CN101887134A - Infrared window protective film material, use thereof and preparation method thereof - Google Patents
Infrared window protective film material, use thereof and preparation method thereof Download PDFInfo
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- CN101887134A CN101887134A CN2010101955098A CN201010195509A CN101887134A CN 101887134 A CN101887134 A CN 101887134A CN 2010101955098 A CN2010101955098 A CN 2010101955098A CN 201010195509 A CN201010195509 A CN 201010195509A CN 101887134 A CN101887134 A CN 101887134A
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Abstract
The invention belongs to the technical field of infrared optical thin films and particularly relates to novel transitional metal Zr and Hf nitride optical thin films, use thereof and a preparation method thereof. The infrared window protective film material consists of transitional metal Zr and Hf nitrides and can be expressed as (Zr, Hf)Nx, wherein x represents the nitrogen content; and the value of the x ranges from 1.0 to 1.5. The material is particularly suitable to be used for manufacturing far-infrared band ZnS and ZnSe infrared window protective films which have high transmissivity, high hardness and low internal stress. The films can be made by various methods such as physical gas-phase deposition or chemical gas-phase deposition and have a promising prospect.
Description
Technical field
The invention belongs to the infrared optical thin film technical field, be specifically related to the nitride optical thin films of a kind of novel magnesium-yttrium-transition metal Zr, Hf and its use with and preparation method thereof.
Background technology
The kind of optical material that can be used in 8～12 μ m far infrared bands is very limited, and among limited different materials, ZnS, ZnSe are two kinds of materials using at most.ZnS, ZnSe have good optical property at 8～12 mu m wavebands, and still, they also have very significant disadvantage simultaneously, and wherein, extremely low hardness makes ZnS, ZnSe be easy to be scratched in application, thereby causes the inefficacy of its optical window.
Up to the present, people after deliberation multiple ZnS, ZnSe protective layer material, comprising diamond-film-like and Ge-C film, PB film and diamond thin etc.Diaphragm as ZnS, ZnSe window, diamond-film-like and Ge-C film have certain rigidity, but the stress of this film is too big, thereby be difficult in the thicker diamond-film-like of coating on ZnS, the ZnSe window, therefore diamond-film-like is to the protective effect of ZnS, ZnSe window limited (Waddell, Ewan M; Gibson, Desmond R; Meredith, J.Proceedings of SPIE-The International Society for Optical Engineering, v 2286, p 364-375,1994).Diamond thin itself has high hardness; be considered to the best diaphragm material of infrared window; but the mode of deposition of diamond film is too harsh; thereby be difficult in and prepare the enough good adamas diaphragm of enough areas, adhesion (Moller A J on ZnS, the ZnSe window; ReeceD M; Hudson M D.Diamond and Related Materials, 1997,6:386).The PB film is the best diaphragm material that up to the present is used for ZnS, ZnSe window, but preparing the PB film need use great toxicity phosphine and borine, thereby the application of PB also comparatively limited (Clark, C.C.1; Haddow, Source:Proceedings of the SPIE-The International Societyfor Optical Engineering D.1, v 4375,307-14,2001).Therefore, seek a kind of diaphragm material that can be applied to ZnS, ZnSe infrared optical window and have very high actual value.
In order to satisfy ZnS, ZnSe infrared optical window active demand to the diaphragm material; the present invention proposes a kind of nitride material and its preparation method that is used to make transition metal Zr, the Hf of far infrared band ZnS, ZnSe optical window diaphragm, this diaphragm can provide effective protection to infrared optical window commonly used such as ZnS, ZnSe.
Summary of the invention
The objective of the invention is to have high permeability for infrared optical window, especially ZnS, the ZnSe optical window of using at 8～12 mu m wavebands provides a kind of, have a New Functional Protective Coating of high rigidity and low internal stress simultaneously.
A kind of infrared window protective film material of the present invention, described material is made up of the nitride of magnesium-yttrium-transition metal Zr, Hf, and composition is that (wherein x represents the numerical value of nitrogen content for Zr, Hf) Nx.
Further, the span of described x is 1.0≤x≤1.5.
