CN107473600A - A kind of whole soln prepares the method for mixing sulphur antimony selenide nano-rod film - Google Patents

Abstract

The invention relates to a method for preparing a sulfur-doped antimony selenide nanorod thin film from a complete solution. This includes the following steps: dissolving the mixed powder of antimony powder, selenium powder and sulfur powder in the mixed solvent of ethanedithiol and ethylenediamine obtained in the previous step, stirring until dissolved; spin coating the obtained precursor solution on the glass substrate, After drying, repeat the spin-coating-drying steps until the thickness of the precursor film on the glass substrate is 900nm-1100nm; anneal the obtained precursor film at 300°C-350°C for 10min-30min, and finally obtain the sulfur-doped antimony selenide nanometer stick film. The invention has the advantages of simple preparation process, low cost and convenient operation; dense, uniform and impurity-free Sb ₂ (Se _1-x S _x ) ₃ nanorod thin film can be obtained.

Description

A kind of method for preparing sulfur-doped antimony selenide nanorod film from whole solution

technical field

The invention belongs to a new method for preparing Sb ₂ (Se _1-x S _x ) ₃ nanorods, which uses a mercaptoamine solvent system to dissolve elemental powder, and performs sulfur element doping to obtain uniform and impurity-free Sb ₂ (Se _1-x S x ) _x ) ₃ nanorods, belonging to the technical field.

Background technique

In the past ten years, one-dimensional semiconductor nanomaterials have attracted extensive attention of researchers due to their superior optoelectronic properties and great application potential in optoelectronic devices. Antimony selenide has become one of the research hotspots due to its green color, low toxicity, good chemical stability, direct band gap (1.0～1.2eV) and high light absorption coefficient (>10 ⁵ ). The commonly used methods for preparing Sb ₂ Se ₃ are water Thermal method, solvothermal method, VLS method, etc. These methods use antimony chloride or antimony oxide as the precursor source, all of which have the disadvantages of long time consumption, high consumption, and easy introduction of miscellaneous items.

Contents of the invention

The object of the present invention is to provide a new method for preparing Sb ₂ (Se _1-x S _x ) ₃ nanorods from a full solution to address the defects and deficiencies in the prior art. The method adopts a mixed solvent of ethylenediamine and ethanedithiol to dissolve elemental selenium powder, antimony powder, and sulfur powder, and through the good solubility of thiolamine solvent to antimony powder, selenium powder, and sulfur powder, it is prepared by dissolving and recrystallizing. Sb ₂ (Se _1-x S _x ) ₃ with uniform size and impurity-free sulfur doping was obtained, and the absorption of the film was adjusted by adjusting the ratio of sulfur powder in the precursor powder. The preparation process of the invention is simple, low in cost and quick. The prepared uniform and pure sulfur-doped antimony selenide nanorods can be applied in photovoltaic industry, photodetector field and other fields.

Technical scheme of the present invention is:

A method for preparing a sulfur-doped antimony selenide nanorod film from a full solution, comprising the following steps:

The first step: ultrasonically clean the glass substrate in isopropanol, acetone and ethanol in sequence, dry it and then clean the surface with a plasma cleaner;

Step 2: Mix ethanedithiol and ethylenediamine to obtain a mixed solvent; wherein, the volume ratio is ethanedithiol:ethylenediamine=1:4～12;

The third step: configure the precursor solution: dissolve the mixed powder of antimony powder, selenium powder and sulfur powder in the mixed solvent obtained in the previous step, and stir until dissolved in an oil bath at 60°C to 90°C; wherein, every 2ml of mixed solvent is added 1.6mmol Sb powder; molar ratio Sb:Se:S=2:3(1-X):3X, X=0.1-0.7;

Step 4: Spin-coat the precursor solution obtained in the previous step onto the glass substrate, dry it at 140-160 degrees, then spin-coat the precursor solution again, and repeat the spin-coating-drying steps until the precursor film on the glass substrate Thickness 900nm ~ 1100nm;

Step 5: annealing the obtained precursor film at 300° C. to 350° C. for 10 minutes to 30 minutes, and finally obtaining a sulfur-doped antimony selenide nanorod film.

