JP6586029B2 - Semiconductor manufacturing equipment parts and semiconductor manufacturing equipment using the same - Google Patents

Description

  Embodiments generally relate to a component for a semiconductor manufacturing apparatus and a semiconductor manufacturing apparatus using the same.

Various processes such as a CVD (chemical vapor deposition) process, a PVD (physical vapor deposition) process, and an etching process are used in a semiconductor manufacturing process. A semiconductor element is manufactured by forming a conductive thin film, forming an insulating film, exposing, etching, and the like on a silicon substrate.
In the CVD process, a reaction system molecule gas or a mixed gas of a reaction system molecule gas and an inert carrier is allowed to flow on the substrate, and the products resulting from reactions such as hydrolysis, autolysis, photolysis, and oxidation-reduction are removed. This is a step of vapor deposition on a substrate. CVD can lower the reaction temperature relatively. In the CVD process, a thin film can also be formed using plasma discharge or light irradiation.
The PVD process is a method of depositing a thin film on a substrate in a gas phase by a physical method. Examples of the PVD method include resistance heating vapor deposition, electron beam vapor deposition, ion plating, ion beam deposition, and sputtering. In addition, a thin film is formed using heating or an electron beam in a vacuum or under reduced pressure.
The etching process is a process of patterning the thin film. Etching is broadly classified into wet etching and dry etching. Wet etching is a method using an acidic or alkaline chemical. Further, dry etching is a method using reactive species (ion, high-speed neutral particles, radicals, etc.) in plasma. Therefore, dry etching is also called plasma etching.
Since wet etching uses a chemical reaction by a chemical solution, a wide range of etching is possible. Dry etching can control reaction mechanisms such as chemical reactions and physical reactions. For this reason, dry etching is suitable for fine processing of the order of microns (μm) or less.

Thus, the manufacturing process of a semiconductor element is performed combining the CVD process, the PVD process, and the etching process. In recent years, with the miniaturization of wiring, a process accompanied by heat such as plasma is mainly used. In addition, as a process becomes more complicated, a single-wafer type semiconductor manufacturing apparatus is mainly used. A single wafer type semiconductor manufacturing apparatus performs processes such as an etching process in each room.
A conventional component for a semiconductor manufacturing apparatus was provided with a sprayed film made of metal oxide particles such as Y ₂ O ₃ as disclosed in Japanese Patent No. 4585260 (Patent Document 1). Since Y ₂ O ₃ is excellent in plasma resistance, generation of particles can be suppressed.
A component for a semiconductor manufacturing apparatus having a thermal spray film of metal oxide particles has excellent plasma resistance. On the other hand, a metal oxide has a low thermal conductivity as a physical property of the material itself. Thermal spray films made of materials with low thermal conductivity have low heat dissipation. The thermal spray film having low thermal conductivity cannot sufficiently dissipate heat when the semiconductor manufacturing apparatus is operated.
Japanese Patent No. 5566891 (Patent Document 2) discloses a component for a semiconductor manufacturing apparatus including a sprayed film made of nitride particles.

Japanese Patent No. 4585260 Japanese Patent No. 5566891

Patent Document 2 discloses that the use of nitride particles (such as AlN) improves the suppression of particles and the durability to radicals (such as chlorine and fluorine).
On the other hand, in the thermal spraying method in which nitride particles are heated, an oxide is easily formed by reacting with oxygen in the atmosphere. If an oxide is present in the nitride particle film, the thermal conductivity of the film decreases. In particular, when an oxide is present at the interface between the base material and the nitride particle film, the adverse effect on heat dissipation is great.
The problem to be solved by the present invention is to provide a component for a semiconductor manufacturing apparatus provided with a nitride particle film having good heat dissipation.

  The semiconductor manufacturing device component according to the embodiment is a semiconductor manufacturing device component in which a nitride particle film in which nitride particles or oxynitride particles are deposited on a base material is provided. The interface between the base material and the nitride particle film The ratio of the maximum peak of oxide to the maximum peak of nitride (maximum peak of oxide / maximum peak of nitride) is 0.1 or less (including zero) when XRD analysis is performed. is there.

The figure which shows an example of the components for semiconductor manufacturing apparatuses concerning embodiment.

