CN102041555A - Preparation method of CuInS2 nanocrystalline material - Google Patents
Preparation method of CuInS2 nanocrystalline material Download PDFInfo
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Abstract
The invention relates to a preparation method of CuInS2 nanocrystalline material which has a copper pyrite structure and a controllable size and is prepared by taking curpic oleate, indium oleate precursor and elemental sulphur as the raw material by a one-step chemical method. The invention has the advantages that the preparation method of the CuInS2 nanocrystalline material has simple operation, easy repetition, high purity of obtained CuInS2 nanocrystalline material,moderate reaction condition and no pollution, greatly lowers cost and is suitable for large-scale industrial production. The CuInS2 nanocrystalline material provided by the invention has quantum size effect, can serve as the adsorption material of solar cells and has an important meaning to the practical application of the material in the solar cell fiel.
Description
Technical field
The present invention relates to photoelectric material and technology of preparing thereof, be specially a kind of CuInS
2The preparation method of nanocrystalline material.
Background technology
Semi-conductor ternary chalcongen Compound I-III-VI
2(I=Cu, Ag; III=Ga, In; VI=S, Se is Te) owing to the widespread use at aspects such as photoelectric material, biomarker and photochemical catalysis is subjected to people's attention.As a kind of typical ternary compound, CuInS
2Semi-conductor has been subjected to extensive studies, because it has a lot of advantages, for example CuInS as a kind of good photoelectric material
2Be the direct band-gap semicondictor material, energy gap is 1.53 eV, and near the required best energy gap value (1.45 eV) of solar cell material, and energy gap is insensitive to variation of temperature.CuInS
2The uptake factor of material is up to 10
5Cm
-1The order of magnitude, with its light absorbing zone as solar cell, thickness only needs 1 ~ 2 μ m.CuInS
2Can make high-quality p type and n type film, be easy to make homojunction, by Theoretical Calculation prediction, CuInS
2The efficiency of conversion of solar cell is 28% ~ 32%, and this is the highest in all photovoltaic devices, is suitable as very much the light absorbing material of solar cell.
At present, for CuInS
2Nanocrystalline preparation mainly comprises following several method: single source precursor method, hydro-thermal or solvent-thermal method etc.For example, Hepp etc. is by at the single source presoma (PPh of 200 ~ 250 ℃ of thermolysiss
3)
2CuIn (SEt)
4Obtain the CuInS of size about 2 ~ 4 nm
2, resulting nanocrystalline colloidal sol has at room temperature been observed very difficult fluorescent effect (S. L. Castro, S. G. Bailey, R. P. Raffaelle, et al. Chem. Mater., 2003 of finding, 15 (16): 3142-3147) of block materials.M. G. Norton etc. by uv-radiation [(TOP)
2CuIn (SR)
4] (TOP) (octyl)
3P; R=n-Pr (1), t-Bu (2)) organism has obtained the CuInS about about 2 nm
2Nano particle (J. J. Nairn, P. J. Shapiro, B. Twamley, et al. Nano Lett., 2006,6 (6): 1218-1223).Xie and Qian etc. water heat and solvent-thermal method have respectively synthesized CuInS
2Nanocrystalline (Y. Jiang, Y. Wu, X. Mo, et al. Inorg. Chem., 2000,39 (14): 2964-2965 about nanometer rod and 13 ~ 17 nm; W. M. Du, X. F. Qian, J. Yin, et al. Chem. Eur. J., 2007,13 (31): 8840-8846).In addition, by using injection, Peng etc. use general in non-ligand solvent octadecylene, and chemically stable reactant has obtained the monodispersed CuInS about 2 ~ 20 nm
2Nanocrystalline, by introducing coordination agent, can regulate and control nanocrystalline Cu, In, the atomic ratio of S (R. G. Xie, M. Rutherford, X. G. Peng J. Am. Chem. Soc., 2009,131 (15): 5691-5697).Yet adopt the nanocrystalline material of method for preparing to have certain weak point: synthesis step is comparatively loaded down with trivial details, and cost is higher, be not suitable for mass preparation, the synthetic nanoparticulate dispersed is relatively poor, and dimensional controllability is bad, and this has all hindered CuInS to a certain extent
2Nanocrystalline practical process in solar cell.
Therefore, this seminar has synthesized the ternary chalcongen Compound C uInS of controllable size by a step chemical method
2Nanocrystalline material, it is dispersed better, and can be used for scale operation, this for its in the practical application of area of solar cell with significant.
