JP2014162698A - Production method of sapphire single crystal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a sapphire single crystal having no foams, capable of suppressing increase of the impurity concentration of raw material molten liquid even when reuse of the raw material molten liquid is repeated, in production of a sapphire ingot by a Czochralski method.SOLUTION: A sapphire ingot is produced by a Czochralski method, and a shoulder part and a tail part of the sapphire ingot are cut off to obtain a core, and the cut-off shoulder part and tail part are used as a part of a production raw material of the sapphire ingot by the Czochralski method of another batch.

Description

  The present invention relates to a method for producing a sapphire single crystal used as an epitaxial growth substrate or an optical material.

  Sapphire (aluminum oxide) single crystals are widely used as nitride compound semiconductors, silicon epitaxial growth substrates, high-strength window materials, and the like. In recent years, demand for LEDs as LED televisions, LED lighting, and the like has been increasing from the viewpoint of energy saving, and thus demand for sapphire substrates for nitride-based compound semiconductor epitaxial growth has been increasing.

  Known methods for producing a sapphire single crystal include Bernoulli method, EFG (Edge-defined Film-fed Growth) method, Czochralski method, kiloporous method, HEM (Heat Exchange Method) method and the like.

  At present, the most common method for growing a sapphire single crystal which is a material for a large substrate having a diameter of 150 mm (which is generally referred to as a 6-inch substrate by those skilled in the art) is the kiloporous method. The kiloporous method is a kind of melt growth method. While the seed crystal in contact with the raw material melt surface is not pulled up or pulled up at an extremely slow speed of 1 mm / hour or less, the heater output is gradually lowered to remove the crucible. By cooling, this is a method of growing a single crystal under the surface of the raw material melt, and a large-diameter single crystal having excellent crystal characteristics can be obtained relatively easily.

  However, the kiloporous method is known to be greatly affected by the growth rate that varies depending on the crystal orientation. In the case of a sapphire single crystal, it is difficult to grow a crystal in the c-axis (Miller index <0001>) direction, In general, a seed crystal with the a-axis (<11-20>) facing the lower surface is brought into contact with a melt and crystal is grown in the a-axis direction (see, for example, Patent Document 2).

  In order to obtain a c-plane sapphire single crystal substrate used for epitaxial growth of a nitride-based compound semiconductor from the sapphire single crystal having the a-axis as the growth direction, the single crystal is obtained using a core drill or the like. It is necessary to cut out a cylindrical body having a desired diameter from the c-axis direction, which is the side direction of the body, and cut it into a disk shape with a multi-wire saw or the like.

  On the other hand, the Czochralski method is a kind of melt growth method similar to the kiloporous method, but it is pulled up while pulling up the seed crystal brought into contact with the raw material melt at a speed of about 0.5 to 10 mm / hour. In this method, a crystal having a desired diameter is grown on the melt surface by adjusting the speed, the number of rotations of the crystal, and the heater output. In the Czochralski method, generally, a crucible made of iridium or the like is directly heated by an induction heating method to form a crystal with a larger temperature gradient than the resistance heating method used in the kiloporous method.

  When crystal growth is performed under such a large temperature gradient, there is an advantage that a crystal can be grown in the c-axis direction because a difference in growth rate for each growth orientation is less likely to occur. In the Czochralski method, a sapphire single crystal grown in the c-axis direction having a diameter and an arbitrary length required for the substrate can be easily obtained. It is characterized by extremely high substrate acquisition efficiency from a single crystal. Conventionally, it has been thought that large / long crystal growth is difficult with the Czochralski method. However, due to the recent progress in research and development, large / long sapphire single crystals can be obtained with the Czochralski method. Technology to train is being established.

JP 2000-82676 A JP 2004-83407 A JP 2008-207992 A

  When a sapphire single crystal is grown using the high frequency heating Czochralski method using an iridium crucible, the raw material melt remaining in the crucible after the growth (hereinafter referred to as residual melt) adheres to the crucible, and the crucible There is a problem that it is very difficult to take out the residual melt without damaging the steel. Therefore, in the continuous production of sapphire single crystals, it is normal to add new raw materials in an amount equivalent to the amount grown (consumed) as single crystals to the residual melt that cannot be taken out, and use them as raw materials for the next crystal growth. is there.