The application of infrared window protective film material of the present invention with the diaphragm of described material as ZnS, ZnSe infrared optical window, has following remarkable advantage:
1. this optical thin film has higher hardness.Test shows, (Zr, Hf) hardness of Nx film can reach the high level of about 20GPa.Obviously, high like this hardness can form, effectively protect ZnS, ZnSe optical window.
2. it has higher infrared transmittivity.Test shows, (Zr, Hf) the Nx film has transmitance up to about 70% at 8～12 μ m infrared bands.Obviously, having high like this infrared optics transmitance is the condition an of necessity to the protective layer material as ZnS, ZnSe optical window.
3. it has lower internal stress.Test shows, (Zr, Hf) the Nx film only contains the internal stress of tens MPa after preparation, and this internal stress size can also be changed by the adjustment of thin film preparation process.Obviously, having low like this internal stress level is a very advantageous conditions to its diaphragm as ZnS, ZnSe optical window.
4. the preparation condition of this film is loose relatively.Because (Zr, Hf) the Nx film is stable higher, and therefore, (Zr, Hf) preparation of Nx film can be selected various methods for use, comprises normal various physical gas-phase deposite methods and the chemical gaseous phase depositing process that adopts in the thin film technique.Obviously, this diaphragm for this infrared optical window is another advantageous conditions.
5. this film has higher adhesion to ZnS, ZnSe optical window material.Because (Zr, Hf) the Nx film stable higher, internal stress is lower, is adding that it and ZnS, ZnSe etc. have similar ionic bonding kind, the therefore (Zr for preparing under general preparation condition, Hf) Nx film, having shown has higher adhesion to ZnS, ZnSe optical window material.
The invention also discloses the preparation method of this infrared window protective film material; described method adopts the radio frequency reaction magnetron sputtering technique; with argon gas as sputter gas; nitrogen is as reacting gas; two kinds of gases are controlled its flow by flowmeter separately; enter reaction chamber after mixing by a certain percentage, the nitride film of deposition one deck transition metal Zr, Hf specifically comprises the steps: on substrate
Before the deposition, regulating substrate temperature is 20～500 ℃, reaction chamber is evacuated to below 6 * 10^-3Pa, feed argon gas then, flow is 8.0～10sccm, and chamber pressure is 0.5～0.6Pa, open the substrate power supply and carry out pre-sputter, substrate bias is-300V, and pre-sputtering time is 20 minutes, and substrate and target are separated by baffle plate in the pre-sputter procedure; After pre-sputter finishes, close the substrate power supply, feed nitrogen, regulate N by flowmeter
2/ Ar throughput ratio is between 0.72～1.2, and deposition pressure is 0.34～0.41Pa, and regulating target power supply power is 100～300W, removes baffle plate, begins deposition, and sedimentation time is 60 minutes.
The another kind of preparation method of this infrared window protective film material disclosed by the invention: the chemical vapour deposition technique that described method using plasma is auxiliary prepares that required (Zr, Hf) the Nx nitride film specifically comprises the steps:
1, reaction chamber is evacuated to below 6 * 10^-3Pa, opens substrate heater in the process that vacuumizes, setting its temperature is 500 ℃, feeds the Ar etching 5 minutes, and the Ar flow is 10sccm, chamber pressure 5000 ± 100Pa;
2, etching is closed the Ar flowmeter after finishing, and is evacuated to once more below 6 * 10^-3Pa, feeds ammonia and tetrachloro Zr or tetrachloro Hf, flow respectively is 25sccm and 5sccm, the conditioned reaction chamber pressure is 5000Pa, opens radio-frequency power supply, and adjusting power is 500W, beginning (Zr, Hf) chemical vapor deposition of nitride film, in deposition process, it is constant that the flow of gas keeps, chamber pressure remains between 5000 ± 100Pa, and sedimentation time is 60 minutes.
In sum, the present invention propose (Zr, Hf) the Nx film has usability preferably, can provide effective protection for ZnS, ZnSe infrared optical window with its film of preparing, has a good application prospect.
Description of drawings
Fig. 1 is the cross-section morphology figure that utilizes the magnesium-yttrium-transition metal ZrNx nitride film that the present invention prepares.
Fig. 2 is the cross-section morphology figure that utilizes the magnesium-yttrium-transition metal HfNx nitride film that the present invention prepares.
