EP2598439A1

EP2598439A1 - Recycling of silicon sawing slurries using thermal plasma for the production of ingots or wafers

Info

Publication number: EP2598439A1
Application number: EP11735480.3A
Authority: EP
Inventors: Etienne Bouyer
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: 2010-07-30
Filing date: 2011-06-10
Publication date: 2013-06-05
Also published as: WO2012013876A1; FR2963337A1; US20130139550A1; FR2963337B1

Abstract

A thermal, advantageously inductive, plasma is used to purify silicon from sawing slurries. For this purpose a thermal plasma is generated and a silicon-containing sawing slurry is subjected to the thermal plasma, so as to deposit silicon on a substrate.

Description

RECYCLING OF SILICON SAWING SLUDGE FOR THE PREPARATION OF INGOTS OR THERMAL PLASMA PLATES

FIELD OF THE INVENTION

The present invention relates to the field of the preparation of silicon (Si) of high quality / purity, especially photovoltaic quality (PV), from sawing sludge.

More specifically, it proposes to treat sawing sludge, generated in the field of photovoltaics or microelectronics, using the inductive thermal plasma technique to purify the silicon contained in these sludges and recover it in the form of ingots. or plates.

PRIOR STATE OF THE ART

The solar industry is currently growing. Today, the share given to silicon (Si) photovoltaic (PV) is preponderant, because mature compared to other potential technologies and candidates. In solar photovoltaic, a preferred way to develop the basic silicon elements derives from the purification of metallurgical Si. The ingots from the successive phases of purification are then cut into slices. This step leads to a production of purified silicon waste, mixed with cutting agents (from the saw, for example SiC, diamond, ...) and lubricants. The estimate of the level of waste can reach 50%.

As already stated, the production of photovoltaic grade silicon is based on the use of metallurgical silicon, which will be purified and then undergo development steps: melting, recrystallization, sawing ingots. These different steps lead to wafers. The sawing step of Si PV ingots generates sawing sludge. This sawing step introduces impurities (for example iron) which must be eliminated as harmful to achieve the level of purity and therefore required PV performance. The reuse of sawing sludge is therefore a constant concern, requiring the recovery and purification of the silicon contained therein. Studies using low temperature processes, for example acid treatment and electrokinetic separation, have revealed the possibility of efficiently purifying silicon from sawing sludge (T.H. Tsai, "Pretreatment of recycling wiresaw slurries - Iron removal using acid treatment and electrokinetic separation ", Separation and Purification Technology, 68 (2009) pp. 24-29).

Other physical and chemical separation methods lead to the production of very pure materials (up to ION), as described in particular in document WO 2009/126922.

However, these methods are very long, ranging from about one hour to one hundred hours. In addition, the acid treatment process emits liquid effluents that will have to be treated. At the end of these processes, the product formed is a purified silicon powder, more or less coarse.

It should be noted that the microelectronics industry also produces waste during the sawing phase. Here again, this waste corresponds to products based on very pure silicon, the recycling of which is an important issue. The present invention is therefore part of the search for new technical solutions for recovering the silicon contained in the sawing sludge of Si ingots.

SUMMARY OF THE INVENTION In its most general aspect, the present invention relates to the use of thermal plasma for the purification of silicon from sawing sludge.

Advantageously, the plasma is an inductive thermal plasma. By sawing sludge, in particular partly purified, is meant silicon particles mainly obtained from purified silicon ingots added contaminants from the tool that was used to saw the ingot, in particular carbon, iron, SiC ... Silicon powders (Si) generally have an average grain size of between 0.1 and 10 micrometers.

It has been shown, in the context of the present invention, that the so-called thermal plasma technique is perfectly suited for the treatment of this material ("feedstock") resulting from the PV solar industry and from the microelectronics industry. . Plasma technique, well known to those skilled in the art, allows to deposit a material ("feedstock"), typically a powder, a liquid or a suspension, by introducing it into a plasma jet, emanating from a plasma torch. In the jet, the material is melted and propelled to a substrate. The melted droplets solidify rapidly and form a deposit on the substrate.

Commonly, the plasma jet can be generated in two ways:

direct current (DC plasma);

by inductive plasma or RF (high-frequency inductive coupling or radio frequency), wherein the energy is transferred by induction of a coil to the plasma jet, through which passes an alternating RF current.

According to the invention, the sawing sludge is advantageously treated by inductive thermal plasma or RF, which offers the possibility of a larger volume of treatment and a higher level of purity.

Indeed, this type of extremely pure plasma does not require an electrode for the generation of plasma. The corresponding plasma device is considered as a high temperature chemical reactor that can be the seat of physical transformations (fusion, evaporation, condensation, purification) and chemical reactions (synthesis, reduction, oxidation, introduction or separation of doping elements). In terms of process, the relatively long residence time in this type of plasma, coupled with high temperatures (> 10,000 K), makes it possible to carry out the physico-chemical transformations mentioned above.

