CN103000381B - A kind of making ZnO/CuInS 2the method of nuclear shell structure nano rod film - Google Patents
A kind of making ZnO/CuInS 2the method of nuclear shell structure nano rod film Download PDFInfo
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- CN103000381B CN103000381B CN201110273864.7A CN201110273864A CN103000381B CN 103000381 B CN103000381 B CN 103000381B CN 201110273864 A CN201110273864 A CN 201110273864A CN 103000381 B CN103000381 B CN 103000381B
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Abstract
The invention belongs to technical field of film preparation, be specially a kind of making ZnO/CuInS
2the method of nuclear shell structure nano rod film and related process parameters.This preparation method is medium template switch method.First, hydro thermal method is adopted, with zinc nitrate (Zn (NO
3)
2)/hexamethylenetetramine (HMT) aqueous solution is growth system, growing ZnO nanorod on ITO electro-conductive glass; Then carry out water-bath with thioacetamide (TAA) for reaction reagent, obtain ZnO/ZnS nuclear shell structure nano rod film; Then, by gained sample at copper nitrate (Cu (NO
3)
2) triethylene glycol (TEG) solution in leave standstill a period of time obtain ZnO/CuS nuclear shell structure nano rod film medium template; Finally, gained sample is put into inidum chloride (InCl
3) TEG solution, in water heating kettle, carry out high-temperature water thermal response, ZnO/CuInS can be obtained at ITO conductive glass surface
2nuclear shell structure nano rod film.The concentration of TAA, Cu (NO have been inquired into simultaneously
3)
2the technological parameter such as concentration, hydro-thermal reaction time on the impact of membrane structure and performance, obtain the high performance ZnO/CuInS of preparation
2the optimal processing parameter of nuclear shell structure nano rod film.
Description
Technical field
The invention belongs to technical field of film preparation, be specially a kind of making ZnO/CuInS
2the method of nuclear shell structure nano rod film and related process parameters.
Technical background
The energy is the material base that mankind modern society exists, and is also simultaneously the direct driving force that human society is developed, and along with the sharp increase of socioeconomic development and population, energy problem becomes one of mankind's significant problem urgently to be resolved hurrily day by day.New and renewable sources of energy is one of material technical field of most in 21 century development of world economy.Come out from first piece of monocrystaline silicon solar cell in 1954, people have been sent in very large hope to utilizing semiconductor solar cell to solve energy crisis.As far back as " six or five ", the Chinese government just lists State Commission for Restructuring the Economic Systems in research and development solar energy and renewable energy technologies, greatly promote the development of China's solar energy and renewable energy technologies and industry, and in recent years, new forms of energy are also studied as primary study funded projects by " 15 " and " 863 " plan etc. of China.
Present various forms of solar cell is come out one after another, according to the difference of material therefor, solar cell can be divided into silicon system solar cell, multi-element compounds thin-film solar cells, polymer multi-layer modified electrode type battery and nanocrystalline chemical solar cell etc.Take polysilicon solar cell as the silica-based solar cell of main flow, cost of material is high, complex manufacturing, and material itself is unfavorable for reducing costs, and which has limited its civil nature; Multi-element compounds thin-film solar cells relates to some rare metals or poisonous and harmful substances, limits its application; Polymer multi-layer modified electrode type battery is also in development at present, and it is short that its maximum deficiency is exactly the life-span.Nano-crystalline photoelectric chemistry solar cell (Nanocrystalline Photoelectrochemical Cells, be called for short NPC battery) also known as
type battery or sensitization solar battery are a kind of novel ceramic base photochemistry solar cells.Lausanne, SUI senior engineer (EPFL) in 1991
professors etc., by the sensitized meso-porous TiO of bipyridine complex of ruthenium (II)
2film light anode, obtains the photoelectric conversion efficiency of 7%, from then on opens the frontier of NPC battery.This battery has the advantages such as the simple and high-photoelectric transformation efficiency of low cost, environmental protection, manufacture craft, under the condition of AM1.0, highest energy transformation efficiency reaches 11.18%, and has the potential advantages raised the efficiency further and reduce costs, and is considered to likely substituted for silicon system battery.The domestic research work also in succession having carried out NPC battery in recent years, and achieve certain achievement, but still there is gap on the whole with abroad.