Fig. 3 is magnesium-yttrium-transition metal (Zr, Hf) X-ray diffracting spectrum of Nx nitride film that utilizes the present invention to prepare.
Fig. 4 utilizes the present invention, and (Zr, Hf) infrared transmittivity of Nx protecting nitride film front and back ZnS substrate sample is with the curve of wavelength variations in preparation on the ZnS substrate.
Fig. 5 utilizes the present invention, preparation on the ZnS substrate (Zr, Hf) nano hardness-displacement curve of ZnS substrate sample before and after the Nx protecting nitride film.
Embodiment
1. select the sputtering method of physical vaporous deposition for use, prepare required (Zr, Hf) Nx nitride film.
2. reaction chamber is evacuated to below 6 * 10^-3Pa, in the process that vacuumizes, open substrate heater, design temperature is 300 ℃, feeds argon gas, and flow is 8.0sccm, chamber pressure is 0.50～0.54Pa, open radio-frequency power supply, regulating substrate bias is-300V to carry out pre-sputter, time is 20 minutes, and target and target are separated by baffle plate in this process.
3. after pre-sputter is intact, close the substrate power supply, regulate argon flow amount to 2.5sccm, open the nitrogen flow valve, regulate nitrogen flow and make the N2/Ar flow ratio 0.72, regulating target power supply setting power input is 100～300W, remove baffle plate, begin deposition, deposition pressure is 0.34～0.41Pa, and sedimentation time is 60 minutes.
4. after deposition finished, powered-down and gas meter were lowered the temperature substrate gradually.
5. for above-mentioned (Zr, Hf) The performance test results of Nx nitride film material
(1) (Zr, Hf) pattern of Nx nitride film and fabric analysis
Obtained (Zr, Hf) cross-section morphology of Nx nitride film as shown in Figure 1, 2, Fig. 3 is the X-ray diffracting spectrum of film.
(2) infrared transmittivity test
Fig. 4 is the curve of the infrared spectrum transmissivity of ZnS substrate coating front and back with wavelength variations, and as we can see from the figure, at 8～12 mu m wavebands, the transmitance of ZnS+HfNx film is more than 70%, and the transmitance of ZnS+ZrNx film also remains on about 70%.
(3) hardness test
Fig. 5 is the nano hardness-displacement curve of the nitride film of transition metal Zr of the present invention, Hf, and we can see from curve, and the hardness number of film is about 20GPa, far above the hardness of ZnS, ZnSe infrared optical window.
(4) thermal shock test
ZnS substrate behind the tubular type constant temperature oven heating plated film at 200 ℃ of insulation 30min, takes out the water of putting into room temperature rapidly, 15 times repeatedly then.Through this test, the protecting nitride film of transition metal Zr, Hf does not peel off or peels off from substrate, and the good bonding force that has between the film base is described.
Embodiment 2
1. select the auxiliary chemical vapour deposition technique of plasma for use, prepare required (Zr, Hf) Nx nitride film.
2. reaction chamber is evacuated to below 6 * 10^-3Pa, opens substrate heater in the process that vacuumizes, setting its temperature is 500 ℃, feeds the Ar etching 5 minutes, and the Ar flow is 10sccm, chamber pressure 5000 ± 100Pa.
3. etching is closed the Ar flowmeter after finishing, and is evacuated to once more below 6 * 10^-3Pa, feeds ammonia and tetrachloro Zr or tetrachloro Hf, flow respectively is 25sccm and 5sccm, the conditioned reaction chamber pressure is 5000Pa, opens radio-frequency power supply, and adjusting power is 500W, beginning (Zr, Hf) chemical vapor deposition of nitride film, in deposition process, it is constant that the flow of gas keeps, chamber pressure remains between 5000 ± 100Pa, and sedimentation time is 60 minutes.
4. after deposition finishes, staged cooling: 450 ℃-350 ℃-250 ℃-150 ℃-20 ℃.
5. (Zr, Hf) The performance test results of Nx nitride film material and Fig. 1-5 is similar to above-mentioned.
Claims (5)
1. infrared window protective film material, it is characterized in that: described material is made up of the nitride of magnesium-yttrium-transition metal Zr, Hf, and composition is that (wherein x represents the numerical value of nitrogen content for Zr, Hf) Nx.