  When a single crystal is grown by the Czochralski method, impurities in the melt tend to remain in the liquid phase due to segregation, so that generally grown crystals are significantly higher in purity than the raw material melt. In other words, impurities are concentrated in the residual melt after completion of the growth. This indicates that the impurities are concentrated in the residual melt as the reuse of the residual melt is repeated in continuous production, and the impurity concentration of the raw material melt increases. As the purity of the raw material melt progresses, the raw material melt enters a state called compositional supercooling in the vicinity of the solid-liquid interface for crystal growth, causing abnormal growth of the crystal, resulting in bubbles in the grown single crystal. It becomes a cause of mixing.

  Thus, when the residual melt is contaminated to a certain level or higher, a step of removing the residual melt from the crucible is required. This process involves a risk of damaging the iridium crucible, and requires a large amount of cost for the deformation of the crucible and the correction of the pinholes that occur when the residual melt is taken out.

  Therefore, as a result of diligent research in view of the above points, the inventors washed shoulder portions and tail portions, which are not used as products, out of sapphire single crystals grown using the Czochralski method, and put them back as raw materials. Thus, the inventors have found that the concentration of impurities as a whole of the molten raw material can be reduced, and as a result, mixing of bubbles can be suppressed, and the present invention has been completed.

  That is, the present invention manufactures a sapphire ingot by the Czochralski method, cuts the shoulder part and the tail part to obtain a core, and uses the cut shoulder part and tail part of the sapphire ingot by another batch of Czochralski method. It is a manufacturing method of a sapphire ingot characterized by using as a part of manufacturing raw material.

  By using the method for producing a sapphire ingot using the shoulder portion and the tail portion as a part of the raw material for producing a sapphire ingot by another batch of the Czochralski method according to the present invention, a single crystal sapphire crystal having less bubbles than conventional ones can be obtained. More repetitive manufacturing becomes possible.

The schematic diagram which shows the structure of a Czochralski method single crystal pulling furnace.

  As a method for producing a sapphire ingot by the Czochralski method in the present invention, a known method can be applied as it is, and an outline thereof will be described as follows.

  That is, sapphire ingot production by the Czochralski method is a batch method, and usually using an example (schematic diagram) of a crystal growing apparatus as illustrated in FIG. An ingot of about 500 mm is pulled up from the raw material melt.

  This single crystal pulling apparatus includes a chamber 1 that constitutes a crystal growth furnace, and a single crystal pulling rod 2 that can be moved up and down by a drive mechanism (not shown) through an opening on the upper wall of the chamber. It is suspended. A seed crystal body 4 is attached to the tip of the single crystal pulling rod via a holder 3, and the seed crystal body is disposed on the central axis of the crucible 5. Further, a load cell 6 for measuring the crystal weight is provided at the upper end of the single crystal pulling apparatus.

  As the crucible 5, a known crucible can be used as a crucible used in the Czochralski method. In general, an opening viewed from the top is circular, has a cylindrical body, and has a flat bottom surface, a bowl shape, or an inverted conical shape. In addition, the material of the crucible is suitable for a material which can withstand the melting point of aluminum oxide as a raw material melt and has low reactivity with aluminum oxide, and iridium, molybdenum, tungsten, rhenium or alloys thereof are generally used. Used. In particular, it is preferable to use iridium excellent in heat resistance and oxidation resistance.

  A heat insulating wall 7a is installed around the crucible so as to surround the bottom and outer periphery of the crucible. Further, a heat insulating wall 7b surrounding the side periphery of the single crystal pulling area above the crucible is provided. The heat insulating walls 7a and 7b can be used without limitation on known heat insulating materials or structures for heat insulation. A material, an alumina-based material, a carbon-based material, a reflective material in which metal plates such as tungsten and molybdenum are laminated, and the like can be used particularly suitably.

  Since the heat insulating wall used here is used in an environment where the temperature difference between the inner surface and the outer surface is very large, the material is likely to be significantly deformed and cracked by repeated heating and cooling. When the temperature gradient in the crystal growth region changes every moment due to such deformation and cracking of the heat insulating wall, stable crystal production becomes difficult. Therefore, the entire heat insulating wall is not composed of a single piece of material, but is composed of a combination of heat insulating materials divided into several parts. It is preferable to reduce the change.