The semiconductor manufacturing device component according to the embodiment is a semiconductor manufacturing device component in which a nitride particle film in which nitride particles or oxynitride particles are deposited on a base material is provided. The interface between the base material and the nitride particle film The ratio of the maximum peak of oxide to the maximum peak of nitride (maximum peak of oxide / maximum peak of nitride) is 0.1 or less (including zero) when XRD analysis is performed. is there.
FIG. 1 shows an example of a component for a semiconductor manufacturing apparatus according to the embodiment. In the figure, 1 is a part for a semiconductor manufacturing apparatus, 2 is a base material, 3 is a nitride particle (oxynitride particle), 4 is a nitride particle film, and 5 is an interface.

A nitride particle film in which nitride particles or oxynitride particles are deposited is provided on a substrate. Examples of the nitride particles include metal nitrides and composite nitrides. Examples of the oxynitride particles include metal oxynitrides and composite oxynitrides. When metal nitride and metal oxynitride are compared, metal nitride is preferred because of its higher thermal conductivity.
The nitride particles or oxynitride particles are preferably one selected from silicon nitride, aluminum nitride, boron nitride, silicon oxynitride, aluminum oxynitride, and boron oxynitride.

The nitride particles or oxynitride particles preferably have an average particle size of 2 μm or less. Furthermore, the average particle size is preferably 1 μm or less. By reducing the average particle size, a dense nitride particle film with small voids can be obtained. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more. If the particle size is too small, management of the film forming process becomes complicated. Therefore, the average particle size is preferably 2 μm or less, and more preferably 0.01 to 1 μm.

Moreover, the measuring method of an average particle diameter takes the arbitrary cross sections of a nitride particle film on an enlarged photograph. As an enlarged photograph, an SEM (Scanning Electron Microscope) photograph is used. The major axis of the nitride particles shown in the enlarged photograph is measured to determine the particle diameter. The average value for 50 nitride particles is called the average particle size.
When the interface between the substrate and the nitride particle film is subjected to XRD analysis, the component for a semiconductor manufacturing apparatus according to the embodiment has a ratio of the maximum peak of oxide to the maximum peak of nitride (maximum peak of oxide / maximum of nitride). The peak is 0.1 or less (including zero).
The interface between the base material and the nitride particle film is a place where the base material and nitride particles (including oxynitride particles) are in direct contact. In the XRD analysis, the region including the interface is irradiated with X-rays and measured. The spot diameter for X-ray irradiation is 100 μm or less. Further, the spot diameter may be about 1 μm using a slit.
The XRD measurement conditions are a Cu target (Cu-Kα), a tube voltage of 40 kV, a tube current of 40 mA, and a scanning range (2θ) of 20 to 100 °.

The maximum peak of nitride indicates the largest peak among peaks based on nitride particles or oxynitride particles constituting the nitride particle film. The maximum peak of oxide is the largest peak among oxide peaks detected separately from the peak of nitride or oxynitride.
The ratio of the maximum peak of oxide to the maximum peak of nitride (maximum peak of oxide / maximum peak of nitride) is 0.1 or less (including zero) means that there are few oxides that are crystallized It is shown that. XRD analysis detects peaks peculiar to crystalline compounds. By detecting the peak, the presence or absence of the crystalline compound can be confirmed. Further, the height of the peak varies depending on the amount of the crystalline compound present. When the amount of the specific crystalline compound is large, the peak corresponding to the specific crystal compound becomes high. Such a tendency is strong in the maximum peak as the main peak.

