CN1304857C - ZnS infrared window transparent increasing protective film and its preparing method - Google Patents

ZnS infrared window transparent increasing protective film and its preparing method Download PDF

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CN1304857C
CN1304857C CNB2005100167373A CN200510016737A CN1304857C CN 1304857 C CN1304857 C CN 1304857C CN B2005100167373 A CNB2005100167373 A CN B2005100167373A CN 200510016737 A CN200510016737 A CN 200510016737A CN 1304857 C CN1304857 C CN 1304857C
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film
zns
refractive index
refractivity
protective film
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CN1687807A (en
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郑伟涛
胡超权
田宏伟
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Jilin University
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Jilin University
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Abstract

The present invention relates to a ZnS infrared window reflection reducing and protecting film and a preparing method thereof. The film belongs to the field of film technology. Lambada 0 of central wavelength is 9.2 mum, and the double-layer reflection reducing and protecting film series of lambda 0/4 to lambda 0/4 are made on a ZnS material base 1. The refractivity of a high refractivity film 2 is from 3.2 to 4.0, and the optical thickness of the high refractivity film is from 2 to 3 mum. The refractivity of a low refractivity film 3 is from 2.3 to 3.0, and the optical thickness of the low refractivity film is from 2 to 3 mum. The preparing method adopts a radio frequency magnetron sputtering method and comprises: Ge is used as a target source, and CH4/Ar is used as electricity discharging gas; the reflection reducing and protecting film of Ge<1-x>Cx is deposited on the ZnS base; two films of Ge<1-x>Cx with different refractivity are made by controlling the flow ratio of CH4 and (CH4 +Ar); the optical thickness of each film is lambada 0/4 by adjusting depositing time. The method of the present invention has the advantages of simplicity, economy, high efficiency and ideal reflection reducing effect.

