Patent Application
20140150715
The present invention relates to a silica container for pulling single-crystal silicon and a producing method thereof.
Silica glass is used for a lens, a prism, and a photomask in a projection aligner (a lithography apparatus) for manufacturing large-scale integration (LSI), a display TFT substrate, an ultraviolet lamp tube, a window material, a reflector, a semiconductor industrial cleaning container, a silicon melt container, and others. However, as a raw material of the silica glass, a compound such as expensive silicon tetrachloride must be used, and a silica glass melting temperature or processing temperature is as considerably high as approximately 2000° C., energy consumption is hence high, and a cost rises. Therefore, a silica glass producing method using a relatively inexpensive natural powdery raw material has been conventionally considered.
Even now, as a method for producing a silica crucible for single-crystal silicon manufacture for devices like LSI, such producing methods as described in Patent Literatures 1 and Patent Literature 2 are used. Each of these methods is a method for putting a quartz powder or a rock crystal powder subjected to an ultra-high purity treatment into a rotating carbon mold, performing molding, then pushing carbon electrodes from above, applying a voltage to the carbon electrodes to cause arc discharge, and increasing an atmospheric temperature to a melting temperature zone (which is assumed to be approximately 1800 to 2100° C.) of the quartz powder, thereby melting and sintering the quartz powder. However, these producing methods have problems in production cost and single-crystal silicon quality. For example, the methods are high costs because the high-purity quartz raw material powder is used; occurrence of gas release at the time of using the crucible because various kinds of impurity gases are dissolved in the produced silica crucible; and the released gases form cavity defects called voids or pinholes in the single-crystal silicon. Further, the inner wall of the crucible is apt to be dissolved because its etching resistance to the silicon melt is low, and thus a serious problem occurs in durability of the silica crucible.
A method for improving the etching resistance to silicon melt of the single-crystal silicon pulling silica crucible is disclosed in Patent Literature 3, and this literature shows an effect of applying or dissolving a crystallization accelerator to or in an inner surface of a silica glass crucible. As the crystallization accelerator, alkaline-earth metal elements Mg, Sr, Ca, and Ba as 2a group elements or Al as a 3b group element are presented. However, in the silica glass crucible described in this literature, because a crucible inner surface is not uniformly recrystallized during pulling single-crystal silicon, etching of the inner sidewall of the crucible by silicon melt is not sufficiently lowered, and durability of the silica crucible is not improved.
Furthermore, Patent Literature 4 discloses technology that reduces emission of crystalline silica particles from a silica crucible inner surface into the silicon melt or technology that strengthens the silica crucible from an outer surface of the silica crucible. As a technique for these technologies, allowing a devitrification accelerator to be present on the surface or the crucible, which is specifically allowing an alkaline earth metal selected from a group including Ba, Mg, Sr, and Be to be included is disclosed. However, in such a silica crucible, the crucible surface is not rapidly recrystallized at the start of pulling the single-crystal silicon, or the entire surface is not uniformly recrystallized, etching of the silica crucible inner surface using the silicon melt is not sufficiently reduced, and durability of the silica crucible is not improved.
As another technique for recrystallizing an inner surface of a silica crucible, Patent Literature 5 discloses that, when the OH group concentration near the surface is set to 115 ppm or more while sloping the OH group concentration at a surface depth of 0.3 to 3 mm, the surface portion can be readily recrystallized without using a crystallization accelerator. However, according to such technology, because an etching amount of the surface portion by the silicon melt is considerably large, there occurs a problem that the surface layer is dissolved when melting blocks of a polysilicon raw material in the silica crucible, and the silica crucible inner surface is not uniformly recrystallized at the time of subsequent pulling of the single-crystal silicon.
Patent Literature 6 discloses a silica container obtained by a sol-gel method at low cost and a producing method thereof. An outer layer of the silica container is a white opaque layer, and an inner layer of the same is a transparent silica glass layer containing carbon. In an example, a transparent silica glass layer with a thickness of 3 mm containing Ba and the OH group is described. Although a certain level of a recrystallization acceleration effect can be recognized in such a silica glass container at the time of using this container, uniform recrystallization on the entire inner surface of the container at start of using the container is further demanded.
