CN105118878A - Antimony compound doping method of CIGS - Google Patents

Antimony compound doping method of CIGS Download PDF

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CN105118878A
CN105118878A CN201510448016.3A CN201510448016A CN105118878A CN 105118878 A CN105118878 A CN 105118878A CN 201510448016 A CN201510448016 A CN 201510448016A CN 105118878 A CN105118878 A CN 105118878A
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cigs
antimonial
compound
doping method
vacuum
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CN105118878B (en
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李宗雨
丘立安
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JIANGSU XIANNENG MATERIAL Co.,Ltd.
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Chengdu Pioneer Materials Inc
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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
    • H01L31/0248—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
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H01L31/0323—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2 characterised by the doping material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
    • H01L21/38—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions
    • H01L21/385—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • 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
    • Y02E10/541—CuInSe2 material PV cells

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Abstract

The invention provides an antimony compound doping method of CIGS, which belongs to the technical field of thin-film solar cells. The antimony compound doping method of the CIGS comprises the steps of: firstly, mixing an antimony compound with a CIGS compound according to required doping amount to obtain a mixture; secondary, smashing the mixture to obtain powder materials; and finally subjecting the powder materials to hot pressed sintering to obtain the CIGS compound doped with the antimony compound. Through the method, the CIGS compound can be doped with the antimony compound evenly, and the conversion efficiency of solar cells can be improved when the thin-film solar cells are manufactured by using raw materials prepared by adopting the method.

Description

The antimonial doping method of CIGS
Technical field
The present invention relates to solar film battery technical field, in particular to the antimonial doping method of CIGS.
Background technology
Copper Indium Gallium Selenide (CIGS) as thin-film solar cell applications by recent two decades, compared with other thin-film solar cells material, its absorption spectrum is wide, can with the high feature of controllability, CIGS is the thin-film solar cells material with extensive use potentiality of a new generation.How to improve the conversion efficiency of CIGS thin film solar cell, be the key issue of this technology always, because it directly has influence on application cost and the commercial value of battery.At present, in CIGS material, the method for antimony dopant (Sb) element is mainly based on the doping method of IBM, is about to the chemical solution containing Sb, the mode provided by rotary turnplate, above the film being sprayed on CIGS, then the CIGS thin film of spraying Sb solution is carried out annealing in process.
But but there is following problems in above-mentioned doping method: the first, the process of the chemical solution of outfit Sb is more complicated, cost is higher; The second, owing to needing by rotary coating machine, the chemical solution of Sb to be sprayed to above CIGS thin film, spray lack of homogeneity, cause tank solution to lose; Three, annealing in process is by the atoms permeating of Sb in CIGS thin film, and in diffusion process, the diffusion uniformity of Sb is poor, speed is slow; Four, whole complex process and cost is relatively high, is unfavorable for the large-scale CIGS thin film solar cell producing doping Sb element.
Summary of the invention
The object of the invention is to the antimonial doping method proposing a kind of CIGS, the method technological process be simple, flexible operation, greatly improve the uniform doping of Sb element in CIGS material, the conversion efficiency of the CIGS solar cell of raising.
An antimonial doping method of CIGS, comprises the following steps:
(A) antimonial and CIGS compound are mixed according to required doping, obtain compound;
(B) above-mentioned compound is carried out pulverization process, obtain powder;
(C) above-mentioned powder is carried out hot pressed sintering, to obtain the CIGS compound of antimony dopant compound.
Preferably, in step (A), antimonial doping needed in CIGS compound is 0.1at% ~ 5at%.
Preferably, the chemical formula of the described CIGS compound in step (A) is CuIn xga 1-xse 2, wherein the span of x is 0.6 ~ 0.8.
Preferably, the described CIGS compound in step (A) is prepared from by vacuum melting.
Preferably, vacuum melting CIGS compound comprises the following steps:
1) by Cu, In, Ga, Se according to 1:y:(1-y): the mixed in molar ratio of 2 is in the first vacuum equipment, and the span of y is the vacuum degree in the 0.6 ~ 0.8, first vacuum equipment is 1 × 10 -2~ 1 × 10 -3pa;
2) heat the first vacuum equipment with the heating rate of 80 DEG C ~ 100 DEG C/h, make the temperature in the first vacuum equipment reach 1130 DEG C ~ 1170 DEG C, be then incubated 3 hours;
3), after insulation terminates, the first vacuum equipment is naturally cooled to less than 50 DEG C.