In addition, the control of plasma process parameters (type and flow rate of gas, pressure, power applied, feedstock introduction mode) makes it possible to determine the purity levels of the silicon obtained. Moreover, the advantage of the use of the inductive thermal plasma is to be able to feed a large quantity (flow) of "feedstock", unlike a thermal plasma generated by direct current.

Due to the nature of the impurities included in the sawing sludge, typically carbon, silicon carbide, iron, the thermal plasma is a method for removing impurities without leaving residues. Thus, in the context of the invention, it has been demonstrated the possibility of using this technique for extracting silicon from the sawing sludge and producing a deposition of purified silicon on a substrate of interest. As already stated, the degree of purity of the silicon deposited depends on the parameters of the applied plasma. In a preferred embodiment, the purity of the deposited silicon is such that it can be used in photovoltaics or in microelectronics.

The invention thus provides a relatively simple, effective and fast way to recycle or reuse these sludge, by extracting or purifying the silicon present therein.

More specifically, the present invention relates to a method of forming a silicon deposit on a substrate which comprises the following steps:

generate a thermal plasma;

subjecting sawing sludge containing silicon to the thermal plasma, to form the deposition of silicon on said substrate.

Note that advantageously according to the invention, the sawing sludge containing silicon does not undergo any prior treatment stage including purification, before being subjected to thermal plasma. In other words, the method according to the invention allows, simultaneously and concomitantly via the thermal plasma, the purification of sawing sludge containing silicon and the formation of a silicon deposit on a substrate.

The thermal plasma is preferably inductive and is conventionally generated, known to those skilled in the art and explained above.

In the context of the invention, the "feedstock" consists essentially of sawing sludge from the sawing of silicon ingots. In practice, it contains silicon dust, as well as residues of the sawing tool, such as iron, SiC, carbon.

The plasma is applied to this "feedstock" which can be in the form of a solid or a suspension.

In a preferred embodiment, the sawing sludge is mixed with a solvent, preferably hydrogenated water, before being subjected to plasma. The addition of solvent makes it possible to adjust the viscosity of the "feedstock". Depending on this viscosity obtained, several methods of introducing the "feedstock" into the plasma are possible. In the preferred case where the inductive spray plasma technique ("Plasma spray suspension" described in document US Pat. No. 5,609,921) is implemented, the biphasic mixture (liquid or solvent + fines derived from the sawing) is atomized with a gas of at least one atom. atomization, such as, for example, argon, or helium, optionally supplemented with hydrogen at a level of 10% by volume, in an atomization probe, so as to obtain drops formed of the solvent and silicon microparticles.

The reducing gas mixture employed is particularly useful for reducing SiC. Alternatively and depending on the viscosity of the "feedstock", it is brought into the plasma center via a propellant of the same nature as before.

When the sawing sludge is subjected to the inductive thermal plasma, the material in the presence, in this case the silicon microparticles, is melted and propelled towards a substrate. In the case where a solvent has been added, it evaporates. The melted droplets solidify and form a deposit on the substrate, according to the principle of thermal spraying.

The substrate may consist of a silicon ingot.

Alternatively, the substrate may be made of a refractory material, advantageously chosen from the following group: molybdenum (Mo), tantalum (Ta), and tungsten (W) and their alloys. In this case, the silicon deposit obtained is advantageously separated or extracted from the substrate, which then plays the role of support. Preferably, the substrate is cooled for example by being supported by a copper substrate holder traversed by a water cooling circuit.

In a preferred manner before the extraction, the silicon deposition is subjected to the application of a plasma jet, allowing its recrystallization in situ. During this step, the substrate may be subjected to rotational or lateral movement. The plasma jet can be implemented in the same way as previously during the purification step using the same apparatus. In fact, all the steps of purification and possible recrystallization can be carried out in the same enclosure. Preferably, for this recrystallization step, use will be made of a mixture of argon and hydrogen H ₂ gas. According to a particular embodiment and when the substrate is a silicon ingot, the method according to the invention thus makes it possible to enrich said ingots. In fact, the present invention provides a solution for reinjecting the sludge by-product sludge into the PV cell manufacturing die.

In an alternative embodiment and in particular when the substrate on which the deposit is made is refractory, the method according to the invention makes it possible to manufacture silicon wafers. As already stated, the parameters of the applied plasma allow the control of the characteristics of the deposited deposit. In practice, the invention allows the manufacture of silicon wafers of thickness between 100 and 300 μιη, of controlled thickness.

BRIEF DESCRIPTION OF THE FIGURES The manner in which the invention can be realized and the advantages which result therefrom will emerge more clearly from the following exemplary embodiments, given as an indication and without being limiting, in support of the appended figures among which:

Figure 1 illustrates a device and a method for reloading silicon ingots through the passage of sawing sludge in an inductive thermal plasma.

FIG. 2 illustrates a device and a method allowing the production of silicon wafers by the passage of sawing sludge in an inductive thermal plasma.

FIG. 3 illustrates a device and a method enabling the crystallization, by in situ heat treatment by plasma, of silicon wafers obtained by the passage of sawing sludge in an inductive thermal plasma.

