WO2003040649A1 - Procede et dispositif de mesure de grandeurs caracteristiques physiques de couches fines optiquement transparentes - Google Patents

Procede et dispositif de mesure de grandeurs caracteristiques physiques de couches fines optiquement transparentes Download PDF

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Publication number
WO2003040649A1
WO2003040649A1 PCT/EP2002/012244 EP0212244W WO03040649A1 WO 2003040649 A1 WO2003040649 A1 WO 2003040649A1 EP 0212244 W EP0212244 W EP 0212244W WO 03040649 A1 WO03040649 A1 WO 03040649A1
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WIPO (PCT)
Prior art keywords
layers
thickness
transparent layers
measured
solid angle
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Application number
PCT/EP2002/012244
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German (de)
English (en)
Inventor
Peter Gehr
René Staub
Original Assignee
Ovd Kinegram Ag
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Publication date
Application filed by Ovd Kinegram Ag filed Critical Ovd Kinegram Ag
Publication of WO2003040649A1 publication Critical patent/WO2003040649A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00—Measuring arrangements characterised by the use of optical techniques
    • G01B11/02—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
    • G01B11/06—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
    • G01B11/0691—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of objects while moving

Definitions

  • the invention relates to a method for measuring the thickness of thin, optically completely or partially transparent layers applied to a carrier moving relative to a sensor, in which the intensity of light radiation reflected by the transparent layers as a function of the light wavelength measured and therefrom the thickness of the transparent layers is determined in comparison with calculations and taking into account the physical parameters, in particular the refractive index, the invention comprising the measurement of the thickness of only a single layer as of several layers and layer sequences.
  • the invention also relates to a device for measuring the thickness of thin, optically completely or partially transparent layers, which are applied to a carrier moving relative to a sensor and which have a spectrally broadband light source, the sensor for measuring the intensity of those reflected by the transparent layers Has light radiation as a function of the light wavelength and a computing device for evaluating the spectral intensity of the reflected light radiation.
  • the thickness of a comparatively thin, transparent, dielectric layer is calculated from the spectral layer Intensity distribution of the light reflected upon irradiation of the layer with spectrally broadband light can be determined.
  • the rule here is that the layer thickness of a highly refractive layer is directly proportional to the wavelength of the maximum of the spectral reflection curve, according to the formula -:
  • n refractive index of the dielectric layer
  • Peak wavelength wavelength of the longest wavelength reflection
  • Layers used material namely ZnS, which has a refractive index of 2.3, a peak wavelength of 550 nm for a layer thickness of 60 nm.
  • Intensity distribution of the reflected light is measured, can be used well when it comes to stationary measurements and enough time is available for the measurement and evaluation.
  • US 5 604581 describes the spectral analysis of reflected light for measuring the thickness of layers in comparison with model calculations. The possibility of a solid angle integration via scattered light is not addressed here.
  • the invention is now concerned with the measurement of the thickness or other physical parameters, for example the peak wavelength, corresponding to thin, transparent or semitransparent layers or layer sequences (which can also have absorbent layers such as metals or semiconductors), this measurement being carried out during or afterwards the thin layers are applied to a moving support and measurement should also be possible when the surface receiving the transparent layers is structured microscopically or macroscopically.
  • This constellation arises, for example, when a transparent, thin, dielectric layer that improves the recognizability of the structure is applied to a carrier film with a structure that has been introduced, for example by replication, with an optical diffraction effect, for example a grating structure, a hologram generated by structuring should.
  • the highly refractive thin layers or sequences of thin layers used in this connection normally have refractive indices between 1.7 and 4.5. Taking into account the commonly used substrates, it can be assumed that a refractive index difference of at least 0.1 to 0.3 between the carrier web or the layer on which the thin, transparent layer is to be applied, and the layer or the thin, transparent layer and the air is given.
  • the layer to be characterized can also be embedded between other, possibly dielectric layers, for example between a replication layer and an adhesive, if the measurement is not carried out immediately when the layer to be measured is applied. If there is a layer sequence, there is also a
  • the reflection-increasing, thin dielectric layer In order to largely prevent falsification of the effects produced by the diffraction structure or the like, the reflection-increasing, thin dielectric layer must be applied with very good thickness constancy, with the aim that the thickness of the dielectric layer should be accurate to within 1 nm can be measured and adjusted accordingly.
