CN103000712A - Ink composition and method for forming the same - Google Patents
Ink composition and method for forming the same Download PDFInfo
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- CN103000712A CN103000712A CN2012103060626A CN201210306062A CN103000712A CN 103000712 A CN103000712 A CN 103000712A CN 2012103060626 A CN2012103060626 A CN 2012103060626A CN 201210306062 A CN201210306062 A CN 201210306062A CN 103000712 A CN103000712 A CN 103000712A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
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Abstract
An ink composition for forming a chalcogenide semiconductor film and a method for forming the same are disclosed. The ink composition includes a solvent, a plurality of metal chalcogenide nanoparticles and at least one selected from the group consisted of metal ions and metal complex ions. The metal ions and/or metal complex ions are distributed on the surface of the metal chalcogenide nanoparticles and adapted to disperse the metal chalcogenide nanoparticles in the solvent. The metals of the metal chalcogenide nanoparticles, the metal ions and the metal complex ions are selected from a group consisted of group I, group II, group III and group IV elements of periodic table and include all metal elements of a chalcogenide semiconductor material.
Description
Technical field
The present invention relates to a kind of prescription and formation method of semiconductor film slurry, particularly relate to prescription and the formation method of sulfide semiconductor film slurry.
Background technology
Because energy starved problem on the earth in recent years, solar cell causes that gradually people pay close attention to.Solar cell can simple zones be divided into silicon wafer solar cell and thin-film solar cells.The silicon wafer solar cell is because technology maturation and the higher main flow that becomes existing market of conversion efficiency.But because material and the production cost of silicon wafer solar cell are high, the method that there is no is at present popularized in market.Relatively, thin-film solar cells normally is made in light absorbing zone on the substrate of amorphous silicon, for example is glass substrate.Compared to the employed silicon wafer substrate of silicon wafer solar cell, the glass substrate low price and do not have the shortage problem.So thin-film solar cells has been regarded as the following product that replaces the silicon wafer solar cell.
Thin-film solar cells can be according to the material category of its absorbed layer, further divide into amorphous silicon, polysilicon, tellurium cadmium (Cadmium Telluride, CdTe), copper indium gallium tin (Copper indium gallium selenide, CIGS), other organic thin film solar cell of dye well etc.Wherein, the present conversion efficiency of CIGS thin-film solar cells can reach 20%, and the conversion efficiency of silicon wafer solar cell is very close.
In addition, a kind of quaternary compound semiconductor material that has with the similar lattice structure of CIGS, copper-zinc-tin-sulfur (Cu
2ZnSn (S, Se)
4, CZTS) thin-film solar cells then because its material all belongs on the earth element that enriches, is easy to obtain and do not have toxicity, becomes the novel thin film solar cell material of recent the supreme arrogance of a person with great power.
Prepare at present the method for CZTS film, normally utilize vacuum equipment to carry out thin film deposition.For example, Japanese Ito and Nakazawa once used atomic beam sputter (atom beam sputtering) to prepare the CZTS film on stainless steel substrate.The people such as Friedl Meier then use hot vapour deposition method to prepare the CZTS film, and to produce conversion efficiency be 2.3% CZTS thin-film solar cells.The people such as Katagiri then use RF altogether sputter add steam vulcanization (cure), or the mode that the electron beam evaporation plating predecessor vulcanizes again makes the CZTS film, its produced CZTS thin-film solar cells conversion efficiency is 6.77%.
As mentioned above, mostly the method for prior art making CZTS thin-film solar cells is to belong to the mode that needs use vacuum equipment.Yet prices are rather stiff for vacuum equipment, and its expense can improve the cost of manufacture of CZTS thin-film solar cells.So, if can use solution process to replace vacuum technology, can effectively reduce the manufacturing cost of CZTS thin-film solar cells.
Summary of the invention
The invention provides a kind of paste composition, this paste composition comprises a solvent, a plurality of metallic sulfide nano-particle, and metal ion and metal complex ion at least one of them.Metal ion and/or metal complex ion distribution be in the surface of a plurality of metallic sulfide nano-particles, and with so that a plurality of metallic sulfide nano-particle be scattered in the solvent.Wherein, the metal that metallic sulfide nano-particle, metal ion and metal complex ion comprise is to be selected from the combination that is made of periodic table I, II, III and IV family element, and comprises all metallic elements of monosulfide semi-conducting material.
It is a kind of in order to form the method for slurry that the present invention more provides, the method comprise form metallic sulfide nano-particle, form comprise metal ion and metal complex ion at least one of them a solution, mix this solution and metallic sulfide nano-particle, and when in aforementioned mixed solution, not comprising all metallic elements of monosulfide semi-conducting material, repeat above step at least one of them and repeat above-mentioned blend step, in order to do so that comprise all metallic elements of this sulfide semiconductor material in the mixed solution.Wherein, the metal of metallic sulfide nano-particle, metal ion and metal complex ion is the metal that is selected from periodic table I, II, III or IV combination that family consists of.
Description of drawings
Figure 1 shows that the preparation method's flow chart according to the slurry of the sulfide semiconductor film of present application for patent embodiment.
Figure 2 shows that the schematic diagram of electric double layer theory.
Figure 3 shows that the enlarged diagram of the suspension metallic sulfide nano-particle of example one.
Figure 4 shows that the enlarged diagram of a plurality of metallic sulfide nano-particles that surrounded by electric double layer in the slurry of example one.
Figure 5 shows that the manufacture method flow chart according to the sulfide semiconductor film of present application for patent embodiment.
Fig. 6 is to Figure 10 shows that respectively use-case one to the slurry of example three, and example six to the slurry of example seven as precursor solution, the XRD analysis figure of the CZTS film of made.
Figure 11 shows that the manufacture method flow chart according to the solar cell of present application for patent embodiment.
Figure 12 shows that the front view of the solar cell of making according to method shown in Figure 11.
Figure 13 shows that the J-V figure of solar cell of the CZTS slurry made of use-case seven.
