TW565536B - Manufacturing method of quartz glass component - Google Patents

Abstract

This invention provides a manufacturing method of quartz glass components, which uses a soluble gel of TEOS as a binder of the quartz powder, and uses a plastic mold with no water absorption to solidify and mold the quartz powder by gel casting to manufacture high purity quartz glass components; the invented method has advantages such as low mold cost and good net-shape forming capability.

Description

565536 ----- Xiang No. 91123052 Car Moon Day Amendment _ V. Description of the Invention (1) The present invention relates to the manufacture of peripherals for silicon wafers, and more specifically refers to a method for manufacturing a quartz glass element. According to the semiconductor industry's equipment used to produce silicon wafers, Quartz glass crucible — straight one of the necessary components, the semiconductor industry for quartz hanging pot quartz _ pure. Degree requirements are generally 9 9 · 9 9 % 'Single crystal manufacturers also insist that the quartz crucible should be transparent, non-bubble, and free of microcrystalline grains (Cristabol i te). In addition, 'high-purity quartz glass film is also a basic component of microchips in the modern micro-electromechanical (Micro-electronics) industry, and even' new-generation wafer processes require that the purity of quartz glass reach 9 9 · 9 9 5%. For traditional amorphous quartz products, even before the production technology has reached a high purity of 9 · 99 · 95%, quartz products have excellent thermal shock resistance (Therma 1 sh 〇ckresistance) and physical and chemical properties. And it is widely used in the electronics industry and the chemical industry. Quartz products can be regarded as a kind of industrial necessities with high economic value. With regard to the manufacturing method of quartz elements, related pre-patent cases are patents such as the Republic of China Announcement No. 4 0 6 1 7 6, No. 2 5 4 9 2 1, No. 3 2 0 6 2 6, No. 440548, etc. Case No. 6381986B1, No. 635587B1, No. 6012304, No. 5385882, No. 5053359, No. 4 7 8 9 3 8 9 No. 4 747 8 6 No. 3, No. 4 5 7 2 7 2 9 No. 4 0 7 248 9 No. 3 8 3 7 8 2 5 No. 3 7 7 5 0 7 7 No. 3 7 6 3 2 9 4 No. 3 5 3 5 8 9 0 etc. … And so on. The traditional methods for making quartz elements mostly use the slurry method (S 1 i p c a s t i n g) or the thermospinning method (R 0 t a t i n g a r c -f u s i ο n m e t h o d). As far as the casting method is concerned, most of the raw materials used are quartz glass powder. After mixing, it is cast into a gypsum mold for molding.

Page 5 565536 Case No. 91123052 Amendment V. Description of the invention (2) The porous quartz is dried and formed within 3 days, and the quartz is damaged and then placed in an induction electric furnace with helium gas for sintering and compaction. The sintering temperature is usually higher than 1720 ° C, and the time is about 6 to 15 minutes. The above are typical manufacturing methods of quartz crucibles in silicon single crystal furnaces used in the current semiconductor industry and large quartz tanks for pickling in semiconductor processes. As far as the thermal spin fusion method is concerned, the quartz slurry is placed in a mold, and the mold containing the quartz slurry is rotated and heated to form the quartz fusion. This method is limited to the production of round tubes or rings. The quartz element is not suitable for manufacturing plate-shaped, tray-shaped or bottomed containers and non-opposed ring-shaped devices. At present, almost all of the quartz crucibles for semiconductor silicon growth are manufactured by the traditional casting method or thermal and spin fusion. Due to process limitations, the quartz crucibles produced by these two methods generally have a quartz purity of 9 9 . Between 9 5% and 9 9. 9 9%, the purity can no longer be improved. Secondly, the traditional casting method uses a porous water-absorbent resin mold or gypsum mold as a dehydration and molding tool. Since the price of the porous water-absorbent resin mold is relatively expensive and affects production costs, there are not many users. Low cost and good water absorption. In the past half century, almost no other materials can replace it as a mold for ceramic and slurry dehydration molding. However, when the semiconductor industry's micro-processing of silicon wafers is gradually moving towards smaller dimensions, The requirements for the purity and accuracy of quartz components are also higher. At this time, using a gypsum mold as a molding medium will produce the following disadvantages: First, the pH value of the slurry (PII value) must be controlled above 7 because the gypsum mold is not suitable for acidity. The environment, for gypsum materials, the best pH value is around 7.5, this limitation will cause restrictions on the particle size and cementation properties of the ultrafine quartz powder. Secondly, when producing high-purity (99.995%) quartz elements, the plaster mold will become a source of contamination for the quartz element, unless the quartz glass is first converted by the plaster mold.

