TW201001529A - Cleaning process of silicon boat, silicon boat, heat treating method of silicon wafer, and silicon wafer - Google Patents

Abstract

To provide a silicon wafer reduced in metal contamination of a contact part with a silicon-made tool, and the manufacturing method of the silicon wafer reduced in metal contamination of the contact part of the silicon wafer with the tool. The cleaning process (treatment S1) of the silicon boat includes a dilute hydrofluoric acid cleaning process (treatment S1-1) cleaning the surface of the silicon boat with dilute hydrofluoric acid; an etching process (treatment S1-2); combined contaminant removal process (treatment S1-3); and a natural drying process (treatment S1-4). The surface of the silicon boat is etched in the etching process with the mixed liquid of nitric acid and hydrofluoric acid to remove a processing distortion layer containing metal impurities and metal impurities (not mixed with an organic matter) on the processing distortion layer. In the combined contaminant removal process in the latter stage, cleaning of the surface of the silicon boat with the mixed liquid of sulfuric acid and hydrogen peroxide solution removes the combined contaminant of the organic matter and metal impurities attached on the surface of the silicon boat.

Description

201001529 VI. Description of the invention: [Technical field of invention] The heat of Shi Xizhou and 矽 wafers The present invention relates to a method for cleaning the raft and a silicon wafer. [Prior Art] It is known from the self-study that in the manufacturing process of the tantalum wafer, there is a step of placing a tantalum wafer in a conventional jig and performing heat treatment. ♦ The syllabary is composed of, for example, a pair of slabs, etc. - a plate-like shape, a base material, and a plurality of pillars connected to the ten-substrate, and a plurality of ribs are supported in the plurality of pillars to support the outer circumference. And the heat treatment is provided by the mother boat in the shape of the & After Ren Hao's processing into a dream boat, if the ancient death, the cut provides the metal impurities in the case of not being cleaned, it will occur from the boat directly or through the environmental pollution in the heat treatment (4). 4 胄 晶圆 遭受 遭受 遭受 遭受 遭受 遭受 遭受 遭受 遭受 遭受 遭受 金属 金属 金属 金属 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 遥 属于 遥 遥In the step, it leads to a decrease in the yield, and the situation of .„, is reduced. Therefore, reducing metal contamination in heat treatment is one of the most important issues. However, the tantalum wafer used for the E 1 substrate is processed by a single crystal grown by the 柒-type long crystal method (hereinafter referred to as ΓCZ method mrj). The single crystal s ^ is in,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

7054-10357-PF 201001529 〇nginated Partlcle, crystal primary particles) The surface of the defect COP will cause the device yield to decrease, thus::: The technology of the COP is known as at 1〇〇〇t to show... , ^ / under the dish, in the animal, rat, ff and chlorine mixed gas, the heat treatment technology of Shi Xi wafer. . . . in the case of heat treatment such as wind or hydrogen, or a mixed gas of argon and hydrogen, compared with the case where the oxidation time W is treated at the same time and temperature: Self-contained metal pollution. The reason is that when it is conditioned in an oxidizing environment, it will cut (4) an oxide film formed on the surface of the wafer. The oxygen: film 1 has a metal π dyeing film to prevent the film's but does not form oxidation in a non-oxidizing environment. Membrane, but w pollution. From the eve boat directly or through the environment, the result of the non-oxidative ring dyeing of the Shixi wafer, which is higher than _ above, especially above the saki, is: ρΓΓ, or a mixture of chlorine and chlorine, etc. It can reduce the metal pollution caused by Shi Xizhou to Shi Xi Wa Wa. This method of preventing pollution from Shi Xizhou on Shi Xi Wa Wa is described in the patent document: HF washing and nitrogen annealing in the painful creation. Preventing contamination of the boat during manufacturing and preventing the contamination of the Shixi wafer. / The person who has proposed a mixture of acid and hydrofluoric acid, and uses a surface engraving (four) boat to perform heat treatment of the broken wafer. [Patent Document 1] Japanese Patent Special Open Cafe 33m No 矽 boat manufacturing order of the first picture) Rebel (table

7054-1Q357-PF 201001529 [Description of the Invention] (Problems to be Solved by the Invention) However, in the conventional cleaning method, 廿& i, Guzhong 'Asia cannot sufficiently remove the pollution of the raft, in the heat treatment step In the middle, J Ming can't fully prevent the pollution from the boat to the Shixi wafer. For example, if the Fe concentration is measured by the ςρν v method (surface photovoltaic method), the Shixi wafer is exposed to the stone 务 务 τ τ τ τ ] 2 The concentration of Fe at the contact portion of 7 liters can only be as large as lxlOI2atoms/cm3. Metal contamination method and twin crystal caused by the object of the present invention

