CN103014631B - Method for preparing color Pr (Sr0.1Ca0.9)2Mn2O7 film - Google Patents
Method for preparing color Pr (Sr0.1Ca0.9)2Mn2O7 film Download PDFInfo
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- CN103014631B CN103014631B CN201210553963.5A CN201210553963A CN103014631B CN 103014631 B CN103014631 B CN 103014631B CN 201210553963 A CN201210553963 A CN 201210553963A CN 103014631 B CN103014631 B CN 103014631B
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Abstract
The invention discloses a method for preparing a color Pr (Sr0.1Ca0.9)2Mn2O7 film on a Pt/Ti/SiO2/Si substrate by using a pulse deposition technique. A Pt (111)/Ti/SiO2/Si (100) substrate is selected; and the Pr (Sr0.1Ca0.9)2Mn2O7 film of which the thickness is within the range of 40-280 nm is synthesized by adjusting the laser energy, oxygen pressure, the deposition speed and pulse times in the deposition process. Along with the change of the thickness of the film, the surface appearance and the crystal orientation of the film are also significantly changed, so that the preparation of films of different colors is realized. The film is bright in color and is free of chemical dye in the preparation process but is a pollution-free coloring way, so that the film has a potential application prospect in printed matters and textiles.
Description
Technical field
The present invention relates to a kind of colored Pr (Sr
0.1ca
0.9)
2mn
2o
7the preparation method of film, belongs to the manufacture field of optics and thin-film material
Background technology
Structure is added lustre to and is referred to by scattering of light, the colorific a kind of approach that adds lustre to of interference and diffraction effect.Ridge, line, facet and the molecule on the many organisms of occurring in nature top layer all can produce reflection and scattering process, thereby produces special colour effect.In life, the color of many objects is that pigment adds lustre to and structure is added lustre to mutually combine and just can be showed.Yet, existing structure adds lustre at present colored fiber and film, it is a kind of chemical, free of contamination approach that adds lustre to of not needing, and has potential application prospect in printed matter, textiles.Pr (Sr
0.1ca
0.9)
2mn
2o
7a kind of Double Perovskite Mn oxide of orthohormbic structure, by (MnO
2)
2pr (Sr, Ca) the O halite layer of layer and insulation is alternately piled up and is formed along c-axis.Its structural anisotropy causes this material to have the abundant physical propertiess such as huge magneto-resistor, electric charge-track be orderly, makes this material become strong correlation electron systematic research focus.In thin-film material preparation process, selected substrate is different, all different to the stress of material production, Surface binding energy, and the surface topography, crystalline orientation that causes formed thin-film material be difference to some extent all.
Summary of the invention
The object of the present invention is to provide a kind of colored Pr (Sr
0.1ca
0.9)
2mn
2o
7the preparation method of film.
The technical scheme that the present invention takes is as follows: a kind of colored Pr (Sr
0.1ca
0.9)
2mn
2o
7the preparation method of film, comprises the following steps:
(1) adopt sol-gel method to prepare Pr (Sr
0.1ca
0.9)
2mn
2o
7target, the Pr that is first 99.9% by purity
6o
11, CaCO
3, SrCO
3and Mn (NO
3)
20.17:0.2:1.8:2 adds in deionized water after weighing in molar ratio, drips HNO
3it is dissolved completely, add subsequently appropriate complexing agent citric acid and ethylene glycol, fully stir, after dissolving completely, put into water bath, at 80 ℃, water-bath is 12 hours;
(2) gel after water-bath is put into loft drier, at 100 ℃, 200 ℃, be dried 12,24 hours respectively successively, after grinding in box-type furnace sintering 5 hours at 500 ℃, after again grinding, at 900 ℃, sintering is 10 hours, again grind, suppress in flakes, at 1400 ℃, calcine 10-58 hour, make Pr (Sr
0.1ca
0.9)
2mn
2o
7target;
(3) select Pt (the 111)/Ti/SiO of market sale
2/ Si (100) substrate, is put into successively in acetone, dehydrated alcohol, deionized water and carries out ultrasonic cleaning, packs in the vacuum chamber of impulse laser deposition system (PLD-450a type) after drying;
(4) open vacuum system, after vacuum tightness is lower than 5Pa, open high vacuum system, final vacuum tightness reaches 10