Description

A kind of ZnS infrared window anti-reflection protective film and preparation method thereof
Technical field
The invention belongs to the thin film technique field, particularly a kind of formation of the anti-reflection protective film that is used for infrared window and dome material and the anti-reflection protective film preparation method that the ZnS material is substrate.
Background technology
Infrared window is indispensable parts in the infrared system, and its function is protection thermal imaging system operate as normal in high-speed flight and under various rugged surroundings.ZnS is infrared window and the dome material of the long wave of first-selection at 8～11.5 μ m, but is subjected to the restriction of intrinsic property, and its surface needs to apply anti-reflection protective film to improve its mechanical property and infrared light transmission performance in actual applications.
The prior art the most close with the present invention is the articles of " infrared and millimeter wave journal " the 19th volume the 4th phase (2000.8) P266～268 publications, and exercise question is " Ge xC 1-xThe application of film in design of infrared anti-reflection diaphragm system and preparation ".It is substrate material that article discloses with far infrared band ZnS commonly used, has designed three layers of symmetrical antireflective and protective films of the two-sided plating of 8～11.5 mu m wavebands, adopts the radio frequency magnetron reactive sputtering to prepare Ge xC 1-xFilm is as the anti-reflection protective film of infra-red material.At preparation Ge xC 1-xFeed the reacting gas CH of vacuum chamber in the film by change 4Flow realize the control of refractive index.
Background technology does not provide Ge 1-xC xThe preparation technology parameter of film; Do not disclose the mechanical property and the thermal shock resistance of film, and these performances are to Ge 1-xC xFilm is vital as the practical application of anti-reflection protective film; Do not provide each Ge yet 1-xC xThe refractive index and the thickness of layer; Three layers of symmetrical antireflective and protective films of prepared two-sided plating have more increased the difficulty to each layer refractive index and the accurate control of thickness because the number of plies is more.
In fact, improving the effective method of the anti-reflection efficient of anti-reflection protective film, is exactly refractive index and the thickness according to the every tunic of the anti-reflection principle design of optics, makes film after the design tie up to the needs that transmissivity in the service band satisfies practical application.Thereby refractive index and the thickness of controlling every tunic exactly are the keys of Experiment Preparation multilayer antireflective and protective films.Yet, the tested person instrument and the influence of factor such as the uniformity of film that plates is bad, film refractive index that records and thickness often exist than mistake, are difficult to obtain desirable antireflective effect in experiment with reference to this test result, and it is difficult to cause anti-reflection research work to design easy preparation often.
Summary of the invention
The technical problem to be solved in the present invention is design λ 0/ 4-λ 0/ 4 (λ 0Be centre wavelength) double-layer anti-reflection diaphragm system, guarantee that film ties up to 8～11.5 μ m and has good antireflective effect; Adopt radio-frequency magnetron sputter method to prepare anti-reflection protective film, open process conditions, and reduce its preparation difficulty.
A kind of ZnS infrared window anti-reflection protective film is a centre wavelength with 9.2 μ m, makes anti-reflection protective film in the substrate of ZnS material; In substrate, deposit high refractive index film and low refractive index film in turn; The refractive index of said high refractive index film is 3.2～4.0, optical thickness 2～3 μ m; The refractive index of said low refractive index film is 2.3～3.0, optical thickness 2～3 μ m.
High refractive index film and low refractive index film are Ge 1-xC xMaterial.
This anti-reflection protective film both can be that the single-surface double-layer film also can be two-sided duplicature.
Said optical thickness is the geometric thickness of film and the product of film refractive index.
The present invention has prepared Ge in the ZnS substrate 1-xC xDouble-layer anti-reflection diaphragm system.Learn that after tested the transmissivity of ZnS substrate is significantly improved behind plated film, the average transmittance of 8～11.5 μ m has improved 9.5%, and the highest anti-reflection value reaches more than 19.3%.
The preparation method of ZnS infrared window anti-reflection protective film of the present invention is that the employing radio-frequency magnetron sputter method is the target source with Ge, CH 4/ Ar deposits Ge as discharge gas in the ZnS substrate 1-xC xAnti-reflection protective film, depositing system radio-frequency power supply frequency is 13.56MHz.Said Ge 1-xC xAnti-reflection protective film is two-layer; Pre-service is polished, is cleaned in the ZnS substrate before deposition; Deposition Ge 1-xC xDuring anti-reflection protective film, regulating underlayer temperature is 100 ℃～300 ℃, and radio-frequency power is in 100W～300W; Substrate biasing-50V～-100V between; During deposition ground floor high refractive index film, CH 4/ (CH 4+ Ar) throughput ratio is 5%, sedimentation time is 12～13 minutes; Then shutdown system vacuumizes and prepares deposition second tunic; During deposition second layer low refractive index film, CH 4/ (CH 4+ Ar) throughput ratio is 40%, sedimentation time is 17.5～18.5 minutes.
