TW568885B - Mesoporous silica film from a solution containing a surfactant and methods of making same - Google Patents

Abstract

The present invention is a mesoporous silica film having a low dielectric constant and method of making having the steps of combining a surfactant in a silica precursor solution, spin-coating a film from this solution mixture, forming a partially hydroxylated mesoporous film, and dehydroxylating the hydroxylated film to obtain the mesoporous film. It is advantageous that the small polyoxyethylene ether surfactants used in spin-coated films as described in the present invention will result in fine pores smaller on average than about 20 nm. The resulting mesoporous film has a dielectric constant less than 3, which is stable in moist air with a specific humidity. The present invention provides a method for superior control of film thickness and thickness uniformity over a coated wafer, and films with low dielectric constant. The present invention is a method of dehydroxylating a silica surface that is hydroxylated having the steps of exposing the silica surface separately to a silicon organic compound and a dehydroxylating gas. Exposure to the silicon organic compound can be in liquid, gas or solution phase, and exposure to a dehydroxylating gas is typically at elevated temperatures. In one embodiment, the improvement of the dehydroxylation procedure is the repetition of the soaking and dehydroxylating gas exposure. In another embodiment, the improvement is the use of an inert gas that is substantially free of hydrogen. In yet another embodiment, the present invention is the combination of the two-step dehydroxylation method with a surfactant templating method of making a mesoporous film.

Description

568885 A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (1) This invention is supported by the government of DE-AC0676RLO183 (^ awarded by the US Department of Energy. Comparative references for related inventions. This application is requested from Application No. 09 / 220,882 (application dated December 23, 1998), 09 / 335,210 (application dated June 17, 1999), 09 / 361,499 (application dated July 23, 1999) And the priority of case No. 09 / 222,569 (filed on December 28, 1998). This application is filed under the serial number of 09 / 361,499 (filed on July 23, 1999, and is currently being applied for.) 〇9 / 335,210 (part of the application on June 17, 1999, pending trial, which is part of the application serial number 09 / 220,882 (December 23, 1998, now abandoned) continues to apply for part of) Part of the application) Continue the application. Field of the Invention The present invention relates generally to porous silica films with nanometer specifications prepared from solution precursors. More specifically, the present invention relates to self-contained surfactants ( Porous dioxide in solution Membranes, and porosity using a special surfactant in a stencil with a special pore size defined by the size of the micelle of the surfactant. The present invention also relates to the use of a combination with a porous silicon dioxide film in a surfactant plate Dehydroxylation to obtain a dielectric constant of less than 3 under ambient humidity conditions. As used herein, the term "silicon dioxide" refers to compounds having silicon (Si) and oxygen (0) and possibly other elements. Moreover, the term "mesoporosity" as used herein refers to a size range greater than 1 nm (but obviously less than micrometers). Generally, this most commonly refers to the application of Chinese National Standard (CNS) A4 just beyond the paper size. Specifications (210 X 297 mm) -------------- tf— ^ ------- (Please read the notes on the back before filling this page) 4 Intellectual Property of the Ministry of Economic Affairs Bureau Consumer Consumption Cooperative System 568885 Α7 ~ ----- B7 V. Description of the invention (2) 1.0nm (10 Angstroms) to tens of nanometers. The term "stability" means absolute stability. Relative stability Or a mixture thereof. Relative stability refers to the relative porosity of the surfactant film from 0 0 / / relative The dielectric constant when the equilibrium condition of degree or vacuum to 50% relative humidity is obtained does not increase by more than about 20%. Absolute stability refers to the dielectric constant under any conditions including humidity conditions of at least 40% relative humidity Keep less than 3. The term "basified" includes partial and complete hydroxylation. The term "basified" includes the surface of the porous silicon dioxide film in the surfactant plate Background of the Invention Porous silicon dioxide films are potentially used as low dielectric constant intermetallic materials, fibers, and other structures for semiconductor devices as low dielectric constant coatings and in catalyst supports. Most of the US semiconductor industry today (1998) is a method of implementing dielectric films between levels, which are silicon dioxide films or derivatives of dream dioxide and fragmented acid salts, or polymer films. Less than 25% porous or non-porous and a dielectric constant (κ) in the range of 3.0 to 4.0. Further reduction of the dielectric constant is expected to improve the operating speed of the semiconductor device, reduce the gravity consumption of the semiconductor device, and reduce the overall cost of the semiconductor device (by reducing the number of metallization levels required). Since air has a dielectric constant of 1.0, introducing porosity is an effective way to reduce the dielectric constant of the film. In addition, because the dielectric substance of the second ginseng oxide has been a standard substance in semiconductor devices, the porous dioxide film is attractive to the semiconductor industry for advanced devices requiring low dielectric constant materials. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). Μ -------- ^ --------- ^ (Please read the notes on the back before filling (This page) 568885 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (3) The characteristic dimensions and design rules of the semiconductor interconnects are sub-150nm within the oversized whole; and the dielectric constant is reduced The hole size of (k < 3) needs to be significantly smaller than the interval between metals. The dielectric constant of a porous membrane depends on the material and pore structure. For a porous silicon dioxide film used in microelectronic devices, the material and hole structure need to be formed with a uniform dielectric constant in the lateral direction of the wafer and in different directions on the wafer. Generally, compared to anisotropic materials and pore structures, isotropic materials and pore structures are worshipped to provide the desired uniformity of the dielectric constant of the film. Furthermore, the low dielectric constant mesoporous films used commercially need to be prepared in a manner compatible with the production line of the semiconductor device manufacturing method, for example, spin coating. For large-area round wafers, other coating techniques (such as immersion coating) are inconvenient because immersion coating requires covering the backside to avoid contamination. Surface topography is also very important for preparing multi-level interconnected structures. For the "patterned" method of integrated copper interconnects to be used on semiconductor wafers of oversize, each dielectric layer is etched, after which copper is deposited, and the structure is chemically and mechanically polished (CMP) planarization. The initial planarization of the low-k interface film lacks a surface texture that is textured at each level of the interconnect. It is important to maintain planarization. Another important consideration for porous dielectric films is mechanical integrity ^ because Its brittleness, it seems impossible to make the porous membrane directly polished using a traditional chemical mechanical polishing (CMP) device, but the dense silicon dioxide or other materials on the porous low-k film can be planarized. . However, even with interstitial layers, porous low-k materials need to have appropriate toughness, compression, and shear strength. This paper is sized to the Chinese National Standard (CNS) A4 (210 x 297 mm) ------- ;. ----- Equipment -------- tli ^ ------- (Please read the note on the back? Matters before filling out this page) 568885 Employee Cooperative Cooperative System A7 B7 5. Description of the invention (4) to resist the stress related to the CMP method. Porous silica films with nanometer size (or mesoporosity) can be made from solution precursors, and can be divided into two types (1) "aerogels or xerogels. Glue / xerogel), where random or irregular pores are introduced by the controlled removal of alcohol-type solvents, and (2) "Mesoporous, a surfactant-type plate-type silicon dioxide film, in which the pores are Formed holes by removing the surfactant. So far, the number of low-dielectric-constant silicon dioxide films with a dielectric constant of 3.0 or lower has successfully proven to be aerogel / xerogel type. Porous silica film. However, the disadvantages of aerogel / xerogel film include: (1) the deposition of aerogel / xerogel requires careful control of the removal of the alcohol used to form the pore structure (for example, in Maintain a controlled atmosphere containing solvents or gelling agents during preparation), (2) the smallest possible pore size typically in an aerogel / xerogel film falls in the range of 10-100 nm, and (3) Limited mechanical strength compared to dense silica films. These shortcomings have prevented these aerogels / The gel's porous silicon dioxide film is applied to semiconductor devices. In order to obtain a porous film with low dielectric constant of any phase material by any method, it is necessary to reduce the number of hydroxyl groups in the structure, especially in the pore structure. The film needs to be 'hydrophobic' in order to stabilize the dielectric properties in humid air. The hydroxylated surface in the porous silicon dioxide film causes a dielectric constant that exceeds that of the dense silicon dioxide (ie, about 4.0). By hydroxylation Physical adsorption of water molecules on the surface can further increase the dielectric constant and effective capacitance of the mesoporous dioxide film. Physical adsorption of water molecules can be caused by processing the membrane in a non-humid atmosphere or in a vacuum or by exposing the membrane Minimize and avoid in humid conditions. Hydroxyl and physically adsorbed water molecules can self-dioxide at high temperature. This paper is sized to Chinese National Standard (CNS) A4 (210 X 297 mm) ---- ---- ^ -------- ^ --- I ----- line (Please read the precautions on the back before filling this page) 7 568885 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs B7 V. Description of the invention (5) Surface In addition .C. J. Brinker and G. W. Scherer in Sol science,

