CN101527261B - Hydro-thermal treatment method capable of improving performance of chalcogen semiconductor film - Google Patents
Hydro-thermal treatment method capable of improving performance of chalcogen semiconductor film Download PDFInfo
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- CN101527261B CN101527261B CN2009100104033A CN200910010403A CN101527261B CN 101527261 B CN101527261 B CN 101527261B CN 2009100104033 A CN2009100104033 A CN 2009100104033A CN 200910010403 A CN200910010403 A CN 200910010403A CN 101527261 B CN101527261 B CN 101527261B
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Abstract
The invention relates to a treatment method capable of improving the performance of a chalcogen semiconductor film prepared by a soft chemical method, in particular to a treatment method of carrying out hydro-thermal treatment in a sulfide or ion aqueous solution to improve the performance of the chalcogen semiconductor film prepared by the soft chemical method. The method comprises the followingsteps: firstly, preparing the 0.01M to 0.3M sulfide or ion aqueous solution; then, pouring the solution into a hydro-thermal reactor and putting the chalcogen semiconductor film precipitated by soft chemical methods such as a chemical-bath method, continuous ion sheath absorption reaction method or an electric-precipitation method into the solution; and finally, carrying out the hydro-thermal treatment to the chalcogen semiconductor film at 160 DEG C to 240 DEG C. Compared with the prior method of thermally treating the film in an H2S atmosphere, an H2Se atmosphere, an inertia atmosphere or vacuum at a high temperature above 400 DEG C, the invention has low reaction temperature, little pollution and simple equipment, is suitable for various substrate surfaces and can remarkably improve the performance of the film, such as the degree of crystallinity, the photoelectricity, and the like.
Description
Technical field
The present invention relates to a kind of heat treatment method that improves film performance, relate to a kind of processing method of improving the chalcogenide film performance of soft chemical method preparation, specially refer to a kind of by in the sulphur or the plasma selenium aqueous solution, carrying out the processing method of hydrothermal treatment consists with the chalcogenide film performance of improving the soft chemical method preparation.
Background technology
With CdS, CuInS
2, CuInSe
2For the representative the chalcogen semiconductor film material at thin-film solar cells, photoconductor, has important application in the transducer, particularly in absorbed layer ETA (Extremely Thin Absorber) area of solar cell as thin as a wafer, because its distinctive high absorption coefficient and chemical stability, can be used as adsorption layer efficiently and improve the conversion efficiency of ETA battery, its preparation is subjected to people's generally attention with application technology always and develops rapidly.
In the ETA battery, the contact need on adsorption layer and porous electrode surface is realized by the process conditions of gentleness, reduces battery efficiency otherwise form defective easily.Reduce preparation cost for reaching, shorten the reaction time, be implemented in and specification requirement such as deposit in the nanoporous substrate, people are summed up as chemical bath (CBD), continuous ionic layer adsorption reaction method (SILAR), electrochemical deposition method methods such as (ED) softening method and are used for preparing chalcogen semiconductor film.But because the chemical method film forming itself exists poor adhesive force, inhomogeneous, the incomplete shortcoming of crystal formation, the film of deposition preparation usually need be at high temperature (more than 400 ℃), at H
2S, H
2Heat-treat in Se, vacuum or the inert atmosphere, not only need expensive vacuum or atmosphere treatment facility, and complex process, contaminated environment easily.Bravely on " applied surface science " (Applied surface science) and " solid film " (Thin solid films) magazine, reported respectively such as 2006 and stone in 2007 and to be equipped with CuInS with continuous ionic layer adsorption reaction legal system
2And CuInSe
2Film, still made sample all need be heat-treated under the argon gas atmosphere protection of certain flow rate, and optimum treatment temperature is 400 ℃ and 450 ℃, and heat treatment time is 1 hour.
The invention provides a kind of method of in the sulphur or the plasma selenium aqueous solution, carrying out hydrothermal treatment consists and improve film crystal formation and photoelectric properties; this method equipment is simple; the treatment conditions gentleness; being used for the ETA battery and can protecting the structural intergrity of the poroid electrode of nanometer, is a kind of new, promising green film Technology for Heating Processing.Still there is not at present relevant patent of invention report.
Summary of the invention
The hydro-thermal treatment method that the purpose of this invention is to provide a kind of performance of chalcogen semiconductor film that can improve the soft chemical method preparation newly, carry out hydrothermal treatment consists by chalcogen semiconductor film in the sulphur or the plasma selenium aqueous solution to chemical bath, SILAR, these soft chemical method preparations of electrodeposition process, reach and improve the film crystal formation, improve the purpose of film performance.
