JP2017194471A - Evaluation method of silica powder appropriate for manufacturing silica glass crucible for pulling up silicon single crystal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an evaluation method of silica powder allowing stable manufacturing of a silica glass crucible having a bubble-free layer.SOLUTION: The evaluation method of silica powder appropriate for forming a bubble-free layer in a silica glass crucible for pulling up a silicon single crystal includes the steps of: measuring the porosity between silica particles in silica powder; melting the silica powder; measuring the bubble content of the silica glass block produced by cooling and hardening the molten silica powder; and determining whether the silica powder is appropriate, on the basis of the porosity in the silica powder and the bubble content of the silica glass block.SELECTED DRAWING: Figure 1

Description

The present invention relates to a silica powder evaluation method suitable for producing a silica glass crucible for pulling a silicon single crystal.

A silicon single crystal by the Czochralski method is manufactured using a silica glass crucible. A silicon single crystal is produced by melting high-purity polysilicon to obtain a silicon melt, bringing the end of the seed crystal into contact with the surface of the silicon melt and pulling it up while rotating. The temperature of the silica glass crucible is about 1450 to 1 in order to keep the solid-liquid interface at the center of the silicon melt surface where the silicon melt is in contact with the single crystal at around 1420 ° C. which is the melting point of silicon.
The temperature is as high as 600 ° C. In silicon single crystal pulling, which may take two weeks or more, the amount of deformation of the rim of the silica glass crucible may be 5 cm or more.

The size of the silica glass crucible is 28 inches (about 71 cm) in diameter and 32 inches (about 8 cm).
1 cm), 36 inches (about 91 cm), 40 inches (about 101 cm), and the like.
The crucible having a diameter of 101 cm is a huge one weighing about 120 kg, and the mass of the silicon melt accommodated therein is 900 kg or more. In other words, when the silicon single crystal is pulled, 900 kg or more of silicon melt at about 1500 ° C. is stored in the crucible.

Such a silica glass crucible has a diameter of 200 to 450 mm (eg, 200 mm, 300 mm).
mm, 450 mm) and a length of 1 to 5 m or more is suitably used for manufacturing a large single crystal silicon ingot. A single crystal silicon wafer manufactured from such a large ingot is preferably used for manufacturing a flash memory and a DRAM.

A silicon wafer used for manufacturing a semiconductor is obtained by slicing a silicon single crystal. With the recent increase in the degree of integration of semiconductor devices, reduction of void defects on the surface of silicon wafers is required.

It is known that void defects can be removed by etching the surface layer of the wafer. However, since the etching process is time-consuming and expensive, it is desired from the electronics field to produce a silicon single crystal free of void defects.

Various methods are known for producing a silicon single crystal free from void defects. One of them is a method for reducing bubbles in a transparent layer in a silica glass crucible for pulling a silicon single crystal. The silica glass crucible for pulling a silicon single crystal is manufactured using powdered silica. According to the rotary mold method, the silica glass crucible is manufactured by (1) depositing silica powder on the rotary mold and (2) melting the silica powder by arc discharge. It is considered that the inclusion of bubbles in the silicon single crystal is one cause of void defects. Therefore, for the purpose of avoiding the mixing of bubbles into the silicon single crystal, the transparent layer of the silica glass crucible is formed from a layer without bubbles.

In order to manufacture a silica glass crucible having a transparent layer, that is, a substantially bubble-free layer, a method for manufacturing a silica glass crucible using a rotating mold capable of sucking a gas component from the inside of the mold is known. Specifically, this is a method in which silica powder is deposited on the inner surface of a mold and arc melting is performed while sucking a gas component with a suction device (Patent Document 1). Further, Patent Document 2 describes a method for determining the presence or absence of a bubble generation factor in a silica glass raw material.

JP2010-143818A JP 2009-007211 A

However, even the method of Patent Document 1 may or may not be able to form a bubble-free layer, and it is difficult to stabilize the quality.

The reason why the quality is not stable has not been clarified so far, and it is impossible to know whether the quality is good or not unless a silica glass crucible is manufactured.

In view of such circumstances, the present invention provides a method for evaluating silica powder that can stably produce a silica glass crucible having a bubble-free layer.

In order to solve the above problems, the present invention provides the following evaluation method. That is, a step of measuring the porosity between silica particles in the silica powder, a step of melting the silica powder, a step of measuring the bubble content of the silica glass block obtained by cooling and curing the fused silica powder, and the silica A silica suitable for forming a bubble-free layer in a silica glass crucible for pulling up a silicon single crystal, the step of determining whether or not the silica powder is a suitable silica powder from the porosity in the powder and the bubble content of the silica glass block This is a method for evaluating powder.