Pre-service is polished, is cleaned in above-mentioned ZnS substrate before deposition, can make it be thinned to 1.0～2.0 μ m with waterproof abrasive paper corase grind ZnS substrate earlier, use the fine grinding of 500# waterproof abrasive paper then, use the twin polishing of M2.5 diamond paste again, last alcohol sonicated 10 minutes, deionized water dries up after washing repeatedly.Can guarantee the adhesion between ZnS substrate and the film like this.
Make the film of quality better, be preferably in deposition Ge 1-xC xBefore the anti-reflection protective film, reaction chamber is evacuated to 6 * 10 earlier -4Pa, and the ZnS substrate heated to 500 ℃ kept 10 minutes, it is temperature required to be reduced to deposition again, can remove like this and be adsorbed on suprabasil air; Before the deposition ground floor high refractive index film and before deposition second layer low refractive index film, earlier to the pre-sputter of Ge target 5～15 minutes, to remove pollutant remaining on the target.
The present invention is by control CH 4, Ar flow proportional obtain the needed ranges of indices of refraction of every tunic in the design, the control sedimentation time obtains the needed optical thickness of every tunic, is difficult to the problem accurately measured thereby avoided film refractive index and thickness in the preparation process.The result shows that the method can solve the difficult problem of present multilayer antireflective and protective films preparation really.This preparation method is simple, economical, efficient, and the antireflective effect ideal has a good application prospect.
Description of drawings
Fig. 1 is the structural representation of ZnS infrared window anti-reflection protective film of the present invention.
Fig. 2 is Ge 1-xC xThe refractive index of material and CH 4/ (CH 4+ Ar) the experiment graph of a relation of throughput ratio.
Fig. 3 is that ZnS substrate single face of the present invention plates two-layer Ge 1-xC xIr transmissivity before and after the film is with the curve of wavelength variations.
Fig. 4 is the two-layer Ge of the two-sided plating of ZnS substrate of the present invention 1-xC xIr transmissivity before and after the film is with the curve of wavelength variations.
Fig. 5 is that two-layer Ge is plated in the ZnS substrate 1-xC xVickers microhardness comparison diagram before and after the film.
Embodiment
The structure of embodiment 1 double-layer anti-reflection diaphragm system
λ of the present invention 0/ 4-λ 0The structure of/4 double-layer anti-reflection diaphragms system as shown in Figure 1.Whole double-layer anti-reflection diaphragm is to be made up of the high refractive index film 2 of ZnS substrate 1, ground floor, the low refractive index film 3 of the second layer.The optical thickness of high refractive index film 2 and low refractive index film 3 all is λ 0/ 4=2～3 μ m.
High refractive index film 2 and low refractive index film 3 are Ge 1-xC xMaterial, wherein x=0.2～0.6.
Because the refractive index (n of ZnS 1=2.2) less, and the Ge that can obtain in the experiment at present 1-xC xThe refractive index of film is bigger, is λ so can plate one deck optical thickness earlier in the ZnS substrate 0/ 4, refractive index is n 2Film, at this moment for central wavelength lambda 0, the system of film and substrate combination can be Y=n with a refractive index 2 2/ n 1Come equivalence, obviously, work as n 2＞n 1The time, Y＞n is arranged 1That is to say, in the ZnS substrate, plate the λ of one deck high index of refraction earlier 0Behind/4 thick retes, the refractive index of substrate is equivalent to from n 1Bring up to n 2 2/ n 1So, plate one deck λ again according to the anti-reflection principle of optics 0/ 4 thick low-refraction n 3Film just can play good antireflective effect.Test shows, the ZnS substrate behind the plated film is significantly improved in the transmissivity of 8～11.5 μ m.
The preparation method of embodiment 2 ZnS infrared window anti-reflection protective films of the present invention
Experimentally, adopt radio-frequency magnetron sputter method with CH 4/ Ar synthesizes Ge as discharge gas in the ZnS substrate 1-xC xDuplicature, this depositing system are FJL-450B type magnetron sputtering and the compound sputtering equipments of ion beam that Shenyang scientific instrument company of the Chinese Academy of Sciences produces, and the radio-frequency power supply frequency is 13.56MHz.Discharge gas CH 4, Ar sends into from vacuum chamber bottom, two kinds of gas respectively by gas control valve, each is through flowmeter, then is mixed into vacuum reaction chamber with certain proportion, connects vacuum air pump below reactor chamber systems, with control reaction chamber pressure at 0.5～2.0Pa.After the glow discharge, CH 4, the positive ion that produces of Ar ionization upwards bombards the Ge target, the Ge atom and the CH that sputter out under effect of electric field 4Decompose the hydrocarbon class plasma generation chemical reaction that produces, in the ZnS substrate, generated Ge at last 1-xC xFilm.Pre-service such as the ZnS substrate need be polished before experiment, cleaning are to guarantee the adhesion of itself and film.Make the good film of matter, should regulate underlayer temperature is 100 ℃～300 ℃, and radio-frequency power is in 100W～300W, substrate bias-50V～-100V between.
