WO2013133110A1

WO2013133110A1 - Cvd device

Info

Publication number: WO2013133110A1
Application number: PCT/JP2013/055263
Authority: WO
Inventors: 阿部　浩二; 本多　祐二; 慶一寺島
Original assignee: 株式会社ユーテック
Priority date: 2012-03-09
Filing date: 2013-02-21
Publication date: 2013-09-12
Also published as: JPWO2013133110A1; JP2017179612A; SG11201405405SA; JP6229136B2

Abstract

Provided is a CVD device wherein it is possible to reduce the particle contamination of a substrate. This CVD device for forming a film on a substrate by means of the CVD method is equipped with a chamber (101), a substrate holder (104) disposed within the chamber and for holding the substrate, and a gas introduction mechanism for introducing a raw material gas into the chamber, wherein a film formed from a material selected from among a metal, a ceramic, a plastic or a cermet is formed on at least one of the following: the inner surface of the chamber; the substrate holder; an attachment prevention plate disposed within the chamber; a tool disposed within the chamber; or a gas shower member for introducing the raw material gas into the chamber in a showering manner.

Description

CVD equipment

The present invention relates to a CVD apparatus in which particles are reduced by surface-treating the inside of the apparatus.

In a film deposition apparatus such as a CVD apparatus, when a thin film is deposited on a deposition target substrate in a chamber, the thin film adheres to the inner surface of the chamber, and the deposited thin film peels off to cause particle contamination on the deposition target substrate. May occur.
Therefore, as a measure for preventing the above-described particle contamination, the inner surface of the chamber is subjected to blasting, or an adhesion-preventing plate subjected to blasting is attached to the inner surface of the chamber. By performing blasting in this way, when the thin film adheres to the inner surface of the chamber or the adhesion-preventing plate, it is a measure to suppress particle contamination by improving the adhesion with the thin film. However, even if this measure is taken, particle contamination cannot be sufficiently suppressed.
As a measure for preventing the above-mentioned particle contamination, there is a method of sticking a particle getter on the inner surface of the chamber. However, for this measure, the particle getter is expensive, causes abnormal discharge when pasted on the electrode surface of the plasma CVD apparatus, and has a fine structure such as an inlet for introducing a shower-like gas into the chamber. There is a problem that it cannot be applied to the substrate to be processed.

An object of one embodiment of the present invention is to provide a CVD apparatus that can reduce particle contamination on a substrate.

Each of the following (1) to (12) is a CVD apparatus according to one embodiment of the present invention.
(1) In a CVD apparatus for forming a film on a substrate by a CVD method,
A chamber;
A substrate holder disposed in the chamber and holding the substrate;
A gas introduction mechanism for introducing a source gas into the chamber;
Comprising
At least one of an inner surface of the chamber, the substrate holder, a deposition plate disposed in the chamber, a jig disposed in the chamber, and a gas shower member for introducing the source gas into the chamber in a shower shape And a film made of any one of metal, ceramics, plastic, and cermet.
(2) In (1) above,
The CVD apparatus characterized in that the material contains 10% by weight or more of at least one of Cr, W and Mo.
(3) In the above (1) or (2),
The material contains Cr 1 wt% or more and 50 wt% or less, WC contains 0 wt% or more and 49 wt% or less, Mo contains 0 wt% or more and 49 wt% or less, and Cr, WC, and Mo are contained. A CVD apparatus comprising 50% by weight or less in total, Fe, Si, C, B, Al and Cu in a total content of 0% by weight to 50% by weight, the balance being made of Ni and inevitable impurities .
(4) In (3) above,
The Fe is contained in an amount of 0 to 10% by weight, the Si is contained in an amount of 0 to 10% by weight, the C is contained in an amount of 0 to 3% by weight, and the B is contained in an amount of 0 to 7% by weight. A CVD apparatus comprising: 1 wt% or less, Al containing 0 wt% or more and 15 wt% or less, and Cu containing 0 wt% or more and 5 wt% or less.
(5) In the above (3) or (4),
The CVD apparatus characterized in that the material contains 9 wt% or more and 20 wt% or less of Cr.
(6) In any one of (3) to (5) above,
The said material contains 3 to 10 weight% of Mo, The CVD apparatus characterized by the above-mentioned.
(7) In any one of (3) to (6) above,
The CVD apparatus characterized in that the material contains WC in an amount of 30 wt% to 40 wt%.
(8) In (2) above,
The CVD apparatus characterized in that the material contains 80% by weight or more of Mo, and the balance is made of impurities and inevitable impurities.
(9) In (8) above,
The CVD apparatus, wherein the impurity is at least one of Fe, Si, and C.
(10) In any one of the above (1) to (9),
A CVD apparatus, wherein the film made of the material is formed by thermal spraying.
(11) In any one of the above (1) to (10),
The CVD apparatus characterized in that the film formed on the substrate is a carbon film.