-4pa; Substrate temperature is risen to 750 ℃ subsequently, regulate oxygen to be depressed into 20Pa;
(5) rotational velocity of target is adjusted to 2.5 revs/min, open ionization switch, regulating voltage is 0.1kv, and regulating the distance of substrate and target is 5cm, it is 1Hz that laser frequency is set, voltage is 20kv (energy is about 300mJ), opens laser apparatus, starts deposit film, every successive sedimentation 300 times, 5 minutes, interval, then carry out pulsed laser deposition next time, pulsed deposition total degree 300-9000 time; Last in-situ annealing 10 minutes, closes laser apparatus, ionization and target rotation, makes substrate temperature drop to room temperature in former atmosphere, obtains colored Pr (Sr
0.1ca
0.9)
2mn
2o
7film;
Adopt respectively X-ray diffractometer, Scanning Probe Microscopy and scanning electron microscope to characterize preparing structure, pattern and the thickness of film, the thickness of discovery film increases with the increase of frequency of depositing, the grain-size of preparing film is 20-120nm, and thickness is 40-280nm; Adopt ultraviolet-visible spectrophotometer to measure preparing the reflection spectrum of film, prepare film to the reflection-absorption spectral limit of visible ray at 460-630nm; By changing the thickness of film, having realized light-wave band is the regulation and control of 460-630nm scope color.
Preparation method of the present invention, when total laser pulse number is 600 times in step (5), can prepare yellow Pr (Sr
0.1ca
0.9)
2mn
2o
7film.
Preparation method of the present invention, when total laser pulse number is 1050 times in step (5), can prepare blue Pr (Sr
0.1ca
0.9)
2mn
2o
7film.
Preparation method of the present invention, when total laser pulse number is 1500 times in step (5), can prepare Pr (Sr azury
0.1ca
0.9)
2mn
2o
7film.
Preparation method of the present invention, when total laser pulse number is 9000 times in step (5), can prepare green Pr (Sr
0.1ca
0.9)
2mn
2o
7film.
The beneficial effect that the present invention obtains is as follows:
The present invention utilizes pulsed laser deposition technique, at Pt/Ti/SiO
2pr (the Sr that has prepared different thickness, different crystal orientation and surface topography on/Si substrate
0.1ca
0.9)
2mn
2o
7film, has realized the adjustable of color in visible region.This preparation method is without any dyestuff, is due to the variation of color due to the structure of film completely, has excellent optical property and good application prospect.By controlling frequency of depositing in deposition process, control the color of film, the method easy handling, has potential application prospect in magnetics, the structure field such as add lustre to.
Accompanying drawing explanation
Colored Pr (the Sr of Fig. 1 for regulate total laser pulse number to prepare according to the present invention
0.1ca
0.9)
2mn
2o
7the stereoscan photograph of film section, the scanning electron microscope shape appearance figure that illustration is this film surface.
Embodiment
Following examples are used for illustrating the present invention.It may be noted that these embodiment are only for the present invention is described, rather than limit the scope of the invention.
Embodiment 1 shows yellow Pr (Sr
0.1ca
0.9)
2mn
2o
7the preparation of film
(1) adopt sol-gel method to prepare Pr (Sr
0.1ca
0.9)
2mn
2o
7target, the Pr that is 99.9% by purity
6o
11, CaCO
3, SrCO
3and Mn (NO
3)
20.17:0.2:1.8:2 adds in deionized water after weighing in molar ratio, drips HNO
3make its dissolving.Add subsequently appropriate complexing agent citric acid and ethylene glycol, fully stir, after it is dissolved completely, put into water bath, at 80 ℃, water-bath is 12 hours.
(2) gel after water-bath is put into loft drier, at 100 ℃, 200 ℃, be dried 12,24 hours respectively successively.After grinding in box-type furnace sintering 5 hours at 500 ℃; After again grinding, at 900 ℃, sintering is 10 hours; Finally again grind, suppress in flakes, at 1400 ℃, calcine 10-58 hour, make Pr (Sr
0.1ca
0.9)
2mn
2o
7target.
(3) select Pt (the 111)/Ti/SiO of market sale
2/ Si (100) substrate, is put into successively in acetone, dehydrated alcohol, deionized water and carries out ultrasonic cleaning, packs in the vacuum chamber of impulse laser deposition system (PLD-450a type) after drying.