565536

King l 91123052 V. Description of the invention (3) Yingbo! Quartz elements can be manufactured by molds, so that quartz can be avoided. Two :: i ... However, this approach is not very economical. (45. Second, there are insufficient degrees, short service life, high temperature resistance (below 4 50 C), slow drying speed, and other shortcomings. ^ Fat: The main purpose is to provide. Provide a solution to solve the problem The method of the missing Shiyang glass components is to use the casting method (〇e 丄 casting) in combination with non-water-absorbing plastic molds to form high-purity stone 奂 glass elements. 本 This invention: one purpose The purpose is to provide a method for manufacturing a quartz sloped glass element whose manufacturing cost is low. Another aspect of the present invention is to provide _ a kind of quartz glass element manufacturing = its moisture-free drying process 'Net_shape fomming' 旎Li Jia. Another object of the present invention is to provide _., Method, the process time of which is longer than that of the conventional technology quartz glass element. In order to achieve the aforementioned purpose, the glass element manufacturing method includes a method. The invention is to provide a quartz glass blasting sand and pure water; b. Set the quartz slope to a predetermined proportion of high purity stone for a fixed time; c. Mix and grind the pre-dissolved gel with quartz glass sand, pure water sand and pure water ; D · Provision for non-absorbent The material ^ = organic metal is added to the mixture, and the formed mold is subjected to agglutination of the casting mold by hydrolysis reaction to form raw and bad materials; e. Take out the raw and bad silicon-oxygen bond and place quartz glass powder Action and continue for a fixed period of time; f · dry and perform the first stage of low temperature heating and heating operation and become cooked; g. The next stage of the bad and then go to the second stage

The sintered compact heat damage can be obtained at a predetermined time to be sintered at high temperature and continued — ——, quartz components. 565536 MM 91123052

V. Description of the invention (4) In addition, the present invention also provides another method for manufacturing a quartz glass element, firstly preparing a predetermined proportion of an organometallic sol gel, high-purity quartz slope glass, and purifying pure water. After the sol gel is mixed with pure water, add / remove the glass with a mold made of non-water-absorbent material to make a slurry: U The quartz glass is formed by the silicon-oxygen bond formed by the hydrolysis reaction, The drying action of the sand is carried out, and the first stage of low temperature heating and the second stage of medium temperature heating time are performed. 'The badness after the seam is dried is sintered at the first temperature and continues to be scheduled ::: and becomes cooked.' Finally, the cooked is given higher. You can get sintered and compact quartz element products below. Here is a detailed description of the steps of Taifa Sundial + Steps: A preferred embodiment, combined with the drawings to make a simple explanation: Figure 1 is a part of the present invention.鲂 — Figure 2 shows the flow chart of the change-promoting Λ embodiment Λ. The effect of the change diagram, 苴 中, ^ | Zhongli on the mechanical strength of the production process is shown in Figure 3-Erao, quartz glass powder weight is 20g. The effect of change in strength on the weight of two grams of Tf glass powder for the mechanical failure during the manufacturing process The catalyst weight is. Changes in the effect of density ^ The weight of glass powder is relative to the quality of the process. ： · The amount of pain relief is the effect of the change, the relative density of the production and the bad during the process is shown in the sixth series. The stone is the change of the effect of the density gj, t ^ Li Xuzhong is bad for the process. Relative to the seventh series, the change reminder was catalyzed, and the catalytic state weight was 25 g. ——Weight relative density

Page 8 565536 ____ Case No. _ Year Month Revision_ V. Description of the Invention (5) 丨 Jing's change chart, in which the quartz glass powder weighs 20 g. FIG. 8 is a pre-engraved texture (convex) on the surface of the mold used in the present invention. Figure 9 is the texture (concave) of the quartz surface during the process of the invention. FIG. 10 is a thermogravimetric analysis chart for the present invention. FIG. 11 is an analysis chart of the DTA thermal difference of the present invention. Fig. 12 (A) is a microstructure diagram of the green body of the present invention. FIG. 12 (B) is a microstructure diagram of the present invention (Sintering body 850). FIG. 11 (C) is a microstructure view of a finished product (F u s i ο n b 0 d y) of the present invention. First, please refer to FIG. 1. A preferred embodiment of the present invention is a method for manufacturing a 5 glass quartz crystal element including the following steps: ^ First, the first step is to take 9 9 · 9 9% of quartz glass sand and remove Ion pure water is used as raw material. The weight percentage of quartz glass sand and pure water is greater than 80 wt%. The second step is to place the quartz glass sand and pure water in a ball mill tank for ball milling for no more than 36 hours. Mix the raw materials. Grinded into quartz glass sand slurry; the first step is based on the sol-gel (or bismuth alcohol) formed by tetraethy 1 orthosilicate (TE0s). Oxygen fired formation> Valley gel) added to the quartz glass sand and mud polymer 'wherein, [tetraethyloxysilane (TE0s) organometallic additives] / water mole ratio is less than 20;

