JPH08169798A - Quartz glass crucible for pulling silicon single crystal - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a quartz glass crucible capable of stably pulling a silicon single crystal. [Structure] The outer layer contains Na, K, and Li respectively.
A transparent silica glass having a content of OH groups of 200 ppm or less, which is a multi-foam quartz glass layer having an Al content of 5 ppm or more and having an Al content of 5 ppm or more, and the high purity amorphous synthetic silica powder is melted in the inner layer portion. Layered quartz glass crucible. The manufacturing method is such that crystalline natural quartz powder or a mixture of the natural quartz powder and synthetic silica powder is supplied into a rotating mold to form a crucible-shaped powder layer, and heating is performed from the inner surface of the powder layer. Then, the powder layer is melted to form a multi-bubble crucible substrate, a high-temperature atmosphere is formed in the substrate, and a high-purity amorphous synthetic silica powder having an OH group content of 170 ppm or less is supplied and partially melted. While adhering the substrate to the inner surface, a transparent synthetic silica glass layer having a predetermined thickness is formed on the inner surface of the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quartz glass crucible for pulling a silicon single crystal. In particular, the present invention relates to a quartz glass crucible for pulling a silicon single crystal having an outer layer and an inner layer.

[0002]

2. Description of the Related Art Conventionally, a quartz glass crucible has been used as a container for containing a silicon melt in the production of a silicon single crystal by the Czochralski method. This quartz glass crucible for pulling up a silicon single crystal is generally manufactured by an arc heating rotary molding method using a purified quartz powder obtained by crushing naturally occurring quartz or quartz and then refining it.

The quartz glass crucible manufactured by this method has a smooth inner surface because the raw material powder layer formed in a crucible shape in the rotating mold is melt-molded by arc discharge heating from the inside. And has a semi-transparent appearance in which fine bubbles are contained at a high density in the layer.
This so-called multi-bubble layer has the function of making the heat transfer from the external heating source to the inside of the crucible uniform, but in the quartz glass crucible for pulling the silicon single crystal, it has the structure of this multi-bubble layer and the inner surface. Is very important for stabilizing the pulling of the silicon single crystal.

[0004] However, as a result of the earnest studies of the improvement of the performance of the quartz glass crucible, the present inventors have found that the inner surface of the crucible is not only smooth but also a predetermined inner surface having this smooth inner surface. It was confirmed that a quartz glass crucible having a two-layer structure, in which the transparent layer having a thickness (about 0.5 mm to 2 mm) and having substantially no bubbles is the inner layer and the outer layer is the multi-bubble layer described above, is extremely excellent. Then, the structure of the crucible and the manufacturing method thereof were proposed (JP-A-1-148718, 1-1).
48782, 1-14883).

In the quartz glass crucibles according to the above inventions, the occurrence of rough skin on the inner surface of the crucible due to the pulling of the silicon single crystal is very small, and the spots of cristobalite are not generated on the inner surface of the crucible. It has the advantage that the pulling can be performed stably and the productivity of the silicon single crystal is significantly improved.

By the way, a high-quality silicon wafer is required for recent VLSI manufacturing, and in order to stably manufacture this high-quality silicon wafer, the purity of the quartz glass crucible should be further improved. Will be required. In order to meet this demand, attempts have been made to use synthetic quartz powder as a raw material powder for crucible production instead of conventional natural quartz powder. For example, U.S. Pat.No. 4,528,163 describes a quartz crucible in which the outer side is formed of natural quartz particles, the inner side is lined with synthetic quartz particles, and a smooth thin amorphous layer is formed on the surface of this lining layer. There is. However, the crucible taught herein has a smooth thin amorphous film on its inner surface, which is at most about 0.1 mm, and the entire layer has a multi-bubble structure, which is Since it is not a crucible having a transparent layer having a substantially bubble-free thickness of about 0.5 mm or more, it cannot be used for a long time such as pulling a single crystal a plurality of times.