Patent Literature 7 discloses a silica container produced by preparing a silica raw material powder doped with crystallization accelerators Ca, Sr, and Ba and a hydrogen gas in advance and discharging, heating, and melting this raw material powder. Although a certain level of a recrystallization acceleration effect in the container can be recognized in this silica container at the time of pulling the single-crystal silicon, uniformly recrystallizing the entire container inner surface at an early stage is insufficient.
Moreover, as technology similar to that in Patent Literature 7, Patent Literature 8 discloses a silica container produced by performing arc discharge heating with respect to a silica raw material powder containing crystallization accelerators Ca, Sr, and Ba in a hydrogen containing gas atmosphere. Although a certain level of recrystallization effect on a container inner surface at the time of pulling single-crystal silicon is likewise recognized in such a container, uniformly recrystallizing the entire container inner surface at an early stage of using the crucible is insufficient.
Patent Literature 9 and Patent Literature 10 disclose that a thickness is increased by devising a shape of an outer wall of a silica crucible as a countermeasure for corrosion (etching) of the silica crucible by the silicon melt. However, since this method does not fundamentally reduce the corrosion (etching) of a silica crucible main body by the silicon melt, oxygen concentration in the silicon melt due to melting of silica glass is greatly increased, impurity metal elements contained in the silica crucible are contaminated, or quality of pulled single crystal silicon becomes poor.
Patent Literature 1: Japanese Examined Patent Application Publication No. H4-22861
Patent Literature 2: Japanese Examined Patent Application Publication No. H7-29871
Patent Literature 3: Japanese Patent No. 3100836
Patent Literature 4: Japanese Patent No. 3046545
Patent Literature 5: International Publication No. WO 2009/113525
Patent Literature 6: Japanese Unexamined Patent Application Publication No. 2010-189205
Patent Literature 7: Japanese Unexamined Patent Application Publication No. 2011-84428
Patent Literature 8: Japanese Unexamined Patent Application Publication No. 2011-121811
Patent Literature 9: Japanese Unexamined Patent Application Publication No. 2011-121842
Patent Literature 10: Japanese Unexamined Patent Application Publication No. 2011-121843
In view of the above-described problems, it is an object of the present invention to provide a silica container that greatly improves etching resistance (corrosion resistance) of a container inner surface to the silicon melt when the entire inner surface made of transparent silica glass of the container is finely crystallized (turned to glass ceramics) within a short time after start of using the container in a case that the silica container is used for pulling single-crystal silicon, and to provide a method for producing such a silica container.
According to the present invention, to solve the above-described problems, there is provided a single-crystal silicon pulling silica container comprising: a transparent layer made of transparent silica glass in an inner side of the silica container, and an opaque layer made of opaque silica glass containing gaseous bubbles in an outer side of the silica container, wherein the transparent layer is constituted of a high-OH group layer that is placed in an inner surface side of the silica container and contains the OH group at a concentration of 200 to 2000 ppm by mass and a low-OH group layer that has the OH group concentration lower than that of the high-OH group layer, and Ba is applied to the inner surface of the high-OH group layer at a concentration of 25 to 1000 μg/cm2.
According to the above-described silica container having the layer (the high-OH group layer) that contains the OH group at a high concentration in the inner surface side of the transparent layer and has Ba applied to the inner surface of the high-OH group layer at a high concentration, when this container is used for pulling single-crystal silicon, the entire inner surface of the high-OH group layer can be finely crystallized (turned to glass ceramics) within a short time after start of using the container. Therefore, etching resistance (corrosion resistance) of the inner surface of the silica container to the silicon melt can be greatly improved.
In this case, it is preferable for a thickness of the high-OH group layer to be 0.5 mm or more and 3 mm or less.
When the high-OH group layer having Ba applied to the surface thereof has such a thickness, the etching resistance of the transparent layer can be sufficiently obtained. Further, at the same time, the silica container can be prevented from deforming at a high temperature during use of the container.
Moreover, it is preferable for the concentration of the OH group contained in the high-OH group layer to be a concentration of 300 to 1500 ppm by mass and the concentration of Ba applied to the inner surface of the high-OH group layer to be 60 to 500 μg/cm2.
When the concentration of the OH group and the concentration of Ba applied to the inner surface in the high-OH group layer are set in this manner, the etching resistance at the time of using the silica container can be more effectively provided.