NPC battery is primarily of the porous type semiconductor TiO of broad-band gap
2or one-dimensional nano structure ZnO etc., sensitizing layer and liquid electrolyte or p-type semiconductor composition.In the brilliant DSSC of Conventional nano, adopt TiO more
2porous membrane, utilizes the specific area that it is higher, adsorbs a large amount of dyestuff, improves sunlight utilance.But, TiO
2porous membrane in there is a large amount of surface states, these surface state energy levels are positioned among forbidden band, form trap, fetter electronics motion in the film, added the transmission time of electronics, also increase the probability of electronics and electrolyte compound simultaneously, add dark current, thus reduce TiO
2the efficiency that battery is total.Therefore, be necessary explore other semiconductor anode side material of use or adopt new structure to make NPC battery.
Be expected to replace TiO
2a kind of semi-conducting material be ZnO.ZnO has and TiO
2similar level structure, can meet the requirement for level-density parameter of dye molecule or inorganic semiconductor absorbed layer equally.During the light anode of the ZnO nanorod that conductive substrates grows as NPC battery, substantially increase light absorption path, electronics is directly transferred to external electrode by the monocrystal rod without interface, avoids TiO
2the electric transmission occurred in porous membrane is will through repeatedly TiO
2jump between granular boundary, can accelerate the separation of photo-generate electron-hole, reduces its compound, thus improves the utilance of photo-generated carrier, increases the efficiency of NPC battery.At present, the efficiency of the NPC battery being light anode material with one-dimentional structure ZnO semiconductor and ideal value also have certain gap, this is mainly because the pH of ZnO stable existence is 7 ~ 12, therefore deposit in case at some acid dyes, ZnO can by corrosion to a certain extent, in addition, the electronics being injected into ZnO also can have compound to a certain degree with dyestuff or electrolyte.The main method that people overcome this difficulty is that making ZnO contacts with dyestuff or the direct of electrolyte to avoid ZnO with the core-shell structure of some other semi-conducting material.CuInS
2i-III-VI
2compound semiconductor, has yellow copper structure, and absorption coefficient is up to 10
5cm
-1, energy gap is 1.53eV, with the optimal absorption scope of sunlight relatively, it is also a kind of environmentally friendly semi-conducting material simultaneously, is applicable to the absorbed layer or the sensitizer that make solar cell.ZnO/CuInS
2nuclear shell structure nano rod film can avoid ZnO to be corroded due to direct contact the with dyestuff or electrolyte, and the potential barrier between nucleocapsid structure can suppress electron-hole recombination reaction, meanwhile, utilizes CuInS
2character, the absorption of light anode to sunlight can be increased, too increase the absorption of light anode to sunlight in visible wavelength range simultaneously, significantly improve the efficiency of NPC battery.
The subject matter of current existence is: with traditional TiO
2light anode material is compared, during the light anode of the ZnO nano-rod array that conductive substrates grows as NPC battery, substantially increase light absorption path, electronics is directly transferred to external electrode by the monocrystal rod without interface, the separation of photo-generate electron-hole can be accelerated, reduce its compound, improve the utilance of photo-generated carrier, thus increase the efficiency of NPC battery.But the pH of ZnO stable existence is 7 ~ 12, therefore deposits in case at some acid dyes or electrolyte, can by corrosion to a certain extent, in addition, the electronics being injected into ZnO also can have compound to a certain degree with dyestuff or electrolyte.In order to optimize One-Dimensional ZnO nano-rod film structure further, improve its photoelectric properties, the present invention, to improve the photovoltaic performance of NPC solar cell for final purpose, adopts medium template switch legal system for high-quality NPC battery ZnO/CuInS
2nuclear shell structure nano rod film, this method preparation technology is simple, can regulate and control again, utilize ZnO/CuInS to the stuctures and properties of film
2nucleocapsid structure avoids ZnO to be corroded due to direct contact the with dyestuff or electrolyte, and the potential barrier between nucleocapsid structure can suppress electron-hole recombination reaction, meanwhile, utilizes CuInS
2character, the absorption of light anode to sunlight can be increased, too increase the absorption of the sunlight to visible wavelength range simultaneously.
Summary of the invention
The object of the invention is to propose a kind of making ZnO/CuInS
2the preparation method of nuclear shell structure nano rod film and related process parameters.