Whether the silica powder is suitable for forming a bubble-free layer of the silica glass crucible can be evaluated by experimentally producing a silica glass crucible. However, since it takes too much time and money to produce a silica glass crucible, generally, a suitable silica powder is evaluated by measuring the bubble content of a silica block prepared by melting silica powder. Yes (
Patent Document 2) (hereinafter, a conventional evaluation method). A conventional evaluation method is to supply silica powder to a heat-resistant container, melt the silica powder in a vacuum atmosphere, and measure the content of bubbles in the silica block in which the silica powder has melted and solidified. It is common. However, the silica powder evaluated as suitable by this method produces silica glass by the Bernoulli method using oxyhydrogen flame melting, but even if it is used for the production of a silica glass crucible by arc melting, it is not always necessary. It does not give good results. In this method, since water vapor, which is a combustion gas from the oxyhydrogen burner, is contained in the silica glass, bubbles are generated when used for pulling a silicon single crystal.

The inventors of the present invention have been analyzing silica powder from which a silica glass block having a low bubble content can be obtained. As a result, initially, the average particle diameter of the silica powder was correlated with the bubble content of the silica glass block. However, it has been clarified that, depending on the silica powder, although the average particle diameter is the same, the silica glass block has a low or high bubble content, resulting in variations in the results. As a result of detailed analysis, it was revealed that the silica powders having variations in the results differed in the porosity of the silica particles before melting. That is, if the particle shape is different, the filling method (filled state) changes even if the average particle diameter is the same.

Based on such a surprising discovery, the present inventors have come to the conclusion that it is not possible to evaluate whether a suitable silica powder is obtained simply by measuring the bubble content in the fused silica glass block. That is, it is a conclusion that it is necessary to consider not only the bubble content of the silica glass block after melting, but also the gap of the silica powder before melting. As a result of further research, the present inventors have found that silica powder having a bubble content of the silica glass block within the specified range with respect to the porosity between the silica particles is not present in the silica glass crucible for pulling up the silicon single crystal. The present invention has been completed by finding that it is suitable for forming a bubble layer. By using the evaluation method according to the present invention,
It becomes possible to identify in advance silica powder that does not generate bubbles in the transparent layer.

FIG. 1 is a schematic diagram showing a state where the objective lens 10 scans the surface 11 of the deposited silica powder. FIG. 2 is a conceptual diagram of silica powder in a heat-resistant container. A hatched portion indicates silica particles, and a white portion indicates a gap. FIG. 3 is a conceptual diagram of a fused silica glass block in a heat resistant container. The hatched portion is silica and the white portion is a gap. FIG. 4 is a conceptual diagram of a method for confirming bubbles in a transparent layer in a silica glass crucible created using synthetic silica powder.

The evaluation method of the embodiment according to the present invention includes a step of measuring a porosity between silica particles in silica powder, a step of melting the silica powder, and a bubble containing silica glass block obtained by cooling and curing the fused silica powder. In a silica glass crucible for pulling up a silicon single crystal, comprising measuring a rate, and determining whether the silica powder is a suitable silica powder from a porosity in the silica powder and a bubble content of the silica glass block This is a method for evaluating silica powder suitable for forming a bubble-free layer. In addition, the silica glass layer that is visually transparent is referred to as a transparent layer, and the bubble-free layer is a silica glass layer in which the bubble content of bubbles having a diameter of 20 to 100 μm is 0.1 or less. Each component will be discussed in detail below.

1 Silica powder The silica powder in this invention is a synthetic silica powder or a natural silica powder. Synthetic silica powder
It is a chemically synthesized silica and has a very low impurity concentration, so it is used for the inner surface layer of a silica glass crucible. The method for producing the synthetic silica powder is not particularly limited, but silicon tetrachloride (SiC
Examples include gas phase oxidation of l ₄ ) (dry synthesis method) and hydrolysis of silicon alkoxide (Si (OR) ₄ ) (sol-gel method). The natural silica powder is a powder produced by pulverizing a natural mineral mainly composed of α-quartz.

2 Silica glass crucible Silica glass crucible is made by supplying natural silica powder to a rotating mold for producing silica glass crucible, supplying synthetic silica powder onto natural silica powder, and melting the silica powder by the heat of arc discharge. A silica glass crucible comprising an inner surface layer (synthetic layer) formed from synthetic silica powder and an outer surface layer (natural layer) formed from natural silica powder is produced. In the initial stage of the arc melting process, the silica powder layer is strongly depressurized to remove bubbles to form a transparent silica glass layer (transparent layer), and then the bubble is contained in the bubble-containing silica glass layer by decreasing the depressurization. (Hereinafter referred to as the “bubble-containing layer”).

