EP2347037A1

EP2347037A1 - Process for forming a non-stick coating based on silicon carbide

Info

Publication number: EP2347037A1
Application number: EP09741363A
Authority: EP
Inventors: Jean-Paul Garandet; Béatrice Drevet; Nicolas Eustathopoulos; Emmanuel Flahaut; Thomas Pietri
Original assignee: Commissariat a lEnergie Atomique CEA
Current assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2008-09-05
Filing date: 2009-09-03
Publication date: 2011-07-27
Also published as: RU2479679C2; KR101451322B1; FR2935618A1; JP2012501944A; BRPI0918852A2; CN102144053B; JP5492208B2; CN102144053A; US20110268958A1; KR20110069043A; FR2935618B1; RU2011107880A; WO2010026342A1

Abstract

The present invention relates to a process for forming a non-stick coating, said coating being formed from grains of silicon carbide, which are surface-coated with a layer of silicon oxide. It also targets the materials having a coating formed by this process.

Description

Process for forming a non-stick coating based on silicon carbide

The present invention aims to provide a new type of surface coating for materials, and more particularly crucibles, intended to be brought into contact with high temperature liquid materials, such as liquid silicon, in order to allow a solidification, for example in the form of ingots.

Photovoltaic cells are mainly made from mono- or poly-crystalline silicon, in dies that involve the solidification of ingots from a liquid bath. The ingot is then cut into platelets which serve as a basis for the manufacture of the cells.

Various techniques have already been described in the literature to prevent adhesion of the solidified material to the crucible.

The most common technique is based on the implementation of a silicon nitride coating on the inner faces of the crucibles to be in contact with the molten silicon. The mechanism proposed to explain the detachment is a rupture, in the deposition zone, due to the differential expansion stresses between the silicon ingot and the thus treated surface-treated silica crucible. Indeed, the mechanical cohesion of the deposition layer is low, the annealing being made at temperatures too low to initiate sintering of the powders.

However, such a coating must, in addition to its ability to ensure the detachment, meet another requirement. It must have sufficient mechanical strength during the contact phase with liquid silicon. A coating having a tendency to flake leads to the dissolution of solid ceramic particles which will be incorporated in the silicon during growth, which is not acceptable. However, the use of silicon nitride powders as non-stick coating does not give complete satisfaction on this second aspect. Buonassisi et al (1) show in particular that the impurities present in the silicon nitride powder can have a negative effect on the photovoltaic properties of the solidified ingots. They also report the presence of silicon nitride particles included in the solidified ingots, the origin of which can be related either to the dissolution of the nitrogen in the silicon, or to the loosening of nitride grains due to insufficient cohesion of the coating. Other coating alternatives and / or techniques for producing such coatings have therefore been developed in parallel.

For example, US Pat. No. 6,491,971 describes a universal technology making it possible to apply a wide variety of coatings such as silicon nitride, silicon carbide, zirconium oxide, magnesium or barium zirconate, on the inner surface of crucible.

The use of silicon carbide as a coating material may, at first glance, seem to be an advantageous alternative. Unfortunately, it is not totally devoid of inconvenience. Thus, great difficulties during the sawing step are associated with the presence of silicon carbide precipitates in the ingots. At the scale of the p-n junction of the photovoltaic cells, the precipitated silicon carbide, on the dislocations and other crystallographic defects, plays the role of a short-circuit and thus limits the performances of the devices (2).

The main object of the invention is to provide a method for producing a non-stick coating which does not have the difficulties or limitations set forth above.

Thus, the invention aims to provide a simple and inexpensive coating system for crucibles intended more particularly for implementation in the field of the manufacture of silicon ingot or other materials. An object of the invention is in particular to provide an economical method of producing a non-stick coating formed of a silicon carbide structure and silicon oxide, as defined below.

More particularly, the invention relates to a method useful for forming a release coating, particularly with respect to solid silicon, on the surface of the face (s) of a material comprising at least the steps of:

(1) having a fluid medium comprising at least one dispersion of silicon carbide grains,

(2) depositing said medium on the surface of the face (s) of the material to be treated in an amount sufficient to provide, upon drying of the applied composition, a film formed at least of silicon carbide grains, (3) exposing the treated material according to step (2) to a heat treatment under an oxidizing atmosphere and under conditions sufficient to cause the formation of a silicon oxide layer on the surface of the silicon carbide grains.