(4) open vacuum system, after vacuum tightness is lower than 5Pa, open high vacuum system, final vacuum tightness reaches 10
-4pa; Substrate temperature is risen to 750 ℃ subsequently, regulate oxygen to be depressed into 20Pa.
(5)) rotational velocity of target is adjusted to 2.5 revs/min, open ionization switch, regulating voltage is 0.1kv; Regulating the distance of substrate and target is 5cm; It is 1Hz that laser frequency is set, and voltage is 20kv (energy is about 300mJ), opens laser apparatus, starts deposit film; Every successive sedimentation 300 times, 5 minutes, interval, carries out twice pulsed laser deposition altogether, and last in-situ annealing 10 minutes, closes laser apparatus, ionization and target rotation, makes substrate temperature drop to room temperature in former atmosphere, obtains yellow Pr (Sr
0.1ca
0.9)
2mn
2o
7film.The profile scanning electromicroscopic photograph that Fig. 1 (a) is this film, the scanning electron microscope shape appearance figure that illustration is this film surface.
Embodiment 2 shows blue Pr (Sr
0.1ca
0.9)
2mn
2o
7the preparation of film
(1) adopt sol-gel method to prepare Pr (Sr
0.1ca
0.9)
2mn
2o
7target, the Pr that is 99.9% by purity
6o
11, CaCO
3, SrCO
3and Mn (NO
3)
2after weighing by certain chemical mol ratio 0.17:0.2:1.8:2, add in deionized water, drip HNO
3make its dissolving.Add subsequently appropriate complexing agent citric acid and ethylene glycol, fully stir, after it is dissolved completely, put into water bath, at 80 ℃, water-bath is 12 hours.
(2) gel after water-bath is put into loft drier, at 100 ℃, 200 ℃, be dried 12,24 hours respectively successively.After grinding in box-type furnace sintering 5 hours at 500 ℃; After again grinding, at 900 ℃, sintering is 10 hours; Finally again grind, suppress in flakes, at 1400 ℃, calcine 10-58 hour, make Pr (Sr
0.1ca
0.9)
2mn
2o
7target.
(3) select Pt (the 111)/Ti/SiO of market sale
2/ Si (100) substrate, is put into successively in acetone, dehydrated alcohol, deionized water and carries out ultrasonic cleaning, packs in the vacuum chamber of impulse laser deposition system (PLD-450a type) after drying.
(4) open vacuum system, after vacuum tightness is lower than 5Pa, open high vacuum system, final vacuum tightness reaches 10
-4pa; Substrate temperature is risen to 750 ℃ subsequently, regulate oxygen to be depressed into 20Pa.
(5)) rotational velocity of target is adjusted to 2.5 revs/min, open ionization switch, regulating voltage is 0.1kv; Regulating the distance of substrate and target is 5cm; It is 1Hz that laser frequency is set, and voltage is 20kv (energy is about 300mJ), opens laser apparatus, starts deposit film; Every successive sedimentation 300 times, 5 minutes, interval, carries out three subpulse laser depositions altogether; Behind 5 minutes, interval, successive sedimentation is 150 times again.Last in-situ annealing 10 minutes, closes laser apparatus, ionization and target rotation, makes substrate temperature drop to room temperature in former atmosphere, obtains blue Pr (Sr
0.1ca
0.9)
2mn
2o
7film.The profile scanning electromicroscopic photograph that Fig. 1 (b) is this film, the scanning electron microscope shape appearance figure that illustration is this film surface.
Embodiment 3 shows Pr (Sr azury
0.1ca
0.9)
2mn
2o
7the preparation of film
(1) adopt sol-gel method to prepare Pr (Sr
0.1ca
0.9)
2mn
2o
7target, the Pr that is 99.9% by purity
6o
11, CaCO
3, SrCO
3and Mn (NO
3)
2after weighing by certain chemical mol ratio 0.17:0.2:1.8:2, add in deionized water, drip HNO
3make its dissolving.Add subsequently and add subsequently appropriate complexing agent citric acid and ethylene glycol, fully stir, after it is dissolved completely, put into water bath, at 80 ℃, water-bath is 12 hours.