  • Such thin, dielectric layers are usually applied in a vacuum, the carrier web moving at a relatively high speed of up to 300 m / min. with respect to the source used for the vapor deposition of the thin layer, and thus also with respect to a possible measuring point or sensor.
  • the invention is based on the object of proposing a method and a device which are suitable for rapidly measuring the thickness of transparent or semitransparent, thin layers or layer sequences without any fluttering of a carrier web or the presence of structures on the surface of a
  • the carrier to which the transparent layers are to be applied has a significant influence on the measurement result, so that, starting from the measured thickness of the transparent layers, the device used to apply the layers can be controlled in order to achieve a predetermined, possibly even locally varying layer thickness.
  • a device according to claim 6 is particularly suitable for carrying out the method according to the invention, which device can expediently be further developed with the features of claims 7 to 20.
  • the illumination or the detection of the light reflected by the carrier with the thin, transparent layer or the layers must take place over a very large solid angle range. This is necessary in order to ensure that, even when there are different surface structures in the area of the thin, transparent layers, that either the small surface sections pointing in different directions are all illuminated approximately uniformly or in the case of highly directed lighting as part of the evaluation of the reflected radiation which includes partial beams reflected in a wide variety of solid angle ranges. If the illumination takes place over a large solid angle range, ie quasi an integral illumination is carried out, then the reflected radiation is accordingly only evaluated over a comparatively narrow solid angle range.
  • a “narrow solid angle range” essentially means a parallel beam path or a beam path whose divergence is less than approximately 5 ° around the central axis of the radiation or detection area.
  • Target intensity curves are calculated curves, the physical characteristics of both the thin, transparent layers and of the carrier and any additional layers that are present being included in the calculation. For example, it is possible to take wavelength-dependent changes in the refractive index into account.
  • the absorption capacity, which can also be wavelength-dependent, can also be taken into account in the calculation.
  • target intensity curves can be calculated over a wavelength range that extends beyond the wavelength range of the light used for the measurement.
  • properties e.g. Determine the peak wavelength of the transparent layers, which are significantly below or above the measurement range that results from the light used, which is a considerable advantage especially for highly refractive, reflection-increasing layers.
  • the invention cannot only be used to measure the thickness of one or more
  • the invention is furthermore not only limited to measurements on thin layers applied to a carrier web. It generally deals with the Application of thin, partially or completely transparent layers (also very thin metal layers) on flat supports, e.g. on rotating CD blanks, or on shaped bodies, e.g. bottles, whereby here, for example, the coating of PET bottles should be considered to ensure their gas tightness to improve. It would also be conceivable to measure the layer thickness on coextruded plastic films with a sufficiently different refractive index.
  • Figure 1 schematically shows a system for applying a thin, transparent dielectric layer to a substrate in a vacuum chamber including the device for thickness measurement when used in a control loop for the system;
  • FIG. 2 schematically shows a section through part of the integrating sphere forming the measuring device, including the track and counter bearing to be measured;
  • Figure 3 is a block diagram of the device for layer thickness measurement
  • FIG. 4 shows, by way of example, the representation of an actual intensity curve resulting from a corresponding measurement in comparison with the appropriate target intensity curve.
  • the system in Figure 1 is shown only very schematically.
  • Corresponding vacuum systems for applying thin layers to a substrate, for example by vapor deposition or sputtering, are generally known, for which reason a detailed explanation should be dispensed with here.
  • the system of FIG. 1 comprises a vacuum container 1, in which a carrier web 2 moves, for example in the direction of the arrow, between an unwinding roller 3 and a winding roller 4.
  • a carrier web 2 moves, for example in the direction of the arrow, between an unwinding roller 3 and a winding roller 4.
  • the carrier web 2 is, of course, guided and supported by means of corresponding rollers, a support roller 5 being indicated only schematically in FIG. 1 in the region of the station serving to measure the layer thickness.
  • the carrier web 2 is covered on one side (in FIG.
  • a thin, dielectric layer for the production of which, for example, an evaporation station 6 can be provided, which can be provided via a corresponding control device 7 is controlled depending on the prevailing working conditions and the desired layer thickness.
  • high-index substances such as ZnS, TiO 2 etc. or low-index substances (such as MgF 2 or SiO x )