A kind of applicable making ZnO/CuInS
2the method of nuclear shell structure nano rod film.This preparation method is medium template switch method.First, hydro thermal method is adopted, with zinc nitrate (Zn (NO
3)
2)/hexamethylenetetramine (HMT) aqueous solution is growth system, growing ZnO nanorod on ITO electro-conductive glass; Then carry out water-bath with thioacetamide (TAA) for reaction reagent, obtain ZnO/ZnS nuclear shell structure nano rod film; Then, by gained sample at copper nitrate (Cu (NO
3)
2) triethylene glycol (TEG) solution in leave standstill a period of time obtain ZnO/CuS nuclear shell structure nano rod film medium template; Finally, gained sample is put into inidum chloride (InCl
3) TEG solution, in water heating kettle, carry out high-temperature water thermal response, ZnO/CuInS can be obtained at ITO conductive glass surface
2nuclear shell structure nano rod film.
The mechanism of action of the present invention is: in the process of aqueous solution growth ZnO nanorod film, because the interface energy between ZnO and substrate is less than the interface energy between ZnO and the aqueous solution, so first ZnO tends to heterogeneous nucleation on the interface between substrate and solution.Interfacial tension between nucleating point and solion depends on the matching degree of nucleating point and precipitated phase structure, and because the substrate adopted when growing the brilliant array of ZnO rod there has been the ZnO Seed Layer of crystallization, so substrate and generation product have identical crystal structure, contribute to ZnO nanorod in crystal seed face along the epitaxial growth of c-axis preferred orientation, finally obtain ZnO nanorod film at ITO conductive glass surface.In the preparation process of ZnO/ZnS nuclear shell structure nano rod film, after gained ZnO nanorod film is put into thioacetamide reaction solution, thioacetamide is hydrolyzed, and decomposites H
2s, in water, electrolysis goes out S
2-.Because the content of ZnS in water amasss constant lower than ZnO, therefore the S in solution
2-can react with ZnO, at the Surface Creation ZnS of ZnO nanorod, thus obtain ZnO/ZnS nuclear shell structure nano rod film medium template.In the preparation process of ZnO/CuS nuclear shell structure nano rod film, gained ZnO/ZnS nuclear shell structure nano rod film medium template is put into the triethylene glycol solution of copper nitrate, the content of CuS amass constant comparatively ZnS be much smaller, so ZnO shell can be converted into CuS, and then obtain ZnO/CuS nuclear shell structure nano rod film medium template.At ZnO/CuInS
2in the preparation process of nuclear shell structure nano rod film, gained ZnO/CuS nuclear shell structure nano rod film medium template is put into the triethylene glycol solution of inidum chloride, at high temperature, through the reduction process of polyalcohol, a carboxyl of triethylene glycol can provide two H to become aldehyde radical.H can provide an electronics and be converted into H
+, bivalent cupric ion can obtain an electronics and be converted into univalent copper ion, at In
3+deposit and obtain required CuInS in case
2, thus obtain required ZnO/CuInS
2nuclear shell structure nano rod film.ZnO/CuInS
2nucleocapsid structure can avoid ZnO to be corroded due to direct contact the with dyestuff or electrolyte, and meanwhile, the potential barrier between nucleocapsid structure can suppress electron-hole recombination reaction, reduces dark current, in addition, utilizes CuInS
2character, the absorption of light anode to sunlight can be increased, too increase the absorption of the sunlight to visible wavelength range simultaneously, thus increase photoelectric current.
The present invention also proposes the related process parameters of above-mentioned preparation method, specific as follows:
The preparation of ZnO nanorod film preparation: zinc acetate addition is 3.295g, the addition of EGME is 50mL, the addition of monoethanolamine is 1.43g, and whipping temp is 50 DEG C, and mixing time is 2h, pull rate is 6cm/min, dip time is 20S, and membrane number of times is 2 times, and interval time is 20min, heat treatment temperature is 400 DEG C, and the time is 1h.Nitric acid zinc concentration is 0.05 ± 0.01mol/L, and the mol ratio of zinc nitrate and hexamethylenetetramine is 1: 1, and hydrothermal system hydrothermal temperature is 90 ± 2 DEG C, and the hydro-thermal time is 4h.The preparation of ZnO/ZnS core-shell nano rod film: the concentration of thioacetamide is 0.02 ~ 0.05 ± 0.005mol/L, and bath temperature is 90 ± 2 DEG C, and water bath time is 7 ± 0.5h.The preparation of ZnO/CuS core-shell nano rod film: the concentration of copper nitrate is 0.05 ± 0.005mol/L, and time of repose is 6 ± 0.5h.ZnO/CuInS
2the preparation of core-shell nano rod film: the concentration of inidum chloride is 0.001 ~ 0.002 ± 0.0005mol/L, and dwell temperature is 200 ± 5 DEG C, and time of repose is 2 ~ 4 ± 0.5h.