Additionally, according to the present invention, there is provided a method for producing a single-crystal silicon pulling silica container, comprising the steps of: preparing a silica powder having a particle size of 10 to 1000 μm as a raw material powder; putting the raw material powder into a mold, temporarily molding the raw material powder into a predetermined shape associated with an inner wall of the mold while rotating the mold, and thereby forming a temporary compact; rotating the temporary compact in the mold, degassing a gas component contained in the temporary compact by reducing a pressure from the outer side of the temporary compact, heating and melting the temporary compact by a discharge heating melting method, and thereby fabricating a silica container having a transparent layer made of transparent silica glass in the inner side and an opaque layer which contains gaseous bubbles and is made of opaque silica glass in the outer side; introducing a water vapor containing gas into the fabricated silica container and continuing the heating in the water vapor containing gas atmosphere to increase the OH group concentration in the inner surface side of the transparent layer; cooling the silica container subjected to the heating in the water-vapor containing gas atmosphere to a room temperature; and applying a Ba compound to the inner surface of the transparent layer of the cooled silica container, drying the Ba compound, and thereby applying Ba to the inner surface of the transparent layer at a concentration of 25 to 1000 μg/cm2, wherein the OH group concentration is set to 200 to 2000 ppm by mass in a region on the inner surface side of the transparent layer by the heating effected in the water vapor containing gas atmosphere and the cooling.
According to such a method, it is possible to produce the silica container having the layer that contains the OH group on the inner surface side of the transparent layer at a high concentration and also having Ba applied to the inner surface at a high concentration at low cost. As described above, such a silica container enables finely crystallizing the entire inner surface side of the transparent layer within a short time after start of using the container when the silica container is used for pulling the single-crystal silicon, thus greatly improving the etching resistance to the silicon melt.
In this case, it is preferable to provide, at the step of cooling, the water vapor containing gas atmosphere in the silica container until a temperature is lowered to at least 200° C. or less.
As described above, when the water vapor containing gas atmosphere is adopted as the atmosphere at the step of cooling, a fluctuation in OH group in the cooling step can be controlled.
When the single-crystal silicon pulling silica container according to the present invention is used for pulling single-crystal silicon, since the entire surface of the high-OH group layer can be finely crystallized in a short time after start of using the container, the etching resistance of the silica container inner surface to the silicon melt can be greatly improved. Further, the method for producing a single-crystal silicon pulling silica container according to the present invention enables producing such a silica container at a low cost.
As described above, the problem to be solved by the present invention is to greatly improve etching resistance (corrosion resistance) of an inner surface of a silica container to silicon melt by finely crystallizing (turning to glass ceramics) an entire inner surface of colorless and transparent silica glass of the container to form crystals such as cristobalite in a short time after start of using the silica container in case of using the silica container for pulling single-crystal silicon.
An improvement in etching resistance of an inner surface of a single-crystal silicon pulling silica container leads to excellent results. For example, although small cavity defects called voids or pinholes may be sometimes generated in single-crystal silicon to be produced, one of causes is assumed to be a silicon monoxide (SiO) gas reacted and generated by etching a silica container surface with silicon melt, and improving the etching resistance enables reducing these cavity defects. Further, likewise, as a cause of inhibition of growth of the single-crystal silicon and generation of dislocations, there is occurrence of foreign particle defects consisting of silica fine particles, and one factor is assumed to be silica (SiO2) particles detached when the surface is roughened by etching of the silica container surface with the silicon melt. Furthermore, when an etching amount of the silica container inner surface is increased, oxygen concentration in the silicon melt rises. Therefore, the improvement in etching resistance contributes to an improvement in single-crystal silicon quality.
In case of using the silica container at a high temperature, impurities contained in the silica container, e.g., alkali metal elements Li, Na, and K, transition metal elements Ti, Cr, Mn, Fe, Ni, Cu, Zn, Zr, Mo, W, and others are diffused and eluted into the silicon melt. The recrystallized silica container surface also has a shield effect for reducing diffusion of these impurity elements into the silicon melt.
Although one silica container is used for pulling one silicon single-crystal in conventional examples, pulling a plurality of silicon single-crystals (multi-pulling) with use of one container has been demanded in terms of a reduction in cost in recent years. As described above, improving the etching resistance of the silica container enables reducing defects, e.g., voids, pinholes, or foreign particles, suppressing an increase in oxygen concentration, and avoiding impurity contamination, whereby multi-pulling of high-quality single crystal can be carried out.
