WO2020124451A1 - 薄膜涂层色度分析设备及其应用、薄膜涂层分类方法 - Google Patents

薄膜涂层色度分析设备及其应用、薄膜涂层分类方法 Download PDF

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WO2020124451A1
WO2020124451A1 PCT/CN2018/122140 CN2018122140W WO2020124451A1 WO 2020124451 A1 WO2020124451 A1 WO 2020124451A1 CN 2018122140 W CN2018122140 W CN 2018122140W WO 2020124451 A1 WO2020124451 A1 WO 2020124451A1
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thin film
film coating
chromaticity
thin
sample
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French (fr)
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唐永炳
周小龙
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46—Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration

Definitions

  • the present application belongs to the technical field of chromaticity analysis of thin film coatings, and specifically relates to a chromaticity analysis device of thin film coatings and its application, as well as a classification method of thin film coatings.
  • Diamond-Like Carbon is an amorphous metastable carbon film composed of diamond-structured sp 3 hybrid carbon, sp 2 hybrid carbon, and a small amount of hydrogen bonded to the above structure Collectively. It has many excellent characteristics such as high hardness, high elastic modulus, friction and wear resistance, corrosion resistance, and high surface finish. It can be widely used in mechanical, electronic, optical, thermal, acoustic, medical and other fields, and has good application prospects.
  • DLC films can be divided into different types, such as: non-hydrogen tetrahedral carbon film (ta-C), hydrogen-containing tetrahedral carbon film (ta-C) :H), non-hydrogen carbon film (aC), hydrogen-containing carbon film (aC:H), polymer-like carbon film (PLC) and graphite-like carbon film (GLC), etc., and not all types of DLC films have high Excellent characteristics such as hardness, high elastic modulus, friction and wear resistance, corrosion resistance, and high surface finish.
  • the first object of the present application is to provide a thin-film coating chromaticity analysis device, which can overcome the above problems or at least partially solve the above technical problems.
  • the second object of the present application is to provide the application of the above-mentioned thin-film coating colorimetric analysis device in thin-film coating colorimetric analysis.
  • the third object of the present application is to provide a method for chromaticity analysis of thin film coatings.
  • the fourth object of the present application is to provide the application of the above-mentioned thin-film coating colorimetric analysis method in thin-film coating classification.
  • the fifth object of the present application is to provide a method for classifying thin film coatings.
  • a thin-film coating colorimetric analysis device which includes a spectrocolorimeter, a light source, and a sample to be measured;
  • the sample to be tested includes a substrate and a thin film coating provided on the upper surface of the substrate;
  • the spectrocolorimeter and light source are arranged above the sample to be measured;
  • the distance between the light source and the sample to be tested is 15-35cm
  • intersection point D The vertical point from the center point of the light source to the sample to be measured is the intersection point D;
  • the straight line from the center point of the light source to the intersection point D is a straight line A, and the straight line from the center point of the spectrocolorimeter to the intersection point D is a straight line B;
  • the angle between the straight line A and the straight line B is 1-15°.
  • the chromaticity analysis device further includes a sample stage, and the sample to be tested is placed on the surface of the sample stage;
  • the spectrocolorimeter is flush with the light source, and the sample to be measured is located directly under the light source.
  • the angle between the straight line A and the straight line B is 5-10°, preferably 10°.
  • the light source is a white LED light source
  • the spectrocolorimeter can meet CIELAB and/or CIELUV color space test requirements.
  • the substrate includes at least one of single crystal silicon, quartz, transparent conductive glass or cemented carbide, preferably single crystal silicon.
  • the roughness of the thin film coating is less than 10 nm, and the thickness of the thin film coating is 20-3000 nm;
  • the thin film coating includes an inorganic non-metallic thin film, preferably a diamond-like thin film or a diamond thin film, and further preferably a diamond-like thin film.
  • the application of the above-mentioned thin-film coating chromaticity analysis device in thin-film coating chromaticity analysis is provided.
  • a thin-film coating chromaticity analysis method including the following steps:
  • the thin film coating includes an inorganic non-metallic thin film, preferably a diamond-like thin film or a diamond thin film, and further preferably a diamond-like thin film.
  • a thin film coating classification method including the following steps:
  • step (b1) Obtain the L*, a*, b*, C ab, and C T of the film coating to be tested according to the above-mentioned film coating colorimetric analysis method, and classify the film coating to be tested in combination with the database obtained in step (a1) ;
  • step (b2) Obtain the L*, v*, u*, C uv and C T of the film coating to be tested according to the above-mentioned film coating colorimetric analysis method, and combine the database obtained in step (a2) to classify the film coating to be tested ;
  • the thin film coating includes an inorganic non-metallic thin film, preferably a diamond-like thin film or a diamond thin film, and further preferably a diamond-like thin film.
  • the present application provides a thin-film coating colorimetric analysis device, which includes a spectrocolorimeter, a light source, and a sample to be measured.
  • the device generates scattered light when irradiating the sample to be tested through the light source, and analyzes the scattered light with a spectrocolorimeter to obtain the chromaticity value of the thin film coating, and obtains the quantitative relationship between the different types of thin film coating and the chromaticity value ,
  • Establish a database and then only need to use the thin film coating color analysis equipment to analyze the thin film coating color, you can judge the type of thin film coating, using the thin film coating color analysis equipment to classify the thin film coating method is simple , Fast and practical, greatly simplifying the film coating classification process, which brings great convenience to practical application.
  • Thin film coating colorimetric analysis equipment can be applied to the classification of diamond-like carbon films. Collect the color and chromaticity information of different phases and different kinds of diamond-like carbon films through the thin-film coating chromaticity analysis equipment, obtain the chromaticity values of different kinds of diamond-like carbon films, and establish the chromaticity value of the diamond-like carbon films and the type The quantitative relationship between them, so that the type of diamond-like carbon film can be judged simply and quickly by measuring the chromaticity value of the diamond-like carbon film to be measured. It greatly simplifies the classification process of diamond-like carbon films, and can alleviate the problems that the current classification of diamond-like films needs to rely on large equipment, complicated operation, and practical application difficulties. It brings great convenience for practical application in production.
  • This application provides a thin-film coating chromaticity analysis device.
  • the thin-film coating chromaticity analysis device can analyze the thin-film coating chromaticity, and then classify the diamond-like carbon film. This classification method is simple and fast, and does not need to be used. Large equipment such as synchrotron radiation source and electrostatic accelerator.
  • This application provides a thin-film coating chromaticity analysis device.
  • the thin-film coating chromaticity analysis device can be used to analyze the thin-film coating chromaticity, and then classify diamond-like carbon films, using the international lighting association CIELAB or CIELUV color space. , That is, to test the appearance color of the DLC film by the test method with the naked eye recently, it is very suitable for the first-line production operation, and has huge application prospects.
  • This application provides a thin-film coating chromaticity analysis device.
  • the thin-film coating chromaticity analysis device can analyze the thin-film coating chromaticity, and then classify the diamond-like carbon film according to the chromaticity C ab and the full chromaticity.
  • C T or chromaticity C uv and full chromaticity C T are used to analyze the type of DLC film, and the color analysis of the film appearance is more comprehensive and closer to the actual value.
  • the thin-film coating chromaticity analysis device can analyze the thin-film coating chromaticity, and then classify diamond-like carbon films, which is different from the traditional DLC film classification method. It is suitable for small-scale small-scale test and pilot test, as well as effective primary selection of DLC film in large-scale mass production.
  • the thin-film coating chromaticity analysis device can analyze the thin-film coating chromaticity, and then classify diamond-like carbon films.
  • the thin-film coating chromaticity analysis device is not only suitable for It is also applicable to DLC film system and other types of film coating materials that meet the preset conditions of this application.
  • Figure 1 is the color analysis equipment for film coating
  • Figure 2 is a color analysis equipment for film coating with a sample stage
  • Example 3 is a distribution diagram of the chromaticity value of the DLC film in Example 1;
  • Example 4 is the relationship between the full chromaticity of the DLC film and the film thickness in Example 1;
  • FIG. 6 is a distribution diagram of the full chromaticity value of the DLC film in Example 2.
  • Icons 1-Spectrophotometer; 2-Light source; 3-Distance; 4-Angle; 5-Test sample; 51-Film coating; 52-Substrate; 6-Sample stage.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “15-35” means that all real numbers between “15-35” have been listed in this article, and "15-35” is just an abbreviated representation of these numerical combinations.
