TW200815629A - Silica glass crucible with barium-doped inner wall - Google Patents

Abstract

A silica glass crucible includes a thin barium-doped inner layer, a stable, bubble-free intermediate layer, and a stable opaque outer layer. The fusion process of the present invention controls the dynamic gas balance at the fusion front where formed grain is melted to dense fused silica. The crucible demonstrates reduced bubble growth during a Czochralski process. As a result of the thin barium-doped layer and the reduced bubble growth, the inner surface of the crucible is uniformly minimally textured during a CZ process. The present crucible is especially suited for intense CZ processes for manufacturing silicon ingots used for solar cells or with silicon that is heavily doped with antimony, boron, or arsenic.

Description

200815629 IX. Inventor's Note: [Ming's shoulder] This application is based on the US Patent Application No. which was filed on September 8, 2, 5, and has a bubble-free and less bubble growth wall. 5 Part of the continuation of 11/223, 158, which is hereby included in the overall reference. 1. Field of the Invention φ This invention relates to the field of ruthenium, and more particularly to a ruthenium having a multi-walled wall containing a ruthenium-doped inner layer. 10 [Prior Art] 2. Background of the Invention

The Czochralsk KCZ) method is well known in the art of crystal rod production of single crystal crucibles, which are made of ingots and used in the semiconductor industry.

In the CZ method, the metal stone is placed in a stone enamel glass jar inside the container, and then the filler is heated and bristled by a heater surrounding the container, and the (10) or the wonderful The stone stone that melted when the temperature was bribed pulled out a single crystal stone. , & method, for example, a large amount of doping and used to make ingots for solar cell users to have a very high degree of reactivity between the bribes and _, when pulled out - 曰 曰 & 飞 非 非 飞 曰When the pry bar is used to cut out the solar cell wafer, it requires a relatively high efficiency, and μ _ is required to be extremely south heat in order to quickly melt the money in the initial stage and the operation time is high. - The fox must mention 5 20 200815629 At the working temperature, the inner surface of the crucible often reacts with the crucible melt. In many cases, the inner surface of the crucible has undergone a morphological change, and it can be seen that the inner surface of the crucible becomes rough during extended cz operations. This rough result may result in the loss of the crystal structure of the pull-out ingot, and the roughness of the inner surface k may make the crucible unusable for the production of the twin rod. When the main part of the inner surface of the crucible is covered by a rough surface, the twin structure at the crystallization-melting interface is broken. This roughened crucible is not suitable for the production of the ingot, and the crucible must be stopped. Crystallized to avoid the production of under-standard rods. 10 15 20 In addition, during the CZ method, the inner surface of the Shixi glass smash may be partially dissolved in the shixi refining compound. The material _ main component seconds and oxygen are not harmful to the sulphur compound. However, (4) the impurities in the inner layer may be During the process, it is transferred to the Shixi refining compound, and the quality of the single crystal pulled out may be destroyed, depending on the pollution range and the nature of the contaminant. The result of an effort to control the shape of the inner surface consists in the coating of a crucible containing an antimony chemical on the inner surface which enhances the devitrification effect on the inner surface of the crucible. This is a phase change from amorphous yttrium to crystal yttrium, which prevents the generation of particles at the yttrium-melt interface. The devitrified layer formed in the 02 process contains a layer of crystalline lamella, and reports It is indicated that it can be dissolved uniformly and maintain a smooth inner surface of the crucible. If the crystal layer formed is too thick, the volume change caused by the phase change causes the layer to rupture, and the melt passes between the crystallized layer and the amorphous layer, which may eventually cause the rupture layer to peel off. 9 9 Furthermore, the bubble 6 6 in the undoped (four) wall below the doped layer will release gas, which may cause the doped layer to form a recess on its inner surface even if the inner surface is not expanded due to loss of axis. And ruptured. [Summary of the Invention] 5 basis

