TW471104B - Low dielectric constant, porous film formed from regularly arrayed nanoparticles - Google Patents

Abstract

The method of the invention produces a low k porous dielectric body with a uniform dielectric characteristic throughout its bulk and about its surface. The method initially starts with a mixture of a solvent, a first quantity of sacrificial nanoparticles and a second quantity of structural nanoparticles. The structural nanoparticles include an organic component. The mixture is concentrated in a manner to allow assembly of the structural nanoparticles into a lattice structure with interspersed sacrificial nanoparticles. The structural nanoparticles are then fused together to enable a rigidification of the structural nanoparticles and lattice structure. Then the sacrificial nanoparticles are removed from the lattice structure to leave voids therein. Finally, the surfaces of the voids are coated with a hydrophobic material. A device constructed in accord with the method is also described.

Description

471104

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Guiming field: _ The present invention is related to the formation of low dielectric constant films, where these film layers have regularly arranged array of nanometer-sized particles and Holes scattered on it. BACKGROUND OF THE INVENTION In order to increase the speed of the micro-electric pre-integrated circuit, the size of the line characteristic area must be reduced. The dielectric material used between components is improved. For example, for a film line with resistance R, the signal speed will vary with 1 / RC (where c is the capacitance between the lines), as long as a low A supporting film with a dielectric constant (that is, having a low κ dielectric constant) can make the capacitance value c smaller, and the speed of the circuit can be increased accordingly. Films with a dielectric constant between 2 and 3 are suitable for use in future high-speed integrated circuits. The inventor Ayers described a method for forming a dielectric layer using nanometer-sized spherical silica made of silicon dioxide in U.S. Patent No. 5,8,092, wherein the dream-resistant nanometer-sized spherical particles are Non-polar organic bell film surrounds 'Ayers uses rice-resistant spherical particles coated with organic film to form a porous dielectric film layer'. The more pores in the film, the lower the dielectric constant, and the dioxide Silicon particles are obtained by TEOS (as a precursor molecule) hydrolyzed and its condensation reaction. The non-polar organic membrane used by Ayers is composed of a fluoroalkyl silane compound. This fluoroalkyl silane compound has only one end bonded to micron-sized particles, so it is flexible. Page 3 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — 丨! I * pack ----- 丨 Order ------- line (Please read the precautions on the back before filling this page) 471104 A7 B7 V. Description of the invention ()

The nano-sized spherical particles used by Ayers contain at least silicon dioxide, and silicon dioxide has a relatively high dielectric constant with a value of about 4, and this silicon dioxide core material will limit the dielectric properties of porous membranes. Decrease of constant. In addition, used by Ayers. The organic film is only connected to nano-sized spherical particles at one position and is soft in nature, so the soft organic compound will be compressed when the dielectric film is formed, and the gap between the nano-sized spherical particles It is reduced. The porosity of the film structure thus formed is only slightly increased, and the dielectric constant of the film is also increased at the same time.

Kapoor et al. In U.S. Patent Nos. 5,598,026 and 5,470,801 describe a method for manufacturing a low-dielectric porous separator, one of semiconductor materials. The porous membrane is obtained by chemical vapor deposition of a mixture of an insulating material and a second extractable material. When the extractable material is removed, the porous structure of the low dielectric insulating material is obtained. However, Kapoor et al. Cannot guarantee the regularity of the interval and the size of the holes formed when the extractable material is removed, and the holes formed by the method used are very large or very small, including the size of large holes and lithographic features. The area is similar in size, so this result is unacceptable 'because of this-the etched hole or trench will intercept a large hole. When these large holes are filled with metal when the line is manufactured, a short-circuit path or a high capacitance will be formed between the metal wires of the phase, which means that the line is defective. In each of the above-mentioned conventional technical references, the 'porous membranes contain irregularly-distributed holes, and these holes make the dielectric characteristics in the dielectric film different depending on the position. In addition, the holes of these conventional film layers. / U size is very different. 