CN103882378B - A kind of preparation method of three boracic acid oxygen calcium yttrium crystal (YCOB) high laser damage threshold anti-reflection films - Google Patents
A kind of preparation method of three boracic acid oxygen calcium yttrium crystal (YCOB) high laser damage threshold anti-reflection films Download PDFInfo
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- CN103882378B CN103882378B CN201410050236.6A CN201410050236A CN103882378B CN 103882378 B CN103882378 B CN 103882378B CN 201410050236 A CN201410050236 A CN 201410050236A CN 103882378 B CN103882378 B CN 103882378B
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Abstract
The invention discloses a kind of preparation method of nonlinear crystal three boracic acid oxygen calcium yttrium plane of crystal high laser damage threshold anti-reflection film.The micromechanism of damage of and anti-reflection film strong for YCOB crystalline anisotropy, the step of the method comprises the hf etching of YCOB substrate, the cold working of YCOB substrate, the ion beam etching of YCOB substrate, the ultrasonic cleaning of YCOB substrate, the vacuum ionic Shu Qingxi of YCOB substrate and YCOB substrate upper film and is coated with.The YCOB anti-reflection film optical characteristics prepared by the present invention is excellent, damage threshold is high, environmental stability good, can process, cleans and thin film preparation process compatibility with existing substrate.Have good process repeatability, controllability strong, be easy to the advantages such as popularization, in the Laser Films field in future, there is wide application prospect.
Description
Technical field
The present invention relates to a kind of method for preparing optical thin film, particularly relate to a kind of preparation method of nonlinear crystal three boracic acid oxygen calcium yttrium plane of crystal high laser damage threshold anti-reflection film.
Background technology
In strong laser system, powerful laser energy very easily produces destruction to the element in system, therefore has very high resisting laser damage requirement to gain media.Due to three boracic acid oxygen calcium yttriums (YCOB) crystal have that damage threshold is high, nonlinear factor is large, transmission region is wide, phase matching ranges greatly, the not easily advantage such as deliquescence, be subject to extensive concern and research in recent years, and be successfully applied in high power laser system.YCOB crystal refractive index is large, can produce stronger Fresnel reflection when laser is incident, and reduce energy utilization efficiency and the stability of laser system, the development therefore for YCOB crystal anti-reflection film is significant.The anisotropy of YCOB crystal itself, problems are brought to the mechanics of the film be coated on crystal and optical property, comprise the unequal power distribution between film and crystal, lower, each difference to thermal expansivity of adhesion of thin film causes temperature to raise easily generation be full of cracks etc., bring huge challenge to film system matching Design and optimized fabrication method.And because YCOB crystal anti-reflection film is used in high power laser system, its performance quality determines the output performance of laser to a great extent, and the damage threshold therefore improving YCOB crystal anti-reflection film is also very crucial research contents.The height of thin film damage threshold value is the coefficient result of many factors, and for anti-reflection film, absorptivity impurity defect is one of factor of most critical.In the whole process of film preparation, all likely introduce defect, be therefore optimized full-flow process in preparation process, the introducing controlling defect is the effective means improving YCOB crystal anti-reflection film damage threshold.
The object of the invention is for the problems referred to above, devising a kind of double wave to grow tall transmission film system, by optimizing whole process preparation technology, controlling the introducing of defect, promote film mechanical characteristics simultaneously, achieve on YCOB crystal the anti-reflection film preparation that transmissivity is high, sticking power is good, damage threshold is high.
Summary of the invention
Because YCOB crystal has anisotropy, difference of thermal expansion coefficients is larger, film is caused easily to chap and poor adhesive force, and in whole preparation process, easily introduce defect impurity, cause thin film damage threshold value to reduce, therefore applicant promotes damage threshold and the mechanical property of YCOB plane of crystal anti-reflection film by the whole process Controlling Technology of base plate carving and corrosion, substrate design, basal-plate ultrasonic cleaning, substrate ion beam etching, substrate ion beam cleaning, electron beam evaporation deposition.
Concrete preparation technology of the present invention and step as follows:
(1) etching liquid YCOB crystal that conventional polishing processes is processed being put into hydrofluoric acid and deionized water (volume ratio 1: 20 proportioning) mixed preparing etches substrate, etching time can obtain best effect at 30min, sub-surface damage layer major part is removed.
(2) nano level colloid silica (SiO is adopted
2) and pitch polishing pad carry out chemically machinery polished, make to show that roughness is less than 5A, reduce microscopic damage, reduce sub-surface damage layer further.