A single-crystal silicon pulling silica container and a producing method thereof according to the present invention will now be described hereinafter in detail with reference to the drawings, but the present invention is not restricted thereto.
A single-crystal silicon pulling silica container according to the present invention will now be described with reference to
As shown in
It is known that Ba has a crystallization accelerating effect of crystallizing silica glass into cristobalite or the like at a high temperature when it is contained in the silica glass. Further, the OH group has an effect of enhancing the crystallization accelerating effect of Ba. However, since the OH group also has an effect of reducing viscosity of the silica glass at a high temperature or degrading etching resistance to silicon melt, there is a preferred concentration range. As described above, in the inner layer (the high-OH group layer 52b) of the transparent layer 52 made of transparent silica glass, when the OH group concentration is set to 200 to 2000 ppm by mass and Ba is applied to the inner surface of the high-OH group layer 52b (i.e., the inner surface of the silica container 72) at a concentration of 25 to 1000 μg/cm2, the entire inner surface of the silica container can turn to a uniform and precise white opaque recrystallized layer in a short time at a high temperature (approximately 1300 to 1600° C.) at the time of using the silica container for pulling the single-crystal silicon.
Furthermore, in the silica container 72 according to the present invention, to prevent the viscosity and the etching resistance of the transparent layer 52 from lowering, the low-OH group layer 52a must be present in the transparent layer 52. That is, in the silica container 72 according to the present invention, the range that the OH group is contained in the above-described range is restricted to a region near the inner surface of the transparent layer 52. It is preferable for the concentration of the OH group contained in the high-OH group layer 52b to be a concentration of 300 to 1500 ppm by mass. Furthermore, it is preferable to set the concentration of Ba applied to the inner surface of the high-OH group layer 52b to 60 to 500 μg/cm2.
The thickness TI2 of the high-OH group layer 52b shown in
A method for producing a single-crystal silicon pulling silica container according to the present invention, by which the above-described silica container 72 can be produced, will now be more specifically explained.
A method for producing the silica container 72 shown in
First, as shown in (1) of
Although this raw material powder 11 can be prepared by, e.g., pulverizing and sizing blocks of silica as follows, the present invention is not restricted thereto.
First, a block of natural silica (rock crystal, quartz, silica, siliceous stones, opal stones, and others which are naturally yielded) having a diameter of approximately 5 to 50 mm is heated in an air atmosphere in a temperature region of 600 to 1000° C. for approximately 1 to 10 hours. Then, the block of natural silica is put into water, rapidly cooled, then taken out, and dried. This treatment can facilitate a subsequent treatment of pulverization and sizing using a crusher or the like, but the processing may advance to a pulverization treatment without performing this heating and rapid cooling treatment.
Subsequently, the block of natural silica is pulverized and sized with use of a crusher or the like, and its particle size is preferably adjusted to 10 to 1000 μm or more preferably 50 to 500 μm, thereby obtaining a natural silica powder.
Then, this natural silica powder is put into a rotary kiln constituted of a silica glass tube having an inclined angle, a hydrogen chloride (HCl) or chlorine (Cl2) gas containing atmosphere is provided in the kiln, and a purification treatment is carried out by performing heating at 800 to 1100° C. for approximately 1 to 10 hours. However, in a product use application that does not require high purity, the processing may advance to a subsequent treatment without performing this purification treatment.
Although the raw material powder 11 obtained after the above-described process is crystalline silica, an amorphous silica glass powder may be used solely or mixed as the raw material powder 11 depending on a use application of the silicon container.
A particle size of the raw material powder 11 is preferably set to 10 to 1000 μm and more preferably set to 50 to 500 μm. Silica (SiO2) purity of the raw material powder 11 is preferably set to 99.99% by weight or more, or it is more preferably set to 99.999% by weight or more. In particular, in case of using the finally produced silica container for pulling LSI single-crystal silicon, it is desirable to set the purity of the raw material powder 11 to 99.999% by weight or more.
When the purity of the raw material powder 11 is low (poor), to avoid moving or diffusing of impurity metal elements from the produced silica container to the inner surface and to silicon accommodated therein, it is preferable for the raw material powder 11 to contain predetermined amounts of Al and the OH group. Al can be contained by using a water or alcohol solution of, e.g., a nitrate, an acetate, a carbonate, a chloride, or the like, putting and immersing the silica powder in such a solution, and then performing drying. As for the OH group, the OH group contained in the natural silica stone from the beginning or water to be incorporated in an intermediate step can be controlled by a gas atmosphere, a treatment temperature, and a time in a subsequent drying process.