Feature of the present invention:
1, medium template switch method technical process is comparatively simple, is easy to realize, and is convenient to control.
2, ZnO/CuInS
2the diameter of nuclear shell structure nano rod is easy to control, CuInS
2the thickness of shell is adjustable.
3, the ZnO/CuInS that diameter can change can be obtained
2nuclear shell structure nano rod film, improves its photoelectric characteristic.
The using method of this preparation technology is as follows:
1, the technological parameter of typical ZnO nanorod film preparation: zinc acetate addition is 3.295g, the addition of EGME is 50mL, the addition of monoethanolamine is 1.43g, magnetic agitation temperature is 50 DEG C, mixing time is 2h, membrane pull rate is 6cm/min, dip time is 20S, and membrane number of times is 2 times, and interval time is 20min, heat treatment temperature is 400 DEG C, heat treatment time is 1h, and nitric acid zinc concentration is 0.05mol/L, and the mol ratio of zinc nitrate and hexamethylenetetramine is 1: 1, hydrothermal temperature is 90 DEG C, and the hydro-thermal time is 4h.
2, the technological parameter of typical ZnO/ZnS core-shell nanometer rod film preparation: the concentration of thioacetamide is 0.05mol/L, and hydrothermal temperature is 90 DEG C, and the hydro-thermal time is 7h.
3, the technological parameter of typical ZnO/CuS core-shell nanometer rod film preparation: the concentration of copper nitrate is 0.05mol/L, and time of repose is 6h.
4, typical ZnO/CuInS
2the technological parameter of core-shell nanometer rod film preparation: the triethylene glycol solution concentration of inidum chloride is 0.0015mol/L, and dwell temperature is 200 DEG C, and time of repose is 3h.
5, the process parameters range of wherein ZnO nanorod film preparation: in zinc nitrate/hexamethylenetetramine hydrothermal system, nitric acid zinc concentration is 0.05 ± 0.01mol/L, the mol ratio of zinc nitrate and hexamethylenetetramine is 1: 1, and bath temperature is 90 ± 2 DEG C, and water bath time is 4h
6, the process parameters range of wherein ZnO/ZnS core-shell nanometer rod film preparation: the concentration of thioacetamide is 0.02 ~ 0.05 ± 0.005mol/L, and bath temperature is 90 ± 2 DEG C, and water bath time is 7 ± 0.5h.
7, the process parameters range of wherein ZnO/CuS core-shell nano rod film: the concentration of copper nitrate is 0.05 ± 0.005mol/L, and time of repose is 6 ± 0.5h.
8, wherein ZnO/CuInS
2the process parameters range of core-shell nano rod film: the triethylene glycol solution concentration of inidum chloride is 0.001 ~ 0.002 ± 0.0005mol/L, and dwell temperature is 200 ± 10 DEG C, and time of repose is 2 ~ 4 ± 0.5h.
9, preparation process presses preceding method.
Embodiment
The invention is further illustrated by the following examples.
Embodiment
The preparation of required solution (colloidal sol): taking zinc acetate addition is 3.295g, joins in 50mL EGME, adds 1.43g monoethanolamine, stirs 2h and obtain required Seed Layer colloidal sol at 50 DEG C; Get zinc nitrate (Zn (NO
3)
2)/hexamethylenetetramine (HMT) mol ratio is 1: the 1 aqueous solution growth system obtaining that concentration is 0.05mol/L; 0.05mol/L thioacetyl amine aqueous solution needed for preparation making ZnO/ZnS nanometer rods nucleocapsid structure film medium template; Get 1mmol copper nitrate to join in 20mL triethylene glycol and join produce solution needed for ZnO/CuS nano-rod film medium template; Get 0.03mmolL inidum chloride to join in 20mL triethylene glycol and join to obtain making ZnO/CuInS
2solution needed for nano-rod film.Film forming procedure: get clean clean ITO electro-conductive glass membrane in colloidal sol, pull rate is 6cm/min, and dip time is 20S, and membrane number of times is 2 times, interval time is 20min, after membrane, ITO electro-conductive glass is obtained ZnO Seed Layer after heat treatment 1h at 400 DEG C; In zinc nitrate/hexamethylenetetramine system, at 90 DEG C, water-bath grows 4h; In thioacetyl amine aqueous solution at 90 DEG C water-bath 7h; Under normal temperature, 6h is left standstill in the triethylene glycol solution of copper nitrate; At 200 DEG C, 3h is left standstill in the triethylene glycol solution of inidum chloride.