(3) carry out ion beam etching to the substrate after chemically machinery polished, remove the polishing settled layer again of more than 100nm, etching time is 20 minutes, and source parameters is electric current 1200mA, voltage 900V.
(4) the deionized water ultrasonic cleaning of the substrate after ion beam etching, removes the grease on substrate and residual particles completely.
(5) by after added for substrate (YCOB), bleed after static 20 minutes, base vacuum is 1 × 10-3Pa again.Because bleed immediately after added, easily introduce defect at substrate surface.Start heated substrates after bleeding, in order to prevent too fast heating from causing substrate to chap, heat-processed is divided into 2 steps, first substrate 30 minutes are slowly heated to 100 degrees Celsius from room temperature, constant temperature 20 minutes, then substrate 20 minutes are slowly heated to 150 degrees Celsius, constant temperature 60 minutes.
(6) before plated film starts, first with ion source, substrate surface is cleaned, remove the particulate pollutant be adsorbed in vacuum pump-down process on substrate.Ion source oxygen flow is 40sccm, and argon flow amount is 25sccm, and voltage is 350V, and electric current is 550mA.The ion beam cleaning time is 60s, this is because effective Ion Cleaning energy can affect the character of the how many and defect of the size of substrate surface defect, this, for the absorption of reduction film, improves its threshold value and have important effect.
(7) electron beam evaporation Assisted by Ion Beam mode is utilized to be coated with the first layer SiO
2material, ion source oxygen flow is 50sccm, and argon flow amount is 5sccm, and voltage is 550V, and electric current is 670mA.Using Assisted by Ion Beam at the first layer, is to increase the sticking power of film on YCOB crystal, improve the stress of film and YCOB crystal simultaneously.Be coated with in the first layer thin-film process, SiO
2speed is 7.4A/s.Because select suitable sedimentation rate can improve the stress of film on YCOB crystal and obtain larger sticking power.
(6) subsequent thin film be coated with employing electron-beam evaporation mode because use electron beam evaporation to be coated with and to make thin film damage threshold value higher and can not introduce defect, this also has positive meaning to its damage threshold of raising.Be coated with in process, HfO
2speed is 1.4A/s, SiO
2speed is 6.5A/s, and at HfO
2rete be coated with in process the active oxygen ion being filled with 60sccm, make metal Hf be coated with in process fully oxidized, avoid because oxygen loss causes the reduction of damage threshold.
(7) plated film terminates rear sample and slowly anneals and aging 10 hours at vacuum chamber, and slowly annealing is to discharge the later stress of film forming, preventing film from chapping.
The present invention is compared with conventional fabrication process, its feature is for YCOB crystal peculiar property and service requirements, to control defect, to improve the method optimizing whole process preparation technology that sticking power is core, effectively improve damage threshold and the sticking power of YCOB crystal anti-reflection film.Key of the present invention is following 2 points:
1., heating comparatively large for YCOB crystalline anisotropy, the thermal expansion coefficient difference easily feature such as be full of cracks, we are to base
The mode that plate carries out ion beam cleaning, step by step slowly heating, electron beam evaporation combines plated film with Assisted by Ion Beam,
Select HfO
2with SiO
2as being coated with material, efficiently solve the problems referred to above.
2., in order to improve the threshold for resisting laser damage of YCOB crystal anti-reflection film, in whole thin-film-coating flow process, carry out the optimization of technique to control defect for core.Before plated film, remove YCOB crystal subsurface defect layer by hf etching, the chemically machinery polished of nano level colloid silica, ion beam etching, washed with de-ionized water, and adopt ion beam cleaning to control plane of crystal defect further.In thin-film-coating process, select suitable parameter, control defect and introduce, and be coated with HfO
2process in be filled with active oxygen, improve further the oxidation efficiency of film to reduce the native defect in film.
Technique effect of the present invention is as follows:
1. what effectively can solve that the features such as YCOB crystalline anisotropy bring is coated with a difficult problem, and the membrane stress coated is less, sticking power is comparatively large and transmissivity is high, can use by normal table in laser system.
2. the YCOB crystal film damage threshold using the inventive method to prepare is high.Compared for the YCOB crystal anti-reflection film not having familiar lacunas Controlling Technology to be coated with, find that the film defects impaired loci that use the inventive method coats is few, damage threshold is improved largely.
3. the inventive method is simple, low cost, reproducible, and in whole preparation process, these method practicality are extremely strong, is suitable for batch production, can meets the market requirement of laser technology fast development, have good economic benefit.
Accompanying drawing explanation
Fig. 1 is the transmittance graph of YCOB crystal 1064nm and 527nm dual wavelength anti-reflection film.