  • the forms of the "lower limit” and the upper limit disclosed in the “range” of this application may be one or more lower limits and one or more upper limits, respectively.
  • each reaction or operation step may be performed sequentially or in order.
  • the reaction methods herein are performed sequentially.
  • a thin-film coating colorimetric analysis device which includes a spectrocolorimeter (1), a light source (2), and a sample to be tested (5);
  • the sample to be tested includes a substrate (52) and a thin film coating (51) provided on the upper surface of the substrate;
  • Spectrocolorimeter (1) and light source (2) are set above the sample to be tested;
  • the distance (3) between the light source and the sample to be tested is 15-35cm
  • intersection point D The vertical point from the center point of the light source to the sample to be tested is the intersection point D;
  • the straight line from the center point of the light source to the intersection point D is the straight line A, and the straight line from the center point of the spectrophotometer to the intersection point D is the straight line B;
  • the angle (4) between line A and line B is 1-15°.
  • the source and model of the spectrocolorimeter are not limited.
  • it can be a spectrocolorimeter that can meet the requirements of CIELAB or CIELUV color space test.
  • the type and source of the light source are not limited, for example, it may be a white LED light source.
  • the white LED light source refers to translucent or opaque, and its surface color refers to any one of white turbidity, milky white, light yellow, cream, or their intermediate colors. Or, it means that the hue is in the range from 5R to 5Y via 5YR, the color saturation is C6 or less, and the brightness is V8.5 or more.
  • the thickness of the film coating does not affect the angle between the light source and the spectrocolorimeter to the foot of the light source to be measured, that is, before and after the film coating is provided on the upper surface of the substrate, the light source and the spectrophotometer
  • the angle from the light source to the foot of the sample to be tested should be basically the same. If the distance between the light source and the sample to be tested is 15-35cm, the thickness of the film coating can be 20-3000nm; at this time, before and after the film coating of this thickness is provided on the upper surface of the substrate, the light source and the spectrophotometer The angle between the light source and the foot of the sample to be tested is basically the same.
  • the thickness of the thin film coating is 20nm, 40nm, 60nm, 65nm, 80nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm , 1500nm, 1600nm, 1700nm, 1800nm, 1900nm, 2000nm, 2100nm, 2200nm, 2300nm, 2400nm, 2500nm, 2600nm, 2700nm, 2800nm, 2900nm or 3000nm.
  • the surface roughness of the thin film coating should be small, for example, it can be a thin film coating with a roughness of less than 10 nm.
  • the arrangement method of the thin film coating on the upper surface of the substrate is not limited, for example, it may be magnetron sputtering, plasma chemical vapor deposition (PECVD), ion beam assisted deposition, pulsed laser deposition or filtered cathode vacuum arc (FCVA) ) Vacuum coating equipment such as deposition provides a thin film coating on the upper surface of the substrate.
  • PECVD plasma chemical vapor deposition
  • FCVA filtered cathode vacuum arc
  • the type of thin film coating is not limited, and it may be an inorganic non-metal thin film.
  • the inorganic non-metal thin film includes but is not limited to a diamond-like thin film or a diamond thin film.
  • the type of substrate is not limited, for example, it may be single-sided polished single crystal silicon, quartz, transparent conductive glass, or cemented carbide. It should be understood that the thin film coating is provided on the polished surface of the substrate.
  • the distance between the light source and the sample to be measured may be any fixed value within the range of 15-35 cm, and it is not optional to readjust the distance between the light source and the sample to be measured before each measurement.
  • the distance between the light source and the sample to be tested is 15cm, 16cm, 17cm, 18cm, 19cm, 20cm, 21cm, 22cm, 23cm, 24cm, 25cm, 26cm, 27cm, 28cm, 29cm, 30cm, 31cm, 32cm , 33cm, 34cm or 35cm.
  • the angle between the straight line A and the straight line B can be any fixed value within the range of 1-15°, and it is not used to readjust the light source and the spectrocolorimeter before each measurement until the light source is perpendicular to the sample to be measured The angle of the foot.
  • the angle between line A and line B is 1°, 2°, 3°, 4°, 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12 °, 13°, 14° or 15°.
  • the present application provides a thin-film coating colorimetric analysis device, which includes a spectrocolorimeter, a light source, and a sample to be measured.
  • the device generates scattered light when irradiating the sample to be tested through the light source, and analyzes the scattered light with a spectrocolorimeter to obtain the chromaticity value of the thin film coating, and obtains the quantitative relationship between the different types of thin film coating and the chromaticity value And build a database. After that, it is only necessary to analyze the chromaticity of the thin film coating by using the chromaticity analyzing device of the thin film coating to determine the type of the thin film coating.
  • the method for classifying thin film coatings using thin film coating colorimetric analysis equipment is simple, fast, and practical, greatly simplifying the thin film coating classification process, and bringing great convenience to practical application in production.
  • the chromaticity analysis device further includes a sample stage (6), and the sample to be tested is placed on the surface of the sample stage.
  • the source of the sample stage is not limited, and may be a test platform with a flat surface, and the optical platform is preferred.
  • the spectrocolorimeter is flush with the light source, and the sample to be measured is located directly below the light source.
  • the angle between line A and line B is 5-10°.
  • this angle range first includes the 2° and/or 10° viewing angle specified by the International Lighting Association that is closest to the human eye, and is also suitable for different operators and Operating environment.
  • the angle between line A and line B is 10°.
  • the substrate is single crystal silicon.
  • the application of the above-mentioned thin-film coating chromaticity analysis device in thin-film coating chromaticity analysis is provided.
  • the type of thin film coating is not limited, and it may be an inorganic non-metal thin film.
  • the inorganic non-metal thin film includes but is not limited to a diamond-like thin film or a diamond thin film.
  • the thin film coating is a diamond-like carbon film.
  • a thin-film coating chromaticity analysis method including the following steps:
  • step S3 If L*, a* and b* are obtained in step S2, the chromaticity C ab and the full chromaticity C T are obtained according to Formula 1 and Formula 2:
  • the thin-film coating colorimetric analysis device is placed in a dark environment, which means that it is not affected by external light sources.
  • placing the sample to be measured refers to placing the sample to be measured at a position that we preset, for example, directly under the light source.
  • turning on the light source and the spectrocolorimeter refers to making it work normally after turning on the power, including turning on the switch, adjusting various parameters, determining the included angle, etc., that is, preparing for all measurements before starting the measurement jobs.
  • L*, a* and b* read the chromaticity information of each sample using the International Lighting Association CIELAB color space
  • L*, v* and u* read the chromaticity of each sample using the International Lighting Association CIELUV color space information.
  • step S2 the spectrocolorimeters corresponding to L*, a*, and b* can achieve the CIELAB color space test requirements, and in step S2, the spectrocolorimeters corresponding to L*, v*, and u* can Achieve CIELUV color space test requirements.
  • the test can be repeated 2-4 times, through the L*, a* and b* obtained each time, or L*, v* and u* Calculate the average value of the chroma parameters of the sample and record the result, and then obtain the chroma C ab and the full chroma C T according to formula 1-4, or obtain the chroma C uv and the full chroma C T.
  • Equation 1 by a plane chromaticity values a * and b * chromaticity C ab, Equation 2 takes into account the brightness L *, chroma C T to obtain full, full chroma C T to better analyze the color of the coating film Chroma value.
  • Equation 4 takes into account brightness L *, chroma C T to obtain full, full chroma C T to better analyze the color of the coating film Chroma value.
  • the thin-film coating chromaticity analysis method uses thin-film coating chromaticity analysis equipment to analyze the chromaticity of the thin-film coating, and then classifies the diamond-like carbon film, using the international lighting association CIELAB or CIELUV color space, that is, using the most recently received eye
  • the test method is used to test the appearance color of DLC film, which is very suitable for the first-line production operation and has huge application prospects.
  • the application of the above-mentioned thin-film coating chromaticity analysis method in thin-film coating classification is provided.
  • the type of thin-film coating is not limited, and it may be an inorganic non-metallic thin film.
  • the inorganic non-metallic thin film includes but is not limited to a diamond-like thin film or a diamond thin film.
  • the thin film coating is a diamond-like carbon film.
