JP6604049B2 - Manufacturing method of semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor device manufacturing method and a semiconductor device.

2. Description of the Related Art Conventionally, a semiconductor device in which various elements such as a micro-electro-mechanical system (MEMS) are accommodated in a hollow structure is known (for example, see Patent Documents 1 and 2). In manufacturing a semiconductor device having such a hollow structure, for example, there is a process in which a sacrificial material is disposed in a portion that becomes a hollow structure, a sealing member is separately formed, and then the sacrificial material is removed by a process such as etching or dissolution. Adopted.
Here, Patent Document 1 and Patent Document 2 describe that as a sacrificial material, for example, silicon oxide such as silicon dioxide, amorphous silicon, photoresist, and other polymer materials are used.

JP-A-2005-123561 JP 2005-341162 A

  The sacrificial material as described above is formed on an insulating film such as a silicon oxide film or a silicon nitride film. Here, as a result of studies by the present inventors, it has been found that there are the following concerns when using a photoresist (photosensitive resin composition) as a sacrificial material.

That is, when a photoresist (photosensitive resin composition) varnish is applied to an insulating film such as a silicon oxide film or a silicon nitride film and patterned into a predetermined shape, the developer is placed between the pattern and the insulating film. There was a concern that the pattern would be easily peeled off.
In addition, when a varnish of a photoresist (photosensitive resin composition) is applied to the insulating film, there is a possibility that the varnish may be repelled on the insulating film, and patterning itself is difficult. .
That is, the shape of the pattern formed from the photosensitive resin composition used as a sacrificial material is effectively stabilized, thereby controlling the shape of the finally obtained semiconductor device having a hollow structure to a predetermined one. It has been desired to establish a method for manufacturing a semiconductor device.

  This invention is made | formed in view of this situation, and provides the manufacturing method of the semiconductor device which can form the shape of the sacrificial material formed with the photosensitive resin composition stably.

According to the present invention,
A method of manufacturing a semiconductor device having a hollow structure,
Preparing a substrate;
Depositing a first film on the substrate;
Hydrophobizing the surface of the first film;
Applying a photosensitive resin composition onto the hydrophobic treated first film to form a film of the photosensitive resin composition;
Patterning the film of the photosensitive resin composition into a predetermined shape, and forming a layer made of a sacrificial material;
Depositing a second film on the sacrificial layer;
Etching the second film to form an opening in the second film;
Removing the sacrificial material through the opening of the second film;
A method for manufacturing a semiconductor device, comprising:
The step of hydrophobizing the surface of the first film is a mode in which a substrate provided with the first film is placed in a chamber and the silylating agent is vaporized and sprayed.
In the step of applying a photosensitive resin composition on the hydrophobic treated first film to form a film of the photosensitive resin composition, the method of applying the photosensitive resin composition is a spin coating method. The
In the step of hydrophobizing the surface of the first film, the pressure condition when vaporizing the silylating agent is 1.2 atm or more and 5 atm or less.
A method for manufacturing a semiconductor device is provided.

  Moreover, according to this invention, the semiconductor device manufactured by the said method is provided.

In the method for manufacturing a semiconductor device of the present invention, since the surface of the first film is subjected to a hydrophobic treatment, the affinity with the photosensitive resin composition is improved. Therefore, the film of the photosensitive resin composition can be stably patterned.
Moreover, in this invention, the layer which consists of sacrificial materials is formed with the photosensitive resin composition, and the hollow structure originating in the shape of this layer is formed. Therefore, it becomes easy to obtain a semiconductor device having a desired shape by stably patterning the film of the photosensitive resin composition as described above.

It is a longitudinal cross-sectional view for demonstrating the manufacturing method of the semiconductor device of this embodiment. It is a longitudinal cross-sectional view for demonstrating the manufacturing method of the semiconductor device of this embodiment. It is a longitudinal cross-sectional view for demonstrating the manufacturing method of the semiconductor device of this embodiment. It is a figure which shows the result at the time of not performing the hydrophobization process in the manufacturing method of the semiconductor device of this embodiment. It is a figure which shows the result at the time of performing the hydrophobization process in the manufacturing method of the semiconductor device of this embodiment.