Crystalline oxides have lower thermal conductivity than nitride particles or oxynitride particles. Moreover, when there are many crystalline oxides, the grain boundary between crystalline oxides will increase. When the grain boundary between oxides increases, it becomes a heat resistance region, and heat dissipation decreases. By setting the maximum peak ratio (maximum peak of oxide / maximum peak of nitride) to 0.1 or less (including zero), the crystalline oxide present at the interface between the base material and the nitride particle film can be reduced. . Thereby, the heat dissipation from a nitride particle film to a base material can be improved.
The maximum peak ratio (maximum peak of oxide / maximum peak of nitride) is preferably 0.1 or less (including zero), more preferably 0.01 or less (including zero). The closer the maximum peak ratio (maximum peak of oxide / maximum peak of nitride) is to zero, the less crystalline oxide.
Moreover, it is preferable that the film thickness of the nitride particle film is 1 μm or more and 200 μm or less. If the film thickness is less than 1 μm, the durability of the film may be insufficient. Moreover, when it exceeds 200 micrometers, there exists a possibility of causing the increase in manufacturing cost. Therefore, the thickness of the nitride particle film is preferably 1 μm or more and 200 μm or less, and more preferably 3 μm or more and 100 μm or less.
The film density is preferably 90% or more. The film density indicates how much nitride particles are packed in the nitride particle film. In other words, it indicates that there are few pores in the nitride particle film. That is, a film density of 90% or more indicates a porosity of 10 vol% or less. If the film density is less than 90%, the film strength may be reduced. Therefore, the film density is preferably 90% or more, more preferably 95% or more and 100% or less.
The film density is measured by SEM observation of the unit area “film thickness × 50 μm” in an arbitrary cross section of the nitride particle film. A value obtained by dividing the total area of the pores shown in the SEM photograph by the unit area is defined as a porosity (vol%). The average value at three arbitrary unit areas is defined as the porosity (vol%), and the value subtracted from 100 is defined as the film density.

Moreover, it is preferable that a base material is a metal member or a ceramic member. As long as the component for a semiconductor manufacturing apparatus according to the embodiment includes the nitride particle film, the material of the base material is not limited. On the other hand, by using a metal member or a ceramic member for the base material, it is possible to improve the heat dissipation and strength of the semiconductor manufacturing apparatus component.
Examples of the metal member include aluminum (Al), copper (Cu), iron (Fe), silicon (Si), or an alloy containing these as a main component. Examples of the ceramic member include metal oxide, metal nitride, metal carbide, or a composite compound thereof (oxynitride or the like). Further, the ceramic member may be a member to which a sintering aid is added as necessary.

The parts for semiconductor manufacturing apparatus as described above are excellent in durability against radicals and have good heat dissipation. Therefore, it can be used for various semiconductor manufacturing apparatuses. As a semiconductor manufacturing apparatus, any one of a CVD process, a PVD process, and an etching process is preferable.
The CVD process is a process using chemical vapor deposition. In the CVD method, a gas of reaction system molecules (or a mixture of reaction system molecules and inert carriers) is flowed over a heated substrate, and generated by reactions such as hydrolysis, autolysis, photolysis, redox, and substitution. This is a film forming method for depositing an object on a substrate. Also, what uses plasma discharge to promote the reaction is called plasma CVD. Since plasma CVD is excited by plasma, the film forming speed can be increased.
In the PVD process, physical vapor deposition is performed in a vacuumed container by heating the vapor deposition material to vaporize or sublimate it, and attach it to the surface of the substrate placed at a remote location, It is to form. Depending on the type of vapor deposition material and substrate, heating is performed by a method such as resistance heating, electron beam, high frequency induction, or laser. Examples of the PVD method include a sputtering method, an ion plating method, and an ion beam deposition method.
The etching process is a surface processing technique using a corrosive action by chemicals or the like. For example, by forming a metal film on the substrate and applying an etching resist to a necessary portion, the metal thin film at a portion where the resist is not applied can be left. Etching processes include wet etching and dry etching.
Further, the wet etching is a liquid etching. Further, dry etching is a method of etching a material with a reactive gas (etching gas), ions, or radicals. Reactive ion etching is a method in which reactive gas is etched by ionizing and radicalizing reactive gas with plasma. Reactive ion etching is a kind of dry etching.

In the semiconductor manufacturing process, one or more of a CVD process, a PVD process, and an etching process are used. In recent semiconductor manufacturing processes, a process using plasma is used from the viewpoint of fine processing and processing speed. Examples of the process using plasma include a plasma CVD process, a sputtering process, and a dry etching process. The semiconductor manufacturing apparatus component according to the embodiment is excellent in plasma resistance. Moreover, heat dissipation is also excellent. The use of plasma involves heating. When the heat dissipation property of the semiconductor manufacturing apparatus component is high, heat is easily released. When the heat dissipation becomes high, the thermal stress between the nitride particle film and the base material can be relieved, so that the durability of the semiconductor manufacturing apparatus component becomes high. Therefore, the semiconductor manufacturing process can be performed with a high yield. Moreover, since the durability of the semiconductor manufacturing apparatus component is high, the replacement frequency can be reduced.
Further, the semiconductor manufacturing apparatus component may be any component mounted in the semiconductor manufacturing apparatus. Examples of such parts include mask materials, inner walls, electrostatic chucks, susceptors, and electrode members.