  • the thin-film coating colorimetric analysis equipment is used in thin-film coating, which is simple, fast and practical, which greatly simplifies the thin-film coating classification process and brings great convenience for practical application in production.
  • the above-mentioned thin-film coating chromaticity analysis method is applied to the classification of diamond-like carbon films.
  • the color and chromaticity information of different phases and different kinds of diamond-like carbon films are collected by the thin-film coating chromaticity analysis method to obtain the colors of different kinds of diamond-like carbon films.
  • the method of classifying the diamond-like carbon film by the analysis equipment is simple, fast and practical, which greatly simplifies the classification process of the diamond-like carbon film, and brings great convenience for practical application in production.
  • a thin film coating classification method including the following steps:
  • step (b1) Obtain the L*, a*, b*, C ab, and C T of the film coating to be tested according to the above-mentioned film coating colorimetric analysis method, and classify the film coating to be tested in combination with the database obtained in step (a1) ;
  • step (b2) Obtain the L*, v*, u*, C uv and C T of the film coating to be tested according to the above-mentioned film coating colorimetric analysis method, and combine the database obtained in step (a2) to classify the film coating to be tested .
  • the classification method of thin film coating is not limited to the type of thin film coating, and may be a diamond-like thin film, a diamond thin film classification, and the like.
  • the thin film coating colorimetric analysis equipment is used to obtain the quantitative relationship between different types of film coatings and the colorimetric value, and establish a database. After that, it is only necessary to analyze the chromaticity of the thin film coating by using the chromaticity analyzing device of the thin film coating to determine the type of the thin film coating.
  • the method for classifying thin film coatings using thin film coating colorimetric analysis equipment is simple, fast, and practical. Therefore, the thin film coating classification process is greatly simplified, which brings great convenience to practical application in production.
  • the diamond-like carbon film classification method is to obtain the color and chromaticity information of different kinds of diamond-like carbon films by using the film coating chromaticity analysis equipment and the film coating chromaticity analysis method, collect data, establish a database, and then establish the diamond-like carbon film chromaticity value Quantitative relationship with the type of diamond-like carbon film, so that the type of diamond-like carbon film can be simply and quickly judged by measuring the chromaticity value of the diamond-like film to be measured. It is simple, fast and practical, which greatly simplifies the classification process of diamond-like carbon films, and brings great convenience to the actual application in production.
  • the single-crystal silicon wafers with single-side polished substrate materials were placed in distilled water, acetone, and absolute ethanol solution for ultrasonic cleaning for 15 minutes, and then the substrate surface was blown dry with dry nitrogen, and finally the sample was placed in an 80 °C drum Dry in the air drying box.
  • the dried sample is fixed on the substrate fixing frame in the PECVD equipment.
  • the deposition time was controlled to prepare DLC films with different thicknesses. Under the conditions that the deposition time is 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, samples #01, #02, #03, #04, #05, #06, #07, #08 .
  • the deposition time is controlled to prepare DLC films with different thicknesses. Under the conditions that the deposition time is 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, samples #09, #10, #11, #12, #13, #14, #15, #16 .
  • FIG. 1 is a thin film coating chromaticity analysis device
  • FIG. 2 is a thin film coating chromaticity analysis device with a sample stage. Place the DLC test sample vertically under the light source in the dark room. The white LED light source of the spectrophotometer is aligned with the horizontal optical platform on which the sample is placed.
  • the spectrocolorimeter is flush with the light source, and a fixed value of 8° is formed between the center of the light source, the spectrocolorimeter and the sample, the DLC sample is prepared according to the deposition time Three-point measurement is performed in sequence, and the respective chromaticity information L*, a*, b* is obtained using the CIELAB color space of the International Lighting Association.
  • FIG. 3 is the chromaticity value distribution diagram of the DLC film in Example 1.
  • the DLC film with no bias applied has a bright appearance (samples #01 to #08 in Figure 5). It can be seen from Figure 3a that the C ab values of samples #01 ⁇ #08 are widely distributed in the chromaticity space.
  • the chromaticity value gradually increases with the increase of the deposition time, and the chromaticity value appears clockwise and periodically around the center.
  • the chromaticity value of DLC film interferes with the phenomenon of color thickness dependence.
  • Figure 4 shows the relationship between the full chromaticity of the DLC film and the film thickness in Example 1. It can be seen from Figure 4 that the color of the DLC film (sample #01-#08) in 4a shows a periodic change, and this periodicity and interference fringes are very good The correspondence is good. The color at this time comes from the structural color produced by the interaction between the amorphous structure of the film and the light.
  • the chromaticity value and the total chromaticity are larger; compare the DLC film with bias applied in 4b (sample #09 -#16), as mentioned above, the chromaticity value is significantly reduced, and when the film thickness is in the same (sample #01-#08) range, there is no obvious periodic change in full chromaticity, and the type of DLC film is significantly different from the former .
  • Example 2 The difference between Example 2 and Example 1 is that the FCVA deposition equipment is used instead of the PECVD deposition equipment, the carbon target is used as the carbon source instead of the acetylene gas, and the pulse bias voltage -800V is used instead of the pulse bias voltage -0V or -500V.
  • the deposition time was 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, and samples #17, #18, #19, #20, #21, #22, #23, #24 were obtained in sequence.
  • FIG. 6 is the distribution diagram of the full chromaticity value of the DLC film in Example 2
  • FIG. 6b is the full chromaticity value of samples #17 ⁇ #24
  • FIG. 6a it is located inside #09 ⁇ #16
  • the unlabeled dot values correspond to the full chromaticity values of samples #17 ⁇ #24
  • the chromaticity values of samples (#17 ⁇ #24) prepared by biasing -800V are all distributed in a*, b* absolute values less than It is within the range of 10 and is located inside samples #09 ⁇ #16, indicating that the two samples also belong to different types of DLC films.
  • the unbiased samples belong to the PLC film (polymer-like carbon film), and the sample applied with the bias voltage of -500V belongs to aC: H thin film (hydrogen-containing carbon film), the sample obtained by FCVA bias application is ta-C: (H) thin film (hydrogen-containing tetrahedral carbon film), it can be seen that the diamond-like carbon thin film classification method can distinguish PLC thin films and aC: H film and ta-C: (H) film, that is, the classification method of diamond-like film is feasible.
  • Example 1 The difference from Example 1 is that the DLC film is prepared by the magnetron sputtering technology instead of the PECVD technology, and the pulse bias voltage is -0V.
  • the L*, a*, b* of the sample are (59.0, -23.0, -34.1), (109.5 , -7.6, 39.8), (74.2, 29.0, 7.5), (76.0, -40.2, 10.5), (86.0, -17.2, 43.5), (64.2, 3.7, 12.3), (53.4, -4.5, -27.8) , (57.6, -28.4, 14.3).
  • Example 1 The difference from Example 1 is that the pulsed laser deposition technique is used instead of the PECVD technique to prepare the DLC film, and the pulse bias voltage is -0V.
  • the L*, a*, and b* of the sample are (109.0, -12.9, -4.1) and (89.0, respectively).
  • Example 1 The difference from Example 1 is that the DLC film is prepared by the radio frequency CVD deposition technology instead of the PECVD technology, and the pulse bias voltage is -0V.
  • the L*, a*, b* of the sample are (91.0, -17.9, -4.1), (89.5 , -9.6, 36.8), (61.2, 33.0, -50.5), (86.0, -16.2, 35.5), (62.0, -9.7, 12.5), (57.2, -53.7, 13.3), (73.1, -47.5, 17.8 ), (68.6, 19.4, -6.9).
  • Example 1 It can be known from Example 1, Example 3 to Example 5 that the thin film coating colorimetric analysis equipment can be used to classify DLC films prepared by different preparation methods.
  • Example 2 The difference from Example 1 is that a DLC thin film is prepared with a quartz glass substrate instead of a single crystal silicon substrate, and the pulse bias voltage is -0V.
  • the L*, a*, b* of the sample are (71.0, -19.9, -5.1), (80.5 , -10.6, 39.8), (55.2, 35.0, -54.5), (81.0, -19.2, 37.5), (63.0, -16.7, 17.5), (46.2, -50.7, 16.3), (76.1, -42.5, 19.8 ), (49.6, 21.4, -10.9).
  • Example 2 The difference from Example 1 is that the DLC thin film is prepared by replacing the single crystal silicon substrate with a transparent conductive glass substrate, and the pulse bias voltage is -0V.