(2) gel after water-bath is put into loft drier, at 100 ℃, 200 ℃, be dried 12,24 hours respectively successively.After grinding in box-type furnace sintering 5 hours at 500 ℃; After again grinding, at 900 ℃, sintering is 10 hours; Finally again grind, suppress in flakes, at 1400 ℃, calcine 10-58 hour, make Pr (Sr
0.1ca
0.9)
2mn
2o
7target.
(3) select Pt (the 111)/Ti/SiO of market sale
2/ Si (100) substrate, is put into successively in acetone, dehydrated alcohol, deionized water and carries out ultrasonic cleaning, packs in the vacuum chamber of impulse laser deposition system (PLD-450a type) after drying.
(4) open vacuum system, after vacuum tightness is lower than 5Pa, open high vacuum system, final vacuum tightness reaches 10
-4pa; Substrate temperature is risen to 750 ℃ subsequently, regulate oxygen to be depressed into 20Pa.
(5)) rotational velocity of target is adjusted to 2.5 revs/min, open ionization switch, regulating voltage is 0.1kv; Regulating the distance of substrate and target is 5cm; It is 1Hz that laser frequency is set, and voltage is 20kv (energy is about 300mJ), opens laser apparatus, starts deposit film; Every successive sedimentation 300 times, 5 minutes, interval, carries out five subpulse laser depositions altogether; Last in-situ annealing 10 minutes, closes laser apparatus, ionization and target rotation, makes substrate temperature drop to room temperature in former atmosphere, obtains Pr (Sr azury
0.1ca
0.9)
2mn
2o
7film.The profile scanning electromicroscopic photograph that Fig. 1 (c) is this film, the scanning electron microscope shape appearance figure that illustration is this film surface.
Embodiment 4 shows green Pr (Sr
0.1ca
0.9)
2mn
2o
7the preparation of film
(1) adopt sol-gel method to prepare Pr (Sr
0.1ca
0.9)
2mn
2o
7target, the Pr that is 99.9% by purity
6o
11, CaCO
3, SrCO
3and Mn (NO
3)
2after weighing by certain chemical mol ratio 0.17:0.2:1.8:2, add in deionized water, drip HNO
3make its dissolving.Add subsequently appropriate complexing agent citric acid and ethylene glycol, fully stir, after it is dissolved completely, put into water bath, at 80 ℃, water-bath is 12 hours.
(2) gel after water-bath is put into loft drier, at 100 ℃, 200 ℃, be dried 12,24 hours respectively successively.After grinding in box-type furnace sintering 5 hours at 500 ℃; After again grinding, at 900 ℃, sintering is 10 hours; Finally again grind, suppress in flakes, at 1400 ℃, calcine 10-58 hour, make Pr (Sr
0.1ca
0.9)
2mn
2o
7target.
(3) select Pt (the 111)/Ti/SiO of market sale
2/ Si (100) substrate, is put into successively in acetone, dehydrated alcohol, deionized water and carries out ultrasonic cleaning, packs in the vacuum chamber of impulse laser deposition system (PLD-450a type) after drying.
(4) open vacuum system, after vacuum tightness is lower than 5Pa, open high vacuum system, final vacuum tightness reaches 10
-4pa; Substrate temperature is risen to 750 ℃ subsequently, regulate oxygen to be depressed into 20Pa.
(5)) rotational velocity of target is adjusted to 2.5 revs/min, open ionization switch, regulating voltage is 0.1kv; Regulating the distance of substrate and target is 5cm; It is 1Hz that laser frequency is set, and voltage is 20kv (energy is about 300mJ), opens laser apparatus, starts deposit film; Every successive sedimentation 300 times, 5 minutes, interval, carries out 30 subpulse laser depositions altogether; Last in-situ annealing 10 minutes, closes laser apparatus, ionization and target rotation, makes substrate temperature drop to room temperature in former atmosphere, obtains green Pr (Sr
0.1ca
0.9)
2mn
2o
7film.The profile scanning electromicroscopic photograph that Fig. 1 (d) is this film, the scanning electron microscope shape appearance figure that illustration is this film surface.