Wherein, description of reference numerals is as follows:
1200 substrates
1210 molybdenum layers
1210 bottom electrodes
1220 sulfide semiconductor films
1230 resilient coatings
1240 top electrodes
1250 metallic contacts
1260 anti-reflective films
210 nano particles
220 solvents
230 electronegative surfaces
240 positively charged ions
250 fixed beds
260 diffusion layers
270 electric double layers
310 artificial gold nano particles
320 electronegative surfaces
330 bronze medals-thioacetamide ion
340 zinc ions
410 artificial gold nano particles
420 solvents
430 electronegative surfaces
440 bronze medals-thioacetamide ion
450 zinc ions
Embodiment
Nominal definition
Following nominal definition is the content in order to the aid illustration present application for patent, but not limits the scope of the invention.
" chalcogen (chalcogen) " refers to the element of VIA family on the periodic table, refers to especially sulphur (sulfur) and selenium (selenium).
" sulfide (chalcogenide compound) " refers to contain the compound of VIA family element on the periodic table.
" sulfide semiconductor film (chalcogenide semiconductor film) " in a broad sense, refers to binary (binary), ternary (ternary) and quaternary (quaternary) sulfide semiconductor material.The binary sulfide compound semiconductor materials for example is to comprise the IVA-VIA group iii v compound semiconductor material.The ternary sulfide compound semiconductor materials for example is to comprise IB-IIIA-VIA family (being called for short I-III-VI family) semi-conducting material.Quaternary sulfide semiconductor material for example is to comprise IB-IIB-IVA-VIA (being called for short I-II-IV-VI family) compound semiconductor materials.
" IV-VI group iii v compound semiconductor material " refers to comprise the compound semiconductor of IVA family element and VIA family element on the periodic table, for example is artificial gold (tin sulfide, SnS).
" I-III-VI group iii v compound semiconductor material " refers to comprise the compound semiconductor materials of IB family, group III A and VIA family on the periodic table, for example be copper indium diselenide (copper indium selenide, CIS) or Copper Indium Gallium Selenide (copper indium gallium selenide, CIGS).
" I-II-IV-VI group iii v compound semiconductor material " refers to comprise the compound semiconductor materials of IB family, IIB family, IVA family and VIA family on the periodic table, for example is copper-zinc-tin-sulfur (Cu
2ZnSn (S, Se)
4, CZTS).
" CIS " in a broad sense, comprises the I-III-VI group iii v compound semiconductor material, and wherein referring to especially comprise chemical formula is CuIn (Se
xS
1-x)
2, the copper indium diselenide/sulphur compound of 0＜x＜1." CIS " more comprises the copper indium diselenide/sulphur compound of non-integer mol ratio, for example is CuIn (Se
0.65S
0.35)
2
" CZTS " in a broad sense, refers to the I-II-IV-VI group iii v compound semiconductor material, and wherein referring to especially comprise chemical formula is Cu
a(Zn
1-bSn
b) (Se
1-cS
c)
2, wherein, the copper-zinc-tin-sulfur/selenium of 0＜a＜1,0＜b＜1,0＜=c＜=1 (copper zinc tin sulfide/selenide) compound." CZTS " more comprises the copper-zinc-tin-sulfur/selenium compound of non-integer mol ratio, for example is Cu
1.94Zn
0.63Sn
1.3S
4In addition, the I-II-IV-VI group iii v compound semiconductor material more comprises the I-II-IV-IV-VI group iii v compound semiconductor material, it for example is copper zinc-tin germanium sulphur (copper zinc tin germanium sulfide) compound, and the I-II-IV-IV-VI-VI group iii v compound semiconductor material, for example be copper indium tin germanium sulphur/selenium (copper zinc tin germanium sulfide selenide) compound.
" slurry (ink) " refers to comprise can be in order to form the precursor solution of semiconductor film." slurry " also refers to " precursor solution (precursor solution) " or " predecessor slurry (precursor ink) ".
" metal sulfide (metal chalcogenide) " refers to comprise the compound of VI family element on metallic element and the periodic table, and wherein, " metal sulfide " refers to the metal sulfide of binary, ternary or quaternary especially.
" dentate (ligand) " refer to can metal ion centered by, around molecule or the ion of metal ion.Dentate can comprise chemical bond and physical force by a bond, forms a metal complex ion with central metallic ions.
" sulfur-bearing dentate (chalcogen-containing ligand) " refers to comprise at least the dentate of VI family element on the one-period table.
" sulfur-bearing metal complex ion " refers to comprise the metal complex ion of sulfur-bearing dentate.
" sulphur source (chalcogen source) " refers to form with metal the sulfur-containing compound of metal sulfide.
" nano particle (nanoparticle) " refers to that size is between the particle of about 2 nanometers (nm) between about 2000 nanometers (nm).
Preparation is in order to form the slurry of sulfide semiconductor film
Referring to Fig. 1, it is the preparation method's flow chart according to the slurry of the sulfide semiconductor film of present application for patent embodiment.
Step 110 is for forming metallic sulfide nano-particle.Metallic sulfide nano-particle can be only to comprise a kind of metallic sulfide nano-particle or comprise not only a kind of nano particle of metal sulfide.For example, metallic sulfide nano-particle comprises a plurality of artificial golds (SnS) nano particle.Or metallic sulfide nano-particle comprises artificial gold (SnS) nano particle and copper sulfide (CuS) nano particle.Metallic sulfide nano-particle can also comprise the multi-element metal sulfide nano-particle, for example is copper tin sulphur (copper tin sulfide, CuSnS) nano particle.In addition, metallic sulfide nano-particle can comprise the nano particle that is made of at least two kinds of metal sulfides.For example, these at least two kinds of metal sulfides are to be selected from the combination that tin sulfide (tin chalcogenide), zinc sulfide (zinc chalcogenide), copper sulfide (copper chalcogenide), indium sulfide (indium chalcogenide) and gallium sulfide (gallium chalcogenide) consist of.