According to one embodiment of the present invention, a CVD apparatus that can reduce particle contamination on a substrate can be provided.

FIG. 1 is a cross-sectional view schematically showing a plasma CVD apparatus according to one embodiment of the present invention.
FIG. 2 is a cross-sectional view schematically illustrating a plasma CVD apparatus according to one embodiment of the present invention.
FIG. 3 is a photograph showing the results of a tape peel test performed on samples 1 to 4 of the example.
FIG. 4 is a photograph showing the results of a tape peel test performed on Sample 5 of the Example.
FIG. 5 is a photograph showing the results of a tape peel test performed on samples 6 to 9 of comparative examples.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it will be easily understood by those skilled in the art that modes and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments below.
(First embodiment)
FIG. 1 is a cross-sectional view schematically showing a plasma CVD apparatus according to one embodiment of the present invention.
The plasma CVD apparatus has a film formation chamber 101, and a lid 102 is disposed on the film formation chamber 101. A film formation chamber 103 is formed in the film formation chamber 101 by covering the film formation chamber 101 with a lid 102.
A stage electrode 104 that holds a deposition target substrate (not shown) is disposed below the deposition chamber 103, and the stage electrode 104 is electrically connected to a high-frequency power source 106. The stage electrode 104 also functions as an RF application electrode and functions as a substrate holder. The periphery and the lower part of the stage electrode 104 are shielded by an earth shield 105.
A gas shower electrode 107 is disposed at a position parallel to the stage electrode 104 above the film forming chamber 103. These are a pair of parallel plate electrodes. The periphery and upper part of the gas shower electrode 107 are shielded by an earth shield 108. The gas shower electrode 107 is connected to the ground potential. The gas shower electrode 107 also functions as a gas shower member that introduces the source gas into the film formation chamber 101 in a shower shape.
Below the gas shower electrode 107 (on the upper surface side of the stage electrode), a plurality of inlets (not shown) for introducing a shower-like source gas are formed on the surface side of the deposition target substrate. A gas introduction path (not shown) is provided inside the gas shower electrode 107. One side of the gas introduction path is connected to the introduction port, and the other side of the gas introduction path is connected to a source gas supply mechanism (not shown). The film forming chamber 101 is provided with an exhaust port 110 for evacuating the inside of the film forming chamber 103. The exhaust port 110 is connected to an exhaust pump (not shown).
On the inner surface of the film forming chamber 101, the inner surface of the lid 102, the stage electrode 104, and the gas shower electrode 107, a sprayed film made of any material of metal, ceramics, plastic, and cermet is formed. This thermal spray film is formed by thermal spraying, and the following films can be used. Note that thermal spraying is a surface treatment method in which particles that are melted or heated to a state close to that by spraying are sprayed onto the surface of the object to form a coating.
The first sprayed film is a film made of a material containing 10% by weight or more of at least one of Cr, W and Mo.
The second sprayed film has a Cr content of 1 to 50% by weight (preferably 5 to 50% by weight, more preferably 1 to 20% by weight, and even more preferably 5 to 15% by weight. % By weight or less, or 9% by weight or more and 20% by weight or less, more preferably 9.50% by weight or more and 16.2% by weight or less, or 1% by weight or more and 10% by weight or less, more preferably 5% by weight or more and 10% by weight or less. And WC is contained in an amount of 0 to 49% by weight (preferably 0.01 to 49% by weight, more preferably 20 to 49% by weight, even more preferably 30 to 40% by weight). Wt% or less, more preferably 30 wt% or more and 35 wt% or less, or 20 wt% or more and 35 wt% or less), and Mo is 0 wt% or more and 49 wt% or less (preferably 1 wt% or more 2 % By weight or less, more preferably 1% by weight or more and 10% by weight or less, still more preferably 3% by weight or more and 10% by weight or less, further preferably 3% by weight or more and 6% by weight or less, and still more preferably 3.83% by weight. 6 wt% or less), and a total of 50 wt% or less of Cr, WC, and Mo, 0 wt% or more and 50 wt% or less of impurities, with the balance being Ni and inevitable impurities. It is a membrane.
The impurities here are Fe, Si, C, B, Al and Cu. In the second sprayed film, Fe is 0% by weight to 10% by weight (or 0.01% by weight to 10% by weight, or 0.01% by weight to 7% by weight, or 2.90% by weight or more). 7 wt% or less) and Si may be contained in an amount of 0 wt% to 10 wt% (or 0.01 wt% to 10 wt%, or 0 wt% to 5 wt%, or 0.01 wt%). % To 5% by weight, or 3.89% by weight, or 0.01% to 3.89% by weight, or 1% to 3.89% by weight, or 2.9% by weight, or 0.01 wt% or more and 2.9 wt% or less, or 1 wt% or more and 2.9 wt% or less) may be contained, and C is 0 wt% or more and 3 wt% or less (or 1.5 wt% or less). Or 0.75 wt% or less, or 0.5 wt% or less B may be contained in an amount of 0 to 7% by weight (or 0.01 to 7% by weight, or 4.5% by weight, or 0.01 to 4.5% by weight). % Or less, or 3.28% by weight or less, or 0.01% by weight or more and 3.28% by weight or less, or 2.3% by weight or less), and Al may be contained by 0 to 15% by weight. (Or 9 wt% or less, or 0.01 wt% or more and 9 wt% or less), and Cu is 0 wt% or more and 5 wt% or less (or 0.01 wt% or more and 5 wt% or less), or 1.9 wt% or less, or 0.01 wt% or more and 1.9 wt% or less).
The third sprayed film is a film made of a material containing Mo and the balance being made of inevitable impurities.
The fourth sprayed film is a film made of a material containing Mo by weight of 80% by weight or more and the balance being made of impurities and inevitable impurities. Here, the impurities are Fe, Si, and C.
Next, a film forming method using the plasma CVD apparatus will be described.
A deposition target substrate (not shown) is inserted into the deposition chamber 103 of the plasma CVD apparatus, and the deposition target substrate is held on the stage electrode 104 in the deposition chamber.
Next, the deposition target substrate is fixed on the stage electrode 104, the deposition chamber 101 is closed with a lid 102, and evacuated with an exhaust pump. Next, a shower-like source gas is introduced from the introduction port of the gas shower electrode 107 to the surface side of the deposition target substrate in the deposition chamber 103. As the source gas, a gas containing carbon is used. Then, the film formation chamber is made a desired atmosphere by controlling to a predetermined pressure, a raw material gas flow rate, etc., and a high frequency (RF) is applied from a high frequency power source 106 to generate plasma, thereby forming a carbon film on the deposition target substrate. Form a film.