10 15

In one embodiment, a method for fabricating a singular slab is specifically proposed, which comprises: feeding a lumpy ruthenium grain along a rotating inner surface to form a block slab The grain is configured such that the radially inner surface faces the inner space of the mold, and the radially outer surface is adjacent to a shape of the inside of the mold, and the grain is heated from the inner space of the mold; Discharging; forming a chemical portion w at the radially inner surface and proceeding toward the radially outer surface; maintaining a pressure difference between the front part of the bribe (the mold) and feeding it higher than The degree of gas is drawn away from the front of the melt until the granules form a layer of transparent glass of the I, A house; thereafter the pressure difference between the front of the melt and the inner wall of the mold is reduced to the gas Feeding at a speed lower than the speed at which it is injected, the ruthenium-doped grain is fed onto the transparent layer; and the yttrium-doped 11-crystal (four) is bonded to the transparent glass Above the layer. According to an embodiment of the present invention, there is specifically proposed a method for fabricating a 1-2 merging horse, comprising: an inner surface of an inner-rotating (four) mo, a layer of crystal grains 35, the block The seed layer has a bottom portion, a portion: and an inner surface of the bulk crystal grain layer; and a "," region is formed inside the mold to at least partially melt the bulk crystal grain layer to form a thick layer; An inner layer containing an inner layer having an average depth of less than (10) is deposited on the inner surface of the bulk day layer. 7 200815629 In accordance with an embodiment of the present invention, a quartz hazard is specifically proposed, which includes an inner layer , having a thickness greater than 2 〇匪 and containing less than about 1% of the bubbles in the cross-sectional area, wherein the crucible is heated for about three hours at a pressure close to "the temperature of the crucible" at a pressure close to 0.1 Pa. After the burn-knot junction test, the diameter of the bubbles in the inner layer is less than about 〇·3 mm •, one layer outside: the layer, the apparent density after the vacuum sintering test is greater than or equal to about 2.05 g/cm 3 ·, a wall, At least including an inner layer and an outer layer, the wall is vacuum-fired The thickness increased after the junction test is less than or equal to about 3%; and the ruthenium doped layer formed on the inner layer is ruthenium. 10 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic side view showing a cross section of a mold in which a crucible is formed. Brother 1A is an enlarged cross-sectional side view of an airway of the exhausted core of the brother 1 diagram. 15 Figure 2 is an enlarged view of the wall of Figure 1. Figures 3 and 4 are graphical illustrations of the method for making a glass crucible using the scale of Figure 1. v Figure 5 is a cross-sectional perspective view of the first conventional technique after use in the C Z method. 20 Figure 6 is a partial enlarged view of Figure 5. Figure 7 is a cross-sectional view taken along line 7-7 of Figure 6. Fig. 8 is a cross-sectional perspective view of the second conventional technique after use in the CZ method. Fig. 9 is a cross-sectional perspective view of the present invention in accordance with the present invention after use in the CZ method 8 200815629. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One aspect of the present invention provides a bismuth glass vortex comprising a layer of the innermost erbium doped layer having a devitrification effect and a thickness sufficient to extend the working time and without An intermediate layer of bubbles and bubbles that further comprises a stable outer layer that hardly expands during repeated pulling of the rod.

The intermediate layer has a bubble free (, BF,,) property which exhibits bubble free growth ("NBG") and is 2 mm or thicker. The thickness of the ruthenium doped inner layer is less than about 0.4 10 mm, but preferably less than about (X2 mm thick. The stability of the outer layer is measured by vacuum sintering test C'VBT), which is close to the temperature of 1650 ° C, close to The thickness change was measured after sintering for about three hours at a pressure of 0.1 Pa and was calibrated to apparent density. More specifically, the thickness increase observed after the VBT was less than 1%, and the apparent density was greater than after VBT. 2·05 g/cm3. One of the viewpoints of the present invention is to feed a large amount of tantalum grains (essentially composed of quartz crystal grains) into a rotating tantalum mold, which forms a piece. Thick wall, then the formed crystal grains are heated to melt the crucible, and a pump connected to the mold pumpes 20 gas for the entire formed crystal grains, and the gas is discharged from the calcined crystal grains, and the gas will follow The grains are melted and discharged. The entire gas is dynamically balanced with the conductivity of a flow channel connecting the inner die face and the pump and the exhaust power of the pump. This dynamic balance is controlled to be located at the front of the formed crystal melt. A large amount of gas phase material can be maintained at a threshold lower than that required to make a layer of BF or NBG bismuth. 9 200815629 2 The crystal formed (4) After the innermost transformation, the surface is moved to the innermost surface of the (four), and thus A layer of germanium doped layer is formed at the innermost surface of the formed grain. The device for making the crucible has a connecting inner root: two „甘免> * *, the surface and the pump flow, and the remaining force Very low, 岐 (four) rate μ Lang required dynamic balance. The flow passage may include a flow resistance such as a line 1, a flow meter, and a venting mold itself. The flow resistance of the gas permeable mold may be (a) a plurality of holes in the graphite mold and a porous material facing the graphite on the inner side of the mold.