The method for preparing metallic sulfide nano-particle comprises: slaine is dissolved in the solvent, for example is dissolved in the water, to form one first aqueous solution; One sulphur source (chalcogen source) is dissolved in the water to consist of one second aqueous solution; And, mix first aqueous solution and second aqueous solution comprise metallic sulfide nano-particle with formation mixed solution.The method more can comprise the step of pH value, stirring or the heating of adjusting mixed solution.In certain embodiments, the pH value of mixed solution is adjusted to about pH7 to about pH14.Metallic sulfide nano-particle comprises size between the particle of about 2 nanometers to about 2000 nanometers.Slaine comprises at least a metal that is selected from following combination: the combination that IB, IIB, IIIB and IVA family element consist of on the periodic table.The preferably is that slaine comprises at least a a kind of metal that is selected from the element combinations such as tin, copper, zinc, germanium, indium and gallium.For example, slaine can be stannic chloride (tin chloride), copper nitrate (copper nitrate), zinc nitrate (zinc nitrate), gallium nitrate (gallium nitrate) or inidum chloride (indium chloride).
The sulphur source comprises the sulphur source predecessor of the single or compound form that can produce sulphion or plasma selenium in solution, comprising sulfur-bearing or contain selenium compound, for example is thioacetamide (thioacetamide), thiocarbamide (thiourea), selenourea (selenourea), hydrogen sulfide (hydrogen sulfide), hydrogen selenide (hydrogen selenide), alkali metal sulphide (alkali metal sulfide), alkaline earth selenides (alkali metal selenide), selenium (selenium), sulphur (sulfur), alkylthio group compound (alkyl sulfide), alkane seleno compound (alkyl selenide) and diphenyl sulfide based compound (diphenyl sulfide).
For example, metallic sulfide nano-particle comprises tin-sulfide (tin sulfide, Sn-S), copper-sulfide (copper sulfide, Cu-S), zinc-sulfide (zinc sulfide, Zn-S), indium-sulfide (indium sulfide, In-S), gallium-sulfide (gallium sulfide, Ga-S), tin-selenides (tin selenide, Sn-Se), copper-selenides (copper selenide, Cu-Se), zinc-selenides zinc selenide (Zn-Se), indium-selenides (indium selenide, In-Se), gallium-selenides (gallium selenide, Ga-Se), copper-Xi-sulfide (copper tin sulfide, Cu-Sn-S), copper-zinc-sulfide (copper zinc sulfide, Cu-Zn-S), zinc-Xi-sulfide (zinc tin sulfide, Zn-Sn-S), copper-indium-sulfide (copper indium sulfide, Cu-In-S), copper-gallium-sulfide (copper gallium sulfide, Cu-Ga-S), copper-indium-gallium-sulfide (copper indium gallium sulfide, Cu-In-Ga-S), copper-Xi-selenides (copper tin selenide, Cu-Sn-Se), copper-zinc-selenides (copper zinc selenide, Cu-Zn-Se), zinc-Xi-selenides (zinc tin selenide, Zn-Sn-Se), copper-indium-selenides (copper indium selenium, Cu-In-Se), copper-gallium-selenides (copper gallium selenide, Cu-Ga-Se) and copper-indium-gallium-selenides (copper indium gallium selenide, Cu-In-Ga-Se).The purpose of using hyphen (that is "-" symbol in chemical formula Cu-S or Cu-Sn-S) herein is in order to represent that this chemical formula comprises all possible combination of described element, and for example copper-sulfide (Cu-S) comprises copper sulfide (CuS) and vulcanizes two bronze medal (Cu
2S).That is the stoichiometric proportion of metallic element and chalcogen (stoichiometry) is not defined as a fixed value, for example 1:1 or 2:1.In addition, the stoichiometric proportion of metallic element and chalcogen also comprises non-integer, for example is Cu
1.8S.
Step 120 comprises formation metal ion and/or metal complex ion.In step 120, can only prepare metal ion or metal complex ion, or prepare simultaneously metal ion and metal complex ion.Formed metal ion can only comprise single metal ion species, for example is copper ion.In other example, can prepare a not only metal ion species, for example prepare copper ion and zinc ion.Similarly, formed metal complex ion can also comprise one or more metal complex ion.The metal of metal ion and metal complex is the element that is selected from periodic table IB, IIB, IIIB and IVA family.
The preparation method of metal ion is dissolved in a slaine in one solvent, for example be dissolved in the water, mode produce metal ion.
The preparation method of metal complex ion for example is one first aqueous solution that slaine formation soluble in water is comprised metal ion, with dentate formation one second aqueous solution soluble in water, and mix first aqueous solution and second aqueous solution to form the metal complex ion.For example, the metal complex ion can be sulfur-bearing metal complex ion.Sulfur-bearing metal complex ion can be prepared from by hybrid metal ion and sulfur-bearing dentate.For example, the sulfur-bearing dentate comprises thioacetamide, thiocarbamide or ammonium sulfide.Sulfur-bearing metal complex ion packet containing metal-thiocarbamide (metal-thiourea) ion, metal-sulfur are for acetamide (metal-thioacetamide) ion or metal-sulfur ammonium ion.For example, metal ion comprises copper ion, tin ion, zinc ion, germanium ion, indium ion or gallium ion.Metal complex ion packet cupric-thiocarbamide ion, tin-thiocarbamide ion, germanium-thiocarbamide ion, copper-thioacetamide ion, tin-thioacetamide ion, germanium-thioacetamide ion, indium-thiocarbamide ion, gallium-thiocarbamide ion, indium-thioacetamide ion and gallium-thioacetamide ion.
The metallic sulfide nano-particle concentration that slurry comprises is about 1% (w/v) to 80% (w/v).Metal ion and/or the concentration of metal complex ion in slurry are about 0.5% (w/v) to 80% (w/v).
Step 130 comprises hybrid metal nano particle and metal ion and/or metal complex ion.
Should be noted that herein step 110 can be before step 120, afterwards, or carry out simultaneously.That is, can prepare first metallic sulfide nano-particle, prepare again afterwards metal ion and/or metal complex ion.In other example, can prepare first metal ion and/or metal complex ion, prepare again afterwards metallic sulfide nano-particle.Perhaps in other example, metallic sulfide nano-particle and metal ion and/or metal complex ion can be in same step preparations.