'It is obvious that such film characteristics are not suitable for complex processing / application in integrated circuits ------------- -Install --- (Please read the phonetic on the back? Matters and then fill out this page) _-* Line · Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 471104 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (). Therefore, it is an object of the present invention to provide a dielectric film with a low k value. The dielectric characteristics over the entire surface and thickness are substantially constant. Another object of the present invention is to provide a dielectric film having a k value of about 2 to 3. OBJECTS AND SUMMARY OF THE INVENTION: The method of the present invention is to produce a porous dielectric body with a low k value, and the dielectric properties of the dielectric body in its bulk material and at its surface are uniform. The method first prepares a solvent, a first amount of dedicated nano-sized particles and a second amount of structured nano-sized particles into a mixture, wherein the structured nano-sized particles contain an organic component and the mixture is concentrated To make structural nanometer-sized particles compose a lattice structure ', and there are dedicated nanometer-sized particles dispersed in the crystal structure. The structured nanoscale particles are then melted together to harden the structured nanoscale particles and the lattice structure. Then, the dedicating nanometer-sized particles are removed from the lattice structure and vacated in them. Finally, the surface of the hole is coated with water-repellent material. Brief description of the drawings: Figure 1 is a flow chart of the method of the present invention; Figures 2a-2c illustrate the nano-scale particles in the three stages of the method of the present invention

------ I --------------- ^ --------- ^ (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 471104 A7 _B7_ V. Description of the invention () Drawing number comparison description: 11 Hexagonal crystals 12 Two-dimensional film layer 13 Dedicated particles Detailed description of the invention: The present invention uses dedicated nano-sized particles and structured nano-sized particles to A low-k dielectric film is formed. In the present invention, a very important feature is that both the diameter of the structured nanometer-sized particles and the dedicated nanometer-sized particles can be selected, and their sizes are substantially uniform. Because these nano-sized particles are approximately uniform in size, they have the property of arranging the particles themselves into a regular crystalline structure during manufacture. This enables the dedication of nano-sized particles to be regular and consistent in the lattice structure. Arranged periodically. Later, after the dedication nanometer-sized particles were removed, the holes were arranged in a regular periodic pattern in the final formed film. Therefore, the porosity of the formed film can be adjusted by selecting the size of the dedication > meter-level particles to meet the required k value of the film. A better material that can provide this kind of dedicated nano-sized particles: the material is composed of germanium and oxygen (that is, germanium dioxide), while tree milk, Fan, anthracene, and related organic compounds and molecular crystals are the second best select. On the other hand, the preferred structural nano-scale particle material is organic hard, its molecular formula is SiaObCeHd ', and its Mohr fraction a is about 0.05 to 0.5, preferably about 0.01 to 0.4, and about 0.15. More preferably to 0.25; Mohr fraction b is about 0.05 to 0.5 'and preferably about 0.1 to 0.4, and more preferably about 0.2 to 0 _ 3 5; Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------- I -------- ^ --------- ^ (Please read the note on the back first Please fill in this page again.) 5. Description of the invention (ear score is about .05 to 0.5, and about 0.15 to 0.4 is better. Moore /, and 々.10 to 0.5 is It is better to use about ....., and :: ΓΓ: about. To. · 5, and the structure of nano-grade materials (because of its high dielectric constant) includes the second best hardening and nitriding dreams. , It can form a lattice structure. Dagger ... Emulsified sand, oxygen-phosphorus structure particles to make nano-scale large-scale wheat burn, organic ♦ Oxy-fired mw =: is the use of thermal decomposition of ions. Silicon pit or tooth silane precursor substance The composition of the aforementioned structural particles is more familiar than the composition of the dielectric particles. # 早 入 〇u lies in the fact that the dielectric constant (k is about 2 to 3) of w carbon particles is theoretically lower than that of conventional silicon oxide particles.. Structure nano-sized particles are coated with organic compounds as Good ... preferable organic compounds should (1) make the particles water-repellent to resist water vapor; ⑺ contains-water-repellent positions, and the positions can be bonded to the particles; (3) reduce the overall dielectric constant of the particles , And (4) make the particles soluble in organic solutions. Examples of such preferred organic compounds may be alkylsilanes or alkane compounds such as XsSiR, where X is an alkoxy group or a halogen, wherein the alkoxy group Carbon is about 1 to 4 in the molecular formula, and R is a gauge