Claims (5)
1. a colored Pr (Sr
0.1ca
0.9)
2mn
2o
7the preparation method of film, is characterized in that comprising the following steps:
(1) adopt sol-gel method to prepare Pr (Sr
0.1ca
0.9)
2mn
2o
7target, the Pr that is 99.9% by purity
6o
11, CaCO
3, SrCO
3and Mn (NO
3)
20.17:0.2:1.8:2 adds in deionized water after weighing in molar ratio, drips HNO
3it is dissolved, add subsequently appropriate complexing agent citric acid and ethylene glycol, fully stir, after dissolving completely, put into water bath, at 80 ℃, water-bath is 12 hours;
(2) gel after water-bath is put into loft drier, at 100 ℃, 200 ℃, be dried 12,24 hours respectively successively, after grinding in box-type furnace sintering 5 hours at 500 ℃, after again grinding, at 900 ℃, sintering is 10 hours, again grind, suppress in flakes, at 1400 ℃, calcine 10-58 hour, make Pr (Sr
0.1ca
0.9)
2mn
2o
7target;
(3) select Pt (the 111)/Ti/SiO of market sale
2/ Si (100) substrate, is put into successively in acetone, dehydrated alcohol, deionized water and carries out ultrasonic cleaning, packs in the vacuum chamber of PLD-450a type impulse laser deposition system after drying;
(4) open vacuum system, after vacuum tightness is lower than 5Pa, open high vacuum system, final vacuum tightness reaches 10
-4pa, rises to substrate temperature 750 ℃ subsequently, regulates oxygen to be depressed into 20Pa;
(5) rotational velocity of target is adjusted to 2.5 revs/min, open ionization switch, regulating voltage is 0.1kv, regulating the distance of substrate and target is 5cm, it is 1Hz that laser frequency is set, and voltage is 20kv, and energy is 300mJ, open laser apparatus, start deposit film, every successive sedimentation 300 times, 5 minutes, interval, carry out again pulsed laser deposition next time, pulsed laser deposition total degree 300-9000 time, last in-situ annealing 10 minutes, closes laser apparatus, ionization switch and target rotation, make substrate temperature drop to room temperature in former atmosphere, obtain colored Pr (Sr
0.1ca
0.9)
2mn
2o
7film.
2. preparation method according to claim 1, is characterized in that in deposit film process, pulsed laser deposition total degree is 600 times.
3. preparation method according to claim 1, is characterized in that in deposit film process, pulsed laser deposition total degree is 1050 times.
4. preparation method according to claim 1, is characterized in that in deposit film process, pulsed laser deposition total degree is 1500 times.
5. preparation method according to claim 1, is characterized in that in deposit film process, total laser pulse number is 9000 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210553963.5A CN103014631B (en) | 2012-12-19 | 2012-12-19 | Method for preparing color Pr (Sr0.1Ca0.9)2Mn2O7 film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210553963.5A CN103014631B (en) | 2012-12-19 | 2012-12-19 | Method for preparing color Pr (Sr0.1Ca0.9)2Mn2O7 film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103014631A CN103014631A (en) | 2013-04-03 |
| CN103014631B true CN103014631B (en) | 2014-08-20 |
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ID=47963739
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|---|---|---|---|
| CN201210553963.5A Expired - Fee Related CN103014631B (en) | 2012-12-19 | 2012-12-19 | Method for preparing color Pr (Sr0.1Ca0.9)2Mn2O7 film |
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| Country | Link |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1170749A (en) * | 1996-07-12 | 1998-01-21 | 南京大学 | Perovskite-like compound as high-temperature magnetic refrigerating working medium |
| CN1622357A (en) * | 2004-12-16 | 2005-06-01 | 中国科学院物理研究所 | Method and device for preparing large area superconducting film adopting pulse laser deposition process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPR026100A0 (en) * | 2000-09-20 | 2000-10-12 | Tamanyan, Astghik | Deposition of thin films by laser ablation |
| JP2011060448A (en) * | 2009-09-07 | 2011-03-24 | Kanagawa Acad Of Sci & Technol | Method of manufacturing transparent conductor, transparent conductor, device, and electronic apparatus |
-
2012
- 2012-12-19 CN CN201210553963.5A patent/CN103014631B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1170749A (en) * | 1996-07-12 | 1998-01-21 | 南京大学 | Perovskite-like compound as high-temperature magnetic refrigerating working medium |
| CN1622357A (en) * | 2004-12-16 | 2005-06-01 | 中国科学院物理研究所 | Method and device for preparing large area superconducting film adopting pulse laser deposition process |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2011-60448A 2011.03.24 |
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