  The opening at the upper end of the heat insulating wall surrounding the single crystal pulling area is closed by the ceiling plate 8 in which the insertion hole for the single crystal pulling bar is formed at least. Thereby, since the single crystal pulling area is accommodated in the single crystal pulling chamber formed by the heat insulating walls 7a and 7b and the ceiling plate 8, the heat retention is greatly improved. The ceiling board should just be formed with the well-known heat insulating material or the structure for heat insulation similarly to the heat insulation wall. Further, the ceiling plate is not necessarily flat and may have any shape as long as the upper end opening of the enclosure of the heat insulating wall is closed except for a perforated portion described later. For example, the shape other than the plate shape may be a truncated cone shape, an inverted truncated cone shape, a shade shape, an inverted shade shape, a dome shape, an inverted dome shape, or the like.

  A high-frequency coil 9 is installed around the outer periphery of the heat insulating wall and approximately the height of the crucible. A high frequency power source (not shown) is connected to the high frequency coil. The high-frequency power source is connected to a control device composed of a general computer, and the output is appropriately adjusted. In addition to analyzing the weight change of the load cell and adjusting the output of the high frequency power supply, the control device also controls the rotation speed of the crystal pulling shaft and crucible, the pulling speed, and the valve operation for gas inflow and outflow. It is common to do.

  As a raw material for producing a sapphire single crystal core for a sapphire substrate for semiconductors, in addition to a shoulder part and a tail part obtained by cutting an ingot described later, a new raw material usually has a purity of 4N (99.99% ) Aluminum oxide (alumina) having the above purity is used. Since impurities are mixed into or between the lattices of the sapphire single crystal and become the starting point of crystal defects, when raw materials with low purity are used, subgrains tend to occur and the crystals tend to be colored. The cause of coloration of the crystal is a color center (color center) caused by crystal defects formed by impurities, which indirectly indicates the number of crystal defects. In particular, since chromium as an impurity significantly affects the coloring, it is preferable to use a raw material having a chromium content of less than 100 ppm.

  Further, a material having a bulk density as high as possible is suitable because it can fill a crucible with a large amount of raw materials and suppress scattering of the raw materials in the furnace. The bulk density of a preferable raw material is 1.0 g / ml or more, more preferably 2.0 g / ml or more. As raw materials having such properties, those obtained by granulating aluminum oxide powder with a roller press or the like, and crushed sapphire (crackle, crush sapphire, etc.) are known.

  On the other hand, the shoulder portion and tail portion as raw materials can be put into the crucible in any shape that can be filled in the crucible. For example, the shoulder portion and the tail portion can be input as they are, or can be input after being crushed / cut into an arbitrary shape. However, since the sapphire single crystal is very hard, it requires labor for crushing / cutting, and there is a concern that impurities from tools etc. may be mixed during crushing / cutting, so the shoulder part and tail part should be put into the crucible in their original form. Is particularly preferred.

  In the Czochralski method, it is not usually possible to single-crystalize the raw material melt, and the crystal growth is completed with the raw material melt having a depth greater than the height of the growth interface (tail) grown in a convex shape. There is a need to. Since the unused portion (residual melt) of the raw material melt is fixed to the crucible during the cooling process, it is difficult to remove it without damaging the crucible. Therefore, conventionally, as a raw material at the time of continuous production, a new raw material having an amount equal to the weight of the single crystal raised to the previous crystal growth is added to the residual melt used for the previous crystal growth to obtain a raw material for the next growth.

  In the present invention, unlike the conventional case, a shoulder portion and a tail portion of a crystal manufactured in the past are added to the residual melt, and the weight of the shoulder portion and the tail portion is subtracted from the weight that was pulled up as a single crystal in the previous crystal growth. It is important to add new raw materials as raw materials for the next breeding. Thus, by making the shoulder part and the tail part part of the raw material, it is possible to suppress an increase in the impurity concentration of the raw material melt and to reduce bubbles mixed in the crystal.