The key of preparation duplicature has 2 points: the one, need the different two membranes of selective refraction rate height, and in experiment, can mainly be control CH by the control experiment parameter 4/ (CH 4+ Ar) throughput ratio, the different two-layer Ge of preparation refractive index 1-xC xFilm; The 2nd, guarantee that experimentally the optical thickness of every tunic is λ 0/ 4.CH when determining every tunic plated film 4/ (CH 4+ Ar) after the throughput ratio, to make the optical thickness of every tunic be λ by adjusting sedimentation time again 0/ 4.The optical thickness of testing film can use infrared spectrometer or photometer.As plating one deck optical thickness λ in the ZnS substrate 0Behind/4 thick retes, this film is that infrared transmission spectra can be at λ 0, λ 0/ 3, λ 0/ 5 ... the optical interference peak occurs Deng many places, therefore just can accurately measure the optical thickness of every tunic by infrared transmission spectra.
Embodiment 3 Ge 1-xC xThe refractive index n of material film and CH 4/ (CH 4+ Ar) the empirical curve of throughput ratio relation
Through repeatedly experiment, refractive index n～CH 4/ (CH 4+ Ar) curve is as shown in Figure 2.Along with CH 4/ (CH 4+ Ar) the increase of throughput ratio, Ge 1-xC xThe refractive index n of film is corresponding to diminish.At CH 4/ (CH 4+ Ar)=5～40% scope, the refractive index n of film is in 2.4～4.0 scope.According to empirical curve, can be at the n that selectes high refractive index film 2 and low refractive index film 3 respectively 2And n 3After, correspondence obtains CH 4/ (CH 4+ Ar) ratio has promptly been determined experiment parameter.
Embodiment 4 preparation methods' most preferred embodiment
Technological process is with embodiment 2.With hot pressing ZnS is substrate, deposition Ge 1-xC xThe film of material, radio-frequency power are 150W, and depositing temperature is 200 ℃, and substrate bias is-75V; 2 process conditions of key of control preparation duplicature:
When in the ZnS substrate, depositing the high refractive index film 2 of ground floor: throughput ratio CH 4/ (CH 4+ Ar) be 5%, sedimentation time is 12 minutes and 36 seconds;
When in the ZnS substrate, depositing the low refractive index film 3 of the second layer: throughput ratio CH 4/ (CH 4+ Ar) be 40%, sedimentation time is 18 minutes.
Embodiment 5 test results
1, ir transmissivity test
Fig. 3 is that ZnS substrate single face of the present invention plates two-layer Ge 1-xC xIr transmissivity before and after the film is with the curve of wavelength variations, as we can see from the figure, and the two-layer Ge of ZnS substrate single sided deposition 1-xC xBehind the film, the average transmittance of 8～11.5 μ m has improved 5.4%.Fig. 4 is the two-layer Ge of the two-sided plating of ZnS substrate of the present invention 1-xC xIr transmissivity before and after the film is with the curve of wavelength variations, as we can see from the figure, and the two-layer Ge of the two-sided plating of ZnS substrate 1-xC xAfter, the average transmittance of 8～11.5 μ m has improved 9.5%, and the highest anti-reflection value has reached 19.3%.
2, hardness test
The vickers microhardness test result as shown in Figure 5, it is that the ZnS substrate deposits two-layer Ge 1-xC xVickers microhardness comparison diagram before and after the film system.For the hardness measurement of film, factors such as magnitude of load, substrate hardness all can influence the measured value of hardness strongly, and the general hardness number of measuring is all comprising the contribution of film hardness and substrate hardness, promptly so-called composite hardness.As seen from Figure 5, along with reducing of load, hardness number raises, this mainly be since load the influence of hour substrate is more little more, the hardness number that record this moment is more near the actual value of film.Show among Fig. 5 that film is the 338kgf/mm of hardness from the ZnS substrate when load is 2.5g 2Brought up to 1276.6kgf/mm 2, the two-layer Ge of this explanation plating 1-xC xAfter the film system, the hardness of ZnS substrate increases substantially.
3, thermal shock test
As the constant temperature thermal source, its temperature is controlled at 200 ℃ with batch-type furnace, sample is put into stove, be incubated after 20 minutes, take out the water that sample is put into room temperature (18.5 ℃) rapidly, 10 times so repeatedly.After the thermal shock test, do not find Ge 1-xC xFilm and ZnS substrate disengaging or film are the phenomenon of explosion, and this illustrates Ge 1-xC xFilm is fine with combining of ZnS substrate, and thermal expansivity is approaching.

