TW392309B - Improved process for producing nanoporous silica thin films - Google Patents

Abstract

A process for forming a nanoporous dielectric coating on a substrate. The process follows the steps of blending an alkoxysilane with a solvent composition and optional water; depositing the mixture onto a substrate while evaporating at least a portion of the solvent composition; placing the substrate in a sealed chamber and evacuating the chamber to a pressure below atmospheric pressure; exposing the substrate to water vapor at a pressure below atmospheric pressure and then exposing the substrate to base vapor.

Description

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 -------- --- B7 V. Description of Invention (1) — '' ~~ ^ · —. Please refer to this application before and after the case This is a tentative application for the benefit of 60 / 〇44,402, which was filed on April 29, 1997, and is hereby incorporated by reference. BACKGROUND OF THE INVENTION The present invention relates to a nanoporous dielectric film and a method for manufacturing the same. This film can be used to make a complete: integrated circuit. Instruction of the prior art In the manufacture of integrated circuits, interconnections of 1? £; delay, power consumption, and contention problems become more significant as the feature size approaches 25 microns and lower. For interlayer dielectric and intermetal dielectric applications, the use of low dielectric constant (κ) materials will mitigate these problems. However, due to industrial considerations, candidate materials with a dielectric constant that are significantly lower than those currently used for dense silica have encountered some disadvantages. The development of most low-dielectric constant materials is the use of spin-on glass and fluorinated plasma for chemical vapor deposition of Si02 'which has κ > 3 ^ some organic and organic polymers have a dielectric constant of about 2.2 In the range of 3.5, however, it has problems of low thermal stability and poor mechanical properties, including low glass transition temperature, sample outgassing, and long-term reliability issues. Another approach to death is to use nanoporous silica, which may have a dielectric constant in the range of about 1 to 3. Porous silica is attractive because it uses precursors similar to those currently used in spin-on-glass (s0G) and CVD SiO2, such as tetraethoxysilane (TEOS), and because it has The ability to carefully control pore size and pore distribution. In addition to having a low dielectric constant, nanoporous hard stones provide other advantages to microelectronic components, including thermal stability to-----4 -_ This paper size applies to China National Standard (CNS) A4 (210X297) By) .. Approved clothing-(Please read the precautions on the back before this page). Ding. I -Ϊ I --- ΙΪ »» 1— Λ7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description (2 up to 900 ° C; small pore size ("microelectronic component characteristics"), the material used means 'silica and its precursors' is widely used in the semiconductor industry; " Fan Yuan's dielectric constant ability; and deposition using tools similar to those used in conventional spin-on-glass processing. Ep patent application EP 〇775 669 A2, which is incorporated herein by reference, illustrates a manufacturing process. Microporous silica film method, this film has a uniform density throughout the thickness of the film. A more porous material will not only result in a lower dielectric constant than a dense material, but it also allows the introduction of other ingredients and processing life. Step. Material issues include the need to make all pores significantly smaller than the feature size of the circuit; strength accompanied by a decrease in porosity; and the role of surface chemistry in permittivity and loss. Density, or its opposite pore yield, is controlled by: Jie Xiong = key nanoporous silica parameter of important properties of materials. These properties can be in a continuous range from 100% porosity to the two ends of dense silica with porosity of 0% Change. When the density increases, the electrical constant and mechanical strength will increase, but the pore size will decrease. The nanoporous silica thin film is made of a mixture of a solvent and a silica precursor, which is a borrowed method, such as spin coating. Coating, dip coating, etc., deposited on the wafer. This precursor must be polymerized after deposition and strong enough so that it does not shrink during drying. Film thickness and density / dielectric constant can be used. The mixture of the two solvents is independently controlled. The solvent will deposit on the substrate

Evaporates during and immediately after the precursor deposition. Partial hydrolysis and condensation products of silica precursors, blood torture / L 〆, and TOSOS on soil horses ’are polymerized by chemical and / or yirewan type until they form a gel layer. Using this research approach, we obtained the entire film -5- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) .--.---- seed coat ----- 1T ------ ^ f 碕 Read the precautions on the back before ^ r on this page) Printed by the Central Standards Bureau of the Ministry of Economy, printed by the Shellfish Consumer Cooperative Λ7 B7 V. Description of the invention (3) Nano with uniform density in thickness Porous silica film. Generally, in a sol-gel process to produce porous stone spar, a liquid catalyst, such as an acid or an alkali, is added to a silica precursor / solvent mixture 'to initiate a polymerization reaction. This catalyst addition is often accompanied by the addition of water, which is one of the reactants in the sintered hydrolysis and condensation reactions that cause polymerization. For semiconductor processing, the requirements for premixing catalysts and precursors cause some serious problems, because a relatively small amount of catalysts and precursors are less than 5 ml in total, and must be accurately measured and mixed This is because the deposition is performed on one wafer at a time. After the catalyst is added, the viscosity of the fluid begins to change. It requires that the deposition operation must be timed from the addition of the catalyst to the deposition. This deposition is a strong function of the viscosity to achieve the same film thickness. The catalyst / precursor solution that has not been deposited at the correct time cannot be used again, resulting in excessive waste. To