  The effect of reducing the impurity concentration when the shoulder portion and the tail portion are used as raw materials can be considered as follows. A commonly used high-purity alumina raw material for growing sapphire single crystals contains several to several tens of ppm of impurities such as silicon and iron. These impurities are hardly taken into the single crystal grown due to segregation, and remain and concentrate in the raw material melt in which almost the entire amount remains.

  Here, using a high-purity alumina raw material that is normally used as a raw material to be added means that a raw material containing impurities is newly added. Is equivalent to charging an ultra-pure raw material containing no impurities. Due to this difference, reintroducing the shoulder and tail as raw materials is not merely a viewpoint of reusing unnecessary crystal scraps, but it suppresses the increase in the impurity concentration of the melt and prevents bubbles in the single crystal. Demonstrates the effect of suppressing mixing.

  The raw material is charged into the crucible installed in the crystal growth furnace, and heated to obtain a raw material melt. The rate of temperature increase until the raw material reaches a molten state is not particularly limited, but is preferably 50 to 200 ° C./hour.

  A seed crystal mounted on a seed crystal holder at the tip of the crystal pulling shaft is brought into contact with the surface of the raw material melt and then gradually pulled to grow a single crystal. The temperature of the raw material melt at the portion where the seed crystal contacts when the single crystal pulling is performed is inevitably a temperature slightly lower than the melting point in order for the crystal to grow stably without causing abnormal growth ( It is known that it becomes a supercooling temperature). In the case of a sapphire single crystal, it is preferably carried out at a temperature of 2000 to 2050 ° C.

  The seed crystal used for pulling is a sapphire single crystal, and the tip vertical direction in contact with the raw material melt surface is an arbitrary desired crystal orientation. The shape of the tip that contacts the raw material melt is not particularly limited, and may be a flat surface or an unspecified surface. Further, the side surface of the seed crystal is not particularly limited, and an arbitrary shape can be selected, but a cylindrical shape or a quadrangular prism shape is preferable.

  Moreover, it is common to have an enlarged part and / or a constricted part and / or a through-hole for holding with a holder above the seed crystal.

  Since the quality of the single crystal to be grown largely depends on the quality of the seed crystal, special attention must be paid to its selection. As the seed crystal, one having as few crystal imperfections as possible, called crystal defects and dislocations, is desirable. The quality of the crystal structure can be evaluated by using a method such as etch pit density measurement, AFM, or X-ray topography on the front end surface of the seed crystal or its vicinity. In addition, since the number of crystal defects tends to increase as the residual stress increases, it is also effective to select a crystal having a low degree of stress by crossed Nicols observation or stress birefringence.

  After contacting the seed crystal with the raw material melt, the shoulder (expanded portion) is formed by controlling the number of revolutions of the seed crystal and / or crucible, the pulling speed, the output of the high frequency coil, etc. After the diameter is expanded, the crystal is pulled up so as to maintain the crystal diameter.

  The extent to which the diameter is increased by the diameter expansion is determined depending on the size of the single crystal to be manufactured. In general, in the growth of the Czochralski method, the larger the crystal diameter, the smaller the subgrain and There is a tendency to generate bubbles. Therefore, for example, from the viewpoint of mass-producing a 6-inch class substrate, the thickness is preferably 150 to 170 mm.

  The pulling can usually be performed at a speed of 0.1 to 20 mm / hour, but if the pulling speed is too low, the amount of crystal growth per unit time is reduced and the productivity is deteriorated, and if the pulling speed is too high, it is grown. Environmental fluctuations are large and subgrains and minute bubbles are likely to occur. Considering the compatibility between productivity and crystal quality, the pulling speed is preferably 0.5 to 10 mm / hour, more preferably 1 to 5 mm / hour.

  During the growth of the single crystal, the seed crystal is preferably rotated at a speed of 0.1 to 30 revolutions / minute about the pulling axis. In addition to the rotation of the seed crystal, the crucible may be rotated at the same rotational speed in the opposite direction or the same direction as the rotation direction of the seed crystal.

