KR101326254B1 - Low Dielectric Thin Films and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to a low dielectric thin film and a method for manufacturing the same, and more particularly, to a low dielectric thin film produced by plasma chemical vapor deposition of a silane compound and a pore-forming material containing an allyl group, and a method of manufacturing the same.
In the method of manufacturing a low dielectric thin film according to the present invention, by using an organic or inorganic precursor having a linear or nonlinear shape, a low dielectric thin film having a significantly lower dielectric constant than that of the related art and a thermally stable low dielectric thin film may be produced. It is possible to reduce the complicated process for the pre- and post-treatment, and to improve the dielectric constant and mechanical properties of the thin film through a process such as heat treatment, there is an effect that can be usefully used in the manufacture of semiconductor devices.

Description

Low Dielectric Thin Films and Method for Preparing the Same

The present invention relates to a low dielectric thin film and a method for manufacturing the same, and more particularly, to a low dielectric thin film produced by plasma chemical vapor deposition of a silane compound and a pore-forming material containing an allyl group, and a method of manufacturing the same.

In recent years, in order to reduce the signal delay (RC delay) of multi-layer metal films used in integrated circuits of ultra high density (ULSI) semiconductor devices, a research has been carried out to form interlayer insulating films used for metal wiring with materials having a low dielectric constant (k≤2.7). Is being actively performed. The low dielectric thin film may be formed of an inorganic material or an organic material, such as an oxide film doped with fluorine (SiO ₂ ) and an amorphous carbon (aC: F) doped with fluorine. Polymer films with relatively low dielectric constant and excellent thermal stability are mainly used as organic materials.

Silicon dioxide (SiO ₂ ) or silicon oxyfluoride (SiOF), which has been mainly used as an interlayer insulating film, has high capacitance and long resistance-current delay time in the manufacture of ultra-high density circuits of 0.5 μm or less. Due to problems such as RC delay time, researches to replace it with a new low dielectric material have been actively conducted, but no specific solution has been proposed.

Low dielectric materials that are currently considered as alternatives to SiO ₂ include BCB (benzocyclobutene), SILK (Dow Chemical), FLARE (fluorinated poly (arylene ether), mainly used for spin coating. Allied Signals), organic polymers such as polyimide, and the like Black Diamond (Applied Materials), Coral (Novellus) used for chemical vapor deposition (CVD) ), SiOF, alkyl-silanes and parylenes, and porous thin film materials such as xerogels or aerogels.

Here, most polymer thin films are formed by a method of chemically synthesizing a polymer, spin coating on a substrate, and then spin casting. The material having the low dielectric constant formed in this way is formed into a dielectric having the low dielectric constant because the thin film density decreases because pores of several nanometers (nm) are formed in the film. In general, the organic polymers deposited by spin coating have advantages of low dielectric constant and excellent planarization, but they are not suitable in terms of application due to poor thermal stability due to lower heat limit temperature of less than 420 ° C. Since pores are large in size and because of this, they are not uniformly distributed in the film, there are various difficulties in manufacturing the device.

In addition, the adhesion to the upper and lower wiring material is poor, high stress due to the thermal curing peculiar to the organic polymer thin film, the dielectric constant is changed due to the adsorption of the ambient moisture, such as the reliability of the device is poor.

Accordingly, Korean Patent No. 0987183 discloses a low dielectric plasma polymer thin film for chemically depositing plasma hexamethyldisiloxane or 3,3-dimethyl-1-butene with plasma, and a method of manufacturing the same. Korean Patent No. 0697669 Discloses a method for preparing a low dielectric plasma polymer thin film for plasma chemical vapor deposition of decamesylcyclopentaxylzeane and a cyclohexane precursor, and a low dielectric thin film prepared therefrom, and Korean Unexamined Patent Publication No. 2003-0002993 Although a method of preparing a low dielectric thin film by plasma chemical vapor deposition of a silicon or silicate precursor material including an ethynyl group has been disclosed, all of them have a problem in that mechanical properties are significantly lowered at low dielectric constants.

In addition, US Patent Publication No. 2006-0079099, US Publication No. 2009-0146265 and US Publication No. 2009-0203225 are prepared by plasma chemical vapor deposition using a single bifunctional precursor having a SiCOH matrix and organic porogen function. Although a method of manufacturing a SiCOH thin film is disclosed, the manufacturing method has a problem in that it is impossible to control the ratio of the matrix precursor and the porogen (porogen) precursor due to the use of a single precursor, thereby limiting the dielectric constant.

Accordingly, the present inventors have made diligent efforts to solve the problems of the prior art, in the case of producing a low dielectric thin film by chemical vapor deposition of a silane compound and a pore-forming material containing an allyl group in the presence of an oxidizing gas, in the conventional spin casting method The present invention has been completed by confirming that it is possible to reduce the complicated process for the generated pre and post treatment, and to improve the dielectric constant and mechanical properties.

It is a main object of the present invention to provide a low-k dielectric thin film and a method of manufacturing the same, which can improve the dielectric constant and mechanical properties of the thin film by a simple process.

In order to achieve the above object, the present invention includes the step of chemically depositing a silane compound and pore-forming material containing an allyl group in a ratio of 1: 0.1 to 1:10 in the presence of an oxidizing gas, followed by heat treatment. It provides a method for producing a low dielectric thin film.

The present invention also provides a silane compound containing an allyl group and a pore-forming material in the presence of an oxidizing gas, which is prepared by chemical vapor deposition with plasma at a ratio of 1: 0.1 to 1:10, and then heat-treated, and has a relative dielectric constant of 2.4 or less, 4.0 to It provides a low-k dielectric thin film having an elastic modulus of 8.5 GPa and a strength of 0.4 ~ 1.0 GPa.

In the method of manufacturing a low dielectric thin film according to the present invention, by using an organic or inorganic precursor having a linear or nonlinear shape, a low dielectric thin film having a significantly lower dielectric constant than that of the related art and a thermally stable low dielectric thin film may be produced. It is possible to reduce the complicated process for the pre- and post-treatment, and to improve the dielectric constant and mechanical properties of the thin film through a process such as heat treatment, there is an effect that can be usefully used in the manufacture of semiconductor devices.

1 is a schematic diagram of a direct plasma apparatus used for producing a low dielectric thin film according to the present invention.
2 is a schematic diagram of a remote plasma apparatus used for producing a low dielectric thin film according to the present invention.
3 is a graph showing the change in dielectric constant with respect to the O ₂ / ATMS flow rate ratio of the low dielectric thin film prepared by the manufacturing method according to the present invention.
Figure 4 is a graph showing the carbon content change with respect to the O ₂ / ATMS flow rate ratio of the low dielectric thin film prepared by the manufacturing method according to the present invention.
Figure 5 is a graph showing the refractive index change with respect to the O ₂ / ATMS flow rate ratio of the low dielectric thin film prepared by the manufacturing method according to the present invention.
6 is a table showing the manufacturing conditions of the low-k dielectric thin film according to the present invention.
7 is a table showing the modulus and hardness of the low-k dielectric thin film manufactured by the manufacturing method according to the present invention.
8 is a graph showing a change in dielectric constant with respect to the AB / ATMOS flow rate ratio of the low dielectric thin film prepared by the manufacturing method according to the present invention.
9 is a graph showing the refractive index change with respect to the AB / ATMOS flow rate ratio of the low dielectric thin film prepared by the manufacturing method according to the present invention.
10 is a graph showing a change in dielectric constant with respect to the CHO / ATMS flow rate ratio of the low dielectric thin film prepared by the manufacturing method according to the present invention.
11 is a graph showing the refractive index change with respect to the CHO / ATMS flow rate ratio of the low-k dielectric thin film manufactured by the manufacturing method according to the present invention.
12 is a graph showing the thickness retention rate before and after heat treatment of the low-k dielectric thin film manufactured by the manufacturing method according to the present invention.

The present invention provides a method for manufacturing a low dielectric thin film, comprising: plasma chemically depositing a silane compound and a pore-forming material containing an allyl group in a ratio of 1: 0.1 to 1:10 in the presence of an oxidizing gas, and then performing a heat treatment. It is about.

Specifically, the allyl group-containing organic silane compound capable of plasma polymerization acts as a matrix of the thin film, and the allyl group-containing benzene compound and epoxy group have excellent compatibility with the allyl group-containing organic silane compound. By injecting pore-forming materials, such as non-linear hydrocarbon compounds, to form nano-pores in the thin film to produce a SiCOH-based low dielectric thin film having a low dielectric constant and high mechanical properties during plasma chemical vapor deposition.

1 and 2 are schematic diagrams of a plasma deposition apparatus that can be used in the present invention, wherein the plasma deposition apparatus of FIG. 1 is a direct plasma apparatus, and the plasma deposition apparatus of FIG. 2 is a remote plasma apparatus. Device.

The direct plasma plasma deposition apparatus is supplied with an oxidizing gas and a reactant (such as a silane compound containing an allyl group) and then supplied to the upper portion of the apparatus. The remote plasma plasma apparatus includes an oxidizing gas and a reactant (allyl group). Contained silane compound, etc.) is supplied to the device through a separate supply device. For example, oxidizing gas may be supplied to the top of the plasma deposition device, and reactants may be supplied through a diffusion ring on the side of the device.

Plasma chemical vapor deposition according to the present invention uses the above-described plasma deposition apparatus, the plasma deposition apparatus is a temperature of the substrate 100 ~ 300 ℃ under a pressure of 0.1 ~ 10 Torr, the ratio of the silane compound and oxidizing gas containing allyl group Is 1: 0.1 to 1:10 and the intensity of the plasma is 30 ~ 100W conditions by plasma reaction to deposit a SiCOH-based low dielectric thin film. At this time, if the pressure of the plasma deposition apparatus is less than 0.1 Torr, a problem that the deposition rate of the thin film is significantly lowered, and if the pressure exceeds 10 Torr, a problem that the thin film is uneven occurs, the temperature of the substrate of the plasma deposition apparatus is 100 ℃ If it is less than the problem occurs that the mechanical properties of the thin film is lowered, if it exceeds 300 ℃ there is a problem that the deposition rate of the thin film is lowered.

In addition, when the ratio of the silane compound containing an allyl group and the oxidizing gas is less than 1: 0.1, a problem occurs that Si-O network is not well formed, and when the ratio exceeds 1:10, the dielectric constant of the thin film is not lowered. If the plasma intensity is less than 30W, the problem of poor formation of the thin film is generated, and if the value exceeds 100W, the dielectric constant is increased.

In the present invention, the oxidizing gas is a Si-O network of the SiCOH thin film to be formed smoothly, consisting of O ₂ , N ₂ O, O ₃ , H ₂ O ₂ , CO ₂ , water vapor and a mixture of these Selected from the group.

In the present invention, the allyl group-containing silane compound is allyltrimethylsilane (allyltrimethylsilane), allyltriethylsilane (allyltriethylsilane), allyltrimethoxysilane (allyltrimethoxysilane), allyltriethoxysilane (allyltriethoxysilane), allyltripropylsilane (allyltripropylsilane), allyltripropoxysilane, and mixtures thereof.

In the present invention, the pore-forming material is plasma chemical vapor deposition together with the allyl group-containing organic silane compound to form a thin film, and nano-sized pores are formed on the thin film prepared by heat treatment to prepare a thin film having excellent insulation can do.

At this time, the ratio of the allyl group-containing organic silane compound and the pore-forming material is 1: 0.1 to 1:10, and when the pore-forming material is added in a smaller amount than the above range, it is difficult to lower the dielectric constant, and it is added in excess of the above range. In this case, the porosity is so high that it is difficult to obtain the insulation properties and chemical resistance required for the interlayer insulating film.

The pore-forming material may be a benzene compound containing an allyl group, a nonlinear hydrocarbon compound containing an epoxy group, cyclohexane, toluene, norbornene, terpinene, xylene, linear Alkenes, nonlinear unsaturated hydrocarbons and mixtures thereof.

The allyl group-containing benzene compound may be allylbenzene, 1-allyl-2-methylbenzene, 1-allyl-3-methylbenzene, 1-allyl-3-methylbenzene, 4-allyl-1,2-dimethoxybenzene, butenylbenzene, pentenylbenzene, and mixtures thereof, preferably Allylbenzene, 1-allyl-2-methylbenzene, 1-allyl-3-methylbenzene and 4-allyl-1,2- Dimethoxybenzene (4-allyl-1,2-dimethoxybenzene).

In addition, the non-linear hydrocarbon compound containing the epoxy group is cyclohexene oxide (cyclohexene oxide), cyclopentene oxide (cyclopentene oxide), cyclobutene oxide (cyclobutene oxide), cyclopropene oxide (cyclopropene oxide), cyclooctene oxide (cyclooctene oxide) ) And mixtures thereof, and preferably cyclohexene oxide, cyclopentene oxide and cyclooctene oxide.

In addition, the linear alkene is selected from the group consisting of ethene, propene, butene, pentene, hexene, octene and mixtures thereof, and the nonlinear The unsaturated hydrocarbon of is selected from the group consisting of cyclopropene, cyclobutene, cyclopentene, cyclopentene, cyclohexene, cyclooctene and mixtures thereof.

In general, the nanopore forming method using spin coating determines the degree of phase separation according to the compatibility between the matrix resin and the pore-forming material. Therefore, it is difficult to accurately control the microenvironment, and there is a problem that phase separation may occur.

However, the combination of the pore-forming material and allyl group-containing organic silane compound according to the present invention is easy to cross-linking between the molecules of the allyl group-containing organic silane compound and the pore-forming material plasma plasma deposition The low dielectric thin film manufactured by using an allyl group-containing organic silane compound has excellent thermal and mechanical properties and can form nano-sized pores uniformly in the thin film without phase separation due to the pore-forming material. Mechanical properties can be improved.

In addition, the thin film prepared according to the present invention is heat-treated at 100 ℃ to 600 ℃ for 0.5 hours to 8 hours, preferably at 420 ℃ for 2 hours to have a low dielectric constant film having a low dielectric constant value and excellent thermal stability It can manufacture. In particular, by using a method of instantaneous heat treatment at 100 ℃ to 600 ℃ for one minute, or spike annealing within 10 seconds can be produced a thin film having excellent dielectric properties even in a short time.

In still another aspect, the present invention provides a silane compound and all pore-forming material containing an allyl group in the presence of an oxidizing gas, which are prepared by chemical vapor deposition in a plasma at a ratio of 1: 0.1 to 1:10, and then heat-treated, and a relative dielectric constant of 2.4 or less. And a modulus of elasticity of 4.0 to 8.5 GPa and a strength of 0.4 to 1.0 GPa.

The low dielectric film according to the present invention has a low dielectric constant of 2.4 or less, and the dielectric constant may be controlled by controlling process conditions during plasma deposition such as pressure, temperature, flow rate of reactants, and heat treatment temperature after deposition. For example, the greater the amount of oxidizing gas than the amount of reactant, that is, the greater the flow rate of the reactants, the lower the carbon content in the thin film, resulting in a lower dielectric constant and a lower refractive index. In addition, the thin film after the heat treatment further reduces the carbon content and the refractive index.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.

Example  One: Low oil field  Preparation of Thin Film 1

A thin film was deposited using the direct plasma apparatus shown in FIG. 1, and allyltrimethylsilane (ATMS) was used as a reactant, and oxygen (O ₂ ) was used as an oxidizing gas. At this time, while controlling the flow rate ratio (O ₂ / ATMS) between oxygen and ATMS in the range of 0.5 to 20, the deposition conditions in the reactor were maintained at a pressure of 1 Torr, a temperature of 30 ° C., and a plasma power of 30 W during the film growth. After deposition, the deposited thin film was heat-treated in an argon atmosphere to prepare a low dielectric thin film. At this time, the dielectric constant change, relative carbon content (Si-CH ₃ / Si-O) change and refractive index change of the thin film according to the flow rate ratio (O ₂ / ATMS) of oxygen and ATMS during deposition are shown in FIGS. 3, 4, and 5, respectively. Shown in

As a result, as shown in Figure 3, the dielectric constant of the thin film prepared as described above was found to be 3.4 ~ 4.2, the thin film dielectric constant after the heat treatment for 1 hour at 420 ℃ appeared to be 2.5 ~ 2.7 through heat treatment It was found that the dielectric constant of the thin film was reduced.

As shown in FIG. 4, as the flow rate ratio of O ₂ / ATMS increases, that is, as the amount of oxygen is relatively increased, the carbon content in the thin film decreases, and the carbon content in the thin film further decreases after heat treatment. As shown in FIG. 5, as the flow rate ratio of O ₂ / ATMS increased, the refractive index indicating the density of the thin film was decreased, and the refractive index after the heat treatment was further decreased.

In addition, the mechanical properties of the thin film manufactured under the respective process conditions and conditions shown in FIG. 6 are shown in FIG. 7. Comparing samples 1 and 2 of FIG. 7, it can be seen that the elastic modulus and hardness increase as the flow rate ratio of O ₂ / ATMS increases. Compared to samples 1 and 3 of FIG. 7, the elastic modulus and hardness increase as the plasma power increases. It was found to be improved. In addition, when comparing the samples 3 and 4 of Figure 7, it can be seen that the elastic modulus and hardness is significantly increased as the deposition temperature is increased, the mechanical properties after the heat treatment for all samples was found to increase. Accordingly, the mechanical properties of the thin film can be controlled by the process conditions, and when the thin film is manufactured by adjusting the deposition temperature to 200 ° C., the prepared thin film has an elastic modulus of 9 to 11 Gpa and a hardness of 1 to 1.6 Gpa. It could be confirmed that the mechanical properties.

Example  2: Low oil field  Preparation of Thin Film 2

Prepared in the same manner as in Example 1, the reaction was used a combination of allyltrimethoxysilane (allytrimethoxysilane, ATMOS) and allylbenzene (allylbenzene, AB). Oxygen (O 2) content during the deposition was fixed, and the AB / ATMOS flow rate ratio was adjusted to show the change in dielectric constant and refractive index of the thin film in FIGS. 8 and 9.

As shown in FIG. 8 and FIG. 9, as the AB / ATMOS flow rate ratio increases, the change in refractive index before and after the heat treatment increases, and the dielectric constant after the heat treatment is 2.2 or less.

Example  3: Low oil field  Preparation of Thin Film 3

Prepared in the same manner as in Example 1, the reaction was used a combination of ATMS and cyclohexene oxide (cyclohexene oxide, CHO). Oxygen (O2) content during deposition was fixed and the CHO / ATMS flow rate ratio was adjusted to show the change in dielectric constant and refractive index of the thin film and the thickness change rate after heat treatment in FIGS. 10 to 12.

As shown in FIG. 10 and FIG. 11, the dielectric constant decreases as the CHO / ATMS flow rate increases, and the change in refractive index before and after the heat treatment is increased. The dielectric constant before the heat treatment is found to be 2.3 to 3.0, whereas The constant was found to be 2.0 to 2.8.

In addition, as a result of measuring the elastic modulus, hardness and low dielectric constant of the thin film prepared under the conditions of Table 1, the thin film having a dielectric constant of 2.4 (sample: 9a) was found to have an elastic modulus of 8.4 Gpa and an intensity of 0.75 Gpa ( Table 2).

* T: plasma device substrate temperature Sample Condition 5
ATMS only O ₂ /ATMS=2.5, T = 120 ℃ 6
CHO / ATMS = 0.5 O ₂ /ATMS=2.5, T = 120 ℃ 7
ATMS only O ₂ /ATMS=0.5, T = 120 ° C 8
CHO / ATMS = 0.5 O ₂ /ATMS=0.5, T = 120 ° C 9
CHO / ATMS = 0.5 O ₂ /ATMS=2.5, T = 210 ° C

* a: sample after heat treatment Sample Modulus of elasticity (Gpa) Hardness (Gpa) Low dielectric constant 5 2.426 0.115 3.2 5a 2.51 0.202 2.8 6 3.903 0.146 2.9 6a 2.405 0.226 2.2 7 2.594 0.167 3.2 7a 2.264 0.195 2.8 8 4.161 0.157 2.8 8a 2.595 0.202 2.2 9 7.452 0.601 2.8 9a 8.421 0.752 2.4

12 shows the thickness retention rate of the thin film after the heat treatment of the CHO / ATMS thin film, the thickness retention after the heat treatment in the experimental range was found to be very excellent as 90% or more.

Comparative Example : Low oil field  Comparison of Thin Films

Table 3 compares the relative dielectric constants, modulus, and strength of the low dielectric thin films prepared in Examples 1 to 3 and the low dielectric thin films disclosed in Korean Patent No. 0697669 and US Patent Publication No. 2006-0079099. will be.

As shown in Table 3, in the case of the low dielectric thin film manufactured in Example 3, it was found that the relative dielectric constant (2.0) was lower than that of the other low dielectric thin films. It was found to be excellent. In particular, in the case of Example 3, it was confirmed that the elastic modulus and strength is excellent at a low dielectric constant.

division Relative dielectric constant Modulus of elasticity burglar Example 1 2.5-2.7 2.4 ~ 11 GPa 0.16-1.6 GPa Example 2 2.1 ~ 2.3 - - Example 3 2.0 ~ 2.4 4.0 ~ 8.5 GPa 0.4 ~ 1.0 GPa Korean Patent Registration No. 0697669 2.1 ~ 2.8 1 to 7.5 GPa 0.2 ~ 0.800GPa Korean Patent Registration No. 0987183 2.4 6 GPa 0.75 GPa United States Patent Application Publication No. 2006-0079099 2.52-2.6 2.9 to 3.8 GPa 0.23GPa

As described above in detail specific parts of the present invention, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be.

Claims (20)

A method of manufacturing a low dielectric thin film comprising the step of chemically depositing a silane compound and a pore-forming material containing an allyl group at a flow rate of 1: 0.1 to 1:10 in the presence of an oxidizing gas, followed by heat treatment.
According to claim 1, wherein the allyl group-containing silane compound is allyltrimethylsilane (allyltrimethylsilane), allyltriethylsilane (allyltriethylsilane), allyltrimethoxysilane (allyltrimethoxysilane), allyltriethoxysilane (allyltriethoxysilane), allyltripropyl A method of manufacturing a low dielectric thin film, characterized in that selected from the group consisting of silane (allyltripropylsilane), allyltripropoxysilane (allyltripropoxysilane) and mixtures thereof.
The method of claim 1, wherein the pore-forming material is a benzene compound containing an allyl group, a non-linear hydrocarbon compound containing an epoxy group, cyclohexane, toluene, norbornene, terpinene, xyl A method for producing a low dielectric thin film, characterized in that it is selected from the group consisting of xylene, linear alkenes, nonlinear unsaturated hydrocarbons, and mixtures thereof.
According to claim 3, wherein the allyl group-containing benzene compound is allylbenzene (allylbenzene), 1-allyl-2-methylbenzene (1-allyl-2-methylbenzene), 1-allyl-3-methylbenzene (1-allyl -3-methylbenzene, 4-allyl-1,2-dimethoxybenzene, butenylbenzene, pentenylbenzene and mixtures thereof Method for producing a low dielectric thin film, characterized in that selected.
The method of claim 3, wherein the non-linear hydrocarbon compound containing an epoxy group is cyclohexene oxide (cyclohexene oxide), cyclopentene oxide (cyclopentene oxide), cyclobutene oxide (cyclobutene oxide), cyclopropene oxide (cyclopropene oxide), cyclooctene A method of manufacturing a low dielectric thin film, characterized in that selected from the group consisting of oxides (cyclooctene oxide) and mixtures thereof.
The linear alkene of claim 3 is selected from the group consisting of ethene, propene, butene, pentene, hexene, octene and mixtures thereof. Method for producing a low dielectric thin film, characterized in that.
The method of claim 3, wherein the non-linear unsaturated hydrocarbon is selected from the group consisting of cyclopropene, cyclobutene, cyclopentene, cyclopentene, cyclohexene, cyclooctene, and mixtures thereof Method for producing a low dielectric thin film, characterized in that selected.
The method of claim 1, wherein the oxidizing gas is selected from O ₂ , N ₂ O, O ₃ , H ₂ O ₂ , CO ₂ , water vapor, and a mixture thereof.
According to claim 1, wherein the chemical vapor deposition using a plasma deposition apparatus, the plasma deposition apparatus is a pressure of 0.1 ~ 10 Torr, the temperature of the substrate is 100 ~ 300 ℃, allyl group containing silane compound and oxide gas A flow rate ratio is 1: 0.1-1: 10, and a plasma power is 30-100W manufacturing method of the low dielectric thin film characterized by the above-mentioned.
The method of claim 1, wherein the heat treatment is performed at 100 to 600 ° C. for 0.5 to 8 hours.
The silane compound and the pore-forming material containing the allyl group in the presence of an oxidizing gas are chemically deposited by plasma at a flow rate of 1: 0.1 to 1:10, and then subjected to heat treatment. Low dielectric film, characterized in that having a strength of 0.4 ~ 1.0 GPa.
12. The method of claim 11, wherein the allyl group-containing silane compound is allyltrimethylsilane (allyltrimethylsilane), allyltriethylsilane (allyltriethylsilane), allyltrimethoxysilane (allyltrimethoxysilane), allyltriethoxysilane (allyltriethoxysilane), allyltripropyl Low dielectric film, characterized in that selected from the group consisting of silane (allyltripropylsilane), allyltripropoxysilane (allyltripropoxysilane) and mixtures thereof.
The method of claim 11, wherein the pore-forming material is a benzene compound containing an allyl group, a non-linear hydrocarbon compound containing an epoxy group, cyclohexane, toluene, norbornene, terpinene, xyl Low dielectric thin film, characterized in that selected from the group consisting of xylene, linear alkene, nonlinear unsaturated hydrocarbons and mixtures thereof.
The method of claim 13, wherein the allyl group-containing benzene compound is allylbenzene, 1-allyl-2-methylbenzene, 1-allyl-3-methylbenzene (1-allyl) -3-methylbenzene, 4-allyl-1,2-dimethoxybenzene, butenylbenzene, pentenylbenzene and mixtures thereof Low dielectric film, characterized in that selected.
The method of claim 13, wherein the allyl group-containing benzene compound is allylbenzene, 1-allyl-2-methylbenzene, 1-allyl-3-methylbenzene (1-allyl) -3-methylbenzene, 4-allyl-1,2-dimethoxybenzene, butenylbenzene, pentenylbenzene and mixtures thereof Low dielectric film, characterized in that selected.
The method of claim 13, wherein the non-linear hydrocarbon compound containing the epoxy group is cyclohexene oxide (cyclohexene oxide), cyclopentene oxide (cyclopentene oxide), cyclobutene oxide (cyclobutene oxide), cyclopropene oxide (cyclopropene oxide), cyclooctene Low dielectric film, characterized in that selected from the group consisting of oxides (cyclooctene oxide) and mixtures thereof.
The method of claim 13, wherein the linear alkene is selected from the group consisting of ethene, propene, butene, pentene, hexene, octene and mixtures thereof Low dielectric film, characterized in that.
The method of claim 13, wherein the non-linear unsaturated hydrocarbon is selected from the group consisting of cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclooctene, and mixtures thereof Low dielectric film, characterized in that selected.
The low dielectric film of claim 11, wherein the oxidizing gas is selected from O ₂ , N ₂ O, O ₃ , H ₂ O ₂ , CO ₂ , water vapor, and a mixture thereof.
The low dielectric film of claim 11, wherein the heat treatment is performed at 100 to 600 ° C. for 0.5 to 8 hours.

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