Academic Press, New York, NY (199) (Brinker et al., 1990) explores the thermal dehydroxylation of silicon dioxide by exposure to very high temperatures in excess of 8001 :. However, semiconductor devices with dielectric films and metal wires cannot generally be processed at temperatures exceeding about 500 ° C. Therefore, the central dehydroxylation method is necessary for the porous silicon dioxide film of semiconductors. EF · Vansant, P. Van de Voort and KC Vrancken on the properties and chemical modification of silica surface, Volume 93, Surface Science and Catalyst Research, Elsevier, New York, NY (1995) and Brinker et al., 1990, describes the procedure of hydroxylation of the surface of silicon dioxide by fluorination or treatment with a silane solution. Aerogel / xerogel-type membranes have been treated by (about fluorination treatment, and (b) a two-step dehydroxylation method (which includes (1) a starting sintered silica solution (eg, the top three in a solvent) Chlorochlorosilane (HMDS)) and (2) are treated in this solution and then treated in a hydrogen-containing gas (for example, '10% hydrogen in nitrogen), which is at a moderate high temperature of 300-450 ° C as ) And debasing. Silane / forming gas (H2 in N2) treatment is discussed in U.S. Patent No. 5,504,042 and Smith and other related patents mentioned by colleagues. In the surface active agent plate film The pores form a regular (hexagonal) array with a special pore size defined by the size of the surfactant micelles. The interfacial slab path can be controlled by the nature of the surfactant and its interaction with the sulphur dioxide species Porosity, pore size and pore shape. For the pores of the degree of harmony, the control of the pore size and style and structure on the pore wall can also cause good mechanical properties. More particularly, the smaller and uniform size of this paper is applicable. Chinese national standard (CNS) A4 specification (210 X 297 mm) --- 丨 丨 1: -----% loading ------ rl ^ i ^ ---- —4 (Please read the precautions on the back first (Fill in this page again) 568885 A7 ______B7 V. Description of the invention (6) The pores can give larger and uneven pores better mechanical properties. Although easier to prepare (not necessary for forming a controlled atmosphere of porosity), mesopores Sex World --- --- (Please read the precautions on the back before filling out this page) Surfactant-type plate-type silicon dioxide film has not been proven to have low media Electrical constant 0 * U.S. Patent Application No. 08 / 921,754 (08/26/97, Bminsma et al., Now U.S. Patent No. 5,922,299) describes the preparation of porous interfacial activity with regular pores by spin coating Dosage plate type dioxide film. The surfactant used is a cationic ammonium-based surfactant. The goal of this operation is a low dielectric constant inner layer in a microelectronic device. US Pat. (People) also reported a dip coating method for preparing a plate type mesoporous dioxide film with a regular hole and a surfactant. Among them, the surfactant used is also a recording-based surfactant. Brinker et al. Used a mercury point electrode on the membrane to measure the dielectric constant, and the reported dielectric constant value was 2.37. Line · > Ministry of Economic Affairs Wisdom Produced by the Consumer Cooperative of the Bureau of Property Bureau. However, the surfactant type plate type mesoporous dioxide film prepared with ammonium surfactant and tested after thermal decomposition (thermal removal) of the surfactant has been found in general semiconductors. Moisture absorption under ambient conditions of device preparation and operating conditions. No dehydroxylation step was reported in Bruinsma et al. Or Brinker et al. Paper on Continuous Mesoporous Silica Films with High Regularity and Large Hole Structure (D. Zhao, P. Yang, N. Melosh, J. Feng, BF Chmelka and GD Stucky, Advanced Materials, Volume 10, 16 No. 1998, pages 1380-13 (85)) explores the application of di-silicone-containing poly (alkylene oxide) triblock copolymers and low-molecular-weight alkyl groups based on silicon dioxide by dip coating Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 568885 Printed by A7 ____B7__, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs V. Explanation of the invention (7) (ethylene oxide) surfactant solution in the membrane A directional or regular large hole structure is formed inside. Low dielectric constants (1.45-2.1) were reported in these films measured after the sintered films. However, the disadvantage of regular holes (for example, hexagonal holes) is the uncertainty of the uniformity of the dielectric constant in different directions on a large wafer. Furthermore, the procedure for dehydroxylation (which is used to maintain a low dielectric constant) has not been reported in the paper by Zhao et al. Therefore, there is a need for a surfactant-type mesoporous silicon dioxide film and a method for preparing the same, which provide a dielectric constant of less than 3, and which meets (but is not limited to) film thickness control and thickness uniformity. Engineering requirements for sentence structure, minimal surface texture and mechanical integrity. The dielectric constant needs to be relatively stable under normal operating conditions including humidity at room temperature, and it must be uniform on a large crystal circle. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a surfactant-type plate-type mesoporous silicon dioxide film, which has properties including (but not limited to) a dielectric constant of less than 3, A film thickness of about 1.5 μm, a film thickness standard deviation less than or equal to +/- 5% standard deviation, an average pore size less than about 20 nm, a low dielectric constant, and combinations thereof. The present invention includes a method for preparing a mesoporous membrane with a surfactant pattern, which has the same serial number as No. 08 / 921,754 (now US Patent No. 5,922,299), the name of the invention, and Porous silica film, fiber, and powder through burst "). Therefore, the present invention is a method for preparing a mesoporous dioxide shatter film, which has the steps of: Silicon oxide precursor solution mixed, spin-coated film, this paper size is applicable to China National Standard (CNS) A4 specification (210 X 297) ^ K ------- (Please read the precautions on the back before filling out this page) 10 568885 A7 _ B7 V. Description of the invention (8) -------------- pack- -(Please read the precautions on the back before filling this page) The membrane is heated to remove the surfactant to form a mesoporous membrane, which is at least partially hydroxylated, and the membrane is hydroxylated. Dehydroxylation to obtain a mesoporous boat. According to the present invention, the choice of the surfactant, the concentration of the components of the silica precursor solution, and their mixture Provide a film having one or more of the characteristics described above. The advantage of a low dielectric constant (k < 3) that is stable under ambient moisture conditions is achieved in accordance with the present invention in conjunction with dehydroxylation, which is included in the electron group Partial or complete removal of hydroxyl groups at temperatures within part of the processing temperature. During dehydroxylation, the radicals can be hydrophobic groups (such as organic Alkyl, siloxane (_ Si-0-Si-) bonding or a mixture of them). Thread · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The surfactant of the coated mesoporous plate type mesoporous membrane will cause fine pores of less than about 20nm. In the most common, the average pore size can be trimmed to about 1 to about 20nm by the surfactant. This pore Desirable in a dielectric film in a size range between horizontal layers that separates metallized circuits in a semiconductor device to minimize diffusion of metal species during repeated heat treatments. Further advantages of the present invention Including its better control of film thickness and control of thickness uniformity of coated wafers, films with low dielectric constant (ie, stable) and irregular holes (which increase the media in different directions on large wafers) Confidence in the uniformity of the electrical constant). A further object of the present invention is to provide a method for dehydroxylation of a hydroxylated silicon dioxide surface to obtain a low dielectric constant. A further object of the present invention is to provide mesoporosity Silicon dioxide film This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 issued) 11 Printed clothing of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 568885 A7 _ B7 V. Method of Invention (9) Spin coating technology resulting in low dielectric constant and no need for atmosphere control. These methods of preparing a mesoporous silicon dioxide film further provide better control film thickness and an average pore diameter of less than 5nm. The present invention is different from the aerogel method by using a special surfactant molecule to homogenize the pores of the spin-coated film. Therefore, the present invention further provides the dehydroxylation effect of the surface of the oxidized silica, which has the steps of: exposing the surface of the oxidized silica individually to a silicon organic compound and a dehydroxylated gas. This silicon organic compound can be a liquid, gas, or solution phase, and exposure to dehydroxylation typically results from elevated temperatures. The present invention has the advantage of providing a mesoporous film of a silicon dioxide material with a low dielectric constant which is stable for a long time. A further advantage of the present invention is that it potentially includes improved safety and lower costs when applied in large formats. In one embodiment, the improvement of the dehydroxylation process is repeated impregnation and exposure of the dehydroxylation gas. In another embodiment, the improvement lies in the use of an inert gas that is substantially free of hydrogen. In another embodiment, the