group, and its carbon is about 8 to 30 in the molecular formula. As noted above, the characteristics of the structure of the dielectric film formed according to the present invention The size of the pores in the film is approximately equal. These pore sizes are controlled by the dedicated nano-sized particles and their diameter (DA), and the pores are arranged in a regular and predictable pattern. Both have controllable size and composition) use, with regularity The size of this paper with the same size of holes is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 471104 A7 B7 Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 5. Description of the invention (a solid film was formed. Manufacturing method description A preferred embodiment of the film manufacturing of the present invention, we can refer directly to the flowchart shown in Figure 1, the preparation method of the nano-level particles of the present invention is the same as the manufacturing method and the description. This method (step 1) first provides a solution of dedicated nano-sized particles formed of germanium dioxide, where the diameter of the western particles is DA, and " nano-sized particles " refers to particles with a diameter of 1 to 10 nm, Denier is preferably from 3 to 3 nm. The shape of these nano-sized particles is approximately spherical, and is characterized by a narrow distribution of particle sizes (that is, the particles are essentially uniform in size and the standard deviation within the size difference is less than 10%). This method further utilizes a structured particle solution, which contains at least silicon, carbon, oxygen, and hydrogen (hydrogen is optional). These particles are roughly spherical, and are characterized by the distribution of particle size and the diameter of the particles is & quot "DB". The synthesis of these nanoscale particles and the phase treatment of the solution will be described later. ^ In the preferred embodiment, 'DB / DA is approximately 0 75 5 Λ. Nano-scale particles are selected at a specific ratio, the ratio of 1 germanium dioxide to 5 silicon oxycarbons outside 卽 1. DB / DA is 0.65 to 0 θ, y 疋-a kind of poor diameter ratio. The germanium dioxide particles (DA) are larger, and they are more heart-warming-in step 2, the solution of germanium dioxide particles and carbon oxidation = ^. 7 fe predescent liquid is mixed to form a random mixture, where 丨, find ~ The ratio of gasification fault particles to 5 finished silica particles is still maintained. ~ Pound 箐, mixed _ page 8 ^ Paper size applies Chinese National Standard (CNS) A4 (21Q X 297 public love) ^- ----- 11 ^ —------- ^ (Please read the notes on the back before filling out this page) 47 11〇4

The substance is evaporated by the solution to form π- / respectively in a volatile solvent, | 7 / called-again to the dispersed colloid ', wherein the viscosity of the solvent is selected to facilitate the use of step 3. At this time, the arrangement of nano-scale particles in this method is shown in Fig. 2a. In step 3, the colloidal solution taught in both directions is bonded to a substrate by an appropriate method ', such as a spin coating method, a titration coating method, or a spray coating method. The m solvent is then slowly removed from the coating by evaporation. This action can be selectively performed in a vacuum of about 60 t + + from a 丹 dandi I formaldehyde. The formed film layer is a solid compound formed by the regular arrangement of germanium dioxide and silicon oxycarbide particles. The ratio of germanium dioxide and silicon oxycarbide particles is 5: 5. So far, the arrangement of nanoscale particles in this method is shown in Figure 2b. It is worth noting that germanium dioxide particles are approximately 1,25 times larger than silicon carbide particles, and the germanium dioxide particles are roughly distributed on the regular lattice position of the silicon carbide particles, and the formed film layer has CaCu5 Lattice structure of nano-scale particles superlattice structure. It is understood that the hole arrangement and ceremonial spacing need not be perfectly perfect in all areas of the film formed by the method of the present invention, as long as this arrangement exists in a substantial portion of the film. The formed film layer is a nano-scale particle superlattice structure with CaCu3-lattice structure as shown in FIG. 3, where the diameter of the structural particles is 0, which is represented by the black circle TF 'and the dedication particles are opened. The circle 圏 indicates it. The "structure particles" are arranged in the shape of connected hexagonal crystals 11 and form an infinite two-dimensional film layer 12; the dedicated particles 13 occupy the center position of every other two-layered hexagonal crystals. 