Preferably, step 2) further comprising the steps of:
2.1) carry out, in the insulation process of 3 hours, also rocking the first vacuum equipment with the frequency of 0.5Htz to the first vacuum equipment.
Preferably, the described antimonial in step (A) is prepared from by vacuum melting, and described antimonial is for comprising Sb 2te 3or Sb 2se 3.
Preferably, vacuum melting antimonial comprises the following steps:
1) by two kinds of elements in binary antimonial according to the mixed in molar ratio of 2:3 in the second vacuum equipment, the vacuum degree in the second vacuum equipment is 1 × 10 -2~ 1 × 10 -3pa;
2) heat the second vacuum equipment with the heating rate of 80 DEG C ~ 100 DEG C/h, make the temperature in the second vacuum equipment reach 360 DEG C ~ 550 DEG C, be then incubated 3 hours and rock the second vacuum equipment with the frequency of 0.5Htz simultaneously;
3), after insulation terminates, the second vacuum equipment is naturally cooled to less than 50 DEG C.
Preferably, the hot pressed sintering in step (C) comprises the following steps:
C1) powder is put into the dry process of row, remove the moisture of powder, obtain dry mash;
C2) insert in hot press by dry mash, the vacuum degree in hot press is 5.0 × 10 -3~ 1.0 × 10 -3pa;
C3) heat hot press makes the temperature of dry mash reach 600 DEG C ~ 700 DEG C, and the operating pressure of hot press is 500 tons, is incubated 2 ~ 4 hours;
C4), after insulation terminates, hot press is cooled naturally, makes the greenhouse cooling of dry mash to room temperature.
Preferably, the process of sieving of described powder, the particle diameter of described powder is 75 μm ~ 150 μm.
Beneficial effect of the present invention:
The invention provides the antimonial doping method of a kind of CIGS, mixed by CIGS material with antimonial, then carry out pulverization process, the mode finally by hot pressed sintering prepares the CIGS compound of antimony dopant compound.Method provided by the invention has the following advantages:
1, by antimonial is doped in CIGS, utilize the CIGS thin film of this antimony dopant compound can significantly improve the light-photoelectric transformation efficiency of CIGS thin film solar cell, compared with the light-photoelectric transformation efficiency of simple CIGS hull cell, conversion efficiency can improve and reaches 19.2% the most at high proportion;
2, technique provided by the invention can make antimony atoms be doped to equably in the middle of the film of CIGS, and doping is convenient to control, and the chalcogen volatilization simultaneously in manufacture craft process also reduces greatly.
3, in the antimonial of doping, containing chalcogen tellurium (Te) or selenium (Se).Tellurium and selenium belong to congeners in the periodic table of elements, have similar valence electron structure.Selenium belongs to the important atom in the CIGS crystal of yellow copper structure, and the atomic ratio occupied is up to 50%.Therefore, in the chalcogenide compound process of antimony dopant, also correspondingly selenium or tellurium atom are brought in the lattice of CIGS, this just reduces the intracrystalline hole of CIGS, dislocation, the even defects count of crystal boundary, thus eliminate the source being caused charge carrier loss in CIGS light-electric transfer process by above-mentioned defect.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, be briefly described to the accompanying drawing used required in embodiment below, should be appreciated that the following drawings illustrate only some embodiment of the present invention, therefore should not be considered to be restriction the present invention being comprised to scope.
The flow chart of the antimonial doping method of the CIGS that Fig. 1 provides for the embodiment of the present invention 1;
The flow chart of the antimonial doping method of the another kind of CIGS that Fig. 2 provides for the embodiment of the present invention 1;
Fig. 3 is that in Fig. 2, CuIn is prepared in vacuum melting 0.7ga 0.3se 2flow chart;
Fig. 4 is that in Fig. 2, Sb is prepared in vacuum melting 2te 3flow chart.
Embodiment
Embodiment 1
Present embodiments provide a kind of at CuIn 0.7ga 0.3se 2middle doping 1at%Sb 2te 3method, it comprises the following steps:
Step one, preparation CIGS compound.