  Hereinafter, a method for manufacturing a semiconductor device according to the present invention will be described with reference to the accompanying drawings based on embodiments. In the present specification, “to” represents the following from the above unless otherwise specified.

(Method for manufacturing semiconductor device)
A manufacturing method of a semiconductor device according to the present embodiment is a manufacturing method of a semiconductor device having a hollow structure,
A step of preparing a substrate (hereinafter also referred to as “(A) step”);
A step of depositing a first film on the substrate (hereinafter also referred to as “(B) step”);
A step of hydrophobizing the surface of the first film (hereinafter also referred to as “step (C)”);
A step of applying a photosensitive resin composition on the hydrophobized first film to form a film of the photosensitive resin composition (hereinafter also referred to as “step (D)”);
Patterning a film of the photosensitive resin composition into a predetermined shape to form a layer made of a sacrificial material (hereinafter also referred to as “(E) step”);
A step of depositing a second film on the layer made of the sacrificial material (hereinafter also referred to as “(F) step”);
Etching the second film to form an opening in the second film (hereinafter also referred to as “(G) process”);
A step of removing the sacrificial material through the opening of the second film (hereinafter also referred to as “(H) step”);
A method for manufacturing a semiconductor device including:
Hereinafter, each process included in the manufacturing method of the semiconductor device according to the present embodiment will be described in order with reference to FIGS.

[Step (A)]
In the method for manufacturing a semiconductor device in the present embodiment, first, a substrate is prepared. Here, the “substrate” may have an interlayer insulating layer 2 formed on the substrate 1 or a wiring layer 3 further formed on the interlayer insulating layer 2 as shown in FIG. Absent.

The substrate 1 can be, for example, a silicon (Si) substrate, a glass substrate, or a sapphire substrate, and is formed in a predetermined plate shape.
The interlayer insulating layer 2 is a layer formed on the substrate 1 and is composed of an inorganic film such as a silicon oxide film (SiO ₂ ), a silicon nitride film (SiN), an aluminum oxide film (Al ₂ O ₃ ), for example. .
The wiring layer 3 is a conductive layer formed on the interlayer insulating layer 2 and can be formed using a metal such as gold (Au) in addition to aluminum (Al) and copper (Cu). The wiring layer 3 has a predetermined shape, and its thickness is, for example, in the range of 100 nm to 10 μm.

[Step (B)]
Subsequently, a first film is formed on the substrate.
In FIG. 1B, this first film is shown as an insulating film 4.
The insulating film 4 is an insulating film formed on the interlayer insulating layer 2 and the wiring layer 3 described above. For example, a silicon oxide film (SiO ₂ ), a silicon nitride film (SiN), an aluminum oxide film (Al ₂ O ₃ ) or other inorganic film.
The first film may be a conductive film, but from the viewpoint of expanding the field of application of the semiconductor device, the insulating film having the above-described insulating property is a particularly preferable aspect. .

[Step (C)]
Subsequently, the surface of the first film is hydrophobized.
That is, in this step, the surface of the insulating film 4 shown in FIG. 1B is subjected to a surface treatment using an appropriate surface treatment agent (hydrophobization treatment agent).

This hydrophobizing treatment can be appropriately selected in consideration of the surface characteristics of the first film and the like.
Specific examples thereof include a “silylating agent” capable of silylating the surface of the first film and a “fluorinating agent” capable of fluorinating the surface of the first film. .
By using these surface treatment agents, the hydrophobicity of the first film can be improved efficiently.