avoid these problems, the deposited precursor film is sequentially contacted with water vapor and then with alkali vapor in any order to initiate the polymerization reaction. Previous researchers have used carrier films, such as nitrogen, to contact carrier gases, such as ammonium hydroxide, and pass gas / vapor mixtures through wafers covered with precursor films. Although the problems of liquid-liquid mixing and the timing of deposition as outlined above are avoided, this research approach has the following problems: maintaining constant = ammonia and water pressure in the carrier gas stream; measuring the actual ammonia and water vapor concentrations in the carrier gas stream requires relative Higher flow rates to minimize reaction time; and disposal of large amounts of ammonia-containing carrier gas. Another suggested research approach is to place wafers with precursor films in a sealed chamber and inject a test / water solution such as ammonium nitrate into the chamber. This research approach avoids—some of the problems outlined above ______- 6- The paper method scales are applicable to the Chinese National Standard (CNS) A4 specification (210x297). ---: ---- ^ 1 ---- -1T ------ (Please read the notes on the back before writing this page) Λ7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4 'But still, it is not allowed to measure its qi The concentration of alkali and water in the layer and long reaction time is required because the gas phase mixing is limited to the gas layer higher than the wafer. The present invention solves these problems by performing a series of processing steps, which enables manufacturing Nanoporous silica with minimal processing time, minimum amount of alkali catalyst usage, and large film thickness and refractive index uniformity / Eight inventions The present invention provides a nanoporous dielectric coating formed on a substrate Layer method, which includes (a) blending at least one alkoxysilane with a solvent composition and selected water, thereby forming a mixture and causing partial hydrolysis and partial condensation of the oxidized oxidized λ and thioxanthine. The mixture is on a substrate while at least a portion of the solvent group is evaporated (C) The substrate is placed in a sealed chamber and the chamber is evacuated to a pressure below atmospheric pressure; (d) the substrate is exposed to water vapor or alkali vapor at a pressure below atmospheric pressure; and ⑷If the substrate is exposed to alkali vapor in step (d), the substrate is exposed to water vapor, or if the substrate is exposed to water vapor in step (d), it is exposed to the test vapor. The invention also provides a semiconductor device made by a method comprising: (a) blending at least one alkoxysilane with a solvent composition and selected water, thereby forming a mixture and causing a portion of the sintered oxygen to burn Hydrolysis and Partial Combination-7- I Paper Size Applies to Chinese National Standard (CNS) A4 Specification (2ΐ〇χ297 公 楚 ---;-: ---- ^-(Please read the precautions on the back before This page),-° 涑 Λ7 V. Description of the invention (5 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, depositing the mixture onto a semiconductor substrate while evaporating at least a portion of the solvent composition; (C) the semiconductor substrate Material is placed in a sealed chamber, and the chamber is evacuated to a pressure below atmospheric pressure; (Φ Expose the semiconductor substrate to water vapor or vapor at a pressure lower than atmospheric pressure; then (e) if the substrate is exposed to alkali vapor in step (d), then expose the semiconductor substrate to water vapor, or If the substrate is exposed to water vapor in step (d), it is exposed to alkali vapor, which will form a nanoporous dielectric silicon coating on the semiconductor substrate. By using the present invention, the nanoporous silicon containing The space of the stone pre-existing wafer is evacuated, and then water vapor and alkali vapor are successively added. The pressure increase after adding each component is a direct measurement of the partial pressure of the component. The surrounding atmosphere has been evacuated, so the mixing problem is minimized, which reduces the film processing time. Brief Description of the Drawings Fig. 1 is a graph of a pressure history of a reaction chamber during a film processing process according to the present invention. Detailed description of the preferred embodiment The first step of the method of the present invention is to form at least one alkoxysilane, a solvent composition, a reaction product using water and a catalytic acid. The water system is added to provide a medium for hydrolyzing the alkoxysilane. The solvent composition preferably contains at least one relatively highly volatile solvent and ----- -8-.: ^-(Please read the precautions on the back before this page), -0 --- line.-I 1. i i --- This paper is suitable for Guancai County (CNS) A4 specification (21GX297 Gongchu B7) 5. Description of the invention (6) At least one relatively low-volatile solvent.

I This reaction product is applied to the substrate, and has raised lines under each β " SD as appropriate. Highly volatile solvents evaporate during and immediately after the reaction product is deposited. The reaction product is hydrolyzed and condensed until a gel is formed. The alkoxysilanes useful in the present invention include those having the following formula:

R-Si-R wherein at least two R groups are independently (^ to alkoxy), and if there are other R groups, they are independently selected from the group consisting of hydrogen, alkyl, phenyl, southernin, and substituted Phenyl. For the purposes of the present invention, the oxy- group includes any other organic group that can be easily cleaved from silicon by hydrolysis at temperatures close to room temperature. The R group may be ethylene glycoloxy Or propylene glycoloxy or the like, but preferably all four R groups are methoxy, ethoxy, propoxy, or printed oxygen by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Best alkoxy Non-exclusive silanes include tetraethoxysilane (TEOS) and tetramethoxysilane. 