CN102161503B - Preparation method of orthorhombic tin dioxide thin film - Google Patents
Preparation method of orthorhombic tin dioxide thin film Download PDFInfo
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- CN102161503B CN102161503B CN2011100515216A CN201110051521A CN102161503B CN 102161503 B CN102161503 B CN 102161503B CN 2011100515216 A CN2011100515216 A CN 2011100515216A CN 201110051521 A CN201110051521 A CN 201110051521A CN 102161503 B CN102161503 B CN 102161503B
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- dioxide thin
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Abstract
The invention relates to a preparation method of an orthorhombic tin dioxide thin film, which comprises the following operation steps that: (i) preparing a tin dioxide target used for pulsed laser deposition: (1) preparing high-purity tin dioxide powder; and (2) preparing the powder into a round block with the diameter of 15mm and the thickness of 4mm at the pressure of 0.4GPa, and sintering the round block for 2 hours at 1150 DEG C to obtain the tin dioxide target used for pulsed laser deposition; and (ii) impacting the target by utilizing a pulsed laser deposition method to obtain the deposited orthorhombic tin dioxide thin film. The preparation conditions of the high-temperature high-pressure orthorhombic tin dioxide thin film at a relatively low pressure and relatively low temperature are discovered in the invention.
Description
Technical field
The present invention relates to a kind of high temperature, the technology of preparing of high pressure quadrature phase tin dioxide thin film under relatively low pressure and lower temperature, is to belong to inorganic oxide film material preparation process technical field.
Background technology
Tin ash is the novel practical functional material that has using value most at present.It is with a wide range of applications in fields such as solar cell, transparency electrode and gas sensors.Under normal conditions, tin ash mainly is present in occurring in nature with the cassiterite form, and cassiterite type tin ash has rutile four directions phase crystal structure, and its electricity, optics and gas sensing characteristic etc. are by extensively and in depth research.Yet, the another kind of crystal structure of tin ash: the quadrature phase, owing to be the HTHP phase, be difficult for synthesizing, its character is surveyed and technical application is stagnated always.Because a series of character such as electricity, optics and gas sensing characteristic of this quadrature phase tin ash it be unclear that so far; Round Realization HTHP quadrature phase tin ash synthesizing under normal condition, could make that this quadrature phase tin dioxide material obtains to use widely.The present invention utilizes pulsed laser deposition technique, through the various parameters and the experiment condition of control impuls laser, under relatively low pressure and lower temperature, has prepared quadrature tin dioxide thin film mutually.
Summary of the invention
The objective of the invention is the problem that exists to prior art, a kind of preparation method of quadrature phase tin dioxide thin film is provided, can under relatively low pressure and lower temperature, prepare quadrature tin dioxide thin film mutually.
For achieving the above object, the present invention adopts following technical proposals: the preparation method of quadrature phase tin dioxide thin film is characterized in that the concrete operations step is following:
A. preparation is used for the tin ash target of pulsed laser deposition: 1. utilize the high-purity tin ash powder of Prepared by Sol Gel Method at 27 ± 2% SnCl
4Dropwise drip 28 ± 2% ammoniacal liquor in the ethanolic solution and make its reaction evenly, detect its pH value in the course of reaction in real time, when pH=7, finish reaction, can observe the leucosol generation; After the ageing 24 ± 0.2 hours, wash for several times, use AgNO with ethanol, acetone
3Detect filter liquor, until detecting less than Cl
-Till; The gained gel is put into vacuum drying chamber 100 ℃ ± 5 ℃ oven dry moisture and washing agent, gets bulk sample; Grind into powder is prepared the tin ash powder of particle diameter 4 ± 0.5 nanometers; 2. its powder is made into 15 ± 2 millimeters of diameters under 0.3～0.5 GPa pressure, 4 ± 0.2 millimeters nahlocks of thickness; Its nahlock 1150 ± 50 ℃ of following sintering 2 ± 0.2 hours, is promptly become the tin ash target of pulsed laser deposition.
B. utilize pulse laser sediment method to impact target, select KrF laser, it is 350 mJ that pulse energy is set, wavelength 248 nm, and frequency 10 Hz, 34 nanoseconds of interpulse period, each pulse injection rate is 5 ± 0.1 J/cm
2Vacuum degree is superior to 1 * 10 when the settling chamber
-6During mbar, begin to introduce pulse laser, beat to said target, the control partial pressure of oxygen is 3 ± 0.1 * 10
-2Pa is deposited on target on the silicon substrate, and this underlayer temperature is 320 ± 10
oC, silicon substrate obtain quadrature phase tin dioxide thin film under these conditions apart from 4 ± 0.1 centimetres of targets.
The present invention has following conspicuous outstanding substantive distinguishing features and remarkable advantage: through control impuls laser parameter and experiment condition, can reach quadrature phase tin dioxide thin film compared with prior art.The inventive method has been sought the preparation condition of HTHP quadrature phase tin dioxide thin film under relatively low pressure and lower temperature.
Description of drawings
Fig. 1 prepares the experimental provision structural representation of quadrature phase tin dioxide thin film for the present invention.