In the fourth step, the spin coating speed is 1000-5000 rpm, and the time is 10-20 s.

In the third step, the molar ratio Sb:Se:S=2:3(1-X):3X, X is preferably 0.1-0.3.

The beneficial effects of the present invention are:

The invention has the advantages of simple preparation process, low cost and convenient operation; dense, uniform and impurity-free Sb ₂ (Se _1-x S _x ) ₃ nanorod thin film can be obtained.

The preparation process of the Sb ₂ (Se _1-x S _x ) ₃ nanorod thin film obtained by the present invention is simple and low in cost; the thin film with adjustable bandgap width is prepared by simply adding sulfur powder to the precursor and spin-coating , has a good application prospect in photodetectors and solar cells.

Description of drawings

Fig. 1 is the SEM figure of the film that the Sb2( _{Se1 - xSx) 3 nanorods} that obtain in embodiment 1, embodiment 3, embodiment 5, embodiment 6 are composed; Wherein, Fig. 1 a is in embodiment 3 The obtained composition is Sb ₂ (Se _1-x S _x ) ₃ x = 0.2 film SEM image; Fig. 1 b is the film obtained in Example 5 with the composition of Sb ₂ (Se _1-x S _x ) ₃ x = 0.5 SEM image; Fig. 1c is the composition obtained in Example 6 as Sb ₂ (Se _1-x S _x ) ₃ x = 0.7; Fig. 1d is the SEM image of the thin film composed of Sb ₂ Se ₃ obtained in Example 1 x =0.7;

Fig. ₂ is the XRD diffractogram of the thin film of Sb2( _{Se1 -} xSx) ₃ nanorods composition obtained in embodiment 1, embodiment 3, embodiment 5, embodiment 6; Wherein, Fig. 2a is the embodiment of The Sb ₂ Se ₃ nanorod film obtained in 1 and the Sb ₂ (Se _1-x S _x ) ₃ obtained in Example 3, Example 5, and Example 6; x=0.2; x=0.5; x=0.7 XRD diffraction patterns of nanorod films. Figure 2b shows the Sb ₂ Se ₃ nanorod film obtained in Example 1 and the Sb ₂ (Se _1-x S _x ) ₃ obtained in Example 3, Example 5, and Example 6, x=0.2; x=0.5 The position of the diffraction peak in the XRD diffraction pattern of the nanorod thin film of x=0.7 in the range of 31°～32.2°;

Fig. 3 is the UV-VIS absorption spectrum of the films composed of Sb ₂ (Se _1-x S _x ) ₃ nanorods obtained in Example 3, Example 5, and Example 6. Wherein, Fig. 3 a is the absorption spectrum of the thin film composed of Sb ₂ (Se _1-x S _x ) ₃ nanorods obtained in embodiment 3, embodiment 5, embodiment 6; Fig. 2 b is the Sb ₂ obtained in embodiment 3 (Se _1-x S _x ) ₃ x=0.2 UV-VIS absorption figure of the nanorod film; Figure 3c is the nanorod film of Sb ₂ (Se _1-x S _x ) ₃ x=0.5 obtained in Example 5 Figure 3d is the UV-VIS absorption figure of the nanorod film with Sb ₂ (Se _1-x S _x ) ₃ x = 0.7 obtained in Example 6.

Fig. 4 is the photoelectric performance IT diagram of the film composed of Sb ₂ (Se _1-x S _x ) ₃ nanorods obtained in Example 1, Example 3, and Example 5.

detailed description

The present invention will be described in detail below in conjunction with accompanying drawing and specific embodiment:

Embodiment 1: the preparation process of Sb ₂ Se ₃ nanorod film

Step 1: Ultrasonic clean the 2cm*2cm glass substrate in isopropanol, acetone and ethanol for 5 minutes, dry it, then clean the surface with a plasma cleaner, and store it for later use;

Step 2: Mix ethanedithiol and ethylenediamine at a volume ratio of 1:10 to obtain a mixed solution;

