtain described five yuan to be combined
Material.Thereby, it is possible to fast and effeciently prepare foregoing semi-conducting material.
According to embodiments of the invention, in step (a), with 100～700 revs/min of rotating speed carry out described ball milling 5～
15 hours.Thus, the photoelectric properties improving the semi-conducting material preparing and the efficiency preparing semi-conducting material are conducive to.
According to embodiments of the invention, the particle diameter of described metal simple-substance mixture is not more than 10 microns.Thus, be conducive to carrying
The photoelectric properties of the semi-conducting material that height prepares and the efficiency preparing semi-conducting material.
According to embodiments of the invention, in step (b), described compressing pressure is not less than 700 MPas.Thus,
Ensure that moulding material is closely knit.
According to embodiments of the invention, in step (b), described metal simple-substance mixture is pressed into a diameter of 10 centimetres
Disk.Thus, be conducive to the carrying out of subsequent step.
According to embodiments of the invention, in step (c), under argon gas atmosphere, carry out described annealing.Thus, energy
Enough avoid raw metal oxidized.
According to embodiments of the invention, in step (c), not higher than 800 degrees Celsius of the temperature of described annealing, cooling
Mode is natural cooling in stove.Thus, the photoelectric properties of the semi-conducting material preparing preferably, if temperature is too high, are prepared
The photoelectric properties of the semi-conducting material obtaining are undesirable.
According to embodiments of the invention, in step (c), the temperature of described annealing is 400～450 degrees Celsius, moves back
The fiery time is 4 hours.Thus, the photoelectric properties of the semi-conducting material preparing are preferable.
In a third aspect of the present invention, the invention provides solaode suction prepared by foregoing semi-conducting material
Receive the purposes in layer.Inventor finds, the foregoing semi-conducting material of the present invention can be effective for preparing solaode
Absorbed layer, and pass through rare earth doped element R, can be effectively improved it in the case of not affecting conversion efficiency of solar cell
Light transmission, provides good optical condition for lower floor's battery in multijunction cell, and the solaode for photovoltaic curtain wall can provide
Good indoor light.In addition, rare earth element has the characteristics that " up-conversion luminescence ", rear-earth-doped semi-conducting material is made to absorb
Discharge after larger range of sunlight and conversion efficiency can be improved with the visible ray of absorbed layer double absorption.
According to embodiments of the invention, described solaode is thin-film solar cells.
In a fourth aspect of the present invention, the invention provides a kind of method forming solar battery obsorbing layer.According to this
Inventive embodiment, the method includes：Using foregoing semi-conducting material as target, by magnetron sputtering, coevaporation
Or silk screen printing, glass substrate or stainless steel lining bottom form described absorbed layer.Thereby, it is possible to quickly and easily form printing opacity
Property the good, solar battery obsorbing layer of high conversion efficiency.
In a fifth aspect of the present invention, the invention provides a kind of solaode.According to embodiments of the invention, described
Solaode includes：Light absorbing zone, described light absorbing zone is formed by foregoing semi-conducting material.Invention Crinis Carbonisatus
Existing, absorbed layer is formed using foregoing semi-conducting material, its light transmission can be effectively improved, be lower floor in multijunction cell
Battery provides good optical condition, and the solaode for photovoltaic curtain wall can provide good indoor light.In addition, rare earth is first
Element has the characteristics that " up-conversion luminescence ", and so that rear-earth-doped semi-conducting material is discharged after absorbing larger range of sunlight can
With the visible ray of absorbed layer double absorption, improve conversion efficiency.
Solaode according to embodiments of the present invention can also have following additional technical feature：
According to embodiments of the invention, described solaode is thin-film solar cells.
According to embodiments of the invention, the thickness of described light absorbing zone is 1～10 micron, preferably 3 microns.Thus, have
Higher conversion efficiency.
According to embodiments of the invention, described solaode further includes：Transition zone, described transition zone is formed at institute
State on light absorbing zone, and described transition zone is formed by foregoing semi-conducting material.Inventor finds, the present invention's
Solaode can avoid using CdS material, thus reducing the pollution to environment.
