EP2542353A1

EP2542353A1 - Method for depositing a layer of organized particles on a substrate

Info

Publication number: EP2542353A1
Application number: EP11705940A
Authority: EP
Inventors: Zoé TEBBY; Olivier Dellea
Original assignee: Commissariat a lEnergie Atomique CEA; Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Current assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2010-03-02
Filing date: 2011-01-28
Publication date: 2013-01-09
Also published as: CN102770218A; WO2011107681A1; CN102770218B; US20120321810A1; KR20130054939A; FR2956991B1; JP2013521111A; FR2956991A1

Abstract

The invention relates to a method for depositing particles in the form of an organized monolayer on a substrate. Said method is characterized in that it includes the following steps: controlled stirring of a bath including at least said particles, and a mixture of solvents consisting of at least 50% by volume of ethanol; immersion of the substrate in said stirred bath; and removal of said substrate from said stirred bath.

Description

METHOD FOR DEPOSITING AN ORGANIZED PARTICLE LAYER

ON A SUBSTRATE

FIELD OF THE INVENTION

The invention relates to a method of depositing a layer of organized particles on a substrate. This method is particularly well suited for large areas, of the order of tens of square centimeters, and for particles having a large size of several hundred nanometers.

Such substrates covered with a layer of organized particles may in particular find application in the field of surface treatment such as "soft" lithography, anti-reflective layers or surface structuring. PRIOR STATE OF THE TECHNIQUE

The two main techniques of the prior art allowing the deposition of monolayers of organized particles are the Langmuir-Blodgett method and the dip coating (dip coating), respectively.

The Langmuir-Blodgett method involves transferring a floating monolayer to a solid substrate after soaking. It thus consists in dispersing the particles in a solvent which is placed on water. While the solvent is partially evaporated, the film of particles floating on the surface of the water is compressed by a movable barrier. This process makes it possible to organize the particles by forcing them or confining them in a minimum space. They thus adopt a compact hexagonal type structure, leaving little free space on the surface. The substrate is then dipped vertically into the solution before being removed. The floating monolayer is thus transferred to the surface of the substrate by capillarity. The substrate can be covered with several monolayers by successive dipping.

Despite its advantages and simplicity, the Langmuir-Blodgett method, which is also widely used in the deposition of organized particles, remains unsuitable for large substrates. In addition, obtaining compact layers by this technique is a long-term process (S. Parvin et al., Side-chain effect on Langmuir and Langmuir-Blodgett film porperties of poly (N-alkylmethacrylamide) -coated magnetic nanoparticle , J. of Colloid and Interface Science, 2007, vol 313, pp. 128-134, BR Jackson et al., "Self-assembly of monolayer-thick alumina-epoxy composite films", Langmuir, 2007, vol 23, 23, pp. 11399-11403).

The "dip coating" technology represents another method commonly used in the field of the deposition of particles organized on the surface of a substrate. This technique is similar to soaking and removing the substrate in a suspension or colloid of particles, thus ensuring the transfer of particles to the surface of the substrate. The two main factors to control in this technique are the particle concentration and the rate of shrinkage. In fact, the control of the concentration of particles makes it possible to obtain compact layers, whereas the determination of the good rate of shrinkage allows the evaporation of the solvent at the level of the meniscus of the solution. The capillary forces thus allow the self-organization of the particles. However, it is important to minimize the immersion time of the substrate in order to avoid the sedimentation of the particles during the deposition of micron particles. Indeed, the forces of gravity cause the sedimentation of particles and can not be neglected.

Unlike the Langmuir-Blodgett method, the "dip coating" method is faster to implement and better adapted to supports of larger dimensions, of the order of several centimeters (Y. Wang, et al. processed large area surface textures based on dip coating ", IEEE, 2008, 978-1-4244-2104-6 / 08).

However, the phenomenon of sedimentation of the particles results in a lack of homogeneity of the solution thus compromising the possibility of creating homogeneous deposits over large areas. The longer the immersion time of the substrate, the more the sedimentation of particles is favored, thus making the results obtained by this deposition process difficult to reproduce.

The present invention provides a deposition process devoid of this pitfall. Thus, this method makes it possible to deposit micron-sized particles or several hundred nanometers, on substrates whose surface can be up to several tens of square centimeters. In addition, it is a simple and quick process to implement for the deposition of organized particles. SUMMARY OF THE INVENTION

Thus, the technical solution proposed in the context of the present invention consists in homogenizing the bath of particles, using a magnetic stirrer or with a circulation of fluid using a pump, creating a flow in the middle with a slight movement on the surface of the liquid.