Advantageously, the coating formed according to the present invention comprises at least one porous layer formed of grains of silicon carbide which are coated at least in part with a nanometric layer of silica. The porosity can be from 30% to 60% by volume. It can be controlled by the initial composition of the fluid.

According to a preferred embodiment, the composition of step (1) further comprises at least one binder. In this alternative, the dry film obtained at the end of step (2) is formed of grains of silicon carbide and of said binder, and the heat treatment exposed in step (3) is suitable for ensuring debinding of this film. .

According to an alternative embodiment, step (2) may be renewed one or more times before implementation of step (3).

According to yet another embodiment, the method according to the invention as defined above can be reproduced at the end of step (3). In this alternative, the layer formed of silicon carbide grains coated with a nanometric layer of silica is covered with a new thickness of the fluid composition as defined in step (1) and this deposited layer undergoes step (3). ) consecutive.

The coating formed in the context of the present invention is advantageous for several reasons. It simultaneously exhibits good adhesion properties to the base material forming the crucible, satisfactory anti-adhesion properties with respect to the ingot formed by solidification of the liquid silicon poured into this crucible and good mechanical resistance to liquid silicon.

The porous layer formed of silicon carbide grains may have a thickness ranging from 5 μm to 1 mm, in particular from 10 to 200 μm.

As regards the silica layer, formed on the surface of the silicon carbide grains, it may have a thickness ranging from 2 to 100 nm, and in particular from 10 to 30 nm.

Other features and advantages of the invention will become more apparent from the following description. This description corresponds to a particular mode of implementation of the invention and is given purely by way of illustration and not limitation. Silicon carbide coating

As is apparent from the foregoing, the method according to the invention involves a first step for applying a fluid medium based on silicon carbide grains on the surface (s) of the material to be treated. The coating derived therefrom has the characteristic of being formed of silicon carbide grains coated wholly or partly with silica.

The silicon carbide grains intended to form this coating generally have a particular size and dispersibility adequate to make them compatible with spray application by conventional methods. Thus, the silicon carbide grains considered in the context of the present invention may have a size less than 5 microns. More particularly, their size varies from 20 nm to 5 μm and in particular from 200 nm to 1 μm.

The amount of silicon carbide grains needed to obtain the coating is for obvious reasons directly related to the surface of the material to be treated. His appreciation is clearly within the skill of those skilled in the art.

These grains are kept in suspension in an inexpensive liquid medium, and more particularly water.

This liquid medium, besides the silicon carbide grains, may contain an effective amount of at least one organic binder having the appropriate chemical and physical properties to facilitate the application of the liquid coating mixture using conventional equipment.

Thus, the organic binder considered in the context of the present invention may be chosen from polyvinyl alcohol, polyethylene glycol or carboxymethylcellulose. For example, the mass ratio of silicon carbide / binder (s) may be at least 3: 1 and more preferably 5: 1.

In a general manner, the fluid medium dedicated to forming the coating according to the invention combines from 0 to 20% by weight relative to its total weight of at least one binder, to 20 to 60% by weight of silicon carbide, the associated liquid medium, usually water, ensuring the balance to 100%.

The corresponding fluid medium is formed by incorporation of silicon carbide grains and generally a binder to the liquid medium, generally water, under agitating so as to form a liquid mixture conducive to an application on the face or faces to be treated of the material in question.

This mixture intended to form the coating may, of course, contain other additives intended either to improve its qualities at the time of spraying and / or application, or to give the corresponding coating additional properties.

For example, they may be polycarbonate dispersing agents, for example carboxylic acid or stearic acid.

The silicon carbide grains, the binder and the solvent considered in the context of the present invention have the advantage of leading to crucible coatings which are non-contaminating for the material to be produced.

Detailed description of the process according to the invention

The method according to the invention involves a first step aimed at applying a fluid medium based at least on silicon carbide grains on the surface or faces of the material to be treated.

For the purposes of the present invention, the term "fluid" means a deformable state, capable of flowing and which is therefore compatible with an application by brush and / or spray gun for example.

In the case of gun application, the generally liquid fluid medium is transferred out of the spray gun at a pressure of compressed air and with a nozzle adjusted to obtain the desired coating thickness.