Page 9 565536 _ tired number 91123052 · MI. .1 V. Description of the invention (6) The fourth step is to add an alcoholic co-solvent (MUTUAL SOLVENT) with the same amount of TEOS as the raw material. , And the right amount = catalyst. 1 King ^ The fifth step is to prepare a branch made of non-porous (non-absorbent) material, such as a plastic mold, to perform the casting action. Tetraethyl ethoxysilane (TE0S) organometallic sol gel can be used. · Quartz glass sand mud in the mold = hydrolysis reaction, and then polymerization reaction occurs to form inorganic high-scoring 'zijuren j 丄 俾 application of the stone Xi oxygen bond to glue the quartz glass sand powder: 广 上The previously exposed bad powders are chemically bonded and supplemented by physical bonds such as lice keys and van der Waals, and the plastic material can be polyethylene #, or polycarbonate plastics; and so on; The six steps are to take out the raw materials and put them in an oven, and keep the temperature below 1 20t and keep the temperature for 4 hours. The temperature is gradually increased. The seventh step is to dry the raw materials after the drying process. No square; thermal resistance mine room φ green wall temperature to 85 (TC and maintain the temperature for 2-3 hours, 俾 will be ancient ^……… Friends & rise and become burned; " Mou organic matter does At the end of the oxidation elimination, the cooked simmered meat is placed in a high, small amount of water vapor to rise to the furnace I in 20 minutes, and the Gas, bell, and cymbal perform high-temperature sintering. With the help of the temperature, the temperature of 10-25 minutes is reduced by 4 minutes. 4: — "Sintered dense Shiyang glass components can be obtained. This example is a quartz crucible. The physical, chemical, and chemical properties of the present invention are as follows: The physical and chemical properties of Hanbiao ° are divided into one, and the mechanical strength is measured as shown in the following figure: Tian 〶A, soil ρ, n 疋 enough bath gel [butyl EOS / MTMS (methyl dimethyl lactyl guanyl guanidine) = 0. 2 ~ 0.3 of __ Wu Dou percentage ratio mixing, mixing 11111 1 1 Μι " " '1 __ m p.565565 __ Case No. 91123052_ ^ 年月 月 __ V. Description of the invention (7) The liquid mixture is mixed with deionized pure water at a molar ratio of about 1: 1 to 1.6 ] Add 20 g of quartz glass powder to complete wetting, then fix the amount of sol and powder, change the amount of alkaline catalyst (DMA, DI-METHY AMIUE, dimethyl ammonium), increase in equal proportions, (0.06g , 0.125g, 0.25g,

0.5 g, 1 g), to test the effect of alkaline catalysts on the strength of failure. The experimental results show that when the catalyst [dimethylammonium (DMA)] is increased by 1 g, the mechanical strength of the raw materials is the highest, but the raw materials are severely deformed (bent), and the surface is cracked, which does not meet the quality, and the catalyst (DMA) is added. At 0 · 125g, the mechanical strength of the raw material is the second, and the surface of the raw material is smooth, without cracks, and without bending. Measurement of relative density of birth and death: The test method is the Archimedes method with mercury as the medium. The birth and death are cut into test pieces of about 1 cm X 1 cm, put into mercury, and then the test pieces are pressed in with a lifter. Density of raw and bad measured in mercury, relative density of raw and bad = raw and bad density + theoretical density of silica sand (2 · 65g / cm 3) X 100%, fixed gel and powder weight, changing the ratio of catalyst can be obtained as The results shown in Figure 4, if the weight of the gel and catalyst (DMA0. 1 25g) is fixed and the powder weight is changed, the results shown in Figure 5 can be obtained.