As mentioned above, metallic sulfide nano-particle and metal ion and/or metal complex ion can comprise one or more metal.In order to prepare to form the slurry of monosulfide semiconductor film, the metal of metal nanoparticle and metal ion and/or metal complex ion should comprise all metallic elements of the sulfide semiconductor material that institute's wish forms.The sulfide semiconductor material for example is to be selected from the combination that IV-VI compounds of group, I-III-VI compounds of group and I-II-IV-VI compounds of group consist of.For example, preparation should comprise three kinds of metals at least in order to the slurry that forms the CZTS film, that is, comprise at least a IB family metal on the periodic table, at least a IIB family's metal and at least a IVA family metal.In some instances, these at least three kinds of metals can be used in respectively step 110 and step 120, and are contained in the formed solution of step 130.In other example, metal nanoparticle and metal ion/metal complex ion can only comprise a kind of metal separately.Namely in the prepared solution of step 130, only comprise two kinds of metals.So the method more comprises step 140 in order to judge whether metal nanoparticle and metal ion and/or metal complex ion comprise all metals of monosulfide semi-conducting material.If do not comprise all required metals, then need repeat abovementioned steps.For example, repeating step 120 makes this slurry comprise the third metal to form metal ion and/or metal complex ion.In other example, also can make slurry comprise the third metal to form metallic sulfide nano-particle by repeating step 110.
In the step 150, the slurry preparation is finished.
In said process, be that to make water be solvent.Yet in other embodiments, solvent comprises polar solvent (polar solvents), for example is alcohols, dimethyl sulfoxide (DMSO) (dimethyl sulfoxide, DMSO) or amino-contained solvent (amines).For example, alcohols comprises methyl alcohol (methanol), ethanol (ethanol) or isopropyl alcohol (isopropyl alcohol).
In addition, in some instances, step 120 and step 130 can be repeatedly, to add more metal ion and/or metal complex ion.
For the feature of slurry of the present invention is described, below with simple declaration electric double layer (electron double layer) theory.Fig. 2 is the schematic diagram of electric double layer theory.In Fig. 2, a nano particle 210 is suspended in the solvent 220.This nano particle 210 comprises one electronegative surperficial 230.Therefore, positively charged ion 240 can be adsorbed in electronegative surperficial 230 of nano particle 210 with electrostatic force.The positively charged ion 240 of part can closely be adsorbed in electronegative surperficial 230, and is referred to as fixed bed (stern layer) 250; And the positively charged ion 240 of part can surround fixed bed (stern layer) 250 in the mode that concentration is successively decreased, and is referred to as diffusion layer 260.Fixed bed 250 and diffusion layer 260 consist of an electric double layer 270.Because nano particle 210 peripheries are coating this electric double layer 270, these nano particles 210 meetings are because of electric double layer 270 formed electrostatic repulsion forces, and each other isolation.Therefore, these nano particles are suspended in the solution 220.
Similarly, in the present embodiment, metallic sulfide nano-particle can be surrounded by metal ion and/or metal complex ion, and therefore is suspended in the solvent.Hereat, this slurry comprises homodisperse particle, and can be in order to form the monosulfide semiconductor film.
Below will prepare with several example explanations the method for the slurry of CZTS films and CIGS film.
Example one
Preparation is in order to form the slurry of CZTS film
The preparation metallic sulfide nano-particle: the 5mmol stannic chloride is dissolved in the 25ml water, to form the aqueous solution (A1).The 4mmol thioacetamide is dissolved in the 40ml water, to form the aqueous solution (B1).Mixed aqueous solution (A1) with (B1) to form a reaction solution (C1).In reaction solution (C1), add 12ml 30% ammoniacal liquor (NH
4OH) and under 65 ° of C stirred 1.5 hours.Afterwards, collect the sediment of dark brown in the solution, and analysis confirmation its be artificial gold (SnS).
Preparation metal complex ion: the 7mmol copper nitrate is dissolved in the 5ml water, to form the aqueous solution (D1).The 10mmol thioacetamide is dissolved in the 5ml water, to form the aqueous solution (E1).Mixed aqueous solution (D1) and the aqueous solution (E1) are to form a reaction solution (F1).This reaction solution (F1) was at room temperature stirred 0.5 hour, to form copper-thioacetamide ion.
Collected artificial gold nano particle and reaction solution (E1) are mixed into a mixed solution (G1).
The preparation metal ion: the 4.8mmol zinc nitrate is dissolved in the 5ml water, comprises the aqueous solution (H1) of zinc ion with formation.
At last, the aqueous solution (H1) and mixed solution (G1) are mixed and stirred to form a slurry all night.
Figure 3 shows that the enlarged diagram of the suspension artificial gold nano particle that example one is prepared.As shown in Figure 3, artificial gold nano particle 310 comprises one electronegative surperficial 320.Copper-thioacetamide ion 330 and zinc ion 340 are all positively charged, and are adsorbed in electronegative surperficial 320 of artificial gold nano particle 310 by electrostatic force.
See also in addition Fig. 4, it is depicted as the enlarged diagram of a plurality of metallic sulfide nano-particles that surrounded by electric double layer in the slurry of example one.As shown in Figure 4, a plurality of artificial gold nano particles 410 are suspended in the solvent 420.Each artificial gold nanoparticle 410 attached bag contains an electronegative outer surface 430.In addition, also comprise copper-thioacetamide ion 440 and zinc ion 450 in the slurry 420.Positively charged copper-thioacetamide ion 440 and 450 of zinc ions are adsorbed in the electronegative outer surface 430 of artificial gold nano particle 410.Because each artificial gold nano particle 410 is surrounded by positive charge ion, these particles each other can be mutually exclusive.Therefore, these artificial gold nano particles 410 can be suspended in the solvent 420.
Because each artificial gold nano particle is all surrounded by copper-thioacetamide ion and zinc ion, that is copper-zinc-tin-sulfur (Cu
2ZnSnS
4, CZTS) four kinds of required elements of quaternary compound semiconductor material: copper, zinc, tin and sulphur, all mutually close each other because of each artificial gold nano particle.That is this slurry is that the elements such as copper, zinc, tin and sulphur are mixed to get very uniformly solution, and can be in order to prepare the CZTS film.