Summary of the invention
The objective of the invention is provides a kind of CuInS at above-mentioned existing problems
2The preparation method of nanocrystalline material promptly adopts a step chemical method to prepare ternary chalcongen Compound C uInS
2Nanocrystalline, and realized its controllable size, this method is simple to operate, good reproducibility, reaction conditions gentleness, non-environmental-pollution and goods purity height, greatly reduces production cost, is suitable for large-scale industrial production.
Technical scheme of the present invention:
A kind of CuInS
2The preparation method of nanocrystalline material, described CuInS
2Nanocrystalline material is that a kind of monodispersed, size is the CuInS of 2 ~ 10nm
2Nanocrystalline, its preparation method may further comprise the steps:
1) with sodium oleate and cupric chloride or indium chloride is dissolved in normal hexane, deionized water and the alcoholic acid mixing solutions and be to carry out underpressure distillation under 0.1 ~ 0.2MPa in force value, stirring reaction 2 ~ 5h under 40 ~ 80 oC then, wash then 3～5 times and revolve to steam and remove remaining normal hexane, promptly obtain presoma cupric oleate and oleic acid indium;
2) presoma cupric oleate and the oleic acid indium that makes mixed with oleic acid, the oleyl amine solvent that is dissolved with elemental sulfur is added in the above-mentioned mixing solutions, temperature be 70 ~ 100 ℃, vacuum tightness be 0 ~-the 0.1MPa vacuum condition under, behind reaction 20 ~ 50 min, charging into Ar, is 170 ~ 200 ℃ and the whipped state product of reaction 30 ~ 80 min formation dark red down in temperature at last;
3) prepared product is cooled to room temperature after, add ethanol and make it precipitation, be centrifugal 5 ~ 20 min under the condition of 6000 ~ 10000 rpm at rotating speed then, the gained throw out is washed 3 ~ 5 times with normal hexane;
4) black precipitate that obtains is dispersed in again formation black ink sap-shape thing in the toluene solution, is prepared CuInS
2Nanocrystalline sample.
In described normal hexane, deionized water and the alcoholic acid mixing solutions, the volume ratio of each component is 2:1:0.5 ~ 3.
Described presoma cupric oleate, oleic acid indium and oleic mass ratio are 1:1:2 ~ 5.
The ratio of the consumption of described sodium oleate and cupric chloride or indium chloride and normal hexane, deionized water and alcoholic acid mixing solutions is 1mmol:(1 ~ 1.5) ml.
The total amount of described cupric oleate and oleic acid indium and oleic amount ratio are 1mmol:(1 ~ 2.5) ml.
The amount ratio of described elemental sulfur and oleyl amine solvent is 1mmol:(2 ~ 20) ml.
The total amount of described cupric oleate and oleic acid indium and the mol ratio of elemental sulfur are 1:1 ~ 2.
Chemical reaction mechanism of the present invention, as follows:
Oleyl amine is owing to have some special nature such as strong alkalescence, chelating ability as a kind of sorbent material to remove the too much heat that generates in the dereaction, the selected solvent of doing.Elemental sulfur can be dissolved in the oleyl amine and discharge S
2-Simultaneously, oleyl amine is easy to a Cu as reductive agent
2+Be reduced to Cu
+In experiment, oleic acid is as a kind of weak coating, and its amount is fixed in reaction.Be reflected in oleyl amine and the oleic mixed solvent and carry out, the nano-cluster that is generated is coated fully by the oleyl amine molecule.Therefore, oleyl amine is compared with oleic acid, and the oleyl amine particle has stronger bonding force.And the solvent oleyl amine is at control product C uInS
2Nanocrystalline play important effect when big or small.
Advantage of the present invention and beneficial effect are: the present invention as reactant, is a solvent with the oleyl amine of oleic acid and different amounts with cupric oleate, oleic acid indium and elemental sulfur, prepares monodispersed ternary chalcongen Compound C uInS by a step chemical method
2Nanocrystalline, and realized its controllable size, this method is simple to operate, good reproducibility, reaction conditions gentleness, non-environmental-pollution and goods purity height, greatly reduces production cost, is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is infrared spectra (FTIR) curve of presoma cupric oleate and oleic acid indium.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the S1 sample of preparation.
Fig. 3 is the XPS spectrum figure of the S1 sample of preparation, and wherein: overall diagram is (a), and Cu2p is (b), and In3d is (c), and S2p is (d).
Fig. 4 is the S1 sample (a) of preparation and infrared spectra (FTIR) curve after the aftertreatment (b).
Fig. 5 is transmission electron microscope (TEM) figure (a) of the S4 sample of preparation, high-resolution-ration transmission electric-lens (HRTEM) figure (b) and particle size dispersion histogram (c).
Fig. 6 is CuInS
2Nanocrystalline forming process schema.