Specific examples of compounds that can be used as silylating agents include trimethylchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, tri-i-propylchlorosilane, tri-n-butylchlorosilane, tri-t-butylchlorosilane, trimethyl Bromosilane, triethylbromosilane, tri-n-propylbromosilane, tri-i-propylbromosilane, tri-n-butylbromosilane, tri-t-butylbromosilane, propyltrichlorosilane, butyltrichlorosilane, isobutyltrichlorosilane , Hexyltrichlorosilane, cyclohexyltrichlorosilane, octyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane, octadecyltrichloro Halogenated alkyl silanes such as run; hexamethyldisilazane, hexaethyldisilazane, hex-n-propyldisilazane, hexa-i-propyldisilazane, hexa-n-butyldisilazane, hexa-t-butyldi Silazanes such as silazane; quaternary alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane; Trimethoxymethylsilane, triethoxymethylsilane, tri-n-propoxymethylsilane, trimethoxyethylsilane, trimethoxy-n-propylsilane, trimethoxy-i-propylsilane, triethoxyethylsilane, triethoxy-n-propylsilane, Triethoxy -Propylsilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyl Trimethoxysilane, phenyltriethoxysilane, i-butyltriethoxysilane, decyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyl Tertiary alkoxyalkylsilanes such as methoxysilane and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane; dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydi-n-propylsilane, dimethoxydi-i-propylsilane, diethoxy Secondary alkoxyalkylsilanes such as dimethylsilane and diethoxydiethylsilane; first methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, ethoxytriethylsilane, n-propoxytrimethylsilane, n-propoxytriethylsilane and the like Grade alkoxysilanes.
Among the above compound groups, hexamethyldisilazane, hexaethyldisilazane, hex-n-propyldisilazane, hexa-i-propyldisilazane, hexa-n-butyldisilazane, hexa-t-butyldisilazane. A compound having a Si—NH—Si structure in the molecule is preferably used. When a compound having such a structure is used, the silylating agent is converted into ammonia molecules (NH ₃ ) when the surface treatment is performed, so that it can be easily excluded from the system.
Moreover, hexamethyldisilazane (HMDS) can be illustrated as a particularly preferable silylating agent from the viewpoint of availability.
Moreover, these compounds may be used alone or in combination of two or more.

Similarly, the fluorinating agent may be appropriately selected from those capable of modifying a polar group such as a hydroxyl group (—OH group) existing on the surface of the insulating film 4.
Examples of such fluorinating agents include trifluoromethyl iodide, trifluoromethyl bromide, trifluoromethyl chloride, difluoromethyl iodide, difluoromethyl bromide, and difluoromethyl chloride.

The surface treatment using the hydrophobizing agent is performed, for example, by applying a liquid hydrophobizing agent or vaporizing and spraying the hydrophobizing agent.
The temperature of the hydrophobizing treatment can be appropriately set in consideration of the hydrophobizing agent used and the components of the first film.

As a more specific aspect, there may be mentioned an aspect in which the substrate 1 (substrate) provided with the above-described insulating film 4 (first film) is placed in a chamber and the silylating agent is vaporized and sprayed. This vaporization may be performed under normal pressure conditions or after adjusting the pressure.
Note that such processing can be performed using an apparatus as described in JP-A-10-41214, for example.
The lower limit of the temperature at which the silylating agent is vaporized is, for example, 40 ° C. or higher, preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. Moreover, as an upper limit of the temperature at the time of vaporizing a silylating agent, it is 300 degrees C or less, for example, Preferably it is 250 degrees C or less, More preferably, it is 200 degrees C or less. By adopting such a temperature condition, it becomes easy to adjust the speed of silylation for the insulating film 4 (first film).

Moreover, as a pressure condition for vaporizing the silylating agent, both a reduced pressure condition and a pressurized condition can be employed.
The lower limit value of the pressure when the decompression condition is adopted is, for example, 0.01 atmosphere or more, preferably 0.1 atmosphere or more. Further, the upper limit value of the pressure when the decompression condition is adopted is, for example, 0.9 atm or less, and preferably 0.8 atm or less.
By adopting such conditions, surface treatment can be performed at a temperature sufficiently lower than the boiling point of the silylating agent (for example, when using hexamethyldisilazane, the boiling point: 125 ° C.). Life can be extended.
The lower limit of the pressure when the pressurizing condition is adopted is, for example, 1.2 atm or more, and preferably 1.5 atm or more. Moreover, the upper limit value of the pressure when the pressurizing condition is adopted is, for example, 10 atm or less, and preferably 5 atm or less.
By adopting such conditions, it becomes easy to adjust the vaporization rate of the silylating agent, and it becomes easy to impart desired water repellency to the first film.