Example two
This example is can comprise in the slurry two kinds of metallic sulfide nano-particles with example one difference, that is, wherein a kind of by the artificial gold nano particle of copper complex ion/copper ion encirclement, and another kind is Zinc sulfide nano-particle.
The preparation metallic sulfide nano-particle: the 5mmol stannic chloride is dissolved in the 40ml water, to form the aqueous solution (A2).The 4mmol thioacetamide is dissolved in the 40ml water, to form the aqueous solution (B2).Mixed aqueous solution (A2) with (B2) to form a reaction solution (C2).In reaction solution (C2), add 10ml 30% ammoniacal liquor (NH
4OH) and under 65 ° of C stirred 1.5 hours.Afterwards, collect the sediment of dark brown in the solution, and analysis confirmation its be artificial gold (SnS).
Preparation metal complex ion and metal ion: the 7mmol copper nitrate is dissolved in the 5ml water, to form the aqueous solution (D2).The 5mmol thioacetamide is dissolved in the 5ml water, to form the aqueous solution (E2).Mixed aqueous solution (D2) and the aqueous solution (E2) are to form a reaction solution (F2).This reaction solution (F2) was at room temperature stirred 0.5 hour, to form copper-thioacetamide ion and copper ion.
The artificial gold nano particle is mixed to form mixed solution (G2) with reaction solution (F2).
Preparation metal ion: the 4.8mmol zinc nitrate is dissolved in the 5ml water, comprises the aqueous solution (H2) of zinc ion with formation.
Mixed solution (G2) mixed with the aqueous solution (H2) and stirred 10 minutes to form mixed solution (I2).
Preparation metallic sulfide nano-particle and slurry: the 29mmol ammonium sulfide is added in the mixed solution (I2), and stir to form a slurry all night.
Example three
This example and example two differences are that the slurry of this example comprises two kinds of metallic sulfide nano-particles, and various metallic sulfide nano-particles surface coat separately different types of metal ion and/the metal complex ion.
The preparation metallic sulfide nano-particle: the 2.5mmol stannic chloride is dissolved in the 25ml water, to form the aqueous solution (A3).The 2mmol thioacetamide is dissolved in the 25ml water, to form the aqueous solution (B3).Mixed aqueous solution (A3) with (B3) to form a reaction solution (C3).In reaction solution (C3), add 10ml 30% ammoniacal liquor (NH
4OH) and under 65 ° of C stirred 1.5 hours.Afterwards, collect the sediment of dark brown in the solution, and analysis confirmation its be artificial gold (SnS).
Preparation metal complex ion and metal ion: the 3.8mmol copper nitrate is dissolved in the 5ml water, to form the aqueous solution (D3).The 3mmol thioacetamide is dissolved in the 5ml water, to form the aqueous solution (E3).Mixed aqueous solution (D3) and the aqueous solution (E3) are to form a reaction solution (F3).This reaction solution (F3) was at room temperature stirred 0.5 hour, to form copper-thioacetamide ion and copper ion.
The artificial gold nano particle is mixed to form mixed solution (G3) with reaction solution (F3).
Preparation metal ion and metallic sulfide nano-particle: the 2.8mmol zinc nitrate is dissolved in the 5ml water, to form the aqueous solution (H3).With in the water-soluble solution of 22mmol ammonium sulfide (H3) to form reaction solution (I3).
At last, mixed solution (G3) is mixed with the aqueous solution (I3), to form a slurry.
Example four
This example is before forming metallic sulfide nano-particle with example one difference, can form first Precursor of Nano Particles.
Preparation Precursor of Nano Particles: 2.5mmol artificial gold and 2mmol sulphur are dissolved in the ammonium sulfide solution of 5ml concentration 40% ~ 50%, and stir to form a reaction solution (A4) all night.
Preparation metal complex ion and metal ion: the 3.8mmol copper nitrate is dissolved in the 2ml water, to form the aqueous solution (B4).The 4mmol thioacetamide is dissolved in the 6ml water, to form the aqueous solution (C4).Mixed aqueous solution (B4) and the aqueous solution (C4) also at room temperature stirred 20 minutes, to form a reaction solution (D4).
Reaction solution (A4) is mixed with reaction solution (D4), to form mixed solution (E4).
Preparation metal ion: the 2.8mmol zinc nitrate is dissolved in the 2ml water, to form the aqueous solution (F4).
At last, mixed solution (E4) is mixed with the aqueous solution (F4) and stirred to form a slurry all night.
Example five
This example and example four differences are to comprise copper-thiourea complex ion in the slurry of this example.
Preparation Precursor of Nano Particles: the 2.5mmol artificial gold is dissolved in the ammonium sulfide solution of 5ml concentration 40% ~ 50%, and stirs to form a reaction solution (A5) all night.
Preparation metal complex ion and metal ion: the 3.8mmol copper nitrate is dissolved in the 5ml water, to form the aqueous solution (B5).5.9mmol thioacetamide is dissolved in the 5ml water, to form the aqueous solution (C5).Mixed aqueous solution (B5) and the aqueous solution (C5) also at room temperature stirred 20 minutes, to form a reaction solution (D5).
Reaction solution (A5) is mixed with reaction solution (D5), to form mixed solution (E5).
Preparation metal ion and metallic sulfide nano-particle: the 2.8mmol zinc nitrate is dissolved in the 2ml water, to form the aqueous solution (F5).The 33mol ammonium sulfide is dissolved in the aqueous solution (F5), to form a reaction solution (G5).
At last, mixed solution (E5) is mixed with the aqueous solution (G5) and stirred to form a slurry all night.
Example six
This example is that with example one difference this example before forming metallic sulfide nano-particle, forms first metal ion and/or metal complex ion.
Prepare the first metal ion: the 1.07mmol stannic chloride is dissolved in the 2ml water, and stirs 5 minutes to form an aqueous solution (A6).
Prepare the second metal ion: the 1.31mmol zinc nitrate is dissolved in the 2ml water, to form an aqueous solution (B6).