present invention is a combination of a two-step dehydroxylation method and an interfacial active agent type plate method for preparing a mesoporous membrane. The method for preparing a mesoporous silicon dioxide film has the general steps described in the joint application No. 08 / 921,754, which is hereby incorporated by reference, that is, combining a surfactant in a silicon dioxide precursor solution Spin coating a film, and heating the film to remove a surfactant to form a mesoporous film that is at least partially hydroxylated, and dehydroxylating the hydroxylated film to obtain a mesoporous film . According to the present invention, the improvement includes the two steps of dehydroxylation to make the hydroxylated film covered by this paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). * ------- • Order ------ I-- < Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 568885 A7 B7 V. Description of Invention (1G) Dehydroxylation, which is to individually expose the hydroxylated film to a silicon organic compound and a dehydroxylated gas to obtain a mesoporous film with a low dielectric constant. Further improvements are implemented in any of the above embodiments by using a polyoxyethylene ether compound as a surfactant. Advantages are small polyoxyethylene surfactants used in spin-coated films according to the present invention, which can form fine pores of less than about 5 nm. The most common is that the average pore diameter can be trimmed to a size range of about 2 to about 5 nm by a surfactant. This average hole diameter is desirable for a horizontal interlayer dielectric film of a metallized line within a separated semiconductor device, which minimizes the diffusion of metal species during repeated thermal processing. These small polyoxyethylene ether surfactants are different from surfactants used to make large polyoxyalkylene-based oxide "block copolymers" with pores larger than 511111. Further advantages of the present invention include a method that provides better film thickness control and thickness uniformity of coated wafers, films with low dielectric constant, and spin coating technology that does not require atmosphere control. The subject matter of the present invention is specified and explicitly stated in the conclusion section of the specification. However, the structure and operation method and its further advantages and purposes can be understood by referring to the following description in conjunction with the drawings, where similar reference letters refer to similar elements. The figure briefly illustrates that the first figure shows the pores of the membrane as a function of the surfactant / TE 0 S mole ratio in the spin coating solution containing polyoxyethylene ether surfactant, which is based on CXE01 〇 polyoxygen It is determined by the analysis of the nuclear reaction of the Ethylene surfactant series. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---------- t -----— — — — — (Please read the notes on the back before (Fill in this page) 13 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives 568885 A7 V. Description of the invention (11) Figure 2 shows the function of the dehydroxylation procedure prepared with c ^ EOw polyoxyethylene ethyl surfactant Dielectric constant of mesoporous membranes slabbed with surfactants (measured at room temperature under ambient conditions of humid air). Figure 3 shows the dielectric constant of a porous membrane with a polyoxyethylene ethyl ether surfactant as a function of the dehydroxylation procedure (measured at room temperature under ambient conditions of humid air). ). Figure 4a shows the low-angle heart-ray spectrum of a mesoporous silica prepared with c ^ EOw polyoxyethylene ether surfactant. The x-ray beam follows the radial direction of the circular wafer. Figure 4V > shows the low-angle x-ray spectrum of a mesoporous silicon dioxide film prepared with a C ^ EOio polyoxyethylene ether surfactant. The x-ray beam ^ is along the tangent direction of a circular wafer. Figure 5 is an electron transmission microphase showing the microstructure of a mesoporous silica film prepared with a Ci2Eio polyoxyethylene ether surfactant. Figure 6a shows the surface profile of a mesoporous silica film prepared with (^ # 0 ^ polyoxyethylene ether surfactant). Figure 6b shows C! 2EO! 〇 polyoxyethylene Surface distribution curve of mesoporous silicon dioxide film prepared by a surfactant. Fig. 7 is a graph of the elastic modulus of mesoporous silicon dioxide film measured with slight nicks as a function of the engraved load. Figure 8a is a low-angle X-ray diffraction spectrum of a mesoporous silica film prepared with a C ^ EOw polyoxyethylene ether surfactant. The mole ratio of the surfactant / TEOS is 〇 9. 9. X · The ray beam is along the radial direction of the circular wafer. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----------------- --Order ---: ------- (Please read the notes on the back before filling this page) 14 568885 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, made A7 B7 V. Description of Invention (12) Article Figure 8a is a low-angle X-ray diffraction line diffraction spectrum of a mesoporous silica film prepared with C ^ EOio polyoxyethylene surfactant. The mole ratio of surfactant / TEOS is 0.19.X - The line beam is along the tangential direction of the circular wafer. Figure 9a shows the low-angle x-ray diffraction spectrum of the mesoporous silicon dioxide film prepared by aC ^ EOio polyoxyethylene ether surfactant. Interface activity The mole ratio of the agent / TEOS is 0.30. The X-ray beam is along the radial direction of the circular wafer. Figure 9b shows the preparation of mesoporous silica with C ^ EOw polyoxyethylene ether surfactant. The low-angle X-ray diffraction spectrum of the film. The mole ratio of the interfacial cleaner / TEOS is 0.30. The X-ray beam is along the tangential direction of a circular wafer. Figure 10a shows < 314〇10 and Low-angle χ · ray diffraction spectrum of mesoporous silica film prepared by C ^ EO * polyoxyethylene scale surfactant. Molar ratio of total surfactant / TEOS is 0.20.X · The ray beam is along the radial direction of the circular wafer. Figure 10b shows the low-angle ray diffraction spectrum of the mesoporous silicon dioxide film prepared with C ^ EOio and Ci2E04 polyoxyethylene surfactants. The molar ratio of total surfactant / TEOS is 0.20. The X-ray beam is along the tangential direction of a circular wafer. Figure 11a shows the C ^ E Low-angle X-ray diffraction spectrum of mesoporous silica film prepared by Ow's polyoxyethylene ether surfactant. Molar ratio of surfactant / TEOS is 0.20. X-ray beam is along the circle The shape of the wafer is radial. This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) ----- I ----- ------ line (please read the notes on the back before filling out this page) 15 568885 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13) The first lb picture is shown in C ^ EOio Low-Angle X-Ray Diffraction Spectra of Polyporous Ethyl Ether Surfactants from Mesoporous Silica Films. The molar ratio of surfactant / TEOS is 0.20. The X-ray beam is tangential to the circular crystal circle. Figure 12a shows the low-angle x-ray diffraction spectrum of a mesoporous silica film prepared with c ^ EOw polyoxyethylene ether surfactant. The molar ratio of surfactant / TEOS is 0.20. The X-ray beam follows the radial direction of the circular crystal circle. Fig. 12b shows the low-angle ray diffraction spectrum of a mesoporous dioxide film prepared with a polyoxyethylene ether surfactant of CuE01 (). The molar ratio of surfactant / TEOS is 0.20. The X-ray beam is tangential to the circular crystal circle. Fig. 12c shows a low-angle x-ray diffraction spectrum of a mesoporous silicon dioxide film prepared with a polyoxyethylene ether surfactant of C ^ EOw. The molar ratio of surfactant / TEOS is 0.20. The X-ray beam follows the radial direction of the circular crystal circle. The scanning area is located approximately 90 ° (rotated) from the scanning area in Figures 12a and b. Fig. 12d shows a low-angle ray diffraction spectrum of a mesoporous oxide oxide film prepared with a polyoxyethylene ether surfactant of C18EO10. Molar ratio of surfactant / TEOS is 0.20. The X-ray beam is tangential to the circular crystal circle. The scanned area is approximately 90 in the scanned area in Figures 12a and b. (Rotating). Figure 13 is a plot of various medium porosity materials. The dielectric constant of the material is plotted against time. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 16 --- II ------ % Equipment ------- 1 · "1 * ------- (Please read the notes on the back before filling out this page) 568885 Employee Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs • Cooperative“ P system A7 B7 Five (14) Description of the preferred embodiment The present invention is a mesoporous silica film (surfactant-type plated mesoporous silica film) prepared from a solution containing a surfactant, which has The property includes (but is not limited to) a dielectric constant of less than 3, a film thickness of about 0.ium to about 1.5um (also about 0.2um to about 1.5um), less than or equal to + " 5% standard The standard deviation of the deviation of the film thickness is less than about 20 nm (more preferably less than about 10 nm, and most preferably less than about 5 nm) the average pore size, regular or irregular pores, and combinations thereof. According to the present invention, the porosity is more than 30%, preferably more than 40%, and more preferably more than 5000/0. The invention includes a method for preparing a mesoporous silicon dioxide film, which forms a hydroxylated film by stenciling and spin-coating a silicon dioxide precursor solution containing a surfactant, as described in the joint application 08 / The same general procedure described in the case No. 921,754, which is incorporated herein by reference, is then subjected to chemical debasing to form a mesoporous dioxide film. Therefore, the present invention is a method for preparing a mesoporous silicon dioxide film, which has the steps of combining a surfactant in a silicon dioxide precursor solution, forming a film by spin coating, and heat-treating the film to remove the interface. An active agent, and forming a hydroxylated mesoporous film, and chemically dehydroxylating the hydroxylated film to obtain a mesoporous dioxide film having a low dielectric constant. The silica precursor solution includes a silica precursor, an aqueous solution, a