First, Cu, In, Ga, Se take each component according to the ratio of weight ratio 19.7%:24.9%:6.5%:48.9%, and in order to improve the quality of CIGS product, Cu, In, Ga, Se all adopt >=purity of 99.99%.Preferably, Cu, In, Ga, Se are all by pulverization process, so that it can fully mix.
Secondly, above-mentioned four kinds of components are positioned in container, make the vacuum degree in container reach 1.8 × 10 -3pa, then makes container be in air-tight state.Container preferably adopts highly purified quartz ampoule.
Again, container is put into heater and heats, in the present embodiment, heater adopts resistance-heated furnace.With heating rate 80 DEG C/h of heating containers, the temperature in container is made to reach 1158 DEG C.When container reaches 1158 DEG C, this temperature 3 hours, so that each component is reacted.At maintenance 1158 DEG C of high temperature simultaneously, container, constantly with the frequency vibration of 0.5Htz, makes each component mix, fully contact, so that reaction is carried out more fully.
Finally, below container Temperature fall to 50 DEG C is made.In temperature-fall period, each component forms the CuIn of polycrystalline ﹑ according to the stoichiometric ratio of compound gradually 0.7ga 0.3se 2quaternary compound, thus the CuIn obtaining the full selenizing of Dan mono-﹑ 0.7ga 0.3se 2compound.
Step 2, preparation Sb 2te 3compound
First, by purity higher than Sb and Te of 4N according to part by weight: Sb39%, Te61%, put into container, afterwards container bled process, make the vacuum degree in container reach 3.0 × 10 -3pa, rear enclosed exhaust tube, make its container be in air-tight state.
Secondly, container is put into resistance-heated furnace and heats, be heated to 540 DEG C from room temperature, firing rate controls at 80 DEG C/h.After container is heated to 540 DEG C, be incubated 3 hours, simultaneously with the frequency vibration container of 0.5Htz, react fully to make Sb and Te.
Again, by above-mentioned under the temperature conditions of 540 DEG C, fully after reaction 3 hours, keep container 3.0 × 10 -3under the vacuum degree condition of Pa below Temperature fall to 50 DEG C, namely obtain chalcogenide compound Sb 2te 3.
Step 3, be doped with the Sb of 1at% by hot pressed sintering preparation 2te 3cIGS compound
First, by Sb 2te 3compound and CIGS compound are positioned in the vapor tight tank of applying argon gas according to the ratio that part by weight is 2:98;
Secondly, be positioned over by closed container on planetary ball mill and carry out ball-milling treatment, prepare powder, the average-size of powder is 75 μm.In order to ensure the uniformity of powder particle size, powder can also sieve process.After preparing powder, drying process can be carried out to it, particularly, powder can be positioned in the baking box of 100 DEG C, toast 2 hours, to remove the moisture of powder adsorption.After powder drying, be stored in the casing with controlled humidity, the temperature in casing controls at 80 DEG C.
Again, hot pressed sintering preparation doping Sb is carried out 2te 3cIGS compound, detailed process is as follows:
The first, the powder of preparation is positioned in highly purified graphite jig, then graphite jig is put into the cavity of hot press, make the vacuum degree in cavity be 3 × 10 -3pa.
The second, hot press is warming up to 690 DEG C, pressure rises to 500 tons, allow under the situation of the high temperature of graphite jig in this hot press cavity, high pressure and maintain 3.1 hours.
Three, hot pressing is after 3.1 hours, with 50 DEG C/cooling rate cooling hourly, until cavity inner temperature is down to room temperature.The whole pressing cycle of the present embodiment is 16 hours.After hot press cavity is reduced to room temperature, graphite jig is taken out in cavity, the mould of preparation is departed from graphite jig pah, can obtain being doped with 1at%Sb according to required atomic ratio 2te 3cIGS material.
By above step, prepare and be doped with 1at%Sb 2te 3cIGS material.This material is highdensity bulk, by grinding machine bulk is processed into the geometry needed for the sputtering backboard used in solar battery thin film preparation process, thus the sputtering target material needed for obtaining.This target sputters the film of gained in plasma chamber, is doped with 1at%Sb exactly in strict accordance with required atomic ratio 2te 3cIGS solar battery obsorbing layer film.