3 Evaluation Method Silica powder is supplied to a heat-resistant container by free-falling in the same manner as in the case of manufacturing by a rotary molding method under atmospheric pressure. The silica powder that protrudes from the container is worn to flatten the observation surface. By doing so, it becomes the same filling as filling the silica powder by the rotational mold method. The heat-resistant container
Although it will not specifically limit if it is a raw material which can endure use at high temperature, For example, they are a ceramic type composite material and a carbon fiber reinforced carbon composite material (C / C composite). The size of the heat-resistant container is not particularly limited. For example, the length is 10 to 50 mm, the width is 10 to 50 mm, and the height is 10 to 3
Specifically, a rectangular parallelepiped container 30 mm long × 40 mm wide × 20 mm high can be selected.

The porosity in silica powder is measured. The gap between the silica particles can be measured in a non-contact manner using an optical detection means provided with a light receiving device that receives reflected light of light irradiated on the silica powder.

The light emitting means for irradiating light in this optical detection means may be built-in, or may utilize an external light emitting means. Moreover, it is preferable to use what can be scanned along the surface of the silica powder deposited in the heat-resistant container, for example, an optical detection means can be performed using a confocal microscope. A confocal microscope is preferable because an image without blur can be obtained. As irradiation light, in addition to visible light, ultraviolet light, and infrared light, laser light or the like can be used, and any light can be used as long as it can detect a gap between silica particles. The light receiving device is selected according to the type of irradiation light. For example, an optical camera including a light receiving lens and an image unit can be used. In order to detect the gap between the silica particles, it is preferable to receive only light generated at the condensing point. In order to receive only light generated at the condensing point, it is preferable to provide a pinhole in front of the photodetector included in the light receiving device. The focal length is not particularly limited, but is preferably 0.1 mm to 3 mm deep from the surface, for example, 0.3 to 1.0 mm.

As a measuring method, as shown in FIG. 1, the objective lens 10 of the optical detection means is attached to the heat-resistant container 12.
The gap between the silica particles is measured by disposing it in contact with the surface 11 of the deposited silica powder and scanning in the scanning direction 13. Other scanning methods include a sample scanning method and a laser scanning method. In the sample scanning method, the stage on which the sample is placed is
This is a method of acquiring a two-dimensional image by driving in the Y direction. Laser scanning method uses X laser
This is a method in which the sample is two-dimensionally scanned by being applied in the Y direction. Any scanning method may be adopted.

The average value may be adopted by measuring the porosity at a plurality of measurement points. For example, three places may be measured and the average value may be sufficient. The measured porosity may be converted into an arbitrary parameter, for example, area, area ratio, and ratio. If the gap is unclear as a result of the measurement, the focus may be shifted in the direction of the X axis, the Y axis, or the Z axis.

The porosity between the silica particles before melting is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less, and may be at least 1% or more. “Porosity”: n
And is the area of a partition S, the total area of the cross-sectional area of the silica powder to be deposited in the compartment and S _p, for example, can be determined as follows.
Porosity: n = ((S−S _p ) / S) × 100
Further, the total area of the gap when the S _n, can be calculated by the following equation.
Porosity: n = (S _n / S) × 100

A heat-resistant container containing silica powder is placed in a furnace, and the temperature in the furnace is raised to a temperature at which the silica powder melts. As the heat source, for example, a carbon heater can be selected. The heating rate in the furnace is not particularly limited as long as the temperature does not change so rapidly that the gas component in the silica powder expands and bursts. For example, the heating rate may be 50 to 300 ° C./min. The temperature at which the silica powder is melted is not particularly limited, but is preferably about 1500 to 2600 ° C., which is the temperature at the time of arc melting, for example, 1500, 1600, 1700, 1800, 190.
0, 2000, 2100, 2200, 2300, 2400, 2500, or 2600, which may be within the range of any two numerical values exemplified here. By setting the temperature within this temperature range, it is possible to reproduce temperature conditions close to arc melting. The heating time is preferably 20 to 60 hours, more preferably 30 to 50 hours after reaching the melting temperature. The melting of the silica powder may be performed under atmospheric pressure. By melting under atmospheric pressure, the properties of the target silica powder can be analyzed in more detail. When performed under vacuum, it may be, for example, between 1.0 × 10 ⁴ Pa and 1.0 × 10 ⁵ Pa, preferably 2.0.
× 10 ⁴ Pa.