疋 For the purposes of the present invention, relatively high volatility solvents are those whose evaporation temperature is lower than, and preferably, those which are significantly lower than Those with relatively low volatility solvents. Relatively volatile solvents preferably have a boiling point of about 120 ° F or lower, more preferably about R. C or lower. Suitable high volatility solvents include non-exclusively. Methanol, ethanol 'n-propanol' isopropanol, n-butanol and mixtures thereof. Can be used with other paper rulers Degree of National Finance (CNS) Λ4 specification (2 丨 Fifth, description of the invention (formerly known as: knife phase valley <other relatively high volatile solvents are well-developed? Measured by the artist. _ 'W ， 可 谷 易The relatively low-volatility agent composition system is significantly higher than that of the phase-contained lacquer, which is the same as the hair-steering degree. The better agent composition preferably has an I point of about volatile or higher. The biotransportable solvent composition is about 2.... And polyphenols, including glycols, such as == di = U, 4-butanetriol, 1Α3_ τtriol, 2 · methyl · propyl H 2-. Methyl M, 3 · propylene glycol, butanediol '2 · methyl ♦ two glycol, four: glycol, triethylene glycol monomethyl ether, glycerol and mixtures thereof. Other compatible with other ingredients The lower volatility solvent composition can be easily measured by those skilled in the art. The selected acid is used to catalyze the reaction of the alkoxysilane with a relatively high volatility solvent, a relatively low volatility solvent and water. A suitable acid is nitric acid, and compatible organic acids, which are volatile, meaning that they will form from the process under the operating conditions of this method. The reaction product evaporates, and it does not introduce impurities into the reaction product. The alkoxysilane composition is preferably about 3% to about 50% of the weight of the overall blend. % Is present. A more preferred range is from about 5% to about 45%, and most preferably from about 10% to about 40%. The cereal component is preferably about 2% by weight of the entire blend. % To about 90%. A preferred range is about 30% to about 70%, and most preferably about 40% to about 60%. When both high and low volatility solvents are present, high volatility The solvent component is preferably stored in an amount of about 20% to about 90% of the weight of the entire blend. -10- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) Λ7 V. Description of the invention (8 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs. Printed by the Industrial and Consumer Cooperatives-11-about 30% to about 70%, and most preferably about 40% to about two times. When all of them are present, the low-volatile solvent component = based on the weight of the whole joint] to the appointment. The amount exists. More preferably, it is about 3% to about Satoshi, and most preferably about 5% to about 20%. The molar ratio of water to money ' is preferably from about 0 to about 50. A more preferred range is about 10 and most preferably about 0.5 to about 1.5. The acid is present in a catalytic amount, == ex situ by this artist. The molar range of the acid pair is preferably ooow \ 0 to about 0.2, more preferably about 0 to about 005, and most preferably about 0.005 to about 0.02. Then, the alkoxysilane-containing composition is coated on a substrate, and optionally has a line pattern on its surface, and a dielectric film is formed on this surface. This layer is applied relatively uniformly. Typical substrates are those suitable for processing into integrated circuits or other microelectronic devices. Suitable substrates for the present invention include non-exclusive semiconductor materials such as orbital gallium (GaAs) 4, and stone-containing compositions such as crystalline stone, polycrystalline stone, amorphous stone, Crystal silicon and II, Huameng (Si02) 'and mixtures thereof. When lines exist, they are typically formed by conventional lithographic techniques and can be composed of metal 'oxides, nitrides or oxynitrides. Appropriate materials for the line include silica 'nitride silicon: titanium nitride, tantalum nitride, aluminum alloy, copper, copper alloy', hafnium, tungsten, and silicon oxynitride. These lines are the conductors or insulators of the integrated circuit. It is typically closely spaced from each other at a distance of about 20 microns or less, preferably 1 micron or less' and more preferably about 0.05 to about 1 micron. The solvent, usually a more volatile solvent, is then allowed to evaporate at least partially. More volatile solvents evaporate in seconds or minutes. This paper size is in accordance with Chinese National Standard (CNS) Λ4 specification (2l0x297 mm)-. Outfit-(Please read the precautions on the back before ^^ this page). Γ — IK II:--?- 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 _B7 5. In the description of the invention (9), the film was a viscous liquid of silica precursor and lower volatile solvents. Optionally, use slightly higher temperatures to speed up this step. This temperature may range from about 20 ° C to about 80ec, preferably from about 20 ° C to about 50 ° C, and more preferably from about 20 ° C to about 35 ° C. The wafer is placed in a sealed chamber and quickly evacuated to empty. In a preferred embodiment, the pressure through the suction chamber ranges from about 0.001 Torr to about 0.1 Torr. &amp; After that, the coating was sequentially exposed to water vapor and alkali vapor. For the purposes of the present invention, the alkali vapor system includes a gaseous base. Preferably, the coating is first exposed to water vapor and then to alkaline vapor, but, in an alternative embodiment, the coating may be exposed to alkaline vapor first and then water vapor. The first of the two exposures was performed so that the subsequent pressure in the chamber was maintained at sub-atmospheric pressure. The second exposure can be performed at atmospheric pressure, sub-atmospheric pressure, or super-atmospheric pressure. In a preferred embodiment, after the wafer is placed in a sealed chamber and the chamber is evacuated to empty, the valve is opened to the water storage tank and water vapor is quickly filled into the chamber. The partial pressure of water vapor PH20 is controlled by the length of time the valve is opened and the temperature of the liquid water storage tank is maintained. Due to the low vapor pressure of water, the room pressure after water addition is much lower than the surrounding environment. During water vapor addition, the pressure rise in the chamber is a direct measure of the water vapor partial pressure. In this preferred embodiment, the pressure range of the suction chamber