By Sb in this enforcement 2te 3be doped into single CuIn 0.7ga 0.3se 2in compound, except being doped with Sb element, also introduce Te element simultaneously.The introducing of Te element can fill up the hole of Se atomic lattice in CIGS crystal, thus decreases the hole density of CIGS crystals.Meanwhile, superfluous Te atom correspondingly can also reduce other defect intracrystalline, such as dislocation (Dislocations) or segregate on the crystal boundary face of CIGS.Because the defect of CIGS crystals such as lattice vacancy, dislocation, or crystal boundary etc. is the loss source of charge carrier in light-electricity conversion, therefore this method is by doping Sb and Te element, and charge carrier when also just correspondingly reducing CIGS thin film generating runs off.In addition, this method can avoid the such as loss of Te in preparation process of high volatile volatile element.By the doping method of powder metallurgy blending processes of powders, Sb atom and Te atom are uniformly distributed in CIGS material, when preparing CIGS solar battery thin film by plasma sputtering technique, foreign atom can be made to be evenly distributed in inside CIGS thin film, to have carried out the distribution of Sb element in CIGS material by annealing diffusion compared to existing there is significant progressive and advantage.
Utilize the CuIn of above-mentioned acquisition 0.7ga 0.3se 2the thin-film solar cells of preparation, its conversion efficiency is 15.60%; Utilization is doped with 1at%Sb 2te 3cuIn 0.7ga 0.3se 2the thin-film solar cells of manufacture of materials, its conversion efficiency is 18.20%, and can show that the conversion efficiency of solar cell improves 2.6%, concrete parameter is in table 1.Wherein Voc is the open circuit voltage of solar cell, and Jsc is the short-circuit current density of solar cell, the fill factor, curve factor of FillFactor system solar cell.
Table 1
Embodiment 2
Present embodiments provide a kind of at CuIn 0.6ga 0.4se 2middle doping 4at%Sb 2te 3method, it comprises the following steps:
Step one, preparation CIGS compound.
First, Cu, In, Ga, Se take each component according to the ratio of weight ratio 20%:21.6%:8.8%:49.6%, and in order to improve the quality of CIGS product, Cu, In, Ga, Se all adopt >=purity of 99.99%.Preferably, Cu, In, Ga, Se are all by pulverization process, so that it can fully mix.
Secondly, above-mentioned four kinds of components are positioned in highly purified quartz ampoule container, make the vacuum degree in container reach 2.5 × 10 -3pa, then makes container be in air-tight state.Container preferably adopts.
Again, container is put into heater and heats, in the present embodiment, heater adopts resistance-heated furnace.With heating rate 80 DEG C/h of heating containers, the temperature in container is made to reach 1169 DEG C.When container reaches 1169 DEG C, this temperature 3 hours, so that each component is reacted.At maintenance 1169 DEG C of high temperature simultaneously, container, constantly with the frequency vibration of 0.5Htz, makes each component mix, fully contact, so that reaction is carried out more fully.
Finally, below container Temperature fall to 50 DEG C is made.In temperature-fall period, each component forms the CuIn of polycrystalline ﹑ according to the stoichiometric ratio of compound gradually 0.6ga 0.4se 2quaternary compound, thus the CuIn obtaining the full selenizing of Dan mono-﹑ 0.6ga 0.4se 2compound.
Step 2, preparation Sb 2te 3compound
First, by purity higher than Sb and Te of 4N according to part by weight: Sb39%, Te61%, put into container, afterwards container bled process, make the vacuum degree in container reach 3.0 × 10 -3pa, rear enclosed exhaust tube, make its container be in air-tight state.
Secondly, container is put into resistance-heated furnace and heats, be heated to 540 DEG C from room temperature, firing rate controls at 80 DEG C/h.After container is heated to 540 DEG C, be incubated 3 hours, simultaneously with the frequency vibration container of 0.5Htz, react fully to make Sb and Te.
Again, by above-mentioned under the temperature conditions of 540 DEG C, fully after reaction 3 hours, keep container 3.0 × 10 -3under the vacuum degree condition of Pa below Temperature fall to 50 DEG C, namely obtain chalcogenide compound Sb 2te 3.
Step 3, be doped with the Sb of 4at% by hot pressed sintering preparation 2te 3cIGS compound
First, by the Sb of 7.45% (weight) 2te 3compound and 92.55% (weight) CIGS compound is positioned in the vapor tight tank of applying argon gas.
