CN105977334B - A kind of preparation method of stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film - Google Patents
A kind of preparation method of stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film Download PDFInfo
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- CN105977334B CN105977334B CN201610527980.XA CN201610527980A CN105977334B CN 105977334 B CN105977334 B CN 105977334B CN 201610527980 A CN201610527980 A CN 201610527980A CN 105977334 B CN105977334 B CN 105977334B
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Abstract
The invention discloses a kind of preparation method of stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film, the Sn of different-thickness is first sputtered on FTO electro-conductive glass with magnetic control sputtering device, weigh different amounts of sulphur powder, vulcanization obtains SnS in tube furnace2, respectively washed 3 times with absolute ethyl alcohol, distilled water, it is vacuum dried.Again with magnetic control sputtering device in SnS2Sn is sputtered on electro-conductive glass, vacuum-sintering in tube furnace is placed on, target product is obtained.The method of this law magnetron sputtering obtains the Sn of densification, sinters obtain target product by solid phase reaction under vacuo.This method is simple to operate, environmentally safe, and reaction time is short, forms fine and close film.
Description
Technical field
The invention belongs to semiconductor optoelectronic transition material and inorganic solar cell field, relate generally to one kind and can be used for nothing
The preparation method of the stannic disulfide of machine solar cell/trisulfides two tin/stannous sulfide hetero-junction thin-film.
Background technology：
In the last few years, with fossil energy and the increasingly depleted of non-renewable energy resources, the world is just being absorbed in an energy crisis,
Actively finding regenerative resource to substitute fossil energy in various countries.Scientists are used in the various new energy of searching,
It is wherein the most extensive with the research to solar energy, it is the preferred material of new energy because solar energy is inexhaustible, nexhaustible,
The very big concern of various countries researcher is especially received with the research of solar cell and application in the utilization form of solar energy.
In recent years, inorganic nano-crystal hetero-junction thin-film solar cell causes the broad interest of researcher.And tin sulfide is a kind of
Inexpensively, free of contamination semi-conducting material, and sulphur, tin element rich content, by the extensive concern of domestic and foreign scholars.SnS2It is n
Type semi-conducting material, can be 2.44 eV with band gap, can be good at absorbing solar energy；SnS is p-type semiconductor material, can band band
Gap is 1.3 eV, Sn2S3Can be 1.09 eV with band gap, have good Spectral matching with sunshine.There are many methods to prepare at present
Hetero-junction thin-film, mainly has chemical vapour deposition technique, cryogenic vulcanization method, hydro-thermal method, spray pyrolysis, continuous ionic layer absorption anti-
The methods such as method are answered, equipment needed for these methods is simple to operation, easy film forming, thickness are controllable, but be difficult to obtain crystallinity good
Product and the more difficult control of product morphology, the combination of gained sample and substrate are insecure.In addition, can be used in wet chemistry method preparation process
To some organic ligands or surfactant, it is difficult to remove completely in the product, can be to the battery device of gained film assembling
Photoelectric properties have a huge impact.
The content of the invention
In order to overcome above-mentioned deficiency of the prior art, the invention provides a kind of method of use magnetron sputtering in conduction
The metal tin thin film of densification is obtained in glass FTO substrates, and SnS is obtained by the method vulcanized in the tube furnace of sulphur atmosphere2It is thin
Film, then layer of metal tin thin film is sputtered, then vacuum-sintering obtains SnS/Sn in tube furnace2S3/SnS2Hetero-junction thin-film, behaviour
Make simple, be obtained in that finer and close continuous hetero-junction thin-film.
The object of the present invention is achieved like this：
The preparation method of a kind of stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film, by the pipe in sulphur atmosphere
Formula stove is obtained to the method that the metal tin thin film that the method using magnetron sputtering is obtained in electro-conductive glass FTO substrates is vulcanized
SnS2Film, then one layer of tin thin film is sputtered, then vacuum-sintering obtains SnS/Sn in tube furnace2S3/SnS2Hetero-junction thin-film,
Film morphology is uniform and fine and close.