Embodiment
This is described in further detail the present invention by specific examples, as follows:
YCOB crystal 1064nm and 527nm dual wavelength anti-reflection film are coated with
1. plated sample preparation product YCOB crystalline size is 10*10*3mm.The structure of this film system is: SL (HL) ^3A, S are substrate YCOB crystal, and A is air, and H is high-index material HfO
2, L is low-index material SiO
2, every layer film thickness is 190nm/54.8nm/62.53nm/119nm/22nm/165.54, and filming equipment is that Japanese light is speeded coating equipment OTFC-1800, and configuration ion source is 17cm radio-frequency ion source.
2. be coated with by previous process steps, etched by the etching liquid of the YCOB substrate hydrofluoric acid after conventional polishing and deionized water (volume ratio 1: 20 proportioning) mixed preparing, etching time is at 30min.Substrate washed with de-ionized water after chin erosion, then use nano level colloid silica (SiO
2) and pitch polishing pad carry out chemically machinery polished, surfaceness <5A, the substrate after polishing with ionic fluid chin erosion, etching time is 20 minutes, and source parameters is electric current 1200mA, voltage 900V.Substrate washed with de-ionized water after ion beam etching, removes the grease on substrate and residual particles completely.Then put on the work rest of filming equipment by YCOB crystal, start to bleed after static 20 minutes, base vacuum is 1 × 10-3Pa.Substrate (YCOB) heat-processed is divided into 2 steps, first substrate is slowly heated to 90 degrees Celsius from room temperature with 20 minutes, constant temperature 20 minutes, then substrate was slowly heated to 140 degrees Celsius with 20 minutes, constant temperature 20 minutes.Before plated film starts, during with ion source to base-plate cleaning, oxygen flow 30sccm, argon flow amount 30sccm, voltage 350V, electric current 550mA.During plated film, height low-index material uses metal Hf and SiO respectively
2ring.When being coated with the first layer SiO2 material, ion beam assisted depositing parameter is: oxygen flow 50sccm, argon flow amount 5sccm, voltage 550V, electric current 670mA; SiO
2speed be 8A/s.Be coated with subsequent film and adopt electron-beam evaporation mode, HfO
2speed is 2A/s, SiO
2speed is 8A/s, is being coated with HfO
2the oxygen being filled with 60sccm in the process of rete provides ion-oxygen.After being coated with end, taken out after slow cooling is aging.
3. tested by the sample spectrophotometer be coated with, locate transmissivity at 1064nm and 527nm and be greater than 99%, spectrum property meets the user demand in high power laser system completely.Concrete curve of spectrum Fig. 1 in the description of the drawings.
4. on nanosecond laser damage testing platform, carry out damage check, adopt 1-on-1 testing standard, the damage threshold of this sample is greater than 10J/cm2 (laser parameter is λ=532nm, pulsewidth 10ns).
The YCOB crystal 1064 be coated with this invention and 527nm dual wavelength anti-reflection film, its spectral response curve meets service requirements completely, and damage threshold is higher, has very strong practical value.
Claims (4)
1. a preparation method for nonlinear crystal three boracic acid oxygen calcium yttrium plane of crystal high laser damage threshold anti-reflection film, is characterized in that comprising the following steps:
1) hf etching of YCOB substrate after conventional polishing: the etching liquid that the YCOB substrate after conventional polishing puts into hydrofluoric acid and deionized water mixed preparing is etched, removes settled layer more completely;
2) floating polishing of YCOB substrate: adopt floating polishing technique, uses pitch polishing pad, by SiO
2polishing powder is dissolved in deionized water, carries out polishing, by Roughness Surface on Control at below 5A to fused quartz substrate;
3) ion beam etching of YCOB substrate: use RF ion source to etch the YCOB substrate after polishing, remove the polishing settled layer again of more than 100nm;
4) ultrasonic cleaning of YCOB substrate after ion beam etching: use ultrasonic cleaning technology to remove the residual particles of substrate surface grease and more than 300nm;
5) the vacuumizing and heat of YCOB substrate: by Controlling System, substrate is heated step by step, make temperature slowly increase, and constant temperature 1 hour;
6) YCOB substrate upper film preparation: use ion source to carry out vacuum ionic Shu Qingxi to YCOB substrate, uses electron beam evaporation method to prepare HfO subsequently on YCOB substrate
2/ SiO
2film;
Step 2) in SiO used
2the median size of polishing powder is less than 1 μm, and the concentration of polishing powder is less than 2%, and surface of polished roughness is less than 5A;
Step 3) in after YCOB substrate polishing, use RF ion source to etch the YCOB substrate after polishing, remove the polishing settled layer again of more than 100nm, etching time is 20 minutes, and source parameters is electric current 1200mA, voltage 900V;
Step 5) in YCOB crystal is put on the work rest of filming equipment, start to bleed after static 20 minutes, base vacuum is 1 × 10
-3pa; Substrate (YCOB) heat-processed is divided into 2 steps, first substrate is slowly heated to 100 degrees Celsius from room temperature with 30 minutes, constant temperature 20 minutes, then substrate was slowly heated to 150 degrees Celsius with 20 minutes, constant temperature 60 minutes;
Step 6) in plated film time height low-index material use metal HfSiO respectively
2ring; Be coated with the first layer SiO
2during material, ion beam assisted depositing parameter is: oxygen flow 50sccm, argon flow amount 5sccm, voltage 550V, electric current 670mA; SiO
2speed be 8A/s; Be coated with subsequent film and adopt electron-beam evaporation mode, HfO
2speed is 2A/s, SiO
2speed is 8A/s, is being coated with HfO
2the ion oxygen of 60sccm is filled with in the process of rete; After being coated with end, taken out after vacuum 10 hours slow coolings are aging.
