CN104060235A - Preparation method for increasing grain size of copper, cadmium, tin and sulphur thin film by doping selenium element - Google Patents
Preparation method for increasing grain size of copper, cadmium, tin and sulphur thin film by doping selenium element Download PDFInfo
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- CN104060235A CN104060235A CN201410326642.0A CN201410326642A CN104060235A CN 104060235 A CN104060235 A CN 104060235A CN 201410326642 A CN201410326642 A CN 201410326642A CN 104060235 A CN104060235 A CN 104060235A
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Abstract
The invention relates to a preparation method for changing grain size of a copper, cadmium, tin and sulphur (Cu2CdSnS4) thin film by doping selenium element. The preparation method is characterized in that magnetron sputtering is carried out on a copper, cadmium, thin and sulphur prefabricated film by adopting a copper, cadmium, thin and sulphur single target material, the selenium element doping and vulcanization thermal treatment are carried out on the prefabricated film, thus obtaining a high-quality copper, cadmium, thin and sulphur thin film with a relatively large grain size which can be 2mm at most. The preparation method has the advantages of simple technology, low cost, easy operation and strong repeatability and is beneficial to industrialization development of a solar battery with a copper, cadmium, thin and sulphur absorption layer.
Description
Technical field
The present invention relates to improve by selenium element doping the preparation method of copper cadmium tin sulphur film grain-size, adopt single target material magnetron sputtering copper cadmium tin sulphur prefabricated membrane, then the heat of vulcanization processing of prefabricated membrane being carried out to selenium element doping improves copper cadmium tin sulphur film grain-size, make film grain-size reach 2 mm, belong to thin film solar cell Material Field.
Background technology
Copper cadmium tin sulphur is a kind of direct band gap compound semiconductor, and optical band gap is 1.0～1.2eV, and its ABSORPTION EDGE high energy side uptake factor is up to 10
4cm
-1, identical with copper-zinc-tin-sulfur film, be used to prepare the absorption layer of thin film solar cell.Compare copper-zinc-tin-sulfur film, its band gap is relatively little, so copper cadmium tin sulphur can be used as the desirable absorption layer in the stacked solar cell, cascade solar cell of different band gap.At present, adopt the copper cadmium tin sulphur thin-film technique of single target material sputter postcure simple, stability, homogeneity is relatively good, its shortcoming is: adopt the less 500～600nm that is approximately of copper cadmium tin sulphur film grain-size of preparation in this way, less grain-size can cause crystal boundary to increase, and this has disadvantageous effect to solar cell device.Therefore, employing can effectively increase the grain-size of film by the heat of vulcanization processing of Magnetron Sputtering Thin Film being carried out to selenium element doping, thereby reaches the object of the solar battery thin film absorption layer of synthetic large crystal grain.
Summary of the invention
The object of the invention is to overcome the less problem of the simple sulphide film grain-size of current employing.The present invention adopts the heat of vulcanization processing of selenium element doping can effectively increase the grain-size of film.
The object of the invention is to implement like this: single copper cadmium tin sulphur target is carried out to magnetron sputtering, and substrate adopts soda-lime glass, and underlayer temperature is 500
oc, sputtering power is 60W, passing into argon gas initial vacuum degree is 7 × 10
-4pa, the same terms is prepared 3 identical copper cadmium tin sulphur prefabricated membranes (a), (b), (c).The prefabricated copper cadmium tin sulphur film (a) good to sputter again, (b), (c) adds respectively 30mg sulphur powder, and 5mg selenium powder+25mg sulphur powder is put in three identical sealing graphites after 10mg selenium powder+20mg sulphur powder.By copper cadmium tin sulphur film (a), (b), (c) carry out respectively the high-temperature quick processing that condition is identical.X x ray diffraction analysis x shows (Fig. 2): three the copper cadmium tin sulphur films (a) after thermal treatment, (b), (c) all belong to sulphur cadmium yellow tin ore (Cernyite) structure, do not find dephasign, and lattice parameter increases with the increase of putting into selenium powder content, illustrate: selenium element doping is in copper cadmium tin sulphur structure, and Se, appears in replacement sulfur position
sinstead type defect (plasma selenium radius is greater than sulfonium ion radius).X ray energy spectrum proves (Fig. 3), and along with putting into the increase of graphite selenium powder quality, the content of selenium in copper cadmium tin sulphur improves constantly.Micromorphology analysis shows (Fig. 4), along with the increase of selenium content, the grain-size of copper cadmium tin sulphur film has obtained significantly improving, the grain-size of the film (c) that selenium content is the highest can reach 2mm, meets the grain-size of absorption layer in optimal solar energy hull cell.Illustrate by the preparation method of selenium element doping raising copper cadmium tin sulphur film grain-size and can effectively solve the less problem of simple sulfuration rear film grain-size.
The advantage that the present invention increases the method for copper cadmium tin sulphur film grain-size is:
(1) technique is simple, repeatable high.
(2) crystalline quality of raising film makes copper cadmium tin sulphur film grain-size reach perfect condition.
Brief description of the drawings
(1) Fig. 1 is process flow sheet.
(2) Fig. 2 is the X-ray diffractogram of the different cure conditions of copper cadmium tin sulphur film.
(3) Fig. 3 is X-ray energy spectrum analysis and the stoicheiometry of the different cure conditions of copper cadmium tin sulphur film.
(4) Fig. 4 is the microscopic appearance surface analysis figure of the different cure conditions of copper cadmium tin sulphur film.