  • low-index substances such as MgF 2 or SiO x
  • the carrier web can be made of a wide variety of materials.
  • the method according to the present invention is used in particular when the surface of the carrier web to be provided with the thin dielectric layer is structured, in particular has a different structure in different areas.
  • the surface of the carrier web can, for example, be mirror-smooth, have a stochastic matt structure or a lattice structure, which are often structures such as those used with elements that have an optical diffraction effect, for example Security elements for securities such as banknotes or the like are used and are generally known. These structures have, for example, grating frequencies of over 1,000 / mm and grating depths of a few hundred nm and have a significant influence on the measurement of any parameters of the dielectric layer.
  • the procedure is usually that a deformable layer, for example a thermoplastic lacquer layer, is applied to a carrier web, into which the diffraction-optically effective structure is then introduced by means of replication. It is also conceivable that further layers are present between the replication layer and the carrier web, which layers can also influence the measurement of the reflected intensity.
  • a deformable layer for example a thermoplastic lacquer layer
  • a so-called “Ulbricht ball” 8 is arranged in the vacuum chamber 1, the size ratios not being shown correctly in FIG. 1.
  • the Ulbricht ball 8 can, for example, have an inner diameter of less than 50 mm, while the overall diameter is one Vacuum chamber 1 is of the order of 1 m or significantly more.
  • the integrating sphere 8 has on its side facing the carrier web 2 and thus the thin layer whose thickness is to be measured, a measuring opening 9 through which both light emerges on the carrier web 2 and light reflected by the carrier web 2 enters, such as this is indicated by the double arrow 10.
  • a spectrally broadband lamp 11 for example an essentially white light-generating incandescent lamp, which is coupled to the integrating sphere 8 via a light guide 12, is used to illuminate the measuring area on the carrier web 2, in such a way that the light exit point 13 is approximately at Is offset 90 ° with respect to the measuring opening 9. That at the light exit point 13 in the interior 14 of the integrating sphere 8 light is reflected several times in all possible directions on the correspondingly coated inner surface of the cavity 14 of the integrating sphere 8, so that the light emerging from the measuring opening 9 comes uniformly from a large solid angle range.
  • a sensor 16 for example a spectral photometer, is coupled to the cavity 14 of the integrating sphere 8 at point 15, approximately opposite the measurement opening 9, also via an optical fiber 12a.
  • the exit point 15 for the radiation used for the measurement does not lie on the plumb bob 17 on the carrier web 2 but is at a small angle ⁇ x, generally about 8 °, relative to this plumb bob 17. added.
  • a converging lens can expediently be provided, which has the effect that only a spot with a limited diameter, for example a spot with a diameter of approximately 3 mm, is imaged on the surface of the carrier web 2 in the light guide 12a and correspondingly only radiation from the latter Surface area is forwarded to the sensor 16 via the light guide 12a.
  • FIG. 2 A more detailed illustration of the integrating sphere 8 can be seen in FIG. 2.
  • the design of the cavity 14 of the integrating sphere 8, which is known per se, ensures that the light used for illumination strikes the carrier web 2 with the dielectric layer lying on the support roller 5 from a large solid angle range.
  • an aperture 22 in the form of a radially inwardly facing, partially circular disk is provided between the impingement area 21 of the light emerging at the light exit point 13 on the wall 20 of the cavity 14 of the integrating sphere 8 and the measuring opening 9 ,
  • the sensor 16 of the system according to FIG. 1 is connected to the control unit 7 via the arrangement shown in more detail in FIG. 3.
  • This arrangement comprises an arithmetic unit 23 with a first arithmetic unit 24, a second arithmetic unit 25 and a comparator unit 26, a display device 27 and a controller 28 serving for direct control of the control unit 7.
  • the first computing unit 24 of the computing device 23 as indicated by the arrow 29, for example via a keyboard or other input devices, corresponding characteristic values relating to the substances to be taken into account when measuring the layer thickness are entered.
  • the thicknesses, refractive indices and absorption factors of the various layers present are considered as characteristic values, e.g. the carrier web itself, if it is transparent or translucent, can be included in the calculation.
  • layers present on the carrier web for example a replication layer into which the structures having an optical diffraction effect are replicated, or thin layers already applied beforehand.
  • the first arithmetic unit 24 also takes into account the data of the dielectric layer to be applied, a specific thickness being specified in each case.
  • the refractive indices and absorption it is also possible to take the wavelength dependence into account.
  • the first computing unit for different thicknesses of the dielectric layer calculates the theoretical target intensity curves 30 for the light reflected with corresponding illumination with white light, with the given layers and the lighting and composition and layer structure of the various layers