According to embodiments of the invention, for described light absorbing zone and transition zone, the class of R in the semi-conducting material being adopted
Type is different.Presented with different valence state in a semiconductor material by different rare earth elements, p-type can be formed respectively and N-shaped is partly led
Body, such that it is able to the absorbed layer using the foregoing semi-conducting material of different for doping rare earth elements as solaode
And transition zone, the use of the serious CdS of environmental pollution thus, not only can be avoided, and absorbed layer and transition zone have identical
Crystal structure, can form good Lattice Matching, reduce defect.
Specific embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this
Bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to literary composition in the art
Offer described technology or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, all
For can by city available from conventional products.
In one aspect of the invention, the invention provides a kind of semi-conducting material.According to embodiments of the invention, described
The chemical composition of semi-conducting material is：CuInxGayR1-x-ySe2, wherein, 0 ＜ x ＜ 1,0 ＜ y ＜ 0.5, and x+y ＜ 1, R is choosing
At least one from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ru, Sc and Y.Inventor finds,
This semi-conducting material of the present invention can be by rare earth doped element R, permissible effective for preparing the absorbed layer of solaode
In the case of not affecting conversion efficiency of solar cell, effectively improve its light transmission, carry for lower floor's battery in multijunction cell
For good optical condition, the solaode for photovoltaic curtain wall can provide good indoor light.In addition, being based on rare earth element
The interelectric transition of 4f, rare earth element has the characteristics that " up-conversion luminescence ", so that rear-earth-doped semi-conducting material is absorbed bigger
Discharge after the sunlight of scope and conversion efficiency can be improved with the visible ray of absorbed layer double absorption.
According to embodiments of the invention, R is at least one in Nd, Pm, Sm, Eu and Gd, Tb and Dy.Thus, will
When this semi-conducting material is used for the absorbed layer of solaode, there is preferable light transmission and conversion efficiency.
According to embodiments of the invention, 0.5 ＜ x<1.Thus, this semi-conducting material is used as the absorbed layer of solaode,
Preferably, conversion efficiency is higher for light transmission.
According to embodiments of the invention, x is more than y.Thus, this semi-conducting material is used as the absorbed layer of solaode, has
Beneficial to its light transmission of raising and conversion efficiency.
According to embodiments of the invention, its chemical composition is one of following：CuIn0.6Ga0.3Sm0.1Se2；
CuIn0.6Ga0.3Gd0.1Se2；CuIn0.7Ga0.2Nd0.1Se2；CuIn0.6Ga0.35Pm0.05Se2；CuIn0.6Ga0.35Eu0.05Se2；
CuIn0.7Ga0.25Tb0.05Se2；And CuIn0.56Ga0.42Dy0.02Se2.Thus, this semi-conducting material is used as solaode
Absorbed layer, light transmission and conversion efficiency are preferable.
In a second aspect of the present invention, the invention provides a kind of method preparing semi-conducting material noted earlier.According to
Embodiments of the invention, the method includes：
(1) metal simple-substance mixture is provided, described metal simple-substance mixture contain the metal simple-substance Cu of predetermined ratio, In,
Ga, R and Se.
According to embodiments of the invention, the purity of described metal simple-substance Cu, In, Ga, R and Se is all not less than 99.99%.By
This, the semi-conducting material preparing has preferably photoelectric properties.
According to embodiments of the invention, described predetermined ratio can be the stoichiometric proportion of semi-conducting material, however, ability
Field technique personnel are appreciated that in actual fabrication process, as long as the quasiconductor with specified chemical composition can be prepared
Material, the proportioning of each raw material can have certain deviation, and those skilled in the art can be adjusted flexibly according to practical situation.
(2) being based on described metal simple-substance mixture, forming five yuan of composites containing Cu, In, Ga, R and Se, to obtain
Obtain described semi-conducting material.Using the method, can fast and effeciently prepare foregoing semi-conducting material, and operate
Simply, convenient and swift, suitable industrialized production.
According to embodiments of the invention, in step (2), the method for five yuan of composites of preparation is not particularly limited, this
Skilled person can select according to practical situation.According to some embodiments of the present invention, can by mechanical attrition method or
The described five yuan of composites containing Cu, In, Ga, R and Se of coevaporation method preparation.Thus, simple to operate, production efficiency is higher,
There is no particular/special requirement to equipment, it is easy to accomplish industrialized production.