The aqueous solution (A6) is mixed with the aqueous solution (B6) and stirred 15 minutes to form an aqueous solution (C6).
Preparation metal complex ion: the 1.7mmol copper nitrate is dissolved in the 1.5ml water, to form the aqueous solution (D6).The 3mmol thiocarbamide is dissolved in the 3ml water, to form the aqueous solution (E6).Mixed aqueous solution (D6) and the aqueous solution (E6) also at room temperature stirred 20 minutes, to form a reaction solution (F6).
The aqueous solution (C6) is mixed with reaction solution (F6) and stirred 10 minutes, to form a mixed solution (G6).In other embodiments, mixed solution (G6) can be stirred under 60 ° of C.
Form metallic sulfide nano-particle and slurry: be that 40% ~ 50% ammonium sulfide solution adds in the mixed solution (G6) with 1.5ml concentration, and stir or ultrasonic vibrating 30 minutes all night, to form slurry.
Example seven
The difference of this example and example six is to comprise selenium in the slurry of this example.
Prepare the first metal ion: the 1.07mmol stannic chloride is dissolved in the 2ml water, and stirs 5 minutes to form an aqueous solution (A7).
Prepare the second metal ion: the 1.31mmol zinc nitrate is dissolved in the 2ml water, to form an aqueous solution (B7).
The aqueous solution (A7) is mixed with the aqueous solution (B7) and stirred 15 minutes to form an aqueous solution (C7).
Preparation metal complex ion: the 1.7mmol copper nitrate is dissolved in the 1.5ml water, to form the aqueous solution (D7).The 3mmol thiocarbamide is dissolved in the 3ml water, to form the aqueous solution (E7).Mixed aqueous solution (D7) and the aqueous solution (E7) also at room temperature stirred 20 minutes, to form a reaction solution (F7).
The aqueous solution (C7) is mixed with reaction solution (F7) and stirred 10 minutes, to form a mixed solution (G7).In other embodiments, mixed solution (G7) can be stirred under 60 ° of C.
Form metallic sulfide nano-particle, metal complex ion and slurry: 0.1g selenium powder end is dissolved in 1ml concentration 40% ~ 50% ammonium sulfide solution, to form the aqueous solution (H7).The aqueous solution (H7) mixed with mixed solution (G7) and stir all night or ultrasonic vibrating 30 minutes to form slurry.
Example one is the preparation method in order to the slurry that forms the CZTS film to example seven.Below, will be with the example explanation preparation method in order to the slurry that forms the CIGS film.
Example eight
Preparation is in order to form the slurry of CIGS film
Prepare the first metal ion: the 0.5mmol gallium nitrate is dissolved in the 2ml water to form an aqueous solution (A8).
Prepare the second metal ion: the 0.5mmol inidum chloride is dissolved in the 2ml water, to form an aqueous solution (B8).
The aqueous solution (A8) is mixed with the aqueous solution (B8) and stirred 15 minutes to form an aqueous solution (C8).
Preparation metal complex ion: the 1.0mmol copper nitrate is dissolved in the 2ml water, to form the aqueous solution (D8).The 5.9mmol thiocarbamide is dissolved in the 5ml water, to form the aqueous solution (E8).Mixed aqueous solution (D8) and the aqueous solution (E8) also at room temperature stirred 20 minutes, to form a reaction solution (F8).
The aqueous solution (C8) is mixed with reaction solution (F8) and stirred 10 minutes, to form a mixed solution (G8).In other embodiments, mixed solution (G8) can be stirred under 60 ° of C.
Form metallic sulfide nano-particle and slurry: 1.5ml concentration 40% ~ 50% ammonium sulfide solution is added mixed solution (G8), and stir or ultrasonic vibrating 30 minutes all night, to form a slurry.
Utilize precursor solution to form the sulfide semiconductor film
Referring to Fig. 5, it is depicted as the flow chart according to the sulfide semiconductor film formation method of present application for patent one embodiment.
The method comprises step 510, and this step comprises at least precursor solution of one of them of metallic sulfide nano-particle and metal ion and metal complex ion in order to preparation.This precursor solution can be prepared according to step shown in Figure 1.
Step 520 comprises to be coated precursor solution on one substrate, and forms a liquid level of precursor solution on substrate.
The method of coating comprises drippage rubbing method (drop casting), spin-coating method (spin coating), soak rubbing method (dip coating), scraper for coating method (doctor blading), showering curtain type coating (curtain coating), ramp type coating (slide coating), atomizing coating (spraying), R-joining formula coating (slit casting), liquid level bending-type coating (meniscus coating), wire mark (screen printing), ink jet type printing (ink jet printing), offset rotary formula printing (flexographic printing), bat printing (pad printing) or intaglio printing (gravure printing), the present invention does not limit.Substrate can be rigid substrate, for example glass substrate, or soft substrate, for example sheet metal or plastic base.In certain embodiments, before the coating precursor solution, can form first a molybdenum (molybdenum, Mo) layer on the substrate.
Step 530 comprises the formed liquid level of dry aforementioned precursor solution to form a precursor film.In this drying steps, solvent can be removed by volatilization.Drying means for example is to comprise substrate is positioned in boiler tube (furnace), the baking box (oven), or is placed on the hot plate (hot plate).Take the precursor solution of CZTS film as example, aforementioned drying steps can be about 25 ° of C in temperature to carry out under about 600 ° of C, and the preferably is for to carry out under 350 ° of C to 480 ° of C.The optimum drying temperature is 425 ° of C.More than aforementioned coating and drying steps can repeat once, for example be repetition 3 to 6 times.The thickness of the precursor film that makes at last for example is between 5000 nanometers (nm) between about 1 nanometer (nm).
Step 540 comprises makes this precursor film carry out a tempering process (anneal) to form the sulfide semiconductor film.The temperature of CZTS precursor film for example is between about 300 ° of C to 700 ° of C, and the preferably is between about 480 ° C to 650 ℃.Optimum tempering temperature is 540 ° of C.In this example, tempering process can carry out 10 minutes under about 540 ℃.In certain embodiments, tempering process can carry out in the environment of sulfurous gas.
