JP2002203848A - Vacuum/gas phase reactor for dehydroxylating and alkylating porous silica - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vacuum/gas phase reactor for dehydroxylating and alkylating a porous silicate film. SOLUTION: A substrate is exposed to high vacuum to be heated, quickly and effectively treated by silane, and performed in the vacuum/gas phase reactor performing the dehydroxylating and alkylating reaction of the gas phase. In addition, in order to promote silylating and improve processing efficiency, a quasi-catalyst surface acted as both of an activator making chemical species a high energy state or a high activate state and a scrubber removing the by- product of the possibility and reaction of catalyst breakage produced in silylating reaction is designed to be included. One embodiment is a hot filament reactor (figure 1) having a metal-made heating solid surface in the chamber of the reactor processing a meso-porous film wafer. The other embodiment is an infrared reactor and a flange reactor. A processed film indicating low dielectric constant and high elastic modulus is formed by silylating the meso- porous film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to, for example, mesoporous silica films on wafers or substrates.
The present invention relates to a reactor for dehydroxylation and alkylation of a porous silicate membrane (such as a film). More specifically, a vacuum / gas phase reactor capable of forming a film having a low dielectric constant (low-K) and a high elastic modulus (high-E) at a relatively low temperature compatible with semiconductor interconnect manufacturing. About.

[0002]

The reaction involves the capping of polar hydroxyl groups on the surface of a porous silicate, resulting in a non-polar hydrophobic surface. The porous silicate includes silica and an organic silicate having an alkyl group or an alkylsilane group. Liquid / liquid phase processing involves the immersion of a substrate (typically supported on a silicon wafer) in pure silane or a silane solution, followed by a solution wash. Gas phase processing is generally more efficient and involves treating the substrate with silane or other organic chemicals for dehydroxylation in the gas phase at elevated temperatures and / or reduced pressure. The substrate is exposed to a vacuum before and after the silane treatment. Such a gas phase treatment is described in a currently pending U.S. patent application Ser. No. 413,062. This application is assigned to Battelle Memorial Institute, Inc. in Richland, Washington, as is the case with the present application. The disclosure of this application is incorporated herein by reference to the number of that application. Increased efficiency of treatment with vacuum / gas phase silane or chemicals for dehydroxylation (hereinafter referred to as "silylation")
Due to the improved accessibility of silane or chemicals for dehydroxylation to some of the hydroxyl groups after evacuation of pores having a pore diameter in the range of 10 to 20 Angstroms (10-20 °). Conceivable.

[0003]

Vacuum / gas phase for dehydroxylation and alkylation of porous silicate membranes capable of forming films with low dielectric constant and high modulus at relatively low temperatures It is intended to provide a reactor.

[0004]

The reactor used for the gas-phase silylation reaction is to expose a substrate to a high vacuum in the reactor, heat the substrate to a target temperature, and use silane as quickly and efficiently as possible. Ideally, it can be processed.

[0005] Various reactor designs can perform such treatments on the membrane. However, the particular design of the present invention can affect the quality of the final product. In order to further promote silylation and improve processing efficiency, the reactor is an `` activator '' that brings the species into a high energy or high activity state, and
Possibility of catalyst destruction generated by silylation reaction (possible po
scrubbe to remove isons and reactive by-products
r)) as a quasi-catalytic surface
surfaces). One of the embodiments described herein involves placing a hot, preferably metallic-solid surfac, preferably in a metal, in a chamber of a reactor in which a plurality of wafers having a mesoporous membrane are placed.
e) Hot filament reactor with hot filament
reactor). Another embodiment is an infrared reactor (IR) having an upper quartz window and a lower quartz window sealing the upper and lower perimeters of an aluminum ring to form a heated chamber.
reactor). Finally, a flange reactor (flange) having a flange base and lid forming an extremely small chamber inside for the wafer and heated by conduction from a heated sand bath.
reactor). By subjecting the mesoporous film to a silylation treatment, a treated film having a low dielectric constant (K) and a high elastic modulus (E) is formed.

[0006] The subject matter of the invention is particularly pointed out with particularity in the last part of this specification. However,
The structure, operation, and their advantages and objects will be best understood by referring to the following description in conjunction with the accompanying drawings. In these drawings, the same reference numerals indicate the same components.

[0007]

DETAILED DESCRIPTION OF THE INVENTION Recently, various types of gas phase reactors have been designed. These reactors operate under high vacuum conditions at high temperatures or under silane gas (eg, trimethyliodosilane (TMI
S), chemicals or agents for gas-phase dehydroxylation (such as hexamethyldisilazane (HMDS), or other suitable silanes) (dehydroxylating agents) or the substrate in non-silane gas Takes into account the processing. However, there are a number of design differences that cause different product qualities. Three specific embodiments of the present invention, "hot filaments"
t) ”reactor,“ infrared (IR) ”reactor,“ flange (f
lange) "reactor will be described with reference to Figures 1 to 6, respectively. It should be understood that not all parts are explicitly shown in the perspective views of the three reactors shown in FIGS. 2, 4 and 6.

Referring first to FIGS. 1 and 2, a hot filament reactor 10 includes a base 14 made of stainless steel.
Aluminum container (or vacuum container) supported by
2 is provided. O- with a machine groove
The inner chamber 16 of the reactor, which is sealed with a ring, preferably comprises a plurality of equally spaced thin thermal insulators supporting a heating element 20 in which a bare nichrome wire is spirally or coiled. Consists of a sex plate 18. A plurality of wafers 22 coated with an insulator film are placed between heaters 20 and after evacuating the chamber, the heaters are heated to the temperature of the wafer (eg, 350-475 ° C., preferably about 375 ° C.). (Between about 500 ° C. and 425 ° C.). Subsequent to the high temperature vacuum treatment, silane is introduced into chamber 16 via air supply valve 24a. The removal of silane and the evacuation of the chamber are performed via the exhaust valve 24b. in this way,
The silane is (a) in direct contact with the heating coil, (b) convection, and
(c) Heated by radiation. Also, when gaseous by-products form, they also come into contact with the heating coil. The metal surfaces of the reaction chamber, including the aluminum and stainless steel porous inner surfaces of the vessel and the coiled heating element, are vacuum /
It heats up during the silane treatment and acts as a scrubber and activator to enhance the dehydroxylation and alkylation treatment.

In an embodiment of the reactor 10, the chamber 16 has a volume of about 21 liters. The filament is periodically energized by the controller to maintain the filament at or near the target temperature throughout the process. The on / off duty cycle varies between the silane gas phase process and the vacuum phase process. Hot filament reactor 10 consumes relatively little power, for example, only about 1 kilowatt (kW). The base 14 has a plurality of equally-spaced grooves machined in its flat upper surface to accommodate five heating coil plates 18 and four four-inch diameter wafers 22 as shown.
The wafers are accommodated in an alternate arrangement such that heating coil plates are placed on both sides. Within the spirit and scope of the present invention, those skilled in the art will appreciate that chamber 16 can be configured to accommodate one or more 8 inch or 12 inch diameter wafers by simply changing the diameter of reactor vessel 12. Will understand. Reactor 10 preferably takes about 42 minutes in minutes.
It heats up to the target wafer temperature of 5 ° C and cools down in about 1 to 2 hours. With this embodiment of the invention, a vacuum of less than about 50 mTorr (more preferably, less than 1 mTorr) is achieved.

[0010] The mesoporous thin film is silylated in a hot filament reactor 10 to provide a low dielectric constant (about 2.
A mesoporous film having a dielectric constant of 1 or less and a high elastic modulus (an elastic modulus of about 3.5 gigapascals (GPa) or more) is formed. Importantly, these properties are relatively low (~ 350 ° C to 475 ° C) compatible with semiconductor interconnect fabrication
It is achieved in.

3 and 4, the infrared reactor 26 comprises:
There is an upper array 28 and a lower array 30 (eg, 15 for each array) of a plurality of quartz tube infrared lamps 32, the array comprising a sealed chamber 34 between the arrays.
Located directly above and below. The chamber 34 has two quartz windows 36 and 38 separated by a water-cooled aluminum ring 40. Quartz windows 36 and 38
Allows the infrared radiation from the infrared lamp arrays 28 and 30 to pass directly into the chamber and be absorbed by the array of wafers 22 so that the wafers quickly reach the target temperature (eg, 350 ° C. to 475 ° C.). , Preferably about
(375 ° C to 425 ° C). (Those skilled in the art will understand that only the wafer will be hot.) The aluminum ring 40 is below ambient temperature to protect the O-ring vacuum seals 42 and 44 of the quartz windows 36 and 38. While maintained, those skilled in the art will appreciate that the aluminum ring 40 may be heated within the spirit and scope of the present invention. Following the high temperature vacuum treatment, one (or more) type of gas phase silane is introduced via two small inlet valves 46a and 46b and exhausted via two large exhaust valves 46c and 46d. As the silane gas enters chamber 34, it begins to condense on the cold aluminum, resulting in reflux during the silylation process. The silane is maintained at a fixed reflux temperature and pressure; for example, the conditions under which reflux is observed through the top quartz window throughout the process are generally between about 100 ° C. and 400 ° C., and perhaps about 200 ° C. To 300 ° C. There is no hot surface in the reaction chamber 34 other than the surface of the silicon wafer.

In an embodiment of the reactor 26, the diameter of the cylindrical chamber 34 is about 34 cm and the depth is preferably about 6.5 c.
m, volume is about 5 liters, and can accommodate up to seven 4-inch diameter wafers or one 8-inch diameter wafer. These wafers are supported within chamber 34 by six pointed star-shaped thin quartz rod-like structures (not shown), which minimize interference with infrared radiation. Infrared reactor 26 consumes a relatively large amount of power, about 11 kW, to achieve the desired high vacuum of less than about 10 ^-5 Torr in minutes. Also, the consumption of chemical substances for dehydroxylation of the infrared reactor 26 is small, and the amount of waste generated is small. The wafer is heated to a target temperature (eg, 350 ° C. to 475 ° C., preferably about 425 ° C.) in a few minutes, and the seven 4-inch wafers arranged in a substantially hexagonal shape are uniformly heated. The cooling time is relatively short, for example about
Less than 0.5 hours. Within the spirit and scope of the present invention,
In the chamber of the infrared reactor 26, a heated bare nichrome wire and / or a heated piece of stainless steel may be placed in close proximity to the wafer to perform the activation and cleaning described above, thereby providing low activation. A mesoporous film having a dielectric constant and a high elastic modulus is formed.

In FIGS. 5 and 6, a flanged reactor 48 is shown.
Includes an integrally bolted flange base 50 and flange lid 52 made of stainless steel and a metallic gasket 54 (eg, so-called malleable copper (Cu)) for supporting a single 4-inch wafer 22. A "knife edge" gasket) is secured between them. The flanged reactor 48 may have the same target wafer temperature (eg, 350 ° C. to 475 ° C., preferably about
425 ° C). (Those skilled in the art will appreciate that the sand bath uses a large hemispherical furnace as the heat source and that the sand surrounding the reactor absorbs heat from the heat source.) Inside the O-ring 54, the base 50 The introduction of the silane gas and the evacuation are alternately performed through the air supply valve 58a to the extremely small chamber 56 formed between the lid and the lid 52. The exhaust is performed via an exhaust valve 58b. Stainless steel base 5
One skilled in the art will appreciate that the porous inner surface of the O and lid 52, and possibly the copper O-ring 54, is also a heated solid surface (preferably made of metal) that is in close physical proximity to the wafer 22. . Thus, in this flange reactor embodiment, as in the hot filament reactor embodiment, the fact that these heated solid surfaces can act as scrubbers and / or activators to facilitate the silylation process. Will be appreciated.

The depth of the flange reactor 48 is about 0.8 cm and the volume of the chamber 56 is only about 0.08 to 0.125 liter. One wafer in the reactor 48 is uniformly and continuously heated throughout the processing steps. High vacuum is easily and quickly achieved, and the consumption or depletion of chemicals (dehydroxylating agents) for dehydroxylation is minimal. The heating time and cooling time are each about 1 to 2 hours, and the cycle time for each wafer is relatively long. Due to the relatively small volume of chamber 56, multiple silane treatment cycles are required to introduce one equivalent (based on the calculated amount of hydroxyl groups) of silane. Low dielectric constant k (k is about 2.0 or less) and moderately high elastic modulus E (E
Is about 3 to about 4 GPa).
8 using a mesoporous silica membrane. In contrast to the hot filament reactor 10, in this design, the proximity of the upper and lower stainless steel flanges (eg, a heated solid metal surface) to the wafer in the chamber 56 results in a mesoporous membrane thereon. Contribute to the desired dehydroxylation and alkylation of

[0015] Conventional control devices include (a) dehydroxylation
Inflow and removal of chemicals and vacuuming,
(b) A controlled trace concentration of oxygen gas (O_Two) Or nitrogen gas
(N _Two) Inflow, (c) pressure inside the vessel, (d) inside the chamber
Temperature or wafer surface temperature and / or (e)
To control the temperature of the heating element and the heating surface inside the reactor
Provided in connection with the reactors 10, 26 and 48
Those skilled in the art will understand that

The importance of what is referred to herein as a hot filament or a heated solid (preferably metal) surface surrounded by chemicals for dehydroxylation such as silane gas is described.

When a silane gas (R ₃ SiX or R ₃ SiNH ₂ ) is introduced into a substrate (wafer), the hydroxyl groups on the surface undergo a substitution reaction with the silane gas.

R ₃ SiX (g) + SiOH (s) → SiOSiR ₃ (s) + HX (g)

Alkylsiloxane groups on the surface and HX
(Where X is understood to be a suitable halogen element, such as bromine, iodine or chlorine), the concentration of the siloxyl groups on the surface and the silanol on the adjacent surface generally increases. A second competitive reaction occurs between HX
Catalyzed by

SiOSiR ₃ (s) + SiOH (s) → SiOSi (s) + R ₃ SiOH (g)

This competing reaction ultimately results in removal of polar hydroxyl groups without alkylating the silica surface as desired. Allowing the treatment to continue results in a highly dehydroxylated silica with little or no alkylsiloxane cap. This porous silica reacts with water vapor upon exposure to air at normal humidity to reform polar surface hydroxyl groups.

The present invention is not limited to any particular operating principle, as can be seen from the results of the low dielectric constant and high modulus described below. The presence of a hot filament surface and a heated solid metal surface in the reaction chamber quickly and efficiently removes HX (formed in the first dehydroxylation reaction), and the two atom iodine and hydrogen To form This reduces the rate of secondary competitive reactions and leaves the desired highly dehydroxylated membrane with the alkylsiloxane cap.

[0023] Direct contact with the heating element increases the average kinetic energy of the silane, which may increase the rate of the initial substitution reaction. Hot filaments or heated solid metal surfaces catalyze the formation of highly active intermediate species such as silenium cations, thereby substantially accelerating the silylation process. Examples of the surface of the heated catalyst include those made of metal, ceramic, graphite, and polytetrafluoroethylene. The use of other heated catalyst surfaces is contemplated within the spirit and scope of the present invention.

[0024] With the conventional analysis method, it is impossible to accurately specify the transient gas phase species in the reactor. To support the above hypothesis, manufacture and process the membrane in a simulated reactor,
The main properties were measured. Hot filament reactor 10
The product manufactured in the infrared reactor 26 was measured for dielectric constant, refractive index, and X-ray electron spectroscopy (XPS). For comparison purposes, very rigorous measurements were taken prior to the dehydroxylation step to ensure that the substrates treated in each reactor were identical. XPS measurements allow the analysis of the carbon content of the mesoporous membrane, while refractive index measurements allow the porosity of the membrane to be measured, which is desirable to achieve demonstrated low dielectric constant results. One skilled in the art will appreciate that it must be greater than about 50% to 60%.

For a given porous silica membrane that uses a surfactant to template the pores, the hot filament reactor has a dielectric constant (K)
Have formed a large number of samples having an elastic modulus (E) of 4.0 GPa or more, while the infrared reactor has an elastic modulus (E) of 4.0 GPa or more.
A film exceeding 4.0 GPa and having a dielectric constant (K) of less than 2.0 was not formed. However, the infrared reactor has a dielectric constant (K)
Was 2.0 or less and the elastic modulus (E) was as high as about 3.0 GPa. In addition, the dielectric constant (K) of the flange reactor also
A sample having a modulus of elasticity (E) of not more than 2.0 and as high as about 3.4 GPa was formed.

Within the spirit and scope of the present invention, infrared reactors can be modified to better simulate the reaction mechanisms that take place in hot filament reactors. A first variation is to place a heated nichrome wire in the silanization chamber during processing. Heat rays are not originally used to heat a substrate. Rather, it is used as a silane activator and acid scrubber. Additionally or alternatively, a small reservoir containing solid calcium carbonate (or an alternative alkali (base) material) may be placed inside the reaction vessel to act as an acid scrubber. Further, as previously proposed, the infrared reactor disclosed herein is modified to heat an aluminum ring or a piece of stainless steel suspended inside to provide a scrubber function similar to a hot filament reactor. It is possible to

Generally, the dehydroxylation process in any of these reactor chambers involves alternating treatment in a vacuum and in the environment of the dehydroxylated material. Those of ordinary skill in the art will appreciate that any pressure below 1 atm is evacuated and that the degree of vacuum needs to be better defined. Desirable reactor vacuum pressures according to the present invention are on the order of 1 Torr or less. Such a degree of vacuum is generally high vacuum (10
It is not considered to be ^-5 to 10 ^-7 Torr), nor of course to ultra-vacuum (10 ^-8 to 10 ^-12 Torr or more). The relatively low vacuum described above allows for more convective heating of dehydroxylation chemicals or agents, such as, for example, silanes. By controlling the degree of vacuum, only a trace amount of oxygen is held in the chamber. Instead of alternately supplying and evacuation of gaseous hydroxylation chemicals to the reactor chamber, under certain conditions, the gaseous hydroxylation chemicals and non-nitrogen, e.g. Preferably, the active gas is alternately flowed into the reactor chamber. Such a change to a vacuum phase in the silylation treatment is included in the spirit and scope of the present invention.

Table 1 below shows the results of measurements on mesoporous silica membranes treated using the various reactors described above for dehydroxylation and alkylation. The dehydroxylation and alkylation (eg, silylation) treatment of the present invention comprises:
One of ordinary skill in the art will appreciate that the preparation and firing of the film is preferably followed by the teachings of the above-cited patents or any other suitable technique.

[0029]

[Table 1]

Table 1 is believed to be readily understood by those skilled in the art. The membrane is fired at either 150 ° C. for 2 minutes and 425 ° C. for 2 minutes (here described as 2 + 2), or at 425 ° C. for 5 minutes (here described as 5 + 0). Here, the flange reactor forms a processing film having a low dielectric constant of 2.17 and a high elastic modulus of 3.2 GPa, and the infrared reactor forms a processing film having a low dielectric constant of 2.31 and a high elastic modulus of 3.0 GPa. Note that the formed hot filament reactor formed a treated film with a low dielectric constant of 2.05 and a high modulus of elasticity of 4.4 GPa. The modulus of elasticity (E) was measured using a conventional device that pushed the membrane to various depths below the surface. Referring to the right column of Table 1, those skilled in the art will appreciate that the smaller the difference between K _air and K _N2 , the more hydrophobic the membrane. Also note that this favorable result occurs at higher silylation temperatures.

Mesoporous membranes made by the 0 + 5 calcination step and the dehydroxylation / silylation treatment in the reactor show that the dielectric constant obtained over the entire silylation temperature range is as low as about 2.0. The merchant will understand.

If there are two or more silylation cycles (each cycle containing a silane gas phase or other chemical phase for dehydroxylation, followed by a vacuum phase), the dielectric cycle is higher than in a single cycle. The rate is significantly lower. Therefore, a large number of silylation cycles are desired, but if the dielectric constant is appropriately low without excessively dense carbon-rich organic groups in the pores of the membrane, there is an upper limit to the number of cycles. There is.

Thus, the dehydroxylation and alkylation reactors and processes of the present invention described herein require the field of semiconductor interconnect fabrication and structurally durable low dielectric constant films on substrates. It is possible to form a mesoporous silica film having a low dielectric constant and a high elastic modulus for use in other related applications.

While the principles of the present invention have been illustrated and described in preferred embodiments, it will be readily apparent to those skilled in the art that the present invention may be modified in arrangement and detail without departing from such principles. Should be. Applicant claims all changes falling within the spirit and scope of the claims.

[Brief description of the drawings]

FIG. 1 is a system block diagram of a hot filament reactor device according to a preferred embodiment of the present invention.

FIG. 2 is a perspective view of a hot filament reactor device according to a preferred embodiment of the present invention.

FIG. 3 is a system block diagram of an infrared reactor device according to another embodiment of the present invention.

FIG. 4 is a perspective view of an infrared reactor according to another embodiment of the present invention.

FIG. 5 is a system block diagram of a flange reactor according to still another embodiment of the present invention.

FIG. 6 is a perspective view of a flange reactor according to still another embodiment of the present invention.

 ──────────────────────────────────────────────────続 き Continued on front page (71) Applicant 501436942 O. Box 999, Richland, Washington 99352 U.S. SA (72) Inventor Jerome Birnbaum United States 99352 Washington, Richland, Center Boulevard 109 (72) Inventor Garry Maupin United States 99352 Washington, Richland, Atkins Avenue 218 (72) Inventor Glen Dunham United States 99336 Washington South Huntington Place, Kennewick, Kennewick 902 (72) Inventor Glen Fricksell, United States 99336 Washington, Kennewick, West Endiat Avenue 8907 (72) Inventor Shresh Bascarran United States 99336 Washington, Kennewick, North Pittsburgh 1002 F-term (reference) 5F045 AA03 AB32 AC01 AD04 AD05 AD06 AD07 AD08 AD09 AF03 AF07 AF10 DP15 DP20 DQ10 EB02 EB03 EK08 EK12 EK13 EM02 5F058 BA20 BC02 BD04 BF04 BF23 BF36 BF37 BG01 BG03 BG04 BH03 BH04 BJ02

Claims (42)

[Claims] 1. A reactor for dehydroxylation and alkylation of a porous silica film on a semiconductor wafer, wherein the reactor contains a chemical gas and a vacuum or cleaning gas for dehydroxylation. And a heated solid surface in the vessel for heating a gas of a chemical for dehydroxylation in the vessel; and a porous silica membrane in the vessel during dehydroxylation. A wafer support mechanism for supporting one or more semiconductor wafers, wherein the wafer temperature is maintained between room temperature and 500 ° C. The porous silica film on the substrate of
A reactor characterized by exhibiting a dielectric constant less than about 2.5 and an elastic modulus greater than about 2.5 GPa. 2. The reactor according to claim 1, wherein the heated solid surface is made of metal. 3. The reactor of claim 2, wherein the heated solid metal surface has one or more electrically heated filaments. 4. The one or more filaments,
4. The reactor according to claim 3, wherein the reactor is spirally wound around one or more thermally insulating plates attached to the wafer support mechanism. 5. The reactor according to claim 4, wherein a pair of said one or more thermally insulating plates are disposed very close to both sides of each porous silica wafer. 6. The one or more filaments,
The reactor according to claim 5, wherein the reactor is electrically heated by electric heating. 7. At least one inlet for the controlled introduction of dehydroxylation chemicals into the vessel, and the controlled removal of dehydroxylation chemicals outside the vessel. 7. The reactor of claim 6, including at least one exhaust vent. 8. One or more of one or more wafers
Alternatively, a first temperature measurement management mechanism in the container that measures and manages the temperature of a plurality of surfaces, and a first power supply operably connected to a power supply that performs on / off control of a power supply according to the temperature measurement management mechanism
The reactor according to claim 7, comprising: 9. The air supply port and the air exhaust port are selectively opened and closed according to a predetermined periodic variation parameter, and are operatively connected to the air supply port and the air exhaust port for controlling the pressure in the container. A second control device,
The reactor according to claim 8, wherein the cyclic variation parameter alternately supplies a chemical substance for dehydroxylation to the vessel and evacuates the vessel. 10. The reactor of claim 1, wherein said heated solid surface is formed from a material selected from the group consisting of metal, ceramic, graphite, or polytetrafluoroethylene. 11. The reactor according to claim 1, wherein the heated solid surface is maintained at a temperature of 100 ° C. to 1200 ° C. for dehydroxylation and alkylation. 12. The reactor according to claim 11, wherein the semiconductor wafer having the porous silica film is maintained at a temperature lower than 475 ° C. 13. The heating solid surface may be at 200 ° C. to 800 ° C.
The reactor according to claim 1, wherein the temperature is maintained at a temperature of ° C. 14. The dielectric constant is lower than 2.3 and the elastic modulus is 3.0 GPa.
The reactor of claim 1, wherein the reactor is capable of forming a higher dehydroxylated and alkylated mesoporous membrane. 15. A method for dehydroxylating a mesoporous membrane on a substrate at a low temperature, comprising: placing a substrate in a reactor in physical proximity to a solid surface; Alternately supplying a chemical for dehydroxylation above a defined pressure; and applying a vacuum to the reactor below a defined pressure; and Heating the solid surface to a temperature high enough to activate the material and low enough not to damage the substrate; and combining the chemical for gas phase dehydroxylation with the mesoporous membrane on the substrate. Inducing a response. 16. The method of claim 15, wherein the heating is at a temperature measured at the surface of the substrate between 350 ° C. and 475 ° C. 17. The method of claim 16, wherein the heating is at a temperature measured at a surface of the substrate between 375 ° C. and 425 ° C. 18. The method of claim 17, wherein the gas phase dehydroxylation chemistry comprises a reactive silane. 19. The method of claim 18, wherein said solid surface is made of metal. 20. The method of claim 19, wherein the metallic solid surface includes a high heat capacity filament heated by a power supply. 21. The alternate chemical dehydroxylation chemical supply and vacuuming may include at least one
21. The method of claim 20, wherein the method is repeated a number of times. 22. The method according to claim 21, wherein the alternately supplying and evacuating are such that the supply of the chemical for dehydroxylation and the evacuating are substantially equally timed. The described method. 23. The alternate feeding and vacuuming provides a dehydroxylated material in 2.5 to 15 minutes,
23. The method according to claim 22, comprising applying a vacuum in 2.5 to 15 minutes. 24. The method of claim 23, wherein the supply of the chemical for dehydroxylation is at a pressure greater than 1 Torr. 25. The method of claim 24, wherein the evacuation is at a pressure between 10 ^-3 and 1 torr. 26. The method of claim 25, wherein the evacuation is at a pressure between 10 ^-2 and 1 torr. 27. A mesoporous film on a substrate, wherein the film has a dielectric constant of less than 2.1 and an elastic modulus of more than 4.0 GPa. 28. Placing a film on a substrate in a reactor in physical proximity to a solid surface; and applying a chemical for gas phase dehydroxylation to the reactor above a defined pressure. Alternately feeding and evacuating the reactor below a prescribed pressure; damaging the film on the substrate sufficiently high to activate the dehydroxylation chemistry. Heating the solid surface to a temperature low enough not to induce a reaction between the chemical for gas phase dehydroxylation and the mesoporous membrane on the substrate. 27. The formed film on the substrate according to claim 26. 29. The film of claim 28, wherein the heating is at a temperature measured at the surface of the film on the substrate of between 350 ° C. and 475 ° C. . 30. The film on a substrate formed by the method of claim 29, wherein the heating has a temperature measured at a surface of the substrate between 375 ° C. and 425 ° C. 31. A reactor for dehydroxylating a porous silica wafer, wherein the reactor is sufficiently sealed to contain a gas of a chemical for dehydroxylation, and includes a metal ring and a perimeter of the ring. A container having opposing windows sealed to opposing peripheries of the ring; and irradiating the container and its contents during dehydroxylation with an outer surface of one of the windows. A reactor comprising: one or more adjacent infrared lamp arrays; and a wafer support mechanism for supporting one or more porous silica wafers in the vessel during dehydroxylation. 32. The reactor according to claim 31, wherein said window is made of quartz. 33. The reactor according to claim 31, wherein said ring is made of aluminum. 34. The reactor of claim 31, wherein a pair of infrared lamp arrays are located proximate any outer surface of said window. 35. The apparatus of claim 31, further comprising one or more heated solid surfaces in the vessel for heating a chemical gas for dehydroxylation in the vessel. Reactor. 36. The reactor of claim 35, wherein the one or more heated solid surfaces are one or more electrically heated nichrome wires. 37. The reactor of claim 31, wherein said metal ring is water cooled. 38. The metal ring operates at a controlled temperature between 0 ° C. and 300 ° C.
2. The reactor according to 1. 39. At least one air inlet for controlled supply of dehydroxylation chemical to the vessel, and controlled removal of dehydroxylation chemical out of the vessel. 32. The reactor of claim 31 including at least one exhaust. 40. A temperature measurement and management mechanism in the container for measuring and managing the temperature of one or more surfaces of one or more wafers, and turning on a power supply according to the temperature measurement and management mechanism. 40. The reactor of claim 39, comprising: a first controller operably connected to a power source for performing on / off control. 41. Further, the air supply and exhaust ports are selectively opened and closed according to a predetermined cycle variation parameter, and are operatively connected to the air supply and exhaust ports for controlling the pressure in the container. 41. The apparatus of claim 40, further comprising a second controller, wherein the cyclic parameter alternately supplies a chemical for dehydroxylation to the vessel and evacuates the vessel. A reactor according to claim 1. 42. The method according to claim 42, wherein the predetermined cyclic parameter includes alternately supplying a chemical substance for dehydroxylation to the container and evacuating the container. 42. The reactor according to 41.