According to embodiments of the invention, the method preparing semi-conducting material noted earlier can include：
A the mixture of Cu, In, Ga, R and Se simple substance is carried out ball milling by (), to obtain described metal simple-substance mixture.
According to embodiments of the invention, in step (a), with 100～700 revs/min of rotating speed carry out described ball milling 5～
15 hours.Thus, the photoelectric properties improving the semi-conducting material preparing and the efficiency preparing semi-conducting material are conducive to.
According to embodiments of the invention, the particle diameter of described metal simple-substance mixture is not more than 10 microns.Thus, be conducive to carrying
The photoelectric properties of the semi-conducting material that height prepares and the efficiency preparing semi-conducting material.
B () will be compressing for described metal simple-substance mixture, to obtain moulding material.
According to embodiments of the invention, in step (b), described compressing pressure is not less than 700 MPas.Thus,
Ensure that moulding material is closely knit.
According to embodiments of the invention, in step (b), described metal simple-substance mixture is pressed into a diameter of 10 centimetres
Disk.Thus, be conducive to the carrying out of subsequent step.
C described moulding material is made annealing treatment by (), to obtain described five yuan of composites.
According to embodiments of the invention, in step (c), under argon gas atmosphere, carry out described annealing.Thus, energy
Enough avoid raw metal oxidized.
According to embodiments of the invention, in step (c), not higher than 800 degrees Celsius of the temperature of described annealing, cooling
Mode is natural cooling in stove.Thus, the photoelectric properties of the semi-conducting material preparing preferably, if temperature is too high, are prepared
The photoelectric properties of the semi-conducting material obtaining are undesirable.
According to embodiments of the invention, in step (c), the temperature of described annealing is 400～450 degrees Celsius, moves back
The fiery time is 4 hours.Thus, the photoelectric properties of the semi-conducting material preparing are preferable.
In a third aspect of the present invention, the invention provides solaode suction prepared by foregoing semi-conducting material
Receive the purposes in layer.Inventor finds, the foregoing semi-conducting material of the present invention can be effective for preparing solaode
Absorbed layer, and pass through rare earth doped element R, can be effectively improved it in the case of not affecting conversion efficiency of solar cell
Light transmission, provides good optical condition for lower floor's battery in multijunction cell, and the solaode for photovoltaic curtain wall can provide
Good indoor light.In addition, rare earth element has the characteristics that " up-conversion luminescence ", rear-earth-doped semi-conducting material is made to absorb
Discharge after larger range of sunlight and conversion efficiency can be improved with the visible ray of absorbed layer double absorption.
According to embodiments of the invention, described solaode is thin-film solar cells.
In a fourth aspect of the present invention, the invention provides a kind of method forming solar battery obsorbing layer.According to this
Inventive embodiment, the method includes：Using foregoing semi-conducting material as target, by magnetron sputtering, coevaporation
Or silk screen printing, glass substrate or stainless steel lining bottom form described absorbed layer.Thereby, it is possible to quickly and easily form printing opacity
Property the good, solar battery obsorbing layer of high conversion efficiency.
In a fifth aspect of the present invention, the invention provides a kind of solaode.According to embodiments of the invention, described
Solaode includes：Light absorbing zone, described light absorbing zone is formed by foregoing semi-conducting material.Invention Crinis Carbonisatus
Existing, absorbed layer is formed using foregoing semi-conducting material, its light transmission can be effectively improved, be lower floor in multijunction cell
Battery provides good optical condition, and the solaode for photovoltaic curtain wall can provide good indoor light.In addition, rare earth is first
Element has the characteristics that " up-conversion luminescence ", and so that rear-earth-doped semi-conducting material is discharged after absorbing larger range of sunlight can
With the visible ray of absorbed layer double absorption, improve conversion efficiency.
According to embodiments of the invention, described solaode is thin-film solar cells.
According to embodiments of the invention, the thickness of described light absorbing zone is 1～10 micron, preferably 3 microns.Thus, have
Higher conversion efficiency.
According to embodiments of the invention, described solaode further includes：Transition zone, described transition zone is formed at institute
State on light absorbing zone, and described transition zone is formed by foregoing semi-conducting material.Inventor finds, the present invention's
Solaode can avoid using CdS material, thus reducing the pollution to environment.