Secondly, be positioned over by closed container on planetary ball mill and carry out ball-milling treatment, prepare powder, the average-size of powder is 75 μm.In order to ensure the uniformity of powder particle size, powder can also sieve process.After preparing powder, drying process can be carried out to it, particularly, powder can be positioned in the baking box of 100 DEG C, toast 2 hours, to remove the moisture of powder adsorption.After powder drying, be stored in the casing with controlled humidity, the temperature in casing controls at 80 DEG C.
Again, hot pressed sintering preparation doping Sb is carried out 2te 3cIGS compound, detailed process is as follows:
The first, the powder of preparation is positioned in highly purified graphite jig, then graphite jig is put into the cavity of hot press, make the vacuum degree in cavity be 5.0 × 10 -3pa.
The second, hot press is warming up to 660 DEG C, pressure rises to 500 tons, allow under the situation of the high temperature of graphite jig in this hot press cavity, high pressure and maintain 3.2 hours.
Three, hot pressing is after 3.2 hours, with 50 DEG C/cooling rate cooling hourly, until cavity inner temperature is down to room temperature.The whole pressing cycle of the present embodiment is 16 hours.After hot press cavity is reduced to room temperature, graphite jig is taken out in cavity, the mould of preparation is departed from graphite jig pah, can obtain being doped with 4at%Sb according to required atomic ratio 2te 3cIGS material.
By above step, prepare and be doped with 4at%Sb 2te 3cIGS material.This material is high density bulk, by grinding machine bulk is processed into the geometry needed for the sputtering backboard used in solar battery thin film preparation process, thus the sputtering target material needed for obtaining.This target sputters the film of gained in plasma chamber, is doped with 4at%Sb exactly in strict accordance with required atomic ratio 2te 3cIGS solar battery obsorbing layer film.
Utilize single CuIn 0.6ga 0.4se 2the thin-film solar cells of preparation, its conversion efficiency is 15.81%.This is utilized to be doped with 4at%Sb 2te 3cuIn 0.6ga 0.4se 2the thin-film solar cells of manufacture of materials, its conversion efficiency is 18.26%, and the conversion efficiency of solar cell improves 2.45%, and concrete parameter is in table 2.
Table 2
Embodiment 3
Present embodiments provide a kind of at CuIn 0.7ga 0.3se 2middle doping 2at%Sb 2se 3method, it comprises the following steps:
Step one, preparation CIGS compound.
First, Cu, In, Ga, Se of purity >=99.99% are taken each component according to the ratio of weight ratio 19.7%:24.9%:6.5%:48.9%.
Secondly, above-mentioned four kinds of components are positioned in container, make the vacuum degree in container reach 1.8 × 10 -3pa, then makes container be in air-tight state.
Again, container is put into heater and heats, in the present embodiment, heater adopts resistance-heated furnace.With heating rate 80 DEG C/h of heating containers, the temperature in container is made to reach 1158 DEG C.When container reaches 1158 DEG C, this temperature 3 hours, so that each component is reacted.At maintenance 1158 DEG C of high temperature simultaneously, container, constantly with the frequency vibration of 0.5Htz, makes each component mix, fully contact, so that reaction is carried out more fully.
Finally, below container Temperature fall to 50 DEG C is made.In temperature-fall period, each component forms the CuIn of polycrystalline ﹑ according to the stoichiometric ratio of compound gradually 0.7ga 0.3se 2quaternary compound, thus the CuIn obtaining the full selenizing of Dan mono-﹑ 0.7ga 0.3se 2compound.
Step 2, preparation Sb 2se 3compound
First, by purity higher than Sb and Te of 4N according to part by weight: Sb50.7%, Se49.3%, put into container, afterwards container bled process, make the vacuum degree in container reach 2.0 × 10 -3pa, rear enclosed exhaust tube, make its container be in air-tight state.
Secondly, container is put into resistance-heated furnace and heats, be heated to 390 DEG C from room temperature, firing rate controls at 80 DEG C/h.After container is heated to 390 DEG C, be incubated 3 hours, simultaneously with the frequency vibration container of 0.5Htz, react fully to make Sb and Se.
Again, by above-mentioned under the temperature conditions of 390 DEG C, after fully reacting 3 hours, keep container 2.0 × 10 -3under the vacuum degree condition of Pa below Temperature fall to 50 DEG C, namely obtain chalcogenide compound Sb 2se 3.