  • Carrier web for each thickness value of the dielectric layer results in a specific target intensity curve for the reflected light depending on the respective wavelength.
  • the target intensity curve is determined for each predetermined thickness value of the dielectric layer. All target intensity curves obtained in this way form a family. They are stored, for example, in a memory of the first computing unit, a so-called “look-up table”, in order to be able to access the various target intensity curves particularly quickly.
  • the second arithmetic unit 25 is connected to the sensor 16 via the line 31 and receives from it corresponding information about the actually measured intensity of the reflected light over the wavelength range used. Based on this, the second arithmetic unit determines the respective actual intensity curve 32.
  • the computing device 23 also has a comparator unit 26, which communicates both with the first computing unit 24 and with the second computing unit 25 and has the task of generating the actual intensity curve generated in the second computing unit 25 with the target values generated by the first computing unit 24. Compare intensity curves 30 and select the target intensity curve 30 that best matches the actual intensity curve 32. Each target intensity curve is assigned a specific parameter which corresponds to the measured thickness of the dielectric layer and the basis for calculating the target intensity curve. This parameter is passed on from the comparator unit 26 to the controller 28 via the line 33.
  • the controller 28 compares the parameter arriving via the line 33 with the signal applied to the line 34 and corresponding to the target thickness and then specifies it from line 35 a signal used as a control variable, which serves to control the control unit 7 for the evaporation station 6 and - depending on the parameter determined by the comparator 26 - ensures that the thickness of the deposited layer becomes larger or smaller.
  • Display device 27 connected, which for example displays the target and actual intensity curves 30, 32 on a monitor 36, usually only the target intensity curve 30 appearing on the monitor 36 that best matches the actual intensity curve 32 that has just been determined, and so on to give the operating personnel the opportunity personally to monitor the correct functioning of the device.
  • the display device 27 can of course also be set up to display further data. It is particularly expedient if the display device 27 displays, for example in an alphanumeric field 37, the layer thickness that has just been determined or other physical parameters.
  • the display device 27 in conjunction with the computing device 23 can also be able to illustrate on the monitor 36 the time course of the thickness of the dielectric layer determined in each case.
  • the display device 27 - is designed as well as the computing device 23 - in such a way that the thickness of the dielectric layer can be measured simultaneously at different positions on the carrier web, a corresponding number of integrating balls or other measuring units then also being provided got to.
  • the display device 27 usually has a corresponding option for selecting the corresponding measuring points.
  • the device according to the invention is also provided with the possibility of calibration. This is necessary because the lamps 11 used may cover different spectral ranges or the light generated may have different spectral profiles.
  • calibration can take place, for example, by moving a black or gray surface in front of the measurement opening 9 of the integrating sphere 8 in a special calibration step, the reflection behavior of which is precisely known and can therefore be used to calibrate the computing device. It is advantageous if their reflection value corresponds approximately to that of the measurement object.
  • FIG. 4 shows an example of the display on monitor 36.
  • the visible wavelength range used for the measurement is approximately between 380 nm and 780 nm.
  • the method and the device according to the exemplary embodiment are suitable for measuring the thickness of dielectric layers or layer sequences with refractive indices between 1.7 and 4.5 to an accuracy of approximately 1 nm.
  • a refractive index difference of at least 0.1 to 0.2 is required between the dielectric layer, the thickness of which is to be measured, and the adjacent layers, ie for example the carrier web, possibly intermediate layers or air.
  • the spectral measuring range can be, for example, the visual range (380 nm to 780 nm). However, it is also possible to measure in other wavelength ranges, the wavelength range selected in each case being dependent on the material applied and forming the dielectric layer.
  • An advantage of the procedure according to the invention is to be seen in the fact that the comparison method used also makes it possible to extrapolate to a certain extent, ie also to evaluate actual intensity curves which have no maximum in the measured area. As a result of the correspondence between the actual intensity curve and the calculated target intensity curves, the range, where the maximum should be, can be concluded by extrapolation. Furthermore, it may also be sufficient to use only a few wavelengths for determining the actual intensity level, as a result of which the outlay on equipment can be reduced.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Length Measuring Devices By Optical Means (AREA)