catalyst, and a surfactant. The film is spin-coated with a mixture of a silica precursor solution and a surfactant. Thereafter, the aqueous solvent, catalyst, and surfactant are removed by heating to form a hydroxylated mesoporous silica film. The hydroxylated film is chemically dehydroxylated to form a paper with a low paper size. Applicable to China National Standard (CNS) A4 (210 X 297 meals) ^ -------- ^ ----- ---- ^ (Please read the precautions on the back before filling out this page) 17 568885 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (15) Mesoporous silicon dioxide film with electrical constant. The chemical dehydroxylation is preferably carried out by individually exposing the basalized film to a compound mainly composed of Shixi (such as Shixiyan, pure liquid or pure vapor or solution, or vapor in a carrier gas or gas mixture). , And dehydroxylated gas. The formed mesoporous film has a dielectric constant of less than 3, which remains less than 3 in humid conditions. According to a preferred embodiment of the present invention, the mesoporous surfactant-type plated film with a low dielectric constant (k < 3) can be obtained by one or more dehydroxylation steps, which comprises a mesoporous material The surface removes hydroxyl groups. In this embodiment, the surfactant can be any surfactant, including (but not limited to) non-ionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. And their mixture. The precursor solution may contain a chemical reagent, which includes, but is not limited to, a second interfacial / tongue agent, a smaller hydrophilic molecular compound, an organic co-solvent, and a mixture thereof. The second surfactant includes, but is not limited to, a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a mixture thereof. Smaller hydrophilic molecular compounds include, but are not limited to, glycerol, propylene glycol, ethylene glycol, and mixtures thereof. Organic common solvents include (but are not limited to) □, octane and mixtures thereof. The precursor of oxidized oxide includes (but is not limited to) tetraethyl ortho dreamate (JEOS), tetramethyl ortho silicate ( TM0s), fluorenyltriethoxysilane, phenyltriethoxysilane, difluorenyldiethoxysilane, ethyltriethoxysilane, and mixtures thereof. In a preferred embodiment, the 'aqueous solvent comprises ethanol. Catalyst contains (------- 1 · ----- # 装 ------ · ί order ------- guide (Please read the precautions on the back before filling this page)

-18-568885

V. The invention of the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives printed invention descriptions (16) but not limited to inorganic acids, including (but not limited to) hydrogen acids, nitric acid, sulfuric acid 'organic acids, including (but not limited to) ) Carboxylic acids, amino acids, and mixtures thereof. The carboxylic acid includes, but is not limited to, methanecarboxylic acid, acetic acid, oxalic acid (oxalic acid), butyric acid, and mixtures thereof. Amino acids include, but are not limited to, glycine and nitromethane and mixtures thereof. A preferred nonionic surfactant is a polyoxyethylene surfactant. "Nonionic," a term indicating surfactant chemistry in which cationic (eg, ammonium or sodium ions) or anionic (eg, sulfonate, sulfate, or ions) species does not exist. This application The non-ionic polyoxyethylene ether surfactants described in the case are small molecules containing carbon, hydrogen, and oxygen, and only have a hydroxyl group (-0H) at the hydrophilic end of the polymer. By using these interface activities Agent, and mixed dehydroxylation process, low dielectric constant (ie, low capacitance in the film) is obtained using simple synthesis and processing conditions. In addition, the large film has uniformity, minimal surface texture and dielectric properties. The electrical constant stability is obtained by using these surfactants. The surfactants in this polyoxyethylene group include (but are not limited to) C12H25 (CH2CH2O) 10OH (also known as (: 12ug 0) Or October lauryl ether); c16h33 (ch2ch2o) iooh (also known as c16eo10 or 10 cetyl ether), ci8H37 (CH2CH2O) 10OH (also known as C18EO10 or 10 stearyl ether); C12H25 (CH2CH20) 40H (also known as C12E04 or April Laurel Mystery);

Ci6H33 (CH2CH2〇) 2OH (also known as C10E02 or Twenty-Six Burning Enigma); and mixtures thereof. In addition, polyoxyethylene ether surfactant can be used with other surfactants and smaller hydrophilic molecular compounds (which are applicable to the Chinese National Standard (CNS) A4 specification at this paper scale) (but not limited to this) 210 X 297 mm). 11111 — — — — — — — — — — (Please read the notes on the back before filling out this page) 19 568885 A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (17) Compatibility with ethanol and water in water-based solvents). Combined with the same organic co-solvents as surfactants and their chemical reagents. Use it. Surfactants include (but are not limited to) ammonium-based cationic surfactants: 1 ± agents, such as cetyltrimethylammonium vapor. Organic co-solvents include, but are not limited to, octane and mixtures thereof. Smaller hydrophilic molecular compounds include, but are not limited to, glycerol, propylene glycol, ethylene glycol, and mixtures thereof. Smaller hydrophilic molecular compounds can have higher boiling points and lower vapor pressures than water and ethanol. These smaller hydrophilic molecular compounds may exist in a wall rich in silica, which is formed around the surfactant micelles during spin coating and drying, and when burned, this inclusion may be Smaller holes are left in the silicon dioxide wall. The silica precursor solution is composed of four solution compounds: (1) silica precursor, preferably tetraethyl o-silicate (TEOS); (2) aqueous solvents, such as ethanol, water And mixtures thereof; (3) catalysts for the hydrolysis of the precursors of stone dioxide, preferably acids, such as, for example, hydrogen or hydrogen acids, and (4) surfactants. Since TEOS alone does not dissolve in water, it requires the addition of a co-solvent, preferably ethanol. Although, the preferred solution mixture contains the following molar ratios: TEOS 1.0; water 5; ethanol 5; HCL 0.05; and surfactant 1.7. The molar ratio of surfactant / TEOS can be changed to control the final The pore-volume fraction in the membrane and change the pore volume. Furthermore, those skilled in the art will know that the size and content of surfactants in small polyoxyethylene ethers range widely in different solvent amounts. Middle department is possible. It is not possible to avoid precipitation of silica precursors in the solution before spin coating. The precipitation of the precursor of dioxide dioxide can be carried out by using alcohol as a co-solvent (preferably as the main solvent) and the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) --- I-- ------- ^^ Shang --- I ---- Order --------- (Please read the notes on the back before filling this page) 20 568885 A7 _____ B7 V. Description of the invention (18) Avoid in combination with acidic pH. In addition, precipitation can be avoided by controlling the molar ratio of water to TEOS alone or combining pH. Value, adding alcohol, or both — — — — — — — — — ^-(Please read the precautions on the back before Fill out this page). The stenciled film is made by spinning and coating the silica precursor solution. The solution is dispersed on the surface of the substrate and rotated with a spin coater, for example, at 2000 rpm for 30 seconds. The substrate is preferably a silicon wafer or an aluminum-coated silicon wafer, but it is not limited to these materials. • Line · When using such a solution containing a surfactant, the spin coating technique used in the present invention does not require atmosphere control, and this method can be easily applied to microelectronics preparation. This technique produces films with good thickness uniformity on wafers with small to large surface areas. The film obtained by the method of the present invention has a film thickness of about 0.2um to about 1.5um, and has a thickness deviation of less than +/- 5% standard deviation. For example, a film with a thickness of about 0.8um has a thickness deviation of less than 25nm (0.3 ° / ❶) standard deviation on a 4-inch wafer. The film thickness can be controlled by adjusting the relative ratio of the solution compounds and by changing the rotation rate during deposition. / The Intellectual Property Bureau of the Ministry of Economic Affairs' employee consumer cooperative prints spin-coated, surface-active agent plated films are formed in hydroxylated mesoporous membranes by removing aqueous solvents, acids and surfactants. Removal of aqueous solvents This is typically achieved by heating the spin-coated film. For example, exposing the spin-coated film to a temperature of 115 ° C for 1 hour can complete the drying and increase the concentration of silicon dioxide. Further heat treatment (sintering) of the film, for example, at a temperature of 475 ° C for 5 hours, or at 40 (5 minutes on a hot plate of TC (in > 2 gas), removes the surfactant and forms a blanket Partially hydroxylated mesoporous membrane. 21 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 568885 Printed by A7 B7 I, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, I. Description of Invention (19) Partially hydroxylated film by exposing the partially hydroxylated film to a silicon-based organic compound such as silicon, silane, pure liquid or pure vapor or solution, or vapor in a carrier gas or gas mixture ) And are chemically dehydroxylated to form a mesoporous silica film. Silane can be selected from, but is limited to: trimethyliodosilane, trimethylaerosilane, dimethyldimethoxysilane, Hexamethyldisilazane, dimethyldigasilane, hexaphenyldisilazane, and diphenyltetramethylsilazane. In addition, the silane exposure film can be further exposed to dehydroxylated gas or heat treatment. Silane Processing can be carried out and thereafter vacuumed or inert Gas or forming gas or both. Partially hydroxylated film is preferably dehydroxylated in a two-step process, which includes immersion treatment and exposure to a hexamethyldisilazane solution in an organic solvent The elevated temperature is 112 in N2 gas. Partially hydroxylated films are better that are dehydroxylated in a high temperature process in several steps, which includes an initial vacuum treatment, followed by a vapor phase silane treatment, which The second step is vacuum treatment. The silane / vacuum treatment step is preferably repeated using the same silane or different silanes, and then followed by a high-temperature inert gas or gas-forming treatment. For example, hexamethyldioxide at 10/0 The hydroxylated membrane was immersed in the toluene solution of silazane for 24 hours, and then exposed to H2 in N2 at 400 ° C for 2 hours, resulting in effective dehydroxylation of the mesoporous membrane, and then it was exposed to humid air It exhibits stable dielectric properties. The order of the steps of the dehydroxylation method is preferably repeated once. The formed mesoporous film has a dielectric constant typically less than 2.5 under surrounding humid conditions, and the Permittivity It is stable for a long period of time in a wet atmosphere. Example 1 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) ------------% pack -------- I * Order i * ------- ^ 9— (Please read the notes on the back before filling this page) 22 A7 B7