Prepare by preceding method.
The ZnO/CuInS that diameter is about 200nm can be obtained
2nuclear shell structure nano rod film.
Claims (5)
1. making ZnO/CuInS
2the method of nuclear shell structure nano rod film, is characterized in that, described preparation method is medium template switch method: first, adopts hydro thermal method, with zinc nitrate (Zn (NO
3)
2)/hexamethylenetetramine (HMT) aqueous solution is growth system, growing ZnO nanorod on ITO electro-conductive glass; Then carry out water-bath with thioacetamide (TAA) for reaction reagent, obtain ZnO/ZnS nuclear shell structure nano rod film; Then, by gained sample at copper nitrate (Cu (NO
3)
2) triethylene glycol (TEG) solution in leave standstill a period of time obtain ZnO/CuS nuclear shell structure nano rod film medium template; Finally, gained sample is put into inidum chloride (InCl
3) TEG solution, in water heating kettle, carry out high-temperature water thermal response, ZnO/CuInS can be obtained at ITO conductive glass surface
2nuclear shell structure nano rod film.
2. making ZnO/CuInS according to claim 1
2the method of nuclear shell structure nano rod film, it is characterized in that detailed process and the technological parameter of making ZnO nanometer rods are as follows: joined by 3.295g zinc acetate in 50mL EGME solution, and add 1.43g monoethanolamine, 2h is stirred at 50 DEG C of lower magnetic forces, obtained required colloidal sol, by clean clean ITO electro-conductive glass membrane twice in colloidal sol, pull rate is 6cm/min, dip time is 20s, interval time is 20min, and the ITO electro-conductive glass after membrane is obtained ZnO Seed Layer after heat treatment 1h at 400 DEG C; Then, at zinc nitrate (Zn (NO
3)
2in)/hexamethylenetetramine (HMT) aqueous solution growth system, water-bath growth obtains ZnO nanorod, in this aqueous solution growth system, nitric acid zinc concentration is 0.05 ± 0.01mol/L, the mol ratio of zinc nitrate and hexamethylenetetramine is 1: 1, bath temperature is 90 ± 2 DEG C, and water bath time is 4h.
3. making ZnO/CuInS according to claim 1
2the method of nuclear shell structure nano rod film, it is characterized in that detailed process and the related process parameters of making ZnO/ZnS core shell structural nano rod film are as follows: thioacetamide (TAA) solution being (0.02 ~ 0.05) ± 0.005mol/L by the obtained downward-sloping immersion concentration of ZnO nanorod conducting surface carries out water-bath, bath temperature is 90 ± 2 DEG C, and water bath time is 7 ± 0.5h.
4. making ZnO/CuInS according to claim 1
2the method of nuclear shell structure nano rod film, it is characterized in that detailed process and the related process parameters of making ZnO/CuS nuclear shell structure nano rod film are as follows: by obtained ZnO/ZnS medium template, conducting surface is downward-sloping puts into the triethylene glycol solution that concentration is 0.05 ± 0.005mol/L copper nitrate, in left at room temperature 6 ± 0.5h.
5. making ZnO/CuInS according to claim 1
2the method of nuclear shell structure nano rod film, is characterized in that making ZnO/CuInS
2detailed process and the related process parameters of nuclear shell structure nano rod film are as follows: by obtained ZnO/CuS medium template, the downward-sloping triethylene glycol solution put into concentration and be (0.001 ~ 0.002) ± 0.0005mol/L inidum chloride of conducting surface, in water heating kettle, at 200 ± 5 DEG C, leave standstill (2 ~ 4) ± 0.5h, obtain the ZnO/CuInS of diameter about 150 ~ 250nm
2nuclear shell structure nano rod film.
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| CN104638064A (en) * | 2015-01-26 | 2015-05-20 | 西南交通大学 | Preparation method of ZnO-CuInS2 heterogeneous core-shell structure nanorod array |
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| CN106390979A (en) * | 2016-09-28 | 2017-02-15 | 陕西科技大学 | Preparation method of supported ZnO nano array photocatalysts |
| CN107723686B (en) * | 2017-09-20 | 2020-03-17 | 南京航空航天大学 | Method and equipment for preparing ZnO crystal film |
| CN110201681A (en) * | 2018-09-30 | 2019-09-06 | 湖北工业大学 | A kind of preparation method of air cleaning ZnO/CuS/Ag catalysis material |
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