Japanese Patent Publication No. 62-36974, high-purity synthetic quartz glass article (eg, quartz crucible) by melting a sintered product of a product made from high-purity silicon tetrachloride as a raw material from the surface thereof. Teaches to get.
Further, JP-A-61-44793 discloses a silicon in which an inner layer is formed by melting synthetic quartz powder having an OH group content of 200 ppm or more and an outer layer is formed by melting natural quartz powder having an OH group content of 100 ppm or less. He teaches a quartz glass crucible for pulling a single crystal. However, even if the glass layer is simply formed by melting the synthetic quartz powder in accordance with the teachings of these publications, the obtained glass layer is not sufficiently transparent,
It becomes impossible to stably pull the silicon single crystal. Further, the crucibles disclosed in these two publications do not have a structure having a substantially bubble-free transparent layer having a thickness of 0.5 mm or more on the inner surface, as described above. It does not have the performance of the double-layered crucible that the inventors previously developed.

Further, it is possible to use crystalline synthetic silica as a raw material for forming the synthetic silica glass layer. The crystalline synthetic silica is obtained by hydrolysis of ester silane or sodium silicate or hydrolysis of halogenated silane. The obtained amorphous silica is expensive because it undergoes many steps of producing by refining and pulverizing by crystallizing by heating devitrification using alkali etc. as a seed for crystallization, and it has not reached the stage of economical practical application. .

Synthetic silica powder is generally amorphous and has the advantage of being economical for forming a glass layer. However, it is difficult to obtain smooth skin because the amorphous lysica powder has an unstable melting point, and this property is an obstacle when using the synthetic silica powder.

[0010]

Therefore, in the present invention, in a two-layered silica glass crucible having a transparent layer having substantially no bubbles as an inner layer and a multi-bubble layer as an outer layer, the inner layer has a predetermined thickness ( The problem to be solved is to provide a crucible made of high-purity synthetic silica glass of 0.5 mm or more). More specifically, the problem to be solved by the present invention is that, as the high-purity synthetic silica glass constituting the inner layer, by using synthetic silica gas powder having specific physical properties, the crucible has high mechanical strength. Is maintained and the melting of the crucible material into the silicon melt is constant,
It is to provide a high-purity crucible in which a high-quality silicon single crystal is stably pulled.

[0011]

In order to solve the above problems, according to the present invention, in a quartz glass crucible for pulling a silicon single crystal having an outer layer portion and an inner layer portion, the outer layer portion has Na, K and Li contents of 0, respectively. Al less than 0.3ppm
Formed with a multi-bubble quartz glass layer made by melting crystalline natural quartz powder with a content of 5 ppm or more, and the inner layer is a virtually bubble-free thickness made by melting high-purity amorphous synthetic silica powder. 0.
The structure was made of a transparent synthetic silica glass layer of 5 mm or more.

In the above, it is possible to mix the crystalline natural quartz powder for forming the outer layer with the amorphous synthetic silica powder, and in that case, the Al content of the mixed powder is 5 ppm or more. desirable. In particular, as the amorphous synthetic silica powder forming the inner layer portion, by using non-porous silica glass particles containing 170 ppm or less of OH groups, the objective transparent synthetic silica glass layer having substantially no bubbles. The OH group content of can be 200 ppm or less.

As a means for forming the above-mentioned inner layer portion, that is, a substantially bubble-free transparent synthetic silica glass layer, after forming a vine-shaped outer layer made of a multi-bubble quartz glass layer in a rotating mold, or a process of forming the same. Then, a transparent synthetic silica glass layer is formed on the inner surface of the outer layer. The transparent synthetic silica glass layer was formed by rotating the outer layer together with the mold to form a high temperature atmosphere inside the mold by arc discharge or the like, and the OH group content was 17% in the high temperature atmosphere.
Amorphous synthetic silica powder of 0 ppm or less is supplied. The amorphous synthetic silica powder is at least partially melted and scattered toward the inner surface of the outer layer and adheres to the transparent synthetic silica having a predetermined thickness and substantially no bubbles and an OH group content of 200 ppm or less. Form a glass layer. Further, in another aspect of the present invention, non-porous synthetic silica powder is used. The non-porosity value is measured with a specific surface area of 5 m ² / g or less.

[0014]

[Working] The quartz glass crucible of the present invention has an outer layer of Na,
K and Li contents are each 0.3ppm or less, and Al content is 5ppm
A multi-bubble quartz glass layer obtained by melting the above crystalline natural quartz powder or a mixture of this natural quartz powder and amorphous synthetic silica powder. This multi-bubble quartz glass layer makes the heat conduction from the external heating source to the inside of the crucible uniform, increases the mechanical strength of the crucible, and reduces the thermal deformation when pulling the silicon single crystal (about 1450 ° C). There is. If the crystalline quartz component is unevenly distributed near the outer surface of the outer layer, the thermal deformation can be further reduced.