control. 10 The heat used to melt the formed grains must be strong enough to sinter the melting enthalpy, so that the gas will not be discharged during the CZ process. This gas release will cause bubbles or hyperplastic bubbles to form in the wall, which releases the walls. The expansion causes the degree of melting to be different. In more detail, one aspect of the present invention provides a 15 glass crucible suitable for use in the CZ process, the crucible having a bubble-free intermediate layer having a thickness of 2 mm or more, an opaque outer layer, and a thickness range up to A germanium doped layer of approximately 0.4 mm. The change in wall thickness after VBT (which is an acceleration simulation of the CZ method) is less than or equal to 3%, preferably less than, in other words, the apparent density of the crucible wall is greater than or equal to 2·〇5 g/cm3 after VBT. . These slight thickness variations of 20 degrees result from both the growth of very small bubbles in the opaque layer and the growth and growth of very small bubbles in the inner layer. After VBT, the bubble-free inner layer contains less than 1% of the amount of bubbles in the cross-sectional area, while the individual bubbles do not grow to a diameter greater than 〇.3 mm. The bubble content is the sum of the area of the bubble image divided by the total area of the transmissive optical microscope in the cross-section of the image of 200815629. The bubble size can also be measured using a penetrating optical microscope. The thickness variation of the entire wall is measured using a micrometer, and the opaque layer is preferably estimated to be 50% to 70%, at least 25%, of the wall to meet the excellent heat dissipation characteristics. The apparent density of the opaque layer is preferably greater than 2.05 g/em3 after VBT. Attention is now directed to Figures 1 and 1A, which generally represents a system for melting the crucible of the present invention, the system 10 includes a prayer mold 12 having an inner mold face, and the mold face 14 includes a substantially cylindrical shape. Shaped vertical wall 16. In the mold of Fig. 1, the wall 16 defines a cylindrical 1-inch cavity having a diameter of about 18 inches, but the present invention is equally applicable to a mold having a smaller or larger diameter. There are a plurality of air passages communicating with the inner mold face 14, such as the air passages 18, 20 (as can be seen from Figures 1 and 1A), each air passage including a cylindrical bore and a circular shape on the die face 14. Openings, such as openings 22, 24. Each airway, 15 such as airway 2A in Figure 1A, contains a porous graphite plug, such as a plug base 26, which prevents the vermiculite from being drawn into the airway from the cavity. The air passage communicates with the manifold, such as the manifolds 28, 30, 32, and the manifolds are in turn in communication with a bore 34. A pump (not visible in the figure) is connected to the bore 34, and the pump is assembled through the air passage and finally through the bore 34 to evacuate air from the cavity out of the system. Although it can be seen that the capacity of the pump is typically between approximately 80 and 350 cubic meters per hour, the present invention can be accomplished using pumps outside this range, end view channels, bores, manifolds, valves, and configurations. Depending on the conductivity of the other structures between the die face 14 and the pump. All of the structures disposed between the die face 14 and the pump are referred to herein as a flow channel. 11 200815629 Mold 12 permeable motor (not shown) (10) - vertical axis _ turn 'with-group conventional electrode 38 ' 40 can enter the interior of the prayer mode vertically, the electrode is connected to a traditional DC power supply At 42, it is optional to apply a power ranging from about 300 (four) to a viewing KVA to the electrode. When sufficient power of the foot 5 acts on the electrodes 38, 40, there is a very hot plasma gas around the electrode. Ball 44 is formed. The prayer mold 12 contains a substantially formed (four) 45, and the accident is composed of a layer 46 (enlarged in Fig. 2), which is broken and partially corrected to expose the mold surface 14. The layer 46 comprises an inner layer 46a which is a layer of germanium doped molten germanium having a thickness of up to about 4 mm in thickness; a clear glass intermediate layer 46b having a thickness of usually greater than about 2 Å; and = opaque The glass is made of a thick outer layer 46c. The three layers 46a, 46b, 46c: constitute the wall of the crucible 45, which is formed just in the mold, leaving a thin layer of unmelted crystal grains 46d because the inner mold surface cannot reach the dazzling point of forming crystal grains. 15 generally illustrates the operation of the system 10, as the mold 12 is rotated about the axis 36, the natural quartz crystal grains are placed in the mold, and the outer layer, that is, the first crystal grain received in the mold, can be utilized in July 2001. The method described in the U. Once all of the dies have been loaded into the mold, the electrodes 38, 40 are energized to activate the pump (not visible in the figure). Once the electrode heats the grain to the point where the grain on the innermost surface begins to melt, a melt front is formed and gradually approaches the die face 14 from the innermost surface of the crucible over time, the front of the melt being It is saturated. It will be explained that the 12 200815629 5 gas released from the heated and melting grains, plus the gas extracted from the still crystallized grains ((4) via the inner and upper surfaces of the formed grains) When the material power and the flow channel are transmitted with a certain - predetermined _, the quality of the formed (four) can be precisely controlled. When the crystal grains on the most silk surface are melted, the glutinous grains are replaced by the plasma to form a layer. The innermost lion with a thin layer (4) _ money sliding surface has many requirements for the balance of important parameters. First, It is assumed that the amount of melting enthalpy that is just a function of time is G(t).