According to the present embodiment, a sprayed film made of any of metal, ceramics, plastic, and cermet is formed on the inner surface of the film forming chamber 101, the inner surface of the lid 102, the stage electrode 104, and the gas shower electrode 107, respectively. Yes. For this reason, when a carbon film is deposited on the deposition target substrate in the deposition chamber 101, the carbon film adheres to the inner surface of the deposition chamber 101, and the adhesion between the deposited carbon film and the sprayed film. Therefore, the attached carbon film is difficult to peel off. As a result, particle contamination on the deposition target substrate can be reduced. Further, a sprayed film made of a material containing at least 10% by weight of Cr, W and Mo has good adhesion to the carbon film. Further, Cr is contained in an amount of 1 to 50% by weight, WC is contained in an amount of 0 to 49% by weight, Mo is contained in an amount of 0 to 49% by weight, and Cr, WC and Mo are added in total. The thermal spray film made of a material containing 50% by weight or less has better adhesion to the carbon film. Further, a sprayed film made of a material containing 80% by weight or more of Mo also has better adhesion to the carbon film.
In this embodiment, the sprayed film is formed on the inner surface of the film forming chamber 101, the inner surface of the lid 102, the stage electrode 104, and the gas shower electrode 107, but the sprayed film is formed on the inner surface of the film forming chamber 101, It may be formed on at least one of the inner surface of the lid 102, the stage electrode 104, and the gas shower electrode 107, or other than these, for example, a deposition plate disposed in the film forming chamber, or disposed in the film forming chamber. It may be formed on a jig or the like. That is, by forming a thermal spray film on a portion where a carbon film may adhere during the film formation process, particle contamination on the film formation substrate can be reduced.
The deposition preventing plate is a plate for preventing the carbon film from adhering to the inner surface of the chamber, and is disposed on the inner surfaces of the film forming chamber 101 and the lid 102, for example.
A jig is a general term for instruments that use parts for fixing and mounting. For example, a jig is a processed product for installing or fixing a film formation substrate such as a silicon wafer at a specified position.
In this embodiment, an example of a plasma CVD apparatus is given as an aspect of the present invention, but another CVD apparatus (for example, a thermal CVD apparatus) may be used as another aspect of the present invention.
(Second Embodiment)
FIG. 2 is a cross-sectional view schematically illustrating a plasma CVD apparatus according to one embodiment of the present invention. This plasma CVD apparatus has a symmetrical structure with respect to the film formation substrate (for example, a disk substrate) 111, and is an apparatus capable of simultaneously forming films on both surfaces of the film formation substrate 111. The left side of the deposition target substrate 111 is shown, and the right side is omitted.
The plasma CVD apparatus has a chamber 112, and a hot cathode (cathode electrode) 113 is formed in the chamber 112. Both ends of the hot cathode 113 are electrically connected to an AC power source 115 located outside the chamber 112. One end of the AC power supply 115 is electrically connected to the ground 116.
A horn anode 114 having a funnel shape is disposed in the chamber 112, and the horn anode 114 is electrically connected to a DC power source 117. The positive potential side of the DC power source 117 is electrically connected to the horn anode 114, and the negative potential side of the DC power source 117 is electrically connected to the ground 116.
A substrate holder (not shown) is disposed in the chamber 112, and a deposition target substrate 111 is held on the substrate holder. The deposition target substrate 111 is electrically connected to a DC power source (DC power source) 122 as an ion acceleration power source. The negative potential side of the DC power source 122 is electrically connected to the deposition target substrate 111, and the positive potential side of the DC power source 122 is electrically connected to the ground 116.
A plasma wall 118 is disposed in the chamber 112 so as to cover the space between the hot cathode 113 and the horn anode 114 and the deposition target substrate 111. The plasma wall 118 has a cylindrical shape and is electrically connected to a float potential (not shown).
Thermal spray films are formed on the inner surface of the chamber 112, the substrate holder, the horn anode 114, and the plasma wall 118, respectively. This sprayed film can use the same method and the same material as in the first embodiment.
Next, a method for forming a DLC (Diamond Like Carbon) film on the deposition target substrate 111 using the plasma CVD apparatus illustrated in FIG. 2 will be described.
First, the inside of the chamber 112 is set to a predetermined vacuum state, and for example, toluene (C ₇ H ₈ ) gas is introduced into the chamber 112 as a film forming source gas. After the inside of the chamber 112 reaches a predetermined pressure, the hot cathode 113 is heated by supplying an AC current to the hot cathode 113 by the AC power supply 115. Further, a direct current is supplied to the horn anode 114 by a DC power source 117, and a direct current is supplied to the deposition target substrate 111 by a DC power source 122.
By heating the hot cathode 113, a large amount of electrons are emitted from the hot cathode 113 toward the horn anode 114, and glow discharge is started between the hot cathode 113 and the horn anode 114. Toluene gas as a film forming raw material gas inside the chamber 112 is ionized by a large amount of electrons to be in a plasma state. At this time, the reaction represented by the following formula (1) occurs. Then, the film-forming raw material molecules in the plasma state are directly accelerated by the negative potential of the film formation substrate 111, fly toward the film formation substrate 111, and adhere to the surface of the film formation substrate 111. Is done. As a result, a thin DLC film is formed on the deposition target substrate 111. At this time, the reaction of the following formula (2) occurs on the surface of the deposition target substrate 111.
C ₇ H ₈ + e ⁻ → C ₇ H ₈ ⁺ +2 e ⁻ (1)
C ₇ H ₈ ⁺ + e ⁻ → C ₇ H ₂ + 3H ₂ ↑ (2)
According to the present embodiment, the sprayed films are formed on the inner surface of the chamber 112, the substrate holder, the horn anode 114, and the plasma wall 118, respectively. For this reason, when a DLC film is formed on the deposition target substrate 111 in the chamber 112, the DLC film adheres to the inner surface of the chamber 112 and the like, but the adhesion between the deposited DLC film and the sprayed film is good. The attached DLC film is difficult to peel off. As a result, particle contamination on the deposition target substrate 111 can be reduced.
In this embodiment, the sprayed film is formed on the inner surface of the chamber 112, the substrate holder, the horn anode 114, and the plasma wall 118. However, the sprayed film is formed on the inner surface of the chamber 112, the substrate holder, the horn anode 114, and It may be formed on at least one of the plasma walls 118, or other than these, for example, a jig disposed in the chamber, or a gas shower member for introducing the source gas into the chamber 112 in a shower shape. Also good. That is, by forming a thermal spray film on a portion where a DLC film may adhere during the film formation process, particle contamination on the deposition target substrate can be reduced.
In this embodiment, an example of a plasma CVD apparatus is given as an aspect of the present invention, but another CVD apparatus (for example, a thermal CVD apparatus) may be used as another aspect of the present invention.