3. Relative density measurement of plains: Put plains in a beaker with a metal net at the bottom, and isolate the plains and beakers, add distilled water, the water surface should be at least 3cm above the plains, heat to boiling for 2 hours, and then cool to Room temperature. The apparent density (density value without open pores) test method is Archimedes method with water as the medium. The test results are as follows

Page 11 565536 _ Case No. 91123052_ Year month _ί ± ^ _ V. Description of the invention (8) Figures 6 and 7 are shown. 4. Microstructure replication: In order to investigate whether the bad body made by the gel casting method has the ability to reproduce surface engraving, a mold with embossed characters printed on the surface was used for reproduction and observed with an optical microscope. As shown in Fig. 8 and Fig. 9, it shows the original text and the reprinted text on the quartz. The experimental results show that the gel casting method can make fine engravings. 5. Detection of thermal analysis: As shown in Figure 10, during the manufacturing process, the weight loss (wt%) starts to show a smooth straight line phenomenon (that is, the weight remains the same) after the temperature is 800 ° C. The experimental results show that the weight loss is 0 5%, as shown in Figure 11, when the temperature is about 800 ° C, the endothermic reaction also occurs. The experimental results show that the catalyst (DM A) can be completely removed by burning the raw and bad elements to 850 ° C. The main purpose is to improve the yield of the quartz glass element, so as to shorten the manufacturing process by rapid sintering. 6. Scanning Electron Microscopy (SEM) Analysis: The scanning electron microscope (SEM) is used to observe the damage, failure, and surface structure of the finished product at each stage of the invention. From Figure 12 (A), the powder particles can be clearly seen. Only when they are in contact with each other, it is known through density measurement experiments that the relative density at this stage can reach 5 5 ~ 6 5% '. From Fig. 12 (B), it can be found that the pore space is gradually reduced and the grains have gradually grown. After sintering at this stage, a relative density of 95 to 97% can be reached. It can be clearly seen from Fig. 12 (C) that the surface of the quartz crucible has been completely dense.

Page 12 565536

Page 13 565536 Case No. 91123052 Date of Amendment V. Description of the Invention (10), of course, the problem of contamination of quartz glass components caused by the use of gypsum molds in the traditional casting slurry method will not occur. Secondly, the design and production of non-porous (non-absorbent) plastic molds can be applied to the capabilities of the existing domestic plastic mold industry. Therefore, compared with the conventional technology, the present invention can greatly reduce the injection mold for manufacturing quartz glass products. Difficulty and cost. 4. When the average particle size of the quartz sand is about 10 microns, the density of birth and failure of the present invention can reach 60%. This density is related to the particle size of the quartz powder used. If submicron quartz powder is used in the present invention, The density of births and deaths will increase even more. Secondly, the surface of the bad and the bad in the process of the present invention is smooth and can be used for the micro-grain engraving. If the present invention uses the sub-micron quartz powder, it can be used for the optical-grade glass element. 5. In the production method of the present invention, the pure water system added to the quartz glass sand slurry is used as a reactant and not as a solvent. Water molecules are consumed in the hydrolysis reaction and the polymerization reaction. Therefore, the bad body of the present invention does not contain water after molding. This feature is different from the conventional manufacturing method. 6. In the process of the present invention, the polymerization reaction will form a bad product after the completion. The bad product will not adhere to the mold, can be easily demoulded, and can completely reproduce the pattern lines in the mold. 7. The process of the present invention without water drying In the process of alcohol evaporation, it will only cause a shrinkage of less than 2%. Compared with the traditional casting method, moisture shrinkage will cause a shrinkage of 10 -1 5%. Obviously, the invention has excellent Net-shape forming ability. 8. According to the present invention, the quartz powder system can be successfully demoulded within 8 hours from the completion of the reaction and the mold can be successfully demoulded; and the quartz powder can be pulped, reacted, shaped, demoulded, dried, and burned to All processes such as sintering and compacting can be performed in

Page 14 565536 _case number 91123052_ year month day__ V. Description of the invention (11) It can be completed within 4 hours. The speed of making quartz glass and components is faster than the traditional casting method. In summary, the manufacturing method of the quartz glass element provided by the present invention uses an organic metal sol gel as a binding agent for the quartz powder, a gel casting method (G e 1 casti η g), and non-absorbency. The mold can quickly consolidate the quartz powder, and can produce high-purity stone and glass components, which have the effects of low mold cost and good net-shape forming ability; the reason is that the present invention does meet the invention patent Requirements, apply in accordance with the law.