In the case of providing heat treatment, it can reduce the heat washing method of Shi Xizhou, the boat, and the hot spot of the dream wafer. (Means for Solving the Problem) The method of cleaning the Shi Xizhou of the first month of the month is to perform the heat treatment of the Shixi wafer, using the method of cleaning the stone shoal including the supporting branch of the Shixi wafer. , which is characterized by:

An etching step of removing the surface of the stone boat surface containing the above-mentioned cutting portion, and removing the processing distortion layer of the surface layer of the dream boat; and an organic matter of the organic matter and the metal oxide-containing composite contaminant attached to the surface of the boat A step of removing the composite waste by centrifuging, stapling the % of the metal and removing the metal impurities. In the first invention, the step of dissolving and removing the above-mentioned complex peroxidizing phosgene water is not limited to the method of cleaning the shovel of the second invention which is selective for the specific portion, and the step of removing the pollutants is by using sulfur, The surface of the above boat is washed. Here, the etching process and the overall treatment of the composite contaminant fixture are also covered.

7054-10357-PF 5 201001529 Handling situation. The inventors of the present invention believe that it is conventional to use a gas-gas acid-based boat to perform a wafer heat treatment, and to process a distortion layer in the # , , , , , , , , , , , , , , , , , , , , , 属 属 属 属 属 属 属 属Compatible composite contaminants. In the case of the addition of 1 17(A), """, it is considered that the processing distortion layer 13 (including metal surface layer, processing) is produced in the processing of the 7 boat 1 sound θ of the washing (4). On the distortion layer 13, there is an organic matter (for example, a dream device and a soil used at the time), which is compatible with metal impurities. (4) The mechanical processing is an impurity 14 (incompatible with an organic substance). In the washing of hydrofluoric acid, the processing of the grain-changing impurities can be removed, but it is considered that the processing of the distortion layer 13, θ, and the compound contaminant 15 which is compounded with the metal genus cannot be removed. Hydrofluoric acid is washed: When the boat is treated, the Shixi wafer will be dyed by the environment in the heat treatment or the wafer boat. In particular, the stone is directly contacted by Shi Xizhou and is detected. High concentration of metal impurities. "Selection. One crystal, as shown in Figure 17 (8), when etching with a mixture of acid, it can be used for the 5 and metal impurities 14 (the organic matter I 4 , s, processing distortion layer 13, organic incompatible state) to remove organic matter and metal Complex composite pollutants] 5 wrong. The complex can not be used to carry out the 15 series at the moment of engraving, although it will temporarily leave two: the dye will remain in the mixture, Dan 1 surface, but the surface of Shi Xizhou 1 ,; ^ reattach to the face and it is more difficult to activate the composite pollutant 15 from the center device! Surface ~ C54~10357~pf 6 201001529, even if etching is performed, the object 15 remains. If there is compound pollution, if there are more complex pollutants, j|l I * ^ will partially cover the surface of the dream boat, and the obstruction will not be ruined due to the inclusion of the organic matter. As a result, localized failure will occur. / The effect causes the note to remove the processing distortion. Therefore, when using nitric acid and hydrogen fluoride s eight over the 矽 ,, # U Β π - the chemical solution of this Q is etched, the evening boat, the application of ... round of heat treatment to leave the composite pollutants 15, and not S The fish in the processing distortion layer remaining on the surface of the shoal of the shovel HX is a miscellaneous shellfish, which causes the enamel wafer to be damaged due to the comparison with the plate portion and the inspection portion. The wafer branch of Shi Xizhou is large and complex, so the average surface area of the complex is left on the surface of the boat. After the execution of the money, the valley is still written on the Shixi wafer. . According to the present invention, the metal impurity on the processing distortion layer and the processing distortion layer is removed by using etch m ^ %, and the composite stain _ hard (1) 7 dye removal step on the surface is used to remove the metal impurities of the pollutant. Remove. In addition to the cloud, it will be re-opened, because the complex pollution is not inconsistent with the ancient... In, ... nine, the spoon organic matter will be decomposed and removed, so there will be no 稷σ万朱物 again attached * ^ _ RB, and on the surface occur. To be more detailed, a mixture of sulfuric acid and 4 rfr ςη, deuterated feng shui will produce sulphur I (ff2s〇5). The oxidizing power of the composite of the peroxy surface is very strong, and the fixture is water. Therefore, the surface of the centering device ή6* will be decomposed into carbon dioxide and organic matter will be decomposed and removed. In addition, because of the structure & β ', decomposed with peroxosulfuric acid, there will be no