In the method for manufacturing a semiconductor device of this embodiment, the first film (insulating film 4) is subjected to a hydrophobic treatment as described above. Thereby, appropriate water repellency can be imparted to the first film (insulating film 4), and on the other hand, appropriate affinity with the photosensitive resin composition described later can be exhibited.
As described above, when appropriate water repellency is exhibited as the first film (insulating film 4), the developer and the pattern are formed from the photosensitive resin composition when the pattern is formed from the photosensitive resin composition. ), It becomes difficult to permeate the film and the peeling of the pattern can be suppressed.

The surface-treated first film (insulating film 4) preferably has a contact angle with water, and the lower limit of the contact angle is preferably 50 ° or more, and 55 ° or more. Is more preferable. The upper limit of the contact angle is preferably 85 ° or less, and more preferably 80 ° or less.
Development used when patterning a film formed from the photosensitive resin composition by setting the contact angle of the first film (insulating film 4) to water to a value between the upper limit value and the lower limit value. The liquid diffuses moderately and patterning can be performed stably.
Here, in controlling the contact angle with respect to such water, it is important to appropriately select the hydrophobizing agent and appropriately set the surface treatment conditions. That is, when a silylating agent is used as a hydrophobizing agent, appropriate water repellency can be imparted to the surface of the first film by appropriately selecting the number of carbon atoms bonded to the silicon atom of the silylating agent. .
More specifically, it is preferable to use a silylating agent having a trimethylsilyl group as a silylating agent and capable of chemically bonding the trimethylsilyl group to the surface of the first film.
Examples of such silylating agents include trimethylsilyl chloride, trimethylsilyl bromide, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, hexamethyldisilazane, and the like.

  In addition, after the surface treatment of the first film using the hydrophobizing agent, a cleaning process may be combined for the purpose of removing residues. For example, water or an organic solvent is used in this cleaning process. Organic solvents include alcohols such as methanol and ethanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic compounds such as benzene and toluene; esters such as methyl formate, methyl acetate, and ethyl acetate; and diethyl ether , Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate can be used.

[Step (D)]
Subsequently, a photosensitive resin composition is applied on the hydrophobicized first film to form a photosensitive resin composition film. That is, as shown in FIG. A film 10 of the photosensitive resin composition is formed.
The formation of the film 10 of the photosensitive resin composition is performed as follows, for example. That is, a photosensitive resin composition is applied onto the insulating film 4 by, for example, a coating method to form the photosensitive resin composition film 10 in a thickness range of 100 nm to 10 μm.
Here, as a method for applying the photosensitive resin composition, a known method can be employed, for example, a spin coating method, a spray coating method, a dipping method, a printing method, a roll coating method, or the like can be employed. it can.
When the spin coating method is employed, the lower limit value of the rotational speed can be, for example, a condition of 500 rpm or more, and preferably a condition of 1000 rpm or more. Moreover, as an upper limit of rotation speed, it can be set as conditions of 10,000 rpm or less, for example, and it is more preferable to employ | adopt conditions of 5000 rpm or less.
Further, the lower limit value of the rotation time in the case of employing the spin coating method can be, for example, 1 second or longer, and is preferably 5 seconds or longer. Further, the upper limit value of the rotation time is, for example, 120 seconds or less, and preferably 60 seconds or less.
By combining the above conditions as a spin coating method, it becomes easy to control the film thickness of the desired photosensitive resin composition.

  Here, as the photosensitive resin composition, for example, a varnish-like composition containing an alkali-soluble resin, a photosensitive agent, and an organic solvent is used.

  Examples of the alkali-soluble resin contained in the photosensitive resin composition include novolak resins such as cresol type, phenol type, bisphenol A type, bisphenol F type, catechol type, resorcinol type, pyrogallol type, phenol aralkyl resin, and hydroxystyrene resin. , Acrylic resins such as methacrylic acid resins and methacrylic ester resins, cyclic olefin resins containing hydroxyl groups and carboxyl groups, polyamide resins (specifically, having at least one of a polybenzoxazole structure and a polyimide structure, In addition, a resin having a hydroxyl group, carboxyl group, ether group or ester group in the main chain or side chain, a resin having a polybenzoxazole precursor structure, a resin having a polyimide precursor structure, a resin having a polyamic acid ester structure, etc. Etc., and it can be used singly or in combination of two or more of them.