Chalcogenide film processing method of the present invention is divided into three steps:
(1), with the Na of different quality
2S, Na
2SeSO
3Join in the container with water, stirred 5-30 minute, obtaining molar concentration is even sulphur or the plasma selenium solution of 0.01～0.3mol/L;
(2), pour above-mentioned sulphur or the plasma selenium solution of 50～150ml into water heating kettle, being glass, TiO in different base
2Chalcogen semiconductor film with chemical bath, continuous ionic layer adsorption reaction method, these soft chemical method depositions of electrodeposition process on porous substrate, the substrate of ZnO porous, ito glass, the silicon chip is MnS, PbS, CdS, CuInS
2, CuInSe
2Vertically put in this solution, should guarantee that solution did not have the film surface of required processing fully;
(3), water heating kettle is heated to 160-240 ℃, and insulation 10-120 minute, treat can take out film after water heating kettle at room temperature cools off.
Description of drawings:
Fig. 1 is the MnS film water heat treatment front and back XRD figure of chemical bath method deposition on the glass substrate; Wherein: before a was hydrothermal treatment consists, b was the situation after the hydrothermal treatment consists; Ordinate is a scanning angle, and abscissa is the diffraction peak intensity value;
Fig. 2 TiO
2The CuInSe of electrochemical process deposition in the substrate
2XRD figure before and after the film water heat treatment; Wherein: before a was hydrothermal treatment consists, b was the situation after the hydrothermal treatment consists; Ordinate is a scanning angle, and abscissa is the diffraction peak intensity value;
Fig. 3 TiO
2The CuInS of continuous ion adsorbing method deposition in the substrate
2XRD figure before and after the film water heat treatment; Wherein: before a was hydrothermal treatment consists, b was the situation after the hydrothermal treatment consists; Ordinate is a scanning angle, and abscissa is the diffraction peak intensity value;
XRD figure before and after the PbS film water heat treatment of chemical bath method deposition on Fig. 4 glass substrate; Wherein: before a was hydrothermal treatment consists, b was the situation after the hydrothermal treatment consists; Ordinate is a scanning angle, and abscissa is the diffraction peak intensity value;
XRD figure before and after the CdS film water heat treatment of chemical bath method deposition on Fig. 5 glass substrate; Wherein: before a was hydrothermal treatment consists, b was the situation after the hydrothermal treatment consists; Ordinate is a scanning angle, and abscissa is the diffraction peak intensity value.
Compare with the conventional films heat treatment method, the present invention has following innovative point:
(1), with traditional more than 400 ℃ under the high temperature, at H2S、H
2The method of in Se, inert atmosphere or the vacuum film being heat-treated is compared, and reaction temperature of the present invention is low, is 160-240 ℃, pollutes littlely, and equipment is simple, and can significantly improve equally the degree of crystallinity of film and improve the performances such as photoelectricity of film.
(2), with traditional more than 400 ℃ under the high temperature, at H2S、H
2The method of in Se, inert atmosphere or the vacuum film being heat-treated is compared, because film water heat treatment is all carried out in the aqueous solution with film preparation, has reduced the film cracking probability, and can impel film to regrow, and improves the film surface uniformity.
(3), with traditional more than 400 ℃ under the high temperature, at H2S、H
2The method of in Se, inert atmosphere or the vacuum film being heat-treated is compared, reaction temperature of the present invention and, be suitable for multiple substrate surface, be particularly advantageous in the cavernous structure of protection nanoporous substrate.
Experiment showed, that the present invention is to CdS, MnS, PbS, CuInS with the soft chemical method preparation2、CuInSe
2Etc. multiple chalcogen semiconductor film, all can significantly improve film quality, effectively improve the performances such as its degree of crystallinity and photoelectricity, and technology is simple, the equipment cheapness is fit to suitability for industrialized production.