  • the L*, a*, b* of the sample are (71.0, -19.9, -5.1), (79.5 , -10.6, 38.8), (41.2, 30.0, -59.5), (66.0, -13.2, 39.5), (42.0, -10.7, 15.5), (39.2, -59.7, 16.3), (53.1, -49.5, 25.8 ), (48.6, 23.4, -9.9).
  • Example 2 The difference from Example 1 is that a DLC thin film is prepared by replacing a single crystal silicon substrate with a cemented carbide substrate, and the pulse bias voltage is -0V.
  • the L*, a*, b* of the sample are (100.0, -10.9, -5.1), (85.0 , -11.6, 30.8), (50.2, 35.0, -45.5), (79.0, -12.2, 29.5), (56.0, -7.7, 13.5), (63.2, -45.7, 14.3), (71.1, -36.5, 10.8 ), (56.6, 13.4, -7.9).
  • Example 1 The difference from Example 1 is that the CELLAB color space is used instead of the CIELAB color space to obtain DLC film chromaticity information.
  • the L*, u*, v* of the sample are (90.0, -17.5, -4.2), (88.5 , -9.3, 36.5), (60.2, 32.0, -52.5), (83.0, -15.2, 36.5), (61.0, -10.7, 11.5), (55.2, -50.7, 14.3), (70.1, -46.5, 15.8 ), (65.6, 20.4, -6.5).
  • Example 9 It can be seen from Example 9 that whether the CIELUV color space or the CIELAB color space is used, it can be used to obtain the chromaticity information of the DLC film, and can also be used to classify the diamond-like carbon film.
  • Example 1 The difference from Example 1 is that the DLC film is replaced with a diamond film coating to perform the above analysis.
  • the L*, a*, b* of the sample are (59.0, -25.0, -39.1), (95.5 , -17.6, 30.8), (70.2, 35.0, 9.5), (62.0, -41.2, 12.5), (89.0, -19.2, 40.5), (69.2, 5.7, 14.3), (50.4, -8.5, -29.8) , (70.6, -35.4, 17.3).
  • the thin film coating colorimetric analysis equipment can also detect L*, a*, b* of the diamond thin film coating, that is, we can also use the thin film coating colorimetric analysis equipment to classify the diamond thin film coating .

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Abstract

一种薄膜涂层色度分析设备及其应用、薄膜涂层分类方法，属于薄膜涂层色度分析技术领域。一种薄膜涂层色度分析设备，包括分光色度计（1）、光源（2）和待测样品（5）；待测样品（5）包括基材（52）和设置在基材（52）的上表面处的薄膜涂层（51）；分光色度计（1）和光源（2）设置在待测样品（5）的上方；光源（2）与待测样品（5）的距离为15-35cm；直线A与直线B的夹角为1-15°。通过薄膜涂层色度分析设备获得不同种类薄膜涂层的色度值并基于所获得色度值建立数据库，使得能够通过测定待测薄膜涂层色度值，结合数据库简单快速地判断薄膜涂层的种类。这种分类方法简单、快捷且实用，因此将其应用于类金刚石薄膜分类，可大幅度简化类金刚石薄膜分类过程，从而为实际应用于生产带来极大便利。

Description

薄膜涂层色度分析设备及其应用、薄膜涂层分类方法 技术领域
本申请属于薄膜涂层色度分析技术领域，具体涉及一种薄膜涂层色度分析设备及其应用、薄膜涂层分类方法。
背景技术
类金刚石薄膜(Diamond-Like Carbon，下文简称DLC)是一种由金刚石结构的sp 3杂化碳、sp 2杂化碳和键合于上述结构中少量氢元素构成的非晶亚稳态碳膜的统称。它具有高硬度、高弹性模量、耐摩擦磨损、耐腐蚀、表面光洁度高等诸多优异特性，可广泛用于机械、电子、光学、热学、声学、医学等领域，具有良好的应用前景。根据DLC薄膜中碳的sp 2/sp 3比例和氢含量的不同，DLC薄膜可以分为不同种类，例如：非氢四面体碳膜(ta-C)、含氢四面体碳膜(ta-C:H)、非氢碳膜(a-C)、含氢碳膜(a-C:H)、类高聚物碳膜(PLC)和类石墨碳膜(GLC)等，且并非所有种类DLC薄膜都具备高硬度、高弹性模量、耐摩擦磨损、耐腐蚀、表面光洁度高等优异特性。随着技术的不断发展和工业应用条件及使用场合的日益复杂，尤其是当前精密机械、航空航天、汽车零部件、手机和手表等便携式智能化设备、以及体育器材等其他高端装饰等对镀膜领域的要求越发苛刻，为提高产品观赏性和用户体验度，颜色和外观也越来越重要，因此，如何快速且简便地判断DLC薄膜的种类就变得越来越重要。
国际上，对于DLC薄膜的分类最早是由英国剑桥大学J.Robertson教授在2002年前后提出的DLC薄膜种类三元图。虽然这一方案至今仍有较高的学术意义，但仅限于DLC薄膜定性分类，缺乏实际应用价值。2005和2012年德国工程师协会和日本钻石论坛分别提出了各自的DLC薄膜分类方案。尤其是2012年日本提出的利用基于同步辐射光源的近边X射线精细结构和基于静电加速器的卢瑟福背散射精确分析DLC薄膜中碳的sp 2/sp 3比例和氢含量H wt.％来分类DLC薄膜的方案，具有一定的实际应有潜力。但是，此方案必须使用同步辐射光源和静电加速器等大型设备，对于实际生产的指导意义仍然存在诸多不便。
鉴于此，特提出本申请。
发明内容
本申请的第一个目的在于提供一种薄膜涂层色度分析设备，能够克服上述问题或者至少部分地解决上述技术问题。
本申请的第二个目的在于提供上述薄膜涂层色度分析设备在薄膜涂层色度分析中的应用。
本申请的第三个目的在于提供一种薄膜涂层色度分析方法。
本申请的第四个目的在于提供上述薄膜涂层色度分析方法在薄膜涂层分类中的应用。
本申请的第五个目的在于提供一种薄膜涂层分类方法。
根据本申请第一个方面，提供了一种薄膜涂层色度分析设备，包括分光色度计、光源和待测样品；
所述待测样品包括基材和设置在基材的上表面处的薄膜涂层；
所述分光色度计和光源设置在待测样品的上方；
所述光源与待测样品的距离为15-35cm；
所述光源的中心点到待测样品的垂足为交点D；
所述光源的中心点到交点D的直线为直线A，所述分光色度计的中心点到交点D的直线为直线B；
所述直线A与直线B的夹角为1-15°。
优选地，所述色度分析设备还包括样品台，所述待测样品放置在样品台表面；
优选地，所述分光色度计和光源平齐，所述待测样品位于光源正下方。
优选地，所述直线A与直线B的夹角为5-10°，优选为10°。
优选地，所述光源为白色LED光源；
优选地，所述分光色度计能够实现CIELAB和/或CIELUV颜色空间测试要求。
优选地，所述基材包括单晶硅、石英、透明导电玻璃或硬质合金中的至少一种，优选为单晶硅。