MODES FOR CARRYING OUT THE INVENTION

1 / Reloading of silicon ingots

The implementation of the method according to the invention, in the case where the substrate (2) is a silicon ingot, is illustrated in FIG. 1. In fact and at the end of the process, the silicon ingot is enriched or recharged in silicon.

In a conventional manner, the inductive thermal plasma device comprises the following elements:

a coil 3, inductor of the plasma torch, through which passes an alternating RF current;

a plasma jet 4 for example with argon and with hydrogen (Ar / H ₂ ). In the case of injection into the center of the plasma by atomization, an atomization probe 5 is provided.

The process implemented breaks down into three stages:

1 - Preparation of the feedstock:

The plasma device thus constituted is fed by the "feedstock" 1, constituted in this case by the recovered sludge. For sawing slurries that contain silicon in the form of dust or fines, a solvent, preferably hydrogenated water, is added to adjust the viscosity to the appropriate conditions for atomization.

2 - Atomization of the "feedstock" The biphasic mixture (liquid and fines from the sawing phase, the liquid corresponding to the residual liquid initially contained in the sawing sludge to which a solvent can be added to control the viscosity) is injected into the center plasma, either by atomization, as described in US 5,609,921, or via a propellant, depending on the viscosity.

In practice and as illustrated in FIG. 1 in the case of atomization, an atomizing gas is added to the mixture which then passes into the atomization probe 5. Droplets comprising solvent and silicon microparticles are thus formed. The purpose of the atomizing gas is to split the continuous flow of sludge (possibly with added solvent) into microdroplets. As previously explained, due to having finely divided flavors, the heat treatment in the plasma is more effective. The atomization probe is the device that allows the meeting of the gas flow (atomizing gas) and the liquid vein (sludge) to form the droplets.

3 - Formation of the deposit:

During the passage in the center of the plasma and under the action of the plasma jet Ar / H ₂ 4, the solvent is vaporized, the silicon fines are melted, accelerated and are deposited on the ingot 2 and solidify. Such a process makes it possible to recover materials with a good level of purity and to integrate them directly into the conventional silicon ingot production die, because of the heat input necessary for the shaping of the Si. silicon wafers

The method according to the invention has a second application: as illustrated in FIG. 2, it allows the direct production of Si plates from sawing sludges from Si ingots.

According to this alternative, a method and an equivalent device are implemented: the sludge is introduced into the inductive plasma by atomization and then the Si melted by the plasma is recovered on a substrate 2 'to form a thin Si plate (6 ), generally between 100 and 300 μιη.

The essential difference with respect to the previous example is the nature of the substrate 2 'which is no longer a silicon ingot but a support / substrate planar or not, preferably of a refractory nature. In this way, the formed Si plate 6 does not adhere to the support / substrate of refractory material chosen for its properties of non reactivity with Si.

Preferably, the substrate of refractory nature is itself cooled so that possible chemical reactions with the molten silicon during the deposition on the substrate are avoided. A subsequent step is to extract the formed Si plate 6 from its support 2 '.

Before extraction of the plate and as illustrated in FIG. 3, it is possible to carry out an in situ recrystallization of the plasma formed Si plate 6. This step consists in scanning the Si 6 plate by the plasma jet 4. This treatment thermal offers the advantage of recrystallizing the grains of Si that constitute the plate, by adjusting their size as a function of the passage time of the plasma jet on the surface, but also according to the intrinsic parameters of the plasma (power, composition and flow rates of the gases plasmagenes). In this step, it is possible to animate the substrate or support V in a lateral or rotational movement.

Claims

A method of forming a silicon deposit on a substrate comprising the steps of:

- generate an inductive thermal plasma;

- Mixing silicon-containing sawing sludge with a solvent, preferably hydrogenated water;

- Subjecting this mixture to the inductive thermal plasma, to form the silicon deposit on the substrate.

2. A method of forming a silicon deposition on a substrate according to claim 1, wherein the sawing sludge is subjected to plasma spray.

3. A method of forming a silicon deposition on a substrate according to claim 1, wherein the sawing sludge is subjected to plasma with a propellant, preferably argon.

4. A method of forming a silicon deposit on a substrate according to one of claims 1 to 3, wherein the substrate is a silicon ingot.

5. A method of forming a silicon deposit on a substrate according to one of claims 1 to 3, wherein the substrate consists of a cooled refractory material, preferably selected from the following group: Mo, Ta, W and their alloys.

6. A method of forming a silicon deposition on a substrate according to claim 5, wherein the deposition of silicon is separated from the substrate.

7. A method of forming a silicon deposit on a substrate according to one of claims 4 to 6, wherein the deposition of silicon is subjected to the application of a plasma jet.

8. A method of forming a silicon deposition on a substrate according to claim 7, wherein the substrate is subjected to movement during the application of the plasma jet.

9. Use of the method of forming a silicon deposit on a substrate according to claim 4 for enriching silicon ingots.

10. Use of the method of forming a silicon deposit on a substrate according to one of claims 5 to 8 for the manufacture of silicon wafers, advantageously having a thickness between 100 and 300 μιη.