In the above, the Al content needs to be 5 ppm or more with respect to heat resistance, and the upper limit is not particularly limited, but the Al content of the quartz crystal normally used as a raw material of crystalline natural quartz powder has an Al content of about 60 ppm. Since the heat resistance is not particularly improved even if the amount is further increased, it is industrially advantageous to use crystalline natural quartz powder having an Al content of 5 to 60 ppm.

Further, each of the ions of Na, K and Li, which are alkali elements, has a relatively high diffusion rate at high temperature in quartz glass, which affects the deterioration of the inner layer surface and deteriorates the quality of the silicon single crystal produced. Therefore, it is necessary that the content of each is 0.3 ppm or less. The inner layer is a transparent synthetic silica glass layer formed by melting high-purity amorphous synthetic silica powder and having an OH group content of 200 ppm or less and a thickness of at least 0.5 mm or more. This transparent synthetic silica glass layer with a thickness of 0.5 mm or more is of extremely high purity, and since the OH group content is within a certain range, the amount of melting loss in the silicon melt becomes constant, and the surface of the silicon melt Vertical vibration of the silicon single crystal is suppressed, pulling of the silicon single crystal is stabilized, and as a result, a high quality silicon single crystal having a high resistance value and very few micro defects in the crystal structure can be obtained in high yield.

In order to manufacture the crucible according to the present invention, first, in a rotating mold, after forming a crucible-shaped outer layer made of a multi-bubble quartz glass layer, that is, a substrate, or during the formation process, arc discharge or the like is formed inside the substrate. A high temperature atmosphere is formed by, and the inner surface of the substrate is melted or softened.
In this state, since the amorphous synthetic silica powder is supplied into the high temperature atmosphere, at least a part of the silica powder is melted and scattered toward the inner surface of the crucible, and adheres to the inner surface of the crucible in the molten or softened state. By this adhesion and lamination, a substantially bubble-free transparent synthetic silica glass layer having a predetermined thickness is integrally formed on the crucible substrate.

In the above description, it is important that the amorphous synthetic silica powder is not only highly pure but also non-porous silica glass particles containing an OH group content of 170 ppm or less. If the silica glass particles have a microscopically porous structure, they are supplied to the high temperature atmosphere by the above-described arc discharge, at least partially melted and adhered to the inner surface of the rotating crucible substrate. However, it is not possible to form a transparent synthetic silica glass layer that is substantially bubble-free, since only a layer containing many bubbles is formed.

When non-porous amorphous synthetic silica powder is used, as in one form of the present invention, 5 to 3
It is supplied into the crucible-shaped outer layer substrate at a rate of 00 g / min,
By heating and melting from the inner surface, a bubble-free transparent layer is formed. Also, the problem that a smooth surface cannot be formed due to the use of synthetic silica glass powder is solved.

Even if the OH group content is 170 ppm or more, a bubble-free transparent layer can be easily obtained as an inner layer, but the OH group content of the product inner layer tends to increase slightly compared to the raw material. It will be over 200ppm. When the OH group content in the inner layer is 200 ppm or more, vertical vibration of the silicon melt surface occurs during the silicon single crystal pulling process, which increases the fluctuation of the diameter of the pulled silicon single crystal and increases the pulling defect rate, which is not preferable. . When the OH group content is 500 ppm or more, cutting often occurs during the pulling of the silicon single crystal.

[0021] It contains such a predetermined amount or less of OH groups,
The high-purity amorphous synthetic silica powder that is non-porous is, for example, a so-called sol-gel method in which a raw material such as tetraalkoxysilane or tetrahalogenated silane such as tetramethoxysilane and ethyl orthosilicate is hydrolyzed and dried and sintered. , Synthesizing silica by flame hydrolysis method or other known method and obtaining powder in this synthesis step, or making this synthetic silica into a transparent glass body by, for example, degassing and melting, and crushing this transparent glass body Can be obtained as a non-porous material.

[0022]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. The rotary mold 1 shown in FIG. 1 has a rotary shaft 2, and a cavity 1 a is formed in the mold 1. This mold cavity 1
Multi-bubble quartz glass crucible base body 3 forming an outer layer portion in a
Is arranged. The substrate 3 is a mold 1 for rotating crystalline natural quartz powder having Na, K, Li contents of 0.3 ppm or less and Al content of 5 ppm or more, or a mixed powder of this and amorphous synthetic silica powder. It is manufactured by pre-forming into a desired crucible shape inside, and heating the pre-formed powder from the inner surface to melt and cool the powder.