优选地，所述薄膜涂层的粗糙度小于10nm，所述薄膜涂层的厚度为20-3000nm；
优选地，所述薄膜涂层包括无机非金属薄膜，优选为类金刚石薄膜或钻石薄膜，进一步优选为类金刚石薄膜。
根据本申请第二个方面，提供了上述薄膜涂层色度分析设备在薄膜涂层色度分析中的应用。
根据本申请第三个方面，提供了一种薄膜涂层色度分析方法，包括以下步骤：
S1：将上述薄膜涂层色度分析设备置于黑暗环境中，放置待测样品，打开光源和分光色度计；
S2：利用分光色度计得到L*、a*和b*，或，利用分光色度计得到L*、v*和u*；
S3：根据公式(1)和公式(2)得到色度C ab和全色度C T：
C ab＝[(a*) 2+(b*) 2] 1/2                    (1)，
C T＝[(L*) 2+(a*) 2+(b*) 2] 1/2                (2)，
或，根据公式(3)和公式(4)得到色度C uv和全色度C T：
C uv＝[(u*) 2+(v*) 2] 1/2                    (3)，
C T＝[(L*) 2+(u*) 2+(v*) 2] 1/2                (4)。
根据本申请第四个方面，提供了在薄膜涂层分类中的应用；
优选地，所述薄膜涂层包括无机非金属薄膜，优选为类金刚石薄膜或钻石薄膜，进一步优选为类金刚石薄膜。
根据本申请第五个方面，提供了一种薄膜涂层分类方法，包括以下步骤：
(a1)根据上述薄膜涂层色度分析方法得到已知种类的薄膜涂层的L*、a*、b*、C ab和C T，建立数据库；
(b1)根据上述薄膜涂层色度分析方法得到待测薄膜涂层的L*、a*、b*、C ab和C T，结合步骤(a1)得到的数据库，对待测薄膜涂层进行分类；
或者，
(a2)根据上述薄膜涂层色度分析方法得到已知种类的薄膜涂层的L*、v*、u*、C uv和C T，建立数据库；
(b2)根据上述薄膜涂层色度分析方法得到待测薄膜涂层的L*、v*、u*、C uv和C T，结合步骤(a2)得到的数据库，对待测薄膜涂层进行分类；
优选地，所述薄膜涂层包括无机非金属薄膜，优选为类金刚石薄膜或钻石薄膜，进一步优选为类金刚石薄膜。
本申请提供了一种薄膜涂层色度分析设备，该设备包括分光色度计、光源和待测样品。该设备通过光源照射到待测样品时产生散射光，利用分光色度计对散射光进行分析，得到薄膜涂层的色度值，得到不同种类的薄膜涂层与色度值之间的定量关系，建立数据库，之后只需要利用薄膜涂层色度分析设备对薄膜涂层色度进行分析，即可判断薄膜涂层的种类，利用薄膜涂层色度分析设备对薄膜涂层进行分类的方法简单、快捷、实用，大幅度简化了薄膜涂层分类过程，为实际应用于生产带来了极大的便利。
薄膜涂层色度分析设备可应用于类金刚石薄膜的分类。通过薄膜涂层色度分析设备收集不同品相和不同种类的类金刚石薄膜的颜色及色度信息，获得不同种类类金刚石薄膜的色度值，建立类金刚石薄膜色度值与类金刚石薄膜种类之间的定量关系，从而通过测定待测类金刚石薄膜色度值，简单快速地判断类金刚石薄膜的种类，这种利用薄膜涂层色度分析设备对类金刚石薄膜进行分类的方法简单、快捷、实用，大幅度简化了类金刚石薄膜分类过程，能够缓解当前类金刚石薄膜分类需要依赖大型设备，操作复杂，实际应用困难等问题。为实际应用于生产带来了极大的便利。
本申请提供了一种薄膜涂层色度分析设备，利用该薄膜涂层色度分析设备可对薄膜涂层色度进行分析，进而对类金刚石薄膜进行分类，这种分类方法简单快捷，无需使用同步辐射光源和静电加速器等大型设备。
本申请提供了一种薄膜涂层色度分析设备，利用该薄膜涂层色度分析设备可对薄膜涂层色度进行分析，进而对类金刚石薄膜进行分类，采用国际照明协会CIELAB或CIELUV颜色空间，即利用最近接肉眼的测试方式对DLC薄膜外观颜色进行测试，非常适合生产一线实际操作，具有巨大的应用前景。
本申请提供了一种薄膜涂层色度分析设备，利用该薄膜涂层色度分析设备可对薄膜涂层色度进行分析，进而对类金刚石薄膜进行分类，根据色度C ab和全色度C T或色度C uv和全色度C T来分析DLC薄膜的种类，对薄膜外观颜色分析更全面，更接近于实际值。
本申请提供了一种薄膜涂层色度分析设备，利用该薄膜涂层色度分析设备可对薄膜涂层色度进行分析，进而对类金刚石薄膜进行分类，区别于传统DLC薄膜分类方法，不仅适用于小规模小试及中试实验，也适用于大规模量产过程中对DLC薄膜进行有效初选。
本申请提供了一种薄膜涂层色度分析设备，利用该薄膜涂层色度分析设备可对薄膜涂层色度进行分析，进而对类金刚石薄膜进行分类，薄膜涂层色度分析设备不仅适用于DLC薄膜体系，也适用于其他满足本申请预设条件的其他任意种类薄膜涂层材料。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为薄膜涂层色度分析设备；
图2为有样品台的薄膜涂层色度分析设备；
图3为实施例1中DLC薄膜色度值分布图；
图4为实施例1中DLC薄膜全色度与薄膜厚度关系；
图5为实施例1和2中DLC薄膜样品外观颜色；
图6为实施例2中DLC薄膜全色度值分布图。
图标：1-分光色度计；2-光源；3-距离；4-夹角；5-待测样品；51-薄膜涂层；52-基材；6-样品台。
具体实施方式
下面将结合实施例及附图对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
需要说明的是：
本申请中，如果没有特别的说明，本文所提到的所有实施方式以及优选实施方法可以相互组合形成新的技术方案。
本申请中，如果没有特别的说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。
本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“15-35”表示本文中已经全部列出了“15-35”之间的全部实数，“15-35”只是这些数值组合的缩略表示。
本申请所公开的“范围”以下限和上限的形式，可以分别为一个或多个下限，和一个或多个上限。
本申请中，除非另有说明，各个反应或操作步骤可以顺序进行，也可以按照顺序进行。优选地，本文中的反应方法是顺序进行的。
除非另有说明，本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法或材料也可应用于本申请中。
如图1所示，提供了一种薄膜涂层色度分析设备，包括分光色度计(1)、光源(2)和待测样品(5)；
待测样品包括基材(52)和设置在基材的上表面处的薄膜涂层(51)；
分光色度计(1)和光源(2)设置在待测样品的上方；
光源与待测样品的距离(3)为15-35cm；
光源的中心点到待测样品的垂足为交点D；
光源的中心点到交点D的直线为直线A，分光色度计的中心点到交点D的直线为直线B；
直线A与直线B的夹角(4)为1-15°。
对分光色度计的来源和型号不作限定，例如，可以是能够实现CIELAB或CIELUV颜色空间测试要求的分光色度计。
对光源的种类和来源不作限定，例如，可以是白色LED光源。
白色LED光源是指半透明或者不透明，其表面颜色是指白浊色、乳白色、淡黄色、奶油色或它们的中间色中的任一种颜色。或者，是指色调为从5R经由5YR到5Y的范围，色彩饱和度为C6以下，光亮度为V8.5以上。
可以理解的是，薄膜涂层的厚度不影响光源和分光色度计到光源在待测样品垂足的夹角，即在基材的上表面处设置薄膜涂层前后，光源和分光色度计到光源在待测样品垂足的夹角应当基本一致。若光源与待测样品的距离为15-35cm，则薄膜涂层的厚度可以是20-3000nm；此时，在基材的上表面处设置该厚度的薄膜涂层前后，光源和分光色度计到光 源在待测样品垂足的夹角基本一致。
典型但非限制性的，薄膜涂层的厚度为20nm、40nm、60nm、65nm、80nm、100nm、200nm、300nm、400nm、500nm、600nm、700nm、800nm、900nm、1000nm、1100nm、1200nm、1300nm、1400nm、1500nm、1600nm、1700nm、1800nm、1900nm、2000nm、2100nm、2200nm、2300nm、2400nm、2500nm、2600nm、2700nm、2800nm、2900nm或3000nm。
可以理解的是，薄膜涂层的表面粗糙度应较小，例如，可以是粗糙度小于10nm的薄膜涂层。
对于基材的上表面处的薄膜涂层的设置方式不作限定，例如，可以是利用磁控溅射、等离子化学气相沉积(PECVD)、离子束辅助沉积、脉冲激光沉积或过滤阴极真空电弧(FCVA)沉积等真空镀膜设备在基材的上表面处设置薄膜涂层。