The details of the mechanism of how these Al and the OH group prevent the impurity metal elements from moving and diffusing in the silica glass is unknown, but it can be considered that Al adsorbs positive ions (cations) of the impurity metal elements and suppresses diffusion of them in order to keep electric charge balance of a silica glass network when Al is replaced by Si. Moreover, it is estimated that the OH group produces the effect of adsorbing the impurity metal elements or preventing diffusion thereof by the replacement of a metal ion with a hydrogen ion.
After the raw material powder 11 is prepared, as shown in (2) of
In the step shown (2) of
Then, as shown in (3) of
As a melting and sintering procedure of the temporary compact 41, before starting application of a voltage between the carbon electrodes 212, it is preferable to start supplying a hydrogen containing gas from the inner side of the temporary compact 41. Specifically, as shown in
Then, if the atmospheric gas adjustment is carried out, in a state that supply of the mixed gas is continued, the mold having the temporary compact 41 therein is rotated at a fixed rate, and application of a voltage between the carbon electrodes 212 is started. At this time, the degassing vacuum pump is activated, depressurization is started from the outer side of the temporary compact 41 via the pressure-reducing holes 103 and the pressure-reducing paths 104 and 105, and application of a voltage is also started. When arc discharge (denoted by reference numeral 220 in
Furthermore, heating based on application of the voltage is continued until approximately inner ⅓ to ½ of the total thickness of the temporary compact 41 is molten and turned to transparent or translucent silica glass and approximately remaining outer half of the same is turned to the sintered opaque silica. Through this process, the silica container 71 having the opaque layer 51 and the first transparent layer 52 can be fabricated (see
As the atmospheric gas in the temporary compact 41 during the discharge heating melting step, air or an inert gas can be used depending on a use application of the silica container to be produced, but the OH group concentration in the opaque layer 51 can be adjusted when the hydrogen containing inert gas atmosphere is provided as described above. It is preferable to maintain water vapor content in the supply gas in this step at a low value. A dew point temperature of the supply gas may be controlled to be within ±2° C. of a set value in the range of 15° C. to −15° C. for the purpose of adjusting the OH group content and the water vapor (H2O) content in the opaque layer 51 of the molten and sintered silica container in particular. As a control method, the gas can be supplied through an appropriate dehumidifier apparatus. The concentration of the OH group in the transparent layer 52 is controlled at the subsequent and following steps.
Then, as shown in FIG. 3(4) and
This step of continuing heating in the water vapor containing gas atmosphere is performed continuously with the previous step ((3) of
An arrow denoted by reference numeral 530 in
It is to be noted that the step of heating and melting the temporary compact 41 ((3) of
Then, as shown in (5) of
Based on the heating ((4) of
Then, as shown in (6) of
It is to be noted that, for recrystallization of silica glass, besides Ba, second group calcium (Ca) or strontium (Sr) is also effective, but Ba which is preferable from a viewpoint of segregation coefficient (Ba is apt to remain in the silicon melt) of the single-crystal silicon and the silicon melt is used in the present invention.
The above-described process enables producing the silica container 72 shown in
To preliminarily examine an influence of the OH group concentration and the Ba concentration in regard to recrystallization of the silica glass surface, the following experiment was conducted.
Based on an oxyhydrogen flame hydrolysis method using silicon tetrachloride (SiCl4) as a raw material, each synthetic silica glass containing 0, 60, 100, 300, 1000, or 1500 ppm by mass of the OH group was prepared. Then, a tabular double-side mirror-polished sample having a dimension of 50×50 and a thickness of 3 mm was prepared from each silica glass. Then, barium nitrate alcohol solutions having various kinds of concentration were prepared, and they are applied to surfaces of the respective silica glass samples, and then dried.
Then, each silica glass sample was set in a clean electric furnace having an air atmosphere therein, a temperature was increased from a room temperature to 1500° C. in two hours, each sample was held at 1500° C. for one hour, then a power supply was turned off, and cooling was performed. A white recrystallized state of a surface of each sample was visually observed. Table 1 shows its result.