70 to 75% of the structure formed The space is inorganic before etching. Page 9 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -ft II IV- IIIIII 1 I 1 II (Please read the precautions on the back before filling in this *) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives printed 471104 A8 B8 C8 D8 patent application materials are filled, and after the germanium dioxide component is removed, the filling ratio is reduced to about 55%. In step 4, the silicon oxycarbide particles are cross-bonded due to the addition of heat or radiation, and the formation of the cross-bond is due to the selection of a dual-functional surface stabilizer. When ultraviolet or other sources cause cross-linking, One end will coordinate to a large extent with surface nano-sized particles (for example, for carbon oxide dreams and germanium dioxide particles, siloxy or chlorosilane functions will combine with each other), and the end of the molecule will have chemical Half chemical moieties), these chemical halves azx will be bonded to each other. A preferred example of the structure of the molecule is X3SiR (described above) 'where R is a (. 仏) ^ chain, and η is 1 to 20, The terminal of R is the acrylate group: 〇

A —0 — C — CH = »CH2 〇 The different method is to form an amino compound chain by using a mixture of the R chain terminated by -COOH and the -NH2 group. In step 5, the substrate is placed in water, and the germanium dioxide particles are removed by dissolving into an alkaline aqueous solution. Ultrasonic sanding, mechanical agitation, and gentle heating can be selectively used. To accelerate the dissolution of germanium dioxide particles into the aqueous solution. After the germanium dioxide is dissolved, holes (holes) are formed. At this time, the arrangement of the structure particles formed by this method is shown in Fig. 2c. The water in the pores was slowly exchanged with the intermediate solvent because the porous body was immersed in acetone. The porous body was then placed in a pressure control chamber, which was connected to a carbon dioxide gas source, and the temperature of the porous body sample was 3 Below 1 ° C, the paper size on this page 10 applies Chinese National Standard (CNS) A4 specification (210X297) (please read the precautions on the back before filling this page). 471104 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7. 5. Description of the invention (the pressure of carbon dioxide in the air gradually increased, and gradually increased to 1072 psi (about ten minutes). When the chamber pressure is 1072 psi and the temperature is increased to 3rc, carbon dioxide turns from a high-pressure gas into a supercritical fluid, and the secondary fluid dissolves acetone with the residual water from the pores. Then, the temperature in the room is maintained at about 35 ° C, which is only slightly higher than the critical temperature, and the pressure decreases slowly. This reduces the density of the supercritical fluid and slowly returns the carbon dioxide to the gas state. In this cycle of action, the solvent (acetone and residual water) is removed from the interior without subjecting the porous structure to large surface tension ’, where this surface tension is caused by the solvent being removed by heat or vacuum. From this point of view, the remaining structural particles form a loose cubic lattice structure and are maintained in this loosely arranged lattice structure due to the presence of cross-linked organic molecules. Next, the porous solid is exposed to the humidified air, which will cause water to be absorbed again on the inner surface ', so the degree of exposure to the humidified air should be minimized until all the inner surfaces become water-resistant. (See step 6). In step 6, the amount of residual water absorbed on the surface of the particle is removed, and the inner surface of the hole makes it water-repellent. The substrate was placed in a vacuum furnace at about 150 ° C. The furnace was evacuated, and the porous body sample was left at 150 ° C for about 10 minutes. The furnace is then charged with hexamethyldisilazane or hexaphenyl-disilazane, where the two substances are collected in an inert gas (nitrogen or argon) and the substrate Still maintained at 150. (:. After 20 minutes, the furnace was cooled to room temperature and evacuated, during which it lasted for about 10 minutes. The Chinese national standard (CNS) A4 specification (210 X 297) ) ---------- install -------- order --------- line (please read the precautions on the back before filling this page) A7

471104 V. Description of the invention () In this process, the internal pores are plated with a water-repellent film, so that the porous body will not absorb water vapor, and its nature will become emotional. Subsequently, the furnace is supplied with a pure inert gas' and the substrate is removed. Finally, the formation of the membrane structure is a superlattice structure composed of nanometer-sized particles of silicon oxycarbide, and holes (holes) are arranged in the crystal structure. These holes are formed by holes such as CaCus 0 lattice structure. Regularly arranged at regular intervals. This membrane structure can be regarded as an interlayer stack structure formed by silicon oxycarbide particles, in which the silicon oxycarbide particles are arranged in a connected hexagonal crystal form, and there is a hole in the central part of each hexagonal crystal form. Second Embodiment In the second embodiment of the present invention, the larger number of nanoscale particles are nano, en, or a related molecular crystal ', and its diameter is DA. Next, in step 