对于薄膜涂层的种类不作限定，可以是无机非金属薄膜，无机非金属薄膜包括但不限于类金刚石薄膜或钻石薄膜。
对于基材的种类不作限定，例如，可以是单面抛光的单晶硅、石英、透明导电玻璃或硬质合金。应当理解的是，薄膜涂层设置在基材的抛光面。
应当理解的是，光源与待测样品的距离可以是15-35cm范围内的任一个固定值，并不选用每次测量前都重新调节光源与待测样品的距离。
典型但非限制性的，光源与待测样品的距离为15cm、16cm、17cm、18cm、19cm、20cm、21cm、22cm、23cm、24cm、25cm、26cm、27cm、28cm、29cm、30cm、31cm、32cm、33cm、34cm或35cm。
应当理解的是，直线A与直线B的夹角可以是1-15°范围内的任一个固定值，并不选用每次测量前都重新调节光源和分光色度计到光源在待测样品垂足的夹角。
典型但非限制性的，直线A与直线B的夹角为1°、2°、3°、4°、5°、6°、7°、8°、9°、10°、11°、12°、13°、14°或15°。
本申请提供了一种薄膜涂层色度分析设备，该设备包括分光色度计、光源和待测样品。该设备通过光源照射到待测样品时产生散射光，利用分光色度计对散射光进行分析，得到薄膜涂层的色度值，得到不同种类的薄膜涂层与色度值之间的定量关系，并建立数据库。之后，只需要利用薄膜涂层色度分析设备对薄膜涂层色度进行分析，即可判断薄膜涂层的种类。利用薄膜涂层色度分析设备对薄膜涂层进行分类的方法简单、快捷且实用，大幅度简化薄膜涂层分类过程，为实际应用于生产带来极大的便利。
在一种实施方式中，如图2所示，色度分析设备还包括样品台(6)，待测样品放置在样品台表面。
对于样品台的来源不作限定，可以是表面平整的试验平台，以光学平台为优。
在一种实施方式中，分光色度计和光源平齐，待测样品位于光源正下方。
在一种实施方式中，直线A与直线B的夹角为5-10°。
直线A与直线B的夹角为5-10°时，这一夹角范围首先包括了国际照明协会指定的最接近人眼的2°和/或10°视角，同时也适合于不同操作人员和操作环境。
在一种实施方式中，直线A与直线B的夹角为10°。
在一种实施方式中，基材为单晶硅。
根据本申请第二个方面，提供了上述薄膜涂层色度分析设备在薄膜涂层色度分析中的应用。
将上述薄膜涂层色度分析设备应用于薄膜涂层色度分析中，可使得薄膜涂层色度的分析方便快捷，将待测薄膜涂层设置在基材表面，放置在光源下方，即可得出待测薄膜涂层的色度。
对于薄膜涂层的种类不作限定，可以是无机非金属薄膜，无机非金属薄膜包括但不限于类金刚石薄膜或钻石薄膜。
在一种实施方式中，薄膜涂层为类金刚石薄膜。
根据本申请第三个方面，提供了一种薄膜涂层色度分析方法，包括以下步骤：
S1：将上述薄膜涂层色度分析设备置于黑暗环境中，放置待测样品，并打开光源和分光色度计；
S2：利用分光色度计得到L*、a*和b*，或，利用分光色度计得到L*、v*和u*；
S3：若步骤S2得到了L*、a*和b*，根据公式1和公式2得到色度C ab和全色度C T：
C ab＝[(a*) 2+(b*) 2] 1/2                   (公式1)，
C T＝[(L*) 2+(a*) 2+(b*) 2] 1/2               (公式2)，
若步骤S2得到了L*、v*和u*，根据公式3和公式4得到色度C uv和全色度C T：
C uv＝[(u*) 2+(v*) 2] 1/2                   (公式3)，
C T＝[(L*) 2+(u*) 2+(v*) 2] 1/2               (公式4)。
应当理解的是，薄膜涂层色度分析设备置于黑暗环境中，黑暗环境是指不受外界光源影响。
应当理解的是，放置待测样品指的是，将待测样品放置在我们预先设定的位置上，例如，在光源的正下方。
应当理解的是，打开光源和分光色度计指的是，打开电源后使其能够正常工作，即包括开启开关，调节各项参数，确定夹角等操作，即做好开始测量前的所有准备工作。
“L*、a*和b*”是使用国际照明协会CIELAB颜色空间读取各样品色度信息；“L*、v*和u*”是使用国际照明协会CIELUV颜色空间读取各样品色度信息。
应当理解的是，步骤S2中，L*、a*和b*对应的分光色度计能够实现CIELAB颜色空间测试要求，步骤S2中，L*、v*和u*对应的分光色度计能够实现CIELUV颜色空间测试要求。
应当理解的是，若分光色度计能够实现CIELAB颜色空间测试要求，结合公式1和公式2，得到色度C ab和全色度C T。若分光色度计能够实现CIELUV颜色空间测试要求，结合公式3和公式4，得到色度C uv和全色度C T。
应当理解的是，为了确保得到的薄膜涂层色度信息的准确性，可以重复测试2-4次，通过每次获得的L*、a*和b*，或者L*、v*和u*，求得样品色度参数平均值记录结果，然后再根据公式1-4得到色度C ab和全色度C T，或者，得到色度C uv和全色度C T。
公式1通过平面内色度值a*和b*得到色度C ab，公式2考虑到了明暗度L*，得到全色度C T，全色度C T能够更好地分析薄膜涂层颜色的色度值。
公式3通过平面内色度值v*和u*得到色度C uv，公式4考虑到了明暗度L*，得到全色度C T，全色度C T能够更好地分析薄膜涂层颜色的色度值。
该薄膜涂层色度分析方法利用薄膜涂层色度分析设备对薄膜涂层的色度进行分析，进而对类金刚石薄膜进行分类，采用国际照明协会CIELAB或CIELUV颜色空间，即利用最近接肉眼的测试方式对DLC薄膜外观颜色进行测试，非常适合生产一线实际操作，具有巨大的应用前景。
根据本申请第四个方面，提供了上述薄膜涂层色度分析方法在薄膜涂层分类中的应用。
薄膜涂层色度分析方法应用于分析薄膜涂层时，对于薄膜涂层的种类不作限定，可以是无机非金属薄膜，无机非金属薄膜包括但不限于类金刚石薄膜或钻石薄膜。
在一种实施方式中，薄膜涂层为类金刚石薄膜。
薄膜涂层色度分析设备应用于薄膜涂层的中，简单、快捷且实用，大幅度简化薄膜涂层分类过程，为实际应用于生产带来极大的便利。
上述薄膜涂层色度分析方法应用在类金刚石薄膜分类中，是通过薄膜涂层色度分析方法收集不同品相和不同种类类金刚石薄膜的颜色及色度信息，获得不同种类类金刚石薄膜的色度值，建立类金刚石薄膜色度值与类金刚石薄膜种类之间的定量关系，从而通过测定待测类金刚石薄膜色度值简单快速地判断类金刚石薄膜的种类，这种利用薄膜涂层色度分析设备对类金刚石薄膜进行分类的方法简单、快捷且实用，大幅度简化类金刚石薄膜分类过程，为实际应用于生产带来极大的便利。
根据本申请第五个方面，提供了一种薄膜涂层分类方法，包括以下步骤：
(a1)根据上述薄膜涂层色度分析方法得到已知种类的薄膜涂层的L*、a*、b*、C ab和C T，并建立数据库；
(b1)根据上述薄膜涂层色度分析方法得到待测薄膜涂层的L*、a*、b*、C ab和C T，结合步骤(a1)得到的数据库，对待测薄膜涂层进行分类；
或者，
(a2)根据上述薄膜涂层色度分析方法得到已知种类的薄膜涂层的L*、v*、u*、C uv和C T，并建立数据库；
(b2)根据上述薄膜涂层色度分析方法得到待测薄膜涂层的L*、v*、u*、C uv和C T，结合步骤(a2)得到的数据库，对待测薄膜涂层进行分类。
薄膜涂层分类方法对于薄膜涂层的种类不作限定，可以是类金刚石薄膜、钻石薄膜分类等。
利用薄膜涂层色度分析设备得到不同种类的薄膜涂层与色度值之间的定量关系，并建立数据库。之后，只需要利用薄膜涂层色度分析设备对薄膜涂层色度进行分析，即可判断薄膜涂层的种类。利用薄膜涂层色度分析设备对薄膜涂层进行分类的方法简单、快捷且实用，因此大幅度简化薄膜涂层分类过程，为实际应用于生产带来极大的便利。
类金刚石薄膜分类方法是利用薄膜涂层色度分析设备和薄膜涂层色度分析方法得到不同种类的类金刚石薄膜的颜色及色度信息，收集数据，建立数据库，然后建立类金刚石薄膜色度值与类金刚石薄膜种类之间的定量关系，从而通过测定待测类金刚石薄膜色度值简单快速地判断类金刚石薄膜的种类，这种利用薄膜涂层色度分析设备对类金刚石薄膜进行分类的方法简单、快捷、实用，大幅度简化了类金刚石薄膜分类过程，为实际应用于生产带来了极大的便利。
下面将结合实施例对本申请的技术方案进行进一步地说明。
实施例1
一、我们通过不同的制备方法得到不同的PLC薄膜，然后对得到的不同薄膜利用薄膜涂层色度分析设备结合薄膜涂层色度分析方法进行色度值分析，若不同方法制备得到的PLC薄膜的色度值不同，也就是说，通过薄膜涂层色度分析方法能够将不同的PLC薄膜区分开来，则证明本申请的薄膜涂层色度分析设备能够应用于薄膜涂层色度分析，且利用薄膜涂层色度分析方法能够对类金刚石薄膜进行分类，类金刚石薄膜分类方法可行。