568885 V. Description of the invention (20) Experiments were performed to confirm the efficiency of the preferred embodiment of the present invention. Three different surfactants within the beta polyoxyethylene group were tested: (1) CuH ^ CH ^ H ^ OhoOH ( (Also known as C12EO10 or 10 lauryl mystery); (2) C16H33 (CH2CH2〇) i〇〇H (also known as c16eo10 or 1016); and (3) C18H37 (CH2CH2〇) i. OH (also known as C18EO10 or 10 stearyl). All films with these surfactants were prepared using a solution having the following molar ratio: TEOS: H20: ethanol: gas argonic acid = 1: 5: 5: 0.05. The mole ratio of surfactant / TEOS varies from about 0.005 to about 0.50. All components except TEOS are mixed until a homogeneous solution is obtained. When the molar ratio of the surfactant / TEOS is greater than about 0.2 and the TEOS: H20: ethanol ratio is about 1: 5: 5, the uniformity is more easily heated to about 40 ° C to about 50 by adding the solution. (: And achieved, especially for polyoxyethylene ether surfactant. Heating may not be necessary for more dilute solutions. TEOS was then added and the solution was stirred. After TEOS was added, the solution was aged at room temperature for 20 hours. No precipitate was formed under these solution conditions. The aged solution was dispersed on the surface of a polished 4-inch Si wafer by spin coating with a spin coater at 2000 · ριη for 30 seconds. The formed surfactant film is converted into a mesoporous film by removing aqueous solvents, acids and surfactants. This removal is performed by subjecting the film to a temperature of 115 ° C. 1 It can be achieved in hours. The complete removal of the surfactant from the membrane can be achieved by sintering (heat treatment) at 475 ° C for 5 hours. Prior to the electrical / capacitance measurement, the porosity of the sintered membrane was determined by nuclear reaction analysis (NRA) , And the thickness is measured by a profile meter. NRA porous paper standard 11 Caiguanjia standard (CNSM4 specification (210 X 297)) -------------- ^ ----- --- β --------- ^ (Please read the notes on the back before filling out this page) Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Industrial and Consumer Cooperatives 23 568885 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (21) Sexual data was not used as a correct measure of porosity, but was used as a guide to help determine the selection Film for further electrical / capacitance measurement. Figure 1 shows the NRA-determined porosity of the CxE01 () polyoxyethylene ether surfactant series. This figure shows the use of specific surfactant / TEOS values only Porosity values of different surfactants. For several higher surfactant / TEOS ratios, the evaluation of the properties of the film for electrical properties is not acceptable, and the films formed in this ratio are not further tested. In order to be considered as a dielectric film in a semiconductor device, the thickness of the film needs to be in the range of 0.5 to about 1.2um. In addition, the thickness of the film must be uniform without cracks and major defects or surface defects. It must have non-wet islands, cracks, Films with ring structures, dentate patterns, or misty inclusions are not considered for electrical evaluation. Comet-like deletions on other uniform films (due to dust-like particles on the wafer) It is said to be acceptable 'because it does not cause potential solution properties. Table E1-1 shows the observation of the film properties of these surfactants with different concentrations. Table E1-1 is based on CxEO10. Membrane Properties of Membrane Surfactants》 »Molar ratio of surfactant / TEOS (less than) Membrane properties c12eo10 Membrane properties Ci6EO10 Membrane properties CjgEOjo 0.10 Good acceptable Acceptable 0.17 Good difference 0.24 Poor acceptable Poor 0.30 Poor Acceptance difference 0.40 difference difference 0.50 difference difference difference This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) — · ί -—% equipment ------------ order- 丨 *- ------ (Please read the notes on the back before filling out this page) 24 Printed by the Consumer Cooperatives of the Ministry of Economic Affairs and Intellectual Property Bureau 568885 A7 B7 V. Description of the invention (22) Based on NrA shown in Figure 1 The porosity data and the observation of the properties of the membrane, the second membrane was selected as the electrical measurement. As shown in Table 1, these two films are prepared from a solution containing (1) C12E01G, a surfactant / TEOS mole ratio of 0.17; and (2) a C16EO10 surfactant / TEOS mole ratio of 0.3. 〇 The initial electrical test of the capacitance of these burned films using an accurate LCR meter yielded a higher dielectric constant (ie, capacitance) than would be expected for a porous film, because these films still contain a large amount of hydroxyl groups (- 0Η). Each of these two partially hydroxylated films is thus dehydroxylated by exposing the hydroxylated film to a silane and a dehydroxylated gas, respectively. The membrane was dehydroxylated by treatment with 10% hexamethyldisilazane in toluene solution for 24 hours and exposure to 400 ° C N2 for 2 hours. The sequence of the steps of the dehydroxylation method is repeated once for each film, and the dielectric constant is measured after each of these steps. The capacitance measurement is performed as described below. The back side of the wafer is scratched / etched to expose the unshielded silicon surface, and the metal is deposited by sputtering. On the upper film side, a gold dot array having a diameter of about 2.8 mm was formed by sputtering using a shadow mask. The capacitance was measured at ambient temperature at four points for each sample, and the dielectric constant was measured using film thickness and dot diameter. The dielectric constant data obtained in this way are shown in Figures 2 and 3 (which are two different films). The data in Figure 2 shows that a dielectric constant of 1.80 can be obtained from a film synthesized with a C12EO10 surfactant. The data in Figure 3 shows that the dielectric constant of 1.85 can be obtained from a film synthesized with a C16E01G surfactant. These low dielectric constants indicate the application of these polyoxyethylene ethers in semiconductor devices. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------- ----- Equipment -------- Order --------- line (please read the notes on the back before filling this page) 25 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 568885 A7 _ B7 V. Description of the Invention (23) Amazing guarantee of mesoporous silica in the preparation of surfactants. The low dielectric constants obtained with these films are also relatively stable, ranging from 20-22. (: The temperature and the surrounding laboratory conditions of 40-65% relative humidity increased by less than 5% during 1 day. The dielectric constant will not increase its value afterwards. Mesoporousity of the surfactant plate The hole structure of the film is detected by low-angle X-ray diffraction (XRD) and electron penetration microscopy (TEM). The XRD spectrum of the film on the wafer in different directions (radial and tangential) is as shown in Section 4A As shown in Figure 4B. The spectrum does not contain any peaks in the range of 2 to 6 degrees 20, thereby indicating that the pores are not regular. The TEM microfacies of the film section in Figure 5 indicate that the pores are irregular and have various Isotropic non-porous structure. The pore size is less than 3 nm as measured by TEM microphase and nitrogen adsorption / desorption analysis of powders prepared from the solution by a rapid spray drying method. Planarization of the film and surface morphology Measured by optical profile. The texture of the smallest stripe pattern is observed in these films. The surface profile of the film is observed in Figure 6a. Roughness is generally less than 50 Angstroms in length specifications (Figure 6b) ). The elastic modulus of mesoporous silicon dioxide film is Hysiron P icoindenterTM and measurement using Berkowich money stone tip. This instrument and tip are calibrated with a dense silicon dioxide standard with a modulus of 70 Gpa. Scoring load (50-300uN) and retention time at maximum load (50-900 seconds) ) Investigated. For the measurement parameters used, the depth of the scoring is less than 10% of the film thickness, and therefore the effect of the substrate is not expected to affect the measured value. The measurement modulus of the scoring load for a 300 second residence time The effect of the value is shown in Figure 7 (which is a mesoporous silica film). For this paper size with ~ 55% porosity, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied ------------ Equipment -------- ^ Order --------- (Please read the notes on the back before filling this page) 26 Ministry of Economics and Economics Printed by the Intellectual Property Bureau's Consumer Cooperatives 568885 A7 B7 V. Invention Description (24)