At first, it is quite time consuming to preheat the Shi Xishi to the required melting temperature, 10 because the ratio of melting (4) is slowly increasing, and (4) the grain interface then proceeds rapidly until it approaches the inner surface of the mold, at a certain point. At the front, the front part of the melt reaches saturation. The unmelted crystal remains between the mold and the reactor. We have found that G(1) can be roughly expressed by the error equation. When the melt is driven in, a large amount of gas is released in proportion to the melting rate i5, and the velocity Vl75 of the gas evolution is defined as the volume of gas released per unit weight of molten crystals per unit time: VI = A · aG(t)/at ·_·(1) where A is a proportional constant. The density of the formed grains is insufficient to maintain the front of the melt from the surrounding environment 20, even though the inner surface of the crucible is covered by the high-density glass phase material, air may still pass between the molten wall and the scale mold at the top of the hanging crucible. The grains are melted, so the exhaust system should treat the gas in the leak in addition to the released gas. We have found that the amount of air leakage is proportional to the amount of unmelted grains. More precisely, we find that it is proportional to the cube of (l_erf(t)), where erf(1) 13 200815629 is the error function and B is the proportionality constant. V2=B · (l-erf(1))3 (2) This parameter VI and V2 is the main source of gas that must be removed through the exhaust. The amount of gas released is expressed by equation (7), where P is the pump power, 5 c is the normalized conductance of the flow channel, ie. V3 = P · C (3) At the front of the melt at the grain-melting stone interface, the gas flow is balanced between V3 and (V1 + V2). If the whole equilibrium νι+ν2_ν3 becomes positive, the molten glass will contain more dissolved gas; if it exceeds a certain value qi, 10 will produce bubbles in the smelting stone; if the equilibrium is negative, then (4) Shi Xi Contains less dissolved gases. The bubble-free glass can be made using the second threshold, and the other threshold Q3 is used for the bubble-free growth characteristic, where ^丨 is not necessarily equal to q]. Q3 and Q2 - If the expected value is negative, it is determined that Q3 is larger than Q2 - a negative value, that is, Q3 < Q2. After VBt (which is an accelerated simulation of the Cz method) 15, bubble release or growth can be observed in conventional crucibles - even if the crucible is made to be bubble free. The release or growth of these bubbles is caused by the release of dissolved gases in the inner layer, which is related to the negative value of the equilibrium (V1 + V2 - V3). We have also found that the bubble growth characteristics are strongly affected by the melting temperature. 2〇 Since the refining speed increases with the melting temperature, it is important that the high melting rate increases the gas release rate to meet the NBG requirements. If all the added gas is released when it is not formed, it will form bubbles, which is not conducive to the inner layer.制造's manufacturing goal is to design a device that can maintain (V1+V2_V3) the appropriate 14 200815629 negative value to meet the BF+NBG requirements of the inner layer and the NBG requirements of the outer layer while meeting the layer thickness requirements. More specifically, when an arc supply source (and preferably greater than 950 KVA) greater than 3 〇〇 KVA DC is used, and a gas pump having a capacity greater than 200 cubic meters per hour (and preferably greater than 350 cubic meters per hour) is used (from 5 When the sputum is made of venting (that is, the nominal size is greater than 24 inches), it can control (V1+V2-V3) to form a layer of BF+NBG inner layer and a layer of NBG outer layer. The most obvious limitation in designing such a flaw is that the flow passages, such as lines, joints and valves, must have a minimum cross-sectional area of more than 10 cm2, and preferably a diameter of more than or equal to about 50 mm (i.e., about eg The area of cm2 10). This dimension is in sharp contrast to the prior art in which such a line typically has a diameter of about 12 111111 (i.e., an area of about 113 (: 1112). The narrowest cross section is at the junction with the shaped grains, which must The pressure is maintained small enough to prevent the die from being lowered into the exhaust system. Preferably, each opening of the flow channel at the grain boundary is at least 2 square centimeters (cm2) and more preferably at least 0.6 cm2. A porous material, such as a porous graphite plug 26, has a cross-sectional area as described above and a maximum length of about 25 111111. For mechanical reasons, we have found that 12111111 is most desirable. Next, the square of the invention (4) using the above apparatus will be described. We have found that the main characteristics of B f and 20 NBG are measured during the transition from ♦ grain to smelting. Μ Pre-heat treatment (such as grain calcination), and not post-treatment (ie, after secluding) Sintering) can significantly change the BF or NBG characteristics. Another aspect of the present invention is that BF or Na cannot be completely controlled by the degree of vacuum alone, and it has been confirmed that the injected and removed gases must be balanced. 15 200815629 For the NBG characteristics, the use of Hanging alone in the CZ method must also release 1 body. We have determined that the released gas is closely related to the melting temperature. In other words, strong sintering is the key to NBG. The innermost layer of the extremely thin hanging 钡 钡 炫 炫 炫 炫 晶粒 晶粒 晶粒 晶粒 以 以 以 以 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒 晶粒Miscellaneous /, 砰 ^ 矽 melting is particularly useful.

