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.
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.