1）, sputter with magnetic control sputtering device 50nm, 100nm, 150nm, 200 nm respectively on the FTO glass of washes clean
Metal tin thin film；
2）, respectively weigh the sulphur powder of 0.2g, 0.5g, 0.8g, 1.0g, weigh respectively the sulphur powder of 0.2g and 50nm, 100nm,
150nm, 200 nm metallic tin in tube furnace temperature setting be 300 DEG C, 1h；350 DEG C, 3h；400 DEG C, 4h；450 DEG C, 2h；
Similarly, the metallic tin of the sulphur powder of 0.5g and 50nm, 100nm, 150nm, the 200 nm temperature setting in tube furnace is weighed respectively is
350 DEG C, 2h；300 DEG C, 4h；450 DEG C, 3h；400 DEG C, 1h；Sulphur powder and 50nm, 100nm, 150nm, 200 of 0.8g are weighed respectively
The metallic tin of nm temperature setting in tube furnace is 400 DEG C, 3h；450 DEG C, 1h；300 DEG C, 2h；350 DEG C, 4h；Weigh respectively
The sulphur powder of 1.0g and 50nm, 100nm, 150nm, 200 nm metallic tin in tube furnace temperature setting be 450 DEG C, 4h；400
DEG C, 2h；350 DEG C, 1h；300 DEG C, 3h.Product distilled water, the absolute ethyl alcohol that will be obtained respectively are washed 3 times, vacuum drying；
3）, product obtained above sputtered according to step 2 respectively）The metal tin thin film of middle correspondence thickness, is then placed on
According to step 2 in tube furnace）In corresponding temperature, time vacuum-sintering obtain target product.
The metal tin thin film of densification is obtained on FTO electro-conductive glass base using magnetron sputtering, sulphur atmosphere furnace sulphur is recycled
Change reaction and obtain stannic disulfide film；
Layer of metal tin thin film, and the vacuum-sintering in tube furnace are sputtered on stannic disulfide film, by solid phase reaction
Obtain target product；
The thickness of the magnetron sputtering metal tin thin film is 50 ~ 200nm, and this thickness is primarily to obtain dense uniform
Film, the product obtained under this thickness can meet the demand of various detections；
The temperature of the vulcanized gas is 300 ~ 500 DEG C, and the product obtained under this reaction temperature can meet various
The demand of detection.
Positive beneficial effect：1st, preparation method is simple, and the time is short.The metallic tin for obtaining densification with the method for magnetron sputtering is thin
Film, vulcanization and vacuum-sintering just can obtain SnS/Sn in tube furnace2S3/SnS2Hetero-junction thin-film.
2nd, it is cheap, it is to avoid environmental pollution.Tin, two kinds of element earth rich contents of sulphur, it is nontoxic and cheap, belong to
Environmentally friendly reaction.
Specific embodiment
Below by embodiment, the present invention is described further：
The preparation method of a kind of stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film, by the pipe in sulphur atmosphere
Formula stove is obtained to the method that the metal tin thin film that the method using magnetron sputtering is obtained in electro-conductive glass FTO substrates is vulcanized
SnS2Film, then one layer of tin thin film is sputtered, then vacuum-sintering obtains SnS/Sn in tube furnace2S3/SnS2Hetero-junction thin-film,
Film morphology is uniform and fine and close.
1）, sputter with magnetic control sputtering device 50nm, 100nm, 150nm, 200 nm respectively on the FTO glass of washes clean
Metal tin thin film；
2）, respectively weigh the sulphur powder of 0.2g, 0.5g, 0.8g, 1.0g, weigh respectively the sulphur powder of 0.2g and 50nm, 100nm,
150nm, 200 nm metallic tin in tube furnace temperature setting be 300 DEG C, 1h；350 DEG C, 3h；400 DEG C, 4h；450 DEG C, 2h；
Similarly, the metallic tin of the sulphur powder of 0.5g and 50nm, 100nm, 150nm, the 200 nm temperature setting in tube furnace is weighed respectively is
350 DEG C, 2h；300 DEG C, 4h；450 DEG C, 3h；400 DEG C, 1h；Sulphur powder and 50nm, 100nm, 150nm, 200 of 0.8g are weighed respectively
The metallic tin of nm temperature setting in tube furnace is 400 DEG C, 3h；450 DEG C, 1h；300 DEG C, 2h；350 DEG C, 4h；Weigh respectively
The sulphur powder of 1.0g and 50nm, 100nm, 150nm, 200 nm metallic tin in tube furnace temperature setting be 450 DEG C, 4h；400
DEG C, 2h；350 DEG C, 1h；300 DEG C, 3h.Product distilled water, the absolute ethyl alcohol that will be obtained respectively are washed 3 times, vacuum drying；
3）, product obtained above sputtered according to step 2 respectively）The metal tin thin film of middle correspondence thickness, is then placed on
According to step 2 in tube furnace）In corresponding temperature, time vacuum-sintering obtain target product.