It can be understood from the result of the preliminary experiment shown in Table 1 that, in order to recrystallize a surface of a transparent silica glass body at a high temperature (1500° C. in the preliminary experiment), the OH group must have a concentration of approximately 200 to 2000 ppm by mass, and Ba must be applied to the silica glass surface at a concentration of approximately 25 to 1000 μg/cm2.
The present invention will now be more specifically explained hereinafter based on examples and comparative examples, but the present invention is not restricted thereto.
In accordance with the steps (1) to (6) shown in
Subsequently, a graphite mold 101 shown in
Then, the water vapor containing gas atmosphere was maintained until a temperature becomes 200° C. or less, and the silica container 71 was cooled to a room temperature, and Ba was applied to the entire inner surface of the cooled silica container 71 at 80 μg/cm2, whereby the silica container 72 (see
A silica container was produced like Example 1 except that the concentration of Ba applied to the entire inner surface of the cooled silica container 71 was changed to 480 μg/cm2.
A silica container was produced like Example 1 except that the OH group concentration at the time of increasing the OH group concentration in the inner side of the transparent layer 52 was set to 220 ppm by mass and the concentration of Ba applied to the entire inner surface of the cooled silica container 71 was changed to 40 μg/cm2.
A silica container was produced like Example 1 except that the OH group concentration at the time of increasing the OH group concentration in the inner side of the transparent layer 52 was set to 220 ppm by mass and the concentration of Ba applied to the entire inner surface of the cooled silica container 71 was changed to 800 μg/cm2.
A silica container was produced like Example 1 except that the OH group concentration at the time of increasing the OH group concentration in the inner side of the transparent layer 52 was set to 800 ppm by mass and the concentration of Ba applied to the entire inner surface of the cooled silica container 71 was changed to 60 μg/cm2.
A silica container was produced like Example 1 except that the OH group concentration at the time of increasing the OH group concentration in the inner side of the transparent layer 52 was set to 1200 ppm by mass and the concentration of Ba applied to the entire inner surface of the cooled silica container 71 was changed to 100 μg/cm2.
A silica container was produced like Example 1 except that the OH group concentration at the time of increasing the OH group concentration in the inner side of the transparent layer 52 was set to 800 ppm by mass and the concentration of Ba applied to the entire inner surface of the cooled silica container 71 was changed to 30 μg/cm2.
A silica container was produced like Example 1 except that the OH group concentration at the time of increasing the OH group concentration in the inner side of the transparent layer 52 was set to 1200 ppm by mass and the concentration of Ba applied to the entire inner surface of the cooled silica container 71 was changed to 30 μg/cm2.
A silica container (the outer side is a white opaque silica sintered body, and the inner side is a colorless and transparent silica glass body) was fabricated from the same raw material powder as the raw material powder used in Example 1 by a reduced-pressure arc melting method (an air atmosphere) which is a conventional method. Further, Ba was not applied to the inner surface of the silica container.
A silica container was produced by a normal-pressure arc melting method and a powdery raw material spreading arc melting method as conventional methods. That is, first, a temporary compact was formed from the same raw material powder as the raw material powder in Example 1, and a silica substrate constituted of a white opaque silica glass layer in the outer side and a white translucent silica glass layer in the inner side was fabricated by the normal-pressure arc melting method. A synthetic cristobalite powder (a particle size: 50 to 300 purity: 99.9999% by weight) was spread on the inner side of this silica substrate, and melting was effected, whereby a transparent silica glass layer (an additional inner surface layer) was formed.
The following points were changed from Example 1, and a silica container was produced. Air from which water vapor was removed was used as a heating meting atmosphere of a temporary compact from beginning to end, and processing entered a cooling process without introducing water vapor. Further, the concentration of Ba applied to the entire inner surface of the cooled silica container was changed to 950 μg/cm2.
A silica container was produced like Example 2 except that Ba was not applied to the cooled silica container.
Physical properties and characteristics of each raw material powder used and the silica container produced in each of the examples and the comparative examples were evaluated as follows.
Observation of a two-dimensional shape and measurement of an area of each raw material powder were carried out with use of an optical microscope or an electron microscope. Then, a shape of each particle was assumed to be a perfect circle, and a diameter was calculated from an area measured value. This technique was statistically repeatedly carried out, and the obtained values are listed in Tables 2 to 7 as the values in the particle size range (99% by weight or more of the raw material powder is included in this range).
