The invention relates to a method for characterizing a diffracting surface having a grain structure, and to an apparatus for implementing this method and to an optical head of said apparatus. The invention in particular applies to the characterization and monitoring of the manufacture of assemblies of particles of nanoscale or micron-size dimensions on a substrate.
The order of compact assemblies of colloidal particles is important in a wide variety of applications: photonic crystals, SERS (surface-enhanced Raman scattering) sensors, biological sensors, etc.
At the present time, the order of diffracting structures, such as compact assemblies of colloidal particles, may be measured only using optical-type microscopy techniques or a scanning electron microscope. These techniques are not suitable for the characterization of structures occupying large areas (several centimeters square or more).
The Applicant has developed a process allowing compact films of micron-size or nanoscale particles to be transferred to flexible or rigid substrates. Such a process is described in document WO2012113745 and illustrated by
The process therefore consists in dispensing the particles onto the surface of the carrier liquid. The carrier liquid transports the particles as far as the transfer zone. The particles accumulate in the transfer zone, then also in the lower portion of the inclined plane. The particles present on the inclined plane then exert a pressure that helps order the particles present in the transfer zone. A variant of the process allows a rigid substrate to be used.
In practice, the films of particles produced are made up of “grains” that comprise particles forming a regular lattice of hexagonal unit cells the orientation of which in the plane is specific. The grains differ from one another in the orientation of the elementary unit cell of their lattice. The size of the grains may vary from a few μm2 (microns square) to as much as 1 cm2 (centimeter square) or more; it depends on the size dispersion of the particles and on the parameters of the process (surface pressure, draw rate, activation of the particles, etc.).
When the constituent particles of such a film have suitable dimensions (in the case of spherical particles of silica on a liquid conveyor formed by water, a diameter comprised between about 500 nm and 2.5 μm), it is possible to observe light diffraction effects. The grain structure of the film then results in iridescence forming a random pattern.
The invention aims to provide a method allowing a compact film of micron-sized or nanoscale particles—or more generally a diffracting surface—to be characterized by validation of its structure (related to the shape of the grains), its texture (related to the orientation of the elementary unit cell of each grain) and/or its degree of order. The degree of order is defined as the ratio of the area of regions having a desired orientation to the total observed area.
According to the invention, such an aim is achieved by a method for characterizing a diffracting surface having a “crystal” grain structure, comprising steps consisting in:
a) illuminating in succession said surface with a plurality of light beams having propagation directions inclined at the same angle θi to the normal to the surface and the projections of which onto the surface make different azimuthal angles φij to a reference direction;
b) acquiring an image of said surface in correspondence with each of said light beams; and
c) digitally processing said images to obtain at least one piece of information on at least one property of said surface, chosen from: its grain structure, its texture and its degree of order.
According to various embodiments of this method:
c1) thresholding each of said images in order to attribute to each of its pixels a binary value indicative of a light intensity respectively higher than or lower than a set threshold;
c2) for each image having undergone said thresholding, calculating a proportion P of pixels having the same said binary value;
c3) determining the difference A between the highest value and the lowest value of the proportions P for said images; and
c4) if the value of A is comprised between a first threshold Amin and a second threshold Amax, and if a stop condition is not met, subdividing each image into a plurality of smaller images corresponding to respective regions of the surface to be characterized, grouping the n smaller images corresponding to each of said regions and repeating the substeps c1) to c4) for each group thus obtained;
whereby a value A is attributed to the surface or to each of said regions of the surface.
Another subject of the invention is the application of such a method to the monitoring of a process for manufacturing an assembly of particles of nanoscale or micron-size dimensions. The method according to the invention may be used to characterize the assembly deposited on a substrate, resulting from the manufacturing process, or indeed to carry out inline monitoring of said manufacturing process, by characterizing the assembly in a piece of equipment of the type in
Yet another subject of the invention is an optical head for implementing such a method, comprising:
Said means for selectively illuminating each facet of said first array with a light beam propagating in a direction parallel to said axis of symmetry may in particular comprise: a light source, for directing toward said part a light beam propagating parallel to said axis of symmetry; an optical mask interposed between said light source and said part, said mask being mounted so as to be rotatable about said axis of symmetry and comprising an aperture in correspondence with a facet of said first array; and an actuator for making said optical mask rotate about said axis of symmetry.
Yet another subject of the invention is an apparatus for implementing such a method, comprising:
Other features, details and advantages of the invention will become apparent on reading the description given with reference to the appended drawings, in which:
When an incident light beam Fi of wavelength A illuminates a periodic structure such as a film of particles, the light beam is diffracted into a plurality of orders (diffracted beams Fd) the number of which depends on the number of periods that the structure comprises. In the case of a structure having hexagonal symmetry (case of a film of particles arranged to form compact hexagonal assemblies), for example, diffraction of the first order occurs in 6 spatial directions, forming a hexagonal pattern on a screen E placed normal to the reflected beam (see
When a periodic structure of this type is illuminated with a polychromatic incident beam (comprising a plurality of wavelengths), each wavelength is diffracted in a spatial direction that is specific thereto. The following formulae give the orientation of the diffracted beams Fd relative to the incident beam Fi:
When a diffracting surface SD is illuminated with a polychromatic beam (wavelengths λ1, λ2, λ3, etc.) at an angle of incidence θi, an observer OB located normal to the structure sees the wavelength at which the above equations give θr=0; if none of the illuminating wavelengths meets this condition, the structure appears black to the observer. This is illustrated in
For a given lattice parameter “d”, the angle θi determines the wavelength (the color) of the radiation detected by the observer OB, whereas φi—azimuthal angle of the incident beam relative to the spatial orientation of the elementary crystal unit cell of the diffracting structure—determines the intensity of said detected radiation. Thus, the brightness of each grain of the diffracting structure will depend on its orientation. Thus, acquiring a plurality of images corresponding to different azimuthal angles φij allows the diffracting surface to be characterized by identifying grains (structural information), their orientation (textural information) and their degree of order. This is the principle behind the present invention.