Next, while the mold 1 is rotated, the heat source 5 is attached to the base 3
Insert inside and heat. The base body 3 has an open upper end,
This opening is closed by a lid 7 so as to leave a ring-shaped gap. A high temperature gas atmosphere 8 is formed in the crucible base 3 by the heat source 5, and high purity amorphous synthetic silica powder 6 having an OH group concentration of 170 ppm or less is supplied into the high temperature gas atmosphere 8 little by little from a nozzle 9. The synthetic silica powder 6 may have an amorphous structure having an OH group concentration of 170 ppm or less, but is preferably non-porous in order to obtain a completely transparent silica glass layer (inner layer portion). Further, the synthetic silica powder 6 used in the present invention may have a particle size of 30 to 1000 μm,
The particle size is preferably 100 to 300 μm, and the specific surface area of 5 m ² / g or less is desirable as a measure of non-porosity.

The synthetic silica powder 6 is supplied toward the inner surface of the substrate 3, and when it reaches the inner surface of the substrate 3, at least a part thereof is in a molten state, and by that time, the inner surface of the substrate 3 is also in a molten state and is supplied. The synthetic silica powder 6 adheres to the inner surface of the crucible substrate 3 and constitutes the transparent synthetic silica glass layer 4 which is integral with the substrate and is substantially bubble-free. The synthetic silica powder 6 is supplied from the supply layer 10 through the nozzle 9 while adjusting the supply amount by a measuring feeder. In the embodiment shown in FIG. 1, a semi-transparent quartz crucible substrate 3 which has been formed into a desired shape in advance is placed in a mold 1, and a transparent synthetic silica glass layer 4 is formed on the inner surface thereof. However, crystalline natural quartz powder or a mixed powder of this and amorphous synthetic silica powder is supplied into the rotating mold 1 and distributed along the inner surface of the mold 1 to form a powder layer having a required thickness. The step of forming the transparent synthetic silica glass layer may be performed simultaneously with the step of heating and melting the quartz powder layer from the inner surface while rotating the mold 1 to form the crucible substrate. According to this method, the crucible substrate 3 being manufactured
A high temperature gas atmosphere 8 is formed therein, and synthetic silica powder 6 is supplied into the high temperature gas atmosphere 8 during the production of the crucible substrate, so that there is an advantage that the substrate and the crucible can be formed in the same mold 1. Further, when forming the crucible base 3, the heating conditions are adjusted at the stage of heating and melting the powder layer from the inner surface without vitrifying all of the powder layer, or if necessary, the outside of the mold is cooled, The crystalline natural quartz powder can be unevenly distributed near the outer surface of the crucible base 3.

As a means for heating and melting the quartz powder layer 3 and the synthetic silica powder 6, arc discharge using an electrode 5 of carbon or the like is effective. At least two electrodes, an anode and a cathode, are required as electrodes, but it is also possible to arc discharge with three or more. By adjusting the electrode interval and the distance between the tip of the electrode and the crucible base, the melting of the powder can be controlled and the transparent synthetic silica glass layer 4 can be formed in the crucible base. A lid 7 is placed on the top of the mold 1 to adjust the temperature during melting and heating.
Is installed, but fine powder (particle size 30
It is important that the lid 7 and the mold 1 are not brought into close contact with each other, and a ring-shaped gap is opened, because a sublimation component of silica or silica) is scattered.

FIG. 2 shows a quartz crucible for pulling a single crystal formed by the above method. As already explained, this crucible comprises the outer layer 3 formed as a multi-bubble quartz glass layer and the high-purity inner layer 4 formed of amorphous synthetic silica powder. Inner layer 4 has an OH group content of 200 ppm
The transparent synthetic silica glass layer below has a thickness of 0.5 mm or more. The outer layer 3 has Na, K, and Li contents of 0.3, respectively.
Below ppm, the Al content is above 5 ppm.

[0027]

Example 1 A particle size distribution of 100 to 30 was obtained by the above method.
0 μm crystalline natural quartz powder is fed into a rotating molding die to form a powder layer with a thickness of 14 mm, which is heated and melted from the inside by arc discharge and at the same time amorphous synthetic silica powder is heated to a high temperature by arc discharge. A quartz glass crucible having a thickness of 7.9 mm and a diameter of 14 inches having a transparent synthetic silica glass layer having a thickness of about 1 mm which was supplied into the atmosphere and adhered to the inner surface of the powder layer was prepared.