  Further, as the photosensitizer, a compound capable of generating an acid by light can be used. For example, a photosensitive diazoquinone compound, an onium salt such as a diaryl iodonium salt, a triarylsulfonium salt or a sulfonium borate salt, a 2-nitrobenzyl ester compound, An N-iminosulfonate compound, an imidosulfonate compound, a 2,6-bis (trichloromethyl) -1,3,5-triazine compound, or a dihydropyridine compound can be used.

  Moreover, the photosensitive resin composition of this embodiment can also mix | blend a well-known crosslinking agent suitably. Thus, it becomes easy to hold | maintain the shape at the time of forming a pattern by mix | blending a crosslinking agent as a photosensitive resin composition. In addition, known components used for sacrificial materials can be appropriately blended.

Examples of the organic solvent used in the photosensitive resin composition include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and propylene glycol monomethyl ether. , Dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, and pyruvin Examples include ethyl acid and methyl-3-methoxypropionate. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
Among these, it is preferable that the relative dielectric constant of the organic solvent is 30 or less, more preferably 25 or less, from the viewpoint of developing appropriate affinity with the surface-treated first film (insulating film 4). .
The lower limit value of the relative dielectric constant of the organic solvent is not particularly limited, but is, for example, 5 or more.

The organic solvent used in this step preferably has a product of relative dielectric constant and specific gravity of 30 g / cm ³ or less. By using such an organic solvent, the specific gravity of the photosensitive resin composition as a whole can be lowered while exhibiting an appropriate affinity with the first film (insulating film 4), thereby improving coatability. be able to.

  Moreover, it is particularly preferable to use propylene glycol monomethyl ether acetate (PGMEA) as the organic solvent in view of the high solubility and availability of the alkali-soluble resin and the photosensitizer described above.

[Step (E)]
Subsequently, the photosensitive resin composition film formed in step (D) is patterned into a predetermined shape to form a layer made of a sacrificial material.
This step corresponds to FIGS. 2D to 2E, and is performed, for example, by subjecting the photosensitive resin composition film 10 to a pre-bake step, an exposure step, a development step, and a post-bake step. A material layer 11 is formed.

The lower limit of the pre-baking temperature condition after forming the film 10 of the photosensitive resin composition is, for example, 60 ° C. or higher, and preferably 80 ° C. or higher. Moreover, as an upper limit of the temperature conditions of the prebaking after forming the layer 10 of the photosensitive resin composition, it is 150 degrees C or less, for example, Preferably it is 140 degrees C or less.
Further, the lower limit of the pre-baking time is, for example, 30 seconds or more, and preferably 45 seconds or more. The upper limit of the pre-baking time is, for example, 600 seconds or less, and preferably 300 seconds or less.

  As the actinic radiation used in the exposure step after pre-baking, ultraviolet rays, visible rays, and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. In addition, known exposure conditions such as contact exposure, proximity exposure, same size projection exposure, reduced projection exposure, and scanning exposure can be employed in accordance with the pattern shape to be formed.

As a developing method, an appropriate method may be selected from known methods according to the pattern shape. For example, a paddle method or the like can be adopted.
Examples of the alkaline developer used in the development step include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and first amines such as ethylamine and n-propylamine. Secondary amines such as tertiary amines, diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide An aqueous solution of a quaternary ammonium salt such as tetraethylammonium hydroxide and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used.

Moreover, after performing the above-mentioned development process, as shown in FIG. 2 (e), the film 10 of the photosensitive resin composition is cured by performing a post-baking process, and a final pattern as the sacrificial material layer 11 is obtained. This heating temperature is 160-380 degreeC, for example, More preferably, it is 180-350 degreeC.
Moreover, when heating, it is also a preferable aspect to flow an inert gas such as nitrogen in the heating device to suppress oxidation of the film of the photosensitive resin composition.