Page 15 565536 ^ _ Case No. 91123052 • Year Month Day _ifi_ Schematic: Brief description Figure 1 is a flow chart of a preferred embodiment of the present invention. Figure 2 is a graph showing the effect of changing the catalyst weight on the mechanical strength during the process. The weight of the quartz glass powder is 20 g. Figure 3 is a graph showing the effect of changing the weight of quartz glass and glass powder on the mechanical strength of the process. The catalyst weight is 20 g. Figure 4 is a graph showing the effect of changing the weight of the quartz glass powder on the relative density of the raw materials in the manufacturing process, in which the catalyst weight is 0.1 2 5g. Figure 5 is a graph showing the effect of changing the catalyst weight on the relative density of production and failure in the manufacturing process, in which the weight of the quartz glass powder is 20 g. Fig. 6 is a graph showing the effect of changing the weight of the quartz glass powder on the relative density of the sulfonate in the manufacturing process, wherein the catalyst weight is 0.1 2 5 g. Figure 7 is a graph showing the effect of changing the catalyst weight on the relative density of sulfonate in the manufacturing process, in which the weight of quartz glass powder is 20 g. FIG. 8 is a pre-engraved texture (convex) on the surface of the mold used in the present invention. Figure 9 is the texture (concave) of the quartz surface during the process of the invention. FIG. 10 is a thermogravimetric analysis chart for the present invention. FIG. 11 is an analysis chart of the DTA thermal difference of the present invention. FIG. 12 (A) is a microstructure diagram of the present invention (G r e n b o d y). Fig. 12 (B) is a microstructure diagram of a plain body (Sintering body 850 ° C) of the present invention. Fig. 12 (C) is a microstructure diagram of a product of the present invention (F u s i ο n b 0 (i y)).

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Claims (1)

565536 __Case No. 91123052_year month__ Sixth, the scope of application for patents lyogel. 8. According to the manufacturing method described in item 1 of the scope of patent application, in step d), the non-absorbent material refers to a plastic material. 9. According to the manufacturing method described in item '8 of the scope of the patent application, the plastic material may be polyethylene, polypropylene or polycarbonate resin and other commonly used plastics. 10. According to the manufacturing method described in item 1 of the scope of the patent application, in step d), when the organometallic sol gel is mixed with the quartz glass sand mud, a hydrolysis reaction occurs, and a polymerization reaction occurs after the hydrolysis reaction to form an inorganic polymer polymerization. Quartz sand powder is bonded with silicon-oxygen bond formed by the formation of silicon oxide, which causes the formation of failure. 1 1. According to the manufacturing method described in item 1 of the scope of patent application, in step e), drying in an oven and gradually increasing the temperature from room temperature to below 120 ° C. 1 2. According to the manufacturing method described in item 1 of the scope of the patent application, in step f), the raw materials are slowly heated to 850 ° C in a thermal resistance electric kiln and held at a temperature of 2 to 3 hours. The organics are indeed oxidized and eliminated. .1 3. According to the manufacturing method described in item 1 of the scope of the patent application, wherein in step g), the ripening is placed in a high-temperature rapid 'furnace, and helium and a small amount of water vapor are passed in and heated to 1 in 20 minutes. Above 50 0 ° C and holding temperature for 10-2 5 minutes, the sintering operation is performed at high temperature. 1, 4 · According to the production method described in the scope of the patent application No. 6, wherein in step c), the [tetraethyloxysilane (TEOS) organic metal additive] / mole ratio of water should be less than 2.0. ί 5 · According to the manufacturing method described in item (2) of the scope of patent application, the shrinkage rate of birth and failure is less than 2%. 565536 ____ Case No. 91123052 _ month and year _iLL · _ VI. Application scope of patents. 1 6, — A method for manufacturing quartz glass elements, which is prepared by preparing a predetermined proportion of organometallic sol gel, high purity quartz glass sand and Water, first mix the organometallic sol gel with pure water, then add quartz glass sand, prepare a mold made of non-water-absorptive material for casting, and then hydrolyze the formed silicon oxygen Bonding glues the quartz glass sand powder to form the raw material, and then removes the raw material, and performs the first stage, low-temperature heating and drying action for a predetermined period of time, and then returns the dried raw material to the second stage of medium temperature heating. The firing action becomes maturity, and finally the maturity is sintered at high temperature for a predetermined time to obtain a sintered compact quartz element product. 1 7. According to the manufacturing method described in item 1 or 16 of the scope of the patent application, a co-solvent (MUTUAL SOLVENT) with an amount equal to the amount of the organometallic sol-gel is further added. 1 8. The method according to item 17 of the scope of the patent application, wherein the co-solvent is an alcohol. 19. According to the manufacturing method described in item 1 or 16 of the scope of the patent application, a basic catalyst is further added. Page 19