Abstract

L'invention concerne un procédé de mesure de l'épaisseur d'une couche ou d'une suite de couches transparente ou semi-transparente, disposée sur un support se déplaçant par rapport à un capteur. Par éclairage ou mesure adapté sur une zone spatiale angulaire de taille importante, et mesure ou éclairage adaptée sur une zone spatiale angulaire de taille inférieure, il est possible d'obtenir des conditions de luminosité s'approchant des conditions de luminosité pour une surface plane, même lorsque la surface du support ou de la ou des couches présente des structurations différentes. La détermination de l'épaisseur de la ou des couches transparente est par ailleurs effectuée par comparaison de la répartition d'intensité spectrale de la lumière réfléchie réellement déterminée, avec la répartition d'intensité spectrale déterminée théoriquement par calcul en fonction des grandeurs caractéristiques des matériaux présents. L'éclairage est de préférence réalisé au moyen d'une sphère d'Ulbricht (8) reliée à un calculateur (23) par l'intermédiaire d'un capteur (16), ledit calculateur produisant au moyen d'une première et d'une deuxième unité de calcul (24, 25) et d'une unité de comparaison (26), une grandeur caractéristique permettant de commander l'épaisseur appliquée par l'intermédiaire d'un régulateur (28).
PCT/EP2002/012244 2001-11-06 2002-11-02 Procede et dispositif de mesure de grandeurs caracteristiques physiques de couches fines optiquement transparentes WO2003040649A1 (fr)

Applications Claiming Priority (2)

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DE2001154404 DE10154404C1 (de) 2001-11-06 2001-11-06 Verfahren und Vorrichtung zur Messung physikalischer Kenngrößen von dünnen, optisch transparenten Schichten und Vorrichtung zur Durchführung des Verfahrens
DE10154404.9 2001-11-06

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Cited By (22)

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EP1688704A1 (fr) * 2005-02-04 2006-08-09 Omron Corporation Appareil et procédé d'inspection de couche mince
EP1715289A1 (fr) * 2005-04-21 2006-10-25 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procédé à reflection optique lumineuse
US7985188B2 (en) 2009-05-13 2011-07-26 Cv Holdings Llc Vessel, coating, inspection and processing apparatus
US8512796B2 (en) 2009-05-13 2013-08-20 Si02 Medical Products, Inc. Vessel inspection apparatus and methods
US9272095B2 (en) 2011-04-01 2016-03-01 Sio2 Medical Products, Inc. Vessels, contact surfaces, and coating and inspection apparatus and methods
US9458536B2 (en) 2009-07-02 2016-10-04 Sio2 Medical Products, Inc. PECVD coating methods for capped syringes, cartridges and other articles
US9545360B2 (en) 2009-05-13 2017-01-17 Sio2 Medical Products, Inc. Saccharide protective coating for pharmaceutical package
US9554968B2 (en) 2013-03-11 2017-01-31 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging
US9664626B2 (en) 2012-11-01 2017-05-30 Sio2 Medical Products, Inc. Coating inspection method
US9662450B2 (en) 2013-03-01 2017-05-30 Sio2 Medical Products, Inc. Plasma or CVD pre-treatment for lubricated pharmaceutical package, coating process and apparatus
US9764093B2 (en) 2012-11-30 2017-09-19 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition
US9863042B2 (en) 2013-03-15 2018-01-09 Sio2 Medical Products, Inc. PECVD lubricity vessel coating, coating process and apparatus providing different power levels in two phases
US9878101B2 (en) 2010-11-12 2018-01-30 Sio2 Medical Products, Inc. Cyclic olefin polymer vessels and vessel coating methods
US9903782B2 (en) 2012-11-16 2018-02-27 Sio2 Medical Products, Inc. Method and apparatus for detecting rapid barrier coating integrity characteristics
US9937099B2 (en) 2013-03-11 2018-04-10 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging with low oxygen transmission rate
US10189603B2 (en) 2011-11-11 2019-01-29 Sio2 Medical Products, Inc. Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus
US10201660B2 (en) 2012-11-30 2019-02-12 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition on medical syringes, cartridges, and the like
WO2019156247A1 (fr) * 2018-02-08 2019-08-15 Yokogawa Electric Corporation Dispositif de mesure et procédé de mesure
US11066745B2 (en) 2014-03-28 2021-07-20 Sio2 Medical Products, Inc. Antistatic coatings for plastic vessels
US11077233B2 (en) 2015-08-18 2021-08-03 Sio2 Medical Products, Inc. Pharmaceutical and other packaging with low oxygen transmission rate
US11116695B2 (en) 2011-11-11 2021-09-14 Sio2 Medical Products, Inc. Blood sample collection tube
US11624115B2 (en) 2010-05-12 2023-04-11 Sio2 Medical Products, Inc. Syringe with PECVD lubrication