Fig. 7 is CuInS
2Nanocrystalline sample (S1, uv-visible absorption spectra S4) (Uv-vis) figure, the spectrogram of wherein inner illustration for amplifying.
Fig. 8 schemes (b) and particle size dispersion histogram (c) for transmission electron microscope (TEM) figure (a), high-resolution-ration transmission electric-lens (HRTEM) that the S1 sample amplifies after preparing.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1:
CuInS
2The preparation method of nanocrystalline material, with the example that is prepared as of S1 sample, step is as follows:
1) with 20 mmol sodium oleates and 10 mmol cupric chloride or 10 mmol indium chlorides are dissolved in 30 mL normal hexanes, 15 mL deionized waters and the 20 mL alcoholic acid mixing solutionss and be to carry out underpressure distillation under the 0.1MPa in force value, stirring reaction 4h under 60 oC then, wash then 5 times and revolve to steam and remove remaining normal hexane, promptly obtain presoma cupric oleate and oleic acid indium;
2) presoma cupric oleate and the oleic acid indium mixture 1mmol that makes mixed with 2ml oleic acid (OA), the 15ml oleyl amine solvent that is dissolved with the 1mmol elemental sulfur is dropped in the above-mentioned mixing solutions, in temperature is 80 ℃,, vacuum tightness is-the 0.1MPa vacuum condition under, behind the reaction 30min, charging into Ar, is the product that reaction 60 min form dark red under 180 ℃ of whipped states in temperature at last;
3) prepared product is cooled to room temperature after, add ethanol and make it precipitation, be centrifugal 5 min under the condition of 6000rpm at rotating speed then, the gained throw out is washed 5 times with normal hexane;
4) black precipitate that obtains is dispersed in again formation black ink sap-shape thing in the toluene solution, is prepared CuInS
2Nanocrystalline sample is labeled as S1.
According to prepared presoma cupric oleate of aforesaid method and oleic acid indium infrared spectra (FTIR) curve as shown in Figure 1, be 1718 cm wherein in wave number
-1With 1602 cm
-1The vibrations peak confirmed the existence of C=O to show the formation of cupric oleate and oleic acid indium.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the S1 sample of preparation, and as can be seen from Figure, all XRD diffraction peaks are all corresponding to chalcopyrite CuInS
2(lattice parameter: a=5.52, c=11.13, JCPDS No:085-1575) is observed without any other assorted peak or binary compound, and the CuInS of preparation is described
2Be pure phase, and the broadening of diffraction peak may be because due to particulate diminishes gradually.
Fig. 3 is the XPS spectrum figure of the S1 sample of preparation, and wherein Fig. 3 a is CuInS
2Nanocrystalline overall spectrum figure, carbon derives from background, Fig. 3 b is that Cu 2p is split into 2p3/2(932.5 eV) and 2p1/2(952.0 eV) peak, the peak width at half height of Cu2p3/2 and Cu2p1/2 is respectively 1.9 and 2.3 eV, this has represented Cu
+Peak value.Cu
+Be present in and show Cu in the product
2+Initiator is reduced in reaction process.Similarly, Fig. 3 c is that In3d has divided two peaks 444.6 and 452.3 eV, and this has represented In
3+Peak value.Fig. 3 d is CuInS
2In the spectrogram of S2p, its peak position is in 162.0 eV, promptly with Cu and In coordination respectively.Therefore, CuInS
2Has only Cu in the nanocrystalline product
+, In
3+And S
2-
As seen Fig. 4, is 2919 cm in wave number for the S1 sample (a) of preparation and infrared spectra (FTIR) curve after the aftertreatment (b)
-1, 2850 cm
-1, 1617 cm
-1With 1457 cm
-1The vibrations peak that the place exists has shown that oleyl amine is at CuInS
2The coating on surface, however the disappearance at these vibrations peaks shows the removal of oleyl amine coating.
Embodiment 2:
CuInS
2The preparation method of nanocrystalline material, with the example that is prepared as of S4 sample, step is as follows:
1) with 20 mmol sodium oleates and 10 mmol cupric chloride or 10 mmol indium chlorides are dissolved in 30 mL normal hexanes, 15 mL deionized waters and the 20 mL alcoholic acid mixing solutionss and be to carry out underpressure distillation under the 0.2MPa in force value, stirring reaction 4h under 60 oC then, wash then 5 times and revolve to steam and remove remaining normal hexane, promptly obtain presoma cupric oleate and oleic acid indium;
2) presoma cupric oleate and the oleic acid indium mixture 1mmol that makes mixed with 2ml oleic acid (OA), the 6ml oleyl amine solvent that is dissolved with the 1mmol elemental sulfur is dropped in the above-mentioned mixing solutions, in temperature is 90 ℃,, vacuum tightness is-the 0.05MPa vacuum condition under, behind the reaction 45min, charging into Ar, is the product that reaction 45 min form dark red under 180 ℃ of whipped states in temperature at last;
3) prepared product is cooled to room temperature after, add ethanol and make it precipitation, be centrifugal 15 min under the condition of 8000rpm at rotating speed then, the gained throw out is washed 5 times with normal hexane;
4) black precipitate that obtains is dispersed in again formation black ink sap-shape thing in the toluene solution, is prepared CuInS
2Nanocrystalline sample is labeled as S4.