According to embodiments of the invention, for described light absorbing zone and transition zone, the class of R in the semi-conducting material being adopted
Type is different.Presented with different valence state in a semiconductor material by different rare earth elements, p-type can be formed respectively and N-shaped is partly led
Body, such that it is able to the absorbed layer using the foregoing semi-conducting material of different for doping rare earth elements as solaode
And transition zone, the use of the serious CdS of environmental pollution thus, not only can be avoided, and absorbed layer and transition zone have identical
Crystal structure, can form good Lattice Matching, reduce defect.
Embodiment 1：
(1) according to chemical formula CuIn0.6Ga0.3Sm0.1Se2Weigh five kinds of units of Cu, In, Ga, Sm, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) using planetary ball mill by the simple substance weighing sample mechanical ball milling, Ball-milling Time is 10 hours, ball milling speed
For 400 revs/min, prepare the powder sample of mix homogeneously.
(3) using forcing press, the powder sample that grinding obtains is pressed into the raw material disk of a diameter of 10cm.
(4) under an argon atmosphere, raw material disk is annealed in Muffle furnace, annealing temperature is 450 DEG C, annealing time
For 4 hours, then by raw material disk in stove natural cooling, obtain five yuan of composites, that is, be used for solar battery obsorbing layer
Semi-conducting material CuIn0.6Ga0.3Sm0.1Se2.
Embodiment 2：
(1) according to chemical formula CuIn0.6Ga0.3Gd0.1Se2Weigh five kinds of units of Cu, In, Ga, Gd, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) using planetary ball mill by the simple substance weighing sample mechanical ball milling, Ball-milling Time is 8 hours, ball milling speed
For 500 revs/min, prepare the powder sample of mix homogeneously.
(3) using forcing press, the powder sample that grinding obtains is pressed into the raw material disk of a diameter of 10cm.
(4) under an argon atmosphere, raw material disk is annealed in Muffle furnace, annealing temperature is 450 DEG C, annealing time
For 4 hours, then by raw material disk in stove natural cooling, obtain five yuan of composites, that is, be used for solar battery obsorbing layer
Semi-conducting material CuIn0.6Ga0.3Gd0.1Se2.
Embodiment 3：
(1) according to chemical formula CuIn0.7Ga0.2Nd0.1Se2Weigh five kinds of units of Cu, In, Ga, Nd, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) using planetary ball mill by the simple substance weighing sample mechanical ball milling, Ball-milling Time is 12 hours, ball milling speed
For 400 revs/min, prepare the powder sample of mix homogeneously.
(3) using forcing press, the powder sample that grinding obtains is pressed into the raw material disk of a diameter of 10cm.
(4) under an argon atmosphere, raw material disk is annealed in Muffle furnace, annealing temperature is 450 DEG C, annealing time
For 4 hours, then by raw material disk in stove natural cooling, obtain five yuan of composites, that is, be used for solar battery obsorbing layer
Semi-conducting material CuIn0.7Ga0.2Nd0.1Se2.
Embodiment 4：
(1) according to chemical formula CuIn0.6Ga0.35Pm0.05Se2Weigh five kinds of units of Cu, In, Ga, Pm, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) using planetary ball mill by the simple substance weighing sample mechanical ball milling, Ball-milling Time is 13 hours, ball milling speed
For 600 revs/min, prepare the powder sample of mix homogeneously.
(3) using forcing press, the powder sample that grinding obtains is pressed into the raw material disk of a diameter of 10cm.
(4) under an argon atmosphere, raw material disk is annealed in Muffle furnace, annealing temperature is 450 DEG C, annealing time
For 4 hours, then by raw material disk in stove natural cooling, obtain five yuan of composites, that is, be used for solar battery obsorbing layer
Semi-conducting material CuIn0.6Ga0.35Pm0.05Se2.
Embodiment 5：
(1) according to chemical formula CuIn0.6Ga0.35Eu0.05Se2Weigh five kinds of units of Cu, In, Ga, Eu, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) using planetary ball mill by the simple substance weighing sample mechanical ball milling, Ball-milling Time is 11 hours, ball milling speed
For 400 revs/min, prepare the powder sample of mix homogeneously.