The fused silica powder is cooled and the bubble content of the vitrified silica glass block is measured. What is necessary is just to cool a fused silica powder with completion | finish of a heating. The bubble content P (%) in the silica glass block is calculated by taking the measurement result by an optical detection means such as a confocal microscope into an image processing apparatus. An image of the inner surface of the silica glass block is taken, and the inner surface of the silica glass block is divided into fixed volumes to obtain a reference volume W1, and an occupied volume W2 of bubbles with respect to the reference volume W1 is obtained, and P (%) = (W2 / W1) × 100. The focal length is not particularly limited, but is preferably 0.1 mm to 3 mm deep from the surface,
For example, the depth is 0.3 to 1.0 mm.

Whether the silica powder is optimum or not is evaluated from the porosity between the silica particles and the bubble content in the silica glass block. The method for evaluating whether or not the silica powder is optimal is not particularly limited, but the bubble content of the silica glass block after melting relative to the porosity between the silica particles before melting (hereinafter referred to as the shrinkage index before and after melting) However, it can be evaluated as an excellent silica powder when it is preferably 0.5 or more, more preferably 0.7 or more, and still more preferably 0.8 or more. By defining the numerical value, it is possible to evaluate high-quality silica powder in advance, and no such method has existed so far. On the other hand, when the shrinkage index before and after melting is less than 0.5, a bubble-free transparent layer may not be produced stably. The evaluation may be an area of a gap or a bubble. Further, even when the gaps and bubbles are quantified other than in the area, the result of conversion into the area or calculation of the area using other means may be within the above-described range.

4. Manufacturing method of silica glass crucible Silica glass crucible is (1) while rotating a mold having a bowl-shaped inner surface that defines the outer shape of the silica glass crucible, natural silica powder is placed on the bottom and side surfaces of the silica glass crucible. A silica powder layer is formed by depositing to a thickness and then a synthetic silica powder is deposited to a predetermined thickness, and (2) the silica powder layer is melted by arc discharge and then cooled. Can do.

The melting of the silica powder is preferably performed so that the maximum temperature reached on the inner surface of the rotary mold is 2000 to 2600 ° C.

The arc melting is performed by, for example, AC three-phase (R phase, S phase, T phase) arc discharge. Therefore, in the case of AC three-phase, the silica powder layer is melted by generating arc discharge using three carbon electrodes. Arc melting starts arc discharge at the point where the tip of the carbon electrode is located above the mold opening. Thereby, the silica powder layer in the mold opening vicinity is preferentially melted. Thereafter, the carbon electrode is lowered to melt the silica powder layer in the mold body part, the corner part, and the bottom part.

The bubble content P (%) in the silica glass crucible is calculated by taking the measurement result by an optical detection means such as a confocal microscope into an image processing apparatus. An image of the inner surface of the crucible is taken, and the inner surface of the crucible is divided into fixed volumes to obtain a reference volume W1, and an occupied volume W2 of bubbles with respect to the reference volume W1 is obtained, and P (%) = (W2 / W1) × 100 Is calculated by

1 Measurement of gap (Example 1)
The synthetic silica powder of Example 1 was supplied to a rectangular parallelepiped carbon container 30 mm long × 40 mm wide × 20 mm high in a heat resistant container, and the porosity was measured with a confocal microscope. The focal length was 0.3 mm from the surface. The porosity was calculated based on an arithmetic average value of the gap area at three measurement positions (focal length is the same). The porosity at this time was 7.2%. After measuring the porosity, a heat-resistant container containing synthetic silica powder was placed in the furnace.

The temperature in the furnace was raised using a carbon heater, the furnace temperature was about 2200 ° C., and the synthetic silica powder of Example 1 in the heat-resistant container was melted. After melting at 2200 ° C. for 40 hours, it was left to reach room temperature without opening the furnace. When the temperature reached room temperature, the silica glass block was taken out and the bubble content was measured by the same method as before melting and found to be 4.2%.

Accordingly, it was revealed that the silica powder of Example 1 had a shrinkage index ((bubble content of silica glass block) / (porosity of silica particles)) before and after melting of 0.58.

(Example 6)
Synthetic silica powder (Example 6) of a production lot different from Example 1 in a heat resistant container is 30 mm long
X Width 40 mm x height 20 mm A rectangular carbon container was supplied, and the porosity was measured with a confocal microscope. The measurement method is the same as in Example 1. The porosity at this time was 10.2%. After measuring the porosity, a heat-resistant container containing synthetic silica powder was placed in the furnace.