after water vapor exposure is from about 0.1 Torr to about 150 Torr, preferably from about 1 Torr to about 40 Torr, and more preferably about 5 Torr To about 20 Torr. In a preferred embodiment, the water temperature during the exposure ranges from about 10 ° C to about 60 ° C, preferably from about 15 ° C to about 50 ° C, and more preferably from about 20 ° C to about 40 ° C. In a preferred embodiment, after water exposure, __ This paper size is applicable to China National Standard (CNS) A4 size \ 210X297 mm) '~ --- ·-· ---- button clothes ---- --- ΪΤ ------ (Please read the notes on the back before ^ C on this page) Λ7 B7 V. Description of the invention (1〇 Temperature range in the room is about 1 (rc to about 50Ό, It is preferably about 15τ to about 40 ° C, and more preferably about 20t to about 4 ° C. After the water vapor is added, the alkali vapor is distributed into the chamber. The pressure of the chamber after the alkali is added may be Lies at, above or below atmospheric pressure. If the pressure is higher than atmospheric pressure, the chamber must be designed to resist the total system pressure. As with water vapor, the partial pressure of alkali is directly known from the pressure rise during alkali addition. Because忐 A only contains alkali and water vapor, except for the trace atmospheric gases left from the initial pumping and decompression. Therefore, the diffusion rate of alkali and water is much faster than that without pumping, resulting in a significant increase. Polymerization rate, reducing the processing time per wafer, and greater uniformity across the wafer. Since alkali and water vapor are added separately, their partial pressure is easy Amount, and almost no waste. Only the vapor above the wafer must be removed during deposition. The addition of water and alkali can be reversed, but it is better to add water before the alkali due to its lower vapor pressure. In a preferred embodiment, the pressure range of the suction chamber after the alkali vapor exposure is from about 100 Torr to about 2,000 Torr, preferably from about 400 Torr to about 1,000 Torr, and more preferably about 600 Torr to about 800 Torr. In a preferred embodiment, the temperature range of the alkali during the exposure is about 1 (rc to about 6 (rc, preferably about 15 ° C to about 40). (:, And more preferably about 2 (rc to about 30.0 in a preferred embodiment, and the temperature range in the chamber after the alkali exposure is about 10.0 to about 5 0τ ′, preferably about 15 C. To about 40 C, and more preferably about 20.0 to about 40.0. (^. Suitable bases for use with alkali vapors include non-exclusively ammonia and amines, such as primary, secondary and tertiary Alkylamines, arylamines' alcoholamines, and mixtures thereof having a boiling point of about 200. (: or lower, preferably 100 (&gt; c or lower, and more preferably 25X: or Lower. Better amine Classes are amines, dimethylamines, and tricots. (Please read the precautions on the back before you go to this page. J Printed by the Central Standards Bureau of the Ministry of Economy, printed by the Shellfish Consumer Cooperatives -13- Λ7 B7 Central Standards Bureau of the Ministry of Economic Affairs ec Printed by the Industrial and Commercial Cooperatives 5. Description of the invention (11) Methylamine, n-butylamine, n-propylamine, tetramethylammonium hydroxide, hexahydropyridine and 2-methoxyethylamine. Amines in water The ability to accept protons is measured from the viewpoint of alkalinity constant Kb, and pKb = _logKb. In a preferred embodiment, the range of 'experienced pKb' can range from about less than about 0 to about 9. A more preferred range is about 2 to about 6, and most preferably about 4 to about 5. In a preferred embodiment, the molar ratio of water vapor to test vapor ranges from about 1: 3 to about 1: 100, preferably from about i: 5 to about i: 50, and more preferably about 1: 10 to about 1: 30. Water vapor will cause the continuous hydrolysis of oxyhydrogen ash and oxyhydrogen, and the test will catalyze the condensation of the oxyhydrogen oxyhydroxide to burn the oxyhydroxide, and to increase the proportion, until the coating is green and the gel strength is finally increased. until. The film is then dried in a conventional manner &apos; by evaporation of a solvent of a less volatile solvent. High temperature 'can be used to dry the coating in this step. This temperature can range from about 20 ° C to about 450 ° C, preferably about 5 ° C to about 350 ° C, and more preferably about 175 ° C to about 320 ° C. After the addition is tested ' After the reaction at the desired time, in a few seconds to several minutes please 'rise the chamber pressure to atmospheric pressure. This can be done by adding an inert gas such as nitrogen' and opening the chamber or pumping the test / water mixture through emptying, and Achieved by backfilling with inert gas. The present invention obtains the best understanding by referring to Figure 1. The precursor is deposited on the wafer and the more volatile solvents are continuously evaporated within a few seconds. At ambient pressure, the The wafer is placed in a sealed chamber. The chamber is opened to the source of the air, and the surrounding gas is evacuated, and the pressure of the chamber is reduced. In the next step, water vapor is added and the chamber pressure is increased. During this step The pressure is increased, which is the water pressure (PH2〇). The alkali is steamed -14-&amp; paper wave scale applies Chinese National Standard (CNS) A4 specifications (210 X 297 Gongchu ---.--.---- ^) ------ 1T ------ ^ (Please read the notes on the back before this page) \ Ί \ Ί Central Standards Bureau, Ministry of Economic Affairs Printed by the Industrial and Commercial Cooperatives. 5. Description of the invention (in the case of 12 gas, ammonia, the introduction of the chamber into the room, the fatigue during the step triggers the polymerization reaction. After this, you can: It is the partial pressure check (such as p_). At the required time pressure, as mentioned, the chamber pressure is raised to the ambient pressure. 