The Applicant has thus developed a method making it possible to obtain homogeneous deposits of micron particles or of a few hundred nanometers over large areas by homogenizing the bath, in which the particles are in suspension.

More specifically, the process according to the invention aims at a method of depositing particles in the form of a monolayer organized on a substrate. It is characterized in that it comprises the following steps:

controlled agitation of a bath comprising at least one solvent and at least said particles;

dipping the substrate in said agitated bath;

removing said substrate from said agitated bath.

Advantageously, said bath comprises a solvent mixture consisting of at least 50%, even 60%, 70%, or even more advantageously 80% by volume of a first solvent. In addition, said first solvent is, preferably, ethanol. The volume of the first solvent may represent up to 90% of the volume of the bath.

The deposition of particles consists in covering the surface of a support, and in this case a substrate, by a monolayer of said particles in an organized manner. The particles thus cover the substrate in a compact and homogeneous manner.

By substrate is more particularly meant glass, silicon or DLC (Diamond Like Carbon) deposited on a material.

As already stated, the method according to the invention makes it possible to deposit a monolayer of particles on large substrates. In general, the surface of said substrate is between 5 cm ² and 1 m ² . Typically, it is between 5 and 400 cm ² , more particularly between 25 and 200 cm ² . The deposition process according to the invention is particularly well suited for particles whose size is greater than 100 nm. Advantageously, the particle size is between 500 nm and 2.6 μιη. In a particular embodiment, the particle size is greater than 2.6 μιη. According to another particular embodiment, it is between 500 nm and 1000 nm.

In a common manner, the particles have a spherical shape, their size then being comparable to their diameter. Furthermore and in the context of the process according to the invention, the size of the particles is advantageously monodispersed, the average particle size not varying by more than 5%. In general, the particles are spherical and monodisperse, they thus make it possible to obtain a layer, or deposit, organized.

According to a preferred embodiment, the particles deposited by means of the process of the invention are silica balls or spheres, the diameter of which, as indicated above, is greater than 100 nm and more advantageously between 500 nm and 2.6 μιη. A ball diameter equal to 2.6 μιη is in no way a limit to the present invention. The balls may thus have a diameter greater than 2.6 μιη. In a particular embodiment, it is between 500 nm and 1000 nm.

To implement the process according to the invention, a solution comprising at least one solvent and said particles is firstly prepared. The solution or bath thus obtained is then stirred to ensure homogeneity. Indeed, the controlled stirring of the bath makes it possible to avoid the sedimentation of the large particles. Typically, the bath is agitated when the density of the particles is greater than the density of the solvent mixture, and the particles are large enough to undergo the effects of gravity, they are then likely to decant. In general, these conditions correspond to a density equal to 0.9 g / cm ³ and particles having a diameter equal to 100 nm.

The substrate is then immersed in the bath. Then, it is removed with a withdrawal speed which is determined in particular according to the concentration of the particles. The rate of shrinkage may vary depending on the nature of the substrate and the size of the particles. Advantageously according to the invention, stirring is maintained throughout the process (bath preparation / soaking / removal) and more particularly during the soaking and removal steps. The substrate thus obtained is covered with a monolayer of particles. Several monolayers of controlled thickness and nature can be deposited on the surface of the substrate by repeating the process according to the invention. The first step of the process therefore consists in preparing the bath useful for the deposit.

By solvent is meant a liquid for dispersing the particles. The solution, or the bath, comprises the solvent or solvents, the particles and optionally at least one surfactant.

As already indicated, the stirring makes it possible to homogenize the bath and thus to obtain particle deposits in particular of larger size which are more compact, more homogeneous and reproducible, even on large surfaces. According to a preferred embodiment, the agitation of said bath is provided by a fluid flow, preferably the solution as defined above, using a pump. The flow rate of the pump is adjusted according to the volume of said solution. However, and in practice, it is advantageously between 100 and 500 l / h. Preferably, it is between 200 and 400 l / h and even more advantageously between 250 and 300 l / h.