705H035 7-PF 201001529 Residual in the mixture and reattach to the surface of the clamping fixture. VIII—While the organic matter of the composite pollutant is decomposed and removed, the compound of the composite dye is also mixed with the mixture of sulfuric acid and hydrogen peroxide to the order of the present invention. The money is engraved. The etch step of the boat and the limitation of the composite contaminant removal step can be performed after the etching step is performed, and the composite contaminant removal step can be applied. The possibility of removing the metal-hybridized surface in the processing distortion layer, but the etching step causes, for example, the first-time tongue removal step, even if the metal in the distortion layer is processed, but the composite is used to remove the surface, Another wood removal step can remove the above metal impurities. ^Mountain aspect, if the surface of the boat is contaminated by high concentration of organic matter ^Steps in the middle of the ancient ##0 wood, in the etching 2) ^ H2SiF6#u, series ( The possibility of sputum sputum, S1 〇 s (x<6). In this case, it is best to remove the singularity of the singularity after the step of removing the scorpion. The boat is used to heat the wafer. At the time of the ancient #A ^ of the wafer, the support portion including the circle is characterized in that it is cleaned by any of the methods of the invention, the invention of the invention, or the second method of washing. The boat system can be used for such things as death, impurity expansion, gasification, donor body killing, gas annealing, hydrogen annealing, etc., which can be used for the production of raw materials. p is eliminated, and in 1 〇〇〇 it is subjected to heat treatment in a mixed environment of wind and hydrogen at a high temperature of argon and hydrogen, per gas ~ A., O54-: C357~pf 201001529 The heat treatment method according to the third aspect of the invention is characterized in that the crucible wafer is subjected to heat treatment in an environment composed of argon or hydrogen or a mixed gas of argon and hydrogen. It is characterized in that the heat treatment of the silicon wafer is performed in an environment composed of argon or hydrogen or a mixed gas of argon and hydrogen using the eve of the first month, and the heat-treated tantalum wafer is in contact with the crushing boat. The iron concentration at the location is not full

Among them, the determination of iron concentration is in addition to the aforementioned SPV method, such as sensory (four) plasma mass spectrometry (10), total reflection X-ray spectroscopy (TXRF), atomic absorption spectrometry (AAS), etc. Implementation. According to the present invention, since the heat treatment can be performed using the stone stalk m circle whose surface is hardly contaminated with metal impurities, it is possible to prevent the wafer from being contaminated by metal impurities, and the iron concentration of the ruthenium wafer is less than ixl. According to a sixth aspect of the invention, the Shixi wafer is characterized in that, in the environment in which argon or hydrogen or a mixed gas of argon and hydrogen is used, the heat treatment is performed on the Shixi wafer. The 矽 wafer of the seventh invention is characterized in that the heat treatment of the ruthenium wafer is performed in an environment composed of argon or hydrogen or a mixed gas of argon and hydrogen using the boat of the third invention. The iron concentration of the wafer at the contact position with the above boat is less than lxl〇nat〇ms/cm3. [Embodiment] This embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing a method for manufacturing a germanium wafer according to the present embodiment.

7054-10357-PF 9 201001529 Wafer manufacturing method includes: Shi Xizhou washing step (treatment s), and heat treatment step of Shi Xi wafer (treatment S2). The boat washing step is as follows Step 2: The raft boat 1 that is cleaned by the shoal of the shoal 1 is a pair of plate parts u, /, including the single crystal 多 or polycrystalline 矽 as a material. ^ # r#lI , , ± , , 恧, ·. A plurality of (for example, four) pillars 12 between the pair of plate portions 11. The plate portion 11 is slightly rounded in plane potassium, and the diameter is larger than the diameter of the silicon wafer 2 only in the plate „ A hole (not shown) for the support member is formed in P11. The hole is disposed in an arc of the outer periphery of the plate portion 1 1 at the edge of the plant. The pillar 1 2 has a slightly cylindrical shape and is retained.矽s circle 9 ^ The side surface of each of the pillars 12 is formed to hold the outer peripheral portion of the ruthenium wafer 2 for the outer peripheral portion of the 矽曰曰® 2, and the shape of the stone is in the state of the groove portion 2 , Pillar 2: 1 The groove portion 121 supporting the crucible wafer functions as a support portion of the ancient poetry ++ AR 2. Supporter Japanese yen 12: The pillar 12 is inserted into the hole of the plate portion 11 to assemble !, then "1 2 will form a part of the arc along the slab of the slab, and the configuration of the stone stalks or the ingots of the polycrystalline shovel. The ingot and the scale can be obtained by cutting or grinding. The grinding or cutting (that is, the processing distortion layer 13 (refer to S 16) on the surface of each member 11 and 12 of the Jieshixi 1 which does not contain metal impurities is formed. There are metal impurities 14 on the metal impurities, and 'there are 7 〇5^-: 〇35?- ρρ 201001529 in the processing distortion layer 13 compound pollutants 1 5 ε impurities and organic substances (such as wax, etc.) Layer]q This embodiment is separated from, for example, about 20 // m~30 β m. The sacred method of the stern boat washes the boat 1 surface using dilute hydrofluoric acid S1) '矽理(4), and the surname step (the first step of cleaning the diluted chlorine, the step (treatment S1-3), and the step of removing the island from the natural dry and compounded dyes (processing S1-4). In the step, the state of 矽12, the sub-presentation is decomposed into the components U,