Next, a method for manufacturing a component for a semiconductor manufacturing apparatus according to the embodiment will be described. As long as the semiconductor manufacturing apparatus component according to the embodiment has the above-described configuration, the manufacturing method is not particularly limited, but the following method is a method for obtaining a good yield.
As a film forming method for depositing nitride particles, a film forming method that does not heat the raw material powder more than necessary is preferable. Examples of such a film forming method include an aerosol deposition method (AD method), a supersonic free jet-PVD method (SFJ-PVD method), a cold spray method (CS method), and an impact sintering method (CASP method). It is done. For example, the thermal spraying method is a film forming method in which raw material powder is deposited in a molten state. When the raw material powder is in a molten state, the raw material powder is easily oxidized. When the raw material powder is oxidized, oxide crystals are formed at the interface between the nitride particle film and the substrate.
The AD method, SFJ-PVD method, CS method, and CASP method can all be blown at a supersonic level injection speed without melting the raw material powder. For this reason, nitride particles can be deposited without melting the raw material powder.
Moreover, since AD method and SFJ-PVD method are vacuum processes, oxidation of the raw material powder can be suppressed. On the other hand, since the film forming process is performed in a vacuum chamber, it is not suitable for enlargement. The CASP method is not necessarily performed in a vacuum, and is suitable for upsizing.
The raw material powder preferably has an average particle size of 2 μm or less. Since the raw material powder is prevented from melting as described above, if the average particle diameter of the raw material powder is 2 μm or less, the average particle diameter of the finished nitride particle film can be 2 μm or less. The average particle size of the raw material powder is preferably 2 μm or less, more preferably 1 μm or less.

A method using a target having the same composition as the raw material powder is also effective. The raw material target is irradiated with high energy such as a laser to evaporate the raw material powder at the nanoparticle level. The raw material powder generated by evaporation can be blown toward the substrate. Thereby, the average particle diameter of raw material powder can also be 30 nm or less. It is also possible to increase the film density by reducing the raw material powder. In the case of a film forming method that does not involve melting of the raw material powder, if the raw material powder is formed while flying at supersonic speed, the raw material powder is pulverized by the collision between the raw material powder and the substrate. Similarly, the raw material powder is pulverized when the raw material powder collides with the nitride particle film. If the raw material powder is pulverized too much, the film density may decrease.
In order to prevent oxidation of the base material or raw material powder during film formation, it is effective to perform the film formation step in a vacuum or in an inert atmosphere. It is also effective to clean the surface of the substrate in advance and remove the oxide film on the surface. This method is preferable when nitride is used as the raw material powder.
Moreover, the method of forming into a film in nitrogen atmosphere using a metal target as a raw material is also mentioned. For example, when forming an AlN film, Al is evaporated from an Al target. Next, it is also possible to form a film with Al as AlN by film formation in a nitrogen-containing atmosphere.

(Example)
(Examples 1 to 3, Comparative Example 1)
As a base material, a metal Al plate (length 50 mm × width 50 mm × thickness 1 mm) was prepared. Next, AlN powder was prepared as a raw material powder. Films were formed by the methods shown in Table 1, respectively. The film formation range was a range of 20 mm long × 20 mm wide.
The SFJ-PVD method shown in Table 1 is a supersonic free jet-PVD method, the AD method is an aerosol deposition method, and the CASP method is an impact sintering method. Further, the surface cleaning of the substrate is performed by removing a surface oxide. The SFJ-PVD method uses a pure AlN target (AlN-TG) and performs a film forming process in a vacuum. An AlN target having an average crystal grain size of 30 μm was used.