The metal tin thin film of densification is obtained on FTO electro-conductive glass base using magnetron sputtering, sulphur atmosphere furnace sulphur is recycled
Change reaction and obtain stannic disulfide film；
Layer of metal tin thin film, and the vacuum-sintering in tube furnace are sputtered on stannic disulfide film, by solid phase reaction
Obtain target product；
The thickness of the magnetron sputtering metal tin thin film is 50 ~ 200nm, and this thickness is primarily to obtain dense uniform
Film, the product obtained under this thickness can meet the demand of various detections；
The temperature of the vulcanized gas is 300 ~ 500 DEG C, and the product obtained under this reaction temperature can meet various
The demand of detection.
Embodiment 1
1st, the metal tin thin film of 100 nm thickness is sputtered on the FTO glass of washes clean with magnetic control sputtering device first；
2nd, the distillation sulphur powder for weighing 0.5 g is placed in porcelain boat, with the metal tin thin film of 100 nm thickness in the middle temperature of tube furnace
Degree is set to 350 DEG C, reacts 3 hours；
3rd, by sulphide film obtained above, then the nm thickness of magnetron sputtering 100 metal tin thin film, be then placed on tubular type
Vacuum-sintering obtains target product film in 3 hours at 350 DEG C in stove.
Embodiment 2
1st, the metal tin thin film of 150 nm thickness is sputtered on the FTO glass of washes clean with magnetic control sputtering device first；
2nd, the distillation sulphur powder for weighing 0.8 g is placed in porcelain boat, with the metal tin thin film of 150 nm thickness in the middle temperature of tube furnace
Degree is set to 450 DEG C, reacts 3 hours；
3rd, by sulphide film obtained above, then the nm thickness of magnetron sputtering 150 metal tin thin film, be then placed on tubular type
Vacuum-sintering obtains target product film in 3 hours at 450 DEG C in stove.
Embodiment 3
1st, the metal tin thin film of 50 nm thickness is sputtered on the FTO glass of washes clean with magnetic control sputtering device first；
2nd, the distillation sulphur powder for weighing 0.5 g is placed in porcelain boat, with the metal tin thin film of 50 nm thickness in tube furnace temperature
400 DEG C are set to, are reacted 2 hours；
3rd, by sulphide film obtained above, then the nm thickness of magnetron sputtering 50 metal tin thin film, be then placed on tube furnace
In at 400 DEG C vacuum-sintering obtain target product film within 2 hours.
The present invention mainly prepares SnS/Sn by gas-solid reaction2S3/SnS2Hetero-junction thin-film, with traditional solid phase and liquid
Phase method is very different.Although a kind of method more than the comparing that liquid phase method is, needs when liquid phase process prepares film
Longer time, and the adhesive force for preparing is bad.In the method that non-liquid prepares film, some methods are to original
The purity requirement of material is higher, increased the preparation cost of film.This method is using the method for magnetron sputtering in electro-conductive glass FTO bases
The metal tin thin film of densification is obtained on bottom, and SnS is obtained by the method vulcanized in the tube furnace of sulphur atmosphere2Film, then sputter
Layer of metal tin thin film, then vacuum-sintering obtains SnS/Sn in tube furnace2S3/SnS2Hetero-junction thin-film, simple to operate, energy
It is enough to obtain finer and close continuous hetero-junction thin-film.The invention has the advantages that：1st, preparation method is simple, and the time is short.Use magnetic control
The method of sputtering obtains the metal tin thin film of densification, and vulcanization and vacuum-sintering just can obtain SnS/Sn in tube furnace2S3/SnS2
Hetero-junction thin-film.2nd, it is cheap, it is to avoid environmental pollution.Tin, two kinds of element earth rich contents of sulphur, it is nontoxic and cheap,
Belong to environmentally friendly reaction.
Above case study on implementation is merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, in the ken that the field those of ordinary skill possesses, that is made within the spirit and principles in the present invention is any
Modification, equivalent substitute and improvement etc., are regarded as the protection domain of the application.