5 of the method, a hydrocarbon solvent (any aliphatic or aromatic soot ' such as pentane, hexane, or toluene) can be used to dissolve the molecular crystal particles to leave the silicon oxycarbide particle structure. This is different from the first embodiment in that steps 5 and 6 can be combined into a single step. The HMDS or HPDS is dissolved in a hydrocarbon solvent. The solvent containing HMDS (or HPDS) is used to dissolve larger solvents. A few nano-sized particles, and it is better to perform at a temperature of 100-150 ° c, HMDS (or HPDS) and at the same time react with carbon oxidation of the surface of dream nano-sized particles: • Evening. The third embodiment of the household meal in the present invention In the third embodiment, a relatively large number of nano-sized particles are straight. Page 12 This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). IIIII Packing-I-II Order-- ----- line (Please read the precautions on the back before filling this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 471104 A7 B7

PAA PMMA PGMMA PTBA PS PolyNIPAM V. Description of the invention () The diameter is DA, and it is preferably composed of synthetic tree milk (poly (butyl bisporate)) or PBMA. Other available materials are as follows: poly (propylene Pyranoic acid) Poly (Methyl-based cake associative acid @ Purpose) Poly (Methyl methacrylic acid glycidyl ester) Poly (t-Butyl cake gallate plate) Poly (Acetophenone) Poly (η-isopropyl · · Ammonium propionate) Dedicated nano-sized particles are oxidized by oxygen to remove (rather than dissolve) 'the first advantage is that some dedicated particles are easy to buy (that is, easily available on the market)' · its second advantage For this removal method only one reaction chamber is required when performing steps 5 and 6. The reaction chamber was evacuated, and then filled with active oxygen (that is, a mixture of oxygen molecules and oxygen atoms provided by a remote oxygen plasma and ozone generated by ultraviolet rays), and the substrate temperature was maintained at 200 ° c. _3 50 ° c, the operating conditions must be continuously maintained until a relatively small number of nano-sized particles are converted to 'after rhombohedral oxidation and other oxidation products'. Among them, the adjustment of the oxidation state must be done in a way that does not allow carbon or graphite deposition residues to remain Above the surface of the inorganic nanoscale particles, as this may increase the dielectric constant of the formed film. In the fourth embodiment, most of the structural particles may be composed of silicon dioxide, while the larger few particles (dedication particles) are composed of one of the following [dioxide dioxide, paper size applicable to Chinese National Standards (CNS) A4 specification (210 X 297 mm I .------------ curtain -------- if --------- line C please read 03.意 意 事 顼 save and fill in this purchase) Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 471104 The aforementioned formula ^ is DA. After dedicating the particle tip, it is removed by using the fan method. Fifth Embodiment The fifth embodiment is different from the foregoing figures in the nano-level particles or another suitable tree. Zhashe structure r child, h 'we use ^ machine nano-grade particles as the knot of the majority, and the following 丨 Zhalu, & Wanghua ... as a minority of dedication particles: a-Xin Too: Siliconized silicon, silicon dioxide, or a molecular crystal (such as Fan). The structure of this di 'prime T and meter particles is formed in step 1 to step 3. These particles are subsequently and cross-linked. After that, the dedication particles are removed with appropriate ... decomposition chemicals, among which the germanium dioxide particles are engraved with a test aqueous solution, nitrogen poem and gardenia dioxide are used for hydrofluoric acid Here, the nano-sized particles of molecular crystals (such as using dilute in toluene to remove them, where toluene will swell but will not dissolve the tree milk particle network. Sixth Embodiment In this different embodiment, The diameter of the consecrated particles is DA, and the diameter of the structured particles is DB ', and their correlation is DB / DA = 〇6 ± · 〇5. These particles are mixed in step 1, and the mixing ratio is 13 smaller ones. The ratio of the devotion particle to a larger structured particle. At the end of step 4, the film structure formed is shown in Figure 4 and the structure is formed by the larger structured particles. The cubic lattice structure is arranged. In each cubic unit cell, there are a set of smaller dedicated particles 1 3. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ---- Order --------- line (Please read the note on the back first Please fill in this page again) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 471104 A7 B7_____ V. Description of the invention () Manufacture of structured nanometer particles Square structured nanometer particle materials are prepared by thermal dispersion synthesis. The σ formation method firstly heats a high-boiling-point solvent to about 2000-400C in advance, and any suitable inert substance high-boiling-point solvent can be used. Aromatic acids and materials with substituted aromatic ethers are more suitable. A good solvent source, the preferred mode of the latter is R7 ~ ph-〇-ph-R8, where Ph is phenyl 'and R7 and R can be the same or different, and they are selected from phenyl and about Ci to Cs. Examples of other suitable solvents are aromatic ethers, materials with substituted aromatic hydrocarbons, unsaturated hydrocarbons with high boiling points (such as isacosane or 2,6,1 0,1 5,1 9,23 hexamethyl Hexame thy (tetracosane), and perfluoroolefins (such as perfluoro kerosene). The preferred solvent is phenyl ether at a temperature of about 250 ° C. A stable complex matrix is added to the solvent. Among them, it is a better practice, in which the addition of the complex matrix is discussed below. The base siloxane, organosilane, siloxane, silane, and / or cystanil precursor compounds are placed in a syringe and quickly Injected into the pre-heated solvent, the precursor compound will be rapidly thermally decomposed, and small amorphous silicon-containing particles will nucleate. The solvent is heated for about 30 minutes, and the particles grow. At this time, the size of the particles is about It is 5nm. In addition, the heating time can be increased or shortened to apply to the growth of larger and smaller particles, respectively. The structure of the preferred halosilane precursor compound is R4Si Y3 ', where R4 is about Ci to Cs. , And γ Halogen, and chlorine is preferred. One of the preferred siloxane compounds that can be used in the present invention is hydrogen-half times. Page 15 This paper applies Chinese National Standard (CNS) A4 (210 X 297 mm)- --IIII 1 III 1 *, I 1 II 丨 II · 1 丨 — 丨 — — 丨 _ (Please read the notes on the back before filling out this page) 471104 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention () Hydro-silsesquioxane, the general structure of which is HnSin03 / 2n, where n is about J to. In a comparative example, the precursor compound is an organosiloxane precursor compound. In the invention, the 'organosiloxane compounds are straight, bifurcated, or structured compounds, which contain at least silicon, oxygen, and carbon. The preferred organic compound is sesesquioxanes. Cyclosiloxane. Examples of in silsesquioxane are incomplete condensation and intact sesquioxide. Oxygen burning is one of the incomplete ones whose molecular formula is (fTSi〇3M) n (H2〇) 3n / 2 'Wherein Rs is an alkyl group of about ^ to Cs, and ^ is about 1 to 10. In addition Incomplete condensed silsesquioxane is formed when R3Si (0Η) 3 is heated and water has been removed. Incomplete condensed silsesquioxane is water for partially condensed silsesquioxane. It is formed after removal. Currently available on the market, complete coagulation times + dream oxidizing can be used in the present invention. Η is 6, 8 and 10. Cyclic radical oxygen sintering can also be used as a precursor of the present invention Compounds, the preferred formula of cyclammonium oxide is R3nHn (Si〇) nl Rs2n (Si〇) n, where R5 is about C 'to Cs alkyl' and ^ is about 1 to i0. Another preferred molecular formula is based on CH30 (SiO (CH30) 2) n ', where n is about 1 to 10. More preferred organosiloxanes and organosilane compounds are mixtures of TEOS, TMS, TMXTS, TECTS, cyclotetrasiloxane, cyclopentasiloxane, pentamethylpentaoxane and the above. The above compounds are used to form the preferred ones required by the present invention. Page 16 This paper is in accordance with Chinese National Standard (CNS) A4 ϋ 210 χ 297.

Ilf —------- install ------- -order ------- · line (please read the phonetic on the back? Matters before filling out this page) 471104 Staff Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed A7 B7 V. Description of the invention () Organic silicon particles. For example, the ratio of Si: 0: C of an amorphous particle formed from a mixture of TE0S: TMS: TMCTS as 1: 3: 2 is about 1: 1: 2.3. The carbon content of the particles can be changed by changing the carbon content of this ratio and its precursors. For example, TECTS can be used in the above mixtures instead of TMCTS to increase the carbon content of the particles. When these particles grow to the required size, the reaction is reduced to a low temperature to stop the particles from growing, and then a stable complex matrix is added, where the temperature is less than about 150 ° C, and preferably less than 10CTC , And preferably less than about 60 ° C. The stable complexing base preferably has a structure of XsSiR, where X is an alkoxy group of about C i to C4 or a halogen, and r is an alkyl group of about C8 to Cso. More preferably, R is about the radical 'c12' of c12 to c24 and more preferably about the calcined group of C i 6 to C 2 G. When the stable coordination matrix is added, it is bonded to the particle surface. In addition, these particles can be optionally tempered by raising the solution temperature to 300 to 350 ° C and maintaining the temperature for a certain period of time. Organic coated particles can be deposited using a polar solvent such as ethanol. In addition, some particles of a certain size can be immersed to isolate and purify the particles, and thus form a part of the particles that are