As natural quartz powder, Na 0.1 as an impurity
6ppm, K 0.10ppm, Li 0.22ppm and Al 8.2pp
The high-purity amorphous synthetic silica powder used as the inner layer of quartz powder containing m has a specific surface area of 8, 4, 1 and 0.5 m ² / g with a particle size distribution of 100-300 μm and a different hydroxyl content. I chose an experiment and experimented. The results are shown in the table below.

[Table 1] Table 1 ───────────────────────────────── Sample number Amorphous synthetic silica powder Crucible appearance Raw material Physical properties of ───────────────────────────────── Specific surface area OH groups (m ² / g) (ppm) ── ─────────────────────────────── Sample 1 0.5 62 Shows a bubble-free transparent inner layer. Sample 2 0.5 161 Same as above Sample 3 1 43 Same as above Sample 4 4 73 Same as above Comparative Example 1 0.5 250 Shows a bubble-free transparent inner layer. Comparative Example 2 0.5 620 Same as above Comparative Example 3 8 63 The inner layer becomes semi-transparent including bubbles.

[0029]

Example 2 With respect to the prepared crucible, a silicon single crystal was pulled up and manufactured by an ordinary Czochralski method, and 30 kg of a single crystal silicon ingot having a diameter of 6 inches was continuously manufactured by three crucibles. The average value of the single crystal ratio is shown in Table 2.

[Table 2] Table 2 ─────────────────────── Sample No. Single crystal ratio (%) 1st 2nd 3rd ───── ────────────────── Sample 1 100 90 80 Sample 2 90 90 70 Sample 3 90 90 70 Sample 4 90 80 70 Comparative Example 1 90 50 --Comparative Example 2 80 40 --Comparative Example 3 80 50 ---- ─────────────────────── Samples 1, 2, 3 and 4 of the present invention are stable silicon single crystals. Shows manufacturing.

In the case of Comparative Examples 1 and 2, the third melt was unable to be lifted because the fluctuation of the silicon melt surface was large at the time of the second lift and the crucible expanded, causing a risk of molten metal leak. In Comparative Example 3, the second pulling up becomes unstable,
The third crystal could not be pulled up, but it is presumed that the inner surface of the crucible, especially the silicon melt surface, was corroded so much that the transparent layer was lost.

What is particularly noted here is that in Samples 1, 2, 3 and 4 of the present invention, the transparent layer remained on the inner surface of all of them even after the production of three single crystal silicons. is there.

[0032]

[Embodiment 3] Na 0.41 ppm, K 0.20 ppm, Li 0.2 for the outer layer substrate under the manufacturing conditions of the sample 1 of "Example 1".
A crucible sample prepared by using quartz powder containing impurities of 1 ppm and Al of 7.9 ppm was designated as Comparative Example 4, and at the same time, Na
0.30 ppm, K 0.45 ppm, Li 0.24 ppm, and Al
8.7ppm or Na 0.18ppm, K 0.08ppm, Li 1.9
Crucible samples made of quartz powder containing impurities of ppm and Al of 3.5 ppm are designated as Comparative Examples 5 and 6, respectively, and the results of examining the silicon single crystal ratio in the same manner as in "Example 2" are shown in Table 3. Show.

[Table 3] Table 3 ─────────────────────── Sample No. Single crystal ratio (%) 1st 2nd 3rd ───── ────────────────── Sample 1 100 90 80 Comparative Example 4 100 90 70 Comparative Example 5 100 90 70 Comparative Example 6 90 50 --───────── ─────────────── In Comparative Example 6, since the crucible expanded due to the expansion of the second single crystal, the third crystal was discontinued.

Further, Table 4 shows the measured values of the specific resistance and the oxygen concentration in the central portions of the first and third single crystal silicons produced in Sample 1 and Comparative Examples 4 and 5, respectively.