The method illustrated in Figures 3 and 4 describes how to use the system of the second method to produce (4) 45 shown in Figure 1. To form a layer of massive grains (10), a large-capacity crystal hopper 50, a throttle valve 52, and a supply pipe 54 are used. In Fig. 3, the massive quartz crystal grains 56 are poured into the mold 12 to form a bulk crystal grain layer 48, which is preferably a pure quartz crystal grain. The inlaid block-shaped granules are typically shaped using a shape and a matching internal surface of the blade to the knives 60, in such a manner that the slab layer 48 can be formed to a selected thickness. 15 The melt of the formed crucible grains is shown in Fig. 4, and the electrodes 38, 4 are partially disposed inside the inner cavity of the rotating mold 12, as described above, there is an arc between the electrodes 38, 40. This produces a hot 66 region inside the cavity which is used to melt the bulk seed layer 48 formed in the mold. The melt passes through the formed crystals 20 from near to far (relative to the electrodes 38, 4 〇), and those skilled in the art should understand the mechanism by which the melt passes through the ruthenium grain layer, such as Uchikawa et al. U.S. Patent Nos. 4,935,046 and 4,956,208. After the surface of the formed bulk crystal grain layer 48 is melted, the inner tantalum crystal grains 68 are poured out from the inner tantalum crystal hopper 70 via the supply tube 72, and the inner crystal can be controlled by the inner 16 200815629 grain throttle valve 74. The velocity at which the pellet 68 is injected into the hot 66 region. The electricity generated between the electrodes forms a strong plasma field that pushes the partially melted inner crucible grains 68 outwardly so that they can be deposited on the sides and bottom of the inner surface of the crucible. The inner die 68 passes through the heating zone 66, is at least partially melted by the electric arcing flame in its 5, and is deposited on the surface of the molten bulk seed layer 48. The inner crystal grains 68 are fused with the bulk crystal grain layer to form the inner layer 46a, and the melted inner crystal grains are thus continuously deposited and fused for a period of time to form the inner layer 46a. The thickness of the melted inner layer 46a is controlled by the injection speed of the inner tantalum grains and the supply time of the inner crystal grains of the melt period. The inner diagenetic grain 68 is essentially composed of pure cerium grains doped with cerium, such as natural cerium grains that have been washed to remove contaminants. Alternatively, a synthetic germanium grain doped with germanium may also be used. In the first example, a 15 inch diameter cast is used to form an outer 15 inch 18 inch crucible, such as the crucible 45 in Fig. 1. As shown in Fig. 3, after the base crystal grains 56 are placed in the mold 12 and formed into a bulk crystal grain layer, a free exhaust velocity of about 3 〇〇 m3 / hl is applied via the bore 34. At the same time, the electrodes 38, 40 produce the hot zone 66 in Fig. 4. This forms a front portion of the melt which travels from the inner surface of the massive grains in the mold toward the wall of the mold. After about 20 seconds, the front portion of the melt touches the outermost wall of layer 46b, which forms a clear glass layer 46b. Thereafter, the vacuum pressure is reduced to about 700 Torr, and the front portion of the melt is adjacent to the wall. The layer deflection represents the unmeltedness of the narrower layer, which cannot be heated to dissolve due to the proximity of the mold wall. 17 200815629 (4) 2: After the innermost layer is formed for a period of time, that is, the front part of the refinery is moved, the 钡-doped grains are fed from the hopper 7G to the heat, and the crystal 5 10 15 20 is pushed in the hot zone (10). To the already melted thickness, a tantalum doped layer 46a is thus formed. In this example, the grains 68 are composed of grains of a wt ppm ,, which range from excitation to _ t. The crystals (4) can only be partially ablated by the heating zone, which may not be uniformly distributed. And the innermost layer may be different in doping degree and depth. 'One of the regions may be (4)·lmnmT, but the average is 2 mm. In this example, for a total of 18 gram single-(four), a total of 9 Gg of wt ppm 钡 doped granules are supplied from the hopper 7 。. In this case, the 90 gram doped granules are supplied for about 6 minutes to about 7 minutes and 10 seconds after the start of heating, so that after the formation of the layer 46a, the intermediate layer 46b and most of the thick layer of pine are formed. That is formed. At the beginning of heating, the maximum _3/(4) maximum exhaust flow rate is started, and after the start of the addition, the true U-touch seconds are switched to the full, and when the new compound is substantially completed, the vacuum of 700 Torr is maintained for about 8 minutes. ,. In another example, all parameters were maintained except for the doped grains of (10) grams. This tends to adversely affect the CZ process as the grains are heated in (4) to crack and the refinery passes through the layer 46b' and the grains above about gram expand to a relatively thick layer 46a. · You should use Zhuang's 疋, you don't need to use high-pressure vacuum to form a layer. You can get the advantage of #乂/专钡一层, in other words, you can make the thin inner layer as described above (the average thickness is about 9 〇·2 Mm) Improves the devitrification effect while maintaining a thin enough to prevent the layer from rupturing during expansion during the cz method. 18 200815629 Referring to Figure 5, the first conventional technique 8b includes a layer of molten crucible outer wall 82, which is substantially free of the above-described bubble-free and bubble-free growth characteristics, and has a layer of antimony doped inner layer 84, which is conventionally known. The skill is greater than 〇.2 legs. As can be seen from the enlarged view of the cap, during the melting of a cz, a number of 5 recessed holes, such as recessed holes 85, 86 (as seen in Fig. 7), appear at the bottom and the soil. There is a crack in the joint, which is the hottest area during the cz method. These two recesses and cracks are caused by bubbles that fall into the layer 82 during the fabrication of the crucible. to