almost unidirectionally scattered. The first embodiment of the precipitation of particles of a specific size is related to the increase of a polar solvent. First, a selected amount of a polar solvent is added to an organic film-coated particle mixture. In this process, the largest organic-coated particles first precipitate and can be isolated by centrifugation or filtration equipment. Then, the polar solvent is added to the organic coating particle mixture, so the smaller particles are on page 17. This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 2 mm)! — — — — — — — — — — — —- 丨 丨 Order III — II 丨 — (Please read the notes on the back before filling this page) 471104 A7 ________________ V. Description of the invention () ------------ -Install --- (Please read the precautions on the back before filling out this page) This is the reason. In this way, particles of various sizes can be prepared. In order to form particles that are almost unidirectionally dispersed, the isolated parts can be re-dispersed in a non-polar solvent, and more particles can be selected for precipitation to obtain arbitrary and similar size differences. Diffuse particles in one direction. Here we introduce the second method of selecting the particle size for precipitation, which involves dissolving the particles in a mixture of two solvents: a more volatile and non-polar solvent (such as pentane), and the other is more volatile Weak and polar solvents. When the solvent mixture is slowly evaporated, the content of the more volatile and non-polar solvent decreases, which causes the largest organic coating particles to precipitate. Next, the smaller particles are further evaporated, so that particles of various sizes can be obtained, and particles of various sizes that are nearly unidirectionally dispersed can be obtained as a result. Synthetic line of germanium dioxide particles Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Germanium dioxide particles are synthesized by thermal decomposition, which are the same as those used for silicon oxide particles. A high boiling point solvent is selected, preferably dimethyl ether 'and different from the solvents listed above. Preferred precursors are gaseous germanium oxide and germanium alkoxy groups, wherein the germanium alkoxy group has the structure of GeR4, where R is -0-CH3, -0-CH2CH3, -CUCH2CH2CH3 or 乂 〇-ch2 (ch3) 2. _ The remaining precursors (especially GeX4, where X is chlorine, Mo or Dish) can be mixed with better precursors to enhance the nucleation of particles. However, a 'wrong is not easy to oxidize like a dream', so a door containing 0-20% oxygen can be used. Page 18 This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 471104. A7 B7 改 Modified V. Description of the invention (Environmental air to accelerate the formation of dioxide. The above-mentioned stable coordination matrix used in hard dioxide synthesis can also be used to stabilize germanium dioxide particles. The method for selecting the size is the same as the method for selecting the carbon oxide sand particles described above. The present invention can be understood through the foregoing text description and illustrations. However, it should be understood that the scope of the present invention is not limited to the embodiments described above. , In fact, should include all the implementation of the above embodiments and their equivalent scope, which do not depart from the scope of the attached patent application: the spirit and scope of the change. ——; ------- ik— { (Please read the notes on the back before filling out this page)-11. Printed on paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Claims (1)

471104 ί_ · _ 丨 '丨 丨 ..- || ^ l Amendment A8 B8 C8 D8 Sixth, the scope of the patent application for the number of pairs of patents ~ ~% amended in July 1. A method of manufacturing a porous dielectric Method, the method comprises at least the following steps: a) providing a mixture of a first amount of dedicated nanometer-sized particles and a second amount of structured nanometer-sized particles, wherein the structured nanometer-sized particles include a low organic component; b) Concentrate the mixture 'to make the structural nano-scale particles form a lattice junction. Structure' and dedicate nano-scale particles entangled in the structure; c) process the lattice structure to make the structural nano-scale The first-order particles melt and harden the lattice structure and the porous dielectric body; and d) remove the dedicated nano-scale particles from the lattice structure to leave holes in the lattice. 2. The method as described in item 1 of the scope of patent application, which further comprises the following steps: e) The surface of the hole is plated with a layer of water-repellent material. i -------- ^ --------- line (Please read the notes on the back before filling out this page) Employee Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Printing 3. If the scope of patent application The method according to item 1, wherein the step (c) adds energy to the lattice structure so that the organic component is cross-linked. 