Each silica container was cut by a cutter, and a cross section of the silica container at a central part of a total sidewall height was measured with use of a scale, thereby obtaining a thickness of each layer.
A glass sample obtained from each of the opaque layer portion and the transparent layer portion was cut and prepared, and the OH group concentration was measured by infrared absorption spectrophotometry. However, in regard to a transparent layer inner surface portion, two points at a depth of 0.5 mm and a depth of 1.0 mm from a surface were measured, and an arithmetic mean value was shown. Additionally, in regard to a transparent layer deep portion, two points at a depth of 1.5 mm and a depth of 2.0 mm were measured, and an arithmetic mean value was shown.
Conversion from the infrared absorption to the OH group concentration is based on the following reference.
Dodd, D. M. and Fraser, D. B. (1966) Optical determination of OH in fused silica. Journal of Applied Physics, vol. 37, P. 3911.
Respective flake-like samples were obtained from a portion from the inner surface to a depth of 1 mm and from a portion from a depth of 1.5 mm to a depth of 2.5 mm, solutions thereof were prepared by an acid treatment, and concentration analysis was conducted. The concentration analysis was conducted based on plasma atomic emission spectrometry (ICP-AES), plasma mass spectrometry (ICP-MS), or atomic absorption spectrophotometry (AAS).
Metallurgical grade polysilicon having a purity of 99.9999999% by weight was put into the produced silica container, a temperature was increased to obtain silicon melt, then pulling of single-crystal silicon was repeatedly performed for three times (multi-pulling), and a success rate of single-crystal silicon growth was evaluated. As pulling conditions, an argon (Ar) gas 100% atmosphere was provided in a pulling apparatus (a CZ apparatus), a pulling rate was 0.6 mm/minute, a single-crystal silicon dimension was set to a diameter of 300 mm and a length of 600 mm, and an operating time of one batch was set to approximately 80 hours. Success ratios of repetition of the single-crystal growth for three times were classified as follows.
In the single-crystal silicon continuous pulling, 200 silicon wafers, each of which has a diameter of 300 mm and a thickness of 200 μm and was subjected to double-side polishing, were produced from an arbitrary region of the first single crystal silicon after the multi-pulling of each single crystal silicon. Then, the number of voids, pinholes, and foreign particles present on both sides of each silicon wafer were measured by using a particle detector, a numerical treatment was statistically carried out, and the number of defect-free silicon wafers in 200 silicon wafers were obtained. As a result, the following evaluations were provided in accordance with the numbers of silicon wafers from which voids, pinholes, and foreign particles were not detected.
After end of the evaluation of the single-crystal silicon continuous pulling, each sample having a dimension of 200 mm×50 mm×a sidewall total thickness were cut out from a portion of each silica container near the upper part of the initial silicon melt surface (a portion that is not in contact with the silicon melt) over the total thickness of the silica container sidewall. Then, an evaluation test silica glass container having a crucible shape was additionally prepared, the prepared evaluation test silica glass container was filled with polycrystalline silicon, and melting was effected with use of an electric furnace to obtain silicon melt. A half of a lower portion of each sample was immersed in the silicon melt. In this state, 1500° C. was maintained in the electric furnace for 80 hours, and then each sample was pulled. Subsequently, an etching amount of a surface of each sample on a side which was a silica container inner surface side before cutting was obtained by measuring a cross-sectional thickness by using a scale.
The producing conditions, the measured physical properties, and the evaluation results of the respective silica containers produced in Examples 1 to 8 and Comparative Examples 1 to 4 are collectively shown in the following Tables 2 to 7.
As can be understood from Tables 2 to 7, in each of Examples 1 to 8, the etching resistance of the silica container inner surface was successfully enhanced. Further, the continuous pulling of single-crystal silicon was successfully performed with less voids, pinholes, and foreign particles. That is, in a comprehensive manner, each of the silica containers according to Examples 1 to 8 was more excellent for the single-crystal silicon pulling purpose than each of the silica containers according to Comparative Examples 1 to 4.
It is to be noted that the present invention is not restricted to the foregoing embodiment. The foregoing embodiment is just an illustrative example, and any example that has substantially the same configuration and exercises the same functions and effects as the technical concept disclosed in claims according to the present invention is included in the technical scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-112748 | May 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2013/001839 | 3/18/2013 | WO | 00 | 1/23/2014 |