Then, with example one to the prepared slurry of example three, and example six to the slurry of example seven preparations as precursor solution, form the CZTS film.Prepared CZTS film all has custerite (kesterite) lattice structure via XRD (X-ray diffraction, X-light powder diffractometer) analysis confirmation, and its analysis result is listed in respectively Fig. 6 to Figure 10.
Make solar cell
Referring to Figure 11, be the manufacture method flow chart according to the solar cell of present application for patent one embodiment shown in the figure.Other sees also Figure 12, is the front view according to the solar cell of method making shown in Figure 11 shown in the figure.
The step 1110 of the method is contained in and forms a bottom electrode 1210 on the substrate 1200.For example, the material of substrate 1200 is selected from the combination that following material consists of: glass, sheet metal and plastics.The material of bottom electrode 1210 is selected from the combination that following material consists of: molybdenum (molybdenum, Mo), tungsten (tungsten, W), aluminium (aluminum, Al) and indium tin oxide (Indium Tin Oxide, ITO).In the present embodiment, be to form a molybdenum layer 1210 with sputtering way at substrate 1200.
Step 1120 comprises with a precursor solution at bottom electrode 1210 formation monosulfide semiconductor films 1220.Precursor solution can be prepared according to method shown in Figure 1.In this embodiment, the sulfide semiconductor film is a CZTS film.The thickness that is formed at the CZTS film on the molybdenum layer 1210 is about 0.6 micron (μ m) to 6 microns (μ m).
Step 1130 is included in and forms a resilient coating (buffer layer) 1230 on the sulfide semiconductor film 1120.Resilient coating comprises semi-conductor layer, for example is N-shaped semiconductor layer or p-type semiconductor layer.For example, resilient coating comprises a kind of material that is selected from following combination: cadmium sulfide (cadmium sulfide, CdS), zinc oxide/hydroxide/zinc sulphide mixture (Zn (O, OH, S)), indium sulfide (indium Sulfide, In
2S
3), zinc sulphide (zinc sulfide, ZnS) and zinc-magnesium oxide (zinc magnesium oxide, Zn
xMg
1-xO).In the present embodiment, the N-shaped semiconductor layer on the CZTS film 1220 is cadmium sulphide film 1230.This cadmium sulphide film 1230 can be formed by chemical bath deposition method.In the present embodiment, for example, the thickness of cadmium sulphide film 1230 can be about 20 nanometers (nm) to about 150 nanometers (nm).
Step 1140 is included in and forms a top electrode 1240 on the resilient coating 1230.This top electrode 1240 comprises a transparency conducting layer.For example, top electrode 1240 comprises a kind of material that is selected from following combination: zinc oxide (zinc oxide, ZnO), indium tin oxide (indium tin oxide, ITO), boron doping zinc-oxide (boron-doped zinc oxide, B-ZnO), aluminium-doped zinc oxide (aluminum-doped zinc oxide, Al-ZnO), Ga-doped zinc oxide (gallium-doped zinc oxide, Ga-ZnO) and antimony zinc oxide (antimony tin oxide, ATO).In the present embodiment, the top electrode 1240 on the resilient coating 1230 is formed by the zinc oxide of about 100 nanometers of thickness (nm) and the indium tin oxide of about 130 nanometers of thickness (nm).The method that forms zinc oxide and indium tin oxide for example is sputter.
Step 1150 is included in and forms metallic contact (metal contact) 1250 on the top electrode 1240.Metallic contact 1250 can be formed by nickel/aluminium (nickel (Ni)/aluminum (Al)).The method that forms nickel/aluminum metal contact 1250 for example is the electron beam evaporation plating method.
Step 1160 is included in and forms an anti-reflective film 1260 on the substrate 1200.For example, anti-reflective film comprises a kind of material that is selected from following combination: magnesium fluoride (magnesium fluoride, MgF
2), silica (silicon oxide, SiO
2), silicon nitride (silicon nitride, Si
3N
4) and niobium oxide (Niobium oxide, NbO
x).In the present embodiment, the anti-reflective film that is formed on the substrate is magnesium fluoride film 1260.For example, the method that this magnesium fluoride film can electron beam evaporation plating forms.In the present embodiment, the thickness of magnesium fluoride film for example is 110 nanometers (nm).Afterwards, just finish the making of solar cell.
Figure 13 shows that the J-V figure of the solar cell of the CZTS slurry made that utilizes example seven.According to measurement, the conversion efficiency of this device under AM1.5 standard illumination conditions (1.5AM standard illumination conditions) is 2.7%, open circuit voltage (open circuit voltage, V
Oc) be that 450 millivolts (mV), fill factor, curve factor (fill factor, FF) they are 40.9% and short circuit current (short circuit current density, J
Sc) be 14.8 milliamperes of/square centimeter (mA/cm
2).
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and 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 modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. a paste composition is characterized in that, includes:
One solvent;
A plurality of metallic sulfide nano-particles; And
At least a ion that is selected from metal ion and metal complex combination that ion consists of, it is distributed in the surface of described metallic sulfide nano-particle, and with so that described metallic sulfide nano-particle be scattered in the described solvent;
Wherein, the metal that described metallic sulfide nano-particle, described metal ion and described metal complex ion comprise is to be selected from the combination that is made of periodic table I, II, III and IV family element, and comprises all metallic elements of monosulfide semi-conducting material.
2. paste composition as claimed in claim 1 is characterized in that, described sulfide semiconductor material is to be selected from the combination that is made of IV-VI compounds of group, I-III-VI compound and I-II-IV-VI compound.
3. paste composition as claimed in claim 1 is characterized in that, described metallic sulfide nano-particle comprises at least two kinds of different metal sulfides.
4. paste composition as claimed in claim 1 is characterized in that, described metallic sulfide nano-particle comprises a kind of nano particle, and it is made of at least two kinds of metal sulfides.
5. paste composition as claimed in claim 1 is characterized in that, the metal of described metallic sulfide nano-particle, described metal ion and described metal complex ion is selected from the combination that is made of tin, copper, zinc, germanium, copper, indium and gallium.