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Publication number Priority date Publication date Assignee Title
EP1688704A1 (fr) * 2005-02-04 2006-08-09 Omron Corporation Appareil et procédé d'inspection de couche mince
EP1715289A1 (fr) * 2005-04-21 2006-10-25 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procédé à reflection optique lumineuse
WO2006112706A1 (fr) * 2005-04-21 2006-10-26 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procede de reflexion de la lumiere optique
US9572526B2 (en) 2009-05-13 2017-02-21 Sio2 Medical Products, Inc. Apparatus and method for transporting a vessel to and from a PECVD processing station
US8834954B2 (en) 2009-05-13 2014-09-16 Sio2 Medical Products, Inc. Vessel inspection apparatus and methods
US9545360B2 (en) 2009-05-13 2017-01-17 Sio2 Medical Products, Inc. Saccharide protective coating for pharmaceutical package
US10537273B2 (en) 2009-05-13 2020-01-21 Sio2 Medical Products, Inc. Syringe with PECVD lubricity layer
US10390744B2 (en) 2009-05-13 2019-08-27 Sio2 Medical Products, Inc. Syringe with PECVD lubricity layer, apparatus and method for transporting a vessel to and from a PECVD processing station, and double wall plastic vessel
US7985188B2 (en) 2009-05-13 2011-07-26 Cv Holdings Llc Vessel, coating, inspection and processing apparatus
US8512796B2 (en) 2009-05-13 2013-08-20 Si02 Medical Products, Inc. Vessel inspection apparatus and methods
US9458536B2 (en) 2009-07-02 2016-10-04 Sio2 Medical Products, Inc. PECVD coating methods for capped syringes, cartridges and other articles
US11624115B2 (en) 2010-05-12 2023-04-11 Sio2 Medical Products, Inc. Syringe with PECVD lubrication
US9878101B2 (en) 2010-11-12 2018-01-30 Sio2 Medical Products, Inc. Cyclic olefin polymer vessels and vessel coating methods
US11123491B2 (en) 2010-11-12 2021-09-21 Sio2 Medical Products, Inc. Cyclic olefin polymer vessels and vessel coating methods
US9272095B2 (en) 2011-04-01 2016-03-01 Sio2 Medical Products, Inc. Vessels, contact surfaces, and coating and inspection apparatus and methods
US11724860B2 (en) 2011-11-11 2023-08-15 Sio2 Medical Products, Inc. Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus
US11148856B2 (en) 2011-11-11 2021-10-19 Sio2 Medical Products, Inc. Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus
US11116695B2 (en) 2011-11-11 2021-09-14 Sio2 Medical Products, Inc. Blood sample collection tube
US10189603B2 (en) 2011-11-11 2019-01-29 Sio2 Medical Products, Inc. Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus
US10577154B2 (en) 2011-11-11 2020-03-03 Sio2 Medical Products, Inc. Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus
US11884446B2 (en) 2011-11-11 2024-01-30 Sio2 Medical Products, Inc. Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus
US9664626B2 (en) 2012-11-01 2017-05-30 Sio2 Medical Products, Inc. Coating inspection method
US9903782B2 (en) 2012-11-16 2018-02-27 Sio2 Medical Products, Inc. Method and apparatus for detecting rapid barrier coating integrity characteristics
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