Claims (1)

1, a kind of preparation method of ZnS infrared window anti-reflection protective film, adopting radio-frequency magnetron sputter method is the target source with Ge, CH 4/ Ar deposits Ge as discharge gas in the ZnS substrate 1-xC xAnti-reflection protective film, depositing system radio-frequency power supply frequency is 13.56MHz, radio-frequency power is in 100W～300W, regulating underlayer temperature is 100 ℃～300 ℃, substrate biasing-50V～-100V between; It is characterized in that said Ge 1-xC xAnti-reflection protective film is two-layer; Pre-service is polished, is cleaned in the ZnS substrate before deposition; During deposition ground floor high refractive index film (2), CH 4/ (CH 4+ Ar) throughput ratio is 5%, sedimentation time is 12～13 minutes; Then shutdown system vacuumizes and prepares deposition second tunic; During deposition second layer low refractive index film (3), CH 4/ (CH 4+ Ar) throughput ratio is 40%, sedimentation time is 17.5～18.5 minutes.
CNB2005100167373A 2005-04-22 2005-04-22 ZnS infrared window transparent increasing protective film and its preparing method Expired - Fee Related CN1304857C (en)

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US11092488B2 (en) 2017-02-15 2021-08-17 University Of The West Of Scotland Infrared spectrophotometer
US11891686B2 (en) 2017-02-15 2024-02-06 University Of The West Of Scotland Apparatus and methods for depositing variable interference filters

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CN105296926B (en) * 2015-12-04 2018-06-15 中国航空工业集团公司洛阳电光设备研究所 A kind of anti-reflection composite membrane optical window of hard and preparation method thereof
CN108330440B (en) * 2018-01-05 2020-06-09 昆明凯航光电科技有限公司 3-12 mu m ZnS substrate optical infrared antireflection film and preparation method thereof
CN108983329A (en) * 2018-07-11 2018-12-11 无锡奥夫特光学技术有限公司 Prepare the process of infrared optical window
CN111007584B (en) * 2019-11-21 2021-05-11 天津津航技术物理研究所 Design method of oxide system infrared anti-reflection protective film
CN112698430B (en) * 2020-12-11 2022-05-13 中材人工晶体研究院有限公司 ZnS substrate long-wave infrared anti-reflection protective film and preparation method thereof
CN114264240B (en) * 2021-11-24 2024-03-22 华中光电技术研究所（中国船舶重工集团公司第七一七研究所） Method for detecting thickness uniformity of each film layer of double-layer film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5425983A (en) * 1992-08-10 1995-06-20 Santa Barbara Research Center Infrared window protected by multilayer antireflective coating
CN1188160A (en) * 1997-11-24 1998-07-22 上海大学 Making of optical anti-reflection film by diamond-like and diamond compound film
US5935723A (en) * 1997-06-06 1999-08-10 Raytheon Company Environmentally resistant, infrared-transparent window structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5425983A (en) * 1992-08-10 1995-06-20 Santa Barbara Research Center Infrared window protected by multilayer antireflective coating
US5935723A (en) * 1997-06-06 1999-08-10 Raytheon Company Environmentally resistant, infrared-transparent window structure
CN1188160A (en) * 1997-11-24 1998-07-22 上海大学 Making of optical anti-reflection film by diamond-like and diamond compound film

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11092488B2 (en) 2017-02-15 2021-08-17 University Of The West Of Scotland Infrared spectrophotometer
US11747201B2 (en) 2017-02-15 2023-09-05 University Of The West Of Scotland Infrared spectrophotometer
US11891686B2 (en) 2017-02-15 2024-02-06 University Of The West Of Scotland Apparatus and methods for depositing variable interference filters

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