The third step: configure the precursor solution, mix 1.6mmol Sb powder and 2.4mmol Se powder (that is, no S powder is added in this embodiment, the molar ratio Sb:Se:S=2:3(1-X):3X, X=0 ), dissolved in 2ml of mixed solvent, stirred in an oil bath at 60°C for 7h to dissolve;

Step 4: Spin-coat the precursor solution obtained in the previous step on the glass substrate at a speed of 2000rpm for 20s, and dry it on a heating plate preset at 150°C. After the solvent evaporates, repeat the spin-coating precursor solution-drying step Three times to obtain a precursor film with a thickness of 900nm;

The fifth step: the obtained sample is annealed at 300°C for 10 minutes, and finally a dense and uniform nanorod film of Sb ₂ Se ₃ is obtained. Example 2: Preparation process of Sb ₂ (Se _1-x S _x ) ₃ x=0.1 nanorod film

Step 1: Ultrasonic clean the 2cm*2cm glass substrate in isopropanol, acetone and ethanol in sequence, after drying, clean the surface with a plasma cleaner, and store it for later use;

Step 2: Mix ethanedithiol and ethylenediamine at a volume ratio of 1:10 to obtain a mixed solution;

The third step: configure the precursor solution, mix 1.6mmolSb powder, 2.16mmolSe powder and 0.24mmolS powder (that is, the molar ratio Sb:Se:S=2:3(1-X):3X, X=0.1),), Dissolve in 2ml of mixed solvent, stir in an oil bath at 60°C for 7h to dissolve;

Step 4: Spin-coat the precursor solution obtained in the previous step on the glass substrate at a speed of 2000rpm for 20s, and dry it on a heating plate preset at 150°C. After the solvent evaporates, repeat the spin-coating precursor solution-drying Step three times to obtain a precursor film with a thickness of 900nm;

The fifth step: annealing the obtained sample at 300° C. for 10 min, finally obtaining a dense and uniform nanorod film of Sb ₂ (Se _0.9 S _0.1 ) ₃ .

Example 3: Preparation process of Sb ₂ (Se _1-x S _x ) ₃ x=0.2 nanorod film

Step 1: Ultrasonic clean the 2cm*2cm glass substrate in isopropanol, acetone and ethanol in sequence, after drying, clean the surface with a plasma cleaner, and store it for later use;

Step 2: Mix ethanedithiol and ethylenediamine at a volume ratio of 1:10 to obtain a mixed solution;

The third step: configure the precursor solution, 1.6mmolSb powder, 2mmolSe powder and 0.4mmolS powder (that is, the molar ratio Sb:Se:S=2:3(1-X):3X, X=0.2),), dissolve Dissolve in 2ml of mixed solvent and stir in an oil bath at 60°C for 7h;

Step 4: Spin-coat the precursor solution obtained in the previous step on the glass substrate at a speed of 2000rpm for 20s, and dry it on a heating plate preset at 150°C. After the solvent evaporates, repeat the spin-coating precursor solution-drying Step three times to obtain a precursor film with a thickness of 900nm;

The fifth step: the obtained sample is annealed at 300°C for 10 minutes, and finally a dense and uniform nanorod film of Sb ₂ (Se _0.8 S _0.2 ) ₃ is obtained.

Example 4: Preparation process of Sb ₂ (Se _1-x S _x ) ₃ x=0.3 nanorod film

Step 1: Ultrasonic clean the 2cm*2cm glass substrate in isopropanol, acetone and ethanol in sequence, after drying, clean the surface with a plasma cleaner, and store it for later use;

Step 2: Mix ethanedithiol and ethylenediamine at a volume ratio of 1:10 to obtain a mixed solution;

The third step: configure the precursor solution, mix 1.6mmolSb powder, 1.68mmolSe powder and 0.72mmolS powder (that is, the molar ratio Sb:Se:S=2:3(1-X):3X, X=0.3),), Dissolve in 2ml of mixed solvent, stir in an oil bath at 60°C for 7h to dissolve;

Step 4: Spin-coat the precursor solution obtained in the previous step on the glass substrate at a speed of 2000rpm for 20s, and dry it on a heating plate preset at 150°C. After the solvent evaporates, repeat the spin-coating precursor solution-drying Step three times to obtain a precursor film with a thickness of 900nm;

The fifth step: annealing the obtained sample at 300° C. for 10 min, finally obtaining a dense and uniform nanorod film of Sb ₂ (Se _0.7 S _0.3 ) ₃ .