The surface of each member U, 12 is washed with dilute hydrofluoric acid (the 11 and 12 are immersed in the dilute fluoric acid. Among them, the shovel is washed at a level of about 5% for 11 and 12). The concentration of each of the members 11 and the 12 dilute hydrofluoric acid is preferably 〇5 to 5〇%, and the components of the stern boat 1 are diluted with hydrofluoric acid for, for example, 30 seconds to 30 minutes. The oxide film on the surface can be removed. 12 Surface oxidation 1, 1 2 On the surface, in the dilute hydrofluoric acid washing step, after removing each member u and the film, it is convenient to use pure water from each member of the boat 1 Rinse off the dilute hydrofluoric acid. In the etching step (treatment S1 - 2), brake field II, using a liquid of nitric acid and hydrogen acid, on the components of the boat 1 i, 12 &> The amount of engraving can be as long as it can remove the processing distortion layer of the nozzle of each member 11M2 (four) step, for example, it is preferable to have each of 30"~5Μπι. Thus, as shown in Fig. 3 ^ The hall can't process the layer 13 of the surface of each member U, 12, and the metal impurities 14 present on the work distortion layer 13 are removed.

7〇54-l〇357-PF 11 201001529 Into the mixture of 61% strength nitric acid and 50% hydrofluoric acid, it is best to set the volume ratio of nitric acid to & 4: 1. Furthermore, the etching step + thousand' uses a mixture of nitric acid and hydrofluoric acid, and the components 1丨丨Z of the material 1 are etched, and then the nitric acid attached to the surface of each member J is returned to _, ... ' A mixture of fluoric acid, rinsed off with pure water. Compound pollutants are degraded + γ > " ν (process S1-3) is a mixture of the components 11 and 12 of the boat 1 immersed in sulphuric acid fish, and a mixture of emulsified water (sulfuric acid) In the cleaning, the 福 3 pollutants of the organic matter and metal impurities attached to the surface will be removed. The skin is taken from the mixture of sulfuric acid and hydrogen peroxide. After a long time, 1 1 1 otn 1 〇 member 1 1 , 1 2 is washed, so that the surfaces of the members 11 and 12 are not etched. The use of sulfuric acid and children # _ p Μ, Japanese oxidized hydrazine The peroxysulfuric acid produced by mixing, the various members of the Shi Xizhou 1 , the organic matter on the surface of the Α 2 (for example, the wax used in the processing of the raft, etc.), the machine is mainly solved by the knife into water and carbon dioxide. The organic matter on the surface will be decomposed and removed. ^ In addition, while the organic matter of the composite pollutant 15 is decomposed and removed, the metal impurities of the "15" will also be removed by the liquid mixture. <mixing of cerium oxide water' as shown in Fig. 3, the composite contaminants 15 attached to each member of Shi Xizhou i will be removed. Wherein, when the mixed liquid system uses _ concentration sulfuric acid and 3_ water, it is preferable to mix the sulfuric acid with the cerium peroxide water y. &, J hard acid, and the mixed volume ratio of the sulphurized feng shui is set to 〗: 丨~9 .〗.虱 ., ^ In particular, it is better to set the volume ratio of sulphur bismuth to pervaporation and water to 2 ～ 4 · _ 1 .

7054-10357-PF 12 201001529 The volume ratio of sulphuric acid to sulphuric acid and sulphuric acid is 1~10 relative to lanthanum peroxide. Concentrated barium sulfate peroxidation gas mixture volume ratio, when compared with t water, _, ww relative to peroxidized mouse water 1, if concentrated sulfuric acid is lower than the case, the solution is adjusted, liquid, w, 丨 liquid / 岂Will become more than 16 (TC high temperature, the decomposition of hydrogen peroxide water caused by the consumption tends to be intense, and will ~