Fig. 2 carries out X-ray diffractogram for the present invention to the film for preparing.
Fig. 3 carries out X ray photoelectricity power spectrum phenogram for the present invention to the film for preparing.
Fig. 4 carries out Mossbauer figure for the present invention to the film for preparing.
Fig. 5 carries out X ray electron energy loss spectroscopy (EELS) phenogram for the present invention to the film for preparing.
Fig. 6 carries out grenz ray near side (ns) absorption spectra phenogram for the present invention to the film for preparing.
Fig. 7 and Fig. 8 are the optical property figure of the present invention to the film of preparation.
Fig. 9 forms the mechanism sketch map for the quadrature phase tin dioxide thin film of the present invention's preparation.
Embodiment
Specific embodiment of the present invention is further specified as follows at present.
Embodiment 1
The preparation method of this quadrature phase tin dioxide thin film, the concrete operations step is following:
A. in order to obtain to be used for the tin ash target of pulsed laser deposition, we have utilized Prepared by Sol Gel Method high-purity tin ash powder (99.8 %).Preparation technology and step are: at 27 ± 2% SnCl
4Dropwise drip 28 ± 2% ammoniacal liquor in the ethanolic solution and make its reaction evenly, detect its pH value in the course of reaction in real time, when pH=7, finish reaction, can observe leucosol and produce, ageing was washed several with ethanol, acetone after 24 ± 0.2 hours, used AgNO
3Detect filter liquor, until detecting less than Cl
-Till, the gained gel is put into vacuum drying chamber 100 ℃ ± 5: oven dry moisture and washing agent, bulk sample, grind into powder is prepared the tin ash powder of about 4 ± 0.5 nanometers of particle diameter.Its powder is made into 15 ± 2 millimeters of diameters under 0.3～0.5 GPa pressure, 4 ± 0.2 millimeters nahlocks of thickness.Its nahlock 1150 ℃ of following sintering 2 hours, is promptly become the tin ash target of pulsed laser deposition.
B. utilize pulse laser sediment method to impact target, select KrF laser, it is 350 mJ that pulse energy is set, wavelength 248 nm, and frequency 10 Hz, 34 nanoseconds of interpulse period, each pulse injection rate is 5 ± 0.1 J/cm
2Vacuum degree is superior to 1 * 10 when settling chamber (Chamber)
-6During mbar, begin to introduce pulse laser, beat to target (Target), the control partial pressure of oxygen is 3 ± 0.1 * 10
-2Pa is deposited on target on silicon (100) substrate, and underlayer temperature is 320 ± 10
oC, silicon substrate is apart from 4 ± 0.1 centimetres of targets.Can obtain quadrature phase tin dioxide thin film under these conditions.Experimental provision is as shown in Figure 1.
Present embodiment and embodiment 1 are identical, to gained quadrature phase tin dioxide thin film research experiment:
X-ray diffraction (XRD) research shows: the main indices of crystallographic plane (Fig. 2 a-i) of the quadrature phase tin dioxide thin film that makes and quadrature be the standard X-ray diffraction of tin ash (PDF document number: 78-1063, Fig. 2 a-iii) basically identical mutually, for example: quadrature phase tin ash (111), (112); (113), (002), (006), (115); (200), (117), (222), (130); But can not get rid of (101) of cubic phase tin monoxide, (110) (224) and (119) face; (002), (200), (112) and (211) face (PDF document number: 85-0712).Therefore, need ample evidence and confirm further whether this film is quadrature phase tin ash.Simultaneously, its film is placed half a year, further carry out X-ray diffraction (Fig. 2 a-ii) research and show: this film is stable, and thing does not change mutually.
X-ray photoelectron can show in the research of (XPS) spectrum: peak value is consistent with respectively the Sn3d of tin ash with 486.5 eV positions 495.0
3/2And Sn3d
5/2Binding energy (Fig. 2 b).530.5 eV peak values are corresponding to the binding energy of O1s in the illustration, and the oxide that this tin is described possibly be a tin ash.But,, be tin dioxide thin film so be difficult to this film of strong deduction because the peak position of the X-ray diffraction peak position of tin monoxide and tin ash and x-ray photoelectron power spectrum is very approaching.
Embodiment 3
The preparation method of present embodiment and embodiment 1 are identical, and gained quadrature phase tin dioxide thin film is done following experimental study:
Mossbauer (M ssbauer) spectrum research shows: isomeric moves (IS) and quadrupole splitting (QS) value is respectively 0 mm/s and 0.6 mm/s, and this experiment has fully proved tin, and (Fig. 3 a) for+4 valence states.
The research of X ray electron energy loss (EDS) spectrum shows: the percentage composition of tin and oxygen atom is respectively 33.4 % and 66.6 % in the film, that is: the atom proportioning of tin and oxygen is 1:2.(Fig. 3 b).Infer thus: this film consists of tin ash and has got rid of the possibility of tin monoxide.