During agitation, the beads do not remain on the surface of the solution but they are sucked up and rejected by the pump. In practice, the pump creates a flow in the medium, in this case the mixture of at least the solvent and at least the particles, with a slight movement on the surface of the liquid.

Alternatively, the agitation of said bath can be provided by means of a magnetic stirrer. The speed of rotation of the corresponding magnetic bar is adjusted according to the volume of said bath. It is typically between 100 and 5000 rev / min, more preferably between 200 and 600 rev / min.

As already mentioned, the particles to be deposited using the process according to the invention are dispersed in a solvent mixture advantageously comprising at least 50%, even 60%, 70%, or even more advantageously 80% by volume of ethanol. Depending on the nature of the substrate intended to be covered with a monolayer of organized particles, the deposition process according to the invention is carried out using a second solvent selected from water and butanol. Thus for a substrate whose contact angle with water is low (5 to 30 ° for glass and silicon), the second solvent is preferably water. The particles are therefore dispersed in a water / ethanol mixture. Water regulates the evaporation of the solvent mixture to avoid problems of reproducibility in case of too rapid evaporation. The volume ratio between the two solvents is preferably 4/1 in order to attenuate the formation of holes at the top and overlaps at the bottom, with respect to the monolayer in the case of evaporation that is too slow.

For a given substrate, the angle of contact with water reflects the ability of the water to spread over the surface of the substrate by wettability. It is accepted by those skilled in the art that the angle of contact with water is defined by the angle between the surface of the substrate and the tangent to the drop of water at the point of contact with the surface of the substrate on which the drop of water was deposited.

As already said, the second solvent is preferably water to ensure the deposition of large particles on a glass substrate. In contrast, according to another particular embodiment of the invention, butanol is advantageously chosen as the second solvent for a substrate type DLC.

Thus, when the substrate has a fairly strong contact angle with water, the solvent mixture is preferably composed of ethanol / butanol with a 4/1 volume ratio. The presence of butanol makes it possible to wet the DLC type substrate for which the angle of contact with the water is approximately 70 °. Ethanol promotes the organization of particles but also a fairly rapid evaporation and thus avoids the formation of holes at the top and overlays at the bottom, compared to the monolayer in case of evaporation too slow.

Typically, the deposition method according to the invention is thus provided with a mixture of two solvents, the volume ratio between the first solvent, preferably being ethanol, and the second solvent being advantageously equal to 4/1. . The use of a mixture of more than two solvents, advantageously with ethanol as the majority solvent (at least 50% by volume) is also conceivable in the context of the present invention. Advantageously, the concentration of the particles in the bath is between 50 g / l and 500 g / l, more advantageously between 80 and 200 g / l.

In particular, when the substrate intended to be covered with a monolayer of particles has a contact angle with water of less than or equal to 45 °, the bath may also contain a surfactant, to improve the homogeneity of the deposit. Thus, the addition of a surfactant such as Triton ^® X-100 may be necessary to wet the substrate well. The second step is therefore to perform the soaking of the substrate to be coated in the stirred bath.

Typically, the soaking time of the substrate in the bath is between 0.5 seconds and 15 minutes.

The third step is to remove the substrate from the stirred bath.

Typically, the rate of shrinkage of the substrate is between 2 cm / min and 50 cm / min, more preferably between 5 and 30 cm / min.

During this removal step, the particles stick to the substrate by capillarity. The rate of shrinkage is notably related to the concentration of the particles in the bath but also to the size of said particles. A high concentration of the particles leads to a slower withdrawal rate.

Thus, the present invention makes it possible to improve the deposition of large particles on large size substrates by homogenizing the bath in which the particles are in suspension. The present invention makes it possible to deposit a monolayer of large sized organized particles on substrates whose surface may be of the order of tens of square centimeters. This method also makes it possible to overcome the phenomenon of sedimentation of particles observed in the so-called "dip coating" method. The arrangement of the particles is compact and orderly. In summary, the present invention makes it possible to deposit monolayers of large particles on the surface of various substrates of large size. Agitation of the solution further comprising the solvents with the majority ethanol and the particles makes it possible to deposit in a very organized manner.

EXAMPLES OF CARRYING OUT THE INVENTION

The invention and the advantages thereof will appear better from the following figures and examples, without limitation.

FIG. 1 shows a glass substrate, with a surface area of 10 × 10 cm ² , covered with a monolayer of SiO ₂ beads of 500 nm in diameter using the method according to the invention on a photographic plate ( A) or SEM (B) (SEM = Scanning Electron Microscopy).