The high porosity membrane made of Ci2E01G polyoxyethylene scale surfactant is 14-17Gpa. The relative modulus of porous silica related to dense silica is in reasonable agreement with the calculation of porous solids, mainly closed or open porous. The relatively high modulus of the porous membrane indicates resistance to GMP in the preparation of interconnects. Example 2 An experiment was performed to confirm the preparation of various polyoxyethylene ether surfactants alone or in combination in a mesoporous silica film with a low dielectric constant. The components of the spin-coating solution containing the type and amount of surfactant used for each solution, and the dielectric constant of the selected film are shown in Table E2 ". All components except TEOS were mixed To obtain a uniform solution. In this experiment, the components were added in the following order: surfactant, ethanol, water, and acid. Before adding other solution components, when the surfactant is solid at room temperature, the interface activity The agent is heated to about 30 to 4 ° C. to melt the surfactant. Heating the surfactant is not necessary, but a homogenous solution can be obtained more easily by this procedure. Then TEOS is added and the solution is stirred. After TEOS is added, the solution is It was aged for 20 hours at room temperature and spin-coated with a spin coater at 2000 rpm for 30 seconds and dispersed on the surface of a polished 4-inch Si wafer. The formed surfactant film was formed by a series of three hot plates. It is heated to transform into a mesoporous membrane. The highest hot plate temperature is about 400 ° C °. The membrane selected by this group undergoes a dehydroxylation process, which is processed in a hexamethyldisilazane solution. After 2% H2 as described above / N2 treatment 'and the dielectric constant of the film is measured. The table shows that the dielectric constant of the film less than 2.25 can be obtained using more than one surfactant. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 27 -------- install -------- order --------- line (please read the precautions on the back before filling this page) 5 _____ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 568885 A7 __ B7 Description of the invention (25) Table E1-2 Sample composition; mole ratio 〇 · 1 C1JEO1 η 0.1 C16E0lft CC25 1 5 10 0.05 0.13 CnEOtn 0.13 ClfiEOin CC26 1 5 10 0.05 0.15 CnE0lft 0.15 C ^ EOin 2.16 CC27 1 5 5 0.05 0.06 CnE0lft 0.06 C18E〇2〇CC28 1 5 5 0.05 0.1 CnEOln 0.1 CjEO o 2.11 CC29 1 5 5 0.05 l 0.1 C ,, E0] n 0.1 c15eo4 CC30 1 5 5 0.05 0.13 CnEOin 0.13 CnE04 CC31 1 5 5 h 0.05 0.15 CnEOin 0.15 CnEOd 2.23 Example 3 Interfacial activity with polyoxyethylene ether The irregular hole structure of the film made by the agent is denser by low-angle X-ray diffraction Probe, to determine any characteristics of the X- ray spectra of these films. The components of the spin coating solution containing the type and amount of surfactant used for each solution are shown in Table E3-1. All components except TEOS are mixed until a homogeneous solution is obtained. In this experiment, the components were added in the following order: surfactant, ethanol, water, and acid. Before the other solution components are added, when the surfactant is solid at room temperature, the surfactant is heated to about 30 to 40 ° C to melt the surfactant. Heating of the surfactant is not necessary, but a homogenous solution can be more easily obtained by this procedure. TEOS was then added and the solution was stirred off. After TEOS was added, the solution was aged at room temperature for 20 hours and spin-coated using a spin coater at 2000 rpm for 30 seconds to disperse on the surface of a polished 4-inch Si wafer. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 meals) ------------ installation -------- * order -------- ^ _wl (Please read the notes on the back before filling this page) 28 568885 A7 B7 V. Description of the invention (26) Table E3-1 Composition: Mo Θ: Proportion Sample # TEOS h2o EtOH HC1 HN03 Surfactant 144-3 -ID 1 5 5 0.05 0.19 CI2EO, 〇CC22C 1 5 10 0.05 0.3 C ^ EOjo CC29A 1 5 5 0.05 0.1 c12eo10 0.1 C12EO4 CC81-1B 1 5 20 0.05 0.2 C16EO10 CC83-1B 1 5 20 0.05 0.2 C18EO10 Ministry of Economic Affairs Intellectual Property The surfactant-type plated film formed by the bureau's consumer cooperative was converted into a mesoporous film by heating on a series of three hot plates. The maximum hot plate temperature is about 400 ° C. The two membranes selected by this group, 143-3-I-D and CC22C, were subjected to a dehydroxylation procedure, which included treatment in a hexamethyldisilazane solution, followed by 2% H2 / N2t treatment as described above. The film is detected by X-ray diffraction using experimental parameters as described below. The X-ray spectrum was obtained in a concealed area of 1 cm x 1 cm, and the center of mass of the concealed area was located about 3.5 cm from the center of the wafer. The spectra were obtained in the radial and tangential directions of the X-ray beam relative to a circular wafer. Scan range: 1.00-6.00 degrees (20) Scan rate: 0.05 degrees / 10 seconds Scan format: continuous (ie, non-stage scanning) Diffractometer: Philips X, PertMPD (PW3040 / 00 type) X · Ray source: sealed ceramic tube, Long-Fine Focus (LFF) Cu anode (Cu κ α-radiation) x-ray power: 40kV, 50mA (2000W) goniometer radius: 250mm --------- ------ Loading --- (Please read the precautions on the back before filling out this page) Previous σ ·; Line. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 29 568885 Printed by A7 B7, Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (27) Incident beam optical mirror: • 0.04 Rad Soller slit stylized automatic scattered slit (10mm point length) _ 10mm beam cover (10mm dot width) Received optics: • 0.04 Rad Soller seam calls for stylized automatic anti-scattering seam (10mm point length) Lu stylized receiving seam (0.2mm) for curved concave graphite monolith Detector: Xe proportional calculator 144-3-ID: X · ray spectra corresponding to the radial and tangential directions are shown individually in Figures 8a and 8b As shown. The intensity of the diffracted and reflected beams steadily increases as they approach a lower angle, because a larger percentage of the direct beam reaches the detector, even if the system components are carefully arranged and the sample height is controlled relative to the path of the incident and reactive beams. Even if the intensity is increased, there is a peak near the j i degree 20 of the second spectrum. Electron permeation microscopy of thin sections of this film did not show regular porosity. The studied membrane area did not show any regular geometric arrangement of holes, especially the long-range geometric arrangement. CC22C: The χ-ray spectra corresponding to the radial and tangential directions are shown individually in Figures 9a and 9b. In the tangential direction, it has a peak at about u degrees, but in the radial direction, it does not have a significant peak. Only increased intensity with lower angles was observed. CC29C: The spectra corresponding to the radial and positive lines are shown individually in Figures 10a and 10b. In the radial and tangential directions, it is about ^ 2 This paper is a timely standard (CNS) A4 size ⑽ x 297 public compound ------------ install -------- tri ^ ------- (Please read the notes on the back before filling out this page) 30-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 568885 A7 B7 V. Description of the invention (28) The degree has a wave. CC81-1B: The ray spectra corresponding to the radial and tangential directions are shown in Figure 11a and lib respectively. In the radial and tangential directions, it has peaks at about M to 1.2 degrees. C83-1B: The two sets of x-ray spectra obtained from this sample are shown in Figure 12d and 12d. One set (radial and tangential) is obtained at about 1/4 of the wafer (about 90 degrees of rotation of the wafer) with the other. In the graphs i2a and i2b, the spectra obtained in the radial and tangential directions in a region do not show clearing peaks at low angles. However, each spectrum in 12c, i2d of another region on the second sample contains a single peak at about 1.1 · 1.2 · 20. Electron transmission microscopy of thin sections of this film did not show regular porosity. The films studied in these areas did not show any regular geometric arrangement of holes, especially long-range geometric arrangements. In this example, the observation of X-ray reflection and electron transmission at low angles is combined with the observation of X-ray reflection and electron transmission by TEM in Example 1. The geometry of the special rule, the crystal structure of the pores (especially the long range) is consistent. The irregular porosity is characterized by X-ray diffraction peaks (about 0.75 to about 2 degrees 20) at very low angles. ). It should be noted that this peak has not been observed for irregular porosity at 100% of this time. Example 4 Dehydroxylation of mesoporous silicon dioxide film using silane in vapor form at room temperature can produce less than 2.5 The dielectric constant. The mesoporous membrane on a silicon wafer is placed in a stainless steel reaction vessel with an internal volume of ~ 0.08 lcm3. This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm). -------- Order --------- line (please read the precautions on the back before filling this page) 5 coffee 85 printed by the Intellectual Property Bureau of the Ministry of Economic Affairs employee consumer cooperative Α7 Β7 i, invention Note (29). Reaction vessel (high temperature valve assembled with inlet and outlet Connected to the high vacuum tube via the true pipe fittings. The reactor was placed in a sand bath and the temperature was monitored using a thermocouple uniformly deployed in the reactor. The initial heating step (0 minutes to 2 hours) was placed in high vacuum (~ l〇-5torr). At the desired temperature in the reactor chamber, it is opened to the dream phase of the vapor phase. The pressure of the dream vapor depends on its boiling point or near the boiling point. It depends. After the desired time has elapsed, the chamber is placed under vacuum. The treatment of the mesoporous membrane specifically includes vacuum treatment, followed by one or more silanes in the vapor phase, and thereafter Vacuum treatment at one or more temperatures of 298 to 723K (25 to 450C). The duration of vacuum treatment and dream house treatment is changed from 5 minutes to 2 hours. This procedure is for the samples exemplified in Table E4-1. The system repeats several cycles. When cooling, the wafer is removed from the reaction container, and then a gold electrode is deposited on the surface and placed in a tube furnace and processed to form a gas radon (2% Η2 / N2) for 2 hours. Film The capacitance is measured under ambient conditions. The membrane is also placed under a dry nitrogen stream The capacitance of the film is measured. Finally, the wafer is placed in a sealed glass container that contains a beaker filled with water to simulate 100% relative humidity