[Table 4] Table 4 ────────────────────────────── Single crystal sample Resistivity value Oxygen concentration (Ωcm) ( X10 ¹⁸ atm / cc) ────────────────────────────── Single crystal produced from Sample 1 1st 1300 1.6 3rd 1200 1.5 Single crystal produced in Comparative Example 4 1st crystal 1300 1.8 3rd crystal 300 1.6 Single crystal produced in Comparative Example 5 1st crystal 1200 1.9 3rd crystal 180 1.7 ─────────────────── ───────────── As can be seen from Table 4, the single crystal silicon produced by pulling up with the sample 1 of the present invention shows a stable high resistance value and a stable oxygen concentration. In Comparative Examples 4 and 5, it is presumed that it was due to the influence of the alkali concentration in the outer layer of the crucible, but a high resistance value could not be obtained by the third pulling.

[0034]

[Embodiment 4] Using the same raw material as in Sample 1 of "Embodiment 1", first, a quartz powder layer of the outer layer portion is formed in a rotating mold, and then an amorphous synthetic silica powder is supplied to the quartz die. After forming an amorphous synthetic silica powder layer on the inner surface of the powder layer, it was heated and melted from the inside by arc discharge to produce a 14-inch quartz crucible with a thickness of 8 mm. The inner layer was not visible to the naked eye. When the single crystal ratio of this crucible was examined in the same manner as in Experimental Example 2, the first crystal ratio was 80%, but the second crystal ratio decreased to 50%.

[0035]

[Embodiment 5] Na 0.21 ppm and K 0.13 pp as impurities
In a quartz powder having a particle size distribution of 100 to 300 μm and containing m, Li 0.19 ppm and Al 11.4 ppm, the impurity concentration Na <
0.01 ppm, K <0.05 ppm, Li <0.01 ppm Al 0.
O at 02 ppm, Fe <0.05 ppm and Cu <0.01 ppm
A mixed powder in which equal amounts of amorphous synthetic silica powder having a specific surface area of 0.4 m ² / g having a particle size distribution of 100 to 300 μm and having an H group of 83 ppm was mixed was used as a raw material for forming a crucible outer layer, and the synthetic silica powder was used for an inner layer of the crucible. As a raw material, a quartz glass crucible having a thickness of 8.0 mm and a diameter of 14 inches having a synthetic silica glass transparent layer having a thickness of 1.1 mm on the inner surface was prepared by the method described in the example of the present invention, and the single crystal was prepared by the method described in the experimental example 2. When the crystal ratio was examined, good results similar to those of Sample 1 in Table 2 were obtained.

[0036]

According to the quartz crucible of the present invention, the heat resistance of the crucible is extremely large, the crucible is not deformed when the single crystal is pulled, and the inner surface of the crucible is not substantially corroded. Even if a single crystal is pulled, a high crystal ratio can be maintained while maintaining a high resistance single crystal that could not be conventionally maintained, and a high quality silicon single crystal can be obtained in a high yield. Further, in the production of the quartz crucible of the present invention, without using a crystalline material which was conventionally expensive as a raw material of the synthetic silica glass layer of the inner layer of the crucible,
The quartz crucible of the present invention can be industrially advantageously manufactured for the first time by using a non-porous synthetic silica glass powder that is easy to manufacture.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a rotary molding device for producing a quartz crucible used in the method of the present invention,

FIG. 2 is a partially cutaway perspective view of a quartz crucible obtained by the method of the present invention.

[Explanation of symbols]

 1 rotation type, 1a cavity, 2 rotation axis, 3 crucible base (outer layer part), 4 transparent synthetic silica glass layer, 5 electrode (carbon), 6 synthetic silica powder, 7 lid, 8 high temperature gas atmosphere, 9 nozzle, 10 hopper .

Claims (4)

[Claims] 1. A quartz glass crucible for pulling a silicon single crystal having an outer layer portion and an inner layer portion, wherein the outer layer portion has Na, K, and Li contents of 0.3 ppm or less, respectively, and an Al content of 5 ppm or more. A multi-bubble quartz glass layer, the inner layer portion being a transparent silica glass layer having an OH group content of 200 ppm or less formed by melting high-purity amorphous synthetic silica powder, for pulling a silicon single crystal Quartz glass crucible. 2. The quartz glass crucible according to claim 1, wherein the outer layer is formed by melting natural quartz powder or fused quartz powder of the natural quartz powder and amorphous synthetic silica powder. Crucible. 3. The quartz glass crucible according to claim 1 or 2, wherein the inner layer portion has a thickness of at least 0.5 mm. 4. The quartz glass crucible according to any one of claims 1 to 3, wherein the outer layer portion has a crystalline quartz component unevenly distributed near the outer surface.