(Example samples 1 to 5)
Five sprayed films shown in Table 1 are formed on the surface of the substrate made of SUS by a spraying method. The thermal spraying method at this time is a gas flame spraying method using powder. In this way, Samples 1 to 5 each having five sprayed films formed on the substrate surface were prepared (see Table 1).
(Comparative sample 6-9)
Samples 6 and 7 were prepared by blasting the surface of a substrate made of SUS and Al (see Table 2). In this blasting process, an alumina material having a particle size of F36 was used.
Also, Al and Cu sprayed films are formed on the surface of the substrate made of SUS by the same spraying method as Samples 1-5. Thus, samples 8 and 9 were prepared in which sprayed films of Al and Cu were formed on the substrate surface (see Table 2).
Next, DLC films were formed on the sprayed films of Samples 1 to 5, 8, and 9 and on the substrates of Samples 6 and 7, respectively, under the following film forming conditions.
Film forming apparatus: Plasma CVD apparatus shown in FIG. 1 Starting material: Toluene (C ₇ H ₈ )
Gas flow rate: 30sccm
Gas pressure: 0.5Pa
High frequency output frequency: 13.56 MHz
High frequency output: 300W
DLC film thickness: 100 nm
Next, a tape peeling test was performed on each of the samples 1 to 9 on which the DLC film was formed by the following test method.
The tape peeling test was performed according to JIS K 5400. The DLC film was cut into a grid pattern with a 1 mm interval with a cutter knife, the tape was attached, and then the tape was peeled off.