According to the pattern of the prepared S4 sample of aforesaid method and particle size dispersion situation as shown in Figure 5.As seen, the CuInS of preparation
2The particle size of nanocrystalline sample is approximately 2.5nm, utilizes histogram further to confirm the result of TEM particle size dispersion.As can be seen, its spacing is 3.19 on the high resolution transmission plot (HRTEM), and corresponding crystal face is (112) face.
Described according to embodiment 1 and 2, with CuInS
2Nanocrystalline forming process flow process is illustrated as shown in Figure 6, and oleyl amine (OLA) is owing to have some special nature such as strong alkalescence, chelating ability as a kind of sorbent material to remove the too much heat that generates in the dereaction, the selected solvent of doing.Elemental sulfur (S) can be dissolved in the oleyl amine and discharge S
2-Simultaneously, oleyl amine is easy to a Cu as reductive agent
2+Be reduced to Cu
+In experiment, oleic acid (OA) is as a kind of weak coating, and its amount is fixed in reaction.Be reflected in oleyl amine and the oleic mixed solvent and carry out, the nano-cluster that is generated is coated fully by the oleyl amine molecule.Therefore, oleyl amine is compared with oleic acid, and the oleyl amine particle has stronger bonding force.And the solvent oleyl amine is at control product C uInS
2Nanocrystalline play important effect when big or small.Along with the amount increase of oleyl amine, the size of the nano particle that generates increases gradually.The size of nano particle is relevant with the speed of nanocrystalline nucleation and growth, and more the oleyl amine of a large amount can reduce nucleation and process of growth as stablizer, and then produces bigger nanocrystalline.
According to embodiment 1 and 2 prepared CuInS
2It is nanocrystalline that (S1, S4) uv-visible absorption spectra of sample (Uv-vis) as shown in Figure 7.Obtained as can be seen CuInS
2Nanocrystalline sample does not all have tangible absorption peak, yet has very wide ABSORPTION EDGE, this shows that they can be used as the absorbing material of solar cell, owing to there not be clearly absorption peak, from the ultraviolet figure of their amplifications relation between granular size and the band gap as can be seen.Granular size is the CuInS of 2.5 nm
2Nanocrystalline (S4) calculates band gap by formula Eg=1240/ λ (ABSORPTION EDGE) is 1.90 eV, than traditional block CuInS
2Material (Eg=1.53 eV) blue shift.Blue shift may be owing to quantum confined effect, because the nanocrystalline particle of preparation is less than its bohr exciton radius (8.1 nm).When the size of particle (S1) is that 9.8nm(is greater than 8.1 nm) time, resulting band gap is 1.50 eV, this is consistent with corresponding block band gap, shows that quantum limitation effect is just inessential when particle during greater than its bohr exciton radius.
Embodiment 3:
CuInS
2The preparation method of nanocrystalline material is prepared as example with the amplification of S1 sample:
Described according to embodiment 1, the amount of reactant cupric oleate, oleic acid indium precursor and elemental sulfur etc. is increased to original 20 times, be that presoma cupric oleate and oleic acid indium mixture are 20mmol, oleic acid is 40ml, elemental sulfur is 20mmol, oleyl amine is 300ml, can obtain the CuInS that granular size is about 9.7nm under the same conditions
2Nanocrystalline pure phase, as shown in Figure 8.This illustrates CuInS provided by the invention
2The preparation method of nanocrystalline material can be used for large-scale industrial production.
The result shows, CuInS provided by the invention
2The preparation method of nanocrystalline material, the product controllable size, favorable dispersity, simple to operate, easily repetition, purity height, reaction conditions gentleness, pollution-free greatly reduce cost, are suitable for large-scale industrial production.In addition, CuInS provided by the invention
2Nanocrystalline material has quantum size effect, can be used as the absorbing material of solar cell.