for 1 to 3 days. Then, the sample is removed and the capacitance is Measured again in indoor air. Several different silanes were tested, including trisiodonyl iodine silane, stilbene-based gas sintered silicon, dimethyl dimethoxy stilbene, and hexamethyl stilbene ammonia. The experimental results of trimethyl moth-fired and hexamethyl-particulate-gas fired are shown in Table E4-1. These results confirm that depending on the silane used and the processing conditions, the results on mesoporous silica The low dielectric constant (< 2 · 5) can be achieved by a procedure including exposing a mesoporous silicon dioxide film to silane. This exposure procedure can occur under high humidity conditions. These results indicate that by dehydroxylation of silane to be included in the silane, this paper is compliant with China National Standard (CNS) A4 (210 X 297 mm). IIII I ---- 丨 ---- II Γ ^ — — — — — — (Please read the notes on the back before filling out this page) 32 568885 A7 B7 V. Description of the invention (30) Remove the gas phase or physics in the porous membrane before and / or after the processing step The procedure for adsorbed species takes effect. Removal of this gas phase or physically adsorbed species can be accomplished by processing in a vacuum or in a flowing forming gas, or by processing in other flowing inert gases such as high-purity depleted nitrogen or argon. Table E4-1 Sample # Silane pressure (Torr) Total Morse temperature ° c Time * (minutes) Cycles (petane treatment) K, (in air) K, (in flowing nitrogen) K In air after 100% humidity) ** JB-3 (Ch3) 3SiI 36 Torr 0.16 275 60 1 1.66 1.57 1.91 JB-6 (Ch3) 3SiI 30 Torr 0.17 400 10 3 1.73 1.65 1.72 JB-8 HMDS * ** 19 Torr 0.17 350 10 5 1.77 1.67 1.86 * Silane treatment time, min. Generally, the vacuum time is the same. ** Exposure to 100% humidity ~ 15 hours, and then immediately install in the surrounding air --- (Please read the note on the back first Please fill in this page again.) Enter = 0. The printed capacitance measured by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs *** Hexamethyldisilazane believes that these processes are best completed in the chamber, in which the temperature of the membrane is controlled The required gas can be supplied into the chamber in an appropriate order, and the chamber is pumped in a vacuum before and / or after being exposed to the silane. An experimental reaction chamber designed for dehydroxylation of a mesoporous silicon dioxide film supported on a silicon wafer, which can be an individual independent chamber or part of an integrated rotary trajectory tool . The stainless steel chamber was constructed to support this paper. The size of the paper is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). Line-33 Printed by the Ministry of Economic Affairs and Intellectual Property Bureau Employees' Cooperatives 568885 A7 One B7 V. Invention Description ) 4, 6, 8 and 12 inch wafers. Under high vacuum, the chamber will be maintained at an outside pressure of i atmosphere, and the cooling seal on the front door will maintain a vacuum of 10.5 Torr. The internal self-heating rack will heat up to 500C, and the internal circulation is determined by the fan. After the initial vacuum treatment, the gaseous silane is pumped into the chamber of the desired pressure, and thereafter a vacuum is applied again. The cycle is repeated as many times as necessary to achieve the desired degree of dehydroxylation. After the final vacuum treatment, the forming or inert gas is pumped into the chamber. Example 5 Mono- and di-alkyl-substituted alkoxysilanes can be used as spin coatings containing surfactants for the preparation of low dielectric constant mesoporous silicon dioxide films with a dielectric constant of < 2.5 Extra silica precursor in solution. A series of solutions were prepared as described in Example 1, but methyltriethoxysilane and dimethyldimethoxylithium were added to tetraethoxylithium at 1 mole ratio. Individual mole ratios of TEOS to alkyl-ethoxysilanes from 0.95: 0.05 to 0.25: 0.75 are made. The surfactant used was a molar ratio of 10 lauryl ^ surfactant to the silica precursor, 0.17. The silicon wafer was spin-coated with this solution and heat-treated as described in Example 2. The selected coated wafers were subjected to dehydroxylation as described below. The coated silicon wafer was placed in a stainless steel reaction vessel having an internal volume of ~ 0.081 cm3. The reaction vessel (the high temperature valve assembled with the inlet and outlet) is connected to the high vacuum tube through a true fitting. The reactor was placed in a sand bath and the temperature was monitored using a thermocouple evenly distributed throughout the reactor. The initial heating step (0 minutes to 2 hours) was performed in a chamber placed under high vacuum (~ 10.5 Torr). At the desired temperature in the reactor chamber, it is opened to the vapor phase of silane. The pressure of silane vapor is based on its boiling point or close to the size of this paper. Applicable to China National Standard (CNS) A4 (210 X 297). ----------- I installed! !! 1 · Order --- I ----- (Please read the notes on the back before filling out this page) 34 568885 V A7 B7 Description of Invention (32) The boiling point of the silane vapor pressure depends. After the desired time has elapsed, the chamber is placed under vacuum. The treatment of mesoporous membranes specifically includes vacuum treatment, followed by vacuum treatment with one or more silanes in the vapor phase, and then vacuum treatment with one or more of the temperatures of 298 to 723K (25 to 450C). . The duration of vacuum treatment and silane treatment varies from 5 minutes to 2 hours. While cooling, the wafer was removed from the reaction vessel, after which gold electrodes were deposited on the surface. The capacitance of the film is measured under ambient conditions. The membrane was also placed under a stream of dry nitrogen and the capacitance of the membrane was measured. The bonding system of a wafer is shown in Table E5-1. Table E5-1-ϋ n ϋ ί 1 ϋ n β— · ϋ I 1_1 I · ϋ ϋ (Please read the precautions on the back before filling out this page) Sample # Molar ratio of silicone to dehydroxylated silane (Pressure) Total millimolar silane time (minutes) Temperature CC) Cycles K, Air K, Nitrogen JB-21 0.85 TEOS 0.15 Methyl triethoxide (CH3) 3SiI 17 Torr 0.23 10 390 5 2.24 2.23 ·. The present invention further includes an improvement of a step and method for desiliconization to hydroxylation of the surface of hydroxylated silicon dioxide. The basic two-step method of debasing is to individually expose the surface of the silicon dioxide to (丨) silicon compounds and (2) dehydroxylated air. The improvement of the present invention lies in (a) repeating this basic two-step method and achieving a dielectric constant value of less than 2.25; (b) using a substantially hydrogen-free inert gas as a dehydroxylated gas and achieving a safer Dehydroxylation method; (0 combined with the two-step method and the method of surfactant formulation to prepare a mesoporous film; and (d) a mixture of these. The paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm)-Line. Printed by the Consumers ’Cooperative of the Ministry of Economic Affairs and the Intellectual Property Bureau 35 568885 Printed by the Employees’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (33) Hydroxylated film The film is individually exposed to silicon organic compounds (preferably silane) and dehydroxylated gas to perform dehydroxylation. Exposure to silane can be silane vapor, silane liquid, silane solution or a mixture thereof. In the silane solution, The solvent is preferably non-aqueous, for example, toluene. The silane may be trimethylchlorosilane, hexamethyldisilazane, or a mixture thereof. The exposure to the dehydroxylated gas is preferably at an elevated temperature. The hydroxylated gas can be an inert gas or a mixture of inert gases containing hydrogen. The inert gas is essentially hydrogen-free, meaning that it does not have hydrogen or does not affect the content of dehydroxylation. Less than detectable The limit of the content of hydrogen has practically no effect on the dehydroxylation system. The dehydroxylation of the film based on polyoxyethylene ether surfactant is a preferred embodiment. However, this method is used to remove the hydroxylation. The lower dielectric constant achieved by the chemical process can also be obtained on films made from other surfactants (including but not limited to ammonium (CTAC) surfactant-based films). Example 6 Reported here In the example, C12H25 (CH2CH20) 丨 OH (also known as Ci2E01〇4 lauryl ether) is used as a surfactant to introduce porosity in the membrane. The data is also based on another surfactant of the same group, CaHWCI ^ CI ^ OhoOH (also known as C16E01 () or 10 hexadecyl ether) was obtained on the prepared film by using some debasing treatments as described below. All film systems have the following properties: Ear ratio solution made TEOS: H20 : Ethanol: Hydrogenic acid = 1: 5: 5: 0.05. Molar ratio of surfactant / TEOS is 0.17. All components except TEOS are mixed to obtain the paper standard applicable to China National Standard (CNS) A4 specifications ( 210 X 297 public love) ------------ install -------- * order -------- (Please read the precautions on the back before filling this page) 36 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 568885 A7 B7 V. Description of the invention (34) Homogeneous solution. Then add TEOS and stir the solution. After TEOS is added, the solution is stirred at room temperature for ~ 20 hours, and then polished. Spin coating on 4 inch Si wafers. After spin coating, the film was kept at 115 ° C for at least 1 hour to completely dry and increase the concentration of silicon dioxide, and then calcined at 475 ° C for 5 hours. The calcined film is subjected to one or more of the following dehydroxylation treatments: a) immersed in 10% HMDS in toluene solution for 20-24 hours, then sonicated in isopropanol and flowed at room temperature Dry under nitrogen. This procedure is hereinafter referred to as "HMDS (L)". b) Heat treatment at 400 ° C in flowing 2% H2-98 ° / ON2 gas for 2 hours. This procedure is hereinafter referred to as "2% H2". c) Heat treatment at 400 ° C in flowing argon for 2 hours. This procedure is hereinafter referred to as "Ar". d) The membrane was submerged with pure HMDS for 15 seconds, rotated at 2000 rpm, and then the membrane was submerged with isopropyl alcohol for 