Embodiment
The performance of implementation procedure of the present invention and material is illustrated by embodiment:
Embodiment one
At first 10g vulcanized sodium and 90g water are added in the reaction vessel, stir and made even mixing in 10 minutes; Pour above-mentioned sulphion solution into water heating kettle, the MnS film that deposits on substrate of glass with chemical bath is vertically put in this solution, should guarantee that solution did not have the film surface of required processing fully; Water heating kettle is heated to 160 ℃, and is incubated 30 minutes, can take out film after waiting water heating kettle at room temperature to cool off.The present invention sees the following form to the facilitation of the photoelectric properties of MnS film, and degree of crystallinity is improved and seen Figure of description 1:
| ? | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s? |
| Before the |
10 4 | 3.4? | 220? | 0.8? | 10? |
| After the |
10 4 | 3.2? | 15? | 15? | 60? |
Embodiment two
At first 5g sodium thiosulfate and 95g water are added in the reaction vessel, stir and made even mixing in 15 minutes; Pour above-mentioned sulphion solution into water heating kettle, using electrochemical deposition method at TiO
2The CuInSe that deposits in the substrate
2Film is vertically put in this solution, should guarantee that solution did not have the film surface of required processing fully; Water heating kettle is heated to 200 ℃, and is incubated 60 minutes, can take out film after waiting water heating kettle at room temperature to cool off.The present invention is to CuInSe
2The facilitation of the photoelectric properties of film sees the following form, and degree of crystallinity is improved and seen Figure of description 2:
| ? | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s? |
| Before the |
10 5 | 0.9? | 320? | 3.5? | 5? |
| After the |
10 5 | 1.0? | 20? | 50? | 55? |
Embodiment three
At first 8g vulcanized sodium and 92g water are added in the reaction vessel, stir and made even mixing in 30 minutes; Pour above-mentioned sulphion solution into water heating kettle, using the continuous ion adsorbing method at TiO
2The CuInS that deposits in the substrate
2Film is vertically put in this solution, should guarantee that solution did not have the film surface of required processing fully; Water heating kettle is heated to 180 ℃, and is incubated 20 minutes, can take out film after waiting water heating kettle at room temperature to cool off.The present invention is to CuInS
2The facilitation of the photoelectric properties of film sees the following form, and degree of crystallinity is improved and seen Figure of description 3:
| ? | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s? |
| Before the |
10 5 | 0.9? | 300? | 3.5? | 5? |
| After the |
10 5 | 1.0? | 20? | 20? | 70? |
Embodiment four
At first 15g vulcanized sodium and 85g water are added in the reaction vessel, stir and made even mixing in 25 minutes; Pour above-mentioned sulphion solution into water heating kettle, the PbS film that deposits on substrate of glass with chemical bath is vertically put in this solution, should guarantee that solution did not have the film surface of required processing fully; Water heating kettle is heated to 170 ℃, and is incubated 35 minutes, can take out film after waiting water heating kettle at room temperature to cool off.The present invention sees the following form to the facilitation of the photoelectric properties of PbS film, and degree of crystallinity is improved and seen Figure of description 4:
| ? | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s? |
| Before the |
10 4 | 0.3? | 350? | 1.5? | 1? |
| After the |
10 5 | 0.3? | 40? | 30? | 40? |
Embodiment five
At first 9g vulcanized sodium and 91g water are added in the reaction vessel, stir and made even mixing in 35 minutes; Pour above-mentioned sulphion solution into water heating kettle,, should guarantee that solution did not have the film surface of required processing fully vertically putting in this solution with the CdS film that on substrate of glass, deposits with chemical bath; Water heating kettle is heated to 190 ℃, and is incubated 45 minutes, can take out film after waiting water heating kettle at room temperature to cool off.The present invention sees the following form to the facilitation of the photoelectric properties of CdS film, and degree of crystallinity is improved and seen Figure of description 5:
| ? | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s? |
| Before the |
10 4 | 2.0? | 400? | 4.5? | 10? |
| After the |
10 4 | 2.4? | 30? | 35? | 60? |
Claims (1)
1. hydro-thermal treatment method that improves chalcogen semiconductor film crystal formation and photoelectric properties is characterized in that this hydro-thermal treatment method is divided into three steps:
(1), with the Na of different quality
2S or Na
2SeSO
3Join in the container with water, stirred 5-30 minute, obtaining molar concentration is even sulphur or the plasma selenium solution of 0.01～0.3mol/L;
(2), pour above-mentioned sulphur or the plasma selenium solution of 50～150ml into water heating kettle, being glass, TiO in different base
2Chalcogen semiconductor film with chemical bath, continuous ionic layer adsorption reaction method, these soft chemical method depositions of electrodeposition process on porous substrate, the substrate of ZnO porous, ito glass, the silicon chip is MnS, CdS, PbS, CuInS
2, CuInSe
2Vertically put in this solution, should guarantee that solution did not have the film surface of required processing fully;
(3), water heating kettle is heated to 160-240 ℃, and insulation 10-120 minute, can take out film after waiting water heating kettle at room temperature to cool off.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100104033A CN101527261B (en) | 2009-02-16 | 2009-02-16 | Hydro-thermal treatment method capable of improving performance of chalcogen semiconductor film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100104033A CN101527261B (en) | 2009-02-16 | 2009-02-16 | Hydro-thermal treatment method capable of improving performance of chalcogen semiconductor film |
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|---|---|
| CN101527261A CN101527261A (en) | 2009-09-09 |
| CN101527261B true CN101527261B (en) | 2010-12-01 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102080221B (en) * | 2009-11-30 | 2012-09-26 | 比亚迪股份有限公司 | Method for depositing cadmium sulfide film by chemical water bath |
| CN102251235B (en) * | 2011-07-07 | 2013-03-13 | 中南大学 | Preparation method of Cu-Zn-Sn-S thin film |
| CN102963936A (en) * | 2012-11-14 | 2013-03-13 | 陕西科技大学 | Preparation method of gamma-MnS thin film with branch-shaped structure |
| CN109524547B (en) * | 2018-10-10 | 2020-05-19 | 华中科技大学 | Preparation method and application of novel inorganic hole transport layer material |
| CN109513450B (en) * | 2018-12-07 | 2021-05-25 | 信阳师范学院 | CdS nanotube and spiral CuInS2Heterostructure composite material and preparation method thereof |
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