FIG. 2 shows a glass substrate with a surface area of 5 × 5 cm ² , covered with a monolayer of SiO ₂ beads of 1 μιη in diameter using the method according to the invention on a photographic plate (A ) or MEB (B). FIG. 3 shows a DLC-type substrate with a surface of a few square centimeters covered with a monolayer of SiO ₂ beads of 500 nm diameter on an SEM plate.

FIG. 4 shows a glass substrate coated with a monolayer of silica beads of 2.6 .mu.m in diameter using the method according to the invention on a photographic plate (A) or SEM (B).

EXAMPLE 1 This example is illustrated in FIG. 1. A suspension of silica beads containing 108 g / l of particles is prepared by mixing 65 g of SiO ₂ beads of 500 nm in diameter and 100 drops of Triton X- ^100®. in 480 ml of ethanol and 120 ml of water. The agitation of the mixture is carried out with a circulation of fluid using a pump (270 1 / h). A glass substrate with an area of 10 x 10 cm ² is immersed in the mixture.

The substrate is removed from the mixture at a speed of 17 cm / min. EXAMPLE 2 This example is illustrated in FIG.

Silica bead suspension a 150 g / 1 particles was prepared by mixing 30 g of beads of Si0 ₂ of 1 μιη diameter and 40 drops of Triton X-100 ^® in 160 ml of ethanol and 40 ml of water . Stirring of the mixture is provided by a magnetic stirrer (430 rpm). A glass substrate with a surface area of 5 x 5 cm ² is immersed in the mixture.

The substrate is removed from the mixture at a speed of 21 cm / min.

EXAMPLE 3 This example is illustrated in FIG.

A suspension of silica beads containing 150 g / l of particles is prepared by adding 7.5 g of SiO ₂ beads with a diameter of 500 nm in a mixture composed of 40 ml of ethanol and 10 ml of butanol. Stirring of the mixture is provided by a magnetic stirrer (360 rpm). A DLC type substrate of a few square centimeters is immersed in the mixture.

The DLC-type substrate is removed from the mixture at a rate of 7 cm / min.

EXAMPLE 4 This example is illustrated in FIG.

A suspension of silica beads containing 300 g / l of particles is prepared by adding 72 g of SiCte beads with a diameter of 2.6 μιη in a mixture composed of 200 ml of ethanol and 40 ml of water. Stirring of the mixture is provided by a magnetic stirrer (400 rpm). A glass substrate with an area of 20 cm ² is immersed in the mixture.

The glass-like substrate is removed from the mixture at a rate of 28 cm / min.

Claims

A method of depositing particles in the form of an organized monolayer on a substrate comprising the following steps:

controlled agitation of a bath comprising at least said particles and a solvent mixture of at least 50% by volume of ethanol; dipping the substrate in said agitated bath;

removing said substrate from said agitated bath.

Depositing method according to claim 1 characterized in that the size of the particles is greater than 100 nm, advantageously between 500 nm and 2.6 μιη.

Deposition process according to one of claims 1 and 2, characterized in that the agitation of the bath is ensured by a circulation of fluid using a pump.

Deposition process according to one of claims 1 and 2, characterized in that the agitation of the bath is ensured by means of a magnetic stirrer.

Deposition process according to one of the preceding claims, characterized in that the solvent mixture consists of two solvents, the second solvent being chosen from water and butanol.

Deposition process according to claim 5, characterized in that the volume ratio between the ethanol and the second solvent is equal to 4/1.

Deposition process according to one of the preceding claims, characterized in that the particles are spherical and monodisperse.

Deposition process according to one of the preceding claims, characterized in that the particles are silica balls or spheres.

Depositing method according to one of the preceding claims, characterized in that the substrate is glass or DLC (Diamond Like Carbon).

10. The deposition method according to one of the preceding claims, characterized in that the surface of the substrate is between 5 cm ² and 1 m ² .

11. Deposition method according to one of the preceding claims, characterized in that the concentration of particles in the bath is between 50 g / 1 and 500 g / 1-

12. The deposition method according to one of the preceding claims, characterized in that the substrate removal rate is between 2 cm / min and 50 cm / min.

13. Deposit method according to one of the preceding claims, characterized in that the bath further contains a surfactant.