The sufficient effect of removing the organic matter from the sulfuric acid concentration (4); = the volume ratio of the acid to the hydrogen peroxide water, when the hydrogen peroxide water is higher than 99, the hydrogen peroxide water will not Stable,: When the net is unable to obtain sufficient active oxygen 'and the organic matter such as the separation and removal of sulfuric acid is difficult to be oxidized', it will be enclosed in the system, so it is best to avoid rabbits, in sulfuric acid and hydrogen peroxide. The time for immersing the various structures in the mixture of water is preferably, for example, 3 sec., usually (1 〇 2 〇 〇 混合 与 与 与 与 与 与 过 过 过 过 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜舟卜: In the above mixture, the finest in Beiyu is the highest temperature....1 The time of the gong around the knives is 'the mixture will then be attached to the surface of the stone s The hydrogen-water mixture is rinsed off with pure water. 吼夂& In addition, in the composite contaminant removal step, in order to adjust the oxidizing power of the mixture of sulfuric acid and chemical = water, it is also possible to combine sulfuric acid with hydrogen peroxide. Heating, for example, depending on the mixture, into a 4:12. , Li: Adjustment of the heater, etc. Use the natural drying of S1: 'Execution... (natural drying step (process to end the washing step of Shi Xizhou 1) ^054-10357-pp 13 201001529 For example, each of the above-mentioned washing steps is assembled into a combination of the stone and the scorpion U and 12, and the pick-up is in the ditch portion i 21 a of the pillar 12 of the stone eve 1 and then the raft is smashed. - 1 inserted in the eve of the yen 2, the demon production:; does not heat the furnace 'and heat treatment. ... The conditions of the treatment are, for example, in an argon environment, ... heart hours. 4 =: T 亍 heat treatment of the outer periphery of the wafer 2 - In part, as shown in Fig. 4, it will be contacted and the surface of the groove portion 121 of the yoke column U will be contacted. The metal impurity concentration (ie, the iron concentration) is less than X 〇 at〇ins/cm3 ( According to the SPV (surface photovoltaic method) method, the following effects can be obtained according to the present embodiment. In the step of cleaning the boat of the boat 1, the mixture of the acid and the hydrofluoric acid is used to perform the 纟χ1 of the boat i. 'The mixture of sulfuric acid and hydrogen peroxide water is used to wash the surface of the second rise 1 : 3, :: The metal impurities on the processing chip layer 13 can be removed from the water 2: In the composite contaminant removal step, the organic matter 疏 using the acid and the chlorine peroxide 1 (4) 15 will be decomposed into 2 匕 carbon and water. By this, the organic matter on the surface of the '1 boat 1 will be removed. Another factor: the organic matter will be _decomposed' so there will be no residual organic matter in the mixture and reattach to the surface of the boat i Concerns: In the case where the organic matter of the composite pollutant 15 is decomposed and the metal of the material 15 is mixed by the sulfuric acid and the hydrogen peroxide water, the step of the surname and the composite contaminant removal step 705^- 〇357'pp 201001529, can be used to remove the processing distortion layer 13 and the surface 14 of the boat i, and the composite pollutants 15 can be greatly reduced, and the surface of the boat can be greatly reduced. , can reduce the transfer of metal impurities from the 5th eve of the boat, and the Japanese yen 2. _ This can reduce the contamination caused by the metal impurities in Shi Xi Wafer 2 . So 'after heat treatment (four) wafer 2 outer peripheral part is in the branch with dreams