Example 5: Preparation process of Sb ₂ (Se _1-x S _x ) ₃ nanorod film when x=0.5

Step 1: Ultrasonic clean the 2cm*2cm glass substrate in isopropanol, acetone and ethanol in sequence, after drying, clean the surface with a plasma cleaner, and store it for later use;

Step 2: Mix ethanedithiol and ethylenediamine at a volume ratio of 1:10 to obtain a mixed solution;

The third step: configure the precursor solution, dissolve 1.6mmol of Sb powder, 1.2mmol of Se powder and 1.2mmol of S powder in 2ml Mix the solvent, stir in an oil bath at 60°C for 7 hours to dissolve;

Step 4: Spin-coat the precursor solution obtained in the previous step on the glass substrate at a speed of 2000rpm for 20s, and dry it on a heating plate preset at 150°C. After the solvent evaporates, spin-coat again and repeat four times to a thickness of 900nm ;

The fifth step: the obtained sample is annealed at 300°C for 10 minutes, and finally a dense and uniform nanorod film of Sb ₂ (Se _0.5 S _0.5 ) ₃ is obtained.

Example 6: Preparation process of Sb ₂ (Se _1-x S _x ) ₃ nanorod film when x=0.7

Step 1: Ultrasonic clean the 2cm*2cm glass substrate in isopropanol, acetone and ethanol in sequence, after drying, clean the surface with a plasma cleaner, and store it for later use;

Step 2: Mix ethanedithiol and ethylenediamine at a volume ratio of 1:10 to obtain a mixed solution;

The third step: configure the precursor solution, dissolve 1.6mmol Sb powder, 0.72mmol Se powder and 1.68mmol S powder molar ratio Sb:Se:S=2:3(1-X):3X, X=0.7), dissolve in 2ml and mix Solvent, stirred in an oil bath at 60°C for 7 hours to dissolve;

Step 4: Spin-coat the precursor solution obtained in the previous step on the glass substrate at a speed of 2000rpm for 20s, and dry it on a heating plate preset at 150°C. After the solvent evaporates, spin-coat again and repeat four times to a thickness of 900nm ;

Step five: annealing the obtained sample at 300° C. for 10 min, and finally obtain a dense and uniform nanorod film of Sb ₂ (Se _0.3 S _0.7 ) ₃ .

(a) (b) (c) (d) in Fig. 1 is the SEM figure of embodiment 3,5,6,1 respectively, as can be seen from figure (d) and (a), along with the doping of sulfur The size of the nanorods becomes larger with the increase of the amount of sulfur added. When the amount of sulfur added is X=0.1～0.3, the size of the nanorods becomes thicker and longer than that of X=0, and the film becomes dense without obvious holes. When the doping amount of sulfur is from X=0.5 to X=0.7 in Figures (b) and (c), the nanorods become thinner and shorter than when X=0.1-0.3, and the compactness of the film becomes worse and worse. It can be seen that the addition of sulfur has a beneficial effect on the morphology of nanorods. When the amount of sulfur added reaches X = 0.1-0.3, the nanorods have the largest size and the most dense film is the best doping content.

Fig. 2 is the XRD diffraction pattern of embodiment 1, 3, 5, 6, as can be seen from the figure, along with the increase of sulfur doping, the diffraction peak of XRD diffraction pattern has obvious red shift, and there is no diffraction of other substances peak, proving the effective doping of sulfur element.

