CN1818126A - Complex alloy thin film with hydrogen-inducing off-coloring function and production thereof - Google Patents
Complex alloy thin film with hydrogen-inducing off-coloring function and production thereof Download PDFInfo
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- CN1818126A CN1818126A CN 200610023261 CN200610023261A CN1818126A CN 1818126 A CN1818126 A CN 1818126A CN 200610023261 CN200610023261 CN 200610023261 CN 200610023261 A CN200610023261 A CN 200610023261A CN 1818126 A CN1818126 A CN 1818126A
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Abstract
The invention is about the La-Mg-Ni alloy and the multiple alloy film which can change the color by the H2. The alloy firm has the low hydriding condition, the quick hidriding speed and the big photo-electricity character, good stability and long life. The alloy material forms the alloy film through the codeposition or deposition separately by the sputter method, then to form the nanometer alloy film after the annealing. The alloy film can be used for the H2 detector, temperature bulb, the building materials, the car back mirror, optical logic door, the satellite and the communication apparatus.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of alloy film material and preparation method thereof.Prepared alloy firm has " hydrogen-inducing off-coloring " function, can be used for making optical logic gate, optoelectronic switch, hydrogen gas detector and temperature sensor etc.
Background technology
Interaction between hydrogen and the transiting group metal elements is materialogy and physical important research field.1996, professor R.Griessen of Dutch Vrije College Physics system found that metal Y film can very fast absorption hydrogen atom under room temperature and 1atm hydrogen pressure, at first generates hydride YH
2, be transformed into YH then
3Follow this phase transition process, the optical property of Y film has become the light transmission of inhaling behind the hydrogen by inhaling non-light transmittance before the hydrogen.With it simultaneously, the electrical properties of Y film also is transformed into the semi-conductor inhaled behind the hydrogen until isolator from inhaling metallic conductor before the hydrogen.Further experiment confirms that again metal La film also can produce same optics and electrical phenomena after inhaling hydrogen.Because this physical phenomenon has reversibility, therefore utilize this principle can develop a kind of hydrogen and cause the switchable window device of alert and resourceful type.This window device will be at material of construction (aspect energy-conservation), and optical logic gate, satellite and communication aspect have important use to be worth.1997, people such as Dutch Philip breadboard Van der Sluis were at Gd
1-yMg
yH
xAlso find same physical phenomenon in the alloy firm of (y＞0.4).Compare with the La film with Y, this alloy firm not only has good oxidization resistance energy and lower material cost, and all shows the good light transmittance energy in whole visible-range.The range of choice of material has not only been widened in this technical new breakthrough, has also stepped an important step to the practicability direction simultaneously.The T.J.Richardson researcher of calendar year 2001 U.S. Lao Lunsi Berkeley National Laboratory finds that again the Mg-H film also has light transmission.Compare with above-mentioned two kinds of materials, Mg-H has high contrast gradient, the high-transmission rate after promptly inhaling the preceding high-reflectivity of hydrogen and inhaling hydrogen.Calendar year 2001, people such as P.van der Sluis utilize GdMgH
4And WO
3Made an all solid state device, can realize the optical conversion of energy of device by the mode that changes voltage, and have cycle life preferably.
Yet although pure rare earth system hydrogenation property is good, the high Mg-Ni system of RE-Mg system optical contrast cost is low, oxidation-resistance is strong, it is not good that they all exist optical property, and thin film stability is poor, inhales shortcomings such as hydrogen desorption kinetics difference.
Summary of the invention
The objective of the invention is to obtain good in optical property, thin film stability strong, inhale the hydrogen desorption kinetics performance good have complex alloy thin film of hydrogen-inducing off-coloring function and preparation method thereof.
A kind of multicomponent alloy micro/nano level thin-film material with hydrogen-inducing off-coloring function that the present invention proposes is based on the La-Mg-Ni alloy and the La-Mg-Ni-M complex alloy thin film that forms, and M is one or more Pd, Al or other rare earth element.
Among the present invention, the composition of La-Mg-Ni-M complex alloy thin film is La
xMg
yNi
zM
100-x-y-z, 0≤x≤60,0≤y≤30,0≤z≤40 wherein.
Among the present invention, this film is based on the La-Mg-Ni alloy and the complex alloy thin film that forms.
Among the present invention, the thickness of film is between the 10nm-200 μ m.
A kind of preparation method with multicomponent alloy micro/nano level thin-film material of hydrogen-inducing off-coloring function of the present invention's turnover is to prepare the La-Mg-Ni-M thin-film material by sputtering method.
Among the present invention, sputtering method is electron beam evaporation, magnetron sputtering or ion sputtering.