In the m-phase contact portion 21 of the groove u, the iron concentration is less than 1 x l0 atoms/cm 3 °. In the present embodiment, when the crushing boat 1 is washed, the composite pollution is performed after the etching step is applied. Object removal step. In the surname step, the metal impurities in the processed sacrificial layer 13 removed by the engraving are likely to be attached to the activated surface due to the surname, but the composite contaminant is implemented by performing the etching step. The removal step can remove the metal impurities by using the composite contaminant removal step even in the process of 'processing the metal impurities on the surface of the distorted layer 13 reattachment surface'. Therefore, a boat J having a lower concentration of surface metal impurities can be obtained. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope of the object of the present invention are encompassed by the present invention. For example, in the above embodiment, in the step of washing the boat, the composite contaminant removal step is performed after the etching step is performed, but it is not limited thereto, and the composite contaminant removal may be performed as shown in FIG. After the step, the surname step is implemented. For example, when the surface of the boat 1 is seriously polluted by wax or metal, if the etching step by using nitric acid and hydrofluoric acid is used, the composite stain is more than 7复合54-1〇357-PFt 15 201001529. First implementation, then the boat ι table situation. In contrast, the deposition of the contaminated film may be carried out. After the composite contamination step is performed, the compound of the wax can be used to remove the wax temple organic matter on the surface of the boat 1 by performing the organic matter m removal step of the wax. The knife is removed, so it is not easy to be contaminated. After the # 钱 刻 step to form a dip, can also etch the front part of the step 盥 pollutant removal step. Each of them has a composite a. Thus, by performing a composite contaminant removal step in multiple times, a boat having a surface with less metal impurities can be obtained. Further, in the above embodiment, 'when the surname is applied to, the mixture of nitric acid and gas acid is used, but not only brown is limited thereto, but the reinforcing distortion layer 13 capable of removing the surface layer of the material i is used. (4) Liquid can be. Further, in the above embodiment, in the composite contaminant removing step, although a mixed solution of sulfuric acid and hydrogen peroxide water is used, it is not limited to this, and 1% of the composite contaminant i 5 attached to the surface of the boat 1 The organic matter is decomposed and the composite pollutants 15 are removed. Furthermore, in the above-described embodiment, in the washing step of Shi Xizhou i, both the plate portion u and the pillar 12 constituting the stone stalks are washed, but the present invention is not limited thereto, and may be only The pillar 12 is washed. Furthermore, in the above embodiment, the step of washing the boat includes a dilute hydrofluoric acid washing step, an etching step, a composite contaminant removing step, and a natural drying and drying step, but is not limited thereto. For example, between the etching step and the composite dye removing step, a dilute hydrofluoric acid washing step for removing a thin oxide film formed by the etching of the surface of the boat 1705-705-pf 1p 201001529 is formed. C. In the latter stage of the composite contaminant removal step, a dilute hydrofluoric acid washing step can also be designed in order to completely remove the mixture of sulfuric acid and hydrogen peroxide used for the composite fouling. Further, in the above-described embodiment, the boat 1 is targeted for the report shown in Fig. 2, and the y is not limited thereto, and the plate substrate has 3 or more f.

In the case of the case, the manufacturing of the present invention may be carried out using a sample formed by the body. In the above embodiment, the 'rights are used for heat treatment, and the invention is not limited to this'. The stone plating method for the pick-and-spray plating, etc. 'planting state' [Examples and comparisons] Next, the specifications of the tantalum wafers which are described in the examples of the present invention are as follows: [Table 1] 111 『 Diameter 200 mm Surface orientation---- (100) Type P-type dopant-type resistivity 1 ~ 50 Q · cm Oxygen concentration 10~15xl〇17atoms/cc (Example 1) In the order shown in Figure 6矽 Wafer fabrication. 1. 矽 boat cleaning steps

'7〇54-l〇357-PF 17 201001529 Firstly, 'single crystal squid with single crystal ruthenium as raw material, immersed in hydrofluoric acid solution for 5 minutes, and formed on the surface of 矽冉矣, 稀打 7丹The oxygen is removed. Then, the boat is treated with pure water and the acid washing step). Dilute hydrogen Next, the mixture was immersed in a mixture of 96% sulfuric acid and 30% hydrogen peroxide water in a volume ratio, and placed at 3. Minutes::1 is a mixture of sulfuric acid and hydrogen peroxide water from the surface of the boat. Convenient cleaning with pure water (composite contaminant removal step). Shown, secondly, the stone shoal was immersed in a 5% dilute hydrofluoric acid solution. After 5 minutes, the stone was washed with pure water for 10 minutes (second dilute chlorine acid washing step). Then, in the shoe engraving solution of acid and 5_fluoric acid in a volume ratio of 4:1, the boat is immersed in (4), and on the surface of the boat (4) 1 boat: the engraving system is set to 5Mra. Then, the boat was taken out from the etching solution and washed with pure water for 20 minutes (etching step). After J, Shi Xizhou, in a 5% dilute hydrofluoric acid solution, after 5 minutes, use pure water to wash the boat for 10 minutes (the third diluted hydrofluoric acid washing step will be such a boat Natural drying (natural drying step) 2. The heat treatment step of the wafer is to remove the C0P (CrystaI Originated Particle) near the surface of the Japanese yen, and use the rafting process of the raft to perform the heat treatment of the 矽 wafer. The outer peripheral part of the silicon wafer is embedded in the pillar groove of Shi Xizhou, and the boat is placed in the heat treatment furnace 1 after 12 hours, argon environment