二、验证类金刚石薄膜分类方法
(1)样品制备
首先将单面抛光的衬底材料单晶硅片分别依次放入蒸馏水、丙酮、无水乙醇溶液中超声清洗15min，然后用干燥氮气将衬底表面吹干，最后再将样品放入80℃鼓风干燥箱中烘干。
并将烘干后的样片，固定在PECVD设备中的衬底固定架上。
关闭真空腔室，抽真空。当真空室压强抽到5.0×10 -3Pa以后，使用质量流量计向真空室内通入氩气(纯度99.99％)流量50sccm，施加脉冲偏压-100V，开启微波电源功率50W，产生等离子体，对基底进行清洗，清洗时间10min。
之后导入乙炔气体(纯度99.8％)流量30sccm和氩气流量20sccm，在脉冲偏压-0V，微波功率50W条件下，控制沉积时间制备不同厚度的DLC薄膜。在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品#01、#02、#03、#04、#05、#06、#07、#08。
同样的，在脉冲偏压-500V，微波功率50W条件下，控制沉积时间制备不同厚度的DLC薄膜。在沉积时间依次为5min、10min、15min、20min、25min、30min、35min、40min的条件下，依次得到样品#09、#10、#11、#12、#13、#14、#15、#16。
(2)色度值测量
如图1或图2所示，图1为薄膜涂层色度分析设备，图2为有样品台的薄膜涂层色度分析设备。在暗室中将DLC测试样品垂直放置于光源正下方，分光色度计的白色LED光源，对准放置样品的水平光学平台。确定光源与样品台高度为25cm，分光色度计与光源平齐，光源中心、分光色度计、样品三者之间形成夹角为8°的固定值后，对所制备DLC样品按照沉积时间不同依次进行三点测量，使用国际照明协会CIELAB颜色空间得到各自色度信息L*、a*、b*。
(3)色度值分析
利用公式1和2通过计算求得DLC样品色度值C ab和全色度值和C T，如图3所示，图3为实施例1中DLC薄膜色度值分布图。未施加偏压的DLC薄膜外观颜色鲜艳(图5中样品#01～#08)。通过图3a可知，样品#01～#08的C ab值广泛分布在色度空间色度值高位，随着沉积时间的增加薄膜厚度逐渐递增，色度值围绕中心呈现顺时针周期性环绕，出现DLC薄膜色度值干涉色厚度依赖的现象。
与之相对，施加偏压-500V的样品虽然厚度和色度值都出现类似顺时针环绕分布的情况(如图3b)，但色度值明显处在未施加偏压样品的内部(图3b中样品#09～#16的数据点对应于图3a内部的未标号的数据点)，表现出弱的干涉色厚度依赖现象。
图4为实施例1中DLC薄膜全色度与薄膜厚度关系，由图4可知，4a中DLC薄膜(样品#01-#08)颜色呈现周期性变化，并且这一周期性和干涉条纹很好的对应良好，此时的颜色来源于薄膜的无定型结构与光的相互作用而产生的结构色，色度值及全色度都较大；对比4b中施加偏压的DLC薄膜(样品#09-#16)，如前所述，色度值明显降低，薄膜厚度处于同样(样品#01-#08)范围内时，全色度没有出现明显周期性变化，DLC薄膜种类与前者有明显区别。
根据文献X.L.Zhou,et al.,Diam.Relat.Mater.,73(2017)232-240可知，未偏压样品(样品#01～#08)属于PLC薄膜(类高聚物碳膜)，而施加偏压-500V的样品(样品#09～#16)属于a-C:H薄膜(含氢碳膜)，由此可知，类金刚石薄膜分类方法能够区分PLC薄膜和a-C:H薄膜，即类金刚石薄膜分类方法验证可行。
实施例2
实施例2与实施例1的不同之处在于，以FCVA沉积设备代替PECVD沉积设备，以碳靶为碳源代替乙炔气体，以施加脉冲偏压-800V代替脉冲偏压-0V或-500V，在沉积时间依次为45min、50min、55min、60min、65min、70min、75min、80min的条件下，依次得到样品#17、#18、#19、#20、#21、#22、#23、#24。
如图5所示，通过对比未施加偏压(样品#01～#08)，偏压-500V(样品#09～#16)所制备样品，与偏压-800V的样品(#17～#24)比较，外观颜色明显不同，#01～#08样品外观颜色鲜艳，样品#09～#16外观颜色鲜艳度较之前者明显减弱，样品#17～#24只有墨绿和灰褐两种鲜艳度很弱的颜色。
同时，如图6所示，图6为实施例2中DLC薄膜全色度值分布图，图6b为样品#17～#24的全色度值，图6a中，位于#09～#16内部的未标号的点值对应于样品#17～#24的全色度值，偏压-800V所制备出样品(#17～#24)的色度值都分布在a*、b*绝对值小于10的范围内且都位于样品#09～#16内部，说明两种样品同样属于不同种类DLC薄膜。
根据文献X.L.Zhou,et al.,Appl.Phys.Lett.,110(2017)201902可知，未偏压样品属于PLC薄膜(类高聚物碳膜)，而施加偏压-500V的样品属于a-C:H薄膜(含氢碳膜)，FCVA施加偏压得到的样品为ta-C：(H)薄膜(含氢四面体碳膜)，由此可知，类金刚石薄膜分类方法能够区分PLC薄膜、a-C:H薄膜和ta-C：(H)薄膜，即类金刚石薄膜分类方法验证可行。
实施例3
与实例1的不同之处在于，以磁控溅射技术代替PECVD技术制备DLC薄膜，且脉冲偏压为-0V。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品的L*、a*、b*分别为(59.0，-23.0，-34.1)、(109.5，-7.6，39.8)、(74.2，29.0，7.5)、(76.0，-40.2，10.5)、(86.0，-17.2，43.5)、(64.2，3.7，12.3)、(53.4，-4.5，-27.8)、(57.6，-28.4，14.3)。
实施例4
与实例1的不同之处在于，以脉冲激光沉积技术代替PECVD技术制备DLC薄膜，且脉冲偏压为-0V。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min 的条件下，依次得到样品的L*、a*、b*分别为(109.0，-12.9，-4.1)、(89.0，-10.6，35.8)、(51.2，36.0，-48.5)、(75.0，-13.2，30.5)、(60.0，-8.7，14.5)、(59.2，-46.7，15.3)、(70.1，-40.5，12.8)、(60.6，15.4，-6.9)。
实施例5
与实例1的不同之处在于，以射频CVD沉积技术代替PECVD技术制备DLC薄膜，且脉冲偏压为-0V。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品的L*、a*、b*分别为(91.0，-17.9，-4.1)、(89.5，-9.6，36.8)、(61.2，33.0，-50.5)、(86.0，-16.2，35.5)、(62.0，-9.7，12.5)、(57.2，-53.7，13.3)、(73.1，-47.5，17.8)、(68.6，19.4，-6.9)。
由实施例1、实施例3-实施例5可知，利用薄膜涂层色度分析设备，可对不同制备方法制备得到的DLC薄膜进行分类。
实施例6
与实例1的不同之处在于，以石英玻璃衬底代替单晶硅衬底制备DLC薄膜，且脉冲偏压为-0V。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品的L*、a*、b*分别为(71.0，-19.9，-5.1)、(80.5，-10.6，39.8)、(55.2，35.0，-54.5)、(81.0，-19.2，37.5)、(63.0，-16.7，17.5)、(46.2，-50.7，16.3)、(76.1，-42.5，19.8)、(49.6，21.4，-10.9)。
实施例7
与实例1的不同之处在于，以透明导电玻璃衬底代替单晶硅衬底制备DLC薄膜，且脉冲偏压为-0V。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品的L*、a*、b*分别为(71.0，-19.9，-5.1)、(79.5，-10.6，38.8)、(41.2，30.0，-59.5)、(66.0，-13.2，39.5)、(42.0，-10.7，15.5)、(39.2，-59.7，16.3)、(53.1，-49.5，25.8)、(48.6，23.4，-9.9)。
实施例8