The preparation method of present embodiment and embodiment 1 are identical, and the quadrature phase tin dioxide thin film that obtains is done following experimental study:
The grenz ray near side (ns) absorbs the research of (XANES) spectrum and shows: through comparing quadrature phase tin ash, the Sn M of cubic phase tin ash and cubic phase tin monoxide
4,5The XANES spectrum, the surface electronic structure of finding quadrature phase tin ash is more similar in appearance to cubic phase tin ash, and conduction band is that (Fig. 4 a) for 499 eV.Above-mentioned five aspect experimental result synthetic proofs: our film of preparation is a quadrature phase tin dioxide thin film.
Optical property measurement under the room temperature is found: the transparency of this quadrature phase tin dioxide thin film is to be superior to conventional cubic phase tin ash.Band gap (the E of this quadrature phase tin dioxide thin film
g=4.02 eV) be greater than cubic phase tin ash (E
g=3.6 eV) (Fig. 4 b and 4c).
Embodiment 5
The preparation method of present embodiment and embodiment 1 are identical, and gained quadrature phase tin dioxide thin film is done following experimental study:
Forming process and the basic reason (Fig. 5) that band gap is widened of this quadrature phase tin dioxide thin film that we have proposed oxygen exchange reaction mechanism pragmatize mainly is four kinds of oxygen nucleic (O
2, O
2 -, O
-And O) realizes that through basic coupled reaction step laser feather sedimentary deposit and quadrature exchange electronics mutually and form quadrature phase tin dioxide thin film between the layer.
Claims (2)
1. the preparation method of a quadrature phase tin dioxide thin film is characterized in that the concrete operations step is following:
A. preparation is used for the tin ash target of pulsed laser deposition: 1. utilize the high-purity tin ash powder of Prepared by Sol Gel Method, at 27 ± 2% SnCl
4Dropwise drip 28 ± 2% ammoniacal liquor in the ethanolic solution and make its reaction evenly, detect its pH value in the course of reaction in real time, when pH=7, finish reaction, can observe the leucosol generation; After the ageing 24 ± 0.2 hours, wash for several times, use AgNO with ethanol, acetone
3Detect filter liquor, until detecting less than Cl
-Till; The gained gel is put into vacuum drying chamber 100 ℃ ± 5 ℃ oven dry moisture and washing agent, gets bulk sample; Grind into powder is prepared the tin ash powder of particle diameter 4 ± 0.5 nanometers; 2. its powder is made into 15 ± 2 millimeters of diameters under 0.3～0.5 GPa pressure, 4 ± 0.2 millimeters nahlocks of thickness; Its nahlock 1150 ± 50 ℃ of following sintering 2 ± 0.2 hours, is promptly become the tin ash target of pulsed laser deposition;
B. utilize pulse laser sediment method to impact target, select KrF laser, it is 350 mJ that pulse energy is set, wavelength 248 nm, and frequency 10 Hz, 34 nanoseconds of interpulse period, each pulse injection rate is 5 ± 0.1 J/cm
2Vacuum degree is superior to 1 * 10 when the settling chamber
-6During mbar, begin to introduce pulse laser, beat to said target, the control partial pressure of oxygen is 3 ± 0.1 * 10
-2Pa is deposited on target on the silicon substrate, and this underlayer temperature is 320 ± 10
oC, silicon substrate obtain quadrature phase tin dioxide thin film under these conditions apart from 4 ± 0.1 centimetres of targets.
2. the preparation method of quadrature phase tin dioxide thin film according to claim 1; It is characterized in that making said quadrature phase tin dioxide thin film and at room temperature carry out optical property measurement; The transparency of this quadrature phase tin dioxide thin film should be superior to conventional cubic phase tin ash, the band gap E of this quadrature phase tin dioxide thin film
g=4.02 eV are greater than the band gap E of cubic phase tin ash
g=3.6 eV.
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| CN102418070A (en) * | 2011-09-22 | 2012-04-18 | 上海大学 | Preparation method of tin dioxide gas-sensitive fractal material |
| CN108878858B (en) * | 2018-05-07 | 2022-03-18 | 青岛大学 | Tin dioxide thin film material, lithium battery and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100030A (en) * | 1985-04-01 | 1986-06-10 | 天津大学 | Thin film SnO 2 gas-sensitive element and manufacture method thereof |
| US20020127386A1 (en) * | 2001-02-06 | 2002-09-12 | Miki Ogawa | Thin film having porous structure and method for manufacturing porous structured materials |
| CN1475798A (en) * | 2003-07-10 | 2004-02-18 | 上海大学 | Manufacturing method of stannic dioxide nano sensor |
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2011
- 2011-03-04 CN CN2011100515216A patent/CN102161503B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100030A (en) * | 1985-04-01 | 1986-06-10 | 天津大学 | Thin film SnO 2 gas-sensitive element and manufacture method thereof |
| US20020127386A1 (en) * | 2001-02-06 | 2002-09-12 | Miki Ogawa | Thin film having porous structure and method for manufacturing porous structured materials |
| CN1475798A (en) * | 2003-07-10 | 2004-02-18 | 上海大学 | Manufacturing method of stannic dioxide nano sensor |
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