The preparation process of the inventive method is as follows:
(1) material that will constitute thin film composition is smelted into block alloy, adds the M element and form the many first block alloys of La-Mg-Ni-M in fusion process;
(2) with alloy after the melting or pure component starting material, under high vacuum or UHV condition, by electron beam evaporation, magnetron sputtering or ion sputtering method, concurrently vapour depositing is controlled the alloy firm that forms heterogeneity by changing sedimentation rate; The pure component starting material are by the deposit multilayer film, and the thickness of regulating every layer film is controlled the component proportions of final film;
(3) under 100-300 ℃ temperature, the film that makes in (2) was annealed 5-100 hour at vacuum condition or under protection of inert gas, form alloy firm.
Among the present invention, the alloy firm of formation deposits the protection against oxidation layer of pure palladium of one deck or pure nickel again.
Among the present invention, the protection against oxidation layer thickness is 2-50nm.
Thin-film material described in the present invention is as the application of hydrogen gas detector, temperature sensor, variable color ceiling, photo chromic glass, photoelectricity logical gate or optoelectronic switch.
Further the preparation process of narration La-Mg-Ni alloy firm is as follows:
1, the preparation of block alloy
Under the protective atmosphere of room temperature and nitrogen or argon gas,, weigh La, Ni and the Mg of certainweight by the composition requirement of design; Under high vacuum, utilize the high-frequency induction method to carry out melting then, make the block alloy of heterogeneity, as La-Ni alloy, La-Mg alloy, Mg-Ni alloy or La-Mg-Ni alloy etc.Can add an amount of M unit in the process and usually carry out material modification, contain the polynary block alloy of M with formation, wherein M is one or more metals, and M can be Pd, Al and other rare earth element.
2, film preparation
With the multicomponent alloy after the melting or pure La, thin film composition materials such as pure Ni, pure Mg, under high vacuum or UHV condition (10
-6Pa～10
-9Pa), by methods such as electron beam evaporation, magnetron sputtering, ion sputterings, carry out single source or multi-source hydatogenesis.When utilizing the multi-source concurrently vapour depositing, control the alloy firm that forms heterogeneity by regulating homologous sedimentation rate not; When utilizing single source hydatogenesis multilayer film, control the composition of final film by the thickness of regulating every layer film.
3, annealing forms alloy firm
After the deposition, under appropriate temperature, film was being annealed 5-100 hour under the UHV condition or under the protection of rare gas element (as nitrogen, argon gas), forming alloy firm.
4, thinfilm protective coating
Pass through the sputtering sedimentation layer protective layer at last on film surface again, material is pure palladium or pure nickel.
The present invention can effectively overcome the prior art shortcoming by preparation La-Mg-Ni block alloy with based on this novel material of La-Mg-Ni-M complex alloy thin film that such La-Mg-Ni alloy forms.This alloy firm reaches " synergistic effect " by the effect of each constituent element of performance, obtains to be better than the over-all properties of current material.The present invention for design and preparation based on hydrogen gas detector, temperature sensor, the material of construction (energy-conservation aspect) of La-Mg-Ni-H thin-film material, automobile rearview mirror, the window device of optical logic gate, satellite and communication aspect lays the foundation.
The photoelectric properties test shows, the transmissivity contrast reaches 7000: 1 before and after the La-Mg-Ni-M alloy firm hydrogenation that the present invention makes, and resistivity contrast has also reached 1000: 1.Can be used as a kind of novel material of producing hydrogen gas detector, temperature sensor, photoelectricity logical gate and optoelectronic switch.
Description of drawings
Fig. 1 by left-to-right be successively the preparation LaNi, La
3Ni and LaNi
3Block alloy figure.
Fig. 2 is the unannealed alloy firm that is coated with 2nm protective layer Ni of preparation, and substrate is a glass.
Fig. 3 is the alloy firm figure after the annealing that is coated with 2nm protective layer Ni for preparing, and substrate is a glass.
Fig. 4 has face that 10nm protective layer Ni is arranged for the alloy firm after the hydrogenation, and substrate is a glass.
Fig. 5 is the transmitted light spectrogram of LaMgNi alloy firm before and after hydrogenation after annealing.
Embodiment
Embodiment 1:
1) block alloy preparation
Under the protective atmosphere of room temperature and nitrogen or argon gas, weighed 1: 1,1: 3 and the La and the Ni of 3: 1 molar weights, under high vacuum, utilize induction heating to carry out melting then, make LaNi, La
3Ni and LaNi
3Block alloy.In order to guarantee the homogeneity of composition, the alloy that upset has been solidified, melt back, the block alloy for preparing at last is as shown in Figure 1.
2) thin film deposition
With LaNi alloy after the melting and pure Mg, under UHV condition (10
-9Pa), by electron beam evaporation, hydatogenesis has the multilayer film of ABABAB structure.Every layer of LaNi 1.5nm wherein, totally 25 layers; Every layer of 1.5nm of Mg, totally 25 layers.
3) thinfilm protective coating
Again by sputtering sedimentation one deck nickel protection layer, thickness is 2nm on film surface.The film of preparation gained is seen accompanying drawing 2.Among Fig. 2, Fudan University's badge under the film is covered fully, and it is gloomy that film is, at the bottom of transmissivity and the reflectivity, and the specific absorption height.