The essential element of this optical head is a transparent part PO (
The inclination of the facets FR2 is chosen such that the angle θi has the desired value, which is generally comprised between 10° and 80°, preferably between 25° and 50°, and which may especially be 34°. It must not be forgotten to take into account the refraction of the beam when it exits the part P0.
Assuming now that the beam F0 is moved such that its point of entry into the part PO traces a circle centered on the axis AS, each time the illuminated facet FR1 changes, the azimuthal angle of the beam Fi in turn changes. Considering for example the case where each array of the part comprises M=36 facets, such that the angle made by two consecutive facets is 10°, under these conditions 36 beams Fi having azimuthal angles spaced by steps of 10° will be obtained.
The selective illumination of the facets of the optical part may be obtained in a plurality of different ways. One particularly simple solution, illustrated in
The light beam FL may be polychromatic and spatially incoherent and for example be a beam of incoherent white light. In this case, the light source SL may especially be a light-emitting diode. The use of a monochromatic source such as a laser may lead to a better analysis performance, but experiments have shown that white light leads to satisfactory results while allowing simpler and less expensive equipment to be used.
The camera C that acquires the images may be fastened to the center of the bottom surface of the part PO. It is important for the images to be acquired when a single facet FR1 and a single facet FR2 are illuminated, and not during the transitions.
A diffracting surface of hexagonal structure must, in order to be satisfactorily characterized, be illuminated at a plurality of angles of incidence over a period of 60°. It has been verified that it is enough to acquire 6 images with six light beams having azimuthal angles φij=10°=10°, 20°, 30°, 40°, 50°, 60°; more generally, N beams with φij=φ0+j·(60°/N), φ0 being a constant, will possibly be used. N must in general be higher than or equal to 3, and preferably higher than or equal to 6. As a general rule, the higher the value of N the more precise the characterization of the surface but the longer the processing and acquisition time. Generally, it therefore does not seem to be advantageous to make N higher than 12 or even 24.
In operation, i.e. when the illumination is turning around the zone of the surface in question, the processing means is continuously processing at least 6 images taken consecutively and stored in a FIFO (First In, First Out) stack. In other words, once a block of 6 images has been analyzed, image No 1 is erased, the numbers of the remaining images are decremented by 1 and a new image having the number 6 in the image file is considered. The analysis is carried out each time the stack is updated.
The first step of the processing consists in thresholding the images in the stack in order to obtain a black-and-white image, the white pixels corresponding to bright zones of the image (high light intensity) and the black pixels corresponding to zones of low light intensity (
The second step of the processing consists in calculating the proportion P of white pixels in each image (P=1: completely white image; P=0: completely black image). These values are represented in
If A is higher than a threshold Amax, generally of about 0.9, the observed diffracting surface is considered to have an order of high quality, and the analysis may terminate. If A is lower than a threshold Amin, generally of about 0.2, the observed diffracting surface is considered to be disordered (amorphous), and the analysis may terminate. If A is comprised between Amin and Amax, this means that a plurality of grains are being observed at the same time; the analysis must continue to identify these grains and any amorphous regions also present. In this case, as illustrated in
In addition, for high or intermediate values of A, that image from the six which contains the most white pixels indicates the privileged illumination angle provoking the maximum diffraction of the observed film of particles. With each observed image or imagette, it is thus possible to associate a privileged angular orientation of the incident beam and therefore to determine the orientation of the hexagonal patterns located in the corresponding region of the surface. This is information on the texture of the film.
Step 4: On the basis of the processing protocol described above, it is possible to reconstruct an image formed of squares of different sizes depending on the number of subdivisions (
The squares forming the image belong to one of the following three categories:
This analysis makes it possible in the end to determine:
1) The structure of the film of particles by considering the squares for which A<Amin, which correspond to amorphous zones or to grain boundaries;
2) the texture of the film of particles by considering, for each square for which Amin≦A, the privileged orientation of the incident beam; and
3) the degree of order of the film of observed particles. This degree is a quality indicator calculated with the following expression: degree of order ORD=1−(SNC/STOT), where SNC is the area of the regions of said surface to which a value A≦Amin has been attributed and STOT is the total area of the observed portion of the surface.
In a conventional way, image-processing steps aiming to improve or optimize the quality of the images will possibly be associated with the protocol described above. These steps will for example aim to decrease illumination drift in order to increase the reliability of the analysis.
A plurality of variants of the protocol may be envisioned. For example, each image may be subdivided into a number other than four of images of smaller size. In the case of a subdivision into four quadrants, as in the above example, it is advantageous for the initial image to be square and comprise a number of rows and columns given by a power of two.
The method of the invention is particularly suitable for monitoring in real time a process for manufacturing regular assemblies of nano- and micro-particles such as the process described in document WO2012113745. Specifically, the optical head may be easily integrated into an apparatus for implementing such a process; furthermore, a sufficiently large area of diffracting surface (of 1 cm2 or more) may be characterized. However, this is not a limitation, and the invention may be suitable for many other applications.
Number | Date | Country | Kind |
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13 51870 | Mar 2013 | FR | national |
Filing Document | Filing Date | Country | Kind |
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PCT/IB2014/059267 | 2/26/2014 | WO | 00 |