(3) using forcing press, the powder sample that grinding obtains is pressed into the raw material disk of a diameter of 10cm.
(4) under an argon atmosphere, raw material disk is annealed in Muffle furnace, annealing temperature is 450 DEG C, annealing time
For 4 hours, then by raw material disk in stove natural cooling, obtain five yuan of composites, that is, be used for solar battery obsorbing layer
Semi-conducting material CuIn0.6Ga0.35Eu0.05Se2.
Embodiment 6：
(1) according to chemical formula CuIn0.7Ga0.25Tb0.05Se2Weigh five kinds of units of Cu, In, Ga, Tb, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) using planetary ball mill by the simple substance weighing sample mechanical ball milling, Ball-milling Time is 9 hours, ball milling speed
For 550 revs/min, prepare the powder sample of mix homogeneously.
(3) using forcing press, the powder sample that grinding obtains is pressed into the raw material disk of a diameter of 10cm.
(4) under an argon atmosphere, raw material disk is annealed in Muffle furnace, annealing temperature is 450 DEG C, annealing time
For 4 hours, then by raw material disk in stove natural cooling, obtain five yuan of composites, that is, be used for solar battery obsorbing layer
Semi-conducting material CuIn0.7Ga0.25Tb0.05Se2.
Embodiment 7：
(1) according to chemical formula CuIn0.56Ga0.42Dy0.02Se2Weigh five kinds of Cu, In, Ga, Dy, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) using planetary ball mill by the simple substance weighing sample mechanical ball milling, Ball-milling Time is 10 hours, ball milling speed
For 400 revs/min, prepare the powder sample of mix homogeneously.
(3) using forcing press, the powder sample that grinding obtains is pressed into the raw material disk of a diameter of 10cm.
(4) under an argon atmosphere, raw material disk is annealed in Muffle furnace, annealing temperature is 400 DEG C, annealing time
For 4 hours, then by raw material disk in stove natural cooling, obtain five yuan of composites, that is, be used for solar battery obsorbing layer
Semi-conducting material CuIn0.56Ga0.42Dy0.02Se2.
Embodiment 8：
(1) according to chemical formula CuIn0.6Ga0.3Sm0.1Se2Weigh five kinds of units of Cu, In, Ga, Sm, Se according to stoichiometric proportion
The simple substance sample of element, wherein each simple substance sample purity is more than 99.99%.
(2) cleaned glass is sunk to the bottom and put in coevaporation equipment, be heated to 400-500 DEG C.
(3) pass through five yuan of evaporations, control evaporation rate and the time of each simple substance, prepare and meet stoichiometric proportion
CuIn0.6Ga0.3Sm0.1Se2Solar battery obsorbing layer.
Using same method, it is possible to use the semi-conducting material preparing in embodiment 2-7 forms solaode
Absorbed layer.
Embodiment 9：
(1) respectively prepare in embodiment 1-7 five yuan of composites (i.e. semi-conducting material) are made target.
(2) respectively different targets are fixed on target frame, and cleaned substrate are fixed on the work rest of sputtering stove
On.
(3) open vacuum system, make vacuum in sputtering stove reach 3 × 10-5It is passed through argon after Torr, make pressure reach 0Pa,
Start plated film.
(4) stop after the absorbed layer of 3 μm of evaporation respectively, respectively obtain different solar battery obsorbing layers.
Embodiment 10：
(1) CuIn that will prepare in embodiment 20.6Ga0.3Gd0.1Se2Target made by five yuan of composites.
(2) by CuIn0.6Ga0.3Gd0.1Se2Target is fixed on target frame, and cleaned substrate is fixed on sputtering stove
Work rest on.
(3) open vacuum system, make vacuum in sputtering stove reach 3 × 10-5It is passed through argon after Torr, make pressure reach 0Pa,
Start plated film.
(4) evaporation thickness is 3 μm of CuIn0.6Ga0.3Gd0.1Se2Stop after absorbed layer, obtain solar battery obsorbing layer.
(5) CuIn being 80nm with above-mentioned same method evaporation thickness0.6Ga0.3Sm0.1Se2Transition zone, obtain final product
CuIn0.6Ga0.3Sm0.1Se2/CuIn0.6Ga0.3Gd0.1Se2Solaode absorptive transition layer.