6. paste composition as claimed in claim 1 is characterized in that, described solvent comprises polar solvent.
7. paste composition as claimed in claim 1 is characterized in that, described solvent comprises at least a solvent that selects Free water, methyl alcohol, ethanol, isopropyl alcohol, dimethyl sulfoxide (DMSO) and amino-contained combination that solvent consists of.
8. one kind in order to form the method for slurry, it is characterized in that, includes:
Form metallic sulfide nano-particle;
Formation comprises at least solution of one of them of metal ion and metal complex ion;
Mix described solution and described metallic sulfide nano-particle; Wherein, the metal of described metallic sulfide nano-particle, described metal ion and described metal complex ion is to be selected from the combination that periodic table I, II, III and IV family consist of; And
When described metallic sulfide nano-particle, described metal ion and described metal complex ion do not comprise all metallic elements of monosulfide semi-conducting material, repeat aforementioned formation step at least one of them, and repeat described blend step.
9. as claimed in claim 8ly it is characterized in that in order to form the method for slurry, more comprise adjust described reaction solution the pH value to about pH7 to about pH14.
10. method as claimed in claim 8 is characterized in that, described slaine comprises the salt that is selected from by pink salt, mantoquita, zinc salt, germanium salt, indium salt and gallium combination that salt consists of.
11. as claimed in claim 8ly it is characterized in that in order to form the method for slurry, described sulphur source comprise sulfur-containing compound and selenium-containing compound at least one of them.
12. as claimed in claim 8ly it is characterized in that in order to form the method for slurry, form comprise metal ion and metal complex ion at least the described step of the described solution of one of them comprise:
Dissolve a slaine in a solvent to form metal ion;
Form the sulfur-bearing dentate; And
Mix described metal ion and described sulfur-bearing dentate.
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| US13/234,158 US8771555B2 (en) | 2011-05-06 | 2011-09-16 | Ink composition |
| US13/234,158 | 2011-09-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923515A (en) * | 2014-04-10 | 2014-07-16 | 北京工业大学 | Method for preparing ink capable of being used for preparing Cu2ZnSnS4 solar cell absorption layer film |
| WO2016191998A1 (en) * | 2015-06-01 | 2016-12-08 | Baoshan Iron & Steel Co., Ltd. | Method of preparing metal chalcogenide nanomaterials |
| CN111621201A (en) * | 2014-07-31 | 2020-09-04 | C3奈米有限公司 | Metal nanowire inks for forming transparent conductive films with fused networks |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101520538B1 (en) * | 2013-06-03 | 2015-05-15 | 연세대학교 산학협력단 | Hybrid ink for high quality CZTSSe absorber layer |
| KR101621743B1 (en) * | 2013-07-19 | 2016-05-17 | 주식회사 엘지화학 | Manufacturing Method of CI(G)S Nano Particle for Preparation of Light Absorbing Layer and CI(G)S Nano Particle Manufactured thereof |
| TWI583013B (en) | 2013-08-01 | 2017-05-11 | Ｌｇ化學股份有限公司 | Ink composition for manufacturing light absorption layer of solar cells and method of manufacturing thin film using the same, method of synthesizing core-shell structure nanoparticles, thin film, and thin film solar cell |
| KR101792314B1 (en) | 2014-11-04 | 2017-10-31 | 주식회사 엘지화학 | Copper Calcogenide Nano Particle for Manufacturing Light Absorbing Layer of Solar Cell and Method for Manufacturing the Same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009137637A2 (en) * | 2008-05-09 | 2009-11-12 | Board Of Regents, The University Of Texas System | Nanoparticles and methods of making and using |
| CN101651171A (en) * | 2009-09-17 | 2010-02-17 | 上海交通大学 | Preparation method of ormolu sulfur solar energy absorbing layer film |
| CN101733409A (en) * | 2009-12-10 | 2010-06-16 | 浙江大学 | Preparation method of copper and indium alloy ink and application thereof |
| EP2305600A1 (en) * | 2009-09-28 | 2011-04-06 | Rohm and Haas Electronic Materials, L.L.C. | A selenium/ group 1B ink and methods of making and using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120098799A (en) * | 2009-11-25 | 2012-09-05 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles |
-
2012
- 2012-08-01 JP JP2012171003A patent/JP2013064108A/en active Pending
- 2012-08-24 CN CN2012103060626A patent/CN103000712A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009137637A2 (en) * | 2008-05-09 | 2009-11-12 | Board Of Regents, The University Of Texas System | Nanoparticles and methods of making and using |
| CN101651171A (en) * | 2009-09-17 | 2010-02-17 | 上海交通大学 | Preparation method of ormolu sulfur solar energy absorbing layer film |
| EP2305600A1 (en) * | 2009-09-28 | 2011-04-06 | Rohm and Haas Electronic Materials, L.L.C. | A selenium/ group 1B ink and methods of making and using same |
| CN101733409A (en) * | 2009-12-10 | 2010-06-16 | 浙江大学 | Preparation method of copper and indium alloy ink and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923515A (en) * | 2014-04-10 | 2014-07-16 | 北京工业大学 | Method for preparing ink capable of being used for preparing Cu2ZnSnS4 solar cell absorption layer film |
| CN111621201A (en) * | 2014-07-31 | 2020-09-04 | C3奈米有限公司 | Metal nanowire inks for forming transparent conductive films with fused networks |
| US11512215B2 (en) | 2014-07-31 | 2022-11-29 | C3 Nano, Inc. | Metal nanowire ink and method for forming conductive film |
| US11814531B2 (en) | 2014-07-31 | 2023-11-14 | C3Nano Inc. | Metal nanowire ink for the formation of transparent conductive films with fused networks |
| CN111621201B (en) * | 2014-07-31 | 2024-03-01 | C3奈米有限公司 | Metallic nanowire inks for forming transparent conductive films with fused networks |
| WO2016191998A1 (en) * | 2015-06-01 | 2016-12-08 | Baoshan Iron & Steel Co., Ltd. | Method of preparing metal chalcogenide nanomaterials |
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