Step 3, be doped with the Sb of 2at% by hot pressed sintering preparation 2se 3cIGS compound
First, by Sb 2se 3compound and CIGS compound are positioned in the vapor tight tank of applying argon gas according to the ratio that part by weight is 2.9:97.1;
Secondly, be positioned over by closed container on planetary ball mill and carry out ball-milling treatment, prepare powder, the average-size of powder is 75 μm.In order to ensure the uniformity of powder particle size, powder can also sieve process.After preparing powder, drying process can be carried out to it, particularly, powder can be positioned in the baking box of 100 DEG C, toast 2 hours, to remove the moisture of powder adsorption.After powder drying, be stored in the casing with controlled humidity, the temperature in casing controls at 80 DEG C.
Again, hot pressed sintering preparation doping Sb is carried out 2se 3cIGS compound, detailed process is as follows:
The first, the powder of preparation is positioned in highly purified graphite jig, then graphite jig is put into the cavity of hot press, make the vacuum degree in cavity be 2 × 10 -3pa.
The second, hot press is warming up to 642 DEG C, pressure rises to 500 tons, allow under the situation of the high temperature of graphite jig in this hot press cavity, high pressure and maintain 3.1 hours.
Three, hot pressing is after 3.1 hours, with 50 DEG C/cooling rate cooling hourly, until cavity inner temperature is down to room temperature.The whole pressing cycle of the present embodiment is 16 hours.After hot press cavity is reduced to room temperature, graphite jig is taken out in cavity, the mould of preparation is departed from graphite jig pah, can obtain being doped with 2at%Sb according to required atomic ratio 2se 3cIGS material.
By above step, prepare and be doped with 2at%Sb 2se 3cIGS material.This material is high density bulk, by grinding machine bulk is processed into the geometry needed for the sputtering backboard used in solar battery thin film preparation process, thus the sputtering target material needed for obtaining.This target sputters the film of gained in plasma chamber, is doped with 2at%Sb exactly in strict accordance with required atomic ratio 2se 3cIGS solar battery obsorbing layer film.
In the present embodiment, utilize single CuIn 0.7ga 0.3se 2the thin-film solar cells of preparation, its conversion efficiency is 15.60%.This is utilized to be doped with 2at%Sb 2se 3cuIn 0.7ga 0.3se 2the thin-film solar cells of manufacture of materials, its conversion efficiency is 18.60%, and the conversion efficiency of solar cell adds 3%, and the ratio of raising is 19.2%.Concrete parameter is in table 3.Wherein Voc is the open circuit voltage of solar cell, and Jsc is the short-circuit current density of solar cell, the fill factor, curve factor of FillFactor system solar cell.
Table 3
Embodiment 4
Present embodiments provide a kind of at CuIn 0.8ga 0.2se 2middle doping 5at%Sb 2se 3method, it comprises the following steps:
Step one, preparation CIGS compound.
First, Cu, In, Ga, Se of purity >=99.99% are taken each component according to the ratio of weight ratio 19.4%:28.1%:4.3%:48.2%.
Secondly, above-mentioned four kinds of components are positioned in container, make the vacuum degree in container reach 3.8 × 10 -3pa, then makes container be in air-tight state.Container preferably adopts highly purified quartz ampoule.
Again, container is put into heater and heats, in the present embodiment, heater adopts resistance-heated furnace.With heating rate 80 DEG C/h of heating containers, the temperature in container is made to reach 1138 DEG C.When container reaches 1138 DEG C, this temperature 3 hours, so that each component is reacted.At maintenance 1138 DEG C of high temperature simultaneously, container, constantly with the frequency vibration of 0.5Htz, makes each component mix, fully contact, so that reaction is carried out more fully.
Finally, below container Temperature fall to 50 DEG C is made.In temperature-fall period, each component forms the CuIn of polycrystalline ﹑ according to the stoichiometric ratio of compound gradually 0.8ga 0.2se 2quaternary compound, thus the CuIn obtaining the full selenizing of Dan mono-﹑ 0.8ga 0.2se 2compound.