During the period of the law, these bubbles will grow and release gas, thus producing the cloaked and sunken surface of the cockroach in Figure 6, which may release particles into the melt during the cz method. When it is severe enough, Cz The melt in the process may penetrate into the layer 82, which is not what I want. # It can be seen from Fig. 7 that the bubbles forming the recesses 85, 86 also form the channels π, 88, 疋8〇, which are connected to the right stem and the interface between the doped layer 84 and the layer 82. The crucible melt will penetrate into the interface 89. In Fig. 8, another crucible 90 is formed similar to 坩埚 in Fig. 5, and also includes a layer of outer molten wall 92 and an inner side doped layer 94. During the 15 cz melt, layer 94 will delaminate (usually marked between 9 and 8 = leaving a gap. Another portion of layer 94 (usually labeled as delaminating and (d)) thus causing the surface of layer 92 to The cz_ is exposed to the compound. The situation is caused by the fact that the layer 94 loses its transparency and volume axis during the CZ melting, and the two cases (4) cz method have an adverse effect. Finally, the figure 9 shows the hanging grass 45. (in the figure of fl), after a cz method, there is an obvious melting line 1〇〇 on the 2 shape series. This melting line is formed by a month between the month of the month and the end of the air. It can be seen that the surface below the melting line has a minimal uniform structure due to exposure to the bismuth melt, however there is no rupture, dent, delamination or spalling of the erbium doped layer in the prior art, The two examples are generally as described and illustrated in Figure 9. 5 Those skilled in the art will be able to implement the present invention in full accordance with the teachings herein. For a more complete understanding of the present invention, numerous details have been set forth, in other examples. , not yet detailed description The present invention is not intended to be unnecessarily obscured. The present invention has been described in terms of its preferred embodiments, and the specific embodiments shown and described herein are not intended to be limiting, and no doubt It is to be understood that the present invention may be susceptible to various modifications and modifications of the invention. The invention is intended to include all combinations and sub-combinations of various elements, features, functions and/or properties described herein. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic side view showing a cross section of a mold in which a crucible is formed. Fig. 1A is an enlarged cross-sectional side view of an air passage of the hanging scale mold of Fig. 1. 20 Fig. 2 Fig. 1 is a magnified view of the wall of the wall. Figures 3 and 4 are diagrams illustrating the method of making a stone sac in the mold of Fig. 1. Fig. 5 is the first known technique. A cross-sectional perspective view after use. 20 200815629 Figure 6 is a partial enlarged view of Figure 5, and Figure 7 is a cross-sectional view taken along line 7-7 of Figure 6. Figure 8 Kind of knowledge A sectional perspective view of a crucible in the CZ method Yi used after the first 5 9 The picture shows the completed crucible of the present invention in a sectional perspective view after the CZ method used.