The temperature in the furnace was raised using a carbon heater, the furnace temperature was about 2200 ° C., and the synthetic silica powder of Example 2 in a heat-resistant container was melted. After melting at 2200 ° C. for 40 hours, it was left to reach room temperature without opening the furnace. When the temperature reached room temperature, the silica glass block was taken out and the bubble content was measured by the same method as before melting and found to be 4.0%.

Therefore, it was revealed that the silica powder of Example 6 had a shrinkage index ((porosity of silica glass block) / (bubble content of silica particles)) before and after melting of 0.39.

(Examples 2-5, 7-10)
Similarly, the shrinkage index before and after melting was measured using synthetic silica powders with different product lots. Table 1
These are the porosity before melting | fusing, the bubble content rate of a silica glass block, and the shrinkage | contraction index before and behind melting regarding Examples 1-10.

2 Production of silica glass crucible Silica glass crucibles were produced by the rotational molding method using the synthetic silica powders of Examples 1 to 10. The diameter of the mold was 32 inches (81.3 cm), the average thickness of the silica powder layer deposited on the inner surface of the mold was 15 mm, and arc discharge was performed with three electrodes of three-phase alternating current. In the arc melting process, the energization time was 90 minutes, the output was 2500 kVA, and the silica powder layer was evacuated for 10 minutes from the start of energization.

Three silica glass crucibles were prepared using each synthetic silica powder, and the crucible was sliced in the thickness direction as shown in FIG. 4 and polished to a thickness of 2 mm to confirm the bubbles in the transparent layer 25. Bubbles were measured using a confocal microscope. The results are shown in Table 2.

The silica glass crucibles using the synthetic silica powders of Examples 1 to 5 are all confirmed to be a bubble-free transparent layer, and can stably produce a silica glass crucible having a bubble-free layer. It was. On the other hand, the silica glass crucible using the synthetic silica powder of Examples 6 to 10 is 5
It was confirmed that all the silica glass crucibles had locations with a bubble content of more than 0.1%, and silica glass crucibles having a bubble-free layer could not be stably produced.

(Comparative Example 1)
A silica glass crucible was prepared in the same manner as described above except that synthetic silica powder determined to have no bubble generation factor based on the method described in Examples of Patent Document 2 (Japanese Patent Application Laid-Open No. 2009-007211), Bubbles were measured using a confocal microscope. The results are shown in Table 2.

From the above results, it became clear that by using the evaluation method according to the present invention, it is possible to evaluate (determine) silica powder in which bubbles are not generated in the transparent layer in advance.

DESCRIPTION OF SYMBOLS 10 Objective lens 11 Surface 12 Heat-resistant container 13 Investigation direction 21 Direct copper part 22 Corner part 23 Bottom part 24 Bubble layer 25 Transparent layer 26 Slice piece

Claims (7)

A step of measuring the gap between the silica particles by scanning the surface of the silica powder deposited in the heat-resistant container in a non-contact manner with the objective lens of the optical detection means of the confocal microscope; and
The area of a certain section is S, the total area of the cross-sectional area of the silica powder deposited in the section is Sp, and the porosity n is
n = ((S−Sp) / S) × 100
Or
The area of a certain section is S, the total area of the gaps of the silica powder deposited in the section is Sn, and the porosity n is
n = (Sn / S) × 100
The process obtained by the formula of
Melting the silica powder;
A step of measuring the bubble content of the silica glass block obtained by cooling and curing the fused silica powder;
Determining whether or not the bubble content of the silica glass block with respect to the porosity n of the silica particles is within a specified range.
A method for evaluating silica powder suitable for forming a bubble-free layer in a silica glass crucible for pulling a silicon single crystal.   The evaluation method according to claim 1, wherein the porosity n of the silica particles is 15% or less and 1% or more.   The evaluation method according to claim 1, wherein the bubble content of the silica glass block with respect to the porosity n of the silica particles is obtained by (bubble content of the silica glass block) / (porosity of the silica particles).   The evaluation method according to claim 1, wherein the prescribed range is 0.5 or more.   The evaluation method according to claim 1, wherein the specified range is 0.7 or more.   The evaluation method according to claim 1, wherein the prescribed range is 0.8 or more.
A silica powder suitable for forming a bubble-free layer of silica powder is selected using the method for evaluating silica powder according to any one of claims 1 to 6, and arc melting is performed using the suitable silica powder. A method for producing a silica glass crucible, characterized by producing a silica glass crucible by a method.