Step 2, preparation Sb 2se 3compound
First, by purity higher than Sb and Se of 4N according to part by weight: Sb50.7%, Se49.3%, put into container, afterwards container bled process, make the vacuum degree in container reach 2.0 × 10 -3pa, rear enclosed exhaust tube, make its container be in air-tight state.
Secondly, container is put into resistance-heated furnace and heats, be heated to 390 DEG C from room temperature, firing rate controls at 80 DEG C/h.After container is heated to 390 DEG C, be incubated 3 hours, simultaneously with the frequency vibration container of 0.5Htz, react fully to make Sb and Se.
Again, by above-mentioned under the temperature conditions of 390 DEG C, fully after reaction 3 hours, keep container 2.0 × 10 -3under the vacuum degree condition of Pa below Temperature fall to 50 DEG C, namely obtain chalcogenide compound Sb 2se 3.
Step 3, be doped with the Sb of 5at% by hot pressed sintering preparation 2se 3cIGS compound
First, by Sb 2se 3compound and CIGS compound are positioned in the vapor tight tank of applying argon gas according to part by weight, Sb 2se 37.13%, CIGS92.87%;
Secondly, be positioned over by closed container on planetary ball mill and carry out ball-milling treatment, prepare powder, the average-size of powder is 75 μm.In order to ensure the uniformity of powder particle size, powder can also sieve process.After preparing powder, drying process can be carried out to it, particularly, powder can be positioned in the baking box of 100 DEG C, toast 2 hours, to remove the moisture of powder adsorption.After powder drying, be stored in the casing with controlled humidity, the temperature in casing controls at 80 DEG C.
Again, hot pressed sintering preparation doping Sb is carried out 2se 3cIGS compound, detailed process is as follows:
The first, the powder of preparation is positioned in highly purified graphite jig, then graphite jig is put into the cavity of hot press, make the vacuum degree in cavity be 1 × 10 -3pa.
The second, hot press is warming up to 618 DEG C, pressure rises to 500 tons, allow under the situation of the high temperature of graphite jig in this hot press cavity, high pressure and maintain 3 hours.
Three, hot pressing is after 3 hours, with 50 DEG C/cooling rate cooling hourly, until cavity inner temperature is down to room temperature.The whole pressing cycle of the present embodiment is 16 hours.After hot press cavity is reduced to room temperature, graphite jig is taken out in cavity, the mould of preparation is departed from graphite jig pah, can obtain being doped with 5at%Sb according to required atomic ratio 2se 3cIGS material.
By above step, prepare and be doped with 5at%Sb 2se 3cIGS material.This material is high density bulk, by grinding machine bulk is processed into the geometry needed for the sputtering backboard used in solar battery thin film preparation process, thus the sputtering target material needed for obtaining.This target sputters the film of gained in plasma chamber, is doped with 5at%Sb exactly in strict accordance with required atomic ratio 2se 3cIGS solar battery obsorbing layer film.
Based on CuIn 0.8ga 0.2se 2the thin-film solar cells of preparation, its conversion efficiency is 15.29%; Based on being doped with 5at%Sb 2se 3the CIGS thin film solar cell of CIGS manufacture of materials, its conversion efficiency is 17.39%, and the conversion efficiency of solar cell improves 2.1%, and concrete parameter is in table 4.Wherein Voc is the open circuit voltage of solar cell, and Jsc is the short-circuit current density of solar cell, the fill factor, curve factor of FillFactor system solar cell.
Table 4
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. an antimonial doping method of CIGS, is characterized in that, comprise the following steps:
(A) antimonial and CIGS compound are mixed according to required doping, obtain compound;
(B) above-mentioned compound is carried out pulverization process, obtain powder;
(C) above-mentioned powder is carried out hot pressed sintering, obtain the CIGS compound of antimony dopant compound.
2. the antimonial doping method of CIGS according to claim 1, is characterized in that, in step (A), antimonial doping needed in CIGS compound is 0.1at% ~ 5at%.
3. the antimonial doping method of CIGS according to claim 2, is characterized in that, the chemical formula of the described CIGS compound in step (A) is CuIn xga 1-xse 2, wherein the span of x is 0.6 ~ 0.8.
4. according to the antimonial doping method of the CIGS one of claims 1 to 3 Suo Shu, it is characterized in that, the described CIGS compound in step (A) is prepared from by vacuum melting.