Embodiment
Embodiment
By cuprous sulfide, Cadmium Sulfide, tin disulfide mixes according to mol ratio 1:1:1, adopts agate mortar to grind, and the time is 4h, the powder mixing is carried out hot-forming, and temperature is 700
oc, obtaining chemical element proportioning is the copper-zinc-tin-sulfur single target material of 2:1:1:4, adopts rf magnetron sputtering sputter copper-zinc-tin-sulfur film on soda-lime glass, processing condition are: underlayer temperature: 500
oc, argon gas flow velocity: 30ccm, sputtering power: 60W, sputtering pressure: 0.1Pa, sputter initial vacuum degree: 7 × 10
-4pa.Obtain 3 copper cadmium tin sulphur prefabricated membranes with identical sputtering condition, use respectively (a), (b), (c) represent.By film (a), (b), (c) add respectively 30mg sulphur powder, 5mg selenium powder+25mg sulphur powder, after 10mg selenium powder+20mg sulphur powder, put in three identical sealing graphites, graphite is put into quick anneal oven successively, annealing furnace temperature rise rate is 5
oc/s.When annealing furnace temperature rises to 550
owhen C, insulation 15min, naturally cooling.Fig. 2 is the x x ray diffration pattern x of the different cure conditions of copper cadmium tin sulphur film, and its diffraction peak is copper cadmium tin sulphur (Cernyite) phase diffraction peak, does not find the second-phase relevant to impurity, illustrates that the copper cadmium tin sulphur obtaining is single-phase structure.And after sulfuration, copper cadmium tin sulphur thin film crystallization degree improves, relatively film (a), (b) (112) diffraction peak and (c), diffraction peak is gradually to little angular variation, and halfwidth diminishes gradually, raising along with selenium doping is described, instead type defect Se
sconstantly increase, grain-size constantly increases.Fig. 3 is that x Ray Energy Spectrum Analysis and the stoicheiometry of the different cure conditions of copper cadmium tin sulphur film shows: selenium doping improves constantly, especially in film (c), and Se/ (Se+S)=0.42.Fig. 4 is the microscopic appearance surface analysis figure of the different cure conditions of copper cadmium tin sulphur film, along with the increase of selenium content, copper cadmium tin sulphur film grain-size constantly increases, grain-size maximum in film (c), for 2mm, the requirement that increases grain-size that the content of selenium in copper cadmium tin sulphur contributes to increase film and reach desirable solar battery obsorbing layer is described.
Claims (3)
1. one kind is improved the preparation method of copper cadmium tin sulphur film grain-size by selenium element doping, it is characterized in that adopting copper cadmium tin sulphur single target material to carry out magnetron sputtering, film after sputter is mixed to the heat of vulcanization processing of selenium element, will obtain the copper cadmium tin sulphur film of large grain-size.
2. one kind is improved the preparation method of copper cadmium tin sulphur film grain-size by selenium element doping, it is characterized in that processing with respect to simple sulfur heat-transmission processing through the heat of vulcanization after selenium doping, can effectively improve the grain-size of copper cadmium tin sulphur film, its grain-size can reach 2 mm, and copper cadmium tin sulphur film is sulphur cadmium yellow tin ore (cernyite) structure.
3. improve the preparation method of copper cadmium tin sulphur film grain-size according to selenium element doping claimed in claim 1, it is characterized in that the heat of vulcanization processing that copper cadmium tin sulphur film by single target material being carried out to magnetron sputtering carries out selenium element doping can effectively solve the less problem of simple sulfur copper cadmium tin sulphur sputtered film grain-size, the copper cadmium tin sulphur film grain-size after doped selenium element can reach 2 mm.
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| CN201410326642.0A CN104060235A (en) | 2014-07-10 | 2014-07-10 | Preparation method for increasing grain size of copper, cadmium, tin and sulphur thin film by doping selenium element |
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| CN201410326642.0A CN104060235A (en) | 2014-07-10 | 2014-07-10 | Preparation method for increasing grain size of copper, cadmium, tin and sulphur thin film by doping selenium element |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611019A (en) * | 2017-10-17 | 2018-01-19 | 吉林化工学院 | A kind of preparation of columnar grain copper-zinc-cadmium-tin-sulfur-selenium thin film absorbed layer and its application in solar cells |
| CN115872439A (en) * | 2022-12-09 | 2023-03-31 | 湖北工业大学 | Method for preparing film for promoting growth of copper-zinc-tin-sulfur particles by nano-crystal |
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| CN102712495A (en) * | 2009-11-25 | 2012-10-03 | 纳幕尔杜邦公司 | Syntheses of quaternary chalcogenides in cesium, rubidium, barium and lanthanum containing fluxes |
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| US20140026949A1 (en) * | 2012-07-26 | 2014-01-30 | International Business Machines Corporation | Ohmic contact of thin film solar cell |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611019A (en) * | 2017-10-17 | 2018-01-19 | 吉林化工学院 | A kind of preparation of columnar grain copper-zinc-cadmium-tin-sulfur-selenium thin film absorbed layer and its application in solar cells |
| CN107611019B (en) * | 2017-10-17 | 2020-03-27 | 吉林化工学院 | Preparation of columnar crystal grain copper-zinc-cadmium-tin-sulfur-selenium film absorption layer and application of absorption layer in solar cell |
| CN115872439A (en) * | 2022-12-09 | 2023-03-31 | 湖北工业大学 | Method for preparing film for promoting growth of copper-zinc-tin-sulfur particles by nano-crystal |
| CN115872439B (en) * | 2022-12-09 | 2023-11-17 | 湖北工业大学 | Method for preparing film for promoting growth of copper zinc tin sulfide particles by nanocrystalline |
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Application publication date: 20140924 |