CN109802011A - A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air - Google Patents
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air Download PDFInfo
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- CN109802011A CN109802011A CN201910064971.5A CN201910064971A CN109802011A CN 109802011 A CN109802011 A CN 109802011A CN 201910064971 A CN201910064971 A CN 201910064971A CN 109802011 A CN109802011 A CN 109802011A
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Abstract
The present invention discloses a kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air.This method is by CuO, ZnO and SnO2Mixed slurry be coated in the glass substrate that cleans up, form oxide precursor film；Then oxide precursor film and sulphur powder are sealed in air environment in the container of resistance to vulcanization reaction；Finally the container after sealing is put into tube furnace or Muffle furnace, heating is made annealing treatment, and the copper-zinc-tin-sulfur film is obtained.The method of the present invention has many advantages, such as that high temperature vulcanized annealing process is simple, Preparation equipment is cheap, sulphur powder utilization rate of raw materials is high, environmentally protective, is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to solar cell materials and device arts, and in particular to vulcanization annealing preparation in a kind of air
The method of copper-zinc-tin-sulfur film.
Background technique
As world population growth and environmental pollution are increasing to the pressure of the energy, energy problem increasingly causes people
Concern.Therefore it finds and a kind of clean reproducible new energy and be particularly important to substitute traditional fossil energy.It compares
In other renewable energy, solar energy has many advantages, such as source universal, safety non-pollution, long-term renewable, naturally at
For a kind of more appropriate alternative energy.And solar battery is that a kind of have efficacious prescriptions for what solar energy was directly translated into electric energy
Formula.
In numerous solar batteries, compound film solar battery as a kind of low cost solar battery in recent years
Obtain vast development.Copper indium gallium selenide series thin film solar battery is as one of more successful compound film sun
Energy battery, is commercially used and produces.Further develop however, expensive indium gallium limits it.Copper-zinc-tin-sulfur has as one kind
It hopes the absorption layer material for replacing CIGS thin-film, is just causing the extensive concern of people.It has suitable band gap (1.5eV),
Higher absorption coefficient (105cm-1), the advantages that theoretical conversion efficiencies are high and raw material sources are abundant.
Currently, the method for preparing copper-zinc-tin-sulfur film mainly includes vacuum method and antivacuum method.In order to obtain high quality
Copper-zinc-tin-sulfur film, these two kinds of methods all will inevitably introduce vulcanization annealing.High temperature vulcanized annealing can promote film brilliant
Grain growth reduces film defects, improves solar battery efficiency.Currently, according to the difference of sulphur source can be divided into hydrogen sulfide gas and
The vulcanization annealing of solid-state sulphur powder.Annealing has preferable reactivity in hydrogen sulfide atmosphere, but hydrogen sulfide has toxicity, large-scale
Produce the problems such as there are security risk and exhaust emissions.Annealing, which refers to, in sulphur steam forms it into steaming by heating solid-state sulphur powder
Vapour pressure, then react to form copper-zinc-tin-sulfur with precursor thin film.After pyroreaction, sulphur steam can condense to form solid-state again
Sulphur.Therefore, sulphur powder vulcanization have the advantages that safe and non-toxic, inexpensive, be easy to large-scale production etc. it is a variety of, obtained more concerns
And research.
It finds through being retrieved to prior art Patent Application Publication, copper-zinc-tin-sulfur film is carried out as sulphur source using solid-state sulphur
The patent application of annealing aspect has very much, such as obtains fine and close copper-zinc-tin-sulfur precursor thin-film using electro-deposition plated film, then will
The precursor thin-film and 100~2000mg sulphur powder, which are placed under vacuum condition, carries out vulcanization annealing, obtains the copper-zinc-tin-sulfur
It absorbs layer film (application number 201410021101.7)；For another example first using polynary target double target co-sputtering preparation copper and tin sulphur and zinc sulphide
Preformed layer then carries out preformed layer and carries out alloy treatment, the preformed layer Jing Guo alloy treatment is finally put into vulcanizing oven in normal pressure
Copper-zinc-tin-sulfur film (application is obtained after carrying out vulcanization annealing (570 ~ 590 DEG C, 25 ~ 35 minutes) and natural cooling under nitrogen protection
Number 201510612081.5).Meanwhile by retrieval existing literature discovery, currently employed solid sulphur powder vulcanization prepares copper-zinc-tin-sulfur
Film is to be placed in sample in vacuum or inert atmosphere with sulphur powder to anneal.The Cu/Sn/Zn that such as thermal evaporation is obtained
Laminate film is put into nitrogen protection atmosphere, and it is thin to carry out 560 °C of vulcanizations 2 hours available copper-zinc-tin-sulfurs of annealing to it using sulphur powder
Film (517 (2008) 1457-1460 of Thin Solid Films)；For another example oxide nano particles precursor film and sulphur powder is same
When be put into vacuum tube furnace, using vacuum pump obtain 1Pa background vacuum, finally make under vacuum conditions sulphur steam and oxidation
Object forerunner film reaction and obtain copper-zinc-tin-sulfur film (276 (2015) 145-152 of Journal of Power Sources).