5. the antimonial doping method of CIGS according to claim 4, is characterized in that, vacuum melting CIGS compound comprises the following steps:
1) by Cu, In, Ga, Se according to 1:y:(1-y): the mixed in molar ratio of 2 is in the first vacuum equipment, and the span of y is the vacuum degree in the 0.6 ~ 0.8, first vacuum equipment is 1 × 10 -2~ 1 × 10 -3pa;
2) heat the first vacuum equipment with the heating rate of 80 DEG C ~ 100 DEG C/h, make the temperature in the first vacuum equipment reach 1130 DEG C ~ 1170 DEG C, be then incubated 3 hours;
3), after insulation terminates, the first vacuum equipment is naturally cooled to less than 50 DEG C.
6. the antimonial doping method of CIGS according to claim 5, is characterized in that, step 2) further comprising the steps of:
2.1) carry out, in the insulation process of 3 hours, also rocking the first vacuum equipment with the frequency of 0.5Htz to the first vacuum equipment.
7. the antimonial doping method of CIGS according to claim 1, is characterized in that, the described antimonial in step (A) is prepared from by vacuum melting, and described antimonial is for comprising Sb 2te 3or Sb 2se 3.
8. the antimonial doping method of CIGS according to claim 7, is characterized in that, vacuum melting antimonial comprises the following steps:
1) by two kinds of elements in binary antimonial according to the mixed in molar ratio of 2:3 in the second vacuum equipment, the vacuum degree in the second vacuum equipment is 1 × 10 -2~ 1 × 10 -3pa;
2) heat the second vacuum equipment with the heating rate of 80 DEG C ~ 100 DEG C/h, make the temperature in the second vacuum equipment reach 360 DEG C ~ 560 DEG C, be then incubated 3 hours and rock the second vacuum equipment with the frequency of 0.5Htz simultaneously;
3), after insulation terminates, the second vacuum equipment is naturally cooled to less than 50 DEG C.
9. the antimonial doping method of CIGS according to claim 1, is characterized in that, the hot pressed sintering in step (C) comprises the following steps:
C1) powder is put into the dry process of row, remove the moisture of powder, obtain dry mash;
C2) dry mash is inserted in hot press, the vacuum degree 5 × 10 in hot press -3~ 1.0 × 10 -3pa;
C3) heat hot press makes the temperature of dry mash reach 600 DEG C ~ 700 DEG C, and the operating pressure of hot press is 500 tons, is incubated 2 ~ 4 hours;
C4), after insulation terminates, hot press is cooled naturally, makes the greenhouse cooling of dry mash to room temperature.
10. the antimonial doping method of CIGS according to claim 1, is characterized in that, the process of sieving of described powder, and the particle diameter of described powder is 75 μm ~ 150 μm.
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Publication number Priority date Publication date Assignee Title
CN101217178A (en) * 2007-12-26 2008-07-09 中国科学院上海硅酸盐研究所 A preparation method for antimonide molybdenum base thermoelectric material
CN101307397A (en) * 2008-04-15 2008-11-19 成都先锋材料有限公司 Vacuum smelting method and apparatus for copper-indium-gallium-selenium photovoltaic material
CN103194722A (en) * 2013-03-28 2013-07-10 深圳首创光伏有限公司 Target material for manufacturing solar battery
CN103643052A (en) * 2013-10-25 2014-03-19 北京科技大学 Preparation method for homogenization of super magnetostrictive material solidified microstructure
WO2014069652A1 (en) * 2012-11-05 2014-05-08 三菱マテリアル株式会社 Sputtering target and manufacturing method therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101217178A (en) * 2007-12-26 2008-07-09 中国科学院上海硅酸盐研究所 A preparation method for antimonide molybdenum base thermoelectric material
CN101307397A (en) * 2008-04-15 2008-11-19 成都先锋材料有限公司 Vacuum smelting method and apparatus for copper-indium-gallium-selenium photovoltaic material
WO2014069652A1 (en) * 2012-11-05 2014-05-08 三菱マテリアル株式会社 Sputtering target and manufacturing method therefor
CN103194722A (en) * 2013-03-28 2013-07-10 深圳首创光伏有限公司 Target material for manufacturing solar battery
CN103643052A (en) * 2013-10-25 2014-03-19 北京科技大学 Preparation method for homogenization of super magnetostrictive material solidified microstructure

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