[Description of main components] 10...System 46b...Intermediate layer 12...Mold 46c...Thick outer layer 14...Inner mold surface 46d···Unfused grain 16...Vertical wall 48···Grade layer 18, 20... Air passages 50, 70... hoppers 22, 24... openings 52, 74... throttle valves 26... plugs 54, 72 · · supply tubes 28, 30, 32... manifolds 56, 68 · · · seconds die 34 ···膛孔58...substrate die 36...vertical axis 60"·scraper 38,40···electrode 66...hot zone 42...power supply 82...outer wall 45,80,90···sweet 84...silver Doped inner layer 46...layer 85,86···recessed hole 46a···inner layer 87,88···channel 21 96 ... 200815629 98... peeling layer 100···melting line 89···interface 92...melting wall 94 ···钡Doped layer

twenty two

Claims (1)

200815629 — 5 • X. Patent application scope: 1. A method for producing a molten crucible, comprising: feeding a massive crucible grain along an inner surface of a rotating mold to block the crucible The die is disposed with the radially inner surface facing the inner space of the mold, and the radially outer surface is adjacent to a crucible shape inside the mold; heating the block-shaped germanium grains from the inner space of the mold; and discharging the gas from the heated crystal grains Forming a front portion of the melt at the radially inner surface and proceeding toward the radially outer surface; 10 maintaining a pressure difference between the front portion of the melt and the inner wall of the mold, and feeding it higher than The velocity of the gas is drawn away from the front of the melt until the crucible grains form a layer of transparent glass greater than about 2 mm; thereafter the pressure difference between the front of the melt and the inner wall of the mold is lowered. Until the gas is drawn away from the front of the melt at a rate below which it is injected; feeding the erbium-doped germanium grains to the transparent glass layer; and fusing the germanium-doped germanium grains to the transparent On the glass layer . 2. The method of claim 1, wherein feeding the erbium-doped germanium grain 20 onto the transparent glass layer comprises: at least partially melting the erbium-doped germanium grain; and doping the germanium with germanium The crystal grains are fused in the transparent glass layer. 3. The method of claim 2, wherein the air is pumped through the massive ruthenium grains into a plurality of inlets and outlets distributed in the inner wall of the mold, including 23 200815629 at least a portion of the transparent glass layer forming phase at least Qm3 /_ A speed pumping. 4. The method of claim 2, wherein the ruthenium is doped with a yttrium having a range of about 70-200 ppm. 5 5. The method of claim 2, wherein the cerium doped second grain is doped with about 100 ppm of cerium, and wherein the cerium doped cerium grain is fed onto the transparent glass layer comprises The outer diameter of each cm of the bulk crystal grain layer is fed with crystal grains of about 2 gram to about 8.5 gram. 6. The method of claim 2, wherein the size of the locker die is between about 100 and about 300 microns. 