Fig. 3 is respectively the UV-VIS absorption figure of embodiment 3, 5, 6 of different sulfur doping amount, along with the increase of doping amount, the bandgap of Sb ₂ (Se _1-x S _x ) ₃ nanorod film changes with increases with the increase of X. When X=0, the band gap E _g =0.92eV; when X=0.1, the band gap E _g =1.20eV; when X=0.2, the band gap E _g =1.22eV; when X=0.3, the band gap E _g =1.23eV; When X=0.5, the band gap E _g =1.26eV; when X=0.7, the band gap E _g =1.32 eV. It can be seen that this method successfully adjusts the band gap of the film through the doping of sulfur, so that the band gap can be adjusted from 0.92eV to 1.32eV, and the selective absorption of light of different wavelengths can be realized.

Fig. 4 is the photoelectric performance IT graph of embodiment 1, 3, 5, and square is the IT performance graph when not doping sulfur X=0, and circle is the IT performance graph when adding sulfur X=0.2 in right amount, and triangle is sulfur The IT performance graph when the incorporation amount X=0.5. The test is carried out under the condition that the interdigital distance is 10um, the interdigital length is 1000um, the substrate is _SiO2 , the bias voltage is 3V, and the light intensity of the xenon lamp is 70mW/ ^cm2 . for 10 seconds. When X=0 without adding sulfur, the photocurrent is 0.76μA, the dark current is 0.19μA, and the photoresponse switching ratio is about 4. When sulfur is mixed with X=0.1～0.3, the size of the photodark current is basically Same as X=0.2, when X=0.2, the maximum photocurrent is 2.18μA, the dark current is 0.27μA, and the on/off ratio of the photoresponse (ratio of photocurrent to dark current) is about 8. Compared with the time without adding sulfur, when X=0.1～0.3, the photocurrent has a great improvement. As the content of sulfur increases to X=0.5, the photocurrent drops rapidly. When the value of X increases to 0.7 The nanorod thin film has no photoresponse, and it can be seen that the doping of sulfur element with an appropriate amount of X=0.1-0.3 can improve the photoelectric performance of the Sb ₂ (Se _1-x S _x ) ₃ nanorod thin film.

Those skilled in the art can easily understand that those skilled in the art can implement according to the instructions. The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any modification, equivalent replacement and improvement, etc., shall be included in the protection scope of the present invention.

Matters not covered in the present invention are known technologies.

Claims (3)

1. a kind of method that full solution prepares sulfur-doped antimony selenide nanorod thin film is characterized in that the method may further comprise the steps: The first step: ultrasonically clean the glass substrate in isopropanol, acetone and ethanol in sequence, dry it and then clean the surface with a plasma cleaner; Step 2: Mix ethanedithiol and ethylenediamine to obtain a mixed solvent; wherein, the volume ratio is ethanedithiol:ethylenediamine=1:4~12; The third step: configure the precursor solution: dissolve the mixed powder of antimony powder, selenium powder and sulfur powder in the mixed solvent obtained in the previous step, and stir until dissolved in an oil bath at 60°C to 90°C; wherein, every 2ml of mixed solvent is added 1.6 mmol Sb powder; molar ratio Sb:Se:S=2:3(1-X):3X, X=0.1-0.7; Step 4: Spin-coat the precursor solution obtained in the previous step onto the glass substrate, dry it at 140-160 degrees, then spin-coat the precursor solution again, and repeat the spin-coating-drying steps until the precursor film on the glass substrate Thickness 900nm ~ 1100nm; Step 5: annealing the obtained precursor film at 300° C. to 350° C. for 10 minutes to 30 minutes, and finally obtaining a sulfur-doped antimony selenide nanorod film. 2. The method for preparing sulfur-doped antimony selenide nanorod thin films from the whole solution according to claim 1, characterized in that in the fourth step, the spin coating speed is 1000 ~ 5000rpm, and the time is 10 ~ 20s. 3. The method for preparing sulfur-doped antimony selenide nanorod film from the whole solution according to claim 1, characterized in that in the third step, the molar ratio Sb:Se:S=2:3 (1-X) : In 3X, X is preferably 0.1-0.3.