4 It can be evacuated to empty first, and then backfilled to the junction = relatively high porosity, low dielectric constant, tangent polymer combination Ray aI I formed on the material. The silicon-containing polymer composition preferably has a dielectric number of about U to about 3.5 ', more preferably about 13 to about 30, and most preferably about 1.5 to about 2.5. The composition has a pore size ranging from about ^ microns to about ⑽ nanometers', more preferably from about 2 nanometers to about 3 nanometers, and most preferably from 3 micrometers to about 20 nanometers. The silicon-containing The composition comprises a density of pores in a range of about αm to about b g / cm2, more preferably about 025 to about 1.6 g / cm2, and most preferably about 0.4 to about 2 g / cm2. The following non-limiting examples are provided to illustrate the invention. Example 1 This example illustrates a method in which the precursor is rotated Accumulate on the silicon wafer 'and then age the wafer in the chamber for a specific period of time and then dry it. The aging process in the chamber is as follows. This chamber is evacuated and water vapor is distributed to different pressures over a fixed time to distribute ammonia Gas to a higher pressure, after a fixed time ', pump again, after a fixed time, and then backfill with inert gas to increase the pressure in the chamber to the surrounding pressure. A precursor is produced by mixing while stirring 61 ml Tetraethoxy seconds, 61 ml of tetraethylene glycol, 4.87 ml of deionized water, and 0.2 ml of 1M nitric acid (concentrated HNO3, diluted to 1M). Then, the mixture was refluxed while continuously stirring for 1.5 hours, then -15- This paper size is applicable to China National Standards (CNS) M specifications (210x297 mm).: Approval of clothing -------, 1T ------ ^ (Please read the precautions on the back first (This page) A7 A7 Pressure after printing water feed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (mbar) (Tor) 7 (5.32) 14 (10.64) Refractive index 1.257 1.123 Thickness A 2450 4850 V. Description of the invention (13) After cooling. A portion of this precursor was diluted with ethanol at 55 wt.% While stirring. Approximately 1.5 milliliters of this diluted precursor was deposited on a 4 Infrared wafer on a spin chuck and spin-coated at 2500 rpm for 10 seconds. In this way, two films are deposited. Each film was placed in an aging chamber, which was disrupted to 1 mbar (0.76 Torr) within 30 seconds. Water vapor was distributed to the chamber up to 7 mbar (5.32 Torr) for the first wafer (from a storage tank of deionized water at 0 ° C) and 14 mbar (10.64 for the second wafer) Support) (from the storage tank of deionized water, under 25, c); leave the wafer under this pressure for 30 seconds. Distributing ammonia gas to the chamber 'pressure of 855 mbar (649.8 Torr) to the first wafer and 809 mbar (614_84 Torr) to the second wafer; leave the wafer at this pressure 1 minute. The chamber was evacuated for 30 seconds to 2 mbar (1.52 Torr) and immediately back-filled with air to ambient pressure. Place the film at 90. (: Heating plate for 2 minutes, then baking in an oven at 175χ for 3 minutes, and then baking in another oven at 400 ° C for 3 minutes. Remove the wafer and measure by ellipse after cooling The thickness and refractive index are measured technically. The refractive index can be linearly related to the porosity of the film. The refractive index is 10000 /. Porosity, and L46 is a dense silica with 0% porosity. The measurement results are shown. The following table: Moli (mbar) (Torr) 855 (649.8) 80 (614.84) after ammonia feed Example 2 / Example The example illustrates a method in which the precursor is spin-deposited on a silicon wafer 'Then the wafer is aged in the chamber for a certain period of time and dried. In the chamber (the aging procedure is as follows. This chamber is evacuated and the water vapor is distributed to a fixed pressure paper size iti? (--16- (210X297 Γ I.-G Thread (please read the notes on the back before this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 ----------- B7 V. Description of Invention (14 ) Force 'after a fixed time, the ammonia gas is distributed to a higher pressure, after different times &gt;' Pump again 'through the solid After a certain period of time, the pressure in the chamber was raised to ambient pressure by backfilling with inert gas. A precursor was produced by mixing while stirring 61 ml of tetraethoxysilane and 61 ml of tetraethylene glycol '4.87 ml of deionized Water and 0 2 ml of 1M nitric acid. Then, the mixture was refluxed 'while continuously stirring for 1.5 hours, and then cooled. A portion of this precursor was diluted 55% by weight in methanol' while stirring. About 15 ml of this diluted first was negatively charged 'Deposited on a 4-inch leaf-second wafer on a spin chuck and spin-coated at 2500 rpm for 10 seconds. Two films were deposited in this way. Each film was placed in an aging chamber' which was within 30 seconds It is evacuated to 1 mbar (0 76 Torr). Water vapor is distributed to the chamber to 16 mbar (12.16 Torr) (from a deionized water storage tank at 25 ° C), and the wafer is placed in Leave at this pressure for 30 seconds. Distribute ammonia into the chamber to a pressure of 809 mbar (614.84 Torr); leave the first wafer at this pressure for 1 minute and the second wafer for 3 minutes Pump down the chamber for 30 seconds to 2 mbar (1.52 Torr), then immediately empty The gas was filled back to ambient pressure. Then, the film was placed on a 90X: hot plate for 2 minutes, then 175. (: roasted in a cypress for 3 minutes, then dried in another flood box at 400 ° C Bake for 3 minutes. Then remove the wafer and measure the thickness and refractive index by ellipsometry after cooling. The measurement results are shown in the table below. The refractive index thickness after NH3 addition

Aging time (minutes) A 1 1.104 7150 3 1.085 8050 Example 3 This example illustrates a method in which a precursor is spin-deposited on a silicon crystal. This paper is sized to apply the Towel Standard (CNS) A4 (21〇297). ------.---- Withered clothes ------ 1Τ ------ ^ (Please read the notes on the back before this page] Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives Making Λ7 B7____ V. Description of the invention (15), and then aging the wafer in the chamber for a specific time and drying. The aging procedure in the chamber &gt; is as follows. This chamber is evacuated and water vapor is distributed to a fixed pressure. After a fixed time, the ammonia gas is distributed to different high pressures. After a fixed time, the gas is pumped again, after a fixed time, and then backfilled with an inert gas, the pressure in the chamber is raised to the ambient pressure. A precursor is produced. The method is to mix and carry 61 ml of tetraethoxy silicon roast, 61 ml of tetraethylene glycol, 4.87 ml of deionized water, and 0.2 ml of osmium nitric acid. Then, the mixture is refluxed while continuously stirring for 1.5 hours, and then cooled .Some part of this precursor to 曱Dilute 55 weight 0 / 〇 while stirring. Approximately 15 ml of this diluted precursor is deposited on a 4-inch silicon wafer on a spin chuck and spin-coated at 2500 rpm for 10 seconds. Three films were deposited. Each film was placed in an aging chamber, which was evacuated to 1 mbar (0 76 Torr) in 30 seconds. Water vapor was distributed to the chamber to 15 mbar (11 · 4 Torr) (from the deionized water storage tank 'at 25 ° C)' and leave the wafer under this pressure for 30 seconds. Ammonia gas was distributed to this chamber, 270 milliseconds for the first wafer Bar (205.2 Torr) pressure, 506 mbar (384.56 Torr) for the second wafer and 809 mbar (614.84 Torr) for the third wafer. Leave the wafer at this pressure for 3 minutes The chamber was then evacuated for 30 seconds to 2 mbar (1.52 Torr), and then immediately backfilled with air to ambient pressure. Then, the film was placed at 90. (: heating plate for 2 minutes, and then at 175 C Bake for 3 minutes in an oven, then bake for 3 minutes in another 400 ° C. Then remove the wafer and measure the degree of ellipse after cooling Thickness and refractive index. The measurement results are shown in the table below. ------- -18-This paper size is applicable to Chinese countries ---.--.---- seed clothing ------ ΐτ ------ # (Please read the precautions on the back before this page) Λ7 B7 Refractive index 1.155 1.123 1.085 Thickness A 4250 5200 8050 V. Description of the invention (16) 'Ammonia feed pressure (mbar) (Torr) 270 (205.2) 506 (384.5) 855 (649.8) Example This example illustrates a method in which a precursor is spin-deposited on a silicon wafer, and then the wafer is aged in the chamber for a specific time and dried. The aging procedure in the room is as follows. Pump the chamber, distribute water vapor to a fixed pressure, and after a fixed time, distribute amine vapor to a fixed pressure, after a fixed time, evacuate again, after a fixed time, and then increase the pressure in the chamber by backfilling with inert gas. To ambient pressure. Manufacturing-a kind of precursor, by mixing and stirring 61 ml of tetraethoxysilane, 61 ml of tetraethylene glycol, 4.87 ml of deionized water and 0.2 ml of 1M nitric acid. Then, the mixture was refluxed 'while being continuously stirred for 1.5 hours, and then cooled. Then, a part of this precursor was diluted by 55% by weight in ethanol while stirring. To this dilute precursor, 0.3 weight percent of a solution consisting of 1 part of Fluorad FC-430 surfactant (3M) and 9 parts of ethanol was added. Approximately 1.5 ml of this diluted precursor was deposited onto a 4-inch leap second wafer on a spin chuck and spin-coated at 2500 rpm for 10 seconds. The film was placed in an aging chamber, which was evacuated to 1 mbar (0-76 Torr) in 30 seconds. Water vapor was distributed into the chamber to 14 mbar (10 04 Torr) (from a storage tank of deionized water at 25 ° C), and the wafer was left at this pressure for 30 seconds. Next, 'n-butylamine vapor (from an n-butylamine storage tank at 25 ° C) was dispensed into the chamber to 16 mbar (1216 Torr) for 2 minutes. Pump down the chamber for 30 seconds to 5 mbar (3.8 Torr), and then immediately backfill the air to the household.-Meal ------ ΐτ ------ ^ (Please read the precautions on the back first Reprint I) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -19- Λ7 --------- ____ B7 V. Invention Description (17) — ~ '—— Press $. The wafer was placed on a 9 ° C hot plate for 2 minutes, and then baked in a 175 ×: 'phase for 3 minutes' and then baked in another 400 ×: oven for 3 knives. Then remove the crystal E, and measure the thickness and refractive index by ellipsometry after cooling. This film has an average thickness of 3650 and a refractive index of 114. Example 5 This example illustrates a method in which the towel is rotated by the precursor Deposited on broken wafers, and then aged the wafers in the chamber for a specific period of time. The aging process for silylation and subsequent drying to neutrality is as follows. The chamber is evacuated to make the water vapor flow at a relative humidity. After passing through the chamber, after the solidification time, the chamber is evacuated again to different pressures, and the ammonia gas is distributed to a higher pressure (above 200 mbar) (above 152 粍). After a fixed time, the pump is evacuated again. After a fixed period of time, the pressure in the chamber was raised to ambient pressure by backfilling with an inert gas. A precursor was made by mixing and stirring 18816 ml of tetraethoxysilane and 122 ml of triethylene glycol monomethyl ether. , 151 ml of deionized water and 0.62 ml of 1M nitric acid. Then, the mixture was refluxed while continuously stirring for 1.5 hours, and then cooled. Then, a part of this precursor was diluted by 50% by weight with ethanol while stirring. About 15 ml of this diluted precursor was deposited to rotate Spin-coated on a 4-inch silicon wafer on a chuck, and spin-coated for 30 seconds at 25,000 prints. Three films were deposited in this way. Each film was placed in an aging chamber 'which was tied to within ~ 8 seconds It was evacuated to 6 mbar (4 56 Torr). Compressed air was passed through the bubbler and entered the chamber at a rate of 2 liters / minute for 2 minutes' to produce a relative humidity of 75 // in the chamber. Then, the three wafers were individually evacuated to 206 mbar (156.56 Torr), 393 mbar (298.68 Torr) and 603 mbar (458.28 Torr). The first wafer was then individually allocated to 426 Millibar ______- 20- _ This paper size applies to the Chinese National Standard (CNS) Μ specification (2IOX297). F Please read the notes on the back before this page] • Binding. Threading, Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Cooperatives Printed by Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 B7 V. Description of the invention (18) (323.76 Torr), 632 bar (480.32 Torr) and 814 mbar (618.64 Torr), and then »after this addition, the films were aged under this pressure for 2 minutes. After aging, the films were aged The chamber was evacuated again, this time to ~ 5 mbar (3.8 Torr), and then back-filled with air to ambient pressure. The wafer was then removed from the aging chamber and placed back on the spin chuck with 30 ml of solution For washing, the solution is composed of acetone mixed with 15 ml of hexamethyldisilazane. The wafer is rotated at 250 rpm for 15 seconds while the film is washed, and then the speed is increased to 1000 rpm. After 15 seconds or more, the film Steam on the chuck. This solution is prepared at least one hour before use, but it must not be prepared more than 8 hours before use. After the film has been stripped, the wafer is placed in a 170 ° C oven for 3 minutes, followed by a 320 ° C oven for 3 minutes. The wafer is then removed and the thickness and refractive index are measured by ellipsometry. The results of the measurements are shown in the table below. Pressure after water feed Pressure thickness after ammonia feed (mbar) (Torr) (mbar) (Torr) A 206 (156.56) 426 (323.76) 1.126 8500 393 (298.68) 632 (480.32) 1.126 8500 603 ( 458.28) 814 (618.64) 1.15 7500 Example 6 This example illustrates a method in which precursors are spin-deposited on broken wafers, and then the wafers are aged in the chamber for a specific period of time. dry. The aging procedure in the chamber is as follows. Water vapor at a fixed relative humidity is passed through the chamber. After a fixed time, the chamber is evacuated to a fixed pressure again, and ammonia gas is distributed to different pressures. After a fixed time, One pump down over a fixed time 9 and then the pressure in the chamber was raised to ambient pressure by backfilling with inert gas. Manufacture a kind of precursor, the way is to mix the same _-21-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ---.--: ---- buttoning clothes ------ 1T ------ ^ (Please read the precautions on the back first, then the _ page) Λ7 B7 ---- V. Description of the invention (stirred at 19 o'clock_16 ml of tetraethoxysilane, i22 ml of three Ethylene glycol monomethyl ether, 15.1 ml of deionized water and 0.62 ml of 1M nitric acid. Then, the mixture was refluxed while continuously stirring for 1.5 hours, then cooled, and then, a part of this precursor was diluted 50 weight with ethanol %, While mixing. About 1.5 ml of this diluted precursor is deposited onto a 4 inch silicon wafer on a spin chuck and spin-coated at 2500 rpm for 30 seconds. Each film was placed in an aging chamber, and compressed air was passed through the bubbler through it and entered the chamber at a rate of 2 liters / minute for 2 minutes to generate a relative humidity of 75% in the chamber. Then, the chamber was evacuated to 195 mbar (148 2 Torr). Immediately after this evacuation, ammonia gas was distributed to it, and the first wafer reached 42 0 mbar (319_2 Torr) pressure, 615 mbar (4764 Torr) for the second and 808 mbar (614.08 Torr) for the third. After this addition, the films were aged under this pressure. 2 minutes. After aging, the chamber is evacuated again, this time to ~ 5 mbar (3.8 Torr), and then back-filled with air to ambient pressure. The wafer is then removed from the aging chamber and placed back into rotation The chuck was washed with 30 liters of solution, which was composed of acetone mixed with hexamethyldisilazane. Rotate the wafer at 250 rpm for 15 seconds while washing the film, and then increase the speed to 1000 rpm After 15 seconds or more, the film is evaporated to dryness on the chuck. This solution is prepared at least one hour before use, but it must not be prepared more than 8 hours before use. After the film has been washed, place the wafer in ΐ7 〇ι oven for 3 minutes, followed by 320 × oven for 3 minutes. Then the wafer was removed and the thickness and refractive index were measured by ellipsometry. The measurement results are shown in the table below. r--Shang ------ order ------ line (please read the precautions on the back before reading this page) Economy Ministry of Central Standards Bureau employee consumer cooperatives cracked

V. Description of the invention (20B7 'Ammonia feed pressure (mbar) (Torr) 420 (319.2) 615 (476.4) 808 (614.08) Refractive index_ U20 1.120 1.120 Example thickness A 7950 7950 8000 The example printed by the consumer cooperative is to illustrate a method of rounding, and then aging the wafer in the chamber, and then spin-deposit the aging in the chip to avoid aging for a specific time and dry. The aging sequence is as follows. Make the fixing deeper than the chamber. The calendar contains a solid weight AL, and the water vapor flows through the calendar, time, and then, and then the chamber is again-distributed ammonia to a fixed pressure, after a period of time, set the time, and then make the pressure in the chamber intelligent From two, one-time pumping through Lithium Ethyl Jf type is mixing while stirring _ Lithyl Ethyl Silicone Pit '122ml di-r water and I pen Lithine-Brazil early methyl ether, 15.1ml go to X And 0.62 ml of 1M nitric acid. Then, the mixture was refluxed while cooling. Then, a part of this precursor was diluted with 50% by weight of B, while stirring. About 15 ml of this diluted First 'deposited onto a 4-inch wafer on a spin chuck, and Transfer coating at 2500 hours for 30 seconds. Three films were deposited in this manner. Each film was placed in an old chamber, and compressed air was passed through the bubbler through it and entered at a rate of 2 liters / minute. In this chamber, it took 2 minutes to produce a relative wet sigh of 75% in the chamber. Then, the chamber was individually evacuated to 120 mbar (9 mil 2 Torr), 316 mbar (274.36 Torr), and 560 mbar (level 6 Torr). Immediately after this pumping, the ammonia gas was distributed to a pressure of 800 mbar (608 Torr) in each case, and the films were aged for 2 minutes. After the aging, the recrystallizing chamber of the chamber is separated from the alcoholic rotation by -23 degrees. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297). A7 Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Print B7 V. Description of the invention (21) Extraction, this time to ~ 5 mbar (3.8 Torr), and then backfill with air to ambient pressure. After this period, the wafer is placed at 170 ° C oven for 3 minutes, followed by 320 ° C oven for 3 minutes to dry. After cooling each wafer, borrow oval Measure the thickness and refractive index of the film. The measurement results are shown in the following table. 1120 Refractive index thickness pressure before the NH3 feed (mbar) (Torren) 120 (91.2) 1.237 3300 361 (274.36) 1.210 3650 560 (425.6) 1.220 3400 As is clear from the foregoing examples, the nanoporous dielectric silicon-containing composition can be made by a post-deposition step which exposes the deposited film to a sealed chamber which is evacuated to a pressure below atmospheric pressure. The water vapor in the medium is then exposed to the alkali vapor. --------------------------------- Order the line (Please read the precautions on the back before this page) -24- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

39 ^ 309 A8 B8 C8 D8 VI. Application for Patent Scope Printed by the Central Ministry of Economic Affairs of the Ministry of Economic Affairs and Consumer Cooperatives__ A method for forming a nanoporous dielectric coating on a substrate, which includes (a) blending at least one The alkoxysilane and the solvent composition and selected water, thus forming a mixture and causing partial hydrolysis and partial condensation of the alkoxysilane; (b) depositing the mixture on a substrate while evaporating at least a portion of the solvent The composition; (c) placing the substrate in a sealed chamber 'and evacuating the chamber to a pressure below atmospheric pressure; (d) exposing the substrate to water vapor or alkali vapor at a pressure below atmospheric pressure; Then (e) if the substrate is exposed to alkali vapor in step (d), the substrate is exposed to water vapor, or if the substrate is exposed to water vapor in step ⑼, it is exposed to alkaline vapor. 2. For example, please use the method of patent No. η, in which the substrate in step 基材 is exposed to water vapor in step ⑼, and then exposed to alkali vapor in step (e). 3. As claimed in the method of item j of the patent scope, wherein the substrate is exposed to alkali vapor in step ⑼, and then exposed to water vapor in step (e). 4. The method as claimed in item # of the patent, wherein step ⑷ is performed at a pressure lower than atmospheric pressure. 5_If applying for patent Fan Gudi! Item method. 6. The method according to item 1 of the scope of patent application is carried out under atmospheric pressure. 7. The method according to item 1 of the patent application, wherein step (e) is at atmospheric pressure, where step (e) is at high pressure, and the solvent composition contains a phase ---.--------- ---- Order ------ Line ./V (Please read the note on the back ^ before filling this page) ------____ -25- (210X297 ^ 392309 Taxi and other volatile solvents and phases 8. If you apply for a special sterilization-"low volatile lotion. The method of "Patent Patent Scope" page, where solvent-high volatile solvent and relatively low: broad phase and relatively high volatile solvent are in step ⑼ ... V at least-part 9, = = hair paste is in the subsequent step ( "Evaporation is at least-Shao, and ^ Nuwanfa, where relatively higher volatility" complexes have a low concentration or lower, and each agent composition has a boiling point of about 175. (: or higher.-Fat The method according to item 8, wherein the relatively highly volatile solvent 1 contains one or more components selected from the group consisting of methanol ethanol 'n-propanol, isopropanol, n-butanol, and mixtures thereof' and wherein The relatively low volatility solvent composition contains an alcohol or a polyhydric alcohol. U_ As in the method of claim 1, the step (a) includes joining water in the mixture. 12. As in the method of claim n, Wherein the step is advanced-the step includes blending a catalytic amount of acid in the mixture. 13. The method according to item 1 of the patent application, wherein the alkoxysilane contains one or more components selected from the group consisting of tetraethoxysilane and tetraethoxysilane. Methoxysilane. Consumers of the Central Bureau of Standards of the Ministry of Economic Affairs Cooperative cooperative seal «. 14_ If the method of the scope of patent application, the alkali vapor contains one or more components selected from the group consisting of ammonia, amines and mixtures thereof. 15. If the method of the scope of patent application, the water The molar ratio of steam to alkali steam ranges from about 1: 3 to about 1: 100. 16. The method according to item 1 of the patent application range, wherein the alkali steam has? 1 \ from about below 0 to about 9..- 26 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 392309 Patent application scope 17 · = Method of applying for patent scope item 1, in which the oxyl group has the following R R-Si-R R economy The Central Sample Rate Bureau® C Industrial Consumer Cooperative Co., Ltd. printed at least two of these groups were unveiled as "Moxy groups, and if they had hiding groups, they were independently selected from the group consisting of hydrogen, alkyl, phenyl, Since the green, substituted phenyl. 18. The method of claim 17 in the scope of patent application, wherein each R is methoxy, oxy or propoxy. 19. The method of scope of the patent application,! The microporous dielectric coating has a dielectric constant of from about 1.1 to about 35. 20. As patented The method of the scope item i, wherein the substrate includes a ferroconductor material. 21_ The method of the scope of the application for a patent item}, wherein the substrate includes silicon or gallium. 22. A coated substrate, which is Formed by a method as described in the scope of patent application item 1. 23. A semiconductor device manufactured by a method including (a) blending at least one alkoxysilane and a solvent composition and selecting Water, thus forming a mixture and causing partial hydrolysis and partial condensation of lanthanide ^^ B-line-27- This paper size is applicable to China National Standard (CNS) A4 grid (210X29 * 7 mm) J 392309 contains I D8 5 ', patent application scope (b) deposit the mixture onto the semiconductor substrate while evaporating at least a part of the solvent composition; (c) place the semiconductor substrate in a sealed chamber and place the The chamber is evacuated until the pressure is lower than atmospheric pressure; ⑷ the semiconductor substrate is exposed to water vapor or alkali vapor at a pressure lower than atmospheric pressure; and then (e) if the substrate is exposed to alkali vapor in step (d), Expose the semiconductor substrate to water vapor Or, if the substrate in step (d) exposed to water vapor in the system, it is exposed to alkaline vapor, which will form a nano-porosity dielectric coating on the silicon semiconductor substrate. (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -28- This paper size uses the Chinese National Standard (CNS) A4 size (210X297 mm)