  The furnace pressure during the pulling of the single crystal may be any of under pressure, normal pressure, and reduced pressure, but it is convenient to carry out under normal pressure. The atmosphere is preferably an inert gas such as nitrogen or argon, or an atmosphere containing oxygen in an amount of 0 to 10% by volume in the inert gas.

  The length of the straight body portion of the single crystal is arbitrary, but it is preferably 200 mm or more, more preferably 250 mm or more so that the substrate can be efficiently processed with a multi-wire saw. When the length of the straight body is less than 200 mm, in order to efficiently cut with a multi-wire saw, additional steps such as connecting a plurality of cores with precisely aligned orientations and cutting with a multi-wire saw after increasing the total length to 200 mm or more This is not preferable because the production efficiency is lowered and the production cost is increased. On the other hand, if the length exceeds 500 mm, the temperature environment change in the hot zone in the furnace being grown tends to be too large, and stable growth tends to be difficult.

  Thus, after pulling up the sapphire single crystal having a desired straight body diameter and length, the single crystal is separated from the raw material melt. The method of separating the single crystal from the raw material melt is not particularly limited, such as a method of separating by increasing the heater output (increasing the temperature of the raw material melt), a method of separating by increasing the crystal pulling speed, a method of separating by lowering the crucible, etc. Any method may be adopted. In order to reduce the temperature fluctuation (heat shock) at the moment when the single crystal is separated from the raw material melt, the crystal diameter is gradually decreased by gradually increasing the heater output or gradually increasing the crystal pulling speed. It is effective to perform tail processing.

  The single crystal separated from the raw material melt is cooled to a temperature at which it can be taken out from the furnace. A faster cooling rate can increase the productivity of the growth process, but if it is too fast, the stress strain remaining inside the single crystal will increase, causing crushing and cracking during cooling and later processing, There is a possibility that an abnormal warpage may occur in the substrate obtained. On the other hand, if the cooling rate is too slow, the time for occupying the crystal growth furnace becomes long, and the productivity of the growth process decreases. Considering these, the cooling rate is preferably 10 to 200 ° C./hour.

  In the straight body part of the sapphire single crystal obtained by the above manufacturing method, a high-intensity halogen lamp is placed inside the crystal in the dark room, in addition to bubbles that can be confirmed with room light such as fluorescent lamps. There are no microbubbles that can be visually confirmed by irradiation, or the vertical length of the part having bubbles is 3% or less of the total length.

  The sapphire obtained by the production method of the present invention is a single crystal but does not have subgrains that can be confirmed by X-ray topography, that is, a true single crystal or a material close thereto. The measurement conditions of the X-ray topograph for confirmation of the subgrain are shown in Table 1 below.

  In the present invention, in a grayscale image photographed under the above-described conditions and represented by shades of 256 gradations of lightness 0 (black) to 255 (white), the surface having a boundary where the lightness differs by 16 or more (and to it) When the accompanying grain boundary is not recognized, it is assumed that there are no subgrains that can be confirmed by X-ray topography. Note that the determination can be made simply by the presence or absence of striae that can be observed by crossed Nicols or the like in a dark room.

  In the present invention, a straight body portion serving as a core is obtained by cutting the shoulder portion and the tail portion of the sapphire ingot thus obtained. Although the said cutting method is not specifically limited, Although it can cut | disconnect by a well-known method, if a specific example is given, it will cut | disconnect using an inner peripheral blade, an outer peripheral blade, a band saw, a wire saw, etc.

  A feature of the present invention is that the shoulder portion and the tail portion, which are cut as described above and are not commercialized, are used as a part of a raw material for producing a sapphire ingot by another Czochralski method. The effect is as described above.

  As described above, impurities such as iridium may adhere to the surface of the shoulder portion and tail portion used as raw materials, but these are preferably removed beforehand using a grinder or the like. Also, when cutting the shoulder and tail from the grown single crystal, the surface may be contaminated with cutting fluid etc., so after washing with pure water, ethanol, acetone, isopropyl alcohol etc. It is preferable to use as a raw material after washing with a water-soluble organic solvent and drying.

  Hereinafter, embodiments of the present invention will be described in more detail with specific experimental examples, but the present invention is not limited thereto.