2. the preparation method of nonlinear crystal three boracic acid oxygen calcium yttrium plane of crystal high laser damage threshold anti-reflection film according to claim 1, it is characterized in that: described step 1) in etching liquid be hydrofluoric acid and deionized water (volume ratio 1: 20 proportioning) mixed preparing, etching time is 30 minutes.
3. the preparation method of nonlinear crystal three boracic acid oxygen calcium yttrium plane of crystal high laser damage threshold anti-reflection film according to claim 1, is characterized in that: described step 4) in hyperacoustic frequency be 1 megahertz, use soda acid cleaning solution, proportioning is NH
4oH:H
2o
2: H
2o=1: 4: 10, ultrasonic time 30-60 minute, ultrasonic power is 2-3Kw, uses deionized water rinsing 2 times, then dry up with dry air after ultrasonic cleaning.
4. the preparation method of nonlinear crystal three boracic acid oxygen calcium yttrium plane of crystal high laser damage threshold anti-reflection film according to claim 1, it is characterized in that: described step 6) in use argon gas and oxygen mix plasma body to clean substrate surface, the purity of xenon and oxygen is better than 99.999%, throughput ratio is 1: 1, the ion beam cleaning time was 60 seconds, ion beam voltage is 350V, and ion beam current is 550mA.
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| CN104973794A (en) * | 2015-05-28 | 2015-10-14 | 同济大学 | Ion beam etching apparatus and method of optical substrate for laser film element |
| CN106199801B (en) * | 2016-08-31 | 2018-04-03 | 奥普镀膜技术（广州）有限公司 | A kind of 40G100G optical filters thin-film-coating method |
| CN106435487B (en) * | 2016-10-10 | 2018-07-06 | 同济大学 | A kind of preparation method of lithium triborate crystal high laser damage threshold anti-reflection film |
| CN106925565B (en) * | 2017-02-09 | 2018-08-24 | 同济大学 | A kind of etch cleaner method of lbo crystal |
| JP6917807B2 (en) * | 2017-07-03 | 2021-08-11 | 東京エレクトロン株式会社 | Substrate processing method |
| CN109262377B (en) * | 2018-11-15 | 2019-09-03 | 首都师范大学 | For being passivated the polishing process of CsI (TI) plane of crystal defect |
| CN110007377A (en) * | 2019-04-15 | 2019-07-12 | 南京波长光电科技股份有限公司 | A kind of picosecond laser high power anti-reflection film and preparation method thereof |
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| CN102825028A (en) * | 2012-09-11 | 2012-12-19 | 同济大学 | Cleaning method of glazed surface of YCOB crystal |
| CN102965614A (en) * | 2012-11-23 | 2013-03-13 | 同济大学 | Preparation method of laser film |
| CN103231302A (en) * | 2013-04-12 | 2013-08-07 | 同济大学 | Method for obtaining super-smooth surface low-sub-surface-damage crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102825028A (en) * | 2012-09-11 | 2012-12-19 | 同济大学 | Cleaning method of glazed surface of YCOB crystal |
| CN102965614A (en) * | 2012-11-23 | 2013-03-13 | 同济大学 | Preparation method of laser film |
| CN103231302A (en) * | 2013-04-12 | 2013-08-07 | 同济大学 | Method for obtaining super-smooth surface low-sub-surface-damage crystal |
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