Claims (7)
1. CuInS
2The preparation method of nanocrystalline material is characterized in that: described CuInS
2Nanocrystalline material is that a kind of monodispersed, size is the CuInS of 2 ~ 10nm
2Nanocrystalline, its preparation method may further comprise the steps:
1) with sodium oleate and cupric chloride or indium chloride is dissolved in normal hexane, deionized water and the alcoholic acid mixing solutions and be to carry out underpressure distillation under 0.1 ~ 0.2MPa in force value, stirring reaction 2 ~ 5h under 40 ~ 80 oC then, wash then 3～5 times and revolve to steam and remove remaining normal hexane, promptly obtain presoma cupric oleate and oleic acid indium;
2) presoma cupric oleate and the oleic acid indium that makes mixed with oleic acid, the oleyl amine solvent that is dissolved with elemental sulfur is added in the above-mentioned mixing solutions, temperature be 70 ~ 100 ℃, vacuum tightness be 0 ~-the 0.1MPa vacuum condition under, behind reaction 20 ~ 50 min, charging into Ar, is 170 ~ 200 ℃ and the whipped state product of reaction 30 ~ 80 min formation dark red down in temperature at last;
3) prepared product is cooled to room temperature after, add ethanol and make it precipitation, be centrifugal 5 ~ 20 min under the condition of 6000 ~ 10000 rpm at rotating speed then, the gained throw out is washed 3 ~ 5 times with normal hexane;
4) black precipitate that obtains is dispersed in again formation black ink sap-shape thing in the toluene solution, is prepared CuInS
2Nanocrystalline sample.
2. the described CuInS of claim 1
2The preparation method of nanocrystalline material is characterized in that: in described normal hexane, deionized water and the alcoholic acid mixing solutions, the volume ratio of each component is 2:1:0.5 ~ 3.
3. the described CuInS of claim 1
2The preparation method of nanocrystalline material is characterized in that: described presoma cupric oleate, oleic acid indium and oleic mass ratio are 1:1:2 ~ 5.
4. the described CuInS of claim 1
2The preparation method of nanocrystalline material is characterized in that: the ratio of the consumption of described sodium oleate and cupric chloride or indium chloride and normal hexane, deionized water and alcoholic acid mixing solutions is 1mmol:(1 ~ 1.5) ml.
5. the described CuInS of claim 1
2The preparation method of nanocrystalline material is characterized in that: the total amount of described cupric oleate and oleic acid indium and oleic amount ratio are 1mmol:(1 ~ 2.5) ml.
6. the described CuInS of claim 1
2The preparation method of nanocrystalline material is characterized in that: the amount ratio of described elemental sulfur and oleyl amine solvent is 1mmol:(2 ~ 20) ml.
7. the described CuInS of claim 1
2The preparation method of nanocrystalline material is characterized in that: the total amount of described cupric oleate and oleic acid indium and the mol ratio of elemental sulfur are 1:1 ~ 2.
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| CN107059131A (en) * | 2017-04-21 | 2017-08-18 | 南京信息工程大学 | A kind of semiconductor nano and preparation method and application |
| CN108910939A (en) * | 2018-08-06 | 2018-11-30 | 桂林电子科技大学 | A kind of ultra-thin CuInS2Nanometer sheet and its preparation method and application |
| CN108910939B (en) * | 2018-08-06 | 2020-11-10 | 桂林电子科技大学 | Ultrathin CuInS2Nanosheet and preparation method and application thereof |
| CN109647373A (en) * | 2018-11-28 | 2019-04-19 | 天津大学 | Black oxidation indium ultrathin nanometer piece and preparation method thereof and photo-thermal catalytic applications |
| CN110983425A (en) * | 2019-12-31 | 2020-04-10 | 中国科学技术大学 | Ag2HgS2Single crystal and method for producing the same |
| CN111662703A (en) * | 2020-05-09 | 2020-09-15 | 中国科学院广州能源研究所 | CuInS2Green fluorescent quantum dot with/ZnS/ZnS/ZnS multilayer core-shell structure and preparation method thereof |
| CN111662703B (en) * | 2020-05-09 | 2023-11-03 | 中国科学院广州能源研究所 | CuInS 2 Green fluorescent quantum dot with/ZnS/ZnS multilayer core-shell structure and preparation method thereof |
| CN114570937A (en) * | 2022-03-04 | 2022-06-03 | 北京市科学技术研究院分析测试研究所(北京市理化分析测试中心) | Synthesis method of superfine monodisperse nano Ag |
| CN114570937B (en) * | 2022-03-04 | 2024-03-29 | 北京市科学技术研究院分析测试研究所(北京市理化分析测试中心) | Synthesis method of superfine monodisperse nano Ag |
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