Example 1
50 kg of high-purity alumina (AKX-5 manufactured by Sumitomo Chemical Co., Ltd.) having a purity of 4N (99.99%) was charged as a starting material into an iridium crucible. The crucible containing the raw materials was placed in a high-frequency induction heating type Czochralski crystal pulling furnace, and the inside of the furnace was evacuated to 100 Pa or less, and then introduced to atmospheric pressure with nitrogen gas containing 1.0 vol% oxygen. After reaching atmospheric pressure, the gas having the same composition as above was introduced into the furnace at 2.0 L / min, and evacuation was performed so that the furnace pressure was maintained at atmospheric pressure. The heating of the crucible was started and gradually heated over 9 hours until reaching the temperature at which the aluminum oxide raw material in the crucible melts. After appropriately adjusting the heater output with reference to the state of convection on the surface of the raw material melt (spoke pattern), while rotating the seed crystal of a square columnar sapphire single crystal whose tip is a c-plane at a speed of 1 revolution / minute The tip of the seed crystal was brought into contact with the raw material melt. After further finely adjusting the heater output so that the seed crystal did not melt and the crystal did not grow on the surface of the raw material melt, the pulling of the seed crystal was started at a pulling rate of 2 mm / hour.

  Crystal growth was performed while appropriately controlling the heater output so that the crystal diameter estimated from the change in the weight of the load cell would be the desired diameter. After the diameter expansion to 165 mm was completed, the pulling rate was increased to 3 mm / hour while maintaining the diameter of 160 to 170 mm, and the pulling was continued. After the length of the straight body part reached 300 mm, the heater output was gradually increased to perform tail treatment, and then the single crystal was separated from the raw material melt at a pulling rate of 10 mm / min.

  The separated single crystal was cooled to room temperature over 30 hours. As a result, a sapphire single crystal having a c-axis in the vertical direction and a diameter of 160 mm and a length of the straight body portion of 300 mm was obtained. This single crystal weighed approximately 30 kg. Further, when this single crystal was observed with a high-intensity halogen lamp in a dark room, no bubbles or the like were observed inside the crystal, and no striae or the like was observed even in crossed Nicol observation.

  The upper part (shoulder part) and the lower part (tail part) of the crystal were cut from the above single crystal with a band saw, and the obtained upper and lower cut surfaces of the straight body of the single crystal were adjusted to a c-plane with a surface grinder. Then, after making it cylindrical shape with a diameter of 150 mm with a cylindrical grinding device, an orientation flat was formed on a predetermined side surface, and a sapphire single crystal core without a bubble having an axial direction of c axis with a diameter of 150 mm and a length of 300 mm was obtained.

  Impurities such as iridium adhering to the surfaces of the shoulder and tail were removed with a grinder, then washed with water, and then washed with ethanol. The shoulder part and tail part (total of about 5 kg) are added to the residual melt after the completion of crystal growth, and about 25 kg of the high-purity alumina raw material is added to make the raw material for the next crystal growth. Went. When this operation was repeated, it was possible to grow 12 crystals without bubbles continuously.

Comparative Example 1
Crystal growth is carried out in the same procedure as in the embodiment except that the shoulder and tail portions are not used as raw materials, and about 30 kg of the high-purity alumina raw material is added to the residual melt after completion of the growth and used as the raw material for the next crystal growth. Carried out. As a result, it was possible to grow crystals without bubbles 10 times in succession, but in the crystals grown after the 11th time, bubbles were mixed in a region exceeding 3% of the length of the straight body in the straight body. It was.

1: chamber 2: single crystal pulling rod 3: seed crystal holder 4: seed crystal body 5: crucible 6: load cell 7a, 7b: heat insulating wall 8: ceiling plate 9: high frequency coil

Claims (2)

  Manufacture a sapphire ingot by the Czochralski method, cut the shoulder and tail of the sapphire ingot to obtain a core, and manufacture the sapphire ingot by the Czochralski method of another batch of the cut shoulder and tail A method for producing a sapphire ingot, which is used as a part of a raw material.   When using the shoulder and tail as part of a raw material for producing sapphire ingots by other batches of the Czochralski method, the shoulder and tail are washed with water and then washed with a water-soluble organic solvent before being used as a raw material. Item 2. The production method according to Item 1.

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