15 seconds, and then rotated at 2000 rpm. The capacitance measurement is performed as described below. After film deposition and processing, the back side of the wafer is scratched / etched to expose the exposed silicon surface, and the gold layer is then sputter deposited. On the upper film side, an array of gold dots (about 2.8 mm in diameter) is formed by spraying using a shadow mask. The capacitance was measured at 4 points for each sample, and the dielectric constant was measured using film thickness and point diameter. The average dielectric constant obtained in this way is shown in Table E6-1. For some samples subjected to the final heat treatment in a hydrogen-containing gas or argon, the samples are electrodeposited with gold before the final heat treatment. Capacitance is measured before and after heat treatment. Table E6-1 also shows that the size of the paper connected to the film after some treatment is applicable to China National Standard (CNS) A4 (210 X 297 mm) 37 ------------ -^ -------- ^ --------- ^ (Please read the notes on the back before filling out this page) 568885 A7 B7_V. Description of the invention (35) Angle of contact. Table E6-1 Effect of Dehydroxylation Treatment on the Dielectric Constant of Mesoporous Silicon Dioxide Films Prepared with C12E01G Polyoxyethylene Ether Surfactant Description of Dehydroxylation Procedure Sample ID Water Contact Angle-" Measurement of Hydrophobicity "Dielectric Constant 2% H2 103-2-1-B1 12 ° 2.67 HMDS (L) XL-92-2 3.34 HMDS (L)» 2% H2 103-2-1-A1 112-MII- D1 2.41 HMDS (L) »2% H2» HMDS (L) 103-2-1-A2 112-1-III-D1 75 ° 2.14 2.56 HMDS (L) »2% H2» HMDS (L) > > 2% H2 103-2-1-B2 72. 1.74 2.12 HMDS (L) »Ar 112-1-III-D2 42 ° 1.95 HMDS (L)» Ar »HMDS (L) 112-1-III-D2 2.55 HMDS (L)» Ar »HMDS (L)» Ar 103-2-1-C1 2.24 HMDS spin coating》 2% H2 »HMDS spin coating 103-2-1-C1 2.48 HMDS spin coating >> 2% H2» HMDS spin coating >> 2% H2 2.10 --- --------- Equipment -------- * Order —.------- (Please read the notes on the back before filling out this page) Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative The data printed in Table E6-1 can lead to two conclusions. First, compared to the untreated silicon dioxide film, all processes result in a low dielectric constant in the film. Second, the dielectric constant of ~ 2.50 can be obtained after treatment with a silane solution and in an inert wine or a hydrogen-containing gas at a moderately elevated temperature. In a film (103-2-1A2), a dielectric constant as low as 1.74 can be obtained after secondary treatment in silane and secondary treatment in 2% H2 / N2. In another membrane (103-2-1-B2), a dielectric constant as low as 1.95 can be obtained by a single treatment in a silane solution and a single treatment in argon. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 38 5 85 85 A7 B7 1. Description of the invention (36) For many samples listed in the E6 · 1 table, the capacitance is also a function of time in The gold electrode was measured immediately after sputter deposition or immediately after the final heat treatment of the electrode sample was removed from the furnace. The dielectric constant system as a function of the aging time of up to 2-3 days is shown in Figure 13. Except for only 2% (2 of 40 (TC-treated film (Film 103-2-1 · B1), all samples show excellent capacitance (dielectric constant) stability over time at room temperature. Aging measurement The relative humidity during the period is ~ 40-65%. The low dielectric constant obtained from the film that has been treated with HMDS solution and exposed to a dehydroxylated gas heated to 400 ° C is also very stable for a long period of time. The ambient laboratory conditions at a temperature of 20-22 ° C and a relative humidity of 40-65% increased by less than 5% a week. The small change in the dielectric constant of this aging study seems to be related to the humidity change during the experiment Related. For example, in this experiment, the capacitance measured at the highest humidity value is slightly higher than the capacitance value measured at the lowest humidity value. It has been shown and described, but it is obvious to those skilled in the art that many changes and improvements can be made without departing from the broader aspects of the present invention. Therefore, the scope of the appended patents is intended to cover the scope of the present invention. The spirit and scope of the invention All these changes and improvements within 0 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 39 I i —--— I —-— — — — — — ^ --- I ----- ^ (Please read the notes on the back before filling this page)

Claims (1)

September 3, 1992) 568885 Patent Application No. 88122804 Patent Application Patent Application Amendment 1. A mesoporous silicon dioxide film made from a solution containing a surfactant, the film has less than 3 The dielectric constant, which has relative stability and absolute stability in a humid atmosphere, has a film thickness of 0 // m to, and an average pore diameter of less than or equal to 20 nm. 2. The porous silicon dioxide film according to item 1 of the scope of patent application, wherein the average pore diameter is less than or equal to 0 nm. 3. The mesoporous silicon dioxide film according to item 1 of the patent application range, wherein the thickness has a standard deviation of less than +/- 5%. 4. For example, the mesoporous silicon dioxide film of the scope of the patent application, wherein the porosity of the mesoporous silicon dioxide film is irregular, and the irregularity is characterized by the lack of a normal geometric arrangement of pores. 5 · If the scope of patent application is the first! The porous SiO2 film in the item has a thickness of 0/1 // m to 1.5 / zm and a standard deviation of the thickness, wherein the standard deviation is less than +/- 5%. 6 · The scope of patent application! The mesoporous silica film, wherein the dielectric constant of the mesoporous silica film is less than 3. 7. If the scope of patent application is the first! The mesoporous dioxygen cut film has an irregular porosity, which is characterized by the lack of a main X-ray diffraction peak in the range of 2 to 6 degrees 20. 8. If the scope of patent application is the first! The term "porous hafnium dioxide" in the item has an irregular porosity, a positivity line lacking pores, and is characterized by an X-ray diffraction peak between 0.75 and 2 degrees 20. 9. If the scope of patent application is the first! The porous mesoporous dioxide film has a small paper strength and is applicable to China @ 家 标 半 （邙 S） M M 袼 （2κ） χ297 公 楚） Please read the meaning of the back Φ and fill in the page 40 568885 6. Apply for a patent with a dielectric constant in the range of 2.5 and an average hole diameter less than or equal to 5η m. The porous mesoporous dioxide film, in which the film is a surfactant / platenization solution of the dream dioxide by evaporation, and then debasing, the film is characterized by irregularities Porosity. 11. The mesoporous dioxide film as claimed in item 10 of the application, wherein the dehydroxylation of the porous film comprises the following steps: a. Exposing the porous film to silane; b. From the porous The membrane removes gaseous and physically adsorbed species. 12. · A method for preparing a mesoporous membrane, the method includes the following steps: (a) combining a precursor of silicon monoxide with an aqueous solvent, a catalyst, and a surfactant to form a precursor solution; (b) enabling the precursor The solution is spin-coated to form a plated film, which is characterized by irregular porosity; (c) removing the aqueous solvent, the catalyst, and the surfactant from the mold plate film to form a hydroxylated film; and (d ) Dehydroxylating the hydroxylated film to obtain the mesoporous silicon dioxide film. 13. The method according to item 12 of the patent application range, wherein the irregular porosity is characterized by a lack of a main X-ray diffraction peak in a range of 2 to 6 degrees 20. 14. The method of claim 13 in which the surfactant is a polyoxyethylene ether surfactant. 41 ............ Installation-(Please read the precautions on the reverse side before copying this page). Order-The iridium scale of this paper applies Chinese national standards (CNS) M specification (2) 0X297 public incineration Α8 Β8 ~ -___ BCS8 Apply for a patent-— --- 15 · If the method of applying for the scope of the patent No. 13, wherein the surfactant is selected from the-surfactant 2. Mix the chemical reagent and organic co-solvent of smaller hydrophilic molecular compounds (characterized by molecular weight lower than or equal to 115G). 16. The method according to item 15 of the application, wherein the second surfactant is selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and the like. Mixture: 17. The method of claim 15 in which the smaller hydrophilic molecular compound is selected from the group consisting of glycerol, propylene glycol, and ethylene glycol. 18. The method according to item 13 of the patent application scope, wherein the dioxo precursor is selected from the group consisting of tetraethyl ortho petrate (TEOS), tetramethyl ortho petrate (Te0s), fluorenyl Triethoxysilane, phenyltriethoxysilane, difluorenyldimethoxylithium, ethyltriethoxysilyl, and mixtures thereof. 19. The method of claim 13 wherein the aqueous solvent comprises ethanol and water. For example, the method of claim 13 of the patent scope, wherein the mixing-precursor solution is further mixed with an acid, wherein the acid is selected from inorganic acids, organic acids and mixtures thereof. 21. The method according to claim 13, wherein the dehydration process occurs in the presence of a silicon-based organic compound in the vapor phase. & The method according to item 21 of the patent application, wherein the main organic compound is silane. 23. The method of claim 22, wherein the amidine is selected from the group consisting of trimethyl vermiculite, trimethyl gas stone, dimethyldimethoxy stone, dimethyl dimethylate and Applicable to China National Standard: Standard (CNS) M specification (2) (to public fan) (Please read the precautions on the back before filling this page) 42 568885 A8 B8 C8 D8 VI. Scope of patent application Dioxane, hexaphenyldisilazane, diphenyltetramethylsilazane and hexamethyldisilazane. Install ........ # ....... line. (Please note on the back of Μίδ before writing This page) 43 This paper size applies to Chinese national standards (G〇4 size (2) 0 × 297 pulp)