Claims (5)
1. the preparation method of a kind of stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film, it is characterised in that：Using magnetic
The method for controlling sputtering sputters the metallic tin of different-thickness and different amounts of the sulphur powder not equality of temperature in tube furnace on FTO electro-conductive glass
Degree, vulcanize under different time, the product for obtaining recycles the metallic tin of magnetron sputtering correspondence thickness, be then placed in tube furnace not
Vacuum-sintering obtains target product under synthermal, different time；
The method for preparing stannic disulfide/trisulfides two tin/stannous sulfide hetero-junction thin-film of the invention, its specific step is：
1）, sputter with magnetic control sputtering device the metal of 50nm, 100nm, 150nm, 200 nm respectively on the FTO glass of washes clean
Tin thin film；
2）, respectively weigh the sulphur powder of 0.2g, 0.5g, 0.8g, 1.0g, weigh respectively the sulphur powder of 0.2g and 50nm, 100nm,
150nm, 200 nm metallic tin in tube furnace temperature setting be 300 DEG C, 1h；350 DEG C, 3h；400 DEG C, 4h；450 DEG C, 2h；
Similarly, the metallic tin of the sulphur powder of 0.5g and 50nm, 100nm, 150nm, the 200 nm temperature setting in tube furnace is weighed respectively is
350 DEG C, 2h；300 DEG C, 4h；450 DEG C, 3h；400 DEG C, 1h；Sulphur powder and 50nm, 100nm, 150nm, 200 of 0.8g are weighed respectively
The metallic tin of nm temperature setting in tube furnace is 400 DEG C, 3h；450 DEG C, 1h；300 DEG C, 2h；350 DEG C, 4h；Weigh respectively
The sulphur powder of 1.0g and 50nm, 100nm, 150nm, 200 nm metallic tin in tube furnace temperature setting be 450 DEG C, 4h；400
DEG C, 2h；350 DEG C, 1h；300 DEG C, 3h, product distilled water, the absolute ethyl alcohol that will be obtained respectively is washed 3 times, vacuum drying；
3）, product obtained above sputtered according to step 2 respectively）The metal tin thin film of middle correspondence thickness, is then placed on tubular type
According to step 2 in stove）In corresponding temperature, time vacuum-sintering obtain target product.
2. the preparation side of a kind of stannic disulfide according to claim 1/trisulfides two tin/stannous sulfide hetero-junction thin-film
Method, it is characterised in that：The metal tin thin film of densification is obtained on FTO electro-conductive glass base using magnetron sputtering, sulphur gas is recycled
Atmosphere stove vulcanization reaction obtains stannic disulfide film.
3. the preparation side of a kind of stannic disulfide according to claim 1/trisulfides two tin/stannous sulfide hetero-junction thin-film
Method, it is characterised in that：Layer of metal tin thin film, and the vacuum-sintering in tube furnace are sputtered on stannic disulfide film, by solid
Phase reaction obtains target product.
4. the preparation side of a kind of stannic disulfide according to claim 1/trisulfides two tin/stannous sulfide hetero-junction thin-film
Method, it is characterised in that：The thickness of the magnetron sputtering metal tin thin film is 50 ~ 200nm.
5. the preparation side of a kind of stannic disulfide according to claim 1/trisulfides two tin/stannous sulfide hetero-junction thin-film
Method, it is characterised in that：The temperature of the vulcanized gas is 300 ~ 500 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1619406A1 (en) * | 2004-07-21 | 2006-01-25 | Quartz Techno Srl | Additive based on tin sulphides for producing blends for friction linings |
| CN101378090A (en) * | 2008-09-26 | 2009-03-04 | 合肥工业大学 | Tin sulfide film solar battery |
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| US9761446B2 (en) * | 2013-05-08 | 2017-09-12 | University Of Houston System | Methods for the synthesis of arrays of thin crystal grains of layered semiconductors SnS2 and SnS at designed locations |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1619406A1 (en) * | 2004-07-21 | 2006-01-25 | Quartz Techno Srl | Additive based on tin sulphides for producing blends for friction linings |
| CN101378090A (en) * | 2008-09-26 | 2009-03-04 | 合肥工业大学 | Tin sulfide film solar battery |
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