FIG. 3 is a photograph showing the results of a tape peel test performed on samples 1 to 4 of the example. FIG. 4 is a photograph showing the results of a tape peel test performed on Sample 5 of the Example. FIG. 5 is a photograph showing the results of a tape peel test performed on samples 6 to 9 of comparative examples.
As shown in FIG. 3, FIG. 4 and Table 1, Samples 1, 3 and 4 of the example obtained a result (◯) that the adhesion between the DLC film and the sprayed film was good, and Sample 5 of the example was DLC. The results show that the adhesion between the film and the sprayed film is particularly good (サンプル), and the sample 2 of the example is inferior to the samples 1, 3, and 4 in adhesion between the DLC film and the sprayed film, but has a certain degree of adhesion. A result (Δ) was obtained.
On the other hand, as shown in FIG. 5 and Table 2, the samples 6 to 8 of the comparative example had a result (x) that the adhesion between the DLC film and the substrate or the sprayed film was poor, and the sample 9 of the comparative example was The adhesion between the DLC film and the sprayed film was better than that of Samples 6 to 9, and a result (Δ) having a certain degree of adhesion was obtained.
According to this embodiment, when a DLC film is formed on the deposition target substrate in the chamber, even if the DLC film adheres to the inner surface of the chamber or the like, the adhesion to the DLC film is shown in Table 1. By forming the sprayed film on the inner surface of the chamber or the like, it was confirmed that the adhered DLC film was not easily peeled off, and as a result, particle contamination on the deposition target substrate could be reduced.

DESCRIPTION OF SYMBOLS 101 ... Film-forming chamber 102 ... Cover 103 ... Film-forming chamber 104 ...

Stage electrode

105, 108 ... Earth shield 106 ... High frequency power source 107 ... Gas shower electrode 110 ... Exhaust port 111 ... Substrate to be formed 112 ... Chamber 113 ... Cathode electrode ( Hot cathode)
114 ... Anode electrode (horn anode)
115 ... AC power source 116 ... Ground 117 ... DC power source 118 ... Plasma wall 122 ... DC power source

Claims

In a CVD apparatus for forming a film on a substrate by a CVD method,
A chamber;
A substrate holder disposed in the chamber and holding the substrate;
A gas introduction mechanism for introducing a source gas into the chamber;
Comprising
At least one of an inner surface of the chamber, the substrate holder, a deposition plate disposed in the chamber, a jig disposed in the chamber, and a gas shower member for introducing the source gas into the chamber in a shower shape And a film made of any one of metal, ceramics, plastic, and cermet.
In claim 1,
The CVD apparatus characterized in that the material contains 10% by weight or more of at least one of Cr, W and Mo.
In claim 1 or 2,
The material contains Cr 1 wt% or more and 50 wt% or less, WC contains 0 wt% or more and 49 wt% or less, Mo contains 0 wt% or more and 49 wt% or less, and Cr, WC, and Mo are contained. A CVD apparatus comprising 50% by weight or less in total, Fe, Si, C, B, Al and Cu in a total content of 0% by weight to 50% by weight, the balance being made of Ni and inevitable impurities .
In claim 3,
The Fe is contained in an amount of 0 to 10% by weight, the Si is contained in an amount of 0 to 10% by weight, the C is contained in an amount of 0 to 3% by weight, and the B is contained in an amount of 0 to 7% by weight. A CVD apparatus comprising: 1 wt% or less, Al containing 0 wt% or more and 15 wt% or less, and Cu containing 0 wt% or more and 5 wt% or less.
In claim 3 or 4,
The CVD apparatus characterized in that the material contains 9 wt% or more and 20 wt% or less of Cr.
In any one of Claims 3 thru | or 5,
The said material contains 3 to 10 weight% of Mo, The CVD apparatus characterized by the above-mentioned.
In any one of Claims 3 thru | or 6,
The CVD apparatus characterized in that the material contains WC in an amount of 30 wt% to 40 wt%.
In claim 2,
The CVD apparatus characterized in that the material contains 80% by weight or more of Mo, and the balance is made of impurities and inevitable impurities.
In claim 8,
The CVD apparatus, wherein the impurity is at least one of Fe, Si, and C.
In any one of Claims 1 thru | or 9,
A CVD apparatus, wherein the film made of the material is formed by thermal spraying.
In any one of Claims 1 thru | or 10,
The CVD apparatus characterized in that the film formed on the substrate is a carbon film.