However, existing solid-state sulphur powder vulcanization annealing technology all refers to vacuum or inert atmosphere (nitrogen or argon gas), to moving back
The requirement of fiery equipment is high, cost costly, be unfavorable for the large-scale production of copper-zinc-tin-sulfur film.
Summary of the invention
The purpose of the present invention is to provide it is a kind of it is easy to operate, annealing can be vulcanized in air and prepare copper-zinc-tin-sulfur
(Cu2ZnSnS4) film method.This method is with inexpensive oxide nano particles, i.e. CuO, ZnO and SnO2Mixed slurry
For presoma, uniform, high quality solar battery obsorbing layer copper-zinc-tin-sulfur film is prepared by annealing by vulcanizing in air.
To achieve the above object, the technical scheme adopted by the invention is that:
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air, comprising the following steps:
1) by CuO, ZnO and SnO2Mixed slurry be coated in the glass substrate that cleans up, form oxide precursor film；
2) above-mentioned oxide precursor film and sulphur powder are sealed in the container of resistance to vulcanization reaction in air environment；
3) container after sealing is put into tube furnace or Muffle furnace, heating is made annealing treatment, and the copper zinc-tin is obtained
Sulphur film.
The molar ratio of element in mixed slurry described in step 1) are as follows: n (Cu)/n (Sn+Zn)=0.8, n (Zn)/n (Sn)=
1.2。
The concentration of mixed slurry described in step 1) is 200-220mg/ml.
The method of coating described in step 1) is knife scraping method or spin-coating method, and oxide precursor film thickness is 1 ~ 5 micron.
Glass substrate described in step 1) is plating molybdenum glass substrate or soda-lime glass substrate, and the glass substrate is by following pre-
Processing: will plating molybdenum glass successively immerse conventional detergent, deionized water, ethyl alcohol, in acetone soln, then with deionized water ultrasound
And it rinses well.
The container of resistance to vulcanization reaction described in step 2 be quartz glass tube or stainless steel tube, internal diameter be 1 ~ 5cm, length be 5 ~
25cm。
The minimum usage amount of sulphur powder described in step 2 is depending on the container volume of resistance to vulcanization reaction.
Annealing temperature described in step 3) is 400~600 DEG C, and annealing time is 10min~300min.
Annealing process described in step 3), oxide precursor film are begun to warm up from room temperature simultaneously with sulphur powder, heating rate 40-
50℃/min
The invention adopts the above technical scheme, with annealing process is simple, equipment is uncomplicated, low raw-material cost, material use
The advantages that rate is high is suitable for large-scale industrial production.The principle of the present invention is:
1) oxide precursor film and solid-state sulphur powder are sealed in a container in air environment, keep it complete with external environment
Isolation manufactures anaerobic, water-less environment without using vacuum pump or inert atmosphere in this process.
2) sealing system is heated to high temperature, since sulphur can distil at 120 DEG C or more, obtained sulphur steam can preferentially with sky
21% oxygen reaction in gas generates sulfur dioxide, and sulfur dioxide can be considered as inert gas in subsequent sulfidation.Except this
Except, remaining 78% nitrogen is inert gas in air, this is made high temperature vulcanized to be able to carry out completely and obtain high-quality copper zinc
Tin sulphur film.
The present invention has following prominent the utility model has the advantages that the invention proposes a kind of at low cost, simple words of preparation process
Vulcanize the method for obtaining copper-zinc-tin-sulfur film in air atmosphere.It is reported according to Patents documents, other to prepare copper-zinc-tin-sulfur thin
The method for annealing of film usually requires to carry out under high vacuum environment or inert atmosphere, and process is complicated, and required equipment is expensive.Therefore
Present invention employs being vulcanized in simple closed air atmosphere, it is thin to obtain solar battery obsorbing layer copper-zinc-tin-sulfur
Film specifically has the beneficial effect that the following: 1) present invention is for the first time in air using confined space to oxide precursor
It carries out high temperature vulcanized annealing and obtains copper-zinc-tin-sulfur film；2) vulcanization has both sides benefit in air atmosphere: first, being sulphur
Annealing device is without expensive high-vacuum equipment；Second, the sulphur powder in closed container can be recycled, it is pollution-free.
Detailed description of the invention
With reference to the accompanying drawing, the invention will be further described.
Fig. 1 is the sealing quartz glass device of 1 air cure of the embodiment of the present invention.
Fig. 2 is the XRD diagram of copper-zinc-tin-sulfur film prepared by the embodiment of the present invention 1.
Fig. 3 is the SEM figure of copper-zinc-tin-sulfur film prepared by the embodiment of the present invention 1.
Specific embodiment
In order to which present invention may be better understood, now the present invention is described further by way of examples.
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air, comprising the following steps:
1) glass substrate is successively immersed conventional detergent, deionized water, ethyl alcohol, in acetone soln, it is then super with deionized water
Sound is simultaneously rinsed well, spare；
By CuO, ZnO and SnO2Mixed slurry (concentration 200-220mg/ml, n (Cu)/n (Sn+Zn)=0.8, n (Zn)/n
(Sn)=1.2 it) is coated in above-mentioned glass substrate by knife scraping method or spin-coating method, forms the oxide precursor with a thickness of 1 ~ 5 micron
Film；
2) above-mentioned oxide precursor film and sulphur powder are sealed in internal diameter in air environment is 1 ~ 5cm, and length is the stone of 5 ~ 25cm
In English glass tube or stainless steel tube；
3) container after sealing is subjected to the high temperature anneal, selects tube furnace or Muffle furnace for heating source, before making oxide
It drives film to start to warm up from room temperature simultaneously with sulphur powder, heating rate is 40-50 DEG C/min, is eventually held in 400~600 DEG C, heat preservation
10~300min is then slowly cooled to room temperature, and obtains the copper-zinc-tin-sulfur film.
The chemical reagent involved in the present invention arrived is purchased in Chinese medicines group chemical reagents corporation, sulphur powder buying in
Aladdin Chemistry co.ltd plates molybdenum glass or soda-lime glass buying in scientific and technological (Ningbo) Co., Ltd of raw Yangxin material
With Luoyang Long Yao Glass Co., Ltd..
Embodiment 1
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air:
1, plating molybdenum glass substrate is successively immersed into conventional detergent, deionized water, ethyl alcohol, in acetone soln, then deionized water
Ultrasound is simultaneously rinsed well, by CuO, ZnO and SnO2Mixed slurry (concentration 200mg/ml, n (Cu)/n (Sn+Zn)=0.8, n
(Zn)/n (Sn)=1.2)) it is coated on by knife scraping method and plates molybdenum glass surface, obtain oxide precursor film；
2, above-mentioned oxide precursor film and 0.3g sulphur powder be sealed in internal diameter is 2.5cm, length is 15cm's in air environment
In quartz ampoule；
3, high-temperature heat treatment will be carried out after the quartzy seal of tube, selects tube furnace for heating source, keep sulphur powder and oxide precursor film same
When started to warm up from room temperature, 40 DEG C/min of heating rate is eventually held in 580 DEG C, keeps the temperature 30min, then progressively cools to room
Wen Hou obtains copper-zinc-tin-sulfur film.
Film manufactured in the present embodiment is tested using XRD, figure it is seen that film obtained is pure phase
Copper-zinc-tin-sulfur；Film manufactured in the present embodiment is tested using SEM, from figure 3, it can be seen that copper-zinc-tin-sulfur obtained is thin
Film densification is smooth, uniformity is high.
Embodiment 2
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air:
1, soda-lime glass substrate is successively immersed into conventional detergent, deionized water, ethyl alcohol, in acetone soln, then deionized water
Ultrasound is simultaneously rinsed well, by CuO, ZnO and SnO2Mixed slurry (concentration 200mg/ml, n (Cu)/n (Sn+Zn)=0.8, n
(Zn)/n (Sn)=1.2)) pass through knife scraping method coated on soda-lime glass surface, obtain oxide precursor film；
2, above-mentioned oxide precursor film and 0.2g sulphur powder are sealed in the stone that internal diameter is 2cm, length is 10cm in air environment
In English pipe；
3, high-temperature heat treatment will be carried out after the above-mentioned quartzy seal of tube, selects tube furnace for heating source, makes sulphur powder and sull
It is started to warm up simultaneously from room temperature, 40 DEG C/min of heating rate, is eventually held in 530 DEG C, kept the temperature 60min, then progressively cool to
After room temperature, copper-zinc-tin-sulfur film is obtained.
Embodiment 3
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air:
1, plating molybdenum glass substrate is successively immersed into conventional detergent, deionized water, ethyl alcohol, in acetone soln, then deionized water
Ultrasound is simultaneously rinsed well, by CuO, ZnO and SnO2Mixed slurry (concentration 200mg/ml, n (Cu)/n (Sn+Zn)=0.8, n
(Zn)/n (Sn)=1.2)) it is coated on by knife scraping method and plates molybdenum glass surface, obtain oxide precursor film；
2, above-mentioned oxide precursor film and 0.6g sulphur powder are sealed in the stone that internal diameter is 3cm, length is 25cm in air environment
In English pipe；
3, high-temperature heat treatment will be carried out after the above-mentioned quartzy seal of tube.It selects tube furnace for heating source, makes sulphur powder and sull
It is started to warm up simultaneously from room temperature, 40 DEG C/min of heating rate, is eventually held in 600 DEG C, kept the temperature 120min, then progressively cool to
After room temperature, copper-zinc-tin-sulfur film is obtained.
Embodiment 4
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air:
1, plating molybdenum glass substrate is successively immersed into conventional detergent, deionized water, ethyl alcohol, in acetone soln, then deionized water
Ultrasound is simultaneously rinsed well, by CuO, ZnO and SnO2Mixed slurry (concentration 200mg/ml, n (Cu)/n (Sn+Zn)=0.8, n
(Zn)/n (Sn)=1.2)) it is coated on by knife scraping method and plates molybdenum glass surface, obtain oxide precursor film；
2, above-mentioned oxide precursor film and 0.6g sulphur powder are sealed in the stone that internal diameter is 3cm, length is 25cm in air environment
In English pipe；
3, high-temperature heat treatment will be carried out after the above-mentioned quartzy seal of tube.It selects tube furnace for heating source, makes sulphur powder and sull
It is started to warm up simultaneously from room temperature, 5 DEG C/min of heating rate, is eventually held in 400 DEG C, kept the temperature 300min, then progressively cool to
After room temperature, copper-zinc-tin-sulfur film is obtained.
Embodiment 4
A kind of method that vulcanization annealing prepares copper-zinc-tin-sulfur film in air:
1, plating molybdenum glass substrate is successively immersed into conventional detergent, deionized water, ethyl alcohol, in acetone soln, then deionized water
Ultrasound is simultaneously rinsed well, by CuO, ZnO and SnO2Mixed slurry (concentration 220mg/ml, n (Cu)/n (Sn+Zn)=0.8, n
(Zn)/n (Sn)=1.2)) it is coated on by knife scraping method and plates molybdenum glass surface, obtain oxide precursor film；
2, above-mentioned oxide precursor film and 0.5g sulphur powder are sealed in the stone that internal diameter is 3cm, length is 25cm in air environment
In English pipe；
3, high-temperature heat treatment will be carried out after the above-mentioned quartzy seal of tube.It selects tube furnace for heating source, makes sulphur powder and sull
It is started to warm up simultaneously from room temperature, 5 DEG C/min of heating rate, is eventually held in 600 DEG C, kept the temperature 10min, then progressively cool to room
Wen Hou obtains copper-zinc-tin-sulfur film.
Claims (8)
1. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air, it is characterised in that: it includes the following steps
1) by CuO, ZnO and SnO2Mixed slurry be coated in the glass substrate that cleans up, form oxide precursor film；
2) above-mentioned oxide precursor film and sulphur powder are sealed in the container of resistance to vulcanization reaction in air environment；
3) container after sealing is put into tube furnace or Muffle furnace, heating is made annealing treatment, and the copper zinc-tin is obtained
Sulphur film.
2. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air according to claim 1, it is characterised in that:
The molar ratio of element in mixed slurry described in step 1) are as follows: n (Cu)/n (Sn+Zn)=0.8, n (Zn)/n (Sn)=1.2.
3. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air according to claim 1, it is characterised in that:
The concentration of mixed slurry described in step 1) is 200-220mg/ml.
4. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air according to claim 1, it is characterised in that:
The method of coating described in step 1) is knife scraping method or spin-coating method, and oxide precursor film thickness is 1 ~ 5 micron.
5. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air according to claim 1, it is characterised in that:
Glass substrate described in step 1) is plating molybdenum glass substrate or soda-lime glass substrate, and the glass substrate is by following pretreatment: will
Plating molybdenum glass successively immerses conventional detergent, deionized water, ethyl alcohol, in acetone soln, then with deionized water ultrasound and rinses
Completely.
6. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air according to claim 1, it is characterised in that:
The container of resistance to vulcanization reaction described in step 2 is quartz glass tube or stainless steel tube, and internal diameter is 1 ~ 5cm, and length is 5 ~ 25cm.
7. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air according to claim 1, it is characterised in that:
Annealing temperature described in step 3) is 400~600 DEG C, and annealing time is 10min~300min.
8. vulcanizing the method that annealing prepares copper-zinc-tin-sulfur film in a kind of air according to claim 7, it is characterised in that:
Annealing process described in step 3), oxide precursor film are begun to warm up from room temperature simultaneously with sulphur powder, heating rate be 40-50 DEG C/
min。
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| CN114988715A (en) * | 2022-05-25 | 2022-09-02 | 中南大学 | Preparation method of copper-zinc-tin-sulfur film |
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| CN109802011B (en) | 2020-10-16 |
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