4 _ The method as described in item 1 of the scope of the patent application, wherein the structured nano-sized particles are composed of an organic particle, and the structure of the organic hair is SiaObCcHd, wherein the Mohr fractions of a, b, and c are about It is 0.05 to 0.5 and d is about 0 to 0.5. This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 471104 A8 B8 C8 D8. The scope of patent application 5. As described in item 4 of the scope of patent application In the method, the mole fractions of a, b, and c are preferably about 0.1 to 0.4, 0.1 to 0.4, and 0.1 to 0 * 5, respectively; and d is about 0.05 to 0.4. 6. The method as described in item 4 of the scope of patent application, wherein the mole fractions of a, b, and c are preferably about 0 to 5 to 0.25, 0.2 to 0.35, and 0.15 to 0.4, respectively; and d is about 0,1 to 0 · 4 are preferred. 7. The method according to item 1 of the scope of patent application, wherein the dedicated nano-sized particles are composed of germanium and oxygen. 8. The method according to item 1 of the scope of patent application, wherein the dedicated nano-sized particles are composed of molecular crystals. 9. The method according to item 1 of the scope of patent application, wherein the dedicating nanometer-sized particles are composed of at least one of and 赝. 10. The method according to item 1 of the scope of the patent application, wherein the dedicated nano-scale particles are composed of at least one organic polymer. 1 1. The method as described in item 1 of the scope of patent application, wherein the dedicated nano-sized particles are composed of at least one of the following: PBMA, PAA, PMMA, PGMMA, PTBA, PS or polyNIPAM. Page 21 This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) r -------- «. * ------- Order ------- -II (read the precautions on the back before filling this page) 471104 A8 B8 C8 D8, patent application scope 1 2. The method described in item 1 of the patent application scope, wherein the diameter of the dedicated nano-sized particles is larger than that Structural nano-scale particles. 13. The method according to item 1 of the scope of patent application, wherein the removal of the dedicated nano-sized particles in step d) is achieved by using a solvent. 14. The method according to item 1 of the scope of patent application, wherein in step d) the removal of the dedicated nano-sized particles is achieved by oxidizing the dedicated nano-sized particles. 1 5. A device comprising a porous body, the device comprises electrically isolated nanometer-sized particles, and the nanometer-sized particles are melted together, and the device further includes a selected amount of nanometer-sized particles. The large and small ones are uniformly sized pores, and the pores are distributed in the porous body in a substantially periodic manner. 16. The component according to item 15 of the scope of patent application, wherein the electrically isolated nanometer-sized particles are fused together using cross-linked organic molecules. 1 7. The component as described in item 15 of the scope of the patent application, wherein the electrically isolated nano-sized particles include at least a base siloxane, and the molecular formula of the siloxane is SiaObCcHd, wherein a, b and The mole fraction of c is about 0.05 to 0.5, and d is about 0 to 0.5. Page 22 This paper size applies Chinese National Standards (CNS) specifications (210 X 297 mm)-Please read the notes before filling in: Page I! II! II Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 471104 Printed by A8, B8, C8, D8, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of Patent Application 1 8. The components described in item 15 of the scope of patent application, where the Mohr scores of a, b, and (Γ are divided by About 0.1 to 0.4, 0.1 to 0.4, and 0.1 to 0.5 are preferred, and d is preferably about 0.05 to 0_4. 1 9. As described in item 18 of the scope of patent application The elements described above, wherein the Mohr fractions of a, b, and c are preferably about 0.15 to 0.25, 0.2 to 0.35, and 0.15 to 0.4, respectively, and d is preferably about 0.1 to 0.4. 2 0 The component according to item 15 of the scope of the patent application, wherein the electrically isolated nano-sized particles are plated with a layer of water-repellent material. 2 1. The component according to item 20 of the scope of the patent application, wherein the avoidance The water-based material is from hexamethyldisilazane or hexaphenyldisilazane. The element in which the pores are arranged approximately uniformly within only a part of the porous body. 2 3. The element according to item 16 of the patent application range, wherein the cross-linked organic molecule is selected from the group consisting of hydrocarbons In the group consisting of hydrocarbons, hydrocarbons of 'propionic acid and phenylacetic acid end point. 24. The element according to item 15 of the scope of patent application, wherein the size of the uniformly-sized holes is about 0. 5 to about 1 Onm, and the interval between the holes is about 1 to about 20 nm. Page 23 This paper size applies the Chinese National Standard (CNS) A4 regulation ^ (210 X 297 mm) (Please read the note on the back first Please fill in this page again for matters) Yi-nnn I— n I n) 5J · n I n fa 1 Line: