JP4877452B2 - Surface hydrophobizing composition, surface hydrophobizing method, semiconductor device and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for surface hydrophobing and a surface hydrophobing method which can easily and efficiently restore damage on a surface without increasing the density of a layer including a front surface, and generates no corrosive by-product, and to provide a semiconductor device and a manufacturing method thereof. <P>SOLUTION: The composition for surface hydrophobing contains (A) a diacetoxymethylsilane of 0.1-10 wt% and (B) an aprotic solvent. The method of surface hydrophobing includes a process in which the composition for surface hydrophobing contacts the surface of a layer and the layer is heated in this state to form a hydrophobing film 24. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a composition for hydrophobizing a surface of a layer used in an electronic device such as a semiconductor device, a method for hydrophobizing a surface, a semiconductor device, and a method for manufacturing the same.

Currently, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is frequently used as an interlayer insulating layer of a semiconductor device in a large scale integrated circuit (LSI) or the like. In recent years, for the purpose of forming an insulating layer having a more uniform film thickness, a coating type insulating layer called an SOG (Spin on Glass) film mainly composed of a hydrolysis product of alkoxysilane has also been used. It has become so.

  In the manufacturing process of a semiconductor device, various processes are generally performed on an insulating layer. For example, the insulating layer is patterned by etching or the resist is removed by ashing. In some cases, the oxidizing or reducing reactive gas used at that time may cause carbon atoms and hydrogen atoms in the insulating layer to be eliminated to generate hydrophilic silanol groups (Si—OH). As a result, the hygroscopicity of the film is increased, and various device reliability may be lowered by the adsorbed moisture.

In particular, when the insulating layer is an insulating film, the generation of silanol groups means an increase in the dielectric constant, and when the damage is significant, the insulating film may lose its low dielectric constant. .
US Pat. No. 6,383,466 US Patent No. US5504042 US Pat. No. 6,548,113 US Pat. No. 6,700,200 specification Philip G. Clerk, 2 others, Cleaning and Restoring k Value of Porous MSQ Films, Semiconductor International, August 2003, 46 -Page 52 Anil Bhanap, 3 others, Repairing Process-Induced Damage to Porous Insulation ILDs by Post-Ash Treatment proceedings Advanced Metalization, Conference XIX, pp519, 2003)

  The object of the present invention is to make the surface hydrophobic so that it is compatible with the subsequent processing process and can repair surface damage more easily and efficiently without increasing the dielectric constant of the layer including the surface. It is an object of the present invention to provide a method and a surface hydrophobizing composition that can be used to repair surface damage.

  Another object of the present invention is to provide a semiconductor device including a layer subjected to surface hydrophobization treatment by the surface hydrophobizing method and a method for manufacturing the same.

1. The composition for hydrophobizing a surface of the present invention comprises
(A) 0.1 to 10% by weight of diacetoxymethylsilane and (B) an aprotic solvent.

  Here, the composition can be used in contact with the surface of the layer. In this case, the surface can be obtained by etching and / or ashing. In this case, the layer may contain a silicon atom and contain at least one element selected from an oxygen atom, a carbon atom, a hydrogen atom, and a nitrogen atom as a constituent element. Furthermore, in this case, the layer may be an insulating film. Here, the insulating film can be, for example, a film having a relative dielectric constant of 3.0 or less.

  2. The surface hydrophobizing method of the present invention includes a step of heating the layer in a state where the surface hydrophobizing composition is in contact with the surface of the layer.

  In this case, the heating step can include a step of heating the layer at a first temperature and a step of heating the layer at a second temperature higher than the first temperature. Alternatively, in this case, the heating step includes the step of heating the layer at a first temperature, the step of heating the layer at a second temperature higher than the first temperature, and the second temperature. Heating the layer at a higher third temperature.

  3. The semiconductor device of the present invention includes a hydrophobic film obtained by the surface hydrophobization method.

4). The semiconductor device of the present invention is
A semiconductor device including an insulating layer disposed above a substrate,
The insulating layer is provided with a recess,
A hydrophobic film is formed on the inner wall of the recess,
The hydrophobic membrane was obtained by bringing the surface hydrophobizing composition into contact with the inner wall of the recess.

5. The semiconductor device of the present invention is
A semiconductor device including a wiring structure disposed above a substrate,
The wiring structure is
A via layer provided in the first recess;
A wiring layer disposed on the via layer and provided in the second recess,
The first recess is provided in a first insulating layer disposed above the substrate,
The second recess is provided in a second insulating layer disposed above the first insulating layer,
A hydrophobic film is formed on the inner wall of the first recess,
The hydrophobic membrane was obtained by bringing the surface hydrophobizing composition into contact with the inner wall of the first recess.

6). The semiconductor device of the present invention is
A semiconductor device including a wiring structure disposed above a substrate,
The wiring structure is
A via layer provided in the first recess;
A wiring layer disposed on the via layer and provided in the second recess,
The first recess is provided in a first insulating layer disposed above the substrate,
The second recess is provided in a second insulating layer disposed above the first insulating layer,
A first hydrophobic film is formed on the inner wall of the first recess,
A second hydrophobic film is formed on the inner wall of the second recess,
The first hydrophobic film is obtained by bringing the surface hydrophobizing composition into contact with the inner wall of the first recess,
The second hydrophobic film was obtained by bringing the surface hydrophobizing composition into contact with the inner wall of the second recess.

  Here, in the semiconductor device, the via layer and the wiring layer can be integrally formed.

  7). The method for manufacturing a semiconductor device of the present invention includes a step of forming a hydrophobic film by the surface hydrophobization method.

  According to the surface hydrophobizing method of the present invention, the surface hydrophobizing composition of the present invention comprising (A) 0.1 to 10% by weight of diacetoxymethylsilane and (B) an aprotic solvent is used. Thus, the surface damage can be repaired more easily and efficiently without increasing the density of the layer including the surface, and no corrosive by-product is generated. Further, the surface hydrophobizing method of the present invention has consistency with the subsequent processing process. That is, the surface hydrophobizing composition of the present invention is useful for repairing surface damage by hydrophobizing the surface.

  Since the semiconductor device of the present invention includes a layer having a surface hydrophobized by the surface hydrophobizing method, the semiconductor device is excellent in reliability.

  Since the semiconductor device manufacturing method of the present invention includes a step of forming a surface hydrophobized layer by the surface hydrophobizing method, a semiconductor device having excellent reliability can be manufactured.

  Hereinafter, the surface hydrophobizing composition, the surface hydrophobizing method, the semiconductor device and the manufacturing method thereof according to the present invention will be specifically described.

1. 1. Surface hydrophobizing composition and surface hydrophobizing method 1-1. Surface hydrophobizing composition 1-1-1. (A) Diacetoxymethylsilane The surface hydrophobizing composition of the present invention contains (A) 0.1 to 10% by weight of diacetoxymethylsilane. The surface hydrophobic composition of the present invention is more suitable as a spin-on composition.

  The content ratio of (A) diacetoxymethylsilane in the surface hydrophobizing composition of the present invention is more preferably 0.3 to 9% by weight, and further preferably 0.5 to 8% by weight. When the content ratio of (A) diacetoxymethylsilane in the surface hydrophobizing composition of the present invention is less than 0.1% by weight, the hydrophobization does not proceed sufficiently. On the other hand, when the content ratio of (A) diacetoxymethylsilane exceeds 10% by weight, not only the storage stability of the composition is deteriorated, but also after contacting the surface hydrophobizing composition of the present invention with the surface, Excessive presence of (A) diacetoxymethylsilane in the layer including the surface causes hydrolysis and condensation to block the voids in the layer. As a result, the dielectric constant at 200 ° C. of the layer increases. That is, the density of the layer increases.

1-1-2. (B) Aprotic solvent The surface hydrophobizing composition of the present invention contains (B) an aprotic solvent. Thereby, reaction of (A) diacetoxymethylsilane and a solvent can be avoided. Moreover, it is preferable that the boiling point of (B) aprotic solvent is 50-350 degreeC.

  (B) As the aprotic solvent, those exemplified below may be used alone or in combination of two or more. More specifically, examples of the (B) aprotic solvent include ketone solvents, ester solvents, ether solvents, amide solvents, and other aprotic solvents described below.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-hexyl. In addition to ketones, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione, 2 , 4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3, - heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like.

  Examples of ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, and i-acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl acetate Glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

  As ether solvents, ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, tetraethylene glycol di-n-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether Etc.

  Examples of amide solvents include acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N- Examples include formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like.

  Other aprotic solvents include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane. , N-octane, i-octane, cyclohexane, methylcyclohexane), aromatic hydrocarbon solvents (for example, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene), sulfur-containing solvents (for example, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3 -Pro Sultone), acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-3 -Pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1 , 3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, and the like.

  (B) As the aprotic solvent, ketone solvents such as butyl acetate, diethyl ketone, cyclohexanone, and methyl-i-butyl ketone, or aromatic hydrocarbon solvents such as trimethylbenzene and xylene are more preferable.

  The mass of the (B) aprotic solvent in the surface hydrophobizing composition of the present invention is preferably 90 to 99.9% by weight, more preferably 91 to 99.7% by weight, More preferably, it is 99.5% by weight. When the mass of the (B) aprotic solvent in the surface hydrophobizing composition of the present invention is less than 90% by weight, it is difficult to perform uniform coating, while the mass of the (B) aprotic solvent is 99. If it exceeds .9% by weight, the composition hardly remains on the film after spin coating.

1-2. Method for Using Surface Hydrophobizing Composition The surface hydrophobizing composition of the present invention can be used in contact with the surface of the layer. An example of such a layer is a layer containing silicon atoms as a main constituent element. Layers mainly composed of silicon atoms are widely used in electronic devices such as semiconductor devices, liquid crystal display devices, and organic EL devices. In addition, layers containing silicon atoms as main constituent elements are used not only in the electronics industry but also in fields such as the automobile industry, the optical industry, and the bio industry.

  For example, a layer containing silicon atoms as the main constituent element used as an insulating layer in semiconductor devices comprises oxygen atoms, nitrogen atoms, carbon atoms, hydrogen atoms, fluorine atoms, boron atoms, phosphorus atoms, etc. in addition to silicon atoms. More specifically, examples of such a layer include silicon oxide, silicon oxynitride, silicon nitride, silicon carbide, and an insulating film described later. These layers are an interlayer insulating layer for semiconductor devices, a protective layer such as a surface coat film of a semiconductor device, an intermediate layer of a semiconductor manufacturing process using a multilayer resist, an interlayer insulating layer of a multilayer wiring board, and a protective layer for a liquid crystal display device It is useful for applications such as insulating layers.

  A method for producing a layer containing silicon atoms as a main component is not particularly limited, but representative examples include a CVD method (for example, plasma CVD method) and an SOG method (Spin on Glass). In particular, an insulating film manufactured by the SOG method has been used as an interlayer insulating layer of a more miniaturized semiconductor device. For example, the insulating film contains a silicon atom and can contain at least one element selected from an oxygen atom, a carbon atom, a hydrogen atom, and a nitrogen atom as a constituent element.

  In particular, an insulating film of a semiconductor device, which includes a silicon atom and includes at least one element selected from an oxygen atom, a carbon atom, a hydrogen atom, and a nitrogen atom as a constituent element, The layer may be damaged by a manufacturing process (for example, an etching process or an ashing process performed to remove the photoresist). More specifically, carbon atoms and hydrogen atoms in the layer are desorbed by an oxidizing or reducing reactive gas used in the etching process, ashing process, and other processes, and silanol groups (-SiOH ) Is formed, moisture is easily absorbed in the layer. As a result, moisture in the layer increases, and the absorbed moisture may reduce the reliability of the semiconductor device.

  In the case of an insulating film, the moisture content in the layer increases due to the generation of silanol groups (Si—OH), which may increase the dielectric constant and lose low dielectric properties.

  On the other hand, by applying the surface hydrophobizing method of the present invention to the insulating film, the surface hydrophobizing composition of the present invention reacts with silanol groups, so that the surface of the insulating film can be hydrophobized. Thereby, since moisture can be prevented from being absorbed from the surface of the insulating film, the low dielectric constant of the insulating film can be maintained. Thereby, a semiconductor device having excellent reliability can be obtained.

  Next, the surface hydrophobization method using the surface hydrophobizing composition of the present invention will be specifically described with reference to FIGS. FIG. 1 is a view schematically showing a semiconductor device manufactured by using the surface hydrophobizing method according to one embodiment of the present invention, and FIGS. 2 to 5 are steps for manufacturing the semiconductor device shown in FIG. It is sectional drawing which shows typically (the surface hydrophobization method of one embodiment of this invention).

  The layer subjected to the surface hydrophobization method of the present invention is excellent in moisture absorption resistance and exhibits a low relative dielectric constant. Therefore, the interlayer for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM is used. Useful for applications such as insulating layers, protective layers such as surface coating films for semiconductor devices, intermediate layers in semiconductor manufacturing processes using multilayer resists, interlayer insulating layers for multilayer wiring boards, protective layers and insulating layers for liquid crystal display devices, etc. is there.

  Here, the case where the surface hydrophobizing method of the present invention is applied to the insulating layer included in the semiconductor device will be described, but the layer to which the surface hydrophobizing method of the present invention is applied is not limited to the insulating layer of the semiconductor device. The present invention can be similarly applied to layers included in devices other than semiconductor devices.

  The semiconductor device shown in FIG. 1 includes an insulating layer 20 disposed above a substrate (semiconductor substrate) 10. The insulating layer 20 is provided with a recess 22, and a hydrophobic film 24 is formed on the inner wall 22 a of the recess 22. The hydrophobic film 24 is obtained by bringing the surface hydrophobizing composition of the present invention into contact with the inner wall 22 a of the recess 22. The insulating layer 20 is a layer containing, for example, silicon atoms and oxygen atoms as constituent elements.

  The semiconductor device shown in FIG. 1 can be manufactured by the following steps. First, the insulating layer 20 is formed above the substrate 10 (see FIG. 2). As a method for forming the insulating layer 20, the above-described method can be used.

  Next, after a resist layer R1 having a predetermined pattern is formed on the insulating layer 20 by a known photolithography method, the insulating layer 20 is etched using the resist layer R1 as a mask (see FIG. 3). As the etching, a known method (dry etching or wet etching such as RIE (reactive ion etching)) can be used. At this time, the inner wall 22a of the recess 22 is damaged on the surface by etching. More specifically, the surface of the inner wall 22a of the recess 22 is damaged by the etchant used during etching. Thereby, silanol groups (Si—OH) are formed on the surface of the insulating layer 20. In particular, when reactive ion etching is performed, silanol groups are easily formed on the surface of the inner wall 22a of the recess 22 by the reactive ions used as the etchant.

  Next, the resist layer R1 is removed by ashing (see FIG. 4). As the ashing method, for example, plasma ashing using oxygen plasma, ozone ashing using ozone, or wet ashing can be used. Also by this ashing process, the surface of the inner wall 22a of the recess 22 is damaged, and silanol groups are formed on this surface.

  Next, the hydrophobic film 24 is formed on the inner wall 22a of the recess 22 by bringing the surface hydrophobizing composition of the present invention into contact with the surface of the layer (the surface of the inner wall 22a of the recess 22) (see FIG. 5). ). More specifically, the silanol group formed on the surface of the inner wall 22a of the recess 22 reacts with (A) diacetoxymethylsilane contained in the surface hydrophobizing composition of the present invention, so that the silanol group Hydroxyl group (—OH) is substituted with a hydrophobic group to form hydrophobic film 24. That is, the hydrophobic film 24 is obtained by a reaction between (A) diacetoxymethylsilane and a silanol group on the surface of the inner wall 22 a of the recess 22. By forming this hydrophobic film 24, the surface of the inner wall 22a of the recess 22 is hydrophobized.

  The method for bringing the surface hydrophobizing composition of the present invention into contact with the surface is not particularly limited, and examples thereof include spin coating, spraying, vapor deposition, and dipping.

  Further, by forming the conductive layer 26 in the recess 22, the semiconductor device shown in FIG. 1 is obtained.

  By forming the hydrophobic film 24 in the process shown in FIG. 5, it is possible to prevent moisture from being absorbed into the insulating layer 20 from the surface of the inner wall 22 a of the recess 22. Thereby, since the increase in the moisture in the insulating layer 20 can be prevented, the reliability of the semiconductor device can be maintained. In particular, when the insulating layer 20 is an insulating film, when the moisture in the insulating layer 20 increases, the dielectric constant increases, so that the function as a low dielectric film may not be exhibited. On the other hand, the formation of the hydrophobic film 24 can prevent the moisture in the insulating layer 20 from increasing, so that the function as a low dielectric film can be maintained.

  Here, when forming the hydrophobic film | membrane 24, the process of heating the insulating layer 20 can be further included in the state which contacted the said surface hydrophobization composition of this invention. According to this process, since the reaction between (A) diacetoxymethylsilane and the silanol group on the surface of the inner wall 22a of the recess 22 can be further promoted, the hydrophobic film 24 can be formed more easily. . In this case, the heating step may include a step of heating at a temperature of 1 to 3 steps.

  When the heating process is one stage, for example, the heating can be performed at 150 to 350 ° C. within 15 minutes.

  When the heating process is in two stages, the heating process includes heating the layer (insulating layer 20) at a first temperature and heating the layer at a second temperature higher than the first temperature. Process. For example, the heating reaction at the first stage is performed at the first temperature (any temperature of 50 to 250 ° C.) for 5 minutes or less, and the heating reaction at the second stage is performed at the second temperature (150 to 350 ° C.). The heating can be performed within 10 minutes at any one of the above temperatures.

  When the heating process is in three stages, the heating process includes heating the layer (insulating layer 20) at a first temperature and heating the layer at a second temperature higher than the first temperature. And a step of heating the layer at a third temperature higher than the second temperature. For example, the heating reaction at the first stage is performed at the first temperature (any temperature of 50 to 250 ° C.) for 5 minutes or less, and the heating reaction at the second stage is performed at the second temperature (150 to 300 ° C.). The heating reaction in the third stage can be performed at the third temperature (any temperature of 250 to 350 ° C.) for 5 minutes or less. .

  In this invention, it is preferable to perform the said 1-3 steps of heating processes. In the one-step heating process, it is more preferable to set the temperature so that (A) the reaction between diacetoxymethylsilane and silanol groups and the unreacted (A) evaporation (or decomposition) of diacetoxymethylsilane occur simultaneously. . On the other hand, in the two-stage heating process, the reaction of (A) diacetoxymethylsilane and silanol groups in the first-stage heating process, the evaporation of unreacted (A) diacetoxymethylsilane in the second-stage heating process ( It is more preferable to set the temperature at which decomposition occurs. On the other hand, in the three-stage heating process, the reaction between (A) diacetoxymethylsilane and silanol groups in the first-stage heating process, and in the second stage heating process, (A) diacetoxymethylsilane and silanol groups In the third heating step of the reaction, it is more preferable to set the temperature at which evaporation (or decomposition) of unreacted (A) diacetoxymethylsilane occurs. By setting the heating step as described above, the surface can be made more hydrophobic. In the present invention, it is more preferable to perform the three-step heating process.

  As a heating method, a hot plate, an oven, a furnace, or the like can be used. As a heating atmosphere, it can be performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. In particular, a nitrogen atmosphere is preferable.

  Although the case where the surface of the insulating layer 20 is exposed to both etching and ashing has been described here, the surface hydrophobizing method of the present invention is applied to the surface exposed to either etching or ashing. Needless to say, you can. In addition, even if the process is other than etching and ashing, the surface hydrophobization method of the present invention is used when the surface of the insulating layer is chemically and physically damaged by some process (for example, a processing process using plasma). By this, the surface hydrophobizing composition of the present invention can be applied to the surface.

  The processing process using the plasma is not particularly limited, and examples thereof include plasma etching, plasma ashing, plasma CVD, plasma doping, surface treatment using plasma, plasma annealing, and plasma oxidation. . According to the surface hydrophobizing method of the present invention, the surface damaged by such treatment can be hydrophobized.

  According to the surface hydrophobizing method of the present invention, the surface hydrophobizing composition of the present invention is brought into contact with the surface, whereby (A) diacetoxymethylsilane in this composition reacts directly with the surface silanol groups (condensation). ) For this reason, the surface can be reliably hydrophobized.

  In addition, (A) diacetoxymethylsilane used in the surface hydrophobizing composition of the present invention has a hydrogen atom (Si-H) in addition to a methyl group as a hydrophobic group in the molecule. Small and easy to penetrate the surface of the layer. Thereby, since (A) diacetoxymethylsilane and the silanol group of the surface vicinity react rapidly, the surface can be hydrophobized efficiently.

  (A) Diacetoxymethylsilane does not evaporate before contacting the surface, or even after contacting, does not evaporate before reacting. It is also easy to remove from the layer.

1-3. First Semiconductor Device Next, one aspect of the semiconductor device of the present embodiment to which the surface hydrophobizing method of the present invention is applied will be described. FIG. 6 is a cross-sectional view schematically showing the wiring structure 100. The wiring structure 100 functions as a wiring layer and a via layer of the semiconductor device.

  More specifically, the wiring structure 100 includes a conductive layer 90 formed by a dual damascene method. More specifically, the conductive layer 90 includes a via layer 92 and a wiring layer 94 provided continuously on the via layer 92. The via layer 92 is embedded in the first recess 72 provided in the insulating layer (first insulating layer) 120, and the wiring layer 94 is provided in the organic insulating layer (second insulating layer) 220. Embedded in the second recess 74. The installation position of the wiring layer 94 is not particularly limited, and may be a first wiring layer or a second or higher wiring layer. In addition, here, an example in which the surface hydrophobizing method of the present invention is applied to the formation of an insulating layer in a wiring structure formed by a damascene method has been shown. However, the surface hydrophobizing method of the present invention is a damascene method. The present invention is not only applied to a method for manufacturing a wiring structure formed by the above method, but can be applied to a method for manufacturing any layer in a semiconductor device.

  In the semiconductor device shown in FIG. 6, the wiring structure 100 is disposed above the semiconductor substrate 110, disposed on the via layer 92 provided in the first recess 72, disposed on the via layer 92, and second And a wiring layer 94 provided in the recess 74. The first recess 72 is provided in an insulating layer (first insulating layer) 120 disposed above the substrate 10. The second recess 74 is provided in an insulating layer (second insulating layer) 220 disposed above the first insulating layer 120. A hydrophobic film 124 is formed on the inner wall 72 a of the first recess 72. This hydrophobic film 124 is obtained by bringing the above-described composition for hydrophobizing a surface of the present invention into contact with the inner wall 72 a of the first recess 72.

  The first insulating layer 120 is, for example, an MSQ (methylsilsesquioxane) insulating film, and the second insulating layer 220 is, for example, an organic insulating layer. The material of the semiconductor substrate 110 is not particularly limited, but is a compound semiconductor substrate such as a silicon substrate, a sapphire substrate, or GaAs. A second insulating layer 220 is laminated on the first insulating layer 120 with a cap layer 40 interposed therebetween. A diffusion prevention layer 82 is provided on the semiconductor substrate 110. Further, the diffusion prevention layer 82 and the conductive layer 90 are in contact with each other at the bottom surface of the first recess 72. As shown in FIG. 1, the inner walls of the first recess 72 and the second recess 74 may be covered with a barrier layer 80. That is, in this case, the first insulating layer 120 and the via layer 92 are adjacent to each other via the hydrophobic film 124 and the barrier layer 80. The second insulating layer 220 and the wiring layer 94 are adjacent to each other through the barrier layer 80. A cap layer 42 can be provided on the second insulating layer 220.

  Examples of the MSQ insulating film used for the first insulating layer 120 include an SOG film having silicon atoms, oxygen atoms, and carbon atoms as constituent elements.

  The organic insulating layer used for the second insulating layer 220 is selected from, for example, polyarylene, polyarylene ether, polyimide, polybenzoxazole, polybenzobisoxazole, polytriazole, polyphenylquinoxaline, polyquinoline, polyquinoxaline, and the like. An organic insulating film made of polyarylene or polyarylene ether is particularly preferable. In addition, as the second insulating layer 220, one or a combination of two or more of the above organic polymers may be used.

  This wiring structure 100 can be formed, for example, by the following method. 6 to 11 are cross-sectional views schematically showing one manufacturing process of the wiring structure 100.

  First, after forming the diffusion prevention layer 82 above the semiconductor substrate 110, the first insulating layer 120 is formed on the diffusion prevention layer 82 by, for example, the SOG method (see FIG. 7). Next, the stopper layer 40, the second insulating layer 220, and the cap layer 42 are sequentially formed on the first insulating layer 120 (see FIG. 7). Note that the second insulating layer 220 can be formed by coating, for example, in the same manner as the first insulating layer 100. In this case, since a laminated structure can be formed with only one device (spin-on process device), it greatly contributes to an improvement in throughput during semiconductor manufacturing.

  Next, an opening (through hole) 70 that penetrates the first insulating layer 120, the stopper layer 40, the second insulating layer 220, and the cap layer 42 is formed (see FIG. 8). Specifically, first, after forming a resist layer (not shown) on the cap layer 42, a resist layer R10 having a predetermined pattern is formed by a known photolithography process. The resist layer R10 has a pattern for forming the opening 70 (see FIG. 8). Next, using the resist layer R10 as a mask, the first insulating layer 120, the stopper layer 40, the second insulating layer 220, and the cap layer 42 are etched to form an opening 70 (see FIG. 8). Since the first insulating layer 120 is made of an MSQ insulating film, the etching process causes damage to the surface of the inner wall of the opening 70 to generate silanol groups, as shown in FIG. Next, the resist layer R10 is removed by ashing. As described above, the surface of the inner wall of the opening 70 is further damaged by this ashing process.

  Next, a first recess 72 is formed in the first insulating layer 120, and a second recess 74 is formed in the second insulating layer 220 (see FIG. 9). Specifically, first, after forming a resist layer (not shown) on the cap layer 42, a resist layer R11 having a predetermined pattern is formed by a known photolithography process. The resist layer R11 has a pattern for forming the second recess 74. Next, using the resist layer R11 as a mask, the cap layer 42 and the organic insulating layer 220 are patterned by etching using plasma to form the first recess 72 and the second recess 74. Thereafter, the resist layer R11 is removed by ashing or the like. Alternatively, the second insulating layer 220 may be patterned first to form the second recess 74, and then the stopper layer 40 and the first insulating layer 120 may be patterned to form the first recess 72.

  As an etching method of the cap layer 42 and the first insulating layer 120, an etching method using various plasmas (for example, anisotropic plasma etching, reactive plasma etching, inductively coupled plasma etching, ECR plasma etching) or the like is used. Can be used. The etching method for the second insulating layer 220 and the ashing method for the resist layers R10 and R11 are mainly composed of oxygen plasma treatment, ammonia plasma treatment, hydrogen / nitrogen mixed gas plasma treatment, and nitrogen / oxygen mixed gas. A dry etching process can be exemplified.

  Next, the hydrophobic membrane 124 is formed on the inner wall 72a of the first recess 72 by bringing the surface hydrophobizing composition of the present invention into contact with the surface of the inner wall 72a of the first recess 72 (FIG. 10). The procedure in this step can use the surface hydrophobization method of the present invention described above.

  Next, the barrier layer 80 is formed on the inner walls of the first recess 72 and the second recess 74 by using, for example, a CVD method or a sputtering method (see FIG. 11). Subsequently, a conductive layer 90 (see FIG. 6) is formed in the first recess 72 and the second recess 74. Specifically, for example, after a copper seed layer (not shown) is formed by a PVD method, a conductive material 90a is embedded in the first recess 72 and the second recess 74 by a plating method (see FIG. 11). Next, the conductive material 90a is planarized by CMP. As a result, the portion of the conductive material 90a formed above the cap layer 42 is removed, and the conductive layer 90 is obtained (see FIG. 6). That is, the via layer 92 is formed in the first recess 72, and the wiring layer 94 is formed in the second recess 74. Next, a stopper layer 84 is formed on the conductive layer 90 and the cap layer 42 as necessary. Through the above steps, the wiring structure 100 is obtained (see FIG. 6).

  In this wiring structure 100, since the hydrophobic film 124 is formed on the inner wall 72 a of the first recess 72 provided in the first insulating layer 120, moisture is first supplied from the inner wall 72 a of the first recess 72. By entering the insulating layer 120, the hygroscopicity of the first insulating layer 120 can be prevented from increasing. Accordingly, the low dielectric property of the first insulating layer 120 can be maintained, so that a semiconductor device with excellent reliability can be obtained.

1-4. Second Semiconductor Device Next, an aspect of the semiconductor device of the present embodiment to which the surface hydrophobizing method of the present invention is applied will be described. FIG. 12 is a cross-sectional view schematically showing a wiring structure 200 included in the second semiconductor device. The wiring structure 200 functions as a wiring layer and a via layer of the semiconductor device. Note that the semiconductor device illustrated in FIG. 12 is an inorganic second insulating layer instead of the second insulating layer 220 which is an organic insulating layer, as compared with the above-described first semiconductor device (see FIG. 6). The difference is that 320 is provided and the cap layer 44 is provided between the first insulating layer 120 and the second insulating layer 320.

  More specifically, the semiconductor device shown in FIG. 12 includes a wiring structure 200 disposed above the substrate 110. The wiring structure 200 includes a via layer 92 provided in the first recess 72, a via And a wiring layer 94 disposed on the layer 92 and provided in the second recess 74. The first recess 72 is provided in the first insulating layer 120 disposed above the substrate 110. The second recess 74 is provided in the second insulating layer 320 disposed above the first insulating layer 120. Further, a hydrophobic film (first hydrophobic film) 124 is formed on the inner wall 72 a of the first recess 72, and a hydrophobic film (second hydrophobic film) 224 is formed on the inner wall 74 a of the second recess 74. Is formed. The first hydrophobic film 124 is obtained by bringing the above-described surface hydrophobizing composition of the present invention into contact with the inner wall 72a of the first recess 72, and the second hydrophobic film 224 is the above-described one. The surface hydrophobizing composition of the present invention was obtained by contacting the inner wall 72a of the second recess 72.

  The second insulating layer 320 can be made of an MSQ insulating film, for example, like the first insulating layer 120. In this case, the second insulating layer 320 can be manufactured in the same process as the first insulating layer 120.

  The semiconductor device shown in FIG. 12 can be manufactured by the same manufacturing process as the first semiconductor device 120 described above except that the hydrophobic film 224 is formed on the inner wall 74 a of the second recess 74. Hereinafter, the description of the manufacturing process similar to that of the above-described first semiconductor device will be omitted, and only the forming process of the hydrophobic film 224 will be described.

  The surface of the inner wall 74a of the second recess 74 provided in the second insulating layer 320 is provided in the first insulating layer 120 by the etching process and the ashing process performed to form the second recess 74. In addition, the silanol group is generated by being damaged in the same manner as the surface of the inner wall 72a of the first recess 72 (see FIG. 13).

  Next, the surface hydrophobization method of the present invention described above is applied to the surface of the inner wall 74 a of the second recess 74 and also to the surface of the inner wall 74 a of the second recess 74. Thereby, the hydrophobic film 124 is formed on the inner wall 72a of the first recess 72, and the hydrophobic film 224 is formed on the inner wall 74a of the second recess 74 (see FIG. 14). By this step, it is possible to prevent moisture from being absorbed from the inner wall 74a of the second recess 74, and thus it is possible to prevent an increase in hygroscopicity of the second insulating layer 320. Therefore, since the low dielectric property of the second insulating layer 320 can be maintained, a semiconductor device with excellent reliability can be obtained. Moreover, since the surface of the inner wall 72a of the 1st recessed part 72 and the surface of the inner wall 74a of the 2nd recessed part 74 can be processed in the same process, a hydrophobization process can be performed efficiently.

1-5. Features of the Present Invention The features of the present invention will be described in comparison with known techniques relating to the modification of the surface of the layer. Techniques for modifying the surface of the layer are disclosed in, for example, Patent Documents 1 to 4 and Non-Patent Documents 1 and 2 described above.

  Among these, the specification of Patent Document 2 (US Pat. No. 5,550,402) discloses a method for improving the porous structure using ammonium fluoride gas. Further, the specification of Patent Document 4 (US Pat. No. 6,700,200) discloses a method of treating the surface of a layer obtained by the SOG method using ammonium fluoride gas. However, it is necessary to pay close attention to corrosion of containers and pipes by ammonium fluoride itself or by-products, and containers and pipes must be replaced as necessary, which may increase manufacturing costs. high. Further, when the surface of the fluorinated surface is covered with, for example, a barrier metal in a subsequent process, for example, there is a high possibility that a problem occurs in the adhesion with the barrier metal. On the other hand, when the surface is hydrophobized using the composition for hydrophobizing a surface of the present invention, no by-product is generated, so that it is not necessary to pay attention to the container or the like. For this reason, the surface can be easily hydrophobized. Moreover, when the said surface is coat | covered with a barrier metal at a subsequent process, an unexpected side reaction does not arise. Therefore, for example, in the case of including a step of forming a barrier metal film as in the damascene process, the surface hydrophobizing using the surface hydrophobizing composition of the present invention can improve the adhesion between the barrier metal and the surface. Can keep good.

  Patent Document 3 (US Pat. No. 6,654,113) discloses a method for dehydrogenating and alkylating a porous silica film using a halogenated organosilane (for example, TMSI). When halogenated organosilane is used, hydrogen halide is generated after the reaction. Since this hydrogen halide is highly reactive, it may react with other substances to form a halide. When including a step of forming a copper wiring in the manufacturing process of a semiconductor device, when dehydrogenating and alkylating using the method described in Patent Document 3, the process is performed after exposing copper to the bottom of the via. In this case, there is a possibility that a reaction product having a metal corrosive property such as a generated halide adheres to the copper wiring. On the other hand, when the surface is hydrophobized using the composition for hydrophobizing a surface of the present invention, no hydrogen halide is generated, and therefore no unexpected side reaction occurs. Therefore, for example, in the case of including a step of forming a copper wiring as in the damascene process, a reaction product having a metal corrosive property can be obtained by hydrophobizing the surface using the surface hydrophobizing composition of the present invention. Therefore, the electrical connection of the wiring can be kept good.

  Furthermore, Non-Patent Document 1 (Philip G. Clerk, two others, Cleaning and Restoring k Value of Porous MSQ Films, Semiconductor International) , August 2003, pp. 46-52) and Patent Documents 1 and 3 (US Pat. No. 6,383,466, US Pat. No. 6,548,113) disclose a processing method using HMDS (hexamethyldisilazane). However, since HMDS is very hydrophobic and has a relatively large molecular size, it is difficult to diffuse into a portion having a hydrophilic silanol group. On the other hand, (A) diacetoxymethylsilane contained in the surface hydrophobizing composition of the present invention has a hydrogen atom (Si—H) as a hydrophobic group in the molecule in addition to a methyl group, Since it has an acetoxy group which is a molecule and has high affinity with silanol as a reactive functional group, it can diffuse smoothly into a portion having a hydrophilic silanol group. Thereby, (A) diacetoxymethylsilane can diffuse from the surface of the layer to the deep part, and can react with a silanol group efficiently. Therefore, since (A) diacetoxymethylsilane can smoothly diffuse into a fine region such as the inner wall of the layer, the surface hydrophobicity is increased even in a fine region such as the inner wall of the layer. Can do.

  On the other hand, under the condition that the content of (A) diacetoxymethylsilane in the surface hydrophobizing composition is higher than 10% by weight, (A) diacetoxymethylsilane existing in excess in the layer undergoes hydrolytic condensation. As a result, the voids in the layer are closed, and the layer density increases. An increase in film density contributes to an increase in dielectric constant.

  On the other hand, according to the surface hydrophobizing composition of the present invention, (A) diacetoxymethylsilane is contained more than necessary in the layer by including 0.1 to 10% by mass of diacetoxymethylsilane. Can be prevented from penetrating. As a result, hydrolysis condensation between (A) diacetoxymethylsilanes in the layer can be suppressed, so that the voids in the layer can be prevented from being blocked, resulting in an increase in layer density. Can be prevented. As a result, a layer having a low relative dielectric constant at room temperature and a layer density that does not increase can be obtained.

  In the present invention, the “relative dielectric constant of the layer at 200 ° C.” is used as an index in order to evaluate the presence or absence of an increase in the layer density.

  Usually, a layer mainly composed of silicon atoms and oxygen atoms (for example, a low-k film made of methylsilsesquioxane) is a silanol in the layer or on the surface of the layer even if the layer is not damaged. Since (Si—OH) exists, the relative dielectric constant of the layer at room temperature is a value affected by the adsorbed water. However, since the adsorbed water in the layer is almost desorbed when heated to 200 ° C., the relative dielectric constant of the layer measured at 200 ° C. is that of the layer not affected by the adsorbed water. It can be said to be a relative dielectric constant.

  If the heating temperature at the time of measuring the relative dielectric constant is lower than 200 ° C., desorption of adsorbed water may not be sufficient. On the other hand, if the heating temperature is higher than 200 ° C., silanol remains in the layer. Hydrolysis condensation occurs between them, and the relative dielectric constant may be lower than the measured value at 200 ° C. In this case, the original relative dielectric constant may not be restored even if exposed to the atmosphere at room temperature after heating. . For this reason, 200 degreeC is preferable as the temperature at the time of measuring a dielectric constant. By using “the relative dielectric constant of the layer at 200 ° C.” as an index, there is an advantage that the relative dielectric constant at room temperature and the relative dielectric constant at 200 ° C. of the film can be measured reversibly and repeatedly.

  An example of a method for measuring the relative dielectric constant of the layer at 200 ° C. is shown below. First, the test piece is kept at room temperature (25 ° C.) with a hot plate, and the relative dielectric constant is measured. Next, the hot plate is heated to 200 ° C. while flowing dry air, and the relative dielectric constant at 200 ° C. is measured. Since the relative dielectric constant at 200 ° C. can ignore the influence of adsorbed water, it is usually lower than the measured value of the relative dielectric constant at room temperature. After the relative dielectric constant is measured at 200 ° C. and left in the atmosphere at room temperature, the relative dielectric constant gradually increases and returns to the value of the relative dielectric constant at room temperature.

  More specifically, (1) by comparing the relative dielectric constant at 200 ° C. and the relative dielectric constant at room temperature in the layer hydrophobized using the surface hydrophobizing composition of the present invention, The amount of can be evaluated. Further, (2) a relative dielectric constant at 200 ° C. in a layer hydrophobized using the surface hydrophobizing composition of the present invention and a relative dielectric constant at 200 ° C. in a layer not subjected to surface hydrophobization Thus, it is possible to evaluate whether or not the layer density has increased.

  That is, in the comparison of (1), when the surface hydrophobized layer has a large difference between the relative dielectric constant at room temperature and the relative dielectric constant at 200 ° C., it is estimated that the layer has a large amount of adsorbed water.

  Further, in the comparison of (2), as described above, it can be said that the relative dielectric constant of the layer measured at 200 ° C. is a value that is not affected by the adsorbed water. It is presumed that the larger the difference between the relative dielectric constant of the layer and the relative dielectric constant at 200 ° C. of the layer that has not been surface-hydrophobized, the greater the layer density increased by heating. When the layer density increases, the electrical characteristics (leakage current and the like) deteriorate, and the performance as an insulating film decreases. That is, in the comparison of (2), the smaller the difference between the relative dielectric constant at 200 ° C. of the surface hydrophobized layer and the relative dielectric constant at 200 ° C. of the non-surface hydrophobized layer, the smaller the layer density. It can be said that this is a layer with a small increase in the electrical properties.

  In particular, since the silanol group (Si—OH) increases in the damaged layer and the amount of adsorbed water increases, the relative dielectric constant at room temperature increases. For this reason, when the surface hydrophobization treatment is performed, it is preferable that the relative dielectric constant at room temperature is low and the increase in the layer density is small.

2. EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the following description shows the aspect of this invention generally, and this invention is not limited by this description without a particular reason. Moreover, each evaluation in an Example was measured as follows.

2-1. Evaluation method 2-1-1. Evaluation of relative dielectric constant and degassing amount Insulating film (film 1; insulating layer in FIG. 15) formed on a silicon substrate (8-inch silicon wafer 310 in FIG. 15) with a film thickness of 100 to 500 [nm] and baked 420), reactive ion etching (RIE) using NH ₃ gas as an etching gas was performed, and the surface of the insulating film was damaged to produce a film 2 (see FIG. 16). Next, the compositions of Example 1 and Comparative Examples 1 and 2 obtained by the method described later were spin-coated on the film 2, respectively, and then subjected to heat treatment on a hot plate, whereby an insulating film having a hydrophobic film 424 ( Membrane 3; see FIG. 17).

  Respective dielectric constant (= k) and degassing amount of the insulating film (film 1) after film formation and baking, the insulating film (film 2) after RIE treatment, and the insulating film (film 3) after contact with the composition evaluated. The degassing amount was determined by measuring the amount of water desorbed when heated to 450 ° C. with a temperature-programmed desorption gas analyzer.

  The degassing amount was evaluated according to the following criteria.

A: Desorption moisture amount is 30% or less of insulating film (film 2) after RIE treatment B: Desorption moisture amount is 30% or more of insulation film (film 2) after RIE treatment In Example 1 and Comparative Examples 1 and 2 The relative dielectric constant at room temperature (25 ° C.) and the relative dielectric constant at 200 ° C. were measured for the film after treatment with the composition (film 3) and the film without treatment with the composition (film 2), respectively. The relative dielectric constant at 200 ° C. was measured after the temperature was raised to 200 ° C. over 35 minutes in a dry plate in dry air and then held at 200 ° C. for 5 minutes. Further, the dielectric constant was calculated from the capacitance value at 10 kHz using an HP16451B electrode and HP4284A Precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.

2-2. Examples and Comparative Examples 2-2-1. Example 1
0.9 g of diacetoxymethylsilane was dissolved in 29.3 g of butyl acetate to prepare a composition having a diacetoxymethylsilane concentration of 3% by weight. This composition was cast on the insulating film (film 2) after the etching treatment by spin coating. Next, this insulating film was heat-treated on a hot plate at 80 ° C. for 5 minutes, and then at 300 ° C. for 5 minutes in a nitrogen atmosphere. Table 1 shows the evaluation results of the insulating film of Example 1 obtained by the above process.

2-2-2. Comparative Example 1
4.5 g of HMDS was dissolved in 25.5 g of toluene to prepare a composition having a HMDS concentration of 15% by weight. This composition was cast on the insulating film (film 2) after the etching treatment by spin coating. Next, this insulating film was heat-treated on a hot plate at 80 ° C. for 4 minutes, and then at 250 ° C. for 2 minutes in a nitrogen atmosphere. Table 1 shows the evaluation results of the film of Comparative Example 1 obtained by the above process.

2-2-3. Comparative Example 2
6.0 g of diacetoxymethylsilane was dissolved in 24.0 g of butyl acetate to prepare a composition having a diacetoxymethylsilane concentration of 20% by weight. This composition was cast on the insulating film (film 2) after the etching treatment by spin coating. Next, this insulating film was heat-treated on a hot plate at 80 ° C. for 5 minutes, and then at 300 ° C. for 5 minutes in a nitrogen atmosphere. Table 1 shows the evaluation results of the insulating film of Comparative Example 2 obtained by the above process.

表１において、ｄk(1)およびｄk(1)は以下の値を表す。
ｄk(1) ＝ （２５℃における膜の比誘電率）−（２００℃における膜の比誘電率）
ｄk(2) ＝ （２００℃における膜の比誘電率）−（２００℃における組成物未処理の膜の比誘電率）
実施例１の絶縁膜によれば、室温（２５℃）における膜の比誘電率は、表面疎水化処理前の室温（２５℃）における膜の比誘電率よりも大きく低下し（つまりシラノールが大きく減少した。）、一方、２００℃における膜の比誘電率は、疎水化処理前の２００℃における膜の比誘電率と同じであり（つまり疎水化処理前後で膜密度の変化は見られなかった）、且つ、脱ガス量評価、および電気特性評価がいずれも良好であった。

In Table 1, dk (1) and dk (1) represent the following values.
dk (1) = (relative permittivity of film at 25 ° C.) − (relative permittivity of film at 200 ° C.)
dk (2) = (relative permittivity of film at 200 ° C.) − (relative permittivity of untreated film at 200 ° C.)
According to the insulating film of Example 1, the relative dielectric constant of the film at room temperature (25 ° C.) is significantly lower than the relative dielectric constant of the film at room temperature (25 ° C.) before the surface hydrophobization treatment (that is, silanol is larger). On the other hand, the relative dielectric constant of the film at 200 ° C. is the same as the relative dielectric constant of the film at 200 ° C. before the hydrophobic treatment (that is, no change in film density was observed before and after the hydrophobic treatment). In addition, the evaluation of degassing amount and the evaluation of electrical characteristics were both good.

  On the other hand, the film obtained in Comparative Example 1 was poor in both degassing amount evaluation and electrical property evaluation. Further, the film obtained in Comparative Example 2 has a good degassing amount evaluation, and the relative dielectric constant of the film at room temperature (25 ° C.) is higher than the relative dielectric constant of the film at room temperature (25 ° C.) before the hydrophobic treatment. However, the relative dielectric constant of the film at 200 ° C. was higher than that of the film at 200 ° C. before the surface hydrophobization treatment (that is, the film density increased after the surface hydrophobization treatment). The electrical property evaluation deteriorated.

  From this result, it was confirmed that the insulating film obtained in Example 1 has a low dielectric constant, high moisture absorption resistance, and has a hydrophobic effect on the surface.

It is sectional drawing which shows typically the semiconductor device of one embodiment of this invention. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. FIG. 4 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 1. It is sectional drawing which shows typically the semiconductor device of one embodiment of this invention. FIG. 7 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 6. FIG. 7 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 6. FIG. 7 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 6. FIG. 7 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 6. FIG. 7 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 6. It is sectional drawing which shows typically the semiconductor device of one embodiment of this invention. FIG. 13 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 12. FIG. 13 is a cross-sectional view schematically showing one manufacturing process of the semiconductor device shown in FIG. 12. In one Example of this invention, it is sectional drawing which shows typically the insulating film (film | membrane 1) after the film-forming and baking produced by evaluation of the dielectric constant and degassing amount. In one Example of this invention, it is sectional drawing which shows typically the insulating film (film | membrane 2) after RIE created by evaluation of a dielectric constant and degassing amount. In one Example of this invention, it is sectional drawing which shows typically the insulating film (film | membrane 3) after RIE created by evaluation of a dielectric constant and degassing amount.

Explanation of symbols

10, 110, 210, 310 Substrate 20, 420 Insulating layer 22, 70 Recess 22a, 72a, 74a Recess inner wall 24, 124, 424 Hydrophobic film 26, 90 Conductive layer 40 Stopper layer 42, 44 Cap layer 72 Recess (first) 1 recess)
74 Concave portion (second concave portion)
80 Barrier layer 82 Diffusion prevention layer 84 Stopper layer 90a Conductive material 92 Via layer 94 Wiring layer 100, 200 Wiring structure 120 Insulating layer (first insulating layer)
124 Hydrophobic membrane (first hydrophobic membrane)
220, 320 Insulating layer (second insulating layer)
224 Hydrophobic membrane (second hydrophobic membrane)
R1, R10, R11 resist layer

Claims (13)

A composition for surface hydrophobization used for a layer containing a silicon atom and containing at least one element selected from an oxygen atom, a carbon atom, a hydrogen atom, and a nitrogen atom as a constituent element,
(A) A composition for hydrophobizing a surface, comprising 0.1 to 10% by weight of diacetoxymethylsilane and (B) an aprotic solvent.   A composition for hydrophobizing a surface used for a layer having a silanol group formed on the surface by at least one treatment selected from a processing process using etching, ashing and plasma,
  The layer contains a silicon atom and includes at least one element selected from an oxygen atom, a carbon atom, a hydrogen atom, and a nitrogen atom as a constituent element,
  (A) A composition for hydrophobizing a surface, comprising 0.1 to 10% by weight of diacetoxymethylsilane and (B) an aprotic solvent. In claim 1 or 2 ,
A composition for hydrophobizing a surface, which is used in contact with the surface of a layer. In any of claims 1 to 3 ,
The composition for surface hydrophobization, wherein the layer is an insulating film. A method for hydrophobizing a surface, comprising the step of heating the surface hydrophobizing composition according to any one of claims 1 to 4 in a state of being in contact with the surface of the layer. In claim 5 ,
The heating step includes
Heating the layer at a first temperature;
Heating the layer at a second temperature that is higher than the first temperature. In claim 5 ,
The heating step includes
Heating the layer at a first temperature;
Heating the layer at a second temperature higher than the first temperature;
Heating the layer at a third temperature higher than the second temperature. We claim 5 comprises a hydrophobic film obtained by surface-hydrophobicized method according to 7 or a semiconductor device. The surface-hydrophobicized method according to any one of claims 5 to 7, comprising the step of forming a hydrophobic film, a method of manufacturing a semiconductor device. A semiconductor device including an insulating layer disposed above a substrate,
The insulating layer is provided with a recess,
A hydrophobic film is formed on the inner wall of the recess,
The said hydrophobic film | membrane is a semiconductor device obtained by making the composition for surface hydrophobization in any one of Claim 1 thru | or 4 contact the inner wall of the said recessed part. A semiconductor device including a wiring structure disposed above a substrate,
The wiring structure is
A via layer provided in the first recess;
A wiring layer disposed on the via layer and provided in the second recess,
The first recess is provided in a first insulating layer disposed above the substrate,
The second recess is provided in a second insulating layer disposed above the first insulating layer,
A hydrophobic film is formed on the inner wall of the first recess,
The said hydrophobic film | membrane is a semiconductor device obtained by making the composition for surface hydrophobization in any one of Claim 1 thru | or 4 contact the inner wall of a said 1st recessed part. A semiconductor device including a wiring structure disposed above a substrate,
The wiring structure is
A via layer provided in the first recess;
A wiring layer disposed on the via layer and provided in the second recess,
The first recess is provided in a first insulating layer disposed above the substrate,
The second recess is provided in a second insulating layer disposed above the first insulating layer,
A first hydrophobic film is formed on the inner wall of the first recess,
A second hydrophobic film is formed on the inner wall of the second recess,
The first hydrophobic film is obtained by bringing the surface hydrophobizing composition according to any one of claims 1 to 4 into contact with an inner wall of the first recess,
The second hydrophobic film is a semiconductor device obtained by bringing the surface hydrophobizing composition according to any one of claims 1 to 4 into contact with the inner wall of the second recess. In claim 11 or 12 ,
The semiconductor device, wherein the via layer and the wiring layer are integrally formed.

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