4) annealing forms alloy
After the deposition, under appropriate temperature, film annealing 48-96 hour under the UHV condition or under as the protection of rare gas elementes such as nitrogen, argon gas, is formed alloy firm.Alloy firm after the annealing is seen accompanying drawing 3.Among Fig. 3, Fudan University's badge under the film is still covered fully, and film is silver lustre white, and transmissivity is low, reflectivity and specific absorption height.
Embodiment 2
With the preparation the LaMgNi alloy firm be example, after the alloy firm hydrogenation as shown in Figure 4.Among Fig. 4, Fudan University's badge under the film is high-visible, and film is water white transparency, and the transmissivity height is at the bottom of reflectivity and the specific absorption.Fig. 5 has compared the variation of its hydrogenation front and back transmissivity.As can be seen from the figure, the transmissivity of film is almost nil before the hydrogenation, and maximum transmission rate reaches 50% after the hydrogenation, and in the 900nm wavelength region, average transmittance is 45% at 400nm.Alloy firm of the present invention has high transmittance in visible-range, can satisfy requirement of actual application.
Claims (11)
1, a kind of multicomponent alloy micro/nano level thin-film material with hydrogen-inducing off-coloring function is characterized in that the La-Mg-Ni-M complex alloy thin film that forms based on the La-Mg-Ni alloy, and M is one or more Pd, Al or other rare earth element.
2, thin-film material as claimed in claim 1, the composition that it is characterized in that the La-Mg-Ni-M complex alloy thin film is La
xMg
yNi
zM
100-x-y-z, 0≤x≤60,0≤y≤30,0≤z≤40 wherein.
3, thin-film material as claimed in claim 1 or 2 is characterized in that this film is based on the La-Mg-Ni alloy and the complex alloy thin film that forms.
4, thin-film material as claimed in claim 1, the thickness that it is characterized in that film are between the 10nm-200 μ m.
5, a kind of preparation method with multicomponent alloy micro/nano level thin-film material of hydrogen-inducing off-coloring function is characterized in that preparing the La-Mg-Ni-M thin-film material by sputtering method.
6, preparation method as claimed in claim 5 is characterized in that sputtering method is electron beam evaporation, magnetron sputtering or ion sputtering.
7, preparation method as claimed in claim 5 is characterized in that preparation process is as follows:
(1) material that will constitute thin film composition is smelted into block alloy, adds the M element and form the many first block alloys of La-Mg-Ni-M in fusion process;
(2) with alloy after the melting or pure component starting material, under high vacuum or UHV condition, by electron beam evaporation, magnetron sputtering or ion sputtering method, concurrently vapour depositing is controlled the alloy firm that forms heterogeneity by changing sedimentation rate; The pure component starting material are by the deposit multilayer film, and the thickness of regulating every layer film is controlled the component proportions of final film;
(3) under 100-300 ℃ temperature, the film that makes in (2) was annealed 5-100 hour at vacuum condition or under protection of inert gas, form alloy firm.
8, preparation method as claimed in claim 7 is characterized in that the alloy firm that forms deposits the protection against oxidation layer of pure palladium of one deck or pure nickel again.
9, preparation method as claimed in claim 8 is characterized in that the protection against oxidation layer thickness is 2-50nm.
10, thin-film material as claimed in claim 1 is as the application of hydrogen gas detector, temperature sensor, variable color ceiling, photo chromic glass, photoelectricity logical gate or optoelectronic switch.
11, thin-film material as claimed in claim 5 is as the application of hydrogen gas detector, temperature sensor, variable color ceiling, photo chromic glass, photoelectricity logical gate or optoelectronic switch.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831619A (en) * | 2010-05-28 | 2010-09-15 | 浙江大学 | Nano-crystalline Mg-Ni multilayer composite film and preparation method thereof |
| CN106248596A (en) * | 2016-08-18 | 2016-12-21 | 上海交通大学 | The In situ spectroscopic ventilation test device of hydrogen-inducing off-coloring function thin film |
| CN107037042A (en) * | 2016-10-19 | 2017-08-11 | 中国石油化工股份有限公司 | A kind of corrosion monitoring coating |
-
2006
- 2006-01-12 CN CN 200610023261 patent/CN1818126A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831619A (en) * | 2010-05-28 | 2010-09-15 | 浙江大学 | Nano-crystalline Mg-Ni multilayer composite film and preparation method thereof |
| CN106248596A (en) * | 2016-08-18 | 2016-12-21 | 上海交通大学 | The In situ spectroscopic ventilation test device of hydrogen-inducing off-coloring function thin film |
| CN106248596B (en) * | 2016-08-18 | 2020-01-07 | 上海交通大学 | In-situ spectrum ventilation testing device for hydrogen-induced color-changing functional film |
| CN107037042A (en) * | 2016-10-19 | 2017-08-11 | 中国石油化工股份有限公司 | A kind of corrosion monitoring coating |
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