Heat treatment is carried out in 7054-10357-PF 18 201001529. (Example 2) Gota 2 is the same as the 7th, the figure is not, the supervised compound pollutant removal & Ke 1 矽 洗 洗 洗 步 、 、 、 与 与 、 、 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻 蚀刻& — The order is reversed. That is, the dilute hydrofluoric acid washing step, the step, the etching step, the second hard contaminant de-washing step, the natural drying step (four) removing step, the third dilute hydrofluoric acid ^ In the order of 7 townships, the rest of the conditions are the same as the washing steps of the boat in Example 1. (Embodiment 3) In the third embodiment, the conditions of # and 夕晶♦ being M # are the same as in the second embodiment. The original crystal of the original crystal boat. (Comparative Example 1) π-term row 依照 According to Fig. 9 1 Washing step of the boat The wafer is manufactured in the order of 7054-10357-pp. The single crystal boat of the material is immersed in 5% dilute hydrogen gas in the middle of the gas. 19 1 The washing step of Shi Xizhou The gyroscope with single crystal ruthenium is used for 5 minutes. Then, in order to remove the IG minutes (four) from the stone eve boat table, two: boat immersed in 5% of the dilute gas, the IG minutes (four) material is dilute acid removal, convenient use, then the boat will be washed from the _ acid washing step ). 2 曰 ..., 'dry (natural drying step). Heat treatment step of day 0 The heat treatment step of the wafer was carried out in accordance with the conditions of (Comparative Example 2) and 彳1. 201001529 5 minutes. Then, in order to remove the dilute hydrogen fluoride from the surface of the boat, the pure water is washed for 1 minute (the first diluted hydrofluoric acid is convenient for use). Next, the name of Shi Xizhou is engraved. Dip in 61% Shaw'). Hydrofluoric acid mixed etching solution (volume ratio of nitric acid to hydrofluoric acid is "under 5% and 矽 矽 矽 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Remove the medium in the etching solution, and then wash it with a pure water clock (remaining step). Line 20 minutes and then 'small boat in a 5% dilute hydrofluoric acid solution to immerse 5 eight knives · ^ children, use / pure The water is washed on the boat for 1 minute (the second thin, ·,, 'talk, step). The hydrofluoric acid washing step then 'will dry the boat naturally (natural drying step). 2. Heat treatment step of wafer a The heat treatment step of the round is carried out in accordance with the condition a (Example 3, Comparative Example 2) of Example 1. The heat-treated furnace is taken out from the heat treatment furnace, and the 埶_押# & The concentration of Fe in the processed wafers (performed by the SPV method). The results of Example 1 are as shown in Fig. 1 'The results of Example 2 are as shown in Fig. 11'. The results of 3 are shown in Fig. 12. The results of Comparative Example 1 are as shown in Fig. 13 'The results of Comparative Example 2 are as shown in Fig. 14. 1 0 to 14 shows the distribution of Fe concentration (ie, contamination due to Fe) after heat treatment. In the first to the right, the part surrounded by the dotted line refers to the connection between the wafer and the boat. . Touch part. Further, 'Figure 15 shows the embodiment 3 and the comparative examples 1, 2, 矽

7C54-l〇357-PF 20 201001529 Wafer (4) Average Fe concentration in the contact portion of the boat.

In the third, it can be confirmed that the iron inferiority of the A-point of the outer circumference of the wafer and the stone stalk is less than Ixl. "-. In the other aspect, in the comparative example 2, the iron concentration in the portion where the outer peripheral portion of the crucible wafer is in contact with the raft is more than lx10'toms/cm3. It is known from the above that in the embodiment 3, the metal contamination of the contact portion between the crucible wafer and the boat can be alleviated.

In addition, only Example 2 and Comparative Example 1 were examined, and the change in the Fe pollution was observed at the time of the heat treatment: the degree of the temperature change. For heat treatment, the tongue 'Example 2 and Comparative Example 1 are both 90CTC, 1000O:, 125 (TC conditions, and the environment is argon atmosphere for 3 minutes (_Ar_3〇inin), 6〇 minutes Ar_6〇min) The conditions were carried out under the conditions of a hydrogen atmosphere for 30 minutes (-hydrogen - 30 min) and 6 minutes (-hydrogen - 60 inin). The time of each condition and the degree of Fe contamination were measured by measuring the Fe concentration by the sPV method. The results are shown in Table 2 and Figure 16. [Table 2] Unit: atoms/cc Temperature Example 2-Ar-30min Example 2-Ar-60min Example 2 - Hydrogen-30min Example 2 - Hydrogen-60min Comparative Example l-Ar-30min Comparative Example l-Ar -60min Comparative Example 1-Hydrogen-30min Comparative Example 1-Hydrogen-60min 900°C 8. OOE+09 1. 60E+10 9. 00E+09 1.40E+10 1.10E+10 2. 70E+10 1.32E+ 10 2. 70E+10 ΙΟΟΟΐ 2. 00E+10 4. 00E+10 1. 50E+10 4.00E+10 4. OOErlO 8. OOE+IO 5.00E+10 7.50E+10 1250〇C 4. 00E+10 9. 00E+10 4.50E+10 8.50E+10 4. 80E+12 8.00E+12 4. 82E+12 1.12E+13 From the case of Comparative Example 1, it is judged that with the increase of high temperature and long time, 矽7054— 10357-PF 21 201001529 The pollution of the boat surface will be transferred to the Naihua wafer _ high. The concentration of Fe causing the germanium wafer was raised relative to this, and was performed by the embodiment 1 of Example 2. (:, ··清况’ is the degree of skillful dyeing, even if b〇min is high, =Ri