2. a kind of infrared window protective film material according to claim 1 is characterized in that: the span of described x is 1.0≤x≤1.5.
3. the application of infrared window protective film material according to claim 1 is characterized in that: with the diaphragm of described material as ZnS, ZnSe infrared optical window.
4. the preparation method of a kind of infrared window protective film material according to claim 1; it is characterized in that: described method adopts the radio frequency reaction magnetron sputtering technique; with argon gas as sputter gas; nitrogen is as reacting gas; two kinds of gases are controlled its flow by flowmeter separately; enter reaction chamber after mixing by a certain percentage, the nitride film of deposition one deck transition metal Zr, Hf specifically comprises the steps: on substrate
Before the deposition, regulating substrate temperature is 20～500 ℃, reaction chamber is evacuated to below 6 * 10^-3Pa, feed argon gas then, flow is 8.0～10sccm, and chamber pressure is 0.5～0.6Pa, open the substrate power supply and carry out pre-sputter, substrate bias is-300V, and pre-sputtering time is 20 minutes, and substrate and target are separated by baffle plate in the pre-sputter procedure; After pre-sputter finishes, close the substrate power supply, feed nitrogen, regulate N by flowmeter
2/ Ar throughput ratio is between 0.72～1.2, and deposition pressure is 0.34～0.41Pa, and regulating target power supply power is 100～300W, removes baffle plate, begins deposition, and sedimentation time is 60 minutes.
5. the preparation method of a kind of infrared window protective film material according to claim 1 is characterized in that: the chemical vapour deposition technique that described method using plasma is auxiliary prepares that required (Zr, Hf) the Nx nitride film specifically comprises the steps:
5.1 reaction chamber is evacuated to below 6 * 10^-3Pa, in the process that vacuumizes, open substrate heater, setting its temperature is 500 ℃, feeds the Ar etching 5 minutes, the Ar flow is 10sccm, chamber pressure 5000 ± 100Pa;
5.2 close the Ar flowmeter after etching is intact, be evacuated to once more below 6 * 10^-3Pa, feed ammonia and tetrachloro Zr or tetrachloro Hf, flow respectively is 25sccm and 5sccm, the conditioned reaction chamber pressure is 5000Pa, opens radio-frequency power supply, and adjusting power is 500W, beginning (Zr, Hf) chemical vapor deposition of nitride film, in deposition process, it is constant that the flow of gas keeps, chamber pressure remains between 5000 ± 100Pa, and sedimentation time is 60 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477579A (en) * | 2010-11-30 | 2012-05-30 | 天津津航技术物理研究所 | Method for obtaining znse/zns optical element |
| CN103443658A (en) * | 2012-03-09 | 2013-12-11 | 住友电气工业株式会社 | Optical component and manufacturing method therefor |
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| CN1100812A (en) * | 1993-04-28 | 1995-03-29 | 美国Boc氧气集团有限公司 | Durable low-emissivity solar control thin film coating |
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| CN101072734A (en) * | 2004-11-08 | 2007-11-14 | 格拉沃贝尔公司 | Glazing |
| CN101231352A (en) * | 2007-06-11 | 2008-07-30 | 北京有色金属研究总院 | HfON/BP antireflecting protective film for infrared optical window and manufacture method thereof |
| JP2009267192A (en) * | 2008-04-28 | 2009-11-12 | Mitsubishi Electric Corp | Manufacturing method for semiconductor device and semiconductor manufacturing device |
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Patent Citations (7)
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| CN1100812A (en) * | 1993-04-28 | 1995-03-29 | 美国Boc氧气集团有限公司 | Durable low-emissivity solar control thin film coating |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102477579A (en) * | 2010-11-30 | 2012-05-30 | 天津津航技术物理研究所 | Method for obtaining znse/zns optical element |
| CN102477579B (en) * | 2010-11-30 | 2015-01-07 | 天津津航技术物理研究所 | Method for obtaining znse/zns optical element |
| CN103443658A (en) * | 2012-03-09 | 2013-12-11 | 住友电气工业株式会社 | Optical component and manufacturing method therefor |
| CN103443658B (en) * | 2012-03-09 | 2016-05-11 | 住友电气工业株式会社 | Optics and manufacture method thereof |
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Application publication date: 20101117 |