与实例1的不同之处在于，以硬质合金衬底代替单晶硅衬底制备DLC薄膜，且脉冲偏压为-0V。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品的L*、a*、b*分别为(100.0，-10.9，-5.1)、(85.0，-11.6，30.8)、(50.2，35.0，-45.5)、(79.0，-12.2，29.5)、(56.0，-7.7，13.5)、(63.2，-45.7，14.3)、(71.1， -36.5，10.8)、(56.6，13.4，-7.9)。
由实施例6-8可知，基材选择单晶硅、石英玻璃、透明导电玻璃或硬质合金时，利用薄膜涂层色度分析设备得到的L*、a*、b*不同，因此，我们在检测已知类金刚石薄膜种类用于建立数据库时，应当采用相同的基材，并且，建立数据库后，检测待测类金刚石薄膜种类时，使用的基材应当与建立数据库使用的基材相同。
实施例9
与实例1的不同之处在于，以CIELUV颜色空间代替CIELAB颜色空间获取DLC薄膜色度信息。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品的L*、u*、v*分别为(90.0，-17.5，-4.2)、(88.5，-9.3，36.5)、(60.2，32.0，-52.5)、(83.0，-15.2，36.5)、(61.0，-10.7，11.5)、(55.2，-50.7，14.3)、(70.1，-46.5，15.8)、(65.6，20.4，-6.5)。
由实施例9可知，不论是利用CIELUV颜色空间，还是利用CIELAB颜色空间，都可用于获取DLC薄膜色度信息，都可用于对类金刚石薄膜进行分类。
实施例10
与实例1的不同之处在于，以钻石薄膜涂层代替DLC薄膜进行上述分析。
在沉积时间依次为10min、20min、30min、40min、50min、60min、70min、80min的条件下，依次得到样品的L*、a*、b*分别为(59.0，-25.0，-39.1)、(95.5，-17.6，30.8)、(70.2，35.0，9.5)、(62.0，-41.2，12.5)、(89.0，-19.2，40.5)、(69.2，5.7，14.3)、(50.4，-8.5，-29.8)、(70.6，-35.4，17.3)。
由实施例10可知，利用薄膜涂层色度分析设备也可检测钻石薄膜涂层的L*、a*、b*，即我们同样可以利用薄膜涂层色度分析设备对钻石薄膜涂层进行分类。
应当理解的是，上述制备方法的说明中未详细描述的内容，均是本领域技术人员容易想到的常用参数，因此可以省略对其的详细说明。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (10)

  1. 一种薄膜涂层色度分析设备，其特征在于，包括分光色度计、光源和待测样品；
    所述待测样品包括基材和设置在所述基材的上表面处的薄膜涂层；
    所述分光色度计和光源设置在待测样品的上方；
    所述光源与待测样品的距离为15-35cm；
    所述光源的中心点到待测样品的垂足为交点D；
    所述光源的中心点到交点D的直线为直线A，所述分光色度计的中心点到交点D的直线为直线B；
    所述直线A与直线B的夹角为1-15°。
  2. 根据权利要求1所述的薄膜涂层色度分析设备，其特征在于，所述色度分析设备还包括样品台，所述待测样品放置在样品台表面；
    优选地，所述分光色度计和光源平齐，所述待测样品位于光源正下方。
  3. 根据权利要求1所述的薄膜涂层色度分析设备，其特征在于，所述直线A与直线B的夹角为5-10°，优选为10°。
  4. 根据权利要求1-3任一项所述的薄膜涂层色度分析设备，其特征在于，所述光源为白色LED光源；
    优选地，所述分光色度计能够实现CIELAB和/或CIELUV颜色空间测试要求。
  5. 根据权利要求1-3任一项所述的薄膜涂层色度分析设备，其特征在于，所述基材包括单晶硅、石英、透明导电玻璃或硬质合金中的至少一种，优选为单晶硅。
  6. 根据权利要求1-3任一项所述的薄膜涂层色度分析设备，其特征在于，所述薄膜涂层的粗糙度小于10nm，所述薄膜涂层的厚度为20-3000nm；
    优选地，所述薄膜涂层包括无机非金属薄膜，优选为类金刚石薄膜或钻石薄膜，进一步优选为类金刚石薄膜。
  7. 权利要求1-6任一项所述的薄膜涂层色度分析设备在薄膜涂层色度分析中的应用。
  8. 一种薄膜涂层色度分析方法，其特征在于，包括以下步骤：
    S1：将权利要求1-6任一项所述的薄膜涂层色度分析设备置于黑暗环境中，放置待测样品，并打开光源和分光色度计；
    S2：利用分光色度计得到L*、a*和b*，或，利用分光色度计得到L*、v*和u*；
    S3：根据公式(1)和公式(2)得到色度C ab和全色度C T：
    C ab＝[(a*) 2+(b*) 2] 1/2       (1)，
    C T＝[(L*) 2+(a*) 2+(b*) 2] 1/2         (2)，
    或，根据公式(3)和公式(4)得到色度C uv和全色度C T：
    C uv＝[(u*) 2+(v*) 2] 1/2            (3)，
    C T＝[(L*) 2+(u*) 2+(v*) 2] 1/2         (4)。
  9. 权利要求8所述的薄膜涂层色度分析方法在薄膜涂层分类中的应用；
    优选地，所述薄膜涂层包括无机非金属薄膜，优选为类金刚石薄膜或钻石薄膜，进一步优选为类金刚石薄膜。
  10. 一种薄膜涂层分类方法，其特征在于，包括以下步骤：
    (a1)根据权利要求8所述的薄膜涂层色度分析方法得到已知种类的薄膜涂层的L*、a*、b*、C ab和C T，并建立数据库；
    (b1)根据权利要求8所述的薄膜涂层色度分析方法得到待测薄膜涂层的L*、a*、b*、C ab和C T，结合步骤(a1)得到的数据库，对待测薄膜涂层进行分类；
    或者，
    (a2)根据权利要求8所述的薄膜涂层色度分析方法得到已知种类的薄膜涂层的L*、v*、u*、C uv和C T，并建立数据库；
    (b2)根据权利要求8所述的薄膜涂层色度分析方法得到待测薄膜涂层的L*、v*、u*、C uv和C T，结合步骤(a2)得到的数据库，对待测薄膜涂层进行分类；
    优选地，所述薄膜涂层包括无机非金属薄膜，优选为类金刚石薄膜或钻石薄膜，进一步优选为类金刚石薄膜。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5550632A (en) * 1990-06-20 1996-08-27 Harata; Hiroaki Method for evaluating gloss and brightness character of coated paint film
CN101568821A (zh) * 2007-02-20 2009-10-28 三菱重工业株式会社 膜质评价方法及其装置、以及薄膜设备的制造系统
CN102269622A (zh) * 2010-06-02 2011-12-07 北京智朗芯光科技有限公司 垂直入射宽带光谱仪
CN102667444A (zh) * 2009-12-18 2012-09-12 纳幕尔杜邦公司 用于涂层测量的方法
CN103459976A (zh) * 2011-04-12 2013-12-18 株式会社尼利可 膜厚测定装置和膜厚测定方法
CN108195469A (zh) * 2018-02-06 2018-06-22 彭忠祥 一种便携式颜色测量仪

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US5550632A (en) * 1990-06-20 1996-08-27 Harata; Hiroaki Method for evaluating gloss and brightness character of coated paint film
CN101568821A (zh) * 2007-02-20 2009-10-28 三菱重工业株式会社 膜质评价方法及其装置、以及薄膜设备的制造系统
CN102667444A (zh) * 2009-12-18 2012-09-12 纳幕尔杜邦公司 用于涂层测量的方法
CN102269622A (zh) * 2010-06-02 2011-12-07 北京智朗芯光科技有限公司 垂直入射宽带光谱仪
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