The obtained nitride particle film is shown in Table 2. The film thickness (μm), the average particle diameter (μm) of the nitride particles, and the film density (%) are measured by measuring an arbitrary cross section in the thickness direction of the nitride particle film with an SEM photograph (magnification 1000 times). A unit area “film thickness × 50 μm” is extracted from the SEM photograph. The average film thickness in the unit area is defined as “film thickness (μm)”. Further, the major axis of the nitride particles reflected in the unit area is obtained, and the average value for 50 grains is defined as “average grain diameter of nitride particles (μm)”. Further, the value obtained by removing the total area of pores reflected in the unit area from the unit area was taken as the film density (%). Each of these operations was carried out for three arbitrary unit areas “film thickness × 50 μm”, and the average values are shown in Table 2.
Further, the XRD peak ratio at the interface between the base material and the nitride particle film was analyzed by XRD at locations where the base material and the nitride particles were in direct contact. The XRD measurement conditions were a Cu target (Cu-Kα), a tube voltage of 40 kV, a tube current of 40 mA, a scanning range (2θ) of 20 to 100 °, and a spot diameter of 1 μm using a slit. From the XRD chart, the ratio of the maximum peak of the oxide crystal to the maximum peak of nitride (AlN) was determined.

As can be seen from the table, the maximum peak ratio (maximum peak of oxide / maximum peak of nitride) of the component for a semiconductor manufacturing apparatus according to the example was 0.1 or less. On the other hand, since the average particle diameter of the raw material powder was large in Comparative Example 1 (CASP method), the density was low. Further, since the substrate surface was not cleaned, the maximum peak ratio (maximum peak of oxide / maximum peak of nitride) was large.
Next, the semiconductor manufacturing apparatus components according to the examples and comparative examples were exposed to a plasma atmosphere to show their durability. Moreover, the thermal conductivity was measured. The results are shown in Table 3.
The thermal conductivity was measured by a laser flash method. Further, the durability to the plasma atmosphere was performed under the following conditions, and the film loss was examined.
Durability test to plasma atmosphere Gas: CF ₄ / O ₂ / Ar = 80/20/10 sccm, 20 mTorr
Output: ICP100W, Bias100W
Exposure time: 12 hours [(30 minutes discharge + 10 minutes cooling) × 24 times]

As can be seen from the table, the durability to plasma was excellent. This is because the formation of an oxide at the interface between the nitride particle film and the base material is suppressed, and thus heat dissipation is excellent. The high film density also enhances the effect.
For this reason, the semiconductor manufacturing apparatus component according to the example is excellent in durability. Therefore, a semiconductor manufacturing apparatus using the semiconductor manufacturing apparatus can manufacture a semiconductor with a high yield. It is also possible to reduce the number of times of maintenance of parts for semiconductor manufacturing equipment.

  As mentioned above, although some embodiment of this invention was illustrated, these embodiment is shown as an example and does not limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, changes, and the like can be made without departing from the spirit of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and equivalents thereof. Further, the above-described embodiments can be implemented in combination with each other.

DESCRIPTION OF SYMBOLS 1 ... Semiconductor manufacturing apparatus component 2 ... Base material 3 ... Nitride particle (oxynitride particle)
4 ... Nitride particle film 5 ... Interface

Claims (7)

In a semiconductor manufacturing apparatus component provided with a nitride particle film in which nitride particles or oxynitride particles are deposited on a substrate, the nitride particles are selected from silicon nitride, aluminum nitride, silicon oxynitride, and aluminum oxynitride The average particle size of the nitride particles is 2 μm or less,
When the interface where the substrate and the nitride particle film are in direct contact is analyzed by XRD at a spot diameter of 1 μm, the ratio of the maximum peak of oxide to the maximum peak of nitride (maximum peak of oxide / maximum peak of nitride) is 0. .01 or less (including zero) for semiconductor manufacturing equipment. When the interface where the substrate and the nitride particle film are in direct contact is analyzed by XRD at a spot diameter of 1 μm, the ratio of the maximum peak of oxide to the maximum peak of nitride (maximum peak of oxide / maximum peak of nitride) is 0. The semiconductor manufacturing apparatus component according to claim 1, wherein the component is 0.001 or less (including zero). Semiconductor manufacturing equipment component according to any one of claims 1 to claim 2, wherein an average particle diameter of the nitride particles is 1μm or less. The film thickness of the nitride particles film 1μm or 200μm or less, the semiconductor manufacturing device component according to any one of claims 1 to claim 3, wherein the film density is 90% or more. The component for a semiconductor manufacturing apparatus according to any one of claims 1 to 4 , wherein the base material is a metal member or a ceramic member. A semiconductor manufacturing apparatus comprising the semiconductor manufacturing apparatus component according to any one of claims 1 to 5 . The semiconductor manufacturing apparatus according to claim 6 , wherein the semiconductor manufacturing process includes any one of a CVD process, a PVD process, and an etching process.

Images