(6) preparation Window layer, top electrode and hearth electrode, obtain thin-film solar cells.
, being detected, result shows to the light transmission and conversion efficiency of the thin-film solar cells preparing, and existing
Copper indium gallium selenium solar cell is compared, and the light transmission of the solaode that the present invention prepares and conversion efficiency are significantly carried
High.
In describing the invention it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or imply relative importance or the implicit quantity indicating indicated technical characteristic.Thus, define " the
One ", the feature of " second " can be expressed or implicitly include one or more this feature.In describing the invention,
" multiple " are meant that two or more, unless otherwise expressly limited specifically.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy describing with reference to this embodiment or example
Point is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be in office
Combine in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be tied by art personnel
Close and combine.
Although embodiments of the invention have been shown and described above it is to be understood that above-described embodiment is example
Property it is impossible to be interpreted as limitation of the present invention, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (7)
1. a kind of solaode is it is characterised in that include：
Light absorbing zone, described light absorbing zone is formed by semi-conducting material, and
Transition zone, described transition zone is formed on described light absorbing zone, and described transition zone is formed by described semi-conducting material,
For described light absorbing zone and transition zone, the chemical composition of the semi-conducting material being adopted is different；
Wherein, the chemical composition of described semi-conducting material is：CuInxGayR1-x-ySe2, 0.5 ＜ x<1,0 ＜ y ＜ 0.5, and x+y
＜ 1, R are at least one in Nd, Pm, Sm, Eu, Gd, Tb and Dy, wherein, described CuInxGayR1-x-ySe2For following it
One：
CuIn0.6Ga0.3Sm0.1Se2；
CuIn0.6Ga0.3Gd0.1Se2；
CuIn0.7Ga0.2Nd0.1Se2；
CuIn0.6Ga0.35Pm0.05Se2；
CuIn0.6Ga0.35Eu0.05Se2；
CuIn0.7Ga0.25Tb0.05Se2；And
CuIn0.56Ga0.42Dy0.02Se2.
2. solaode according to claim 1 is it is characterised in that the thickness of described light absorbing zone is 1～10 micron.
3. solaode according to claim 2 is it is characterised in that the thickness of described light absorbing zone is 3 microns.
4. solaode according to claim 1 is it is characterised in that described solaode is thin film solar electricity
Pond.
5. solaode according to claim 1 is it is characterised in that described semi-conducting material is to make by the following method
Standby：
(1) provide metal simple-substance mixture, described metal simple-substance mixture contains metal simple-substance Cu, In, Ga, R of predetermined ratio
And Se；And
(2) it is based on described metal simple-substance mixture, forms five yuan of composites containing Cu, In, Ga, R and Se, to obtain institute
State semi-conducting material.
6. solaode according to claim 5 is it is characterised in that prepare institute by mechanical attrition method or coevaporation method
State five yuan of composites containing Cu, In, Ga, R and Se,
Optionally, the purity of described metal simple-substance Cu, In, Ga, R and Se is all not less than 99.99%.
7. solaode according to claim 6 is it is characterised in that described semi-conducting material is to make by the following method
Standby：
A the mixture of Cu, In, Ga, R and Se simple substance is carried out ball milling by (), to obtain described metal simple-substance mixture；
B () will be compressing for described metal simple-substance mixture, to obtain moulding material；And
C described moulding material is made annealing treatment by (), to obtain described five yuan of composites,
Optionally, in step (a), described ball milling is carried out 5～15 hours with 100～700 revs/min of rotating speed,
Optionally, the particle diameter of described metal simple-substance mixture is not more than 10 microns,
Optionally, in step (b), described compressing pressure is not less than 700 MPas,
Optionally, in step (b), described metal simple-substance mixture is pressed into a diameter of 10 centimetres of disk,
Optionally, in step (c), under argon gas atmosphere, carry out described annealing,
Optionally, in step (c), not higher than 800 degrees Celsius of the temperature of described annealing, the type of cooling is naturally cold in stove
But,
Optionally, in step (c), the temperature of described annealing is 400～450 degrees Celsius, and annealing time is 4 hours.
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