[Step (F)]
Subsequently, a second film is deposited on the layer made of the sacrificial material in this step.
This step corresponds to the step shown in FIG. 2F, and the insulating film 30 is formed on the sacrificial material layer 11. The insulating film 30 is made of, for example, a silicon nitride film (SiN) or a silicon oxide film (SiO ₂ ), and can be formed by a method such as a CVD (Chemical Vapor Deposition) method.
The thickness range of the insulating film 30 is, for example, in the range of 100 nm to 10 μm.
In the present embodiment, the second film is shown as the insulating film 30. However, the second film can be formed by combining conductive materials such as a metal film.

[Step (G)]
Subsequently, in this step, the second film is etched to form openings in the second film.
This step corresponds to FIG. 3G and an opening is provided in the insulating film 30. This opening can be provided as follows, for example.
That is, after the insulating film 30 is formed, a resist film (not shown) is formed by using a well-known lithography method, and this resist film is used as a mask and is etched by, for example, the RIE (Reactive Ion Etching) method. Then, the formed resist film is removed.

[Step (H)]
Subsequently, in this step, the sacrificial material is removed through the opening of the second film.
This step corresponds to FIG. 3H, and the sacrificial material layer 11 is removed. As a method for removing the sacrificial material layer, for example, an ashing method using oxygen gas or ozone gas can be employed.
The sacrificial material layer constituents ashed by the ashing method are discharged to the outside through the opening of the insulating film 30. As a result, a hollow structure is formed inside the insulating film 30.
In this specification, description will be made on the assumption that a semiconductor device in which the opening is closed by adopting step (I) described later, but depending on the application, operations up to step (H) are performed. However, the semiconductor device may have an opening.

[Step (I)]
Finally, in this step, the opening of the second film is closed to obtain a semiconductor device.
This step corresponds to FIG. 3I. For example, the semiconductor device 100 is obtained by closing the opening of the insulating film 30 with the organic film 40.
The opening of the insulating film 30 can be sealed using a resin component such as polyimide resin, benzocyclobutene resin, fluorine resin, or polyamide resin.
In the present embodiment, the insulating film 30 is sealed with the organic film 40, but an inorganic material or the like can be used as appropriate depending on the use of the semiconductor device.

Here, in this embodiment, the effect when the surface of the first film is subjected to the hydrophobic treatment will be described with reference to FIGS.
FIG. 4 includes an alkali-soluble resin containing an aliphatic resin and a cycloolefin resin, and a photosensitizer without performing a hydrophobic treatment on the surface of the silicon substrate having an insulating film provided on the surface. Using a photosensitive resin composition in which a photosensitive material is dissolved in propylene glycol monomethyl ether acetate (PGMEA), a film of the photosensitive resin composition is formed under the condition of 1000 rpm for 30 seconds, and the substrate is exposed and developed. It is the figure which copied the exposure part with the optical microscope.
On the other hand, FIG. 5 shows that in this embodiment, hexamethylene disilazane (HMDS) is used to hydrophobize the surface of a silicon substrate having an insulating film on the surface, and then the photosensitive resin composition is prepared in the same manner as described above. It is the figure which copied the exposure part in the case of forming this film | membrane and performing exposure and development processing with the scanning electron microscope (SEM). Here, the hydrophobizing treatment with hexamethylene disilazane (HMDS) uses spin coating conditions.
In these experiments, it was confirmed that the contact angle of water with respect to the surface of the substrate that was not hydrophobized was 5 °, and the contact angle of water with respect to the surface of the substrate that was hydrophobized was 70 °. ing.
As can be seen from the comparison of these figures, by subjecting the first film to surface treatment in the present embodiment, the film of the photosensitive resin composition can be stably formed, and the shape of the sacrificial material can be stably stabilized. Can be formed.

Although the present invention has been described based on the embodiments, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention. It is.
Hereinafter, examples of the reference form will be added.
1. A method of manufacturing a semiconductor device having a hollow structure,
Preparing a substrate;
Depositing a first film on the substrate;
Hydrophobizing the surface of the first film;
Applying a photosensitive resin composition onto the hydrophobic treated first film to form a film of the photosensitive resin composition;
Patterning the film of the photosensitive resin composition into a predetermined shape, and forming a layer made of a sacrificial material;
Depositing a second film on the sacrificial layer;
Etching the second film to form an opening in the second film;
Removing the sacrificial material through the opening of the second film;
A method for manufacturing a semiconductor device, comprising:
2. The first film is an insulating film. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.
3. The hydrophobizing step is performed with a silylating agent. Or 2. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.
4). 2. The silylating agent is a compound having a Si—NH—Si structure. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.
5). 2. the silylating agent is hexamethyldisilazane; Or 4. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.
6). 1. The contact angle of the hydrophobized first membrane with respect to water is 50 ° or more and 85 ° or less. Or 5. A method for manufacturing a semiconductor device according to any one of the above.
7). The photosensitive resin composition contains an organic solvent. Or 6. A method for manufacturing a semiconductor device according to any one of the above.
8). 6. The organic solvent has a relative dielectric constant of 30 or less. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.
9. 6. The product of relative permittivity and specific gravity of the organic solvent is 30 g / cm ³ or less. Or 8. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.
10. 1. Or 9. A semiconductor device manufactured by the method according to any one of the above.

  According to the method for manufacturing a semiconductor device of the present invention, the shape of the sacrificial material formed by the photosensitive resin composition can be stably formed. As a result, the semiconductor device having a hollow structure can be stably formed in a desired shape. Can be manufactured.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Interlayer insulating layer 3 Wiring layer 4 Insulating film 10 Photosensitive resin composition film 11 Sacrificial material layer 30 Insulating film 40 Organic film 100 Semiconductor device

Claims (10)

A method of manufacturing a semiconductor device having a hollow structure,
Preparing a substrate;
Depositing a first film on the substrate;
Hydrophobizing the surface of the first film;
Applying a photosensitive resin composition onto the hydrophobic treated first film to form a film of the photosensitive resin composition;
Patterning the film of the photosensitive resin composition into a predetermined shape, and forming a layer made of a sacrificial material;
Depositing a second film on the sacrificial layer;
Etching the second film to form an opening in the second film;
Removing the sacrificial material through the opening of the second film;
A method for manufacturing a semiconductor device, comprising:
The step of hydrophobizing the surface of the first film is a mode in which a substrate provided with the first film is placed in a chamber and the silylating agent is vaporized and sprayed.
In the step of applying a photosensitive resin composition on the hydrophobic treated first film to form a film of the photosensitive resin composition, the method of applying the photosensitive resin composition is a spin coating method. The
In the step of hydrophobizing the surface of the first film, the pressure condition when vaporizing the silylating agent is 1.2 atm or more and 5 atm or less.
A method for manufacturing a semiconductor device.   The method of manufacturing a semiconductor device according to claim 1, wherein the first film is an insulating film.   The method for manufacturing a semiconductor device according to claim 1, wherein the silylating agent is a compound having a Si—NH—Si structure.   The method of manufacturing a semiconductor device according to claim 1, wherein the silylating agent is hexamethyldisilazane.   The method for manufacturing a semiconductor device according to claim 1, wherein a contact angle of the hydrophobized first film with respect to water is 50 ° or more and 85 ° or less.   The method for manufacturing a semiconductor device according to claim 1, wherein the photosensitive resin composition includes an organic solvent.   The method of manufacturing a semiconductor device according to claim 6, wherein the organic solvent has a relative dielectric constant of 30 or less. The organic solvent is propylene glycol monomethyl ether acetate (PGMEA), a method of manufacturing a semiconductor device according to claim 6 or 7. The photosensitive resin composition, an aliphatic resin or an alkali-soluble resin containing a cycloolefin resin, a method of manufacturing a semiconductor device according to any one of claims 1 to 8. In the step of hydrophobic treatment of the surface of the first layer, the temperature in vaporizing the silylation agent 40 ° C. or more and 200 ° C. or less, the semiconductor device according to any one of claims 1 to 9 Production method.

Images