7. The method of claim 2, wherein the thickness of the layer formed by smashing the lock smectite into the transparent glass layer is between about 〇 8 mm and 0.2 mm. 8. The method of claim 2, wherein the air is drawn into the inner wall of the mold via the block 15 crystal/grain, and includes at least a portion of the transparent glass layer to form at least a velocity pumping of about 3 〇〇m3^; wherein the erbium doped cerium grain is mixed with about ppm ppm 钡; wherein the lock doping ♦ grain is fed into the transparent glass layer including per centimeter The outer diameter of the bulk crystal grain layer is about 2 gram to 2 gram large to grasp 5 gram of grain, wherein the size of the erbium doped granule is between about 300 micrometers; and The thickness of the layer of the strontium doped stone is fused to the thickness of the contact layer between about mm and 0.2 mm. 9. A method for making a smelting stalk comprising: 24 200815629 forming a layer of a granular layer on a inner surface of a rotating dies having a bottom and a side And a block-shaped inner layer surface; forming a hot zone inside the mold; 5 at least partially melting the bulk grain layer to form a thick layer; and arranging a layer having an average depth of less than 〇2 mm An inner layer is deposited on the inner surface of the bulk seed layer. 10. The method of claim 9, wherein a ruthenium-containing inner layer having an average depth of less than 0.2 mm is deposited on the inner surface of the bulk seed layer, comprising: at least partially melting the ruthenium-doped twin And entangled the cerium-doped cerium grains on the inner surface of the lumped seed layer. 11. The method of claim 1, wherein the rotary boring die has an inner die face defining a cavity, and further having a plurality of channels formed in the die 15 and communicating with the inner die face, wherein The method further includes extracting gas from the mold at a rate of at least about 300 m3/hr during the beginning of melting of the bulk seed layer. 12. The method of claim 10, wherein the cerium-doped cerium grains are doped with cerium in the range of about 70-200 ppm. The method of claim 10, wherein the cerium-doped cerium grain is doped with about 100 ppm of cerium, and wherein the cerium doped second grain is fed into the dies including per centimeter The outer diameter of the bulk grain layer feeds from about 2 grams to about 8.5 grams of grains. 14. The method of claim 1, wherein the bismuth-doped germanium grain has a size between about 100 and about 300 microns. The method of claim 10, wherein the layer thickness formed by dissolving the cerium-doped germanium crystal grains on the inner surface of the bulk crystal grain layer is between about 0.08 mm and 0.2 mm. . 5 16·—A type of quartz crucible comprising: an inner layer having a thickness greater than 2·〇mm and containing less than about 1% of bubbles in the cross-sectional area, wherein when approaching 1650 degrees (:: temperature, After a vacuum sintering test in which the crucible is heated for about three hours under a pressure of about 0.1 Pa, the diameter of the bubbles in the inner layer is less than about 〇3 mm; and the outer layer has an apparent density of greater than or equal to about 2.05 g/cm3 after the vacuum sintering test; a (four) wall comprising at least an inner layer and an outer layer, the wall having a thickness increased by less than or equal to about 3% after a vacuum sintering test; A layer of germanium doped on top of the inner layer. 17. As claimed in claim 16 of the patent scope, f & 曰 ^ D wherein the ruthenium-doped layer is fused in the transparent transparent glass layer. 18. As claimed in paragraph 17 of the patent application, ^ wherein the tantalum doped layer is doped with germanium in the range of about 70-200 ppm. 19. As claimed in claim 18, wherein the ruthenium doped layer is doped with about ppm of ruthenium. 20. If the scope of claim 18 is applied, the thickness of the tantalum doping layer is between about 0. 08 mm and about 0.2 mm.