For example, such a gun with a 0.4 mm nozzle can be used at a compressed air pressure of 2.5 bar.

This application of the liquid coating mixture can also be carried out by other modes of application, such as, for example, the brush or by soaking the parts in a bath.

These application techniques are clearly within the skill of those skilled in the art and are not described here in detail.

The application of the fluid mixture for forming the coating can be carried out at ambient temperature or at a higher temperature. Thus, the face or faces of the material to be treated according to the invention can be heated so as to be conducive to rapid drying of the applied coating layer. In this embodiment, at least the face or faces of the material to be treated, or even the whole of the material, can be heated to a temperature ranging from 25 to 80 ^° C., especially from 30 to 50 ^° C., thus leading to Evaporation of the solvent.

The liquid mixture dedicated to form the coating is applied on the surface of the face (s) to be treated with a thickness adapted to prevent cracking during drying, for example less than 50 microns.

If necessary, it is possible to proceed to a new application of a layer of the liquid mixture dedicated to form the coating on a first layer of grains of silicon carbide applied and dried, that is to say as formed in result of step (2).

The method according to the invention also comprises a heating step in an oxidizing atmosphere, at a temperature and within a time sufficient to allow the formation of a silicon oxide layer on the surface of the silicon carbide grains, or even the decomposition thermal binder, when it is present.

This step is decisive in many ways.

First, it is intended to generate, on the surface of silicon carbide grains forming the coating, a silicon oxide layer.

This heat treatment is therefore carried out in an oxidizing atmosphere. It is more specifically air.

It therefore also allows if necessary to remove the binder when it is present. The heat treatment is then carried out in a time sufficient to allow the total elimination of the organic binder.

Advantageously, this thermal step is carried out at a temperature below 1095 ^° C.

More particularly, the oxidation step may be carried out in an oxidizing atmosphere for 1 to 5 hours at a temperature ranging from 500 ^° C. to 1050 ^° C., and more particularly from 800 ^° C. to 1050 ^° C.

In the context of the present invention, this heat treatment is in fact carried out at a temperature adjusted so as not to modify the porosity of the coating formed. In other words, this temperature remains below the temperature required to obtain sintering of the coating. Moreover, at the end of this annealing, the coating has a sufficient hardness with respect to the mechanical stresses it will have to undergo, typically less than 50 Shore A. At the end of this heat treatment, the piece is allowed to cool to room temperature.

The present invention also relates to materials having a coating formed by the method as described above.

The material treated according to the invention is advantageously a crucible. This crucible is generally based on silicon, such as silica or silicon carbide but can also be based on graphite.

The invention will now be described by means of the following examples given of course by way of illustration and not limitation of the invention.

Example 1

A slip consisting of 23% silicon carbide powder, 4% PVA polyvinyl alcohol and 73% water in percentages by weight is passed through a planetary mill filled with silicon carbide or agate balls to reduce the losses. agglomerates of powder. The size of the grains of silicon carbide formed is between 500 nm and 1 μm.

Since the objective is only to reduce agglomerates, silicon nitride balls are also conceivable, the risk of nitrogen pollution being very limited.

The fluid medium thus formed is then spray-dried (compressed air pressure 2.5 bar, 0.4 mm nozzle placed at about thirty centimeters from the substrate) on the internal faces of a crucible (of a chemical nature) to be coated. .

The deposit thus obtained is dried with hot air at a temperature below 50 ^° C.

This gives an underlayer with a thickness of about 50 microns made of PVA-bonded silicon carbide grains. This pistoletting and drying procedure is repeated 3 times to obtain a layer which is then subjected to a step of 3 hours at 1050 ^° C. under air for debinding and oxidation of the powders.

Under these conditions, the thickness of the coating finally obtained is of the order of 200 microns, and the thickness of the oxide layer on the silicon carbide grains is of the order of 30 nm.

The coating obtained according to the present invention is very porous.

To prevent the infiltration of the silicon to the crucible and obtain thicker coatings, the procedure of elaboration of a layer (deposition of layers with intermediate drying then high temperature annealing for debinding and oxidation of the powders) can be repeated several times. times.

In general, it is considered that 2 layers are generally sufficient to obtain the desired anti-adherence effect.