SxnTatoms/cm3 is treated with a dish and a long raft, and it is still in the case of F e Zengzhi: Moreover, it is judged that the effect of preventing pollution caused by heat treatment can be prevented. In the case of Example 2, it was confirmed that the effect of the same is true for the oxygen ring 垮 φ. The heat treatment of the brothers is still industrially applicable. The present invention is applicable to the manufacture of semiconductor wafers. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a manufacturing step diagram of a Shixi wafer according to an embodiment of the present invention. Fig. 2 is a perspective view showing the boat in the above embodiment. Fig. 3 is a schematic view showing the principle of the washing step of the boat in the above embodiment. The diagram of the contact portion of the wafer crucible in the above-mentioned embodiment is shown in Fig. 5 is a schematic diagram showing the principle of the cleaning step of the boat in the variation of the present invention. Fig. 6 is a manufacturing sequence diagram of the tantalum wafer of the first embodiment. Fig. 7 is a manufacturing sequence diagram of the tantalum wafer of the second embodiment. Fig. 8 is a manufacturing sequence diagram of the Shiyue wafer of Comparative Example 1. Fig. 9 is a manufacturing sequence diagram of the Shiyue wafer of Comparative Example 2. Fig. 10 is a diagram showing the concentration distribution of the twin crystal and the circle F e of the first embodiment. Figure 11 is a graph showing the F e concentration distribution of the tantalum wafer of Example 2. 7054-10357-pf 22 201001529 Fig. 1 2 is a graph showing the Fe concentration distribution of the tantalum wafer of Example 3. Fig. 13 is a graph showing the Fe concentration distribution of the tantalum wafer of Comparative Example 1. Fig. 14 is a graph showing the Fe concentration distribution of the tantalum wafer of Comparative Example 2. Fig. 15 is a graph showing the average value of the contact portions between the crucible wafer and the crucible in Examples 1 to 3 and Comparative Examples 1 and 2. μ Fig. 16 is a graph showing the average value of the contact portion between the crucible wafer and the crucible when the temperature, time, and environment of the heat treatment were changed. f Figure 17 is a schematic diagram of the conventional washing process. In the 17th (A) diagram, the boat is treated with hydroquinone, and the 17th (B) diagram is used to etch the boat. [Main component symbol description] 1 矽舟(矽制失) 2 Shixi wafer 11 plate part 12 pillar 13 processing distortion layer 14 metal impurity 15 composite pollutant 16 矽 layer 21 contact part 121 groove part

7054—10357-PF 23

Claims (1)

201001529 Seven patent application scope 1. A stone shoal t, + net method for the implementation of 矽 矽 wafers, and includes support for the support of the 矽曰曰 0, which is characterized by : 矣 对 对 对 对 对 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 石 含有 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石The organic matter is decomposed and the complex removal step of the scallop is taken. Composite pollution for removing metal impurities. 2. The method for cleaning the second boat, such as the above-mentioned compound, and the loss of the item, wherein the step is to use sulfuric acid and peroxidized water phase, Japanese solution,斟μ, +, as a gentleman, a hole in the wind and water to wash the surface of the above boat. The stone "胄矽舟" is used for the heat treatment of the silicon wafer, including the support portion supporting the silicon wafer, and the supporting structure is characterized in that: the seat is subjected to the washing method of the patent application scope 1. Washing. The heat treatment method of the Hi-Hi wafer is characterized in that it is used for the heat treatment of the silicon wafer by the application of the argon or hydrogen or the mixed gas of argon and hydrogen. - Heat treatment method for enamel wafers, the third range of ❹μ lies in the use of stencils to form a product, : argon or helium, or a mixture of argon and hydrogen at the age of ^ & ms ® heat treatment 'heat treated Shi Xi Wa Wa, Shang: The concentration of iron at the contact position of Shi Xizhou is less than (4)% — a kind of Xi Yu Yuan, which is characterized by the use of the stone of the third paragraph of the patent application scope 7〇5"10357-^ 2, 201001529 Xizhou, in the environment of heat treatment by argon or helium, on the dream wafer, or in the environment of argon and hydrogen mixed gas, characterized in that the use of patents = Xizhou = money, or a mixture of argon and hydrogen Japanese yen silicon force Ding # heat by stone Xi * wafer after the heat treatment in the iron concentration is less lxl〇nat〇ms position of said contactor / cm3. '7054-10357-PF 25