Example 2

A slurry, consisting of 52% pre-sieved powder, 16% polyethylene glycol (PEG) and 32% water in percentages by weight, is passed through a planetary mill filled with silicon carbide or agate balls to reduce powder agglomerates. . The slip is also passed to the ultrasound.

The slip is then either deposited by spray guns (compressed air pressure of 2.5 bars, 0.4 mm nozzle placed at about thirty centimeters from the substrate) or with the aid of a brush on the crucible to be coated.

The deposit thus obtained is dried in ambient air or hot (temperature below 50 ⁰ C).

This gives an underlayer with a thickness of about 50 microns consisting of powders bound by the PEG. This pistol (or brush) and drying procedure is repeated until the desired layer thickness is obtained.

This layer is subjected to a step of 3 hours at 900 ^° C. under air to dilute and oxidize the powders.

Under these conditions, the thickness of the oxide layer obtained on the silicon carbide grains is of the order of 30 nm. Example 3

A slip, consisting of 57% of previously screened powder and 43% of water in percentages by weight, is passed through a planetary mill filled with silicon carbide balls or agate to reduce powder agglomerates. The slip is also passed to the ultrasound.

This gives an underlayer of a thickness of about 50 microns consisting of powders bound by the Van der Waals forces. This pistol (or brush) and drying procedure is repeated until the desired layer thickness is obtained. This layer is subjected to a step of 3 hours at 900 ^° C. under air to dilute and oxidize the powders.

Under these conditions, the thickness of the oxide layer obtained on the silicon carbide grains is of the order of 30 nm.

Bibliographical references

(1) Buonassisi et al., J. Crystal Growth 287 (2006) 402-407

(2) Bauer et al., Phys. Stat. Ground. (at). 204 (2007) 2190-2195

Claims

A process useful for forming a porous, non-stick coating consisting of silicon carbide grains coated at least in part with a nanometric silica layer at the surface of the face (s) of a material comprising at least the steps of at :

(2) depositing said medium on the surface of the surface (s) of the material to be treated in an amount sufficient to provide, upon drying of the applied composition, a film formed of at least silicon carbide grains, and

(3) exposing the treated material according to step (2) to a heat treatment under an oxidizing atmosphere and under conditions sufficient to cause the formation of a silicon oxide layer on the surface of the silicon carbide grains.

2. Method according to claim 1, wherein step (2) can be renewed one or more times before implementation of step (3).

3. Method according to any one of claims 1 or 2, wherein all of the steps (2) and (3) can be renewed at least once at the end of step (3).

4. Method according to any one of the preceding claims, wherein the composition of step (1) further comprises at least one organic binder.

5. Method according to the preceding claim wherein the binder is selected from polyvinyl alcohol, polyethylene glycol or carboxymethylcellulose.

6. Method according to any one of the preceding claims, wherein the fluid medium associated with step (1) is water-based.

7. Method according to any one of the preceding claims, wherein the fluid medium of step (1) combines from 0 to 20% by weight of at least one binder, to 20 to 60% by weight of silicon carbide. .

8. Process according to any one of the preceding claims, in which step (3) is carried out at a temperature below 1095 ^° C.

9. Process according to any one of the preceding claims, in which the drying of step (2) is carried out at a temperature ranging from 25 to 80 ^° C., in particular from 30 to 50 ^° C.

10. Method according to any one of the preceding claims, wherein step (3) can be carried out in an oxidizing atmosphere for 1 to 5 hours at a temperature ranging from 500 ⁰ C to 1050 ⁰ C, and more particularly from 800 to 1050 ⁰ C.

11. Method according to any one of the preceding claims, wherein the deposition of step (2) is carried out by brush and / or spray.

12. Method according to any one of the preceding claims, wherein the porous layer formed of silicon carbide grains may have a thickness ranging from 5 microns to 1 mm, in particular from 10 microns to 200 microns.

13. The method as claimed in any one of the preceding claims, in which the silica layer, formed on the surface of the silicon carbide grains, may have a thickness ranging from 2 to 100 nm, and in particular from 10 to 30 nm.

The method of any one of the preceding claims, wherein said material is selected from silica, silicon carbide, and graphite